method for making paper, cardboard or paperboard and use

专利摘要:
METHOD FOR INCREASING THE ADVANTAGES OF RESISTANCE AID IN THE PRODUCTION OF PAPER AND PAPERBOARD. The present invention relates to a method for making paper, cardboard or paperboard comprising the steps of: (a) defibrillating an aqueous cellulosic material containing a starch; (b) preventing at least a portion of the starch from being microbially degraded by treating the aqueous cellulosic material containing the starch with one or more biocides; and (h) adding a dry and / or wet strength polymer to the cellulosic material.
公开号:BR112014004225B1
申请号:R112014004225-0
申请日:2012-08-24
公开日:2021-02-02
发明作者:Ludwig Krapsch；Christopher John Mc Gregor；Jean Victor Mallard De La Varende
申请人:Solenis Technologies Cayman, L.P.；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[0001] The present invention relates to a method for making paper, cardboard or paperboard comprising the steps of: (a) defibrillating an aqueous cellulosic material containing a starch; (b) prevent at least a portion of the starch from being microbially degraded by treating the aqueous cellulosic material containing the starch with one or more biocides, which are at least partially added to the cellulosic material in the coarse raw material area, where the cellulosic material has a raw material consistency of at least 2.0%; and (i) adding a dry and / or wet strength polymer to the cellulosic material.
[0002] In addition, the invention relates to a method for increasing the strength of paper, cardboard or paperboard, preferably dry strength and / or wet strength, comprising steps (a), (b) and ( h) as described above. BACKGROUND OF THE PREVIOUS TECHNIQUE
[0003] Resistance polymers (also referred to as resistance resins, resistance aids, resistance additives and others) are used extensively in papermaking. It is often distinguished between dry strength polymers and wet strength polymers, however dry strength polymers often give a degree of wet strength to paper, and vice versa. Today, the most common types of synthetic dry and / or wet strength polymers are based on polyvinylamine or polyacrylamide. Other resins such as poly (vinyl alcohol) or latex are used, but in general these are seen in paper surface applications, rather than as additives for wetted parts. Similarly, styrene acrylic resins have shown superior performance when applied through surface application instead of as raw material additives.
[0004] Various polymers are commercially available as wet or dry strength polymers. They can be classified into the following three categories: (ii) Polymers capable of only forming hydrogen bonds with starch and / or cellulosic fibers, such as certain polyacrylamides, usually do not provide significant degrees of resistance to damp, but can improve resistance to damp. dry paper. (iii) Polymers capable of additionally forming ionic bonds with starch and / or cellulosic fibers, such as highly cationic polyvinylamines, can provide dry resistance and some permanent wet resistance to paper. (iv)) Polymers capable of covalently bonding to cellulosic fibers, such as glyoxylated polyacrylamide and epichlorohydrin polyamide polyamines, achieve dry resistance and temporary or permanent wet resistance of paper.
[0005] Crosslinking agents provide wet resistance as well as dry resistance properties. This material forms a covalent bond with the hydroxyl group on cellulose, and is widely used in applications where wet resistance is tolerated and desired.
[0006] The wet resistance achieved with functionalized epichlorohydrin polymers is of a permanent nature, while the wet resistance achieved with glyoxylated polyacrylamide is of a temporary nature, losing effectiveness during prolonged exposure to water. This allows re-defibrillating the waste or waste paper to be easily achieved without special treatment. The dry resistance obtained is often greater than that achieved with other conventional resistance resins, poly (vinyl alcohol), starches or gums.
[0007] Glyoxylated polymers are typically less effective in systems where there are high levels of anionic (eg, anionic waste), such as secondary fiber supplies. Here, the resin forms a complex with the soluble and insoluble materials, thereby reducing the adsorption of the resin on the fibers. This can be overcome by adding cationic promoters (for example, alum or poly (aluminum chloride), or by careful charge control using other chemical additives in the supply, such as polyamide wet strength resins or cationic binders (I. Thorn et al., Applications of Wet-End Paper Chemistry, 2nd edition, Springer, 2009).
[0008] Dry and / or wet strength resins are not satisfactory in all respects, particularly as they do not always show optimal performance, particularly in papermaking plants having partially or completely closed water circuits.
[0009] Native or chemically modified starch is also used extensively in papermaking. It has been reported that up to 40 kg of starch per ton of paper are used for the production of thin uncoated and coated wood-free papers. Packaging paper made from 100% recovered paper can only be produced economically and in the required quality by adding cost-effective biosynthetic starch products. Therefore, these papers are produced with an average starch consumption of 40 kg t-1, mainly through surface application. An additional 25 kg t-1 is applied as an adhesive to the conversion plant. This means that a high amount of starch is typically returned to the production process through recovered papers, where conventionally it is barely retained on the paper sheet. Therefore, this amount of uncontrolled starch leads to a considerable load in the white water circuit (usual COD levels of 5,000 to 30,000 mg of O2 I-1) and finally also in the residual water (cf. H Holik, Handbook of paper and borard, Wiley-VCH Verlag GmbH & Co. KGaA, 1st ed, 2006, Chapter 3.4.3).
[00010] The starch that is released at the wet end of a papermaking machine by defibrillating waste or scrap paper is not attached to the fiber except through natural retention and usually does not contribute to strength parameters.
[00011] WO 01/36740 A2 discloses methods of making paper or cardboard. In one method, at least one cellulite enzyme composition and at least one cationic polymer composition are introduced into a papermaking pulp almost at the same time to form a treated pulp.
[00012] EP 0.361.763 A2 discloses a paper or paperboard filler flocculating composition comprising aqueous suspension starch particles, and a flocculating agent, for example, a polyacrylamide.
[00013] WO 2005/042843 A1 discloses a papermaking process, in which a first resistance agent is added to a slurry of raw material containing pulp and optionally other additives before being formed in a net at the wet end of a paper making machine.
[00014] DE 24 33 325 A1 discloses a process for the manufacture of paper and cardboard from waste paper in closed circuits.
[00015] WO 2006/060784 A2 discloses an aqueous composition of printing ink and coating containing dye, one or more high molecular weight starches and one or more water-soluble acrylic polymers or copolymers.
[00016] US 2006/289139 A1 discloses a method of improving retention and drainage in a papermaking process. The method provides for the addition of an associative polymer, starch or a starch derivative and optionally a siliceous material to the papermaking pulp.
[00017] US 2005/155731 A1 discloses a papermaking process, in which a first resistance agent is added to a slurry of raw material containing pulp and optionally other additives before being formed into a mesh at the wet end of a paper making machine.
[00018] WO 2009/059888 A1 discloses fiber products, comprising in your body at least 20% by weight of cellulosic fibers, and adequate amounts of an acid and a cationic retention aid for the acid, which can be marked by means of a laser beam.
[00019] WO 2006/014426 A1 relates to the manufacture of insulating paper coating having reduced or improved inhibition of mold and / or fungus growth.
[00020] US 2004/171719 A1 discloses a starch composition that is made by cooking a starch and combining the cooked starch with a polymer, the polymer containing anionic groups or potential anionic groups.
[00021] There is a demand for a method for making paper, cardboard or paperboard that has advantages compared to the methods of the prior art. SUMMARY OF THE INVENTION
[00022] The invention relates to a method for making paper, cardboard or paperboard comprising the steps of: (a) defibrillating an aqueous cellulosic material containing a starch; (b) prevent at least a portion of the starch from being microbially degraded by treating the aqueous cellulosic material containing the starch with one or more biocides, which are at least partially added to the cellulosic material in the coarse raw material area, where the cellulosic material has a raw material consistency of at least 2.0%; and (h) adding a dry and / or wet strength polymer to the cellulosic material.
[00023] Furthermore, the invention relates to a method for increasing the strength of paper, cardboard or paperboard, preferably dry strength, comprising steps (a), (b) and (h) as described above.
[00024] It has been found that treatment of the waste or scrap paper with a sufficient amount of a suitable biocide, for example, an oxidizing and / or non-oxidizing biocide program, during or after defibrillation, can prevent microbiological degradation of the starch contained in the paper waste or refuse thereby decreasing the electrical conductivity of the aqueous phase of the cellulosic material.
[00025] Surprisingly, in a relatively decreased electrical conductivity in this way, the strength performance of dry and / or wet strength polymers such as cellulose reactive polymers that carry aldehyde functional groups can be substantially improved. Thus, it was surprisingly found that by reducing electrical conductivity by adding sufficient amounts of suitable biocides, the consumption of dry and / or wet strength polymers that are necessary to achieve a desired dry strength of paper, cardboard or paperboard , can be substantially decreased. BRIEF DESCRIPTION OF THE DRAWINGS
[00026] Figure 1 shows the dependence of the redox potential (Figure 1A), pH value (Figure 1B), and electrical conductivity (Figure 1C) on the biocide dosage in an experiment that was conducted in a paper mill.
[00027] Figure 2 shows an experiment conducted in a paper mill where increasing the dosage of biocide immediately resulted in a substantial decrease in electrical conductivity from about 2000 μS / cm to about 1500 μS / cm within just 1 day.
[00028] Figure 3 shows the performance dependence of dry and / or wet strength polymers depending on the electrical conductivity of the aqueous phase of the cellulosic material. The performance of the dry and / or wet strength polymer is expressed in terms of an efficiency ratio that takes into account the increase in CMT, tear strength, tensile strength and dosage of the dry strength polymer and / or the damp. DETAILED DESCRIPTION OF THE INVENTION
[00029] The control of microbiological activity in papermaking machines with oxidizing and non-oxidizing biocides is well documented. There is also a vast literature on the use of starch as a wet and / or dry resistance polymer and the use of dry and / or wet resistance synthetic polymers can be used in addition to the starch applied on the wet end and on the surface of the paper sheet or as a total or partial replacement of the starch.
[00030] The invention is related to the use of an effective biocide, for example, an oxidizing and non-oxidizing microbiological control program, not only to prevent the formation of sludge as in the manufacture of conventional paper, but to prevent the degradation of starch ( non-ionic / native / cationic / anionic) present from defibrillation of residual or scrap paper; in combination with the use of a dry and / or wet strength polymer, preferably a cellulose-reactive polymer carrying functional aldehyde groups to improve the strength of the paper, particularly dry strength and / or wet strength.
[00031] It has been found that microbial degradation of starch, which is released, for example, by defibrillating the recycled residual supply, causes a substantial increase in electrical conductivity, particularly in partially or completely closed water circuits. Furthermore, it was found that such starch degradation can be effectively prevented by using appropriate biocides in adequate amounts (amylase control). Surprisingly, the reduction in electrical conductivity thus achieved provides much better dry and / or wet strength performance than conventional dry and / or wet strength polymers such as glyoxylated polyacrylamides and other cellulose-reactive polymers carrying functional groups of cellulose. aldehyde.
[00032] The invention relates to the use of a biocide, for example, an oxidizing and / or non-oxidizing biocide, as the first step preventing the degradation of starch by microbiological activity (amylase control), and the use of a polymer of dry and / or wet strength to improve the dry and / or wet strength properties of paper, cardboard or paperboard.
[00033] Thus, the method according to the invention features a two-step approach: 1.) avoidance of microbiological degradation of starch in streams of cardboard or papermaking machine approaches with 2.) addition of resistance polymers dry and / or wet providing better performance because of the relatively low electrical conductivity achieved through step 1.).
[00034] A first aspect of the invention concerns a method: - for treating a cellulosic material used in the manufacture of paper; and / or - to make a paper product; and / or - to manufacture paper, cardboard or paperboard; and / or - to increase the strength of paper, cardboard or paperboard; preferably dry resistance and / or wet resistance; and / or - to decrease the consumption of dry and / or wet strength polymer; - method, in each case, comprising the steps of: (a) defibrillating an aqueous cellulosic material containing a starch; (b) prevent at least a portion of the starch from being microbially degraded by treating the aqueous cellulosic material containing the starch with one or more biocides, which are at least partially added to the cellulosic material in the coarse raw material area, where the cellulosic material has a raw material consistency of at least 2.0%; and (c) optionally, to distinguish the cellulosic material; (d) optionally, mixing the cellulosic material; (e) optionally, target the cellulosic material; (f) optionally, refine the cellulosic material; (g) optionally, sieve and / or clean the cellulosic material in the coarse raw material area; (h) adding a dry and / or wet strength polymer, preferably having a weight average molecular weight of a maximum of 1,500,000 g / mol, more preferably a maximum of 1,000,000 g / mol, even more preferably a maximum 500,000 g / mol, cellulosic material. (i) optionally, sieve and / or clean the cellulosic material in the area of fine raw material, that is, after diluting the coarse raw material in a fine raw material; (j) optionally, forming a wet sheet of the cellulosic material; (k) optionally, draining the wet sheet; and (l) optionally, drying the drained sheet.
[00035] In a preferred embodiment, the water circuit of the papermaking plant in which the method according to the invention is performed is a recycling system, that is, a closed system. In another preferred embodiment, the water circuit of the papermaking plant in which the method according to the invention is carried out is an open system.
[00036] Preferably, step (b) is performed at least in part simultaneously with step (a) or after step (a). Preferably, step (h) is carried out at least partially after step (a). Preferably, step (h) is carried out at least partially after step (b).
[00037] For the purpose of the specification, the term "undegraded starch" and the phrase "prevent at least a portion of the starch from being microbially degraded" refer to any type of starch that preferably originates from waste paper or refuse and in the course of defibrillation has preferably essentially maintained its molecular structure. This includes mild degrees of degradation, but compared to conventional processes, the structure of the non-degraded starch preferably does not substantially change (in terms of microbiological degradation) during the defibrillation and papermaking processes.
[00038] In a preferred embodiment, the method according to the invention comprises the additional step of adding starch to the cellulosic material. Thus, in this embodiment, the starch that is processed according to the invention preferably originates from two sources: the first source is the starting material, for example, waste paper, already containing starch, and the second source is starch that it is additionally added to the cellulosic material. The additionally added starch can be any type of starch, that is, native, anionic, cationic, non-ionic and others. It can be added to the cellulosic material in the area of coarse raw material or in the area of fine raw material. When added in the coarse raw material area, it is preferably added to the machine box, more preferably to the outlet of the machine box. Alternatively or additionally, the starch can be added to the size press. In a preferred embodiment, the starch is sprayed, for example, in the form of an aqueous solution, between the folds of multi-pleated paper, cardboard or paperboard.
[00039] The basic steps of paper making are known to the skilled artisan. In this regard, for example, C. J. Biermann, Handbook of Pulping and Papermaking, Academic Press; 2nd edition (1996); J. P. Casey, Pulp and Paper, Wiley-Interscience; 3rd edition (1983); and E. Sjõstrõm et al., Analytical Methods in Wood Chemistry, Pulping and Papermaking (Springer Series in Wood Science), Springer; 1st edition (1999).
[00040] The raw material for paper is fiber. For the purpose of the specification, "defibrillation" is to be considered as the process of separating fibers, suitable for papermaking, from cellulosic material such as recovered (residual) paper.
[00041] Modern papermaking typically involves seven basic operations: 1) pre-treatment of the fiber; 2) mixing the fiber; 3) cleaning and sifting the supply; 4) paste distribution and measurement; 5) formation of the network and removal of water by mechanical means; 6) consolidation of the network and removal of water by means of heat; and 7) finishing the sheet, through calendering, ironing, coating, vitrification, or paper conversion.
[00042] In practice, there are numerous variants of the methods for making paper, cardboard or paperboard. However, all of these variants have in common that the general method can be divided into the following sections which will be referred to in the following to define the preferred modalities of the method according to the invention: (I) measurements take place before defibrillation; (II) measurements associated with defibrillation; (III) measurements take place after defibrillation, but still outside the paper-making machine; (IV) measurements take place inside the paper-making machine; and (V) measurements take place after the papermaking machine.
[00043] Sections (I) to (II) typically refer to the processing of a coarse raw material of cellulosic material, while during section (III) the cellulosic material is converted from a coarse raw material to a fine raw material by diluting with water, and section (IV) is thus related to the processing of a fine raw material of cellulosic material. All areas where measurements take place before dilution, preferably during step (III), are preferably referred to as the "coarse raw material area", while the rest are preferably referred to as the "fine raw material area" ".
[00044] In a preferred embodiment of the invention, the water used for defibrillating the cellulosic material containing the starch is placed in contact with at least a part of the biocide, optionally supplied as an aqueous composition, in section (I) of the method for the manufacture of that is, before defibrillation.
[00045] In another preferred embodiment of the invention, the cellulosic material containing the starch is brought into contact with at least a part of the biocide, optionally supplied as an aqueous composition, in section (II) of the papermaking method, that is, in the course of defibrillation. Section (II) covers step (a) of the method according to the invention, whereas the provision of cellulosic material containing starch in the defibrillation device (defibrillator) and its removal are not usually considered to belong to the defibrillation step per se, but are at least partially covered by section (II) as well.
[00046] In yet another preferred embodiment of the invention, the cellulosic material containing the starch is brought into contact with at least a part of the biocide, optionally supplied as an aqueous composition, in section (III) of the papermaking method, i.e. , after defibrillation, but still outside the paper machine. Preferably, the biocide is added to the cellulosic material containing the starch in the coarse raw material area.
[00047] Preferably, defibrillation is the first step in the manufacture of paper where the cellulosic material is brought into contact with substantial amounts of water thereby generating aqueous paste, that is, an aqueous suspension of cellulosic fibers, also referred to as pulp. Said pulp forms an intermediate, fibrous material for the manufacture of paper or cardboard.
[00048] The defibrillation site is referred to as the defibrillator, that is, a reaction vessel used to manufacture an aqueous dispersion or suspension of the cellulosic material. Sometimes, a defibrillator is also referred to as a hydrades defibrillator or hydrodes defibrillator.
[00049] In the event that that recovered (residual) paper is used as the starting material for the papermaking process, the appropriate recovered (residual) paper is typically introduced directly into the defibrillator. The waste paper can also be mixed with a quantity of virgin material to improve the quality of the cellulosic material.
[00050] For the purpose of the specification, the term "cellulosic material" refers to any material comprising cellulose including recovered (waste) paper. In addition, the term "cellulosic material" refers to all intermediate and final products during the papermaking process from which recovered (residual) paper originates, such as dispersions or suspensions of cellulosic material, defibrillated cellulosic material, distinguished cellulosic material, mixed cellulosic material, targeted cellulosic material, refined cellulosic material, sorted cellulosic material and the final paper, cardboard or paperboard. Therefore, the term "cellulosic material" includes pulp, paste, clay, raw material, and others.
[00051] The starch contained in the cellulosic material does not necessarily originate from the cellulose starting material (recycled material and others). It is also possible that the entire amount of the cellulose starting material is virgin material containing no starch and that the starch contained in the cellulosic material originates from another source, preferably from a recirculation unit supplying the defibrillator with recycled water from the wet end of the cell. paper making machine.
[00052] In a preferred embodiment, the cellulosic material containing the starch originates from waste or scrap paper, but can be mixed with, for example, virgin material (=> recycled pulp and mixed pulp, respectively).
[00053] In a preferred embodiment, the starch content of the cellulosic material containing the starch, that is, the waste or scrap paper that is used as the starting material, is at least 0.1% by weight, more preferably at least 0 , 25% by weight, or at least 0.5% by weight, or at least 0.75% by weight, or at least 1.0% by weight, or at least 1.5% by weight, or at least 2 , 0% by weight, or at least 3.0% by weight, or at least 5.0% by weight, or at least 7.5% by weight, or at least 10% by weight, or at least 15% by weight weight, based on the weight of the dry cellulosic material.
[00054] In another preferred embodiment, the starch is added to the cellulosic material, for example, to the virgin material, in the course of papermaking, preferably in the area of coarse raw material. Preferably, a portion of the newly added starch is attached to the cellulosic fibers before the network is formed and the water is drained. Due to the recirculation of at least a portion of the water drained from the pulp, another portion of the starch is returned to the beginning of the general process. In this way, the starch does not necessarily originate from the residual paper, but it can alternatively or additionally also originate from the method itself.
[00055] According to the invention, the cellulosic material contains a starch. For the purpose of the specification, the term "starch" refers to any modified or unmodified starch typically used in papermaking. Starch is a polysaccharide carbohydrate that consists of a large number of glucose units joined by glycosidic bonds. Starch is produced by all green plants as an energy store. Starch is composed of two types of molecules: linear and helical amylose and branched amylopectin. Depending on the origin, native starch usually contains 20 to 25% amylose and 75 to 80% amylopectin. Through physical, enzymatic or chemical treatment of native starch, a variety of modified starches can be prepared, including non-ionic, anionic and cationic starches.
[00056] Preferably, the starch contained in the cellulosic material has an amylose content within the range of 0.1% by weight to 95% by weight
[00057] In a preferred embodiment of the invention, the starch contained in the cellulosic material is substantially pure amylose, that is, it has an amylose content of about 100% by weight. In another preferred embodiment of the invention, the starch contained in the cellulosic material is substantially pure amylopectin, that is, it has an amylopectin content of about 100% by weight. In yet another preferred embodiment, the amylose content is within the range of 22.5 ± 20% by weight, while the amylopectin content is preferably within the range of 77.5 ± 20% by weight
[00058] In a preferred embodiment, the starch is non-ionic, preferably native starch. In another preferred embodiment, the starch is anionic. In yet another preferred embodiment, starch is cationic. In yet another preferred embodiment, starch contains both anionic and cationic charges, while the relative content can be balanced, dominated by anionic charges or dominated by cationic charges.
[00059] In a preferred embodiment, the starch that is contained in the cellulosic material, preferably before defibrillation, has an average molecular weight by weight of at least 25,000 g / mol.
[00060] In a preferred embodiment, the relative weight ratio of starch and cellulosic material (solid contents) is within the range of 1: (20 ± 17.5) or 1: (50 ± 40) or 1: (100 ± 90) or 1: (200 ± 90) or 1: (400 ± 200) or 1: (600 ± 200) or 1: (800 ± 200).
[00061] A person skilled in the art knows that cellulosic material can contain other components besides cellulose, such as chemicals used for the chemical and semi-chemical defibrillation stage, dyes, bleaching agents, fillers, etc.
[00062] If not expressly stated otherwise, the percentages based on the cellulosic material are to be considered as being based on the general composition containing the cellulosic material and the starch (solids content).
[00063] If not explicitly stated otherwise, for the purpose of the specification, the terms "papermaking process" or "papermaking method" refer to papermaking as well as cardboard and papermaking -card.
[00064] For the purpose of the specification, cellulosic starting material for the manufacture of paper, cardboard and / or cardboard from which recovered (residual) paper originates is referred to as "recycling material", whereas the fresh starting material is referred to as "virgin material". It is also possible that a mixture of virgin material and recycling material is used as the starting material for the papermaking process which is referred to herein as "mixing material". In addition, it is also possible that the cellulosic starting material is "refuse" or "coated refuse" (recessed material) which, for the purpose of the specification, will be covered by the term "recycling material".
[00065] For the purpose of the specification, the pulp originating from virgin material, recycling material or mixing material is referred to as "virgin pulp", "recycled pulp" and "mixed pulp", respectively.
[00066] Typically, water is added during the mechanical defibrillation step to the cellulosic material, that is, to the virgin, recycled or mixed material, to produce the respective cellulosic pulp, that is, virgin, recycled or mixed pulp. The respective pulp is usually a fibrous aqueous dispersion or fibrous aqueous suspension of the cellulosic material.
[00067] The mechanical defibrillation process is typically performed by exposing the cellulosic material to mechanical force, more specifically to shear force.
[00068] According to the invention, biocide is present during the defibrillation step and / or is added thereafter, preferably shortly thereafter. Microorganisms that come from waste paper also play a role in the degradation of the starch contained in the waste paper, particularly when the waste paper has been stored for days or months and subjected to the activity of the microorganisms during this storage time. Treatment of waste paper with biocide during defibrillation cannot reverse the effects caused by the activity of microorganisms in the starch during the storage of the waste paper. However, the growth conditions of the microorganisms improve significantly during defibrillation - when the paper comes into contact with the process water - and the inventors found that it is advantageous to add the biocide at this stage of the process. Considering that the degradation usually caused by microorganisms takes longer than a few minutes, the inventors have found that it may also be sufficient to add the biocide soon after defibrillation.
[00069] For this purpose, the cellulosic material containing the starch, that is, the virgin material, recycled or mixed, is placed in contact with the biocide. If the biocide is added shortly after the defibrillation step, it is preferably added to the cellulosic material 1 to 60 minutes after the defibrillation step has ended.
[00070] It is evident to a person skilled in the art to treat the cellulosic material containing the starch with biocide according to the invention, that at least a part of the total amount (total inflow) of biocide is added to the cellulosic material containing the starch in question. any time during the defibrillation step (a), that is, after the defibrillation has started, or shortly after the defibrillation has ended. The biocide can be added continuously or discontinuously.
[00071] For the purpose of the specification, the term "continuously" means that the quantity (inflow) of the biocide for the specific dose is added to the cellulosic material containing the starch without interruption.
[00072] For the purpose of the specification, the term "discontinuously" here means that the addition of the biocide to the cellulosic material containing the starch is performed by means of pulses of a predetermined length which are interrupted for periods during which no biocides are added at this feeding point.
[00073] A knowledgeable person is aware that papermaking processes as such are typically continuous processes. Thus, any "quantity" or "dosage" of biocide, wet and / or dry resistance polymer and other additive, respectively, which is to be added to the cellulosic material refers to a respective "inflow" of said biocide. , dry and / or wet strength polymer and other additive, respectively to achieve a desired predetermined local concentration of the same in the cellulosic material flow. Said inflow can be continuous or discontinuous. Consequently, when the "amount" or "dosage" of biocide, wet and / or dry strength polymer and other additive, respectively, is divided into portions that are added to the cellulosic material in different locations and / or during process steps different, each portion refers to a partial inflow of said biocide, wet and / or dry resistance polymer and other additive, respectively to achieve a desired predetermined local concentration of it, that is, downstream with respect to its point feed.
[00074] Typically, water is added to the cellulosic material, that is, to the virgin material, recycled or mixed, before and / or during the defibrillation step. At least a part of the total amount (total inflow) of the biocide can be dissolved, dispersed or suspended in said residual water to redefibrate the cellulosic material containing the starch, that is, to the virgin, recycled or mixed material.
[00075] In this modality, the biocide and the residual water used for defibrillation can already be brought into contact with each other before the defibrillation has started.
[00076] In a preferred embodiment according to the invention, the biocide comes in contact with the residual water used for defibrillation at least 10 min before defibrillation begins, or at least 30 min, or at least 60 min, or at least at least 120 min, or at least 150 min, or at least 180 min, or at least 210 min, or at least 240 min, or at least 300 min, or at least 360 min, or at least 420 min, or at least 480 min.
[00077] Typically, the defibrillation step (a) can take from several minutes to several hours. In another preferred embodiment, at least a part of the total amount (total inflow) of the biocide is added to the cellulosic material during the defibrillation period.
[00078] For the purpose of the specification, the term "defibrillation period" is defined as the total time that the defibrillation step is performed.
[00079] For example, in case the defibrillation step takes a total time of 1 hour (defibrillation period), the biocide can be added discontinuously or continuously to the defibrillator at any point of time or during any interval of time , for example, up to 120 minutes after the defibrillation step has started.
[00080] In step (b) of the method according to the invention, the cellulosic material containing the starch is treated with one or more biocides, which are at least partially added to the cellulosic material in the coarse raw material area, where the material cellulosic has a raw material consistency of at least 2.0%, preferably thus preventing microbial degradation of at least a portion of the starch. In a preferred embodiment, step (b) is at least partially performed simultaneously with step (a) of the method according to the invention, i.e., biocide treatment is performed during defibrillation. In another preferred embodiment, step (b) is performed after step (a) has completed. A knowledgeable person recognizes that any total or partial overlap of steps (a) and (b) is possible and in accordance with the invention.
[00081] In a preferred embodiment, the total amount (total inflow) of biocide is added discontinuously or continuously to the cellulosic material during the defibrillation step (a); that is, 100% by weight of the total amount (total inflow) of the biocide is added to the cellulosic material, that is, to the virgin material, recycled or mixed, during the defibrillation step (a).
[00082] In another preferred method, other parts of biocide can be added at any time preferably up to 480 min after the defibrillation step (a) has started at any suitable place to prevent degradation of the starch. This modality includes the addition of other parts of the biocide during the defibrillation step (a) or preferably up to 60 minutes after the defibrillation has started. In a preferred embodiment, at least a part of the total amount (total inflow) of the biocide is added to the cellulosic material containing the starch at any time, preferably up to 60 minutes after the defibrillation step (a) has completed.
[00083] In a preferred embodiment, one or more biocides are added to the cellulosic material at at least 2 different feed points, more preferably at least 3 different feed points, and even more preferably at least 4 different feed points at the plant. papermaking where identical or different biocides or combinations of biocides can be added to the various feeding points.
[00084] According to the method of the invention, step (b) preferably serves the purpose of preventing the degradation of the starch that is contained in the cellulosic material by eradicating microorganisms that are otherwise capable of degrading the starch (amylase control) .
[00085] In a preferred embodiment, the one or more biocides are discontinuously added to the cellulosic material in a continuously operational papermaking plant. The one or more biocides are preferably added by means of pulsed feed rates, that is, peaks in the local concentration of the biocide in the cellulosic material reaching the critical local concentration that is necessary to eradicate the microorganisms, thus effectively preventing the starch from being degraded. In other words, cellulosic material passing the biocide feed point (s) is transiently enriched in place through the biocide at predetermined intervals (biocide intervals) that are interrupted at intervals during which no biocide is added locally ( passive intervals).
[00086] Preferably, a biocide interval typically lasts at least about 2 minutes, but it can also last, for example, up to about 120 minutes. Preferably, the biocide is added to the cellulosic material in a papermaking plant that is continuously operational for 24 h through at least 4, 8, 12, 16, 20, 30, 40, 50, 60, 70 or more biocide intervals which are separated from each other by a respective number of passive intervals, in which during each biocide interval, the desired and predetermined local concentration of the biocide in the cellulosic material is achieved.
[00087] In another preferred embodiment, one or more biocides are continuously added to the cellulosic material in a continuously operational papermaking plant.
[00088] Preferably, the biocide is added to the cellulosic material at at least two feeding points, which are located downstream of each other. For example, the biocide is added at a first feed point and at a second feed point being located downstream with respect to the first feed point. Depending on the half-life and the distribution of the biocide in the cellulosic material, the cellulosic material that passes through the second feed point may already contain the biocide that was added to it upstream at the first feed point. Thus, the amount of biocide added locally at the second feed point may be less than the amount added locally at the first feed point to achieve the same desired, predetermined local concentration of the biocide in the cellulosic material that is necessary to eradicate microorganisms. thus preventing the starch from being effectively degraded.
[00089] Preferably, the biocide, more preferably a two-component oxidizing biocide, is added in section (I) and / or (II); and optionally also in section (III) and / or (IV) of the papermaking plant; more preferably in section (I) and / or (II); as well as in section (IV) of a papermaking plant comprising a papermaking machine, where section (I) includes measures taken before defibrillation; section (II) includes measures associated with defibrillation; section (III) includes measures taken after defibrillation, but still outside the papermaking machine; and section (IV) includes measures taken within the papermaking machine.
[00090] At least part of the biocide is preferably added during the defibrillation step (a) or shortly thereafter. As long as the biocide that was initially added during the defibrillation step (a) is not completely removed or consumed in subsequent steps, the biocide is also present in process steps (c), (d), (e), (f) and (g), if any, that follows the defibrillation step (a).
[00091] In a preferred embodiment, at least a part of the remainder of the total amount (total inflow) of the biocide is added to the cellulosic material during any of the steps (c), (d), (e), (f) and / or (g). For example, 50% by weight of the total amount (total inflow) of the biocide can be added continuously or discontinuously, before and / or during the defibrillation step (a) and the remaining 50% by weight of the total amount (total inflow) of the biocide can be added continuously or discontinuously, before, during and / or after the process steps (c), (d), (e), (f) and / or (g).
[00092] As long as the biocide that was added during step (b) and optionally in process steps (c), (d), (e), (f), and (g), if following the defibrillation step (a), is not removed completely in subsequent steps, said biocide is also present in the papermaking machine.
[00093] A wide variety of microorganisms can be found in the defibrillation process. Each type of pulp has its own microbial characteristics. In general, the microorganisms observed in papermaking are species of bacteria, yeast and fungi; algae and protozoa exist, but they rarely cause problems. Problems caused by microorganisms can be very different. Very well-known problems are sludge formation and corrosion.
[00094] Species of the following bacterial genera belong to the usual pulp contaminants: Achromobacter, Actinomycetes, Aerobacter, Alcaligenes, Bacillus, Beggiatoa, Crenothrix, Desulphovibrio, Flavobacterium, Gallionella, Leptothrix, Pseudomonas, Sphearotilus, Thphearotilus, and Thphiootilus, Species of Alcaligenes, Bacillus and Flavobacterium as well as species of the yeast, Monilia, cause pink sludge. Red or brown sludge is caused by bacteria that form ferric hydroxide, namely, species of Crenothrix, Gallionella and Leptothrix. Species of Thiobacillus and Beggiatoa are corrosion bacteria in which they oxidize sulfides to sulfuric acid. Desulphovibrio species are also corrosion bacteria for the opposite reason. Species of the previous genus reduce sulfate to hydrogen sulfide that interacts with the metal to cause corrosion. Metal sulfides are also black, which is another unwanted effect of sulfate-reducing bacteria.
[00095] Among the fungi, the species of the following genera are found most often in the pulp systems: Aspergillus, Basidiomyces, Cephalosporium, Cladosporium, Endomyces, Endomyopsis, Mucor, Penicillium, and Trichoderma. Blue coloring in the wood is caused by Cephalosporium and Cladosporium.
[00096] Finally, the species of the following genera of pulp yeast can be isolated: Monilia, Pullularia, Rhodotorula and Saccharomyces. For further details, refer to H. W. Rossmoore, Handbook of Biocide and Preservative Use, Chapter Paper and Pulp, Chapman & Hall, 1995.
[00097] The most prevalent species expressing amylase and thereby causing starch degradation include Actinomycetes, Aerobacter, Bacillus, Beggiatoa, Desulphovibrio, Flavobacterium, Gallionella, Leptothrix, Pseudomonas, Thiobacillus; Aspergillus, Basidiomycetes, Cephalosporium, Endomyces, Endomycopsis, Mucor, Penicillium; Pullularia, and Saccharomyces.
[00098] Thus, the purpose of adding biocide according to the invention essentially serves the purpose of eradicating one or more of the aforementioned microorganisms and the dosages of the biocide are preferably adapted accordingly.
[00099] The biocide can be gaseous, solid or liquid; organic or inorganic; oxidizing or non-oxidizing.
[000100] The biocide can be used in the substance or in dilution with a suitable solvent, preferably water, in solution or dispersion, suspension or emulsion.
[000101] The biocide can be a one-component biocide, a two-component biocide or a multi-component biocide.
[000102] The biocide preferably has a comparatively short half-life, that is, it is decomposed comparatively quickly thus losing its biocidial action. When a combination of two or more biocides is employed, the half-life of at least one biocide within said combination is preferably comparatively short. Preferably, under the conditions of the method according to the invention (temperature, pH and others), the half-life of the biocide is no more than 24 h, or no more than 18 h, or no more than 12 h, more preferably not more than 10 h, even more preferably not more than 8 h, even more preferably not more than 6 h, most preferably not more than 4 h and in particular not more than 2 h. The half-life of a given biocide can be easily determined through routine experimentation, preferably under the general conditions of the method according to the invention.
[000103] It has been surprisingly found that biocides having a comparatively short half-life are effective in preventing starch degradation by eradicating microorganisms that would otherwise break down starch, but would not cause problems in the wastewater system that typically also has microorganisms that should not be eradicated by the biocide. Still, it has been surprisingly found that biocides having a comparatively short half-life can be used in comparatively high concentrations without causing substantial problems with regard to wastewater treatment.
[000104] In North American biocides to be used in the production of paper and cardboard for use in contact with food, they must be on the approved list of the Food and Drug Administration (FDA).
[000105] In a preferred embodiment, the biocide is selected from oxidizing and non-oxidizing biocides.
[000106] Examples of oxidizing biocides include one-component systems such as ClO2, H2O2 or NaOCl; and two-component systems comprising for example a nitrogenous compound, preferably inorganic ammonium salts in combination with an oxidizer, preferably a halogen source, more preferably a chlorine source, most preferably hypochlorous acid or a salt thereof, such as NH4Br / NaOCl or (NH4) 2SO4 / NaOCl; and two-component systems comprising for example organic biocides in combination with an oxidizer, preferably a halogen source, more preferably a chlorine source, most preferably hypochlorous acid or a salt thereof, such as bromochlor-5,5-dimethylimidazolidine- 2,4-dione (BCDMH) / NaOCl, or dimethylhydantoin (DMH) / NaOCl.
[000107] In a particularly preferred embodiment, the biocide is a two-component oxidizing biocide, where the first component is a nitrogenous compound, preferably selected from ammonia, amines, inorganic or organic ammonium salts, and inorganic or organic amine salts; and the second component is a source of halogen, preferably a source of chlorine. The NH4Br / NaOCl or (NH4) 2SO4 / NaOCl combinations are particularly preferred oxidizing biocides.
[000108] Preferred nitrogen compounds include ammonium salts, methylamine, dimethylamine, ethanolamine, ethylenediamine, diethanolamine, triethanolamine, dodecylethanolamine, hexdecylethanolamine, oleic acid ethanolamine, triethylenetetramine, dibutylamine, tributylamine, glutamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine. methylamine, n-acetylglucosamine, diphenylamine, ethanolmethylamine, diisopropanolamine, n-methylaniline, n-hexyl-n-methylamine, n-heptyl-n-methylamine, n-octyl-n-methylamine, n-nonyl-n-methylamine, n- decyl-n-methylamine, n-dodecyl-n-methylamine, n-tridecyl-n-methylamine, n-tetra-decyl-n-methylamine, n-benzyl-n-methylamine, n-phenylethyl-n-methylamine, n- phenylpropyl-n-methylamine, n-alkyl-n-ethylamines, n-alkyl-n-hydroxyethylamines, n-alkyl-n-propylamines, n-propyl-heptyl-n-methylamine, n-ethyl-hexyl-n-methylamine, n-ethyl-hexyl-n-butylamine, n-phenylethyl-n-methylamine, n-alkyl-n-hydroxypropylamines, n-alkyl-n-isopropylamines, n-alkyl-n-butylamines and n-alkyl-n-isobutylam inas, n-alkyl-n-hydroxyalkylamines, hydrazine, urea, guanidines, biguanidines, polyamines, primary amines, secondary amines, cyclic amines, bicyclic amines, oligocyclic amines, aliphatic amines, aromatic amines, polymers containing primary and secondary nitrogen. Examples of ammonium salts include ammonium bromide, ammonium carbonate, ammonium chloride, ammonium fluoride, ammonium hydroxide, ammonium iodide, ammonium nitrate, ammonium phosphate, and ammonium sulfamate. Preferred nitrogen compounds are ammonium bromide and ammonium chloride.
[000109] Preferred oxidizers include chlorine, alkaline and alkaline earth hypochloride salts, hypochlorous acid, chlorinated isocyanurates, bromine, alkaline and earth alkaline hypobromide salts, hypobromous acid, bromine chloride, halogenated hydantoins, ozone and peroxy compounds such as peroxy compounds alkaline and alkaline earth perborate, alkaline and alkaline earth percarbonate salts, alkaline and earth alkaline persulfate salts, hydrogen peroxide, percarboxylic acid, and peracetic acid. Preferred halogen sources include reaction products of a base and a halogen, such as hypochlorous acid and its salts. Preferred salts of hypochlorous acid include LiOCl, NaOCl, KOCl, Ca (OCl) 2 and Mg (OCl) 2, which are preferably supplied in aqueous solution. Preferred inorganic salts of ammonia include but are not limited to NH4F, NH4Cl, NH4Br, NH4I, NH4HCO3, (NH4) 2CO3, NH4NO3, NH4H2PO2, NH4H2PO4, (NH4) 2HPO4, NH4SO3NH2, NH4IO3, NH4SH, (NH4SH, NH4SH, (NH4) 2SO3, NH4HSO4, (NH4) 2SO4, and (NH4) 2S2O3, Preferred organic ammonium salts include but are not limited to NH4OCONH2, CH3CO2NH4 and HCO2NH4. The amine can be a primary or secondary amine or the amine portion of an amide; for example, urea, or its alkyl derivatives such as N-N’-dimethyl urea, or N’-N’-dimethylurea. The combination of NH4Br and NaOCl is particularly preferred and known for example from US 7,008,545, EP-A 517 102, EP 785 908, EP 1 293 482 and EP 1 734 009. Preferably, the relative molar ratio of said first component is of said second component is within the range of 100: 1 to 1: 100, more preferably 50: 1 to 1:50, even more preferably 1:20 to 20: 1, even more preferably 1:10 to 10: 1, the more preferably 1: 5 to 5: 1 and in particular 1: 2 to 2: 1.
[000110] Compared to strong oxidizers, biocides of this type, that is, combinations of ammonium salts with hypochlorous acid or its salts, have particular advantages.
[000111] For several years, strong oxidizers have been used to control microbial populations in the papermaking industry. Maintaining an effective oxidant level is not always easy or economically viable because the paper process flows exhibit a high and variable "demand" for oxidant. This demand is caused by the presence of organic materials such as fiber, starch, and other colloidal or particulate organic materials in the process. These organic materials react with and consume the oxidizer, making it much less effective in controlling microbial populations. In order to achieve an effective residual oxidant in high-demand systems, such as paper-making machines, the oxidizer must be overfed to exceed the demand in the system. Supercharging strong oxidizers not only leads to higher treatment costs, but can also cause many adverse side effects in the papermaking system. These side effects include increased consumption of dyes and other expensive wet-use additives (eg, optical brighteners and bonding agents), increased corrosion rates, and reduced life. Some oxidants also contribute greatly to the amount of halogenated organic compounds (AOX) produced in the papermaking process. In addition, excessive residues of certain oxidants may be suitable for controlling microbial populations in the volume fluid, but may be ineffective for controlling biofilm due to limited penetration into the biofilm matrix.
[000112] In contrast to strong oxidizers, biocides produced by mixing ammonium salts, such as an ammonium bromide solution, with, for example, sodium hypochloride and fresh water mill under specific reaction conditions can be described as a weak oxidizer. The biocide is produced on the spot and immediately dosed to the paper system. The required dosage depends on several factors, including use of fresh water, recycled water, and the presence of reducing agents. Biocides of this type, therefore, have a comparatively short half-life and therefore do not accumulate, which could cause problems with wastewater treatment. Still, they are not very aggressive, that is, they do not oxidize the other constituents of the cellulosic material, but they are comparatively selective for microorganisms.
[000113] One or two biocides of the oxidizing component of this type can be used alone, or preferably, particularly when the starting material comprises recycled pulp, in combination with non-oxidizing biocides.
[000114] Examples of non-oxidizing biocides include, but are not limited to, quaternary ammonium compounds, benzyl-C12-16-alkyldimethyl chlorides (ADBAC), polyhexamethylenebiguanide (biguanide), 1,2-benzisothiazole-3 (2H) -one (BIT), bronopol (BNPD), bis (trichloromethyl) sulfone, di-iodomethyl-p-tolylsulfone, sulfone, bronopol / quaternary ammonium compounds, benzyl-C12-16-alkyldimethyl chlorides (BNPD / ADBAC), chloride bronopol / didecyldimethylammonium (BNPD / DDAC), bronopol / 5-chloro-2-methyl-2H-isothiazol-3-one / 2-methyl-2H-isothiazole-3-one (BNPD / Iso), NABAM / sodium dimethyldithiocarbamate , N-dimethyldithiocarbamate, sodium N-dithiocarbamate (NABAM), sodium methyldithiocarbamate, sodium dimethyldithiocarbamate, 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 2,2-dibromo-2-cyanoacetamide (DBNPA), DBNPA / bronopol / iso (DBNPA / BNPD / Iso), 4,5-dichloro-2-n-octyl-3-isothiazolin-3-one (DCOIT), didecyldimethylammonium chloride (DDAC), didecyldimethylammonium chloride , alkyldimethylbenzylammonium chloride (DD AC / ADBAC), dodecylguanidine monohydrochloride / quaternary ammonium compounds, benzyl-C12-16-alkyldimethyl chlorides (DGH / ADBAC), dodecylguanidine monohydrochloride / methylene dithocyanate (DGH / MBT), gluteraldehyde (Glut) , gluteraldehyde / quaternary ammonium compounds / benzylcoconut alkyldimethyl chloride (Glut / poo), gluteraldehyde / didecyldimethylammonium chloride (Glut / DDAC), gluteraldehyde / 5-chloro-2-methyl-2H-isothiazol-3-one / 2- methyl-2H-isothiazole-3-one (Glut / Iso), gluteraldehyde / methylene dithocyanate (Glut / MBT), 5-chloro-2-methyl-2H-isothiazole-3-one / 2-methyl-2H-isothiazole- 3-one (Iso), methylene dithocyanate (MBT), 2-methyl-4-isothiazolin-3-one (MIT), metamine oxirane (methanol oxirane), sodium bromide (NaBr), nitromethylidinethimethanol, 2-n - octyl-3-isothiazolin-3-one (OIT), bis (trichloromethyl) sulphone / quaternary ammonium compounds, benzyl-C12-16-alkyldimethyl chlorides (sulphone / ADBAC), synchosene, terbuthylazine, dazomet (thione), tetrakis sulfate (hydroxy ethyl) phosphonium) (THPS) and p - [(diiodomethyl) sulfonyl] toluene (tolyl sulphone), and mixtures thereof.
[000115] A knowledgeable person knows that a simple biocide or a simple multicomponent biocide or a combination of different biocides can be employed.
[000116] In a particularly preferred embodiment of the invention, preferably when the starting material comprises recycled pulp, the biocide is a biocide system, preferably comprising a first biocide composed of an inorganic ammonium salt in combination with a halogen source, preferably a chlorine source, more preferably hypochlorous acid or a salt thereof, and another biocide, preferably selected from non-oxidizing and / or organic biocides, preferably non-oxidizing organic biocides. For the purpose of the specification, unless expressly stated otherwise, the one or more biocides referred to in step (b) may cover said other biocide, if present.
[000117] In a preferred embodiment, the non-oxidizing biocide comprises bronopol (BNPD) and at least one isothiazolone compound (Iso) selected from the group consisting of 1,2-benzisothiazole-3 (2H) -one (BIT), 5 -chloro-2-methyl-4-isothiazolin-3-one (CMIT), 4,5-dichloro-2-n-octyl-3-isothiazolin-3-one (DCOIT), methyl-4-isothiazolin-3-one (MIT), 2-n-octyl-3-isothiazolin-3-one (OIT); and / or a sulfone selected from bis (trichloromethyl) sulfone and di-iodomethyl-p-tolylsulfone. The bronopol / 5-chloro-2-methyl-2H-isothiazole-3-one / 2-methyl-2H-isothiazole-3-one (BNPD / Iso) combination is particularly preferred. In another preferred embodiment, the non-oxidizing biocide comprises compounds carrying quaternary ammonium ions in combination with bronopol (BNPD) or in combination with a sulfone selected from bis (trichloromethyl) sulfone and di-iodomethyl-p-tolylsulfone. The biocide system, preferably comprising an oxidizing biocide and a non-oxidizing biocide is particularly preferred when the residence time of the biocide in the coarse raw material is comparatively long, that is, the point-in-time time when the biocide is added to the material cellulosic to the point in time when the cellulosic material enters the papermaking machine. In a preferred embodiment, the above biocide system comprising a first and another biocide is employed when said residence time is at least 1 h, or at least 2 h, or at least 4 h, or at least 6 h, or at least 8 h, or at least 10 h.
[000118] Said biocide system is particularly preferred when the starting material comprises recycled pulp. When the starting material essentially consists of virgin pulp, however, the addition of another biocide is preferably omitted.
[000119] When such a biocide combination is employed, at least a portion of the first biocide is preferably added to the defibrillator dilution water, while the other biocide is preferably added to the defibrillator outlet and / or to the fiber clarification input.
[000120] Another biocide of one or two components (another biocide) that differs in the nature of the biocide from step (b) (first biocide) can also be added to the cellulosic material containing the starch (not degraded) before, during or after the process steps (c) to (g) and / or after the cellulosic material has been supplied to the papermaking machine.
[000121] In a preferred embodiment, at least part of the remainder of the total amount (total inflow) of the biocide (first biocide) and / or another biocide (another biocide) is added to the subsequent cellulosic material for any of the steps (c) , (d), (e), (f) and / or (g), that is, in the papermaking machine. For example, 50% by weight of the total amount (total inflow) of the first biocide can be added discontinuously or continuously before and / or during the defibrillation step (a) and / or after the process steps (c), (d) , (e), (f) and / or (g), and the remaining 50% by weight of the total amount (total inflow) of the first biocide can be added discontinuously or continuously, in the papermaking machine.
[000122] In a preferred embodiment, another biocide (i.e., another portion of the first biocide and / or another biocide that differs in nature from the first biocide) is added to the cellulosic material containing the starch (not degraded) at the wet end of the machine paper making process, preferably on the flat table. In a preferred embodiment, said other biocide is added to the machine box or mixing box, or to the regulation box, or to the constant part of the papermaking machine. In a preferred embodiment, at least a portion of said other biocide is added to one or more water flows from the papermaking plant selected from the group consisting of defibrillator dilution water, white water (such as white water 1 and / or white water 2), clarified rain water, clear filtrate, and clarification input. Adding at least a portion of said other biocide to the defibrillator dilution water is particularly preferred.
[000123] The dosage of one or more biocides depends on its antimicrobial effectiveness. The biocide is dosed in an amount sufficient to prevent substantial degradation of the starch contained in the cellulosic material according to the invention. Adequate dosages for a given biocide can be determined through routine experimentation or by comparing the number of microorganisms before and after adding the biocide (taking into account that biocides typically require some time to eradicate microorganisms).
[000124] The addition of biocides during the papermaking process has been known for many years. The presence of microorganisms in the pulp and papermaking process is inevitable and thus, steps are taken to control its growth and numbers. It would be unrealistic to try to kill all microorganisms. Otherwise, the goal is typically to control, or suppress, the multiplication of microorganisms and thereby reduce their metabolic activities.
[000125] In conventional methods to manufacture paper, cardboard or paperboard, the accumulation of sludge is one of the most important indicators that microbial growth and microbial activities must be reduced. In conventional methods for making paper, cardboard or paperboard, the biocide is typically added for the conventional purpose of preventing sludge formation, corrosion and / or wet end breakage, controlling wet end deposition or odor control, but not for the purpose of preventing microbial degradation of the starch that is contained in the cellulosic material by eradicating microorganisms that are otherwise capable of degrading the starch with the intention to (re) fix this starch later on to the polymers as described hereinafter.
[000126] The conventional purposes above require comparatively low amounts of biocides keeping only the relatively small sections of the general antimicrobial controlled papermaking plant. In contrast, avoiding starch degradation according to the invention, that is, partial or total eradication of microorganisms that are capable of degrading starch (amylase control), typically requires substantially higher amounts / concentrations of biocide . As still shown in the experimental section, the amount of biocide that is preferably employed according to the invention to prevent starch degradation is at least 2 times, preferably at least 3 times higher than the amount of biocide conventionally employed in the manufacturing processes of starch. paper for conventional purposes. In addition, the distribution of the biocide that is preferably achieved by dosing the biocide at various feeding points located in various sections of the papermaking plant in the method according to the invention to prevent starch degradation anywhere is unconventional. For example, according to the product specification of aqueous ammonium bromide compositions currently marketed as a precursor to microbiological control agent for papermaking, the recommended dosage ranges from merely 150-600 g / t of dry fiber to an active content 35%, which corresponds to a maximum dosage of just 210 g of ammonium bromide per ton of dry fiber. However, by such a conventional biocide treatment, that is, by 210 g / t of dry fiber and without adding another biocide in other locations, the starch that is contained in the rest of the papermaking plant is still substantially degraded.
[000127] In a preferred embodiment of the method according to the invention, step (b) involves reducing the content of microorganisms that are contained in the cellulosic material and are capable of degrading the starch by treating the cellulosic material containing the starch with a sufficient amount of a suitable biocide.
[000128] In another preferred embodiment of the method according to the invention, step (b) involves the avoidance, prevention, suppression or partial or total reduction of starch degradation by microorganisms that are contained in the cellulosic material and that are able to degrade the starch by treating the cellulosic material containing the starch with a sufficient amount of a suitable biocide.
[000129] In another preferred embodiment of the method according to the invention, step (b) involves the partial or total preservation of starch against degradation by microorganisms that are contained in the cellulosic material and that are capable of degrading the starch by treating the cellulosic material containing the starch with a sufficient amount of a suitable biocide.
[000130] Degradation of starch contained in cellulosic material can be monitored by measuring various parameters, for example, pH value, electrical conductivity, ATP (adenosine triphosphate) content, redox potential, and extinction. The microbiological activity needs to be significantly reduced in the entire system, compared to conventional biocide treatments. Thus, the effectiveness of a biocide given in a given amount with respect to its effect in preventing starch degradation can be investigated through routine experimentation, that is, monitoring the pH value, electrical conductivity, ATP content, potential of redox, and / or extinction (iodine test) and comparing the situation without biocide treatment to the situation with biocide treatment after a sufficient equilibration period (typically at least 3 days, preferably 1 week or 1 month).
[000131] A knowledgeable person is fully aware that papermaking plants comprise a water circuit to which more or less fresh water is added (open system and closed system, respectively). The cellulosic material is placed in contact with the process water in the defibrillation step (a), or rather, it is further diluted by adding the process water when the coarse raw material is converted into fine raw material, and is separated from the process water in the papermaking machine where sheet formation takes place. Process water is returned (recycled) through the water circuit to reduce fresh water consumption. The process water parameters in the water circuit are typically balanced, the balance being influenced by the size of the system, added amount of fresh water, properties of the starting material, nature and quantity of additives, and others.
[000132] In a preferred embodiment of the invention, the process water of a continuously operational papermaking plant in which the method according to the invention is carried out, is at least partially recycled. Preferably, at least 5% vol. or at least 10% vol. or at least 25% vol. or at least 50% vol. or at least 75% vol. or at least 90% vol. of the process water are recycled, that is, the fresh water added preferably amounts to a maximum of 95% vol. or at most 90% vol. or at most 75% vol. or at most 50% vol. or at most 25% vol. or at most 10% vol.
[000133] When changing the process conditions according to the invention, for example, by adding higher amounts of biocide at various locations, some parameters spontaneously change locally and reach equilibrium in the entire system within hours or days, for example redox potential, ATP level and oxygen reduction potential (ORP), while other parameters typically need more time to balance, for example pH value and electrical conductivity.
[000134] Typically, the undesired starch degradation leads to a decrease in the pH value of the aqueous cellulosic material. In this way, efficient prevention of starch degradation by eradicating microorganisms due to biocide treatment can be monitored by measuring the pH value of the aqueous phase of the cellulosic material. Preferably, in step (b) of the method according to the invention, the one or more biocides are continuously or discontinuously added to the cellulosic material in quantities so that after 1 month of treatment, preferably after two months of treatment in a manufacturing plant of continuously operational paper, the pH value of the aqueous phase of the cellulosic material has been increased by at least 0.2 pH unit, or by at least 0.4 pH unit, or by at least 0.6 pH unit, or at least 0.8 pH unit, or at least 1.0 pH unit, or at least 1.2 pH unit, or at least 1.4 pH unit, or at least 1.6 pH unit, or by at least 1.8 pH units, or by at least 2.0 pH units, or by at least 2.2 pH units, or by at least 2.4 pH units, compared to pH value that has been measured, preferably at the same location, preferably at the wet end entrance of the papermaking machine immediately before the biocide was added for the first time or before the addition of higher amounts of biocide than conventionally employed was initiated, that is, compared to a situation where the microorganisms were degrading the starch thus causing a decrease in the value of pH. Preferably, in step (b) of the method according to the invention, the one or more biocides are continuously or discontinuously added to the cellulosic material in quantities so that after 1 month of treatment, preferably after two months of treatment in a manufacturing plant of continuously operational paper, the pH value of the aqueous phase of the cellulosic material measured at the wet end entrance of the papermaking machine has been decreased by no more than 2.4 pH units, or by no more than 2.2 units of pH pH, or by not more than 2.0 pH units, or by not more than 1.8 pH units, or by not more than 1.6 pH units, or by not more than 1.4 pH units, or by not more than 1.2 pH units, or by not more than 1.0 pH units, or by not more than 0.8 pH units, or by not more than 0.6 pH units, or by not more than 0.4 pH unit, or by not more than 0.2 pH unit, compared to the pH value of a composition containing the starting material (virgin pulp and recycled pulp, respectively) as well as all additives that were added to the cellulosic material in the corresponding concentrations until they reach the wet end entrance of the papermaking machine.
[000135] Typically, the undesired starch degradation also leads to an increase in the electrical conductivity of the aqueous cellulosic material. In this way, efficient prevention of starch degradation by eradicating microorganisms due to biocide treatment can be monitored by measuring the electrical conductivity of the aqueous phase of the cellulosic material. Preferably, in step (b) of the method according to the invention, the one or more biocides are continuously or discontinuously added to the cellulosic material in quantities so that after 1 month of treatment, preferably after two months of treatment in a manufacturing plant of continuously operational paper, the electrical conductivity of the aqueous phase of the cellulosic material has been decreased by at least 5%, or by at least 10%, or by at least 15%, or by at least 20%, or by at least 25%, or by at least 30%, or by at least 35%, or by at least 40%, or by at least 45%, or by at least 50%, or by at least 55%, or by at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, compared to the electrical conductivity that was measured, preferably at the same location, preferably at the wet end entrance of the manufacturing machine of paper just before the biocide was added for the first time or before the addition of higher amounts of biocide than conventionally employed was initiated, that is, compared to a situation where microorganisms were degrading the starch thereby causing an increase in electrical conductivity. Preferably, in step (b) of the method according to the invention, the one or more biocides are continuously or discontinuously added to the cellulosic material in quantities so that after 1 month of treatment, preferably after two months of treatment in a manufacturing plant of continuously operational paper, the electrical conductivity of the aqueous phase of the cellulosic material measured at the wet end entrance of the papermaking machine has been increased by a maximum of 80%, or a maximum of 75%, or a maximum of 70%, or by at most 65%, or at most 60%, or at most 55%, or at most 50%, or at most 45%, or at most 40%, or at most 35%, or at most maximum 30%, or a maximum of 25%, or a maximum of 20%, or a maximum of 15%, or a maximum of 10%, or a maximum of 5%, compared to the electrical conductivity of a composition containing (raw pulp and recycled pulp, respectively) as well as all additives that have been added to the raw material lulosic in the corresponding concentrations until reaching the wet end entrance of the papermaking machine.
[000136] Preferably, the one or more biocides are continuously or discontinuously added to the cellulosic material in quantities so that, preferably after 1 month of treatment, more preferably after two months of treatment in a continuously operational papermaking plant, conductivity The electrical phase of the aqueous phase of the cellulosic material is a maximum of 7000 μS / cm, a maximum of 6500 μS / cm, a maximum of 6000 μS / cm, or a maximum of 5500 μS / cm, or a maximum of 5000 μS / cm, or a maximum 4500 μS / cm, or a maximum of 4000 μS / cm, or a maximum of 3500 μS / cm, or a maximum of 3000 μS / cm, or a maximum of 2500 μS / cm, or a maximum of 2000 μS / cm, or a maximum of 1500 μS / cm, or at most 1000 μS / cm.
[000137] Preferably, the method according to the invention includes the continuous or discontinuous measurement of at least one parameter selected from the group consisting of redox potential, ATP level, oxygen reduction potential (ORP), pH value and electrical conductivity of the cellulosic material, preferably electrical conductivity, and the regulation of the biocide dosage in view of the measured value for said at least one parameter in order to improve the resistance performance and maintain the improved resistance performance, respectively.
[000138] Preferably, in step (b) of the method according to the invention, the one or more biocides are continuously or discontinuously added to the cellulosic material in quantities so that after 1 month of treatment, preferably after two months of treatment in one continuously operational papermaking plant, the dosage of the dry and / or wet strength polymer, which is added to the cellulosic material in step (h) to achieve a predetermined dry strength and / or wet strength of the paper, can be decreased by at least 5%, or by at least 10%, or by at least 15%, or by at least 20%, or by at least 25%, or by at least 30%, or by at least 35%, or by at least 40%, or by at least 45%, or by at least 50%, or by at least 55%, or by at least 60%, or by at least 65%, or by at least 70%, or at least 75%, or at least 80%, compared to the dosage of the same dry and / or wet strength polymer that was added under otherwise identical conditions immediately before the biocide was added for the first time or before the addition of higher amounts of biocide that conventionally employed was initiated to achieve the same predetermined dry and / or wet strength of the paper, i.e. , compared to a situation where microorganisms were degrading starch thus causing an increase in electrical conductivity and thus requiring higher dosages of dry and / or wet strength polymer to achieve dry resistance and / or resistance to predetermined damp paper.
[000139] Typically, the undesired starch degradation also leads to a decrease in extinction when subjecting the aqueous cellulosic material to an iodine test. In this way, efficient prevention of starch degradation by eradicating microorganisms due to biocide treatment can be monitored by measuring the extinction of the starch that is contained in the aqueous phase of the cellulosic material through the iodine test. Preferably, in step (b) of the method according to the invention, the one or more biocides are added continuously or discontinuously to the cellulosic material in such a way that after 8 hours, preferably after 2 days, more preferably after 3 days of treatment, more preferably after 1 week of treatment in a continuously operational paper-making plant, the extinction of the starch contained in the aqueous phase of the cellulosic material has been increased by at least 5%, or by at least 10%, or by at least 15%, or by at least 20%, or by at least 25%, or by at least 30%, or by at least 35%, or by at least 40%, or by at least 45%, or by at least 50%, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, compared to the extinction that was measured, preferably in the same location, preferably at the wet end entrance of the papermaking machine immediately before the biocide was added for the first time or before the addition of the higher amounts of biocide that conventionally employed was initiated, that is, compared to a situation where microorganisms were degrading the starch thus causing a decrease in extinction . In a preferred embodiment, the extinction of native starch is monitored. This can be done at a particular wavelength (for details the experimental section is referred to). According to the invention, the increase in starch content can be higher. For example, depending on the composition of the starting material, the starch content in the first few moments, that is, when the biocide treatment begins, can be approximately zero.
[000140] In a preferred embodiment, the starch that is contained in the cellulosic material, preferably after the defibrillation step has been completed, has an average molecular weight by weight of at least 25,000 g / mol.
[000141] In a preferred embodiment, the one or more biocides are dosed in an amount so that after 60 minutes the content of microorganisms (MO) in [cfu / ml] in the cellulosic material containing the starch is at most 1, 0 x 107, or a maximum of 5.0 x 106, or a maximum of 1.0 x 106; or at most 7.5 x 105, or at most 5.0 x 105; or at most 2.5 x 105, or at most 1.0 x 105, or at most 7.5 x 104; or at most 5.0 x 104, or at most 2.5 x 104, or at most 1.0 x 104; or a maximum of 7.5 x 103, or a maximum of 5.0 x 103, or a maximum of 4.0 x 103; or at most 3.0 x 103, or at most 2.0 x 103, or at most 1.0 x 103. In another preferred embodiment, the biocide is dosed in an amount so that after 60 minutes the content of micro- organisms (MO) in [cfu / ml] in the cellulosic material containing the starch is a maximum of 9.0 x 102, or a maximum of 8.0 x 102, or a maximum of 7.0 x 102; or at most 6.0 x 102, or at most 5.0 x 102, or at most 4.0 x 102; or a maximum of 3.0 x 102, or a maximum of 2.0 x 102, or a maximum of 1.0 x 102; or at most 9.0 x 101, or at most 8.0 x 101, or at most 7.0 x 101; or at most 6.0 x 101, or at most 5.0 x 101, or at most 4.0 x 101; or a maximum of 3.0 x 101, or a maximum of 2.0 x 101, or a maximum of 1.0 x 101.
[000142] Preferably, the redox potential of cellulosic materials increases by adding the biocide to a value within the range of -500 mV to +500 mV, or from -150 mV to +500 mV, or from -450 mV to +450 mV, or from -100 mV to +450 mV, or from -50 mV to +400 mV, or from -25 mV to +350 mV, or from 0 mV to +300 mV. For example, before the biocide is added, the redox potential of the cellulosic material can be -400 mV and after the addition of the biocide it is increased to a value of, for example, -100 mV to +200 mV.
[000143] A positive redox potential value indicates an oxidative system, while a negative redox potential indicates a reducing system. Suitable methods for measuring redox potential are known to the skilled person. In this regard, for example, H. Holik, Handbook of Paper and Board, Wiley-VCH, 2006 can be mentioned.
[000144] Preferably, the ATP (adenosine triphosphate) level of the cellulosic material, expressed in RLU (relative light units), decreases by adding the biocide to a value within the range of 500 to 400,000 RLU, or from 600 to 350,000 RLU, or from 750 to 300,000 RLU, or from 1,000 to 200,000 RLU, or from 5,000 to 100,000 RLU. For example, before the biocide is added, the ATP level may exceed 400,000 RLU and after the addition of the biocide it is decreased to a value of, for example, 5,000 to 100,000 RLU. In a preferred embodiment, the ATP (adenosine triphosphate) level of the cellulosic material, expressed in RLU (relative light units), decreases by adding the biocide to a value within the range of 5000 to 500,000 RLU, more preferably 5000 to 25,000 RLU.
[000145] ATP detection using bioluminescence provides another method for determining the level of microbial contamination. Suitable methods for detecting ATP using bioluminescence are known to the skilled person.
[000146] In a preferred embodiment, the one or more biocides are dosed for the cellulosic material at a feed rate related to the paper finally produced of at least 5 g / metric ton (= 5 ppm), preferably within the range of 10 g / metric ton to 5000 g / metric ton, more preferably from 20 g / metric ton to 4000 g / metric ton, even more preferably from 50 g / metric ton to 3000 g / metric ton, even more preferably from 100 g / ton metric to 2500 g / metric ton, most preferably from 200 g / metric ton to 2250 g / metric ton, and in particular from 250 g / metric ton to 2000 g / metric ton, based on the paper finally produced.
[000147] In a preferred embodiment, particularly when the biocide is organic and non-oxidizing, for example, bronopol / 5-chloro-2-methyl-2H-isothiazol-3-one / 2-methyl-2H-isothiazole-3-one (BNPD / Iso), the biocide is dosed for cellulosic material at a feed rate related to the paper ultimately produced from 25 to 2,500 g / ton of paper, more preferably 50 to 2,000 g / ton of paper, even more preferably 75 to 1,500 g / ton of paper, even more preferably 100 to 1,250 g / ton of paper, even more preferably 125 to 1,000 g / ton of paper, most preferably 150 to 900 g / ton of paper, and in particular 175 to 850 g / ton of paper, based on the paper finally produced.
[000148] In a preferred embodiment, the one or more biocides comprise a two component system comprising an inorganic ammonium salt and a halogen source, preferably a chlorine source, more preferably hypochlorous acid or a salt thereof, wherein the molar ratio of inorganic ammonium salt to hypochlorous acid or salt thereof is within the range of 2: 1 to 1: 2. Under these circumstances, preferably when the starting material of the process according to the invention comprises recycled pulp, said two-component system is preferably dosed for the cellulosic material at a feed rate related to the paper finally produced of at least 175 g / metric ton, or at least 200 g / metric ton, or at least 250 g / metric ton, or at least 300 g / metric ton; or at least 350 g / metric ton, or at least 400 g / metric ton, or at least 450 g / metric ton, at least 500 g / metric ton, or at least 550 g / metric ton; more preferably at least 600 g / metric ton, or at least 650 g / metric ton, or at least 700 g / metric ton, or at least 750 g / metric ton, or at least 800 g / metric ton, or at least 850 g / metric ton, or at least 900 g / metric ton, or at least 950 g / metric ton, or at least 1000 g / metric ton; or at least 1100 g / metric ton, or at least 1200 g / metric ton, or at least 1300 g / metric ton, or at least 1400 g / metric ton, or at least 1500 g / metric ton; or at least 1750 g / metric ton, or at least 2000 g / metric ton; in each case based on the weight of the inorganic ammonium salt and in relation to the paper ultimately produced. Under these circumstances, preferably when the starting material of the process according to the invention does not comprise recycled pulp, that is, essentially consists of virgin pulp, said two-component system is preferably dosed for cellulosic material at a related feed rate. finally produced paper of at least 50 g / metric ton, or at least 100 g / metric ton, or at least 150 g / metric ton, or at least 200 g / metric ton, or at least 250 g / metric ton, or at least 300 g / metric ton, or at least 350 g / metric ton, or at least 400 g / metric ton, or at least 450 g / metric ton, or at least 500 g / metric ton, or at least 550 g / metric ton, or at least 600 g / metric ton, or at least 650 g / metric ton; or at least 700 g / metric ton, or at least 750 g / metric ton, or at least 800 g / metric ton, or at least 850 g / metric ton, or at least 900 g / metric ton; or at least 950 g / metric ton, or at least 1000 g / metric ton; in each case based on the weight of the inorganic ammonium salt and in relation to the paper ultimately produced.
[000149] In a preferred embodiment, particularly when the biocide is oxidizing, for example, a two component system comprising an ammonium salt and a halogen source, preferably a chlorine source, more preferably hypochlorous acid or a salt thereof, the biocide is dosed for cellulosic material at a concentration of active substance that is equivalent to elemental chlorine at a concentration within the range of 0.005 to 0.500% of active substance such as Cl2 per ton of paper produced, more preferably from 0.010 to 0.500% of active substance like Cl2 per ton of paper produced, even more preferably from 0.020 to 0.500% of active substance like Cl2 per ton of paper produced, even more preferably from 0.030 to 0.500% of active substance like Cl2 per ton of paper produced, the most preferably from 0.040 to 0.500%, and in particular from 0.050 to 0.500% of active substance such as Cl2 per ton of paper produced.
[000150] In another preferred embodiment, particularly when the biocide is oxidizing, for example, a two-component system comprising an ammonium salt and a halogen source, preferably a chlorine source, more preferably hypochlorous acid or a salt thereof, the biocide is dosed for cellulosic material at a concentration of active substance that is equivalent to elemental chlorine at a concentration within the range of 0.005 to 0.100% of active substance such as Cl2 per ton of paper produced, more preferably from 0.010 to 0.100% of active substance like Cl2 per ton of paper produced, even more preferably from 0.020 to 0.100% of active substance like Cl2 per ton of paper produced, even more preferably from 0.030 to 0.100% of active substance like Cl2 per ton of paper produced, the most preferably from 0.040 to 0.100% of active substance as Cl2 per ton of paper produced, and in particular from 0.050 to 0.100% of active substance as Cl2 per ton of paper produced.
[000151] In yet another preferred embodiment, particularly when the biocide is oxidizing, for example, a two-component system comprising an ammonium salt and a halogen source, preferably a chlorine source, more preferably hypochlorous acid or a salt of the same, the biocide is dosed for the cellulosic material in a concentration of active substance that is equivalent to the elemental chlorine in a concentration within the range of 0.010 to 0.080% of active substance as Cl2 per ton of paper produced, more preferably from 0.015 to 0.080% of active substance such as Cl2 per ton of paper produced, even more preferably from 0.020 to 0.080% of active substance as Cl2 per ton of paper produced, even more preferably from 0.030 to 0.080%, most preferably from 0.040 to 0.080% of active substance like Cl2 per ton of paper produced, and in particular from 0.050 to 0.080% of active substance like Cl2 per ton of paper produced.
[000152] Concentrations above the biocide are expressed as equivalent concentrations of elemental chlorine. The determination of the concentration of a biocide (based on active substance) that is equivalent to a particular concentration of elemental chlorine is known to the person of ordinary skill.
[000153] Particularly preferred modalities A1 to A6 with respect to the biocide added in step (b) of the method according to the invention (first biocide) and the additional organic biocide (another biocide) are summarized in Table 1 below: Table 1:

wherein sections (I) to (IV) refer to sections of a papermaking plant comprising a papermaking machine, wherein section (I) includes measures taken before defibrillation; section (II) includes measures associated with defibrillation; section (III) includes measures taken after defibrillation but still outside the paper machine; and section (IV) includes measures taken within the papermaking machine.
[000154] Most of the preferred feed points of the first biocide, which is preferably oxidizing, are located in section (II), (III) and / or (IV) of a papermaking plant. When the feeding point of the first biocide is located in section (I), it is preferably located in the dilution water of the defibrillator of a papermaking plant. When the feeding point of the first biocide is located in section (II), it is preferably located in the defibrillator, preferably at the exit of the defibrillator, or in the dilution water after the defibrillator of a papermaking plant. When the feeding point of the first biocide is located in section (III), it is preferably located in white water, for example, in white water 2, before clarification or at the clarification entrance of a papermaking plant. In preferred embodiments, it is located in the clear filtrate, in the rainwater, and / or in the return water tank of a papermaking plant. When the feeding point of the first biocide is located in section (IV), it is preferably located in white water, for example, in white water 1, preferably before the fan pump, the classification of the fine raw material, and / or the defibrillator refuse from a papermaking plant.
[000155] The most preferred feed points of the other biocide, which is preferably non-organic oxidizer, are located in section (II), (III) and / or (IV) of a papermaking plant. When the feeding point of the other biocide is located in section (I), it is preferably located in the dilution water of the defibrillator of a papermaking plant. When the feeding point of the other biocide is located in section (II), it is preferably located in the defibrillator, preferably at the defibrillator outlet of a papermaking plant. When the feeding point of the other biocide is located in section (III), it is preferably located before the storage of coarse raw material, before the mixing box, before the machine box, before the classification of the coarse raw material, in waste thickeners, in waste defibrillators, in the dilution water after the defibrillator, before clarification or in the clarification input of a papermaking plant. When the feeding point of the other biocide is located in section (IV), it is preferably located in the rainwater for the press section or in the rainwater for the flat table of a papermaking plant.
[000156] In a preferred embodiment, the raw material consistency of the cellulosic material in the defibrillation step (a) is within the range of 3.0 to 6.0%, or 3.3 to 5.5%, or from 3.6 to 5.1%, or from 3.9 to 4.8%, or from 4.2 to 4.6%. In another preferred embodiment, the raw material consistency of the cellulosic material in the defibrillation step (a) is within the range of 10 to 25%, or 12 to 23%, or 13 to 22%, or 14 to 21 %, or 15 to 20%. Suitable methods for measuring the raw material consistency of cellulosic materials are known to the skilled person. In this regard, for example, M. H. Waller, Measurement and Control of Paper Stock Consistency, Instrumentation Systems &, 1983; H. Holik, Handbook of Paper and Board, Wiley-VCH, 2006.
[000157] The defibrillation step (a) can be performed under ambient conditions.
[000158] In a preferred embodiment, the defibrillation step (a) is performed at an elevated temperature. Preferably, the defibrillation step (a) is performed at a temperature within the range of 20 ° C to 90 ° C, more preferably 20 ° C to 50 ° C.
[000159] In a preferred embodiment, the defibrillation step (a) is performed at a pH value of 5 to 13, or from 5 to 12, or from 6 to 11, or from 6 to 10, or from 7 to 9 , The desired pH value can be adjusted by adding acids and bases, respectively.
[000160] In a preferred embodiment according to the invention, the defibrillation step (a) is carried out in the presence of one or more biocides and other auxiliaries. Said other auxiliaries may comprise, but are not limited to, inorganic materials, such as talc, or other additives.
[000161] Typically, defibrillated cellulosic material containing starch (not degraded), that is, virgin pulp, recycled or mixed, can be subjected to other stages of the process all of which are covered by section (III) of the papermaking method , cardboard or paperboard that follow the defibrillation stage (a) of section (II). These steps may include, but are not limited to: (c) distinguishing cellulosic material; and / or (d) mixing the cellulosic material; and / or (e) target cellulosic material; and / or (f) refining the cellulosic material; and / or (g) sifting and / or cleaning the cellulosic material in the coarse raw material area; and / or (h) adding a dry and / or wet strength polymer to the cellulosic material; (i) sifting and / or cleaning the cellulosic material in the area of fine raw material, that is, after diluting the coarse raw material in a fine raw material.
[000162] In this regard, it should be emphasized that the steps mentioned above (c) to (g) and (i) are optional only, meaning that any one, any two, any three or any four of the steps (c) a (g) ) and (i) can be omitted. It is also possible that the six steps (c) to (g) and (i) are omitted during the papermaking process. According to the step of the invention (b), the treatment of the cellulosic material containing the starch with one or more biocides, is mandatory and or can be carried out during the defibrillation step (a) and / or after the defibrillation step (a ). As long as step (b), the treatment of the cellulosic material containing the starch with one or more biocides, is at least partially performed after the defibrillation step (a), or can be performed before step (c) or at any time during the steps mentioned above (c) to (g). However, preferably step (b) is performed before the cellulosic material containing the starch is diluted from a coarse raw material (being processed in the coarse raw material area) to a fine raw material (being further processed in the coarse processing area). fine raw material), that is, before step (i).
[000163] Devices that were suitable for the subsequent steps after the defibrillation step (a) are known to the skilled person. For example, the cellulosic material containing the starch (not degraded) can be pumped from the defibrillator into a raw material barrel, a mixing barrel and / or a machine barrel before it is supplied to the papermaking machine (ie , to the so-called "constant part" of the paper-making machine).
[000164] The time sequence of steps (c) to (g) can be freely selected, meaning that the time sequence of steps (c) to (g) does not necessarily follow the alphabetical order as indicated. However, the order is preferably alphabetical.
[000165] Other process steps such as storing cellulosic material in storage tanks or additional washing and / or sieving steps can be incorporated after any of process steps (a) to (g).
[000166] In a preferred embodiment, the time sequence of the process steps is selected from the group consisting of
where, for the purpose of the specification, the symbol "^" means "followed by"; and other process steps such as storing cellulosic material in storage tanks or additional washing and / or sieving steps can be incorporated after any of process steps (a) to (g). Step (b), the treatment of the cellulosic material containing the starch with the biocide can also be incorporated after any of the steps in process (a) to (g).
[000167] A person skilled in the art is aware that after each of the steps in process (a) to (g), the mixture comprising the cellulosic material and the biocide can be supplied to the storage tanks, before being reintroduced in other steps of the papermaking process process.
[000168] It is also evident to a person skilled in the art that at least a part of the remainder of the total amount (total inflow) of the biocide can be added to the cellulosic material, when it is stored in storage tanks after any of the process steps ( a), (c), (d), (e), (f) and (g).
[000169] In general, the defibrillation step (a) is performed before the cellulosic material containing the starch (not degraded) enters the papermaking machine. In a preferred embodiment, at least a part of the biocide is added to the waste water for defibrillation before or during the defibrillation step to the cellulosic material, that is, to the virgin, recycled or mixed material. Said addition preferably takes place at least 5 minutes, or at least 10 minutes, or at least 20 minutes, or at least 30 minutes, or at least 40 minutes before the cellulosic material is delivered to the wet end of the papermaking machine, for example, through the flow box.
[000170] In a preferred embodiment, said addition preferably takes place within a maximum of 360 minutes, or a maximum of 300 minutes, or a maximum of 240 minutes, or a maximum of 180 minutes, or a maximum of 120 minutes, or a maximum of 60 minutes before cellulosic material to be supplied to the wet end of the papermaking machine, for example, through the flow box.
[000171] Preferably, the period of time during which the cellulosic material comes into contact with biocide is within the range of 10 minutes to 3 days.
[000172] In a preferred embodiment of the method according to the invention, the period of time during which the cellulosic material comes into contact with biocide is at least 10 minutes, or at least 30 minutes, or at least 60 minutes, or at least at least 80 minutes, or at least 120 minutes.
[000173] In a preferred embodiment of the method according to the invention, the period of time during which the cellulosic material comes into contact with biocide is preferably within the range of 12 ± 10 hours, or 24 ± 10 hours, or 48 ± 12 hours, or 72 ± 12.
[000174] The duration of the defibrillation step (a) is not critical to the invention. After the defibrillation step, the pulp according to the invention can be subjected to a distinction step (c), in which the virgin pulp, recycled pulp or mixed pulp is distinguished, preferably in the presence of the biocide.
[000175] After the defibrillation step, the pulp according to the invention can be subjected to a mixing step (d). Mixture (d), also referred to as raw material preparation, is typically carried out in a so-called mixing box, that is, a reaction vessel in which additives such as dyes, fillers (for example, talc or clay) and sizing agents (for example, rosin, wax, additional starch, glue) are added to the defibrillated cellulosic material, preferably to the virgin pulp, recycled pulp or mixed pulp, preferably in the presence of the biocide. Fillers are preferably added to improve the print, smoothness, gloss, and opacity properties. Ironing agents typically improve the water resistance and printability of the final paper, cardboard and / or paperboard. Ironing can also be carried out on the papermaking machine, by applying a surface to the sheet.
[000176] After the defibrillation step, the pulp according to the invention can be subjected to a bleaching step (e). Typically, bleaching (e) is performed to whiten the defibrillated cellulosic material, preferably in the presence of the biocide. In said bleaching process, chemical bleaches such as hydrogen peroxide, sodium bisulfide or sodium hydrosulfide are typically added to the defibrillated cellulosic material to remove the color.
[000177] After the defibrillation step, the pulp according to the invention can be subjected to a refinement step (f). Refining (f) is preferably carried out in a so-called pulp mixer or refiner by fibrillating the fibers of the cellulosic material, preferably in the presence of the biocide. The purpose is preferably to brush and increase the fibrils of the fiber surfaces for better bonding to each other during sheet formation which results in stronger paper. Pulp mixers (eg Hollander mixer, Jones-Bertram mixer, etc.) process batches of pulp while refiners (eg Chaflin refiner, Jordan refiner, single or double disc refiners, etc.) continuously process pulp .
[000178] After the defibrillation step, the pulp according to the invention can be subjected to a sieving step (g). Sieving (g) is preferably applied to remove the unwanted fibrous and non-fibrous material from the cellulosic material, preferably in the presence of the biocide, preferably by the use of rotating screens and centrifugal cleaners.
[000179] Before the cellulosic material enters the papermaking machine, the cellulosic material that is present as a "thick raw material" is diluted with water for "fine raw material". After dilution, the pulp according to the invention can be subjected to an additional sieving and / or cleaning step (i).
[000180] Thereafter, typically near the end of the papermaking process, the cellulosic material is supplied to a papermaking machine where it typically enters the wet end of the papermaking machine.
[000181] This is where section (IV) of the general method for making paper, cardboard or paperboard begins.
[000182] For the purpose of the specification, the term "papermaking machine" preferably refers to any device or component thereof which basically serves to form sheets from an aqueous suspension of the cellulosic material. For example, the defibrillator is not to be considered as a component of the paper-making machine.
[000183] Typically, a papermaking machine has a wet end comprising a flat table and a press section, and a dry end comprising a first drying section, a size press, a second drying section, a calender, and "giant" spools.
[000184] The first section of the wet end of the papermaking machine is typically the flat table where the cellulosic material is supplied through a flow box on the flat table and distributed evenly over the entire width of the papermaking machine and a quantity significant amount of water from the aqueous dispersion or aqueous suspension of the cellulosic material is drained. The flat table, also called the forming section, can comprise a layer or multilayer, where multi preferably means 2, 3, 4, 5, 6, 7, 8 or 9 layers (pleats). Subsequently, the cellulosic material preferably enters the press section of the papermaking machine where the remaining water is removed from the cellulosic material by squeezing, which forms a network of cellulosic material which is in turn preferably supplied to the dry end of the manufacturing machine. of paper.
[000185] The so-called dry end of the papermaking machine preferably comprises a first drying section, optionally a size press, a second drying section, a calender, and "giant" spools. The first and second drying sections preferably comprise several steam-heated drying cylinders where the synthetic fabrics of the dryer can carry the cellulosic material network around the cylinders until the cellulosic material network has a water content of approximately 4 to 12 %. An aqueous solution of starch can be added to the surface of the cellulosic material web to improve the surface for printing purposes or strength properties. Preferably, the network of cellulosic material is then supplied to the calender, where it is smoothed and polished. Subsequently, the cellulosic material is typically wrapped in the so-called "giant" spool section.
[000186] In a preferred embodiment, the method according to the invention is carried out in a papermaking plant which can be considered to have an open water supply and thus an open water circuit. Paper-making plants of this type are typically characterized by an effluent plant, that is, by an effluent stream through which an aqueous composition is continuously drawn from the system.
[000187] In another preferred embodiment, the method according to the invention is carried out in a papermaking plant which can be considered to have a closed water recycling circuit. Paper-making plants of this type are typically characterized by having no effluent plant, that is, there is no effluent flow through which an aqueous composition is continuously drawn from the system, while the paper, of course, contains a little bit of residual moisture. All papermaking plants (closed and open systems) typically allow evaporation of water (gaseous), while closed systems do not allow liquid effluent flows. It has surprisingly been found that the method according to the invention is of particular advantage in such a closed loop of water recycling. Without the method according to the invention, the starch in the liquid phase would concentrate from the recycling step to the recycling step and ultimately end up in a highly viscous pasty composition not useful for any papermaking. By means of the method according to the invention, however, the starch is fixed, preferably fixed to the fibers, thus avoiding any concentration effect from the recycling step to the recycling step.
[000188] In a preferred embodiment, at least 50% by weight of the biocide, which is present during step (b), is still present when the cellulosic material containing the (non-degraded) starch enters the wet end of the food making machine. paper. In case the loss of biocide during the papermaking process is very high, additional parts of the biocide can be added during any of the process steps (c), (d), (e), (f) and / or ( g).
[000189] In another preferred embodiment, a maximum of 50% by weight of the biocide, which is present during step (b), is still present when the cellulosic material containing the starch (not degraded) enters the papermaking machine.
[000190] According to the invention, step (h) comprises adding a dry and / or wet strength polymer to the cellulosic material. Dry and / or wet strength polymers are known to the skilled person. In this regard, for example, C. J. Biermann, Handbook of Pulping and Papermaking, Academic Press; 2nd edition (1996); J. P. Casey, Pulp and Paper, Wiley-Interscience; 3rd edition (1983); H Holik, Handbook of Paper and Board, Wiley-VCH Verlag GmbH & Co. KGaA, 1st ed, 2006; and I. Thorn et al., Applications of Wet-End Paper Chemistry, 2nd edition, Springer, 2009.
[000191] For the purpose of the specification, dry and / or wet strength polymers are to be considered as polymers typically employed to improve the dry and / or wet strength of paper, cardboard or paperboard.
[000192] Dry and / or wet strength polymer can be added to cellulosic material containing starch at any stage of papermaking in the area of coarse raw material, or at any stage of papermaking in the area of matter thin raw. It is evident to a person skilled in the art that at least a part of the total amount (total inflow) of the wet and / or dry strength polymer can be added to the cellulosic material, that is, to the virgin, recycled or mixed material, during or after the defibrillation step (a).
[000193] For the purpose of a descriptive report, the term "coarse raw material area" refers to any papermaking stage where cellulosic material is present as "coarse raw material". Similarly, the term "fine raw material area" refers to any stage of papermaking where cellulosic material is present as fine raw material. Typically, coarse raw material is processed at any stage of the conventional paper or cardboard manufacturing processes that take place before step (i). The terms "coarse raw material" and "fine raw material" are known to the person skilled in the art. Typically, the coarse raw material papermaking machine is diluted before step (i) thus yielding fine raw material. For the purpose of the specification, "coarse raw material" preferably has a solids content (= raw material consistency) of at least 2.0% by weight, preferably at least 2.1% by weight, more preferably at least less 2.2% by weight, even more preferably at least 2.3% by weight, even more preferably at least 2.4% by weight and most preferably at least 2.5% by weight. descriptive report, cellulosic material having the solids content above is preferably to be considered as coarse raw material, while cellulosic material having a lower solids content is to be considered as fine raw material.
[000194] In a preferred embodiment, the dry and / or wet strength polymer is added to the cellulosic material containing the (non-degraded) starch during any of the steps, (a), (c), (d), ( e), (f) or (g), that is, before the cellulosic material containing the (non-degraded) starch is diluted as a "fine raw material" and before the cellulosic material containing the (non-degraded) starch enters on the paper-making machine.
[000195] In a preferred embodiment, the dry and / or wet strength polymer is added to the cellulosic material containing the starch after the biocide has been added. It is also possible that the dry and / or wet strength biocide and polymer are added simultaneously to the cellulosic material containing the starch. In addition, it is possible that a first part of the dry and / or wet strength polymer is added to the cellulosic material containing the starch before a first part of the biocide is added and subsequently a second part of the dry resistance polymer and / or the damp be added, or vice versa.
[000196] In a preferred embodiment, the dry and / or wet strength polymer is added to the cellulosic material containing the starch after the defibrillation step has been completed.
[000197] It is evident to a person skilled in the art that the amount (inflow) of dry and / or wet strength polymer can be added continuously (uninterruptedly) or discontinuously (interruptedly) with respect to a feeding point. In addition, the total amount (total inflow) of dry and / or wet strength polymer can be divided into at least two parts, of which at least one part is continuously or discontinuously added to the cellulosic material containing the starch during or after the defibrillation step (a) and the other part is continuously or discontinuously added elsewhere, that is, to one or more other feeding points.
[000198] In a preferred embodiment, the total amount (total inflow) of the dry and / or wet strength polymer is added to the cellulosic material after the defibrillation step (a) continuously or discontinuously, that is, 100% by weight of the total amount (total inflow) of the dry and / or wet strength polymer are preferably added to the cellulosic material, that is, to the virgin material, recycled or mixed after the defibrillation step (a).
[000199] In a preferred embodiment, at least a part of the total amount (total inflow) of the wet and / or wet strength polymer is added to the subsequent cellulosic material for any of the steps (c), (d), ( e), (f) and / or (g). For example, 50% by weight of the total amount (total inflow) of the dry and / or wet strength polymer can be added continuously or discontinuously, during any of the steps (a), (c), (d), ( e), (f) and / or (g) and the remaining 50% by weight of the total amount (total inflow) of the dry and / or wet strength polymer can be added continuously or discontinuously, in any other processing step , for example, within the coarse raw material area or the fine raw material area.
[000200] The optimum point for adding a dry and / or wet strength polymer may differ from one papermaking plant to another.
[000201] In a preferred embodiment, the dry and / or wet strength polymer is added to the coarse raw material, before the last refinement has taken place. In another preferred embodiment, the dry and / or wet strength polymer is added to the coarse raw material, after the last refinement has taken place. Fine mixing can be essential to obtain the best performance. Therefore, adding to a well-shaken box or lowering the level of the thick stock box is preferred.
[000202] In a preferred embodiment, a dry and / or wet-strength polymer is added to a pipeline where the optimum mixture is achieved through a multi-point injection system.
[000203] Particularly preferred modalities B1 to B4 refer to the preferred feeding points of the dry and / or wet strength polymer according to the invention are summarized in Table 2 here below: Table 2:
in which sections (II) to (IV) refer to the sections of a papermaking plant comprising a papermaking machine, in which section (II) includes measures associated with defibrillation; section (III) includes measures taken after defibrillation but still outside the paper machine; and section (IV) includes measures taken within the papermaking machine.
[000204] Particularly preferred embodiments of the method according to the invention refer to combinations of any of embodiments A1 to A6 as summarized in Table 1 with any of embodiments B1 to B7 as summarized in Table 2; particularly A1 + B1, A1 + B2, A1 + B3, A1 + B4, A1 + B5, A1 + B6, A1 + B7; A2 + B1, A2 + B2, A2 + B3, A2 + B4, A2 + B5, A2 + B6, A2 + B7; A3 + B1, A3 + B2, A3 + B3, A3 + B4, A3 + B5, A3 + B6, A3 + B7; A4 + B1, A4 + B2, A4 + B3, A4 + B4, A4 + B5, A4 + B6, A4 + B7; A5 + B1, A5 + B2, A5 + B3, A5 + B4, A5 + B5, A5 + B6, A5 + B7; A6 + B1, A6 + B2, A6 + B3, A6 + B4, A6 + B5, A6 + B6, A6 + B7.
[000205] The dry and / or wet strength polymer is preferably added to the coarse feedstock, that is, to the coarse feedstock area of the papermaking plant. In a preferred embodiment, the dry and / or wet strength polymer feed point is located in the box, or after, where the defibrillator is located, and / or in the fan pump, or rather, at the manufacturing plant of paper. Preferably, the dry and / or wet strength polymer feed point is located after or in the mixing box before the machine box, and / or before the fan pump of the papermaking plant. Preferably, the dry and / or wet strength polymer feed point is located in the machine box and / or before the fan pump of the papermaking plant. Preferably, the dry and / or wet strength polymer feed point is located at the outlet of the machine box and / or before the fan pump of the papermaking plant. Preferably, the feed point for the dry and / or wet strength polymer is located in the regulation box and / or before the fan pump of the papermaking plant.
[000206] The optimum dosage of a dry and / or wet strength polymer varies from application to application, paper making plant to paper making plant and classification for classification. Preferred dosages fall in the range of 0.2 to 0.5% by weight, based on the active content, although dosages as low as 0.05% by weight have been successful. This is particularly the case when a cationic promoter is employed. Preferred cationic promoters are so-called "anionic waste collectors", preferably selected from the group consisting of polyamines, polyDADMAC, polyaluminium chloride, aluminum hydrochloride and alum.
[000207] The exact dosage typically depends on the balance of the load for the purpose of wet use. Load measurement helps to achieve optimal dosage.
[000208] In a preferred embodiment, the dry and / or wet strength polymer is dosed into the cellulosic material containing the starch at a concentration of at least 50 g / metric ton, or at least 100 g / metric ton, or at least 250 g / metric ton, or at least 500 g / metric ton, or at least 750 g / metric ton, or at least 1,000 g / metric ton, or at least 1,250 g / metric ton, or at least 1,500 g / metric ton metric ton, or at least 2,000 g / metric ton, or at least 3,000 g / metric ton, or at least 4,000 g / metric ton, where metric tons are preferably based on the overall composition containing the cellulosic material, and the grams they are preferably based on the dry and / or wet strength polymer as such (active content). More preferably, the wet and / or dry strength polymer is dosed for the cellulosic material at a concentration of 100 to 5,000 g / metric ton, or 200 to 4,500 g / metric ton, or 250 to 4,000 g / ton metric, or from 300 to 3,500 g / metric ton where the metric tons are preferably based on the general composition containing the cellulosic material, and the grams are preferably based on the dry and / or wet strength polymer, respectively, as such (active content).
[000209] In a particularly preferred embodiment, the dry and / or wet strength polymer is dosed for the cellulosic material in a concentration of 500 to 10,000 g / metric ton, or 500 to 9,000 g / metric ton, or 500 to 8,000 g / metric ton, or 500 to 7,000 g / metric ton, or 500 to 6,000 g / metric ton, or 500 to 5,000 g / metric ton, or 500 to 4,500 g / metric ton, or 500 to 4,000 g / metric ton, or from 500 to 3,750 g / metric ton, or from 500 to 3,500 g / metric ton, or from 500 to 3,250 g / metric ton, or from 500 to 3,000 g / metric ton, or from 500 to 2,500 g / metric ton, or 500 to 2,000 g / metric ton, where metric tons are preferably based on the general composition containing the cellulosic material, and the grams are preferably based on the dry and / or wet strength polymer, respectively , as such (active content, dry basis).
[000210] Preferably, the wet and / or dry strength polymer belongs to any of the following three categories: (i) polymers capable of only forming hydrogen bonds with starch and / or cellulosic fibers, such as certain polyacrylamides, ( ii) polymers capable of forming ionic bonds additionally with starch and / or cellulosic fibers, such as highly cationic polyvinylamines, (iii) polymers capable of covalently bonding to cellulosic fibers, such as glyoxylated polyacrylamide and epichlorohydrin-polyamine polyamide.
[000211] The dry and / or wet resistance polymer can be non-ionic, cationic, anionic or amphoteric.
[000212] For the purpose of the specification, the term "cationic polymer" preferably refers to water-soluble and / or water-swellable polymers, preferably water-soluble polymers having a positive net charge. Cationic polymers can be branched or unbranched, cross-linked or non-cross-linked, grafted or non-grafted.
[000213] For the purpose of the specification, the term "anionic polymer" preferably refers to water-soluble and / or water-swellable polymers, preferably water-soluble polymers having a negative net charge. Anionic polymers can be branched or unbranched, cross-linked or non-cross-linked, grafted or non-grafted.
[000214] A person skilled in the art knows the meaning of the terms "branched polymer", "unbranched polymer", "crosslinked polymer" and "graft polymer". Definitions for these terms can preferably be found in A. D. Jenkins et al. Glossary of Basic Terms in Polymer Science. Pure & Applied Chemistry 1996, 68, 2287-2311.
[000215] For the purpose of the specification, the term "water swellable" preferably refers to the increase in volume of the polymer particles associated with water absorption (cf. DH Everett. Manual of Symbols and Terminology for Physicochemical Quantities and Units. Appendix II, Part I: Definitions, Terminology and Symbols in Colloid and Surface Chemistry. Pure & Applied Chemistry 1972, 31, 579-638). The swelling behavior of polymers can be measured at different temperatures and pH values in water. The swollen weights of the polymers are determined at intervals, after removal of surface water, until equilibrium swelling is achieved. The swelling percentage is preferably calculated using the following equation:% swelling = 100 x [(Pt - W0) / W0], where W0 is the starting weight and Wt is the final weight of the gel at time t (cf. IM El-Sherbiny et al. Preparation, characterization, swelling and in vitro drug release behavior of poly [N-acryloilglycine-chitosan] interpolymeric pH and thermally-responsive hydrogels. European Polymer Journal 2005, 41, 2584-2591).
[000216] The dry and / or wet strength polymers according to the invention can preferably exhibit a swelling% of at least 2.5%, or at least 5.0%, or at least 7.5%, or at least 10%, or at least 15%, or at least 20% measured in demineralized water at 20 ° C and pH 7.4 in phosphate buffer after equilibrium swelling is achieved.
[000217] For the purpose of the specification, the term "polymer" preferably refers to a material composed of macromolecules containing> 10 units of monomers (cf. GP Moss et al. Glossary of Class Names of Organic Compounds and Reactive Intermediates Based on Structure, Pure & Applied Chemistry 1995, 67, 1307-1375).
[000218] The dry and / or wet resistance polymer can each consist of a simple type dry and / or wet resistance polymer or can be contained in a composition comprising different dry and / or wet resistance polymers .
[000219] Dry and / or wet strength polymers can be homopolymers that preferably comprise units of ionic monomers, preferably cationic as the sole monomer component. In addition, dry and / or wet strength polymers can also be copolymers, i.e., bipolymers, terpolymers, quaterpolymers, etc., comprising, for example, different units of ionic monomers, preferably cationic; or ionic, preferably cationic as well as nonionic monomer units.
[000220] For the purpose of the specification, the term "homopolymer" preferably refers to a polymer derived from a monomer species and the term "copolymer" preferably refers to a polymer derived from more than one monomer species. Copolymers that are obtained by copolymerization of two species of monomer are called bipolymers, those obtained from three monomer terpolymers, those obtained from four monomer quaterpolymers, etc. (cf. A. D. Jenkins et al. Glossary of Basic Terms in Polymer Science. Pure & Applied Chemistry 1996, 68, 2287-2311).
[000221] If the wet and / or dry strength polymer is a copolymer, it is preferably a random copolymer, a statistical copolymer, a block copolymer, a periodic copolymer or an alternating copolymer, more preferably a random copolymer . In a particularly preferred embodiment, the dry and / or wet strength polymer is a copolymer with one of the comonomers that are acrylamide or viylamine and vinylamide, respectively. Thus, preferably the dry and / or wet strength polymer according to the invention is preferably based on polyacrylamide or polyvinylamine, which in turn can be obtained by completely or partially hydrolyzing the polyvinylamide.
[000222] A person skilled in the art knows the meaning of the terms "random copolymer", "statistical copolymer", "periodic copolymer", "block copolymer" and "alternating copolymer". Definitions for these terms can be found preferably in A. D. Jenkins et al. Glossary of Basic Terms in Polymer Science. Pure & Applied Chemistry 1996, 68, 2287-2311.
[000223] For the purpose of the specification, the term "ionicity" will refer to the net charge of a polymer as well as its quantitative content, preferably molar, of ionic monomer units based on the total content of monomer units, preferably expressed in % soft.
[000224] Preferably, the dry and / or wet strength polymer comprises monomer units that are derived from radically polymerizable, ethylenically unsaturated monomers. Therefore, in a preferred embodiment, the polymeric main chain of the dry and / or wet strength polymer is a carbon chain that is not interrupted by heteroatoms, such as nitrogen or oxygen.
[000225] Preferably, the dry and / or wet strength polymer independently of one another is derived from ethylenically unsaturated monomers which are preferably radically polymerizable.
[000226] Preferably, the dry and / or wet strength polymer is an ionic polymer, more preferably a cationic, anionic or amphoteric polymer. Preferably, the ionicity of the dry and / or wet strength ionic polymer is at most 95% mole, or at most 90% mole, or at most 85% mole, or at most 80% mole, or at most 75% mole , or a maximum of 70% mole, or a maximum of 65% mole, or a maximum of 60% mole, or a maximum of 55% mole, or a maximum of 50% mole, or a maximum of 45% mole, or a maximum of 40% mole, or at most 35% mole, or at most 30% mole, or at most 25% mole, or at most 20% mole, or at most 15% mole, or at most 10% mole, or at most 5% mole, with relation to the total number of monomer units. If the wet and / or dry strength polymer according to the invention is amphoteric, that is, it comprises anionic as well as cationic monomer units, the preferred ionicities preferably refer to the total content of ionic monomer units including units of anionic and cationic monomers.
[000227] Preferred ionicities, preferably cationicities or anionicities, of the dry and / or wet strength polymer according to the invention are summarized as modalities C1 to C8 in Table 3 here below: Table 3:

[000228] Preferably, the dry and / or wet strength polymer has a weight average molecular weight of a maximum of 1,500,000 g / mol, or a maximum of 1,400,000 g / mol, or a maximum of 1,300,000 g / mol, or a maximum of 1,200,000 g / mol, or a maximum of 1,100,000 g / mol, or a maximum of 1,000,000 g / mol, or a maximum of 900,000 g / mol, or a maximum of 800,000 g / mol, or a maximum of 700,000 g / mol, or a maximum of 600,000 g / mol, or a maximum of 500,000 g / mol, or a maximum of 400,000 g / mol, or a maximum of 300,000 g / mol.
[000229] Preferred average molecular weight weights of the dry and / or wet strength polymer according to the invention are summarized as modalities D1 to D6 in Table 4 here below: Table 4:

[000230] Modalities according to the invention say one of the modalities C1 to any of the modalities particularly C1 + D1, C2 + C8 + D1; C1 + D2, C2 + D2, C3 + D C1 + D3; C2 + D3; C3 + D3; C4 + D C2 + D4, C3 + D4, C4 + D4, C5 + D C3 + D5, C4 + D5, C5 + D5, C6 + D C4 + D6, C5 + D6, C6 + D6, C7 + D6, preferred as regards combinations of C8 as summarized in Table es D1 to D6 as summarized in T 1, C3 + D1, C4 + D1, C5 + D1, C6 + D1 2, C4 + D2, C5 + D2, C6 + D2, C7 + D2 3, C5 + D3, C6 + D3, C7 + D3, C8 + D3 4, C6 + D4, C7 + D4, C8 + D4; C1 + D5 5, C7 + D5, C8 + D5; C1 + D6, C2 + D6 and C8 + D6. all of any 3 with table 4; , C7 + D1,, C8 + D2; ; C1 + D4,, C2 + D5,, C3 + D6,
[000231] Dry and / or wet strength polymers have been available for many years in the paper industry. Preferred examples of the dry and / or wet strength polymers according to the invention include, but are not limited to, natural polymers or semi-synthetic polymers such as starch, or in their native or chemically modified form, and synthetic polymers.
[000232] Preferred synthetic polymers for improving the dry strength and / or wet strength of paper include acrylamide copolymers. Anionic and cationic versions of this chemical are widely used today, usually combined with a cationic promoter, to aid adsorption on paper fibers. Polyacrylamide technology can be enhanced by adding aldehyde reactivity. Glyoxylated polyacrylamides can improve strength through the use of latent reactive aldehyde groups that undergo crosslinking of interpolymers while drying the paper sheet at 80-100 ° C.
[000233] Preferred synthetic polymers to improve dry strength and / or wet strength of paper also include polyamide polyamine polymers, further reacted with epichlorohydrin which has been used successfully in the paper industry for many years as well as resins of wet resistance. These additives are very reactive, especially at pH values greater than about 5, particularly greater than about 6, and temperatures from 30 to 60 ° C. Crosslinking between the polymeric chains occurs within the treated paper sheet, decreasing the solubility of the resin and preventing water from breaking the hydrogen bond of the interfibers. For the purpose of the specification, these polymers encompass and are also referred to as polyamide polymers - polyamine epichlorohydrin, polyamide polymers - amine epichlorohydrin and polyamine polymers - amine epichlorohydrin.
[000234] The invention can be used in a combination with other polymer components in order to further improve the strength properties of the paper product. The polymer components can be cationic, or anionic, or amphoteric, or non-ionic synthetic, or natural polymers, or combinations thereof. Examples include, but are not limited to, cationic starches or amphoteric starches; anionic polymers, such as a polyacrylic acid, copolymers of acrylamide and acrylic acid, and carboxymethyl cellulose; cationic polymers, such as cross-linked polyamidoamines, polydialyldimethylammonium chloride, linear or branched polyamines, polyethyleneimines, hydrolyzed polyvinylamines, copolymers of diallyldimethylammonium chloride and acrylamide, copolymers of 2-acrylamide and partially acrylamide and methyl acrylate and methyl chloride and methylene chloride ; functional polymeric aldehyde compounds, such as glyoxalated polyacrylamides, aldehyde celluloses and functional aldehyde polysaccharides; amphoteric polymers such as acrylamide, acrylic acid, and diallyldimethylammonium chloride, or acrylamide, acrylic acid, and 2-acrylylethyltrimethylammonium chloride; substantially non-ionic water-soluble polymers such as non-ionic polyethylene oxide or polyacrylamide; and water-insoluble latex such as polyvinylacetate or styrene-butadiene copolymers.
[000235] For the purpose of the specification, "substantially non-ionic polymer" are polymers that have a maximum ionicity of 2% mole, more preferably a maximum of 1% mole, that is, a maximum of 1% mole and a maximum of 2% mole, respectively, of all monomer units carrying ionic groups.
[000236] In a preferred embodiment of the method according to the invention, the dry and / or wet strength polymer is selected from the group consisting of: (i) non-ionic, anionic, cationic or amphoteric cell-reactive polymers capable to form crosslinks of covalent interpolymers with cellulose, preferably through functional groups of aldehyde and / or functional groups of 3-hydroxyazetidinium of the dry and / or wet strength polymer; and (ii) natural or synthetic non-ionic, anionic, cationic or amphoteric polymers.
[000237] A knowledgeable person recognizes that the polymer combinations of categories (i) and (ii) above can also be advantageously used in the method according to the invention.
[000238] Preferably, (i) non-ionic, anionic, cationic or amphoteric cellulose-reactive polymers are reaction products - homo or ionic or non-ionic, linear or branched, cross-linked or non-cross-linked copolymers comprising monomer units derived from vinylamides which are optionally completely or partially hydrolyzed; and / or other monomers that form polyamines and / or polyamides such as polyalkylene polyamine and dibasic acids; and / or (meth) acrylamides; or polysaccharides - with epihalohydrin, preferably epichlorohydrin, or with cellulose-reactive agents comprising at least one aldehyde functional group, preferably glyoxal.
[000239] When the wet and / or dry strength polymer is the reaction product of epihalohydrin with a polymer, the latter is preferably a polyamine or a polyaminoamide.
[000240] When the wet and / or dry strength polymer is the reaction product of a cellulose-reactive agent comprising at least one functional group of aldehyde with a polymer, the latter is preferably a copolymer of polyacrylamide or one of acrylamide with one or more ionic monomers, preferably cationic, preferably selected from polydialyldimethylammonium chloride and 2-acrylylethyltrimethylammonium chloride.
[000241] Preferably, the cellulose-reactive agents that are used in the synthesis of the dry and / or wet-strength polymers reactive with cellulose according to the invention comprise at least one functional group capable of reacting with the polymer and at least one aldehyde functional group that remains unreacted once the cellulose-reactive agent has been covalently linked to the polymer through the functional group capable of reacting with the polymer. Said unreacted aldehyde functional groups give the cellulose-reactive polymer thus obtained. For the purpose of the specification, these polymers are also referred to as functional aldehyde polymers.
[000242] In a preferred embodiment, the functional group capable of reacting with the polymer is also an aldehyde functional group. Thus, preferably, cellulose-reactive agents comprise at least two aldehyde functional groups and are preferably selected from the group consisting of glyoxal, glutaraldehyde, succinaldehyde, furan dialdehyde, 2-hydroxydipaldehyde, dialdehyde starch, and combinations thereof.
[000243] Polymeric functional aldehyde polymers preferably comprise glyoxylated polyacrylamides, glyoxylated polyvinylamides, aldehyde-rich cellulose, functional aldehyde polysaccharides, and functional, anionic or nonionic aldehyde cationic starches. Exemplary materials include those disclosed in US 4,035,229; US 4,129,722; US 4,217,425; US 5,085,736; US 5,320,711; US 5,674,362; US 5,723,022; US 6,224,714; US 6,245,874; US 6,274,667; US 6,749,721; US 7,488,403; US 7,589,153; US 7,828,934; US 7,897,013; US2011 / 0083821, WO 00/43428; WO 00/50462 A1; WO 01/34903 A1, all of which are incorporated herein by reference.
[000244] Polymeric functional aldehyde polymers can have a molecular weight of about 10,000 g / mol or greater, more specifically about 100,000 g / mol or greater, and more specifically about 500,000 g / mol or greater. Alternatively, the functional polymeric aldehyde compounds can have a molecular weight below approximately 200,000 g / mol, such as below approximately 60,000 g / mol.
[000245] Additional examples of aldehyde functional polymers for use in the present invention include dialdehyde guar, aldehyde functional wet strength additives further comprising carboxylic groups as disclosed in WO 01/83887; dialdehyde inulin; and the dialdehyde modified anionic and amphoteric polyacrylamides disclosed in WO 00/11046; incorporated herein by reference. Surfactants containing aldehyde as disclosed in US 6,306,249 can also be used.
[000246] When used in the present invention, the functional aldehyde polymers preferably have at least 5 milliequivalents (meq) of aldehyde per 100 grams of polymer, more specifically at least 10 meq, more specifically still about 20 meq or greater, and specifically about 25 meq per 100 grams of polymer or greater.
[000247] Aldehyde-rich cellulose may include cellulose oxidized with periodate solutions, as disclosed in US 5,703,225, enzyme-treated cellulose, such as cellulase-treated cellulose disclosed in WO 97/27363 and aldehyde modified cellulose products disclosed in EP 1,077,286-A1, all of which are incorporated herein by reference.
[000248] In a preferred embodiment, the polymeric aldehyde functional polymer is a glyoxylated polyacrylamide, such as a cationic glyoxylated polyacrylamide. Such compounds include chloroxylated polyacrylamides described in US 3,556,932 and US 3,556,933, which are incorporated herein by reference. Another example of a glyoxylated polyacrylamide is a glyoxylated poly (acrylamide-co-diallyl dimethyl ammonium chloride). Sometimes it may be advantageous to use a mixture of high and low molecular weight glyoxylated polyacrylamides to obtain a desired effect.
[000249] In a particularly preferred embodiment, the cellulose-reactive dry and / or wet strength polymer is selected from glyoxylated polyacrylamide (GPAM), glyoxylated polyvinylamines (GPVAm), polyamine-epi-halohydrin polymers, and polyamine polymers - epichlorohydrin polyamide (PAE).
[000250] Glyoxylated polyacrylamides (GPAM) are typically prepared by treating polyacrylamides, preferably ionic, more preferably cationic acrylamide copolymers with ionic comonomers such as polydialldimethylammonium chloride or 2-acrylylethyltrimethylammonium chloride, with glyoxide. Glyoxal reacts with one of its aldehyde functionalities to the amyl functionality of acrylamide thus functionalizing the polymer through free aldehyde groups.
[000251] Functionalized polyvinylamines, preferably glyoxylated (GPVAm) can be prepared by reacting a starting polyvinylamine with at least one dialdehyde, wherein the starting polyvinylamine is a polymer formed from N-vinylformamide or N-vinylacetamide, which polymer is at least partially hydrolyzed to give a degree of primary amino functionality, before reaction with the dialdehyde. Exemplary dry and / or wet strength polymers of this type include those disclosed in US 2009/0126890, which is hereby incorporated by reference.
[000252] Preferred glyoxylated polyacrylamides (GPAM) according to the invention are glyoxylated cationic copolymers, preferably copolymers of (meth) acrylamide and cationic comonomers selected from polydialldimethylammonium chloride and 2-acrylylethyltrimethylammonium chloride have a molecular weight and preferably have a molecular weight within the range of 200,000 ± 150,000 g / mol, preferably 200,000 ± 100,000 g / mol; and an ionicity of at most 10 mole%, preferably within the range of 3.0 ± 2.9 mole%; or an average molecular weight by weight within the range of 200,000 ± 150,000 g / mol, preferably 200,000 ± 100,000 g / mol; and an ionicity within the range of 25 ± 20 mole%, preferably within the range of 25 ± 10 mole%.
[000253] In a preferred embodiment, a polymer carrying amino groups is reacted with epihalohydrin, preferably epichlorohydrin thus yielding another type of polymer that is capable of forming covalent bonds with cellulose. In this regard, a distinction can be made between polyamine epihalohydrin polymers, polyamide epihalohydrin polymers, and polyamine polyamide epihalohydrin polymers, all of which are preferred dry and / or wet strength polymers. according to the invention. Preferred polyamine-epi-halohydrin polymers and polyamino-polyamide-epi-halohydrin polymers according to the invention include polyaminoamide-epi-halohydrin polymers, polyamidapolyamine-epi-halohydrin polymers, polyamine-polyamide-amine-halo polymers, polymers of amine-polyamide-amine-halo epihalohydrin, and polyamide-epihalohydrin polymers; polyalkylene polyamine-epihalohydrin polymers; polyamineurylene-epihalohydrin polymers; copolyamide-polyurylene-epichlorohydrin polymers; and polyimide-polyarylene-epichlorohydrin polymers. Exemplary dry and / or wet strength polymers of this type include those disclosed in US 2,926,154; US 3,125,552; US 3,311,594; US 3,332,901; US 3,700,623; US 3,772,076 .; US 3,833,531; US 3,855,158; US 3,887,510; US 3,992,251; US 4,035,229; US 4,129,528; US 4,147,586; US 4,450,045; US 4,501,862; US 4,515,657; US 4,537,657; US 4,722,964; US 5,082,527; US 5,316,623; US 5,318,669; US 5,502,091; US 5,525,664; US 5,614,597; US 5,633,300; US 5,656,699; US 5,674,358; US 5,904,808; US 5,972,691; US 6,179,962; US 6,355,137; US 6,376,578; US 6,429,253; US 7,175,740; and US 7,291,695, all of which are incorporated herein by reference.
[000254] Polyamino-polyamide epichlorohydrin (PAE) polymers are typically prepared by a two-step process involving 1.) the condensation reaction between a polyalkylene polyamine (usually diethylenetriamine) and a dibasic acid (usually adipic acid) to form a polyamide lower molecular weight containing various secondary amine functionalities within the polymer main chain; and 2.) the treatment of this lower molecular weight polyamide with epichlorohydrin, mainly by reaction to the functional groups of secondary amine, to form a reactive cationic 3-hydroxyazetidinium chloride and further develop the molecular weight. The formation of unwanted by-products such as dichloropropanol and chloropropandiol is typically suppressed and preferably, the dichloropropanol content is below 1000 ppm, more preferably below 100 ppm and most preferably below 10 ppm.
[000255] The dry and / or wet strength polymer, preferably cellulose-reactive polymer according to the invention preferably comprises a cellulose-reactive polymer, preferably as the sole polymer component; or is contained in a composition comprising two different cellulose-reactive polymers, preferably as the only polymer components; or three cellulose-reactive polymers, preferably as the sole polymer components; or four cellulose-reactive polymers, preferably as the sole polymer components; or even more than four cellulose-reactive polymers, preferably as the only polymer components.
[000256] Depending on the procedure used for the preparation of the dry and / or wet strength polymer, preferably the cellulose-reactive polymer may comprise additional substances such as polyfunctional alcohols, water-soluble salts, chelating agents, free radical initiators and / or their respective degradation products, reducing agents and / or their respective degradation products, oxidants and / or their respective degradation products, etc.
[000257] In a preferred embodiment, (ii) natural or synthetic (ii) non-ionic, anionic, cationic or amphoteric polymers are selected from the group consisting of a) native or chemically modified polysaccharides; preferably selected from native starch, cationic starch, anionic starch, non-ionic starch and carboxymethylcellulose; b) anionic homo or copolymers comprising units of anionic monomers derived from (meth) acrylic acid; optionally in combination with non-ionic monomer units derived from (meth) acrylamide; c) cationic homo or copolymers comprising units of cationic monomers preferably derived from vinylamine, polydialldimethylammonium chloride, 2-acrylylethyltrimethylammonium chloride, and / or ethyleneimine; optionally in combination with non-ionic monomer units derived from vinylamide and / or (meth) acrylamide; d) amphoteric polymers; preferably terpolymers comprising units of monomers derived from (meth) acrylamide, (meth) acrylic acid, and diallyldimethylammonium chloride or 2-acrylylethyltrimethylammonium chloride; e) substantially non-ionic water-soluble polymers; preferably selected from non-ionic polyethylene oxides and polyacrylamide; and f) water-insoluble latex; preferably selected from polyvinylacetate and styrene-butadiene copolymers.
[000258] Homo or preferred anionic copolymers of group b) according to the invention are anionic polyacrylamides, preferably copolymers of (meth) acrylic acid and (meth) acrylamide, and preferably have (i) an average molecular weight by weight within the range 300,000 ± 200,000 g / mol, preferably 300,000 ± 150,000 g / mol; and an ionicity within the range of 10 ± 7.5 mole%, preferably within the range of 10 ± 5.0 mole%; or (ii) an average molecular weight by weight within the range of 300,000 ± 200,000 g / mol, preferably 300,000 ± 150,000 g / mol; and an ionicity within the range of 30 ± 25 mole%, preferably within the range of 30 ± 20 mole%; or (iii) an average molecular weight by weight within the range of 1,300,000 ± 250,000 g / mol, preferably 1,300,000 ± 100,000 g / mol; and an ionicity within the range of 10 ± 7.5 mole%, preferably within the range of 10 ± 5.0 mole%; or (iv) an average molecular weight by weight within the range of 1,300,000 ± 250,000 g / mol, preferably 1,300,000 ± 100,000 g / mol; and an ionicity within the range of 30 ± 25 mole%, preferably within the range of 30 ± 20 mole%.
[000259] Homo or preferred cationic copolymers of group c) according to the invention are cationic polyacrylamides, preferably copolymers of (meth) acrylamide and cationic monomers selected from polydialldimethylammonium chloride and 2-acrylylethyltrimethylammonium chloride, and preferably have (i) weight average molecular weight within the range of 400,000 ± 150,000 g / mol, preferably 400,000 ± 100,000 g / mol; and an ionicity within the range of 25 ± 23 mole%, preferably within the range of 20 ± 18 mole%; or (ii) an average molecular weight by weight within the range of 1,200,000 ± 350,000 g / mol, preferably 1,200,000 ± 150,000 g / mol; and an ionicity within the range of 25 ± 23 mole%, preferably within the range of 20 ± 18 mole%.
[000260] In a preferred embodiment, the dry and / or wet strength polymer is a polyvinylamine (PVAm), preferably a polyvinylamine having a weight average molecular weight of at most 1,500,000 g / mol, more preferably at most 1,000,000 g / mol, even more preferably at most 500,000 g / mol. Polyvinylamines are preferably made by hydrolyzing polyvinylformamide which yields partially or completely hydrolyzed polyvinylformamide. PVAm polymers are very reactive, work in a wide pH range and are quite insensitive to the effects of sulfites, pH, and alkalinity. The mechanisms by which PVAm polymers give resistance to paper are unclear. PVAm polymers are amine-containing polymers that are typically non-self-bonding polymers and, apparently, lack the functionality to covalently bond with hydroxyl or carboxylate groups on pulp fiber. Proposed mechanisms include multiple hydrogen bonding, multiple ion bonding, low temperature amide formation and aminal formation with cellulose chain ends. According to recent findings, dry resistance and / or wet resistance appear to be the result of the entanglement of fibril of two fibers which are thereby linked together.
[000261] Exemplary dry and / or wet strength polymers based on polyvinylamines (PVAm) include those disclosed in US 4,818,341, US 4,940,514, US 4,957,977, US 6,616,807, US 7,902,312, US 7,922,867, US 2009/0145566, US 2010/0108279, all of which are wet and / or dry strength polymers incorporated herein by reference.
[000262] Dry strength and / or wet strength are optimally enhanced by adding a combination of PVAm and an anionic copolymer in a polyvinylformamide base. The strength-enhancing effects of this combination coincide with the strengths achieved in a conventional one-sided bonding press. Combined application of the two chemicals offers the additional benefits of improved dehydration in the flat and press sections, reduced steam consumption levels and higher speeds.
[000263] Preferably, these dry and / or wet strength polymers have a low molecular weight (medium structure) and can preferably be branched. The dosage is preferably within the range of 250 g / ton of dry paper to 5,000 g / ton of dry paper, more preferably 500 g / ton of dry paper to 5,000 g / ton of dry paper.
[000264] In a particularly preferred embodiment of the method according to the invention, the dry and / or wet strength polymer is selected from the group consisting of (i) non-ionic, anionic, cationic or amphoteric cell-reactive polymers capable to form crosslinks of covalent interpolymers with cellulose, preferably through functional groups of the dry and / or wet strength polymer selected from - functional groups of aldehyde, preferably glyoxylated polyacrylamides; and / or - functional 3-hydroxy azetidinium groups, preferably polyamine-epi-halohydrin polymers and polyamino-polyamide-epi-halohydrin polymers; and - synthetic nonionic, anionic, cationic or amphoteric polymers comprising vinylamine units and / or (meth) acrylamide units and having a weight average molecular weight of a maximum of 1,500,000 g / mol, more preferably a maximum of 1,000,000 g / mol, even more preferably at most 500,000 g / mol, preferably nonionic, anionic, cationic or amphoteric polyvinylamine polymers or nonionic, anionic, cationic or amphoteric poly (meth) acrylamide polymers.
[000265] In a preferred embodiment, two dry and / or wet strength polymers having identical or opposite charges are added to the cellulosic material. Preferably, dry and / or wet strength polymers have opposite charges and are based on starches, carboxymethyl celluloses, polyacrylamides, polyvinylamines or combinations of these components.
[000266] Preferably, both polymer components are added after refinement and separated from each other. Preferred feed points are before and after the machine box feed pump. The more separate the two additional components, typically the better the results.
[000267] Preferably, additional compounds are added to the cellulosic material to improve the performance of dry and / or wet strength polymers. Typical examples of such compounds still include promoters.
[000268] The dry strength and / or wet strength performance of dry and / or wet strength polymers may depend on the age and quality of the dry and / or wet strength polymer at the time of use. , wet-paper conditions and drying conditions that can influence the reaction of the dry and / or wet strength polymer with cellulosic fibers if the dry and / or wet strength polymer is reactive with cellulose.
[000269] When the cellulosic material has a high content of anionic impurities (anionic waste) that cannot be easily washed away, fixing agents or so-called "anionic waste collectors" (ATC) can be added to the cellulosic material before dry and / or wet strength polymers are added. Preferred "anionic waste collectors" are selected from the group consisting of polyamines, polyDADMAC, polyaluminium chloride, aluminum hydrochloride and alum.
[000270] When the wet and / or dry strength polymer is cellulose-reactive polyamino-polyamide (PAE) polymers, the preferred anionic waste collectors are preferably polyamino-polyamide epichlorohydrin polymers which are added to the cellulosic material upstream. The cationic charge of these anionic waste collector polyamino-polyamide polymers is preferably significantly higher than that of the polyamino-polyamide epichlorohydrin (PAE) polymers subsequently added as dry and / or wet strength polymers.
[000271] When anionic dry and / or wet resistance polymers are used, it is common to have a strong cationic promoter to ensure that the dry and / or wet resistance polymer is fixed on the anionic fibers. In the case of acidic papermaking conditions, this promoter is preferably alum or poly (aluminum chloride). Under neutral and alkaline papermaking conditions, a synthetic cationic additive is preferably used, for example, a separate polyamine which is preferably added to the upstream cellulosic material, that is, before the dry and / or wet strength polymer be added to the cellulosic material. Feed points after refining are preferred.
[000272] When cationic dry and / or wet strength polymers are employed, cationic promoters such as polyamines can also have a benefit and thus are preferably added to the cellulosic material.
[000273] In addition to adding highly cationic additives that form complexes with anionic impurities that would otherwise impair the adsorption of dry and / or wet strength polymers on cellulosic fibers, anionic polymers are preferably added to additionally increase retention for strength polymers dry and / or wet. Carboxymethylcellulose and anionic polyacrylamides are among the preferred additives. Anionic polymers are preferably added to the coarse raw material after adding the dry and / or wet strength polymer. Addition to the fine raw material is also possible, but less preferred, as it can lead to the formation of deposits. The ratio of the dry and / or wet cationic resistance polymer to the anionic polymer can be critical and need to be adjusted to prevent deposit formation.
[000274] The dry and / or wet strength polymer according to the invention can also be used in combination with an additional retention aid. The term "retention aid", as used herein, refers to one or more components which, when applied to a cellulosic material raw material, improve retention compared to a cellulosic material raw material in which no auxiliary retention is present.
[000275] Suitable retention aids that can be employed in combination with the dry and / or wet strength polymer according to the invention are preferably cationic polymers, including polyvinylamine polymers, or anionic microparticulate materials, including anionic inorganic particles, anionic organic particles, water-soluble anionic vinyl addition polymers, aluminum compounds and combinations thereof. However, it is also possible for the dry and / or wet strength polymer to completely or partially replace retention aids as it may have properties of a retention aid itself.
[000276] Anionic inorganic particles which can be used in combination with the dry and / or wet strength polymer according to the invention include particles based on anionic silica and smectite-type clay.
[000277] Particles based on anionic silica, i.e. particles based on SiO2 or silicic acid, include colloidal silica, different types of polysilicic acid, modified aluminum colloidal silica, aluminum silicates, and mixtures thereof. Usually, particles based on anionic silica are supplied in the form of aqueous colloidal dispersions, so called sols.
[000278] Smectite-type clay that is suitable for use in combination with the wet and / or dry strength polymer according to the invention includes montmorillonite / bentonite, hectorite, beidelite, nontronite and saponite, preferably bentonite.
[000279] Anionic organic particles which are preferably used in combination with the dry and / or wet strength polymer according to the invention include highly cross-linked anionic vinyl addition polymers and derivatives of anionic monomer copolymers such as acrylic acid , methacrylic acid and sulfonated vinyl addition monomers that can be copolymerized with nonionic monomers, such as (meth) acrylamide or (meth) alkyl acrylates; and anionic condensation polymers such as melamine-sulfonic acid sols.
[000280] Aluminum compounds which are preferably employed with the dry and / or wet strength polymer according to the invention include alum, aluminate such as sodium aluminate, aluminum chloride, aluminum nitrate and polyaluminium compounds. Suitable polyaluminium compounds are, for example, polyaluminium chloride, polyaluminium sulphates, polyaluminium compounds containing chloride and sulphate ions, polyaluminium sulphate silicate, polyaluminium compounds and mixtures thereof. Polyaluminium compounds can also contain other anions, including anions derived from phosphoric acid, sulfuric acid, citric acid and oxalic acid.
[000281] Preferably, the dry and / or wet strength polymer and the additional retention aid are employed in such a ratio that retention is improved compared to cellulosic material that either contains the dry strength polymer and / or the damp alone or the additional retention aid alone.
[000282] In a preferred embodiment of the invention, the method comprises the additional step of (j) employing an auxiliary additive typically used in papermaking.
[000283] The invention can be used in combination with other compositions in order to further improve the strength properties of the paper product. The compositions that can be used in combination with the invention can be a cationic polymer, or an anionic, or an amphoteric, or a synthetic non-ionic, or a natural, or combinations thereof. For example, the invention can be used in conjunction with a cationic starch or an amphoteric starch.
[000284] In a preferred embodiment, the method according to the invention does not encompass the addition of cellulosic enzymes to the cellulosic material, preferably not introducing at least one cellulosic enzyme composition and at least one cationic polymer composition to a pulp making pulp. paper around the same time to form a treated pulp.
[000285] Dry and / or wet strength polymers are preferably supplied as a powder or as a water-based solution, sometimes as an emulsion. In this way, the dry and / or wet strength polymer according to the invention can be solid, for example, in the form of a powder, in the form of a solution, dispersion, emulsion or suspension.
[000286] For the purpose of the specification, the term "dispersion" preferably comprises aqueous dispersions, water-in-oil dispersions and oil-in-water dispersions. A person skilled in the art knows the meaning of these terms; in this respect EP 1 833 913, WO 02/46275 and WO 02/16446 can also be referred to.
[000287] Preferably, the dry and / or wet strength polymer according to the invention is dissolved, dispersed, emulsified or suspended in a suitable solvent. The solvent can be water, an organic solvent, a mixture of water with at least one organic solvent or a mixture of organic solvents.
[000288] In another preferred embodiment, the dry and / or wet strength polymer according to the invention is in the form of a solution, in which the polymer is dissolved in water as the only solvent or in a mixture comprising water and at least one organic solvent.
[000289] More preferably, the dry and / or wet strength polymer according to the invention is in the form of a dispersion, an emulsion or a suspension, in which the dry and / or wet strength polymer is dispersed. , emulsified or suspended in a mixture comprising water and at least one organic solvent. Preferably, the dry and / or wet strength polymer is in the form of a dispersion, an emulsion or a suspension, wherein the dry and / or wet strength polymer is dispersed, emulsified or suspended in water as the sole solvent, that is, no organic solvent is present. In another preferred embodiment of the invention, the dry and / or wet strength polymer according to the invention is in the form of a dispersion, wherein the dry and / or wet strength polymer is dispersed in water as the only solvent or in a mixture comprising water and at least one organic solvent. In particular, it is preferred that the dry and / or wet strength polymer dispersion according to the invention is substantially oil-free.
[000290] Suitable organic solvents are preferably low molecular weight alcohols (e.g., methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, etc.), ethers low molecular weight (e.g., dimethylether, diethylether, di-n-propylether, diisopropylether, etc.), low molecular weight ketones (e.g. acetone, butan-2-one, pentane-2-one, pentane-3-one, etc.), low molecular weight hydrocarbons (for example, n-pentane, n-hexane, petroleum ether, ligroin, benzene, etc.) or low molecular weight halogenated hydrocarbons (for example, chloride of methylene, chloroform, etc.) or mixtures thereof.
[000291] The dry and / or wet strength polymer according to the invention can also be a solid, that is, in particulate form, such as in the form of granules, pellets or powders.
[000292] The dry and / or wet strength polymer in the form of a solution, dispersion, emulsion, suspension, granules, pellets, or powder is preferably dispersed, emulsified, suspended, dissolved or diluted in a suitable solvent such as water , an organic solvent, a mixture of water with at least one organic solvent, or a mixture of at least two organic solvents, before being added to the cellulosic material.
[000293] In a particularly preferred embodiment of the method according to the invention, - the one or more biocides comprise an inorganic ammonium salt in combination with a halogen source, preferably a chlorine source, more preferably hypochlorous acid or a sodium salt. same; preferably NH4Br / NaOCl (first biocide); which is preferably added before or during defibrillation; and - an organic, preferably non-oxidizing biocide (another biocide) that is preferably added independently of the first biocide; and - the wet and / or dry strength polymer is capable of forming covalent bonds with the cellulosic fibers, preferably selected from glyoxylated poly (meth) acrylamides and polyamino-polyamide epichlorohydrin polymers.
[000294] In particularly preferred embodiments of the method according to the invention, (i) in step (b) the one or more biocides are continuously or discontinuously added to the cellulosic material in quantities so that - after 1 month of treatment in a plant of continuously operational papermaking, the pH value of the aqueous phase of the cellulosic material has been increased by at least 0.2 pH unit, compared to the pH value that has been measured, preferably at the same location, preferably at the wet end entrance of the papermaking machine immediately before the biocide is added for the first time or before the addition of higher amounts of biocide than conventionally employed has been initiated, that is, compared to a situation where microorganisms were degrading starch; and / or - after 1 month of treatment in a continuously operational paper-making plant, the electrical conductivity of the aqueous phase of the cellulosic material has been decreased by at least 5%, preferably at least 20%, more preferably at least 50%, compared to the electrical conductivity that was measured, preferably at the same location, preferably at the wet end entrance of the papermaking machine just before the biocide was added for the first time or before the addition of higher amounts of biocide than conventionally employed has been initiated, that is, compared to a situation where microorganisms were degrading starch; and / or - after 48 hours, preferably after 8 hours in a continuously operational paper-making plant, the extinction of the starch (corresponding to the concentration of free starch) contained in the aqueous phase of the cellulosic material has been increased by at least 5%, compared to the extinction that was measured, preferably at the same location, preferably at the wet end entrance of the papermaking machine just before the biocide was added for the first time or before the addition of higher amounts of biocide than conventionally employed has been initiated, that is, compared to a situation where microorganisms were degrading starch; and / or - after 48 hours, preferably after 8 hours in a continuously operational paper-making plant, the concentration of ATP in the aqueous phase of the cellulosic material has been decreased by at least 5%, compared to the concentration of ATP that has been measured, preferably at the same location, preferably at the wet end entrance of the papermaking machine immediately before the biocide was added for the first time or before the addition of higher amounts of biocide than conventionally employed has been initiated, that is, compared to a situation where microorganisms were degrading starch; and / or - after 48 hours, preferably after 8 hours in a continuously operational papermaking plant, the redox potential of the aqueous phase of the cellulosic material has been increased to an absolute value of at least -75 mV; and / or (ii) the one or more biocides comprise an ammonium salt; preferably NH4Br in combination with a halogen source, preferably a chlorine source, more preferably hypochlorous acid or a salt thereof; and / or the one or more biocides comprise an ammonium salt, preferably NH4Br in combination with hypochlorous acid or a salt thereof, as the first biocide and an organic, preferably non-oxidizing biocide as another biocide; (iii) the one or more biocides comprise an oxidizing biocide which is employed at a concentration equivalent to a concentration of at least 0.005% of the active substance as Cl2 per ton of paper produced, more preferably at least 0.010% of the active substance as Cl2 per ton of paper produced; and / or (iv) the one or more biocides are added to the coarse raw material, preferably at least a portion of it is added to the dilution water for the defibrillator; and / or (v) the starting material comprises virgin pulp or recycled pulp.
[000295] In a continuously operational papermaking plant in which papermaking can optionally be transiently paralyzed for maintenance purposes, a preferred embodiment of the invention includes the steps: (a) measuring a property of the aqueous phase of the material cellulosic selected from the group consisting of electrical conductivity, redox potential, pH value, ATP concentration and free starch concentration; to a predetermined location of the papermaking plant, preferably to a location in the area of coarse raw material or in the area of fine raw material; (B) making paper, cardboard or paperboard by the method according to the invention comprising steps (a), (b), (h1) and optionally (h2); (C) measure the same property as measured in step (a), preferably at the same location, preferably at the wet end entrance of the papermaking machine of the papermaking plant as in step (a), after time Δt, preferably after at least 1, 2, 3, 4, 5, 10, 14, 21 or 28 days, and compare the value measured in step (C) with the value measured in step (a); and (D) regulating, preferably optimizing the dosage of the biocide added in step (b) and / or the dosage of the dry and / or wet strength polymer added in step (h) depending on the result of the comparison made in step (C) ).
[000296] For the purpose of the specification, optimization preferably means that under minimized consumption of the biocide the substantial change in the measured value (m2 vs. m1) is prevented.
[000297] The method according to the invention is suitable for the manufacture of paper, cardboard or paperboard. Preferably, paper, cardboard or paperboard has an area weight of less than 150 g / m2, from 150 g / m2 to 600 g / m2, or more than 600 g / m2. In a preferred embodiment, the weight of the area is within the range of 15 ± 10 g / m2, or 30 ± 20 g / m2, or 50 ± 30 g / m2, or 70 ± 35 g / m2, or 150 ± 50 g / m2.
[000298] Another aspect of the invention concerns the use of the dry and / or wet strength polymer as defined above in the method for making paper, cardboard or paperboard, to increase the strength of paper, cardboard or paperboard. All of the preferred embodiments that have been described above with respect to the methods according to the invention also apply this aspect of the invention and therefore are not repeated hereinafter.
[000299] Yet another aspect of the invention concerns the use of a biocide or combination of biocides as defined above to reduce the electrical conductivity of the aqueous phase of a cellulosic material in the manufacture of paper, cardboard or paperboard. All of the preferred embodiments that have been described above with respect to the methods according to the invention also apply this aspect of the invention and therefore are not repeated hereinafter.
[000300] Yet another aspect of the invention concerns the use of the biocide as defined above in the method for making paper, cardboard or paperboard, to increase the strength of paper, cardboard or paperboard. All of the preferred embodiments that have been described above with respect to the methods according to the invention also apply this aspect of the invention and therefore are not repeated hereinafter.
[000301] The following examples that further illustrate the invention are not to be interpreted as limiting its scope. EXAMPLES EXAMPLE 1:
[000302] The following experiments were carried out in different commercially used paper mills across Europe. Examples were operated 1 and 4 in a closed system, while the other Examples were operated in open systems. The starting material was, in each case, 100% recycled paper. The following biocides were used in the following dosages and feeding points as summarized in Table 5: Table 5:

CEPI - Confederation of European Paper Industries
[000303] For comparative purposes, it should be noted that ammonium bromide biocide is conventionally used in dosages of 0.005 to 0.008% of active substance like Cl2 per ton of paper produced, that is, the dosage used in the experiments according to the invention is 2 to 10 times higher than the conventional dosage.
[000304] The pH values and electrical conductivity were measured and the results are summarized in Table 6 below: Table 6:
1 Organic biocide in conventional amounts, absence of NH4Br biocide 3 Combination of NH4Br biocide with organic biocide in increased amounts as shown in Table 3
[000305] As can be seen from the experimental results in Table 6, by adding biocide at a sufficient dose and at suitable feeding points distributed in the papermaking plant, a substantial decrease in electrical conductivity and an increase in pH can be achieved.
[000306] Figure 1 shows the dependence of the redox potential (Figure 1A), pH value (Figure 1B) and electrical conductivity (Figure 1C) on the biocide dosage in an experiment that was conducted in a paper mill (adjustment A) . During month 1, the conventional organic biocide was dosed in conventional quantities. During months 2 and 3, the biocide was added according to the invention. During months 4 and 5, the conventional organic biocide was again dosed in conventional quantities. From month 6 onwards, the biocide was added again according to the invention. As can be seen from Figures 1A, 1B and 1C, by adding biocide at a sufficient dose and at suitable feeding points distributed in the papermaking plant, a substantial increase in the redox potential and pH value as well as a substantial decrease in the electrical conductivity can be achieved. EXAMPLE 2:
[000307] Another experiment was conducted in a paper mill that had used conventional, low amounts of biocide (NH4Br / NaOCl, <400 g / t). By increasing the feed rate of this biocide and adding organic, non-oxidizing biocide like another biocide, it could be shown in just one day that the conductivity of the system could be substantially reduced.
[000308] Figure 2 shows that the biocide dosage increase immediately resulted in a substantial decrease in electrical conductivity from about 2000 μS / cm to about 1500 μS / cm within just 1 day. The dotted vertical line to the left indicates when the biocide dosage according to the invention was started, that is, when the conventional addition of NH4Br biocide was changed, the addition of biocide according to the invention, and the vertical dotted line to the right indicates when the biocide dosage according to the invention has been completed, that is, when the conventional addition of NH4Br biocide has been resumed. At the time of the gap between the two vertical dotted lines, the organic biocide was added in addition to the NH4Br biocide according to the invention. EXAMPLE 3:
[000309] 36 experiments that were conducted in 19 paper mills were analyzed with respect to the performance of dry and / or wet strength polymers under dependence on electrical conductivity. The dry and / or wet strength polymers that were employed in the experiments were two different glyoxylated polyacrylamide (GPAM) products, and the GPAM dosage varied between 1.5 and 4 kg / t db vs. cellulosic material with an average of 2.8 kg / t db.
[000310] The results are summarized in Figure 3. The trend line has an R2 value of 0.72 (standard deviation).
[000311] Figure 3 shows the performance dependence of dry and / or wet strength polymers depending on the electrical conductivity of the aqueous phase of the cellulosic material. The performance of the dry and / or wet strength polymer is expressed in terms of an efficiency ratio that takes into account the increase in CMT (result of the concora medium test), tear strength, tensile strength and dosage of the dry and / or wet strength polymer. Efficiency was calculated depending on the increase in resistance in% and on the dosage of the wet and / or dry resistance polymer. A high dosage of dry and / or wet strength polymer with a low increase in paper strength gives poor efficiency, while a low dosage of dry and / or wet strength polymer with a high increase in wet strength. paper gives good efficiency.
[000312] It is clear from Figure 3 that the efficiency ratio is much better when the electrical conductivity is low in any dosage. As can be seen from the experimental data, particularly from the diagram of the ratio of efficiency vs. the electrical conductivity of the wet end: a low electrical conductivity results in a high efficiency of the wet and / or dry resistance polymer, while a high electrical conductivity results in a low efficiency of the dry and / or wet resistance polymer. .
[000313] Consequently, by reducing the electrical conductivity through the addition of biocide according to the invention, the performance of the wet and / or wet strength polymer can be surprisingly increased. EXAMPLE 4:
[000314] This experiment was conducted in a paper mill in order to further demonstrate the advantages of the invention under industrial conditions.
[000315] A comparative assay C was operated without full closed-loop biocide control so that the balanced electrical conductivity was 3500 μS / cm.
[000316] An inventive experiment I was operated with full closed-loop biocide control (Spectrum® XD3899 biocide, Ashland Inc .; added to defibrillator dilution water, white water 1 and 2, and clarified rainwater), so that the balanced electrical conductivity was 1950 μS / cm.
[000317] Each experiment included an experiment in the absence of resistance aid ("C0" and "I0", respectively) as well as an experiment in the presence of resistance aid ("CGPAM" and "IGPAM", respectively).
[000318] All other experimental parameters were kept constant. The experimental results are shown in the table here below:


[000319] 1 Spectrum® XD3899, dosage [concentration of active substance equivalent to elemental chlorine, expressed in% of active substance as Cl2 per ton of paper produced] (*) measured once in the experiment
[000320] It is clear from the above experimental results that due to the total closed circuit biocide control in inventive example I - the electrical conductivity decreased from 3500 μS / cm (C0 and CGPAM) to 1950 μS / cm (I0 and IGPAM); - the oxygen reduction potential (ORP) in the short closed circuit increased from -453 mV (C0 and CGPAM) to +45 (I0 and IGPAM); - the pH value in the short closed circuit increased from 6.24 (C0 and CGPAM) to 6.93 (I0 and IGPAM); - the level of ATP in the short circuit has decreased from about 158,000 (C0 and CGPAM) to about 25,000 (I0 and IGPAM).
[000321] In addition, it is clear that in the absence of full closed-loop biocide control, the GPAM resistance helper improves - the break value by only 2.5% (C0 = 482 kPa; CGPAM = 494 kPa); and - the compression test (SCT) by only 4.3% (C0 = 3.30; CGPAM = 3.44).
[000322] Under the conditions of the present invention, however, the performance of the resistance aid is substantially better than under comparative conditions. Under the control of the total closed circuit biocide, the GPAM resistance auxiliary improves - the break value by 12.6% (I0 = 488 kPa; IGPAM = 550 kPa); and - the compression test (SCT) by 9.9% (I0 = 3.33; IGPAM = 3.66).

权利要求:
Claims (14)
[0001]
1. Method for making paper, cardboard or paperboard, characterized by the fact that it comprises the steps of: (a) defibrillating an aqueous cellulosic material containing a starch to a consistency of raw material of at least 2.0%; (b) treating the aqueous cellulosic material containing the starch with one or more biocides, in which the electrical conductivity of the aqueous phase of the cellulosic material is decreased by at least 5%, compared to the electrical conductivity that was measured at the same location as the manufacturing machine of paper just before the biocide was added for the first time; and / or where the pH value of the aqueous phase of the cellulosic material is increased by at least 0.2 pH units, compared to the pH value that was measured at the same location on the paper-making machine just before the biocide was been added; and (c) adding a dry and / or wet strength polymer to the aqueous cellulosic material; and (d) dehydrating the aqueous cellulosic material, thus producing paper, cardboard or paperboard.
[0002]
2. Method according to claim 1, characterized in that the one or more biocides are dosed in an amount of at least 5.0 ppm, based on the total amount of the composition containing the cellulosic material and the starch.
[0003]
Method according to claim 1, characterized by the fact that the one or more biocides are oxidative biocides.
[0004]
Method according to claim 1, characterized in that the one or more biocides comprise an inorganic ammonium salt in combination with a halogen source.
[0005]
Method according to claim 1, characterized by the fact that in addition to the one or more biocides added in step (b), another biocide is added to the cellulosic material that differs from one or more biocides added in step (b).
[0006]
6. Method according to claim 5, characterized by the fact that the other biocide is added to the papermaking process before defibrillation; with defibrillation; after defibrillation but still before the paper-making machine; and / or the wet end of the papermaking machine.
[0007]
7. Method according to claim 5, characterized by the fact that the other biocide is a non-oxidizing biocide.
[0008]
8. Method according to claim 5, characterized by the fact that the other biocide is an organic biocide selected from the group consisting of quaternary ammonium compounds, benzyl-C12-16-alkyldimethyl chlorides (ADBAC), polyhexamethylenebiguanide ( biguanide), 1,2-benzisothiazole-3 (2H) -one (BIT), bronopol (BNPD), bis (trichloromethyl) sulfone, di-iodomethyl-p-tolylsulfone, bronopol / quaternary ammonium compounds, benzyl-C12 chlorides -16-alkyldimethyl (BNPD / ADBAC), bronopol / didecyldimethylammonium chloride (BNPD / DDAC), bronopol / 5-chloro-2-methyl-2H-isothiazole-3-one / 2-methyl-2H-isothiazol-3-one (BNPD / Iso), NABAM / sodium dimethyldithiocarbamate, sodium N-dimethyldithiocarbamate, N-dithiocarbamate (NABAM), sodium methyldithiocarbamate, sodium dimethyldithiocarbamate, 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT ), 2,2-dibromo-2-cyanoacetamide (DBNPA), DBNPA / bronopol / iso (DBNPA / BNPD / Iso), 4,5-dichloro-2-n-octyl-3-isothiazolin-3-one (DCOIT) , didecyldimethylammonium chloride (DDAC), did chloride echyldimethylammonium, alkyldimethylbenzylammonium chloride (DDAC / ADBAC), dodecylguanidine / quaternary ammonium monohydrochloride compounds, benzyl-C12-16-alkyldimethyl chlorides (DGH / ADBAC), dodecylguanidine / methylene dihydrochloride (MBH) methylene chloride (DGH / ADHAC) Glut), gluteraldehyde / quaternary ammonium compounds / benzylcoconut alkyldimethyl chlorides (Glut / poop), gluteraldehyde / didecyldimethylammonium chloride (Glut / DDAC), gluteraldehyde / 5-chloro-2-methyl-2H-isothiazol-3-one / 2-methyl-2H-isothiazol-3-one (Glut / Iso), gluteraldehyde / methylene dithocyanate (Glut / MBT), 5-chloro-2-methyl-2H-isothiazole-3-one / 2-methyl-2H- isothiazol-3-one (Iso), methylene dithocyanate (MBT), 2-methyl-4-isothiazolin-3-one (MIT), methamine oxirane (methamine oxirane), sodium bromide (NaBr), nitromethylidinethimethanol, 2 -n- octyl-3-isothiazolin-3-one (OIT), bis (trichloromethyl) sulfone / quaternary ammonium compounds, benzyl-C12-16-alkyldimethyl chlorides (sulfone / ADBAC), sinclosene, terbuthylazine, d azomet (thiona), tetrakis (hydroxymethyl) phosphonium sulfate (2: 1) (THPS) and p - [(diiodomethyl) sulfonyl] toluene (tolyl sulfone), and mixtures thereof.
[0009]
9. Method according to claim 1, characterized by the fact that the dry and / or wet resistance polymer is selected from the group consisting of: (i) non-ionic, anionic, cationic or amphoteric cell-reactive polymers capable of to form crosslinks of covalent interpolymers with cellulose through aldehyde functional groups and / or wet and / or wet strength 3-hydroxy azetidinium functional groups; and (ii) natural or synthetic non-ionic, anionic, cationic or amphoteric polymers.
[0010]
10. Method according to claim 9, characterized by the fact that (i) non-ionic, anionic, cationic or amphoteric cellulose-reactive polymers are reaction products: - of homo or ionic or non-ionic copolymers comprising units of derived monomers vinylamides that are optionally completely or partially hydrolyzed, and / or (meth) acrylamides; or polysaccharides - with epichlorohydrin or with cellulose-reactive agents comprising at least one aldehyde functional group.
[0011]
11. Method according to claim 10, characterized by the fact that non-ionic, anionic, cationic or amphoteric cellulose-reactive polymers comprise at least two functional groups of aldehyde and are selected from the group consisting of glyoxal, glutaraldehyde, succinaldehyde, furan dialdehyde, 2-hydroxydipaldehyde, dialdehyde starch, and combinations thereof.
[0012]
12. Method according to claim 9, characterized by the fact that (ii) natural or synthetic nonionic, anionic, cationic or amphoteric polymers are selected from the group consisting of: a) native or chemically modified polysaccharides; b) anionic homo or copolymers comprising units of anionic monomers derived from (meth) acrylic acid; optionally in combination with non-ionic monomer units derived from (meth) acrylamide; c) cationic homo or copolymers comprising cationic monomer units derived from vinylamine, polydialyldimethylammonium chloride, 2-acrylylethyltrimethylammonium chloride, and / or ethyleneimine; optionally in combination with non-ionic monomer units derived from vinylamide and / or (meth) acrylamide; d) amphoteric polymers; e) substantially non-ionic water-soluble polymers; and f) water-insoluble latex.
[0013]
13. Method according to claim 1, characterized by the fact that steps (a) and (b) are carried out in a papermaking plant that is continuously operational, and which also includes the steps: (A) measure electrical conductivity, redox potential, pH value, ATP concentration, and free starch concentration of the cellulosic material containing starch; at a predetermined location of the papermaking plant; (B) measure the same property as measured in step (A) after time (t) and compare the value measured in step (B) with the value measured in step (A); and (C) regulating the dosage of biocide added in step (B) and / or the dosage of the dry and / or wet strength polymer added in step (C) depending on the result of the comparison made in step (B).
[0014]
14. Use of a biocide or combination of biocides, as defined in any of claims 3 to 8, characterized in that it is to reduce the electrical conductivity of the aqueous phase of a cellulosic material in the manufacture of paper, cardboard or paperboard.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112014004225B1|2021-02-02|method for making paper, cardboard or paperboard and use

---

EP2609250B1|2016-08-17|Method for increasing the advantages of starch in pulped cellulosic material in the production of paper and paperboard

---

KR101738397B1|2017-05-22|Method for making of paper, tissue, board or the like

---

BR112012009141B1|2020-10-13|process for the production of paper, cardboard and cardboard that have high dry resistance, and aqueous composition

---

FI127598B|2018-09-28|A method for treating starch in pulp, paper and board making processes

---

Shi et al.2012|Use of optical brightening agents | in the production of paper containing high-yield pulps

---

NZ620422B2|2016-02-02|Method for increasing the advantages of strength aids in the production of paper and paperboard

---

Zakrajšek et al.2009|The influence of modified starch on the process water quality in papermaking and the paper properties

---

US10851498B2|2020-12-01|Increased drainage performance in papermaking systems using microfibrillated cellulose

同族专利:

---

公开号 | 公开日

---

CN103930619B|2016-12-07|

---

AU2012299794B2|2017-03-02|

---

WO2013026578A1|2013-02-28|

---

CA2839129A1|2013-02-28|

---

MX2014001530A|2014-02-27|

---

NZ620422A|2015-10-30|

---

US9388533B2|2016-07-12|

---

CL2014000422A1|2014-09-22|

---

US20140284011A1|2014-09-25|

---

EP2748373A1|2014-07-02|

---

CN103930619A|2014-07-16|

---

RU2614272C2|2017-03-24|

---

KR20140053211A|2014-05-07|

---

KR101676928B1|2016-11-16|

---

BR112014004225A2|2017-03-14|

---

ZA201401152B|2014-12-23|

---

AU2012299794A1|2014-02-20|

---

CA2839129C|2019-01-15|

---

RU2014111074A|2015-09-27|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2926154A|1957-09-05|1960-02-23|Hercules Powder Co Ltd|Cationic thermosetting polyamide-epichlorohydrin resins and process of making same|

---

US3125552A|1960-09-21|1964-03-17|Epoxidized poly amides |

---

US3311594A|1963-05-29|1967-03-28|Hercules Inc|Method of making acid-stabilized, base reactivatable amino-type epichlorohydrin wet-strength resins|

---

US3556932A|1965-07-12|1971-01-19|American Cyanamid Co|Water-soluble,ionic,glyoxylated,vinylamide,wet-strength resin and paper made therewith|

---

US3332901A|1966-06-16|1967-07-25|Hercules Inc|Cationic water-soluble polyamide-epichlorohydrin resins and method of preparing same|

---

US3556933A|1969-04-02|1971-01-19|American Cyanamid Co|Regeneration of aged-deteriorated wet strength resins|

---

US3772076A|1970-01-26|1973-11-13|Hercules Inc|Reaction products of epihalohydrin and polymers of diallylamine and their use in paper|

---

US3833531A|1970-04-22|1974-09-03|Hercules Inc|Reaction products of epihalohydrin and polymers of diallylamine and salts thereof and their use in paper|

---

US3700623A|1970-04-22|1972-10-24|Hercules Inc|Reaction products of epihalohydrin and polymers of diallylamine and their use in paper|

---

CA934892A|1971-06-14|1973-10-02|E. Amy John|Process for preparation of polyalkylene amine-poly-amide resins|

---

US3992251A|1972-11-08|1976-11-16|Diamond Shamrock Corporation|Process of making wet strength paper containing mono primary polyamine and organic dihalide modified, epoxidized polyamide|

---

US3855158A|1972-12-27|1974-12-17|Monsanto Co|Resinous reaction products|

---

DE2433325C2|1974-07-11|1982-07-15|Pelzer & Röhrl, 6500 Mainz|Process for the production of solid paper and cardboard based on waste paper, especially in plants with a closed cycle|

---

US4147586A|1974-09-14|1979-04-03|Monsanto Company|Cellulosic paper containing the reaction product of a dihaloalkane alkylene diamine adduct and epihalohydrin|

---

US4035229A|1974-11-04|1977-07-12|Hercules Incorporated|Paper strengthened with glyoxal modified poly resins|

---

US4129528A|1976-05-11|1978-12-12|Monsanto Company|Polyamine-epihalohydrin resinous reaction products|

---

US4129722A|1977-12-15|1978-12-12|National Starch And Chemical Corporation|Process for the preparation of high D. S. polysaccharides|

---

US4217425A|1978-11-06|1980-08-12|Nalco Chemical Company|Paper fiber additive containing polyacrylamide blended with glyoxal and polymeric diallyldimethyl ammonium chloride as a cationic regulator|

---

DE3135830A1|1981-09-10|1983-03-24|Basf Ag, 6700 Ludwigshafen|METHOD FOR THE PRODUCTION OF WATER-SOLUBLE, NITROGEN-CONDENSING PRODUCTS AND THE USE THEREOF IN PAPER PRODUCTION|

---

US4515657A|1983-04-27|1985-05-07|Hercules Incorporated|Wet Strength resins|

---

US4537657A|1983-08-26|1985-08-27|Hercules Incorporated|Wet strength resins|

---

US4501862A|1983-05-23|1985-02-26|Hercules Incorporated|Wet strength resin from aminopolyamide-polyureylene|

---

DE3506832A1|1985-02-27|1986-08-28|Basf Ag, 6700 Ludwigshafen|METHOD FOR PRODUCING PAPER WITH HIGH DRY RESISTANCE|

---

US4722964A|1986-06-20|1988-02-02|Borden, Inc.|Epoxidized polyalkyleneamine-amide wet strength resin|

---

CA1283748C|1986-06-25|1991-04-30|Takaharu Itagaki|Vinylamine copolymer, flocculating agent and paper strength increasingagent using the same, as well as process for producing the same|

---

DE3706525A1|1987-02-28|1988-09-08|Basf Ag|METHOD FOR PRODUCING PAPER, CARDBOARD AND CARDBOARD WITH HIGH DRY RESISTANCE|

---

DE3724646A1|1987-07-25|1989-02-02|Basf Ag|METHOD FOR PRODUCING PAPER, CARDBOARD AND CARDBOARD WITH HIGH DRY RESISTANCE|

---

DE3810424A1|1988-03-26|1989-10-12|Bayer Ag|NITROGENIC POLYMER COMPOUNDS|

---

US5085736A|1988-07-05|1992-02-04|The Procter & Gamble Company|Temporary wet strength resins and paper products containing same|

---

JP2620806B2|1988-07-11|1997-06-18|星光化学工業株式会社|Papermaking additives and papermaking methods|

---

GB8822577D0|1988-09-26|1988-11-02|Blue Circle Ind Plc|Papermaking filler compositions|

---

US4954538A|1988-12-19|1990-09-04|American Cyanamid Company|Micro-emulsified glyoxalated acrylamide polymers|

---

IL98352A|1991-06-03|1995-10-31|Bromine Compounds Ltd|Process and compositions for the disinfection of water|

---

AT169943T|1991-06-19|1998-09-15|Akzo Nobel Nv|METHOD FOR PRODUCING RESINS BASED ON EPIHALOHYDRINE WITH A REDUCED HALOGEN CONTENT|

---

US5316623A|1991-12-09|1994-05-31|Hercules Incorporated|Absorbance and permanent wet-strength in tissue and toweling paper|

---

US5318669A|1991-12-23|1994-06-07|Hercules Incorporated|Enhancement of paper dry strength by anionic and cationic polymer combination|

---

US5338407A|1991-12-23|1994-08-16|Hercules Incorporated|Enhancement of paper dry strength by anionic and cationic guar combination|

---

TW260726B|1992-09-03|1995-10-21|Hercules Inc|

---

NL9302294A|1993-12-31|1995-07-17|Hercules Inc|Method and composition for preparing wet-reinforced paper.|

---

US5656699A|1994-04-18|1997-08-12|Hercules Incorporated|Oligoamide-epichlorohydrin resins as drainage aids|

---

ES2154740T3|1994-10-03|2001-04-16|Weinstock David|METHOD FOR THE TREATMENT OF LIQUIDS TO INHIBIT DEVELOPMENT OF LIVING ORGANISMS.|

---

US5614597A|1994-12-14|1997-03-25|Hercules Incorporated|Wet strength resins having reduced levels of organic halogen by-products|

---

US6228217B1|1995-01-13|2001-05-08|Hercules Incorporated|Strength of paper made from pulp containing surface active, carboxyl compounds|

---

US5744065A|1995-05-12|1998-04-28|Union Carbide Chemicals & Plastics Technology Corporation|Aldehyde-based surfactant and method for treating industrial, commercial, and institutional waste-water|

---

US5972691A|1995-06-07|1999-10-26|Hercules Incorporated|Dehalogenation of polyamine, neutral curing wet strength resins|

---

US5703225A|1995-12-13|1997-12-30|Kimberly-Clark Worldwide, Inc.|Sulfonated cellulose having improved absorbent properties|

---

DE69704845T2|1996-01-26|2001-12-20|Novozymes As|PRODUCTION OF TOILET PAPER|

---

US5674362A|1996-02-16|1997-10-07|Callaway Corp.|Method for imparting strength to paper|

---

US5723022A|1996-07-11|1998-03-03|Cytec Technology Corp.|Temporary wet strength resins|

---

US5904808A|1996-09-16|1999-05-18|Hercules Incorporated|Processes and compositions for repulping wet strength paper and paper products|

---

EP0960237B1|1997-02-14|2003-05-07|Bayer Corporation|Papermaking methods and compositions|

---

DE19713755A1|1997-04-04|1998-10-08|Basf Ag|Process for the production of paper, cardboard and cardboard with high dry strength|

---

US6103861A|1997-12-19|2000-08-15|Hercules Incorporated|Strength resins for paper and repulpable wet and dry strength paper made therewith|

---

US6179962B1|1997-12-31|2001-01-30|Hercules Incorporated|Paper having improved strength characteristics and process for making same|

---

US6171440B1|1997-12-31|2001-01-09|Hercules Incorporated|Process for repulping wet strength paper having cationic thermosetting resin|

---

WO2000011046A1|1998-08-19|2000-03-02|Hercules Incorporated|Dialdehyde-modified anionic and amphoteric polyacrylamides for improving strength of paper|

---

CO5180563A1|1999-01-25|2002-07-30|Kimberly Clark Co|MODIFIED VINYL POLYMERS CONTAINING MEANS OF HYPHROCARBON HYDROCARBON AND THE METHOD FOR MANUFACTURING|

---

US6274667B1|1999-01-25|2001-08-14|Kimberly-Clark Worldwide, Inc.|Synthetic polymers having hydrogen bonding capability and containing aliphatic hydrocarbon moieties|

---

US6224714B1|1999-01-25|2001-05-01|Kimberly-Clark Worldwide, Inc.|Synthetic polymers having hydrogen bonding capability and containing polysiloxane moieties|

---

WO2000050462A1|1999-02-24|2000-08-31|Sca Hygiene Products Gmbh|Oxidized cellulose-containing fibrous materials and products made therefrom|

---

PT1770109E|1999-06-11|2012-10-02|Hercules Inc|Process of preparing polyamine-epihalohydrin resins with reduced byproduct content|

---

US6228126B1|1999-08-17|2001-05-08|National Starch And Chemical Investment Holding Corporation|Paper prepared from aldehyde modified cellulose pulp and the method of making the pulp|

---

DE19953591A1|1999-11-08|2001-05-17|Sca Hygiene Prod Gmbh|Metal-crosslinkable oxidized cellulose-containing fibrous materials and products made from them|

---

CA2391576C|1999-11-19|2007-04-24|Buckman Laboratories International, Inc.|Paper making processes using enzyme and polymer combinations|

---

AU5511101A|2000-05-04|2001-11-12|Sca Hygiene Products Zeist B.V.|Aldehyde-containing polymers as wet strength additives|

---

CA2409217C|2000-05-17|2007-06-26|Buckman Laboratories International, Inc.|Papermaking pulp and flocculant comprising acidic aqueous alumina sol|

---

DE10041393A1|2000-08-23|2002-03-07|Stockhausen Chem Fab Gmbh|Water-in-oil polymer dispersions with improved environmental compatibility|

---

DE10061483A1|2000-12-08|2002-06-13|Stockhausen Chem Fab Gmbh|Process for the preparation of water-in-water polymer dispersions|

---

US6749721B2|2000-12-22|2004-06-15|Kimberly-Clark Worldwide, Inc.|Process for incorporating poorly substantive paper modifying agents into a paper sheet via wet end addition|

---

US7008545B2|2002-08-22|2006-03-07|Hercules Incorporated|Synergistic biocidal mixtures|

---

WO2004076551A1|2003-02-27|2004-09-10|The University Of Maine Board Of Trustees|Starch compositions and methods of making starch compositions|

---

WO2005042843A1|2003-10-24|2005-05-12|National Gypsum Properties, Llc|Process for making abrasion resistant paper and paper and paper products made by the process|

---

US7291695B2|2004-04-05|2007-11-06|Nalco Company|Stable wet strength resin|

---

US20060008513A1|2004-07-06|2006-01-12|Holbert Victor P|Paper substrates and articles containing antimicrobial components as well as methods of making and using the same|

---

US7897013B2|2004-08-17|2011-03-01|Georgia-Pacific Chemicals Llc|Blends of glyoxalated polyacrylamides and paper strengthening agents|

---

US7488403B2|2004-08-17|2009-02-10|Cornel Hagiopol|Blends of glyoxalated polyacrylamides and paper strengthening agents|

---

DE102004056551A1|2004-11-23|2006-05-24|Basf Ag|Process for the production of paper, cardboard and cardboard with high dry strength|

---

MX2007006615A|2004-12-03|2007-08-02|Sun Chemical Corp|Printing ink and coating compositions containing starch.|

---

MX2007007396A|2004-12-21|2007-08-14|Hercules Inc|Reactive cationic resins for use as dry and wet strength agents in sulfite ion-containing papermaking systems.|

---

DE102004063793A1|2004-12-30|2006-07-13|Stockhausen Gmbh|High cationic polymer dispersions, process for their preparation and their use|

---

US7589153B2|2005-05-25|2009-09-15|Georgia-Pacific Chemicals Llc|Glyoxalated inter-copolymers with high and adjustable charge density|

---

JP4696713B2|2005-06-17|2011-06-08|富士ゼロックス株式会社|Wastewater treatment method|

---

CN101208479A|2005-06-24|2008-06-25|赫尔克里士公司|Improved retention and drainage in the manufacture of paper|

---

US20060289139A1|2005-06-24|2006-12-28|Fushan Zhang|Retention and drainage in the manufacture of paper|

---

CN101405457B|2006-03-16|2011-08-17|巴斯夫欧洲公司|Method for producing paper, paperboard and cardboard having high dry strength|

---

BRPI0712029B1|2006-05-18|2018-12-11|Hercules Inc|process for imparting dry strength, wet strength, creping adhesive property, adhesive property in paper products and / or to aid drainage or water retention in papermaking and use of a michael adduct|

---

RU2318942C1|2006-07-12|2008-03-10|Федеральное Государственное Унитарное Предприятие "Гознак" |Composition for paper manufacturing|

---

US7875676B2|2006-09-07|2011-01-25|Ciba Specialty Chemicals Corporation|Glyoxalation of vinylamide polymer|

---

AR071441A1|2007-11-05|2010-06-23|Ciba Holding Inc|N- GLIOXILATED VINYLAMIDE|

---

KR20100074334A|2007-11-07|2010-07-01|바스프 에스이|New fiber products|

---

WO2011037819A1|2009-09-22|2011-03-31|Sonoco Development, Inc.|Paperboard containing a biocide and method for making the same|

---

CN103180510B|2010-08-25|2015-08-26|索理思科技开曼公司|The method of the superiority of starch in making beating cellulosic material is strengthened when manufacturing paper and paperboard|

---

US9278874B2|2011-09-30|2016-03-08|Kemira Oyj|Prevention of starch degradation in pulp, paper or board making processes using zinc ions and an oxidizing biocide|US8088250B2|2008-11-26|2012-01-03|Nalco Company|Method of increasing filler content in papermaking|

---

EP2761083B1|2011-09-30|2017-06-28|Kemira OYJ|Paper and methods of making paper|

---

CA2858310C|2011-12-06|2021-02-16|Basf Se|Preparation of polyvinylamide cellulose reactive adducts|

---

BR112014032298A2|2012-06-25|2017-06-27|Katayama Chemical Works Co|Cardboard manufacturing process|

---

US9562326B2|2013-03-14|2017-02-07|Kemira Oyj|Compositions and methods of making paper products|

---

ES2688579T3|2013-06-20|2018-11-05|Basf Se|Production procedure of a microfibrillated cellulose composition|

---

CA2918468A1|2013-08-09|2015-05-07|Solenis Technologies Cayman, L.P.|Polyethylene oxide treatment for drainage agents and dry strength agents|

---

US9567708B2|2014-01-16|2017-02-14|Ecolab Usa Inc.|Wet end chemicals for dry end strength in paper|

---

CN104878639A|2014-02-27|2015-09-02|艺康美国股份有限公司|A method of protecting recovered fiber by utilizing a bactericide and a papermaking method by utilizing the recovered fiber|

---

CN104164805B|2014-06-27|2017-01-18|南京林业大学|A method of enhancing papermaking wet-end paper strength by applying betaine amphoteric cellulose|

---

US9702086B2|2014-10-06|2017-07-11|Ecolab Usa Inc.|Method of increasing paper strength using an amine containing polymer composition|

---

US9920482B2|2014-10-06|2018-03-20|Ecolab Usa Inc.|Method of increasing paper strength|

---

MX2017004979A|2014-10-16|2017-09-15|Georgia-Pacific Chemicals Llc|Resin compositions and methods for making and using same.|

---

CN104452480A|2014-11-13|2015-03-25|常熟市常隆包装有限公司|Preparation method of corrugated paper board with insect-resistant efficacy|

---

WO2016108741A1|2015-01-02|2016-07-07|Sca Hygiene Products Ab|Absorbent article|

---

FI127598B|2015-08-27|2018-09-28|Kemira Oyj|A method for treating starch in pulp, paper and board making processes|

---

CN105603819B|2016-01-15|2017-11-07|余晓飞|A kind of sizing agent and preparation method thereof|

---

RU2696382C1|2016-02-16|2019-08-01|Кемира Ойй|Paper production method|

---

US10435843B2|2016-02-16|2019-10-08|Kemira Oyj|Method for producing paper|

---

CA3015649A1|2016-02-29|2017-09-08|Kemira Oyj|A softener composition|

---

CN109072558A|2016-05-13|2018-12-21|艺康美国股份有限公司|Thin paper dust is reduced|

---

CN107447582A|2016-06-01|2017-12-08|艺康美国股份有限公司|Efficient intensity scheme for the papermaking in high charge requirement system|

---

US10612194B2|2016-07-06|2020-04-07|United States Gypsum Company|Gypsum wallboard comprising laminated multi-ply paper cover sheets bonded with a non-ionic polymeric binder and methods|

---

CA3034674A1|2016-08-26|2018-03-01|Structured I, Llc|Method of producing absorbent structures with high wet strength, absorbency, and softness|

---

BR112019002209A2|2016-09-30|2019-05-14|Kemira Oyj|process for producing paper, cardboard or similar|

---

CN106381758B|2016-10-13|2020-04-07|内江师范学院|Application of carboxymethyl chitin as retention and drainage aid|

---

CN106368060B|2016-10-13|2020-04-07|内江师范学院|Ternary microparticle retention and drainage aid system|

---

JP6361766B1|2017-03-15|2018-07-25|栗田工業株式会社|Bacterial spore sterilization method in pulp and paper manufacturing process|

---

FI128324B|2017-06-21|2020-03-31|Kemira Oyj|Method for manufacturing a fibrous web|

---

WO2019035022A1|2017-08-16|2019-02-21|Anavo Technologies, Llc|Tissue paper articles and methods of making and using the same|

---

CA3099853A1|2018-05-14|2019-11-21|Kemira Oyj|Paper strength improving additives, their manufacture and use in paper making|

---

DE102018113273B4|2018-06-05|2020-06-18|Voith Patent Gmbh|METHOD AND DEVICE FOR MIXING LITTLE FIXING AGENT INTO A PROCESS FLOW|

---

JP6696532B2|2018-06-18|2020-05-20|栗田工業株式会社|Paper manufacturing method|

---

CN112673053A|2018-07-19|2021-04-16|凯米拉公司|Cellulose composition|

---

RU2690565C1|2018-11-16|2019-06-04|Общество с ограниченной ответственностью "Уралбумага"|Corrugated cardboard not supporting combustion, and flat sheet of this cardboard|

---

CN111691224A|2019-03-12|2020-09-22|瑞辰星生物技术（广州）有限公司|Modified starch and preparation method and application thereof|

---

CN111691217A|2019-03-12|2020-09-22|瑞辰星生物技术（广州）有限公司|Method for recovering free starch in papermaking white water|

---

WO2021123504A1|2019-12-19|2021-06-24|Kemira Oyj|Process for manufacturing a fibre web|

---

KR102159545B1|2020-04-07|2020-09-23|주식회사 데코페이브|Manufacturing method of road block having a self-cleaning and road block manufactured by the method|

---

WO2021214385A1|2020-04-20|2021-10-28|Kemira Oyj|A method of controlling enzymatic activities and tools related thereto|

---

TR202010400A2|2020-07-01|2021-05-21|Ak Kim Kimya Sanayi Ve Ticaret Anonim Sirketi|Dry and temporary wet strength additive for paper products|

法律状态:
2018-02-06| B25A| Requested transfer of rights approved|Owner name: SOLENIS TECHNOLOGIES CAYMAN, L.P. (CH) |

---

2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

---

2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

---

2020-11-10| B09A| Decision: intention to grant|

---

2021-02-02| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/08/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

EP11006948.1|2011-08-25|

---

EP11006948|2011-08-25|

---

EP12001249|2012-02-24|

---

EP12001249.7|2012-02-24|

---

PCT/EP2012/003582|WO2013026578A1|2011-08-25|2012-08-24|Method for increasing the advantages of strength aids in the production of paper and paperboard|

---