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    ABSTRACT The present invention relates to an application method of enhancing the water repellence of a textile and/ or enhancing a textiles ability to repel water soluble dirt, comprising the steps of: a) Applying an emulsified liquid composition on a textile, wherein said emulsified liquid composition consists of:-Water -Alkylalkoxysilane with said alkyl chain having a length of 10-30 carbons or carbon atoms higher than 12 but equal to or less than 18 -At least one emulsifier, surfactant, thickener and/ or stabilizer - a water soluble acid catalyst and -unavoidable impurities b) Optionally adjusting amount of formulation applied on textile c) Drying the treated textile until dry d) Curing the treated textile at a temperature of between 1oo-2oo°C. e) Optionally removing the non-reacted formulation residue from the treated textile by washing With water and optionally redrying the treated textile Moreover the present invention relates to an an emulsified liquid composition and its useand also to a textile treated according to said method and its use.
    公开号:SE1350303A1
    申请号:SE1350303
    申请日:2013-03-13
    公开日:2014-09-14
    发明作者:Juhanes Aydin
    申请人:Organoclick Ab；
    IPC主号:
    专利说明:

    TECHNICAL FIELD The present invention relates to a method and a water-based chemical formulation for obtaining extremely water-repellent textiles, with good resistance to water and / or weathering.
    Summary of the Invention This invention relates to a method of treating textiles with an aqueous silane emulsion and a method of its preparation.
    Industrially, the aqueous silane emulsion according to the invention is applied to the fabric or textile, which gives a durable, extremely water-repellent fabric.
    The emulsion applied according to the invention comprises an alkoxysilane, an acid, an emulsification system with at least one emulsifier and water. The emulsion according to the invention is stable over time without being separated into two phases. This invention offers an alternative method of using fluorine-based compounds for treating textiles to achieve water repellency, by providing an aqueous silane preparation and a specific application process. The preparation of the invention is the result of the choice of a hydrophobing agent (silane), an (acid-based) catalyst, one or more emulsifiers and water as solvent.
    It is shown that the preparation can be applied Mom industrially relevant process times to provide highly durable and water-repellent textiles.
    The present invention relates to an application method for improving the water repellency of a textile and / or improving the shape of a textile to repel drilling water-soluble dirt, comprising the steps of: a) applying an emulsified liquid preparation to a textile, said emulsified liquid preparation consisting of: Water Alkylalkoxysilane where the said alkyl chain has a length of 10-30 carbon atoms or carbon atoms in a number greater than 12 but equal to or less than 18 At least one emulsifier, surfactant, thickener and / or stabilizer -A water-soluble acid catalyst and 2 - unavoidable contaminants Possibly adjust the amount of formulation applied to the fabric Dry the treated fabric until dry Harden the treated fabric at a temperature of 100-200 ° C e) Any unreacted formulation residues removed from the treated fabric by washing with water and possibly re dry the treated textile Present application m method according to the invention may comprise flakes of the following determinations or features in any combination: An application method according to the invention wherein said emulsified liquid preparation has a pH value below 4.5, or between 1.8 and 4.3, or between 1.9 and 4.2.
    An application method according to the invention, wherein said means of applying said emulsified liquid preparation is selected from exposing, impregnating, stuffing, dipping, spraying, brushing, coating, rolling, foaming, impregnation, vacuum pressure impregnation process or other means of applying said liquid preparation. An application method according to the invention wherein adjustment of the amount of formulation applied to the fabric is done with an industrial padding machine / scarf to apply the emulsion to the substrate and to control the water uptake by adjusting the nip pressure or adjusting the rollers' pneumatic load and water uptake is 30-100 weight percent in relation to untreated textile.
    An application method according to the invention wherein said alkylalkoxysilane in said emulsified liquid preparation is added in a concentration of 2% by weight in proportion to the total amount of emulsified solution.
    An application method according to the invention wherein said acid catalyst in said emulsified liquid preparation is present in a concentration of <8% by weight or 0.01-7% by weight in relation to the total amount of emulsified solution.
    An application method according to the invention wherein said emulsifier or a combination of said emulsifier in said emulsified liquid preparation is present in a concentration of <2% by weight or 0.9-1.1% by weight in relation to the total amount of emulsified solution. An application method according to the invention wherein said water content in said emulsified liquid preparation is 80-97.5% by weight or 87-94% by weight in relation to the total amount of emulsified solution.
    An application method according to the invention wherein said water content in said emulsified liquid preparation is lower than 80% by weight or between and 80% by weight in relation to the total amount of emulsified solution, and wherein additional amount of water can be added before using said application method.
    An application method according to the invention wherein the alkoxy groups in said alkylalkoxysilane are selected from acetoxy, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy. An application method according to the invention wherein said alkylalkoxysilane in said emulsified liquid preparation is selected from the group having an alkyl chain having a number of carbon atoms stone of 12 but equal to or less than 18 carbon atoms.
    An application method according to the invention wherein said alkylalkoxysilane is selected from n-, iso- or mixtures thereof of hexadecyltrimethoxysilane and / or octadecyltrimethoxysilanes. An application method according to the invention wherein the alkyl group in said alkylalkoxysilane is a linear, branched or cyclic carbon chain or an unsaturated and saturated carbon chain.
    An application method according to the invention wherein said alkylalkoxysilane is selected from or isoconfigured hexadecyltrimethoxysilane, hexadecyltriethoxysilane or noktadecyltrimethoxysilanes or mixtures thereof.
    An application method according to the invention wherein said emulsified liquid preparation has a pKa value less than 3.9, or between 1.9 and 3.9.
    An application method according to the invention wherein said water-soluble acid catalysts in said emulsified liquid preparation have a pKa value of 6 or less, or pKa -14-4.
    An application method according to the invention wherein said emulsifier in said emulsified liquid preparation comprises a non-ionic, cationic or anionic emulsifier.
    An application method according to the invention wherein the acid catalyst produces a Lewis or Bronsted acid.
    An application method according to the invention wherein the acid catalyst produces an organic or inorganic acid. An application method according to the invention wherein the acid catalyst is selected from any of paratoluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, malic acid, maleic acid, glyoxylic acid, citric acid, formic acid, pyruvic acid, tartaric acid, phthalic acid, acetylsalicylic acid, malicylic acid, mandilicylic acid acetic acid, hydrochloric acid, sulfuric acid and oxalic acid.
    An application method for maintaining a fabric permanently water-repellent and / or water-soluble dirt-repellent according to the invention, wherein the drying of the treated fabric is carried out at a temperature between 15 and 180 ° C or between 15 and 170 ° C until the fabric is dry.
    An application method for applying a fabric permanently water-repellent and / or repellent to water-soluble dirt according to the invention, where the curing of the treated fabric is carried out at a temperature between mo and 180 ° C or between 150 and 180 ° C until the fabric is dry, at most minutes, for example for 0-5 minutes.
    Furthermore, this invention also relates to: An emulsified liquid preparation used in the application method according to the invention. A textile that is permanently water-repellent and water-soluble dirt-repellent and treated with the application method according to the invention.
    A textile according to the invention wherein the textile has a result in the ISO 4920 spray value of ISO 3 or higher after four or more washes of said textile.
    Use of the emulsified liquid preparation according to the invention according to the application method according to the invention to water a textile permanently.
    Use of an emulsified liquid preparation according to the invention according to the application method according to the invention in order to make a textile permanently dirt-repellent against water-soluble dirt, for example wine, ketchup, coffee or soil.
    Background of the Invention Durable water-repellent surface layers are hydrophobic coatings that are applied to textiles to make them waterproof. However, despite the name, most of the durable water-repellent surface layers on the market tend to wear away over time, and show very poor durability when responding (eg a textile water process or in an acidic environment). Several inventions have been developed to obtain textiles with water-repellent properties. The known methods, however, give textiles with poor wear resistance and wash resistance, and are to some extent responsible for applying to the material. The reason for the unacceptable wash resistance of the mentioned systems is the weak fixation of the hydrophobing agent to the textile fibers.
    In order to achieve lasting water repellency in textiles, it is therefore necessary for the water-repellent coating to form strong covalent bonds to the fibers, with the additional requirement that they should fail the corresponding conditions in e.g. household washing machines or outdoor environment. At the same time, it is obvious that it is not an easy task to achieve these bonds, since very few even hydrophobing agent formulations (for treating cellulose fabrics, for example) meet the combined requirements for the formation of covalent bonds as high conditions of high alkalinity ( pH> 10) at high temperatures 40 ° C), industrially relevant application times for the formulation, acceptable cost and a harmless application process, not to mention a non-existent or slight impact on millions.
    For decades, the application of fluorine compounds has been the preferred method in the manufacture of, for example, water-repellent Udder. The success of fluorocarbons is due to their extreme hydrophobicity and oleophobicity, their extremely low surface tension and their tendency to remain on the fabric. However, despite its proven effectiveness, the application of "fluorocarbons" is very controversial, due to its negative impact on millions and 25 due to studies on animals showing that accumulated fluorocarbons (in the body) can be very dangerous.
    The premise of (non-fluorinated) organosilanes, which are derivatives of silanes containing at least one carbon-silicon bond, that water-repellent surfaces have been known for some time. In particular, the so-called alkoxysilanes and silicon halides (which have at least one hydrophobic component and one to three hydrolyzable alkoxy and halide groups) respectively have been considered as possible candidates for water-repellent hydroxyl-containing surfaces (eg cellulosic materials). This view is based on the knowledge that the reactive groups (alkoxy / halides) of organosilanes in the presence of water are hydrolyzed to form hydroxyl (OH) groups. These groups promote (in theory) the adsorption of the silanes against the OH-containing surface by a hydrogen bonding mechanism. The silanes can then be covalently attached to the surface through a heating process that leads to the release of water. However, the hydrolyzed monomeric organosilanes are highly reactive and capable of undergoing condensation reactions (in solution), leading to the formation of polymeric structures (and gels for a long time). In addition, the high reactivity of said silanes (especially the silicon halides) requires very complicated procedures (to provide for "dry" anhydrous conditions) in order to maintain the silanes in their reactive form, something which has hitherto been considered too complicated and uneconomical. Consequently, there are very few patents that discuss hydrophobicity of textiles with (non-fluorinated) organosilanes. Even fewer patents emphasize the resulting washability / durability. It is clear from the above that non-fluorinated, permanently water-repellent surface layers must be / remain firmly anchored in the substrate, especially under "normal" water conditions, before they can be considered as possible alternatives to the "fluorine counterparts". It is further apparent that the use of organosilanes is not an important task due to their high reactivity, which the inventors know to date has made their application impractical. What is also unattractive from an economic, environmental and practical point of view is the use of organic solvents, such as alcohols, when applying organosilanes or fluorocarbons. Furthermore, the application of organosilanes must be affordable, industrially feasible and more environmentally friendly than the existing "fluorine coating processes". In addition, dangerous solvents should be avoided and the use of water promoted in the stable. The general purpose of preparing a water-based formulation for Ora textile water-repellent is to design a system in which the reactivity of the organosilane is maintained for a long time, which Or use and storage of said formulation is practical, economical and environmentally feasible. It is also important that the process is more environmentally friendly than the current silane processes, which involve the use of different solvents. There is also a need for a durable coating that remains on the fabric after washing. At present, there is no hydrophobing process that meets all (or at least most) of the stated requirements. That has been the reason for the work that led to this invention. In the following, a new organosilane preparation is presented together with its application process, which is assumed to meet the specified requirements.
    Prior Art 7 In patent application PCT / EP2011 / 050066, the inventor describes a method in which organosilanes are used to make cellulose fibers hydrophobic. In this process, alcohols or organic solvents can be used. A strong acid with pKa <1.0 is also used as a catalyst, which must be removed after the material has been treated in order for the water-repellent form to be good. The use of organic solvents and alcohols together with the use of very strong acids is impractical from an industrial point of view in terms of both corrosion, throat aspects, flammability and risk of explosion, as well as in terms of the negative effects on the aesthetic and mechanical properties of the treated material. strong acid. In addition, the acid must be washed away in order for the water-repellent effect to be present, which is not always practically dependent on the material being treated.
    In patent application US20092o6296 the silane formulations described comprise a release agent used to dissolve the formulation components. As mentioned earlier, the use of organic solvents or alcohols is impractical due to flammability, toxicity, etc. frail industrial and neck point of view. In addition, the eye protection, together with the lack of washability, limits their usefulness in the production of durable water-repellent textiles.
    Other documents showing examples of silane formulations and applications are: US5552476, JP2007100276, FR2735705, US2007237901, US4990377.
    Description of the figures Fig. 1 shows criteria for different scales when using the ISO 4920 spray value.
    Fig. 2 shows an example according to the invention which indicates results from the ISO 4920 spray value and relates to the number of washes.
    OBJECTS OF THE INVENTION It is an object of the invention to provide an environmentally friendly, industrially applicable method of treating a textile for all to provide a durable water-repellent shape and / or repellent shape for water-soluble dirt.
    It is a further object of the present invention to provide a chemical formulation consisting of a liquid solution containing a hydrophobing agent in the form of an organosilane, an acid catalyst, a single or a combination of emulsifiers / surfactants / thickeners / stabilizers and water as the sole solvents. A further object of the present invention is an application method comprising a silane-aqueous formulation, stable for a long time, by means of a suitable emulsification system containing a catalyst having a pKa value which does not excessively large the water-repellent form or the aesthetic and mechanical properties of the substrate which has been treated, which contains an emulsifying system which effectively emulsifies the organosilane in water without compromising the stability of the formulation on a negative sail or without all the aesthetic or mechanical properties or reducing the reactivity of the silane over time. Another object of the invention is to provide a method of this kind which is attractive from an economic and environmental point of view.
    A further object of the invention is all the means provided for the industrial use of the method and the chemical formulation in current production methods for textiles.
    These and other features, features and advantages of the invention described herein will become more apparent from the following detailed description thereof.
    DETAILED DESCRIPTION OF THE INVENTION According to the invention, there is provided a method of improving the water repellency of textiles, comprising all the material in a liquid formulation comprising or consisting of an organosilane as hydrophobing agent, an acid acting as a catalyst, a surfactant acting as an emulsifier and water as a solvent, all dry and harden the fiber-based material at an elevated temperature for a sufficient time to obtain the desired improvement.
    According to the invention, the use of the term textiles according to the present invention may comprise textiles, cloths or fabrics and in accordance with the present invention may be natural and / or synthetic textiles and / or woven and / or non-woven textiles and mixtures thereof. Textiles can consist of a net of natural and / or artificial fibers that are often called tract or yarn. Yarns are made by spinning raw fibers of wool, linen, cotton or other materials to make long threads. Textiles are formed by weaving, knitting, crocheting, tying or compressing the fibers (felt). 9 The words fabric and cloth can be used, for example, in textile joining compartments (such as tailoring and sewing) as synonyms for textile. Textile can refer to any material made of interwoven fibers or non-woven fabrics. Fabric refers to any material made by weaving, knitting, spreading, crocheting or joining that can be used in the production of additional goods (clothes, etc.). Tablecloth can be used synonymously with fabric but often refers to a finished piece of fabric that is used for a certain purpose (eg a tablecloth). The term textiles according to the present invention may include all the different types of textiles described above. Textiles according to the present invention can be made of many different types of materials and fibers, for example animal (wool, silk, mohair, cashmere, pygora, camel hair, alpaca, llama, vikunja, guanaco, angora or qiviut, etc.), vegetable (ramie, nettle , silk, cotton, linen, linen, jute or hemp), traced (eg viscose), minerals (asbestos, fiberglass, etc.), and synthetic (nylon, elastane, polyester, acrylic, polyamide, polypropylene, polyurethane and its derivatives, etc.) and sugar-based (corn fiber, coconut, yucca, sisal or bamboo (rayon) fiber, etc.) or protein-based fibers frail plants (peanut and soy-based, chitin-based, milk casein-based, keratin-based or polylactic acid-based). The fabric suitable for treatment according to the present invention is preferably a washable fabric.
    The method of applying the emulsified solution or formulation to the fabric of the invention may be by blotting or dipping or spraying, applying the formulation to the fabric in another manner, for example by means of a stuffing machine or frame or other machine, or for example manually.
    The concept of unavoidable impurities according to this invention may include, for example, small amounts of chemicals which are unavoidable because they are present in small amounts in the supplied ingredients. The treated fabric treated with the application method of the present invention has excellent durable water-repellent shape, even after washing of the garment (with or without detergent). The water-repellent shape after three washes is higher than 3 according to the ISO 4920 spray value, where the fabric is exposed to a standardized amount of water that is sprayed on the fabric to mimic a rain shower. The treated fabric also has an excellent dirt-repellent shape, especially the rejection of water-soluble / hydrophilic dirt, for example but not limited to soil flakes or flakes of ketchup, coffee or yin or water-soluble flakes.
    The present invention also includes the use of the emulsified solution according to the invention to make a textile permanently dehydrating and / or dirt repellent.
    The term all Ora a textile permanently waterproofed or water-repellent and / or dirt-repellent in the present application meant that the fabric is waterproofed or water-repellent and / or dirt-repellent even after being washed four times or more. A sufficient amount of silane is covalently bonded to the surface-treated fabric, which meant that the tM normal water conditions without losing its wad-repellent shape after washing.
    The Emulsified Liquid Formulation The term emulsified solution or emulsified liquid preparation is used to refer to the solution used to treat the fabric to permanently waterproof and / or soil repellent the fabric. Said emulsified liquid preparation according to the invention comprises or consists of an alkylalkoxysilane such as hydrophobing agent, an acid which acts as a catalyst, an emulsifying agent and water as a release agent. The emulsified liquid preparation according to the invention comprises alkyl alkoxysilanes which retain their reactivity even during storage of the formed emulsified liquid preparation according to the invention. In one embodiment, the emulsified liquid formulation of the invention can be stored for at least six months at room temperature without the precursor alkylalkoxysilanes losing their reactivity.
    The emulsified liquid preparation according to the invention consists of: Water -Alkylalkoxysilane wherein the said alkyl chain has a length of 10-30 carbon atoms or 12-30 carbon atoms At least one emulsifier / surfactant / thickener / stabilizer a water-soluble acid catalyst and unavoidable impurities in the liquid ingredients 11 Ingredients the formulation of the invention may have any of the properties of the various alternatives described below: Hydrophobing agent: The hydrophobing agent of the invention is selected from the group of alkylalkoxysilanes and may have any of the properties according to the various alternatives described below. In one embodiment, the alkoxy group of the alkylalkoxysilane in the liquid formulation of the invention is selected from alkoxy groups comprising 1-4 carbon atoms or, for example, containing 2-3 carbon atoms, or, for example, selected from acetoxy, methoxy, ethoxy, propoxy (e.g. n-propoxy , isopropoxy-) or butoxy groups (for example n-butoxy, isobutoxy or tert-butoxy). In one embodiment, the alkylalkoxysilane in the preferred formulation is valid from the alkyltrialkoxysilane class, for example n-, iso- or mixtures thereof, of hexadecyltrimethoxysilane and octadecyltrimethoxysilane (examples of suitable hexadecyltrimethoxysilanes may be one consisting of carbonyl or branched hydroxylsilane iso-hexadecyltrimethoxysilane; alternatively, a mixture of branched and lin * silane is usable: hexadecyltrimethoxysilane, mixture of isomers). In other embodiments, the alkylalkoxysilane according to the invention is an organosilane, further comprising a quaternary ammonium alkyl group such as dimethyloctadecyl [3- (trimethoxysilyl) propyl] ammonium chloride, dimethylhexadecyl [3- (trimethoxysilyl) propyl] ammonium chloride or similar anions as various anions. For example, chloride may be replaced by bromide, iodide, acetate or the like.
    Dimethyl can also be replaced by other alkyl groups, such as ethyl, propyl, butyl, pentyl, hexyl or phenyl.
    In one embodiment, the emulsified formulation of the invention comprises an alkylalkoxysilane having an alkyl chain having a number of carbon atoms of up to 10 but equal to or less than 30 carbon atoms. Said alkyl chain on the alkylalkoxysilane is, for example, a straight and matte carbon chain to enable better packing of the chains in the cellulosic material interface, but also branched, cyclic and / or unsaturated chains are conceivable according to the invention. In other embodiments, the emulsified formulation of the invention comprises an alkylalkoxysilane having an alkyl chain having a number of carbon atoms of up to 10 but equal to or less than 30, or for example having a number of carbon atoms greater than 12 and less than 30, or for example having a alkyl chain having a number of carbon atoms stone of 16 and less than 18. In another embodiment, the emulsified formulation of the invention comprises an organosilane having an alkyl chain which is linear or cyclic with a number of carbon atoms greater than 10 but equal to or less than 30, or for example with a number of carbon atoms greater than 12 and less than 30, or for example with an alkyl chain with a number of carbon atoms greater than 16 and less than 18.
    In one embodiment of the alkylalkoxysilane, said alkyl is straight or branched, saturated or unsaturated C 10 -C 30 alkyl, or C 12 -C 18 alkyl and the alkoxy group is an acetoxy, methoxy, ethoxy, propoxy (e.g. n-propoxy, isopropoxy -) or butoxy group (for example n-butoxy, isobutoxy or tertbutoxy). Said alkyl chain on the alkylalkoxysilane is preferably straight and matte to allow better packing of the chains at the cellulosic material interface, but also branched, cyclic and / or unsaturated chains are conceivable. More preferred is an alkyltrialkoxysilane wherein said alkyl is straight or branched C 12 -C 18 alkyl. Most preferred are alkyltrialkoxysilane where said alkyl is straight or branched C 16 -C 18 alkyl, for example hexadecyltrimethoxysilane and / or octadecyltrimethoxysilane.
    In a preferred embodiment of the invention, the concentration of alkylalkoxysilane in the formulation should be in the range of 1-15% by weight, or 2% by weight or 2-8% by weight or 4-8% by weight, for example 5-7.5% by weight relative to the total amount of formulation to provide excellent hydrophobicity and formulation stability (during the fiber modification process).
    Acid catalyst The acid catalyst in the emulsified formulation according to the invention is selected from a Bronsted acid or a Lewis acid. In one embodiment, the acid catalyst in the emulsified formulation of the invention is valid from the group of acids which are readily soluble in water solvents, having the additional requirements pKa <4 and being active within the system throughout the application process. In addition, the selected acid should not have a large water repellency of the material after treatment. In another embodiment, the pKa value of the acid catalysts is 1.5-4.0 or 1.9-3.9. A pKa value of the acid catalysts below 1.9 can lead to discoloration of the fabric but arida give good water-repellent and dirt-repellent effect. The preferred catalyst in the formulation is valid from the group of acids which are soluble in water. The catalysts should have pKa <4 and they must remain active in the system during the application process. In one embodiment of the invention, the acid yields an organic acid. Examples of acid catalysts which are useful in that none of the emulsifying formulations according to the invention include paratoluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, malic acid, maleic acid, glyoxylic acid, citric acid, formic acid, pyruvic acid, tartaric acid, phthalic acid, acetylsalicylic acid, , malonic acid, glycolic acid and oxalic acid. In one embodiment of the invention, the acid is a non-toxic organic acid. In a preferred embodiment of the invention, the amount of catalyst is equal to or less than 8% by weight. In the most preferred embodiment of the invention, catalysts with pKa less than 4 or pKa between 1.9 and 3.9 are used; The amount of acid catalyst in the formulation is then less than 7% by weight, or between 1 and 7% by weight relative to the emulsified liquid preparation.
    Components According to the present invention, the term emulsifier may also refer to a surfactant Mune, a thickener or a stabilizer. Eli emulsifiers can be ionic or non-ionic. The emulsifier is added to the emulsified liquid preparation for all emulsifying the liquid preparation. The emulsifier can be selected so that it does not discolor the selected textile material and / or does not affect the wear resistance of the textile. The emulsifier can be selected from the group of surfactants which are non-ionic emulsifiers having an HLB value between 7 and 41 and which are capable of emulsifying hydrophobing agents and the acid catalyst in water. In one embodiment of the invention, the emulsifier is a surfactant having an HLB value between 10 and 18, which may be used in conjunction with surfactants having an HLB value between 35 and 41. In one embodiment, the emulsifier does not affect the reactivity of the catalyst and hydrophobing agent. According to the most preferred embodiment of the invention, all-wall surfactants have an HLB value of 11-17 and / or 39-41.
    In one embodiment, the emulsifier comprises a surfactant having an HLB value of 1-41, selected from any or any combination of: carboxylic acids having 9-20 carbon atoms; aliphatically substituted benzene / aromatic sulfonic acids having at least 6 carbon atoms in the aliphatic substituents; aliphatic sulfonic acids having at least 6 carbon atoms in the aliphatic substituents; aliphatically substituted diphenyl ether sulfonic acids having at least 6 carbon atoms in the aliphatic substituents; alkylvate sulfates having at least 6 carbon atoms in the alkyl substituents; alkyl and alkylaryl ether sulphates having at least 6 carbon atoms in the hydrophobic radical and 1 to 40 ethylene oxide (EO) and / or propylene oxide (PO) units; taurider; esters and monoesters of sulphosuccinic acid with monohydric alcohols or alkylphenols having 4 to 30 carbon atoms, optionally ethoxylated with 1 to 40 EO units, and also alkali metal and ammonium salts of the said acids; partial phosphorus esters and their alkali metal and ammonium salts, in particular alkyl and alkylaryl phosphates having 8 to carbon atoms in the organic radical; alkyl ether and alkyl aryl ether phosphates having 8 to carbon atoms in the alkyl radical and the alkylaryl radical, respectively, and 1 to 40 EO units; salts of primary, secondary and tertiary fatty amines having 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid and phosphoric acids; quaternary alkyl and alkylbenzene ammonium salts, more specifically those whose alkyl chain has up to 18 carbon atoms, especially halides, sulfates, phosphates and acetates; alkyl polyglycol ethers, preferably those having 3 to 40 EO units and alkyl radicals having 8 to carbon atoms, alkylaryl polyglycol ethers, preferably those having 5 to 40 E0 units and 8 to carbon atoms in the alkyl and aryl radicals, ethylene oxide-propylene oxide (EO- P0) block copolymers, preferably those having 8 to 40 EO and / or PO units; additives of alkylamines having alkyl radicals of 8 to 22 carbon atoms with ethylene oxide 14 or propylene oxide; alkyl polyglycosides, natural substances and derivatives thereof, sasomlecithin, lanolin, saponins, cellulose, cellulose alkyl ethers and carboxyalkyl celluloses; linear organo (poly) siloxanes containing polar groups containing more specifically the basic elements 0, N, C, S, P, in particular those having alkoxy groups having up to 24 carbon atoms and / or up to 40 EO and / or PO groups ; amino acids substituted with long chain substituents such as N-alkyldi (aminoethyl) glycine or N-alkyl-2-aminopropionic acid salt; betaines, such as N- (3-acylamidopropyl) -N, N-dimethylammonium salts containing a C8-C18 acyl radical and alkylimidazolium betaainers.
    As is known in the art, in addition to the above compounds, examples of stabilizers may also include hydrochloride (HCl) and sodium hydroxide (NaOH). Non-resilient, thermally degradable or volatile surfactants such as amine oxide-based ones can also be used in the repellent surface treatment bath to maximize the final properties of the treated substrate.
    Water Water is present in the emulsified liquid preparation as a solvent, for example in quantities of 80-97% by weight.
    In an embodiment according to the invention, the emulsified liquid according to the invention is a concentrated liquid, comprising smaller water quantities than, for example, 80 percent, and is diluted to contain 80-97% by weight of water before use.
    More specifically, the present invention relates to a method for improving the water repellency of textiles and / or its ability to repel water-soluble dirt, comprising the steps of: a) Applying an emulsified liquid preparation to a textile, wherein said emulsified liquid preparation consists of: Water -Alkylalkoxysilane wherein said alkyl chain has a length of 10-30 carbon atoms or for example 12-30 carbon atoms At least one emulsifier or thickener or surfactant or stabilizer A water-soluble acid catalyst and unavoidable impurities Possibly adjusting on textile Dry the treated textile until it dries Harden the treated textile at a temperature of 100-200 ° C 1 e) Possibly remove unreacted formulation residues from the treated textile by washing with water and then, if necessary, re-dry it In one embodiment available The present invention provides a method of improving the water repellency of textiles, comprising: An application method for all a textile permanently water repellent and / or water soluble repellent comprising the steps of: a) Applying an emulsified liquid preparation having a pH of 1.8 -4.3 on a textile, wherein said emulsion can be stored as an emulsion without being separated into phases and consists of: Water 80-97% (weight percent) of the total amount of emulsified liquid preparation -Trialkylalkoxysilane wherein said alkyl chain has a length of 12-16 carbon atoms and the alkoxy chains have a carbon chain having 1-3 carbon atoms and said alkoxyalkylsilanes in an amount of 2-8% by weight of the total amount of emulsified liquid preparation At least one emulsifier or a combination of emulsifiers in an amount of 0.9- 1.1% by weight of the total amount of emulsified liquid preparation A water-soluble organic acid catalyst with pKa <4 and unavoidable impurities f) If necessary, adjust amount of formulation applied to textile 2g) Dry the treated textile until it is dry Harden the treated textile at a temperature of 100-200 ° C Possibly remove any unreacted formulation residues from the treated textile by washing with water and then possibly drying again The method of the invention can be incorporated by using a standard scarf, a stuffing machine or similar machines for liquid application in a textile manufacturing process, or a spraying, coating or vacuum pressure impregnation process.
    The textile material can be brought into contact with the silanization preparation on any suitable sail, such as by dipping, padding, application with rollers or brush, coating and spraying. The silanization preparation can be brought into contact with textile material in such a way that the material is essentially wetted completely (exposed) or only wetted to a desired depth from the surface of the material to which it is applied.
    According to the method of the invention, the drying continues until the fabric is substantially dry, i.e. has a water content below 5% by weight and t.o.m. save an 2% by weight. In this application, "drying" includes the evaporation of water; "substantially dry" means essentially free of water.
    An important feature of the method of the invention is the curing temperature, which is at least 100 ° C, preferably at least 120 ° C, more preferably at least 140 ° C or 150 ° C, and also up to 200 ° C. The curing temperature of the present invention is 100-200 ° C or 130-180 ° C. The curing time is approximately inversely proportional to the curing temperature. Thus, curing at higher temperatures can be carried out in a correspondingly shorter time, such as a couple of minutes or about 1 minute to 3 minutes in a preheated oven at a temperature of 150 ° C to 200 ° C. One skilled in the art will appreciate that the air convection during drying, the thickness and density of textile materials as well as other physical parameters of the material affect the curing time at a given drying temperature.
    The present invention also comprises the use of the emulsified liquid formulation according to the invention for treating a textile with a sustained release agent and also with the use of a textile treated with the method of application of the present invention for treating a textile with a permanently dirt-repellent against waterless , for example but not limited to ketchup, coffee or yin, or water-soluble flakes.
    DESCRIPTION OF PREFERRED EMBODIMENTS Materials Malic acid, acetic acid, citric acid, glyoxylic acid, pyruvic acid and maleic acid, Sigma Aldrich. NaHCO3, Sigma Aldrich. Tegosoft PC 41 (polyglycerol esters of capric acid HLB 14), Evonik Industries AG. Hexadecyltrimethoxysilane (KH580), Zhejiang Feidian Chemical Co., Ltd. Lutensol T07 (ethoxylates of matt iso-C13-alcohol) HLB - 12, Lutensol T05 (ethoxylates of matt iso-C13-alcohol) HLB 10.5 and Dehydol LS3N (fatty alcohol C12-C14-ethoxylated) HLB - 12, BASF Corp .
    Ethoquad C / 25 (coconut alkyl methyl [olyoxytes (15)] ammonium chloride) HLB 30, AkzoNobel 5 Chemicals Ltd.
    Mash S2 (ethoxy (2) stearyl ether) HLB 4.9, Croda Corp.
    Isooctyltrimethoxysilane, n-octadecyltrimethoxysilane and n-dodecyltrimethoxysilane, ABCR GmbH & Co KG. n-propyltrimethoxysilane, Alfa Aesar GmbH & Co KG. 10 Digital dispersing machine IKA ultra turrax T 25 with dispersing element S25 N-25G / 1713300, manufactured by IKA-Werke GmbH 8z Co KG. Oven Fermax TS 8136. pH feeder Phenomenal pH 1000H, VWR in LLC.
    Standard methods used Determination of resistance to surface watering (spray value) of fabrics: European standard EN 24 920 (ISO 4920: 1981). Principle: A specified amount of water is sprayed on a textile sample mounted on a ring. The sample is arranged at an angle of 0 in relation to the nozzle. The center of the standardized nozzle is arranged at a given distance across the center of the sample. A given amount of water is filled into a container arranged above the nozzle and in connection therewith. Strilvardet is determined visually and / or photographically. The stepwise spray value scale for ISO 1-5 corresponds to 50-100% of the sample having withstood irrigation.
    The scale correlation is all 100% (ISO 5), 97.5% (ISO -5), 92.5% (ISO 4), 90% (ISO +4), 87.5% (ISO -4), 82.5 % (ISO +3), 80% (ISO 3), 77.5% (ISO -3), 72.5% (ISO +2), 70% (ISO 2), 66.67% (ISO -2) , 56.67% (ISO +1), 50% (ISO 1) of the sample has resisted irrigation.
    (See Fig. 1 for an illustrative example of ISO 5-1.) The fabrics were rinsed in a water rinsing program in a washing machine for evaluation. The fabrics were dried in a preheated Fermaks TS 8136 oven at 150 ° C for 5 minutes.
    The water-repellent properties of the treated fabric before and after machine washing with an aqueous solution of a detergent with IEC reference B were evaluated (wash temperature 18 40 ° C / time about 90 minutes) by testing the fabric with the standardized tests SS-EN 24 920.
    These examples are intended to illustrate the invention to those skilled in the art and should not be construed as limiting the scope of the invention as claimed. All percentages in these examples are by weight unless otherwise indicated.
    General method for emulsion preparations used in experiments Emulsions with different pH values In a baker, 1% by weight of emulsifier, 5% by weight of hydrophobing agent and "water a" were introduced 50% by weight of the total amount of emulsification solution, and the mixture was homogenized at 10,000 rpm for 15 minutes. of an IKA ultra turrax T 25 digital dispersing machine with dispersing element S25 N-25G / 1713300 (manufactured by IKA-Werke GmbH & Co. KG). Then, the specified weight percent acid catalyst was dissolved in a certain 15 weight percent "water b" (see Table 1) and added while homogenizing in the hydrophobing agent mixture prepared above. The mixture was homogenized at 10,000 rpm for 15 minutes to give the desired emulsion.
    The amount of "water b" is calculated according to the amount of acid liar determined. The amount of acid can vary (pH mats and must be pH 1.9-4). The amount of "water b" is added after acid is added to reach 100% by weight of the total weight of the emulsion (greater amount of acid, less added amount of "water b").
    Where appropriate, the emulsion was neutralized by mixing the specified weight percent sodium bicarbonate according to Table 1.
    Examples of the invention will now be shown below together with comparative examples: The examples according to the invention below are intended to be exemplary and harmless, not limiting of scope.
    Table 1. Preparation of formulations with different pH values. 2 g Tegosoft PC 41 (1% by weight), 7 g malic acid (3.5% by weight), 10 g KH580 (5% by weight), "water a" = 100 g, "water b" = 81 g. PH: 2.137. (Total amount of emulsified liquid preparation = 200 g) 2 g Tegosoft PC 41 (1% by weight), 2.5 g malic acid (1.25% by weight), 10 g KH580 (5% by weight), H 2 O = loo g, H 2 O b = 85 .5 g. PH: 2,359 (Total amount of emulsified liquid preparation = 200 g) 19 Comparative ex 3: 2 g Tegosoft PC 41 (1% by weight); no acid, 10 g KH580 (5% by weight), H 2 O a = 100 g, H 2 O b = 88 g. pH: 4.222 (Total amount of emulsified liquid preparation = 200 g) Ex 4: 2 g Tegosoft PC 41 (1% by weight), 12 g malic acid (6% by weight), 10 g KH580 (5% by weight), H 2 O a = 100 g, H 2 O b = 76 g. pH: 1.96 (Total amount of emulsified liquid preparation = 200 g) Comparative ex 5: 2 g Tegosoft PC 41 (1% by weight), 7 g of malic acid (3.5% by weight), 10 g of KH580 (5% by weight), H 2 O a = 100 g, H 2 O b = 81 g. PH: 2.137 after which 6, g NaHCO 3 was added to reach pH: 4,782. (Total amount of emulsified liquid preparation = 200 g) Comparative ex 6: 2 g Tegosoft PC 41 (1% by weight), 7 g malic acid (3.5% by weight), 10 g KH580 (5% by weight), H 2 O a = 100 g, H 2 O b = 81 g. PH: 2.137 after which 8, g NaHCO3 was added to reach pH: 7.022. (Total amount of emulsified liquid preparation = 200 g) The pH values were measured with the pH feeder phenomenal pH 1000H (VVVR in LLC) at a temperature of 23 ° C and a relative humidity RH of 50%. The pH feeder was two point calibrated (pH 4 and 7) for the formulations. Examples 1-4 are according to the invention.
    The emulsions were applied to 20 x cm pieces of polyester / cotton fabric 65/35 (white satin fabric, 187 g / m2) by a process comprising immersion in emulsion, compression (water uptake about 80% of the dry fabric), heating and rinsing in water; see Table 2. The water repellency form was determined according to SS-EN 24 920; see Table 3.
    Table 2. Water uptake in textiles (with emulsions described in Table 1) EmulsionWeight of untreated fabric (g) Weight of wet fabric (g) (water uptake%) 6.722 12.01 (78.7%) 6.832 12.20 (78.6 %) 6.857 11.88 (73.3%) 7.298 13.35 (82.9%) Comparative ex 5: 6.984 12.63 (80.8%) Comparative ex 6: 7.916 14.53 (83.6%) According to the results in Table 3, it is clear that all the best hydrophobing effect is achieved with emulsions with a pH set or pH below 4.3. However, the use of the proposed pH (pH lower than 2) results in some discoloration of the fabric, which also falls when the pH value is too high (pH higher than 4), whereby the latter also results in a sharp spray value, ie. proportion of the sample that has stalled against irrigation.
    Table 3. Textiles treated with emulsions according to Tables 1 and 2 according to the application method according to the invention Table 3 shows different ISO 4920 spray values (5-1) after washing 1-5.
    TYg Emulsion fir; 1311 Fore skolj- fling H20- slcolj- ning Wash 1 Wash 2 Wash 3 Wash 4 Wash Comments on treated fabrics White, pe / cotton 65/35, satin wrap Ex 1 pH: 2,137 1 +4 +4 4 +3 (4) + 3 (+4) Discoloration: No very faint some strong discoloration White, pe / cotton 65/35, satin fabric Ex 2 pH: 2,359 1 +4 4 +4 4 3 (+ 3 / -4) 3 (-4) Discoloration: No very faint some strong discoloration White, pe / cotton 65/35, satin wrap Comparing ex 3 pH: 4,222 o 0 Discoloration: No very faint some strong discoloration White, pe / cotton 65/35, satin wav Ex 4 pH: 1.96 1 +4 -4 -3 (+3) -3 (+ 3 / -4) Discoloration: No very faint some strong discoloration White, pe / cotton 65/35, satin wrap Comparative ex pH: 4.782 0-1 1 - - - - Discoloration: No very faint some strong discolouration White, pe / cotton 65/35, satin wrap Comparing ex 6 pH: 7,022 0-1 3 / + 3 2 +1 +1 1 (1) 1 (+1) Discoloration: None very weak some strong discoloration The value in parentheses indicates the scatter value after ironing. Parameters: Curing 5 min / 150 ° C; wash 40 ° C / 90 min; drying mean washes 150 ° C / 15 min. The omitted value (-) is due to 10 pa Odor legal strilvarden. Table 3 shows experimental data for the emulsions described in Table 2.
    Table 4. Different emulsifiers 21 Emulsions (Table 4) were prepared according to the procedure described in Example 1 and used on the same sail to treat 20 x cm pieces of polyester / cotton fabric 65/35; see Table 5. Ex 7, 8 and 1 are all examples of the present invention.
    Table 4. Examples of emulsifying solution according to the invention with different emulsifiers.
    Lutensol T07 (0.4 wt%), Lutensol T05 (0.6 wt%), Malic acid (3.5 wt%), KH580 (5 wt%) and H 2 O (90.5 wt%) (water a 50 wt%, water b 40.5 weight percent). "water b". (100-0.4-0.6-3.5-5 = 90.5 wt% H 2 O) Dehydol LS3N (0.1 wt%), Etoquad C / 25 (0.5 wt%), Brij S2 (0.5 wt% ), malic acid (3.5% by weight), KH58o (5% by weight) and H2O (90.4% by weight) (water a 50% by weight, water b 40.4% by weight). "water b". (100-0.1-0.5-0.5-3.5-5 = 90.4% by weight H 2 O) Ex 1: Tegosoft PC 41 (1% by weight), malic acid (3.5% by weight), KH580 (5% by weight ) and H 2 O (90.5% by weight) (water a 50% by weight, water b 40.5% by weight). "water b". (90.5% by weight H 2 O) Table 5. Water uptake in textiles (with emulsions described in Table 4) Emulsion Weight of untreated fabric (g) Weight of wet fabric (g) (water uptake%) 6,97312,48 (79%) 7,112 .88 (80.5%) 1: 7.103 12.48 (75.7%) The results in Table 6 (with the emulsions from Table 4) show that the choice of emulsifier plays a minor role in the result of the hydrophobicity of the treated fabric and its durability on the fabric when it undergoes machine washing using detergent at 40 ° C.
    Table 6. Textile treated with emulsions according to Table 4 and according to the application method according to the invention Table 6 shows different ISO 4920 spray values (5-1) after washing 1-5. 22 CLOTH Emulsion For rinsing H20 rinsing. mng 'Dry 1' Dry 2 TATOU 3 'Dry 4' Dry Parameters White, pe / cotton 65/35, satin wrap 7 o +4 - + 4 Hardening 5 min / 150 ° C Wash 40 ° C / 90 min Drying 150 ° C / 5 min White, pe / cotton 65/35, satin fabric 8 2 3 + 47 - Hardening 5 min / 150 ° C Wash 40 ° C / 90 min Drying 150 ° C / 5 min White, pe / cotton 65/35 , satin wrap 1 1 ---- Curing 5 min / 150 ° C Wash 40 ° C / 90 min Drying 150 ° C / 5 min Table 7. Temperature and different curing times Emulsion 1 (Tegosoft PC 41 (in weight percent), malic acid (3 , 5% by weight), KH580 (5% by weight) and F120 resid.) Were used to treat polyester / cotton fabric 65 / (Table 7) at different temperatures and with different curing times. The results are summarized in Table 8 and show that longer curing time improves the durability and hydrophobicity of the treated fabric. It will be apparent to those skilled in the art that low curing temperature requires long curing time and that high curing temperature requires short curing time; see Table 7, 8 and Fig. 1.
    Table 7. Water uptake in textiles (with emulsions described in Table 1, ex 1) with comparison of the effect of different curing times for the same emulsion Emulsion Weight of Weight of water Curing time / Temperature untreated fabric (g) tyglgl (water uptake%) See ex 1, Table 1 7.229 12.98 (79.6%) min / 100 ° C See ex 1, Table 1 7.284 13 (78.5%) 5 min / 100 ° C Table 8. Textiles treated with emulsions according to Table 1 and 7 according to the application method according to the invention 23 Table 8 shows different ISO 4920 results (5-1) after washing 1-5.
    FABRIC Emulsion For rinsing H20 rinsing Wash 1 Wash 2 Wash 3 Wash 4 Wash Parameters for application method White, pe / cotton 65/35, satin wrap 1 0 +4 - + 4 / - + 4 + 3 / - 4 + 3 / -4 Hardening 20 min / 100 ° C Wash 40 ° C / 90 min Drying 150 ° C / 5 min White, pe / cotton 65/35, satin wrap 1 0 +2/3 3 +3 + 3 / - 4 +3 3 Curing 5 min / 100 ° C Wash zio ° C / 90 min Drying 150 ° C / 5 min Table 9. Inhalation of alkoxysilanes with chains of different lengths 5 To assess the effectiveness of the hydrophobing agent, several emulsions were prepared according to the procedure described in Example 1, with different alkyl chain lengths on the alkoxysilane component; see Table 9. They have then been used on the same salt as previously described to hydrophobize polyester / cotton fabric 65/35. It is clear that longer alkyl chain on the alkoxysilane promotes lasting hydrophobicity of the treated fabric. 113The results are summarized in Tables Da and 11.
    Table 9. Emulsions containing different types of alkylalkoxysilanes.
    Comparative Example 9: Tegosoft PC 41 (1% by weight), malic acid (3.5% by weight), isooctyltrimethoxysilane (5% by weight) and H 2 O residue. (C8) Ex 10: Tegosoft PC 41 (1% by weight), malic acid (3.5% by weight), n-octadecyltrimethoxysilane (5% by weight) and H 2 O residue. (C18) Tegosoft PC 41 (1% by weight), malic acid (3.5% by weight), ndodecyltrimethoxysilane (5% by weight) and H 2 O residue. (C12) Comparative Example 12: Tegosoft PC 41 (1% by weight), malic acid (3.5% by weight), n-propyltrimethoxysilane (5% by weight) and H 2 O residue. C (3) Ex 1: Tegosoft PC 41 (1% by weight), malic acid (3.5% by weight), KH580 (5% by weight) and H 2 O residue. (C16) Ex Da, 11 and 1 are according to the invention. Ex 9 and 12 dr comparative examples.
    Table 10. Water uptake in textiles (with emulsions described in Table 9) Emulsion Weight of untreated fabric (g) Weight of wet fabric (g) (water uptake%) 7.0912.7 (79%) 7.26813 (78.9% ) 24 Ex ii: 7.163 12.6 (75.9%) Ex 12: 7.206 12.8 (77.6%) Ex 1: 7.103 12.48 (75.7%) Table it. Textiles treated with emulsions according to Table 9 and two according to the application method according to the invention Table 11 shows different ISO 4920 spray values (5-1) after washing 1-5.
    FABRIC Emulsion For rinsing H20 rinsing Wash 1 'FAratt 2 Wash 3 Wash 4 Wash Parameters for application method White, pe / cotton 65/35, satin wrap 9 1 1 1 - - - Hardening 5 min / 150 ° C Wash 40 ° C / 90 min Drying 150 ° C / 5 min White, pe / cotton 65/35, satin fabric 1 -5 / + 4 + 47 - Hardening 5 min / 150 ° C Wash 40 ° C / 90 min Drying 150 ° C / 5 min White, pe / cotton 65/35, satin wrap 11 1 1 1 - - - - Hardening 5 min / 150 ° C Wash 40 ° C / 90 min Drying 150 ° C / 5 min White, pe / cotton 65 / 35, satin fabric 12 0 1 1 - - - Hardening 5 min / 150 ° C Wash 40 ° C / 90 min Drying 150 ° C / 5 min White, pe / cotton 65/35, satin fabric 1 1 ---- Hardening 5 min / 150 ° C Wash 40 ° C / 90 min Drying 150 ° C / 5 min Use of different types of acids and emulsion results on different fabrics Emulsions containing acids other than malic acid and varying amounts of emulsifier and silane were prepared by the same procedure as described in Example 1; see Table 13. 20 x 20 cm pieces of different kinds of fabric were exposed to emulsions according to previous descriptions, hardened, rinsed, washed and sprinkled; see Table 12-15 for a summary of the results.
    Table 12.
    FABRIC Emulsion For rinsing H20 rinsing TATOU 1 Wash 2 TATOU 3 Wash 4 'Wash Parameters for application method White, pe / cotton 65/35, satin wrap Tegosoft PC 41 (1% by weight), acetic acid (20% by weight ), KH580 (5% by weight) and FLO residue. o 2 2 - - - - Hardening 5 min / 150 ° C Wash 40 ° C / go min Drying 15 () ° C / 5 min Table 13. Emulsions containing different types of alkyl alkoxysilanes Tegosoft PC 41 (0.7% by weight), malic acid ( 3.5% by weight), hexadecyltrimethoxysilane (5% by weight) and H 2 O (90.8% by weight) (water a% by weight, water b 40.8% by weight).
    Tegosoft PC 41% by weight), citric acid (2.5% by weight), hexadecyltrimethoxysilane (5% by weight) and H 2 O (91.5% by weight) (water a 50% by weight, water b 41.5% by weight).
    Ex 15: Tegosoft PC 41% by weight), maleic acid (1.5% by weight), hexadecyltrimethoxysilane (5% by weight) and H 2 O (92.5% by weight) (water a 50% by weight, water b 42.5% by weight).
    Tegosoft PC 41% by weight), glyoxylic acid (5% by weight), hexadecyltrimethoxysilane (7% by weight) and H 2 O (87% by weight) (water a% by weight, water b 37% by weight).
    Tegosoft PC 41% by weight), malic acid (3.5% by weight), hexadecyltrimethoxysilane (7% by weight) and H 2 O (88.5% by weight) (water a 50% by weight, water b 38.5% by weight).
    Tegosoft PC 41% by weight), pyruvic acid (1.75% by weight), hexadecyltrimethoxysilane (3% by weight) and H 2 O (93.75% by weight) (water a 50% by weight, water b 43.75% by weight).
    Tegosoft PC 41% by weight), citric acid (2.5% by weight), hexadecyltrimethoxysilane (7% by weight) and H 2 O (89.5% by weight) (water a 50% by weight, water b 39.5% by weight).
    Ex 20: Tegosoft PC 41% by weight), malic acid (5% by weight), hexadecyltrimethoxysilane (5% by weight) and H 2 O (89% by weight) (water a 50% by weight, water b 39% by weight). 26 Table 14.
    Fabric Emulsion (see Tabe1113 and 9) Pre-rinsing H20 rinsing 'Wet 1 Wash Parameters for application method 100% CO Satin 132 g / m2 white Ex 13 1 - + 3 Hardening min / 1 ° C Wash ° C / 90 min Drying 1 ° C / 5 min 100% CO Satin 132 g / m2 white Ex 14 1 4 -3 Hardening min / 1 ° C Wash ° C / 90 min Drying 1 ° C / 5 min 100% CO Satin 132 g / m2 white Ex 3 - -3 Hardening min / 1 ° C Wash ° C / 90 min Drying 1 ° C / 5 min Spandex / nylon 10/90 black Ex 16 1 Hardening min / 1 ° C Wash ° C / 90 min Drying 1 ° C / 5 min Spandex / nylon 10/90 black Ex 17 +2 +4 -Hardening min / 1 ° C Wash ° C / 90 min Drying 1 ° C / min Spandex / nylon 10/90 black Ex 18 +2 - + 4 3 Hardening min / 1 ° C Dry 4o ° C / 90 min Drying 1 ° C / 5 min Spandex / nylon 10/90 black Ex 19 1 -4 -4 4 Hardening min / 1 ° C Wash ° C / 90 min Drying 1 ° C / 5 min Nylon / spandex 80 / white Ex 17 1 4 4- 4 Hardening min / 1 ° C Wash 4o ° C / 90 min Drying 1 ° C / 5 min Nylon / spandex 80 / white Ex 19 1 4 4+ 4+ Hardening 5 min / 1 ° C Wash ° C / 90 min Drying 1 ° C / 5 min 100% p olyester white With cloth handle Ex 4 Hardening: 1 ° C / 5 min Washing: ° C / 90 min Drying: 1 ° C / 5 min 100% nylon brown Ex 1 1 4 Hardening: 1 ° C / 4.5 min Washing: ° C / 90 min Drying: 1 ° C / 5 min 100% cotton white satin 145 g / m2 Ex 1 +3 Hardening: 1 ° C / 5 min Wash: ° C / 90 min Drying: 1 ° C / 5 min Table Table 15 illustrates the treatment (with the emulsion from Ex 1) of recovered polyester fabric 5 with emulsion 1 and subsequent washing (20 times) with spray test results. 27 FABRIC Emulsion For ski: ilk ning 1120- rinsing Wash 1 Wash Wash Parameters for application method Recycled polyester fabric white Ex 1% KH58o 3.5% malic acid 1% TegoSoft 41 in H + 1 +4 4 4 -4 Curing: 150 ° C / 5 min Washing: 40 ° C / 90 min Drying: 150 ° C / 5 min IndustryIlt relevant application parameters In a scaled-up experiment (Fig. 2) emulsion 1, (containing Tegosoft PC 41 (i. 5% by weight) was applied ); malic acid (3.5% by weight); KH580 (7.5% by weight); ("water a" 50 w / w% and "water b" (40.5% by weight)) on polyester / cotton fabric 65/35 (white satin fabric , 187 g / m2) by means of a stuffing machine, clamping frame and drying / hardening oven The fabric roll is then mounted on a jet dyeing machine and rinsed with water (18 min at 7 ° C and drying at 170 ° C for 4 min), after which it was dried in a tension frame connected to a drying oven.
    The parameters used were water uptake: 50%, curing time and temperature 2 min / 170 ° C and drying time and temperature after rinsing: 2 minutes / 170 ° C.
    Fig. 2 summarizes the resulting ISO 4920 spray values Flat test A flat test is challenged based on a test method - see below - which includes flattening with yin, coffee and ketchup. The following flaking water shoes were used: instant coffee (4 g Nescafe Luxury in 100 ml boiling water), rat yin (12.5% alcohol), Heinz ketchup and narrow dirty snot from the curbs at motorways in Stockholm.
    The materials used were an untreated white satin web (65% polyester / 35% cotton, 187 g / m2) and the same web that had been treated with the emulsion described below in a full scale stuffing / curing process (50% water uptake, drying / curing at 170 ° C 28 for 2 minutes, separation in water in a jet engine for 18 minutes at 7 ° C and drying at 170 ° C for 4 minutes; see Fig. 2).
    Tegosoft PC 41 (1% by weight), malic acid (3.5% by weight), KH580 (hexadecyltrimethoxysilane) (7.5% by weight), water 88% by weight.
    Both the untreated and the treated yawn were conditioned for 24 hours at 23 ° C and 50% relative humidity. Two bottles of 5 ml of each liquid and 40 mm Heinz ketchup were added to both the untreated and the treated yawn. After 1 hour, one of each flake was removed with a damp cloth. After 24 hours, the second flake was deposited in the same way. to The wavers were allowed to dry for 24 hours at room temperature, and then the flakes were judged by placing a white paper under the wavers, and the judging was done according to the following scale.
    Table 16: Table 17: The results were as follows: Coffee ih Coffee 24h Rodvin ih Rodvin 24h Ketchup ih Ketchup 24h Dirty silo 1 h Dirty silo 24 h Untreated vav 1 1 1 1 2 2 1 1 Treated vav 4 3 3 4 4 4 As it seems the treated yaw has an average of 4, o, while the result of the untreated yaw is 1.3. Thus, the web that has been treated with the emulsion of the invention is more repellent to aqueous flakes than the untreated web.
    Judging mat 1 Strong flat 2 Clear flat 3 Visible flat 4 Less visible flat 5 No visible flat
    权利要求:
    Claims (27)
    [1] 1. An application method of enhancing the water repellence of a textile and/ or enhancing a textiles ability to repel water soluble dirt, comprising the steps of: a) Applying an emulsified liquid composition on a textile, wherein said emulsified liquid composition consists of:-Water -Alkylalkoxysilane with said alkyl chain having a length of 10-30 carbons or carbon atoms higher than 12 but equal to or less than 18 -At least one emulsifier, surfactant, thickener and/ or stabilizer - a water soluble acid catalyst and -unavoidable impurities b) Optionally adjusting amount of formulation applied on textile c) Drying the treated textile until dry d) Curing the treated textile at a temperature of between 1o0-200°C. e) Optionally removing the non-reacted formulation residue from the treated textile by washing with water and optionally redrying the treated textile
    [2] 2. An application method according to claim 1 wherein said emulsified liquid composition has a pH less than 4.5 or between 1.8-4.3 or between 1.9-4.2.
    [3] 3. An application method according to any of the preceding claims wherein said way ofapplying said emulsified liquid composition is selected from soaking, impregnating, padding,dipping, spraying, brushing, coating, rolling, foam-application, impregnation, vacuum- pressure impregnation process or by other means applying said liquid composition.
    [4] 4. An application method according to any of the preceding claims wherein adjusting amountof formulation applied on textile is made using an industrial padding machine/foulard toapply the emulsion to the substrate and to control the wetuptake by adjusting the nippressure or pneumatic load adjustment of the rolls and wherein the wetuptake is 3o-1oo%. w/ w % in relation to untreated textile . 32
    [5] 5. An application method according to any of the preceding claims wherein saidalkylalkoxysilane in said emulsified liquid composition is added in a concentration of 2-10 w/ w % in relation to the total amount of emulsified solution.
    [6] 6. An application method according to any of the preceding claims wherein said acid catalystin said emulsified liquid composition is at a concentration of < 8 w/w % or between 1-7 w/w % in relation to the total amount emulsified solution.
    [7] 7. An application method according to any of the preceding claims wherein said emulsifier ora combination of said emulsifiers in said emulsified liquid composition is at concentration of < 2w/w % or between 0.9-1.1 w/w % in relation to the total amount emulsified solution.
    [8] 8. An application method for according to any of the preceding claims wherein said watercontent in said emulsified liquid composition is 80-97.5 w/ w %or 87-94 w/ w % in relation to the total amount emulsified solution.
    [9] 9. An application method according to claims 1-7 wherein said water content in saidemulsified liquid composition is lower than 80 w/ w % or between 20-80 w/w % in relationto the total amount emulsified solution and wherein additional amount of water may be added before use of said in said application method.
    [10] 10. An application method according to any of the preceding claims wherein said alkylalkoxysilane wherein said alkoxy groups is selected from acetoxy, methoxy, etoxy, n- propoxy, isopropoxy or n-butoxy, isoboxy or tert butoxy.
    [11] 11. An application method according to any of the preceding claims wherein saidalkylalkoxysilane in said emulsified liquid composition is selected from the group having analkyl chain with a number of carbon atoms higher than 12 but equal to or less than 18 carbons.
    [12] 12. An application method according to any of the preceding claims wherein thealkylalkoxysilane is selected from n-, iso or mixtures thereof of hexadecyltrimethoxysilane and / or octadecyltrimethoxy silanes.
    [13] 13. An application method according to any of the preceding claims wherein the alkyl groupof said alkylalkoxysilane is a linear, branched or cyclic carbon chain or a straight and saturated carbon chain.
    [14] 14. An application method according to any of the preceding claims wherein saidalkylalkoxysilane is selected from n- or iso configured hexadecyl trimethoxysilane, hexadecyl triethoxysilane or n-octadecyl trimethoxy silanes or mixtures thereof. 33
    [15] 15. An application method according to any of the preceding claims wherein said emulsified liquid composition has a pKa of less than 3.9 or between 1.9-3.9.
    [16] 16. An application method according to any of the preceding claims wherein said watersoluble acid catalysts in said emulsified liquid composition has a pKa of 6 or less, or pKa -14 -4
    [17] 17. An application method according to any of the preceding claims wherein said emulsifier in said emulsified liquid composition is a non-ionic or an ionic emulsifier.
    [18] 18. An application method according to any of the preceding claims wherein the acid catalyst is a Lewis- or a Bronstedt acid.
    [19] 19. An application method according to any of the preceding claims wherein the acid catalyst is an organic acid.
    [20] 20. An application method according to any of the preceding claims wherein the acid catalystis chosen from any of para-toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid,malic acid, maleic acid, glyoxylic acid, citric acid, formic acid, pyruvic acid, tartaric acid,phtalic acid, acetylsalicylic acid, salicylic acid, lactic acid, dihydroxy fumaric acid, mandelic acid, malonic acid, glycolic acid, acetic acid, hydrochloric acid, sulfuric acid and oxalic acid.
    [21] 21. An application method for rendering a textile durable water repellent and /or watersoluble dirt repellent according to any of the preceding claims wherein drying the treated textile is performed at a temperature of between 15-180 °C until dry.
    [22] 22. An application method for rendering a textile durable water repellent and /or watersoluble dirt repellent according to any of the preceding claims wherein curing the treatedtextile is performed at a temperature of between 130-18o°C or between 150-180 °C or between 15o-17o °C.
    [23] 23. An emulsified liquid composition used in the application method and described in claims 1-22.
    [24] 24. A textile which is durable water repellent and water soluble dirt repellant treated using the application method described in claims 1-22.
    [25] 25. A textile according to claim 24 wherein the textile has an ISO 4920 spray test result of ISO 3 or higher after five or more washes of said textile.
    [26] 26. Use of the emulsified liquid composition according to claim 23 according to the application method in claims 1-22 to make a textile durable water resistance 34
    [27] 27. Use of a emulsified liquid composition according to claim 23 according to the applicationmethod in claims 1-22 to make a textile durable dirt repellant towards water soluble dirt, for example wine, ketchup, coffee or soil.
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    同族专利:
    公开号 | 公开日
    CA2905219A1|2014-09-18|
    CN105164332A|2015-12-16|
    CA2905219C|2021-03-30|
    JP2016517478A|2016-06-16|
    WO2014139931A3|2014-11-06|
    EP2971326B1|2018-02-28|
    SE537807C2|2015-10-20|
    US20160024707A1|2016-01-28|
    EP2971326A2|2016-01-20|
    KR20150143477A|2015-12-23|
    ES2668315T3|2018-05-17|
    TWI616488B|2018-03-01|
    US10465336B2|2019-11-05|
    CN105164332B|2018-01-05|
    WO2014139931A2|2014-09-18|
    JP6439215B2|2018-12-19|
    RU2663427C2|2018-08-06|
    TW201504348A|2015-02-01|
    RU2015138744A|2017-04-20|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE1350303A|SE537807C2|2013-03-13|2013-03-13|Method and formulation for obtaining fabrics that are water repellent and or repellent for water soluble dirt|SE1350303A| SE537807C2|2013-03-13|2013-03-13|Method and formulation for obtaining fabrics that are water repellent and or repellent for water soluble dirt|
    TW103107564A| TWI616488B|2013-03-13|2014-03-06|Method and composition obtaining water-repellent and or water soluble dirt repellent textiles|
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    RU2015138744A| RU2663427C2|2013-03-13|2014-03-10|Method and composition for obtaining textiles showing water-repellency and repellency against water soluble dirt|
    EP14708574.0A| EP2971326B1|2013-03-13|2014-03-10|Method and composition obtaining textiles showing water-repellency and repellency against water soluble dirt|
    CA2905219A| CA2905219C|2013-03-13|2014-03-10|Method and composition obtaining water-repellent and or water soluble dirt repellent textiles|
    ES14708574.0T| ES2668315T3|2013-03-13|2014-03-10|Method and composition to obtain textiles that have water repellency and water soluble dirt repellency|
    US14/774,743| US10465336B2|2013-03-13|2014-03-10|Method and composition obtaining textiles showing water-repellency and repellency against water soluble dirt|
    CN201480022591.0A| CN105164332B|2013-03-13|2014-03-10|Obtain repellency and/or the method and composition of water-soluble dirt repellency textile|
    KR1020157028657A| KR20150143477A|2013-03-13|2014-03-10|Method and composition obtaining textiles showing water-repellency and repellency against water soluble dirt|
    PCT/EP2014/054552| WO2014139931A2|2013-03-13|2014-03-10|Method and composition obtaining water-repellent and or water soluble dirt repellent textiles|
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