• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    hydrophobically bonded fibrous mat and a method for preparing a bonded mat layer. the invention relates to a layer of hydrophobic bonded fibrous mat, methods for preparing a fibrous mat or a fiber based coating, a multilayer cardboard product comprising at least one intermediate layer formed by said fibrous mat and the use of a thermosensitive surfactant for the aforementioned methods and products. according to the method, microfibrillated cellulose (mfc) and hydrophobic glue are taken to a foam with water and the heat-sensitive surfactant, the foam is brought over a fabric forming of a paper or cardboard machine, is subjected to the removal of water by suction of air through the formation mat, and dried to form a leaf product. alternatively, the foam can be fed over a prefabricated fiber mat and dried to form a coating layer. to avoid the progressive deterioration of the hydrophobic glue, the hydrophilic functionality of the surfactant contained in the mat is finally destroyed by heat. the method uses, for example, akd-based surfactants with a hydrophilic fraction, which are decomposed by heat. if a pulp with a longer fiber length, such as ctmp, is also included, a high volume is obtained, in combination with a high scott bond value, in order to provide better dry and wet tensile strength for products of paper and cardboard.
    公开号:BR112014026790B1
    申请号:R112014026790-1
    申请日:2013-04-25
    公开日:2021-04-06
    发明作者:Isto Heiskanen；Karita Kinnunen；Tuomo Hjelt
    申请人:Stora Enso Oyj；
    IPC主号:
    专利说明:

    [0001] [0001] The present invention relates to a method for preparing a hydrophobically bonded layer of a fibrous mat, a hydrophobically bonded fibrous mat obtainable by said method, and a multi-layer cardboard comprising said mat as at least one of the layers. As a particular aspect, foaming is used in the technique of the invention to produce the fibrous web. Background of the invention
    [0002] [0002] In the paper industry the foam technique, where foam is used as a material transport phase, has been used in both mat formation and mat coating methods. The technique is described, for example, in publications: "The formation of wet-laid mantas by a foaming process" by Radvan, B., Gatward, A. P. J.,, Tappi, vol. 55 (1972) p. 748; a report called "New process uses foam in papermaking instead of avoiding it" by Wiggins Teape Research and Development Ltd., Paper Trade Journal, Nov. 29, 1971; and "The structure and properties of paper formed by a foaming process", by Smith, M. K., Punton, V. W., Rixson, A. G., TAPPI, Jan. 1974, Vol. 57, No. 1, pgs. 107 to 111.
    [0003] [0003] GB 1 395 757 describes an apparatus for producing a foamy fiber dispersion for use in papermaking. A surface active agent is added to the fibrous pulp with an excess fiber length of about 3 mm, to provide a dispersion with an air content of at least 65%, to be discharged into the fabric forming a manufacturing machine. of paper. The goal is to achieve uniform formation of the fibrous blanket over the fabric.
    [0004] [0004] In the mid-1970s the foaming method was successfully demonstrated on a production machine. In the Wiggins Teape Radfoam (Arjo Wiggins) method, fibers were delivered to the wire of a conventional Fourdrinier paper machine suspended in aqueous foam. The development team obtained a 3D non-layered structure on paper manufactured in a Fourdrinier machine for very high concentrations of fibers (3 to 5%) in water, using foam.
    [0005] [0005] When comparing foaming and water methods, a trend is clear. With foaming the mass is higher, but the tensile index is lower. With a more voluminous structure, the structure is more porous, which leads to lower values of tensile index. An interesting result from a comparison of deposition samples with water and foam was that the tensile strength indexes in both cases were very close, although the foaming samples were much more voluminous. The reason for this is unknown and requires further research.
    [0006] [0006] Surfactants used in the foaming process have a negative effect on both the dry and wet tensile strength of a paper blanket.
    [0007] [0007] The loss of tensile strength can be explained by a reduction in the dry tensile strength of a sheet of paper since surfactants are adsorbed on the surfaces of the fibers preventing the hydrogen bonding between the fibers. The initial wet strength is reduced with surfactants, especially for a dry matter content of 8 to 25%, due to a reduction in surface tension, which results from the weakening of the main force that holds the wet sheet together.
    [0008] - porosidade demasiadamente elevada em algumas aplicações, - propriedades de resistência reduzida em comparação com a formação normal a úmido de baixa consistência, - ligação Scott inferior, - resistência à tração inferior e, - módulo de elasticidade inferior. [0008] According to the current understanding, the main problems that have prevented the formation of foam from becoming a standard of the technology of formation of blankets in the production of paper, cardboard and cardboard, are: - too high porosity in some applications, - reduced strength properties compared to normal wet formation with low consistency, - bottom Scott link, - lower tensile strength and, - modulus of lower elasticity.
    [0009] [0009] A particular problem regarding the preparation of fibrous sheets bonded hydrophobically by foaming techniques is that, over time, surfactants tend to spoil the bonding. For its function in an aqueous medium, the surfactant must have a hydrophobic aspect and a hydrophilic aspect, generally hydrophobic and hydrophilic portions as opposite end groups, respectively. However, in the dry mat, the known surfactants, for example, those mentioned in GB 1 395 757, gradually lose their hydrophobic functionality and become totally hydrophilic, thus impairing hydrophobic bonding. So far, foaming has not been applied to the manufacture of hydrophobically bonded paper or cardboard.
    [0010] [0010] With the formation of foam, a larger volume (lower density) can be obtained, in comparison with the normal wet formation. For typical printing and packaging paper and grades of cardboard, the main disadvantages are the loss of modulus of elasticity ("softness") and the internal resistance (Scott connection or Z resistance). However, the same characteristics are advantages in the manufacture of tissue paper. Thus, foaming has been much more common in tissue paper products.
    [0011] [0011] A newer improved papermaking approach, with the aim of improving the drainage and retention of papermaking chemicals in a fibrous blanket formed on a forming fabric, is incorporation of microfibrillated cellulose (MFC) into the pulp suspension. US 6602994 B1 teaches the use of derived MFC with electrostatic or steric functionality for the goals, which include even better mat formation. According to the reference, microfibrils have a diameter in the range of 5 to 100 nm.
    [0012] [0012] However, the disadvantages experienced with MFC are densification and high shrinkage in the drying of the paper, as well as a tendency of the MFC to absorb and retain a substantial amount of water, which increases the energy required for drying and reduces the speed of the paper machine and productivity. For these reasons, MFC has not gained widespread use in the paper industry until now. Brief description of the invention
    [0013] [0013] The object of the present invention is to overcome or reduce the problems mentioned above in relation to printing papers and packaging cartons, by means of finding a method of producing a fibrous layer hydrophobically bonded by foaming, in which the hydrophobic bonding will substantially remain over time. The solution according to the invention is to produce a blanket layer through the steps of (i) adding water, microfibrillated cellulose (MFC), hydrophobic glue, and a heat sensitive surfactant in the form of a foam, (ii) providing foam to a forming fabric, (iii) removing water from the foam on the forming fabric by suction, to form a blanket, (iv) subjecting the blanket to drying, and (v) heating the blanket to suppress functionality hydrophilic of the surfactant.
    [0014] [0014] According to a preferred embodiment of the invention, the surfactant is decomposed by heat, removing the hydrophilic fraction from a hydrophobic residue. For example, US 2005/0250861 A1 describes cleavable thermolabile surfactants, which have a hydrophilic fraction containing a β-keto acid group decomposed by heat into CO2, HCO3- or CO3-2, depending on the pH, while a hydrophobic residue will remain. Preferably, at least most of the thermolabile surfactant will be decomposed by the drying heat as the mat is dried in drying cylinders of a paper or cardboard machine. The rest decomposes on the hot roll of paper or cardboard as produced. However, additional heating of the mat to decompose the residual surfactant before winding can be arranged, if necessary.
    [0015] [0015] Preferably, the hydrophobic glue is alkyl ketene dimer (AKD) or a derivative thereof. However, alkenyl succinic anhydride (ASA), or resin glue can be used as an alternative. The amount of hydrophobic glue is preferably greater than 1 kg / t of dry pulp. The hydrophobicity of the surface of the blanket finished by Cobb water test for 60 seconds is preferably less than 30 g / m2.
    [0016] . Os resultados indicam que o tensoativo seria substancialmente decomposto à medida que a manta atravessa a seção de secagem de uma máquina de papel ou papelão. [0016] The surfactant can advantageously be formed from an AKD precursor by activation with a base, an alcohol or water. The product is a labile ionic surfactant, which decomposes to form a non-hydrophilic ketone by heating. The tests carried out with the foams show that the foam with such AKD-based surfactants decreases progressively with increasing temperature, with the foam being lost in a few minutes, at 95ºC . The results indicate that the surfactant would be substantially decomposed as the blanket passes through the drying section of a paper or cardboard machine.
    [0017] [0017] An alternative approach to suppressing the hydrophilic aspect of the surfactant is to make the surfactant insoluble by heat. An example of such surfactants is C11 ethoxylated linear alcohol. Tomadol®, available from Air Products and Chemicals Inc., can be cited as a commercially representative product.
    [0018] [0018] MFC microfibrils typically have a fiber length of about 100 nm to 10 μm and a fiber diameter of about 3 to 50 nm. The term microfibrillated cellulose (MFC), as used to define the invention, also encompasses nanofibrillated cellulose (NFC).
    [0019] [0019] MFC contained in the foam provides, at least partially, the base of the fibrous mat, and also contributes to the stabilization of the foam by limiting the growth of glue bubble in the foam. For a better stabilization of the foam, protein, such as casein or polyvinyl alcohol (PVOH), can be advantageously incorporated into it.
    [0020] [0020] As surfactants, for example, based on AKD and all soaps, are sensitive to calcium and magnesium present in hard tap water, complexing agents such as EDTA and DTPA can be added to bind Ca and Mg in complex. At the same time the pH of the foam can be adjusted quite high, for example, by means of NaHCCO3 buffer, to prevent the dissolution of CaC03, or CO2 can be supplied to transform any dissolved Ca ++ into CaCO3.
    [0021] [0021] For a fibrous mat newly formed in a forming fabric, preferably, MFC is mixed with a different type of fibrous pulp, usually with the aim of increasing the volume of the mat as formed.
    [0022] [0022] For additional bonding of the mat, starch can also be incorporated into the foam, preferably in an amount of more than 15 kg / t of dry pulp, more preferably above 20 kg / t of dry pulp. Starch improves retention on the forming fabric and has a synergistic effect with MFC, reducing the shrinkage of the mat and improving the resistance of the leaf. The ratio of starch to MFC is generally in the range of 1: 1 to 2: 1.
    [0023] [0023] As an embodiment of the invention, a pulp of a high fiber length, mechanical or chemical, can be incorporated into the foam in combination with MFC. This combination provides substantially increased resistance to paper and cardboard products, preserving low density as sought by the foaming technique.
    [0024] [0024] Usefully the fibrous components incorporated in the foam consist of about 5 to 40% by weight, preferably 10 to 40% by weight of MFC and about 60 to 95% by weight, preferably 60 to 90% by weight of pulp long fibers.
    [0025] [0025] The pulp combined with MFC by definition has a longer fiber length, preferably about 1 mm or more. A pulp particularly suitable for use is chemothermomechanical pulp (CTMP), especially high temperature CTMP. However, other long-fiber celluloses useful for this purpose are chemical pulps, chemomechanical pulps (CMP), thermomechanical pulp (TMP), GW, and other high yield pulps, such as APMP and NSSC.
    [0026] [0026] Without connection with any theory, it is believed that in combination the long fibers of CTMP or similar provide the bulky structure and MFC provides the connection between the long fibers. The method has been found to reach a volume of at least 2.5 cm3 / g, preferably 3 to 7 cm3 / g. The method has also been proven to work well with CTMP milling tailings, which shows the possibility of using less refined pulp for the product, for example, intermediate layer of triple layer cardboard packaging.
    [0027] [0027] In foaming, neither individual long fibers nor MFCs alone are capable of forming flakes, but, nevertheless, MFCs are able to build bridges between individual long fibers, thus providing surprisingly good resistance properties to Blanket.
    [0028] [0028] As the formation of foam prevents the formation of flakes between long fibers, a very good grammage formation can be acquired. This improves the uniformity of the print quality, as there is less gauge variation in the paper and cardboard.
    [0029] [0029] These long rigid CTMP fibers are capable of maintaining the bulky structure in wet pressing and drying, thus offering surprisingly good mass to the sheet.
    [0030] [0030] An interesting result in the comparison of water and foam deposition samples was that the elastic stiffness index was very close in both cases, although the foaming samples were much more voluminous. The reason for this is unknown and needs further research.
    [0031] [0031] According to an embodiment of the invention, a continuous fibrous web is formed on an industrial scale, on a fabric forming in motion of a paper or paper machine, dehydrated by means of suction through the web and the web. formation, and finally dries in a drying section of the paper or cardboard machine.
    [0032] [0032] The mat can be dehydrated by suction of air through the mat and the formation fabric, at a maximum pressure of 0.6 bar, followed by pre-drying by suction of air, at a maximum pressure , about 0.3 bar.
    [0033] [0033] According to yet another embodiment of the invention, the foam is brought to an air content of 60 to 70% by volume, before being supplied to the forming fabric. The consistency of the foamed paste can be 1 to 2% based on the amount of water. The appropriate amount of surfactant in the foam can be in the range of 0.05 to 2.5% by weight, but it will be readily determinable by one skilled in the art. As noted above, the use of hard water requires large amounts of surfactant, or the use of complexing agents to bind Ca and Mg.
    [0034] [0034] Foaming by using long cellulosic fibers and adding microfibrillated cellulose in the foam can be used to produce all grades of paper and cardboard that require the best possible combination of formation with the best possible flexural stiffness.
    [0035] - papelão, incluindo papelão de dobrável para caixa, aglomerado de linha branca, cartão branqueado sólido, cartão cru sólido, cartões para embalagem de líquidos, etc. , - papelão para recipientes, incluindo papelão ondulado, meio ondulado, etc., - papelões especiais, incluindo papelão de núcleo, base de papel de parede, papelão para encadernação de livros, cartão de celulose, etc.. [0035] Such products include, for example, all types of cardboard, such as: - cardboard, including folding carton cardboard, white line agglomerate, solid bleached cardboard, solid raw cardboard, liquid packaging cards, etc. , - cardboard for containers, including corrugated, corrugated, etc., - special cardboard, including core cardboard, wallpaper base, book binding cardboard, cellulose cardboard, etc.
    [0036] [0036] Products also include, for example, grades of paper, such as newsprint, better newsprint, rotonews, MFC, LWC, WFC, art and ULWC.
    [0037] - como camada intermediária em estruturas de múltiplas camadas (papéis e cartões), - na laminação para outras estruturas de papel e/ou camadas de película plástica, - como uma base fibrosa para revestimento por extrusão com plástico, - como isolamento térmico, isolamento de ruido, absorvente de umidade e liquido, - como camada capaz de ser formada em estruturas moldadas, como bandejas, copos, recipientes. [0037] The high strength and high mass structure obtained according to the invention can also be used, for example: - as an intermediate layer in multilayer structures (paper and cardboard), - in lamination to other paper structures and / or layers of plastic film, - as a fibrous base for coating by extrusion with plastic, - as thermal insulation, noise insulation, moisture and liquid absorber, - as a layer capable of being formed in molded structures, such as trays, glasses, containers.
    [0038] [0038] The fiber mat according to the invention, which can be obtained by the process as described in the example above, comprises a mixture of microfibrillated cellulose (MFC) and a pulp of a greater length of fiber, and has a volume of at least 2.5 cm3 / g; preferably a volume of 3 to 7 cm3 / g.
    [0039] [0039] The fiber mat according to the invention can have a Scott bond value of at least 50 J / m2, preferably 120 to 200 J / m2.
    [0040] [0040] The pulp of a greater fiber length in the fibrous mat according to the invention may be of mechanical pulp, preferably CTMP. In general, the fibrous web comprises about 5 to 40% by weight of MFC and about 60 to 95% by weight of pulp of a longer fiber length.
    [0041] [0041] Another bonding component, such as starch, can be included in the blanket.
    [0042] [0042] When the fiber mat according to the invention is used as a single layer of a multi-layered cardboard or cardboard, it can be positioned as an intermediate layer, while the outer surface layers can be fibrous blankets of one volume smaller than said intermediate layer. For example, denser printing layers with a high modulus of elasticity, by means of conventional papermaking techniques, can constitute such outer layers. Multilayer products obtainable using the invention include liquid packaging cartons and cabinets, for example. However, it is possible to produce all layers of a multilayered card using the foaming technique according to the invention. Thus, a bulkier intermediate layer of MFC and CTMP and thinner outer layers of MFC and kraft pulp, or layers of MFC coating only, can each be foamed and glued hydrophobically to prevent rough edge penetration (REP) of liquids for the multilayer cardboard material.
    [0043] [0043] In addition to forming a mat in the fabric of forming a paper or cardboard machine, the invention is also applicable to the provision of a layer of fibrous coating on a fibrous mat of previously formed base. In this case, the method according to the invention comprises the steps of (i) adding water, microfibrillated cellulose (MFC), hydrophobic glue, and a heat sensitive surfactant in the form of a foam, (ii) providing the foam as a coating on said fibrous mat, (iii) drying the coating, and (iv) heating the coating to suppress the hydrophilic functionality of the surfactant.
    [0044] [0044] In coating applications according to the invention, the MFC alone preferably forms the fibrous component of the foam. Otherwise, the various embodiments and parameters discussed above and / or claimed in connection with forming a blanket over a forming fabric are also applicable in said coating applications. An exception, however, is the air content in the foam, which can be up to 80% by volume in coating applications. If desired, pigments, PVOH, carboxymethyl cellulose and other usual surface adhesives and mineral coating components can be incorporated into the foam. Most of the heat-sensitive surfactant will be decomposed by infrared drying the coated mat, any residues in the paper or cardboard produced as a mat roll.
    [0045] [0045] Yet another aspect of the invention is the use of a heat-sensitive surfactant to form a hydrophobically bonded layer of a fibrous mat. This use comprises placing water, cellulosic fibers, glue and said hydrophobic heat-sensitive surfactant in the form of a foam, providing the foam as a layer on a substrate, subjecting the layer to drying, and heating the layer to suppress the hydrophilic functionality of the surfactant. Previously heat-sensitive surfactants had not been used or suggested for use in forming the paper blanket or coating using foam techniques. As applied to hydrophobically bonded blankets and coatings, the invention solves the problem of the present surfactants gradually destroying the hydrophobic bonding. The invention, as well as its benefits, does not depend on the type of cellulosic fibers, but the use of MFC alone for the foam coating and a mixture of long fibers and MFC for a foam-based blanket formation are particularly preferred. Example
    [0046] [0046] The configuration was as follows:
    [0047] [0047] AKD (Precis 900 AKD liquid from Ashland) was used as a surfactant precursor. AKD was activated in a KOH / ethanol / water solution, using a 100-minute protocol. The protocol will give 0.15% ethanol and 1.5% ethanol in pulp to follow, as a by-product, and the pulp will be slightly alkaline for the remaining KOH. The pH will be adjusted to 8 with dilute hydrochloric acid before foaming.
    [0048] [0048] A pulp of 2% dry solid consistency was prepared by diluting with tap water from 16% bleached birch paste. Tap water was used to simulate reality and counts for the precipitation of calcium soap from Ca / Mg ions in water of a hardness of about 3-4 German degrees.
    [0049] [0049] 0.01 g of activated ADK surfactant was added in an amount of 0.01 g per 100 ml of diluted pulp and 0.1 g per 100 ml of diluted pulp.
    [0050] [0050] 200 ml of the pulp and surfactant mixture as obtained were foamed for one minute of mixing at maximum speed in a food type mixer and transferred directly to a 1000 ml measuring cylinder. Foaming was controlled at t = 0, t = 1 min, t = 5 min and t = 10 min, by measuring the foam volume, volume of liquid drained and number of foam expansion (total volume of foam in the cylinder / 200 ml of a non-foamed mixture). Results of
    [0051] [0051] 0.2% surfactant (half of it consumed due to the hardness in water, but which can be fixed by complexing agents or by the fact that the processing liquid is already saturated with calcium-AKD soap, if AKD glue is applied) applied), 200 ml of cellulose (2%), initially, which turns into 170 ml of foamed cellulose, containing 70 ml of air and 100 ml of drained water.
    [0052] [0052] The foam pulp was very stable over time, with no break detected in 10 minutes. The air content was 70/170 or 41%. The bubble glue was rated as satisfactory.
    [0053] [0053] The result indicates that the AKD-based surfactant forms foam in contact with the pulp.
    权利要求:
    Claims (15)
    [0001]
    Method for preparing a hydrophobically bonded layer of a fibrous blanket, comprising the steps of: - bring water, microfibrillated cellulose (MFC), hydrophobic glue, and a heat-sensitive surfactant to a foam form, - supply the foam on a forming fabric, - remove the water from the foam in the formation fabric by means of suction to form a blanket, - subject the blanket to drying, and - heat the mat to suppress the hydrophilic functionality of the surfactant.
    [0002]
    Method according to claim 1, characterized in that the hydrophobic glue is alkyl ketene dimer (AKD) or a derivative thereof.
    [0003]
    Method according to claim 1 or 2, characterized by the fact that the surfactant is decomposed by heat, removing the hydrophilic fraction from a hydrophobic residue.
    [0004]
    Method according to claim 3, characterized in that the surfactant is formed from an AKD precursor by activation with a base, an alcohol or water.
    [0005]
    Method according to claim 1 or 2, characterized in that the surfactant is rendered insoluble by heat.
    [0006]
    Method according to claim 5, characterized in that the surfactant is C11 ethoxylated linear alcohol.
    [0007]
    Method according to any one of the preceding claims, characterized in that a pulp of a higher fiber length is also incorporated in the foam.
    [0008]
    Method according to any one of the preceding claims, characterized in that said pulp of a greater fiber length is mechanical pulp, such as chemitermomechanical pulp (CTMP).
    [0009]
    Method according to any one of the preceding claims, characterized in that the fibrous components incorporated in the foam consist of 5 to 40% by weight of MFC and 60 to 95% by weight of long fiber pulp.
    [0010]
    Method according to any one of the preceding claims, characterized in that a continuous fibrous mat is formed on a forming fabric in motion from a paper or cardboard machine, dehydrated by means of suction through the mat and the forming fabric, and finally dries in a drying section of the paper or cardboard machine.
    [0011]
    Method for providing a hydrophobically coated coating layer on a fibrous blanket, comprising the steps of: - bring water, microfibrillated cellulose (MFC), hydrophobic glue, and a heat-sensitive surfactant to a foam form, - supply the foam as a coating on the said fibrous mat, - subject the coating to drying, and - heating the coating to suppress the hydrophilic functionality of the surfactant.
    [0012]
    Hydrophobically bonded fibrous mat obtainable by the method according to any one of claims 1 to 10, characterized in that the mat comprises a mixture of microfibrillated cellulose (MFC) and a pulp of a longer fiber length, together with a hydrophobic glue , the blanket having a volume of at least 2.5 cm3 / g.
    [0013]
    Multilayer cardboard, characterized by the fact that at least one of the layers is a fibrous blanket according to claim 12.
    [0014]
    Multilayer cardboard according to claim 13, characterized in that the cardboard is the liquid cardboard comprising a fibrous mat according to claim 12 as an intermediate layer, and, on both sides of said intermediate layer, outer layers of a smaller volume than the intermediate layer.
    [0015]
    Use of a heat-sensitive surfactant to form a hydrophobically bonded layer of a fibrous mat as prepared by the method of claim 1, characterized by bringing water, microfibrillated cellulose (MFC), hydrophobic glue and a heat-sensitive surfactant to a form of foam, supply the foam as a layer on a substrate, subject the layer to drying, and heat the layer to suppress the hydrophilic functionality of the surfactant.
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-02| B09A| Decision: intention to grant|
    2021-04-06| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    FI20125463|2012-04-26|
    FI20125463A|FI124556B|2012-04-26|2012-04-26|Hydrophobic-bonded fiber web and process for manufacturing a bonded web layer|
    PCT/FI2013/050471|WO2013160564A1|2012-04-26|2013-04-25|Hydrophobically sized fibrous web and a method for the preparation of a sized web layer|
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