TW201215738A - Process for the coating of textiles - Google Patents

Abstract

The present invention relates to a process for the production of coated textiles in which a textile substrate is firstly brought into contact with an aqueous dispersion comprising at least one inorganic salt and at least one modified cellulose.

Description

201215738 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a coated fabric, wherein the fabric substrate and an aqueous dispersion comprising at least one inorganic salt and at least one modified cellulose are first contact. [Prior Art] It has been known to coat fabrics with plastic to produce synthetic leather for a period of time. Synthetic leather is, for example, used in particular as a shoe upper material, in clothing, as a bag making material or in the interior decoration industry. The main coating material used herein except for other plastics such as PVC is polyurethane. The principle of coating fabrics with polyurethanes is generally described in W. SchrGer, Textilveredlung [Textile Finishing] 1987, 22(12), 459-467. A description of the coagulation method can be found in "New Materials Permeable to Water Vapor", Harro Traubel, Springer Verlag, Berlin, Heidelberg, New York, 1999, ISBN 3-540-64946-8, pages 42-63. The main methods used in the manufacture of synthetic leather are direct coating, transfer coating (indirect coating) and coacervation (wet). The coating of the transfer method is applied to the temporary support as compared to the direct method, followed by a lamination step in which the film is bonded to the fabric substrate and separated by a temporary support (release paper). The transfer method is preferably a fabric substrate which does not allow high tensile stress during coating or a tissue which is not particularly dense. 〇3 201215738 In the coacervation method, usually containing a polyamine phthalate The fabric substrate is coated with a solution in DMF. In the second step, the coated substrate is passed through a DMF/water bath in which the proportion of water is gradually increased. Here, the polyaminophthalic acid ester precipitates and forms a microporous film. Here, the following facts are utilized: DMF and water have excellent mutual solubility and DMF and water are used as solvent/non-solvent pairs of polyamine phthalates. High quality synthetic leathers are particularly coated with agglomerated polyurethane coatings because of their relatively good breathing activity and leather feel. The basic principle of the coacervation method is based on the use of a suitable solvent/non-solvent pair of polyamine phthalate. The greatest advantage of the coacervation method is the availability of microporous, breathable synthetic leather with excellent leather feel. Examples are, for example, the synthetic leather brands Clarino® and Alcantara®. The disadvantage of the coacervation method is that a large amount of DMF must be used as an organic solvent. In order to minimize the exposure of employees to dmf release during manufacturing, additional design measures must be taken, which is a significant increase compared to simpler process representatives. In addition, a large amount of DMF/water mixture must be discarded or disposed of. This is difficult because water and DMF form an azeotrope and therefore can only be separated by steaming. SUMMARY OF THE INVENTION It is therefore an object of the present invention to develop a method of coating a textile substrate that does not require the use of a toxicologically unacceptable solvent " such as, for example, DMF, which still has good properties such as, for example, Good coated fabric.啊休4 201215738 This object has been achieved by a method of making a coated fabric comprising at least the following steps: a) subjecting the textile substrate to an aqueous dispersion comprising at least one inorganic salt and at least one modified cellulose A contacting, b) contacting the textile substrate with an aqueous dispersion B comprising a polyamine phthalate, and c) precipitating the polyurethane in or on the textile substrate. In step a), the textile substrate is contacted with an aqueous solution comprising at least one inorganic salt and at least one modified cellulose. The inorganic salt is preferably one selected from the group consisting of alkali metal salts and alkaline earth metal salts. The inorganic salt is preferably selected from the group consisting of alkali metal halides, alkali metal phosphates, alkali metal nitrates, alkali metal sulfates, alkali metal carbonates, alkali metal hydrogencarbonates, alkaline earth metal teeth, alkaline earth metal nitrates, a salt of the group consisting of alkaline earth metal phosphates, alkaline earth metal sulfates, alkaline earth metal carbonates and alkaline earth metal hydrogencarbonates. The inorganic salt is particularly excellent in sodium, potassium carbonate, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, gasification lock, sulfuric acid town, nitric acid town, gasification mother, nitric acid Word or sulfuric acid word. The inorganic salt is more preferably a nitrate mother, a magnesium silicate, a chlorinated I bow or magnesium chloride. The inorganic salt is preferably in an amount of from 0.1 to 1% by weight based on the total amount of the dispersion A, particularly preferably from 0.5 to 15% by weight, and most preferably from 0.5 to 1% by weight. The amount is present in the dispersion a. The chemically modified cellulose is preferably selected from the group consisting of alkylated cellulose, hydroxyalkylated cellulose, and carboxyalkylated cellulose of 201215738. The chemically modified cellulose is preferably selected from the group consisting of sulfhydryl cellulose, ethyl cellulose, propyl cellulose, hydroxy decyl cellulose, hydroxyethyl ketone, hydroxymethyl cellulose, hydroxypropyl fluorenyl fiber. a compound of the group consisting of mercapto, mercaptomethylcellulose, carboxyethylcellulose, and carboxypropylcellulose. The chemically modified cellulose is particularly excellent in mercapto cellulose or ethyl cellulose. The modified cellulose is preferably from 1 to 5 parts by weight based on the total amount of the dispersion A. /. The amount is particularly preferably in an amount of from 〇〇 pprn to 3% by weight, and is particularly preferably present in the dispersion in an amount of from 400 ppm to 1.5% by weight. Preferably, the fabric substrate is contacted with the aqueous dispersion A for 2 to 4 minutes at room temperature, particularly preferably to 2 minutes, and extremely excellent for 2 minutes to minutes. For the purposes of the present invention, the contact is meant to be partially or completely impregnated, preferably completely impregnated in the dispersion or by hand coating, printing and spray coating the dispersion. After contacting the dispersion A, it is preferred to pass the fabric substrate through a wringer composed of two rolls to remove the excess dispersion A. Preferably, the wringer is set in such a manner that the residual amount of the dispersion liquid eight in the textile substrate is per unit area of the substrate before the substrate is brought into contact with the dispersion B containing the polyamine bismuth acid. The weight (liquid absorption amount) is from 6 to 180% by weight, particularly preferably from 70 to 14% by weight, and particularly preferably from 8 to 120% by weight. . Before the fabric substrate can be contacted with the polyurethane-containing phthalate-containing dispersion 6 201215738 liquid B, the fabric substrate is preferably partially dried by air, infrared or hot roller for 2 to 10 minutes, particularly preferably 1 to 5 minute. The polyurethane present in the dispersion B is not particularly limited as long as it is soluble in water, the term "polyaminophthalate" also encompasses polyurethane-polyurea. A review of polyaminophthalate (PUR) dispersions and processes thereof can be found in Rosthauser & Nachtkamp, "Waterborne Polyurethanes, Advances in the Urethane Science and Technology", Vol. 10, pp. 121-162 (1987). Suitable dispersions are also described, for example, in "Kunststoffhandbuch" [Plastics Handbook], Vol. 7, No. 2, Hauser, pages 24 to 26. The composition of dispersion B used in accordance with the invention may be the following: 1) Organic di- and/or polyisocyanates such as, for example, tetradecyl diisocyanate, hexamethylene diisocyanate (HDI), 2-mercaptopentamethylene diisocyanate, 2,2,4-triazole Hexamethylene diisocyanate (THDI), dodecyl fluorenylene diisocyanate, i,4-diisocyanatocyclohexane, 3-isocyanatodecyl-3,3,5-triazine Cyclohexyl isocyanate (isophorone diisocyanate = IPDI), 4,4'-diisocyanatodicyclohexyl oxime (Desmodur® W), 4,4'-diisocyanato-3,3' - Dimercaptodicyclohexyldecane, 4,4'-diisocyanato-2,2-dicyclohexylpropane, 1,4-diisocyanate benzene, 2,4- or 2,6-diisocyanatoguanidine or a mixture of such isomers, 4,4'-, 2,4- or 2,2,-diisocyanatodiphenylnonane or the like a mixture of structures, 4,4-, 2,4'- or 2,2,-diisocyanato-2,2-diphenylpropane p-xylene diisocyanate and 201215738 α,α,α' , a mixture of α'-tetradecyl-m- or-p-dioxadiisocyanate (TMXDI) and a specific compound thereof. For the purpose of modification, a small amount of the above-mentioned diisocyanate trimer or amine group can be used. Formic acid, double squamous, glandular succinic acid S or carbyl dioxime. Very good for MDI, Desmodur W, HDI and / or IPDI. 2) 1 to 8, preferably 1.7 to 3.5 per molecule Permeans and up to 16,000' are preferably multi-base compounds of up to 4000 (average) molecular weight. Consider low molecular weight poly-based compounds as defined in each case, such as, for example, ethylene glycol, 1,2- The reaction product of 1,3-propanediol, iota, 4-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, glycerol, i 肼+2 propylene glycol and having a molecular weight of 35 〇 To 1〇, 〇〇〇, preferably 840 to 3 00 oligomeric or polymeric hydroxy compounds. Relatively high molecular weight hydroxy compounds include hydroxy polyesters, hydroxy polyethers, hydroxy polythioethers, hydroxypolyacetates, hydroxypolycarbonates and/or known per se carboxylic acid chemistry. The hydroxypolyester guanamine, preferably having an average molecular weight of from 350 to 4,000, has a mean molecular weight of from 840 to 3,000. Particularly preferred are hydroxy polycarbonates and/or hydroxy polyethers. When such materials are used, agglomerates having a specific hydrolysis stability can be obtained. 3a) an acid group containing an acid group and/or a salt form and at least one isocyanate reactive group such as an OH or NH2 group ion or a latent ionic hydrophilic agent. Examples are sodium salt of ethylenediamine-β-ethylsulfonic acid (AAS salt solution), dimethylolpropionic acid (DMPA), dihydroxymethylbutyric acid, hydroxytrimethylacetic acid or 1 molar diamine Preferably, it is isophorone diamine and oxime alpha, and is not a 2012 201238738 saturated carboxylic acid, preferably an acrylic acid adduct. 3b) A mono- and/or difunctional polyethylene oxide or a nonionic hydrophilic agent in the form of a polyethylene-propylene oxide alcohol having a molecular weight of from 300 to 5,000. Particularly preferred are monohydroxy-functional ethylene oxide/propylene oxide polyethers having n-butanol as the main unit having 35 to 85% by weight of ethylene oxide units and having a molecular weight of 900 to 2,500. Preferably at least 3% by weight, in particular at least 6% by weight, of nonionic hydrophilic agent content 4) isocyanate group blocking agents, such as, for example, hydrazine (acetone oxime, butanone oxime or cyclohexanone oxime), secondary Amine (diisopropylamine, dicyclohexylamine), ]11-acid heterocyclic substance (3,5-dimethylpyrazole, imidazole, 1,2,4-triazole), CH-acid ester ( Cm-alkylmalonate, acetate) or indoleamine (ε-caprolactam). Particularly preferred are butanone oxime, diisopropylamine and 1,2,4-di-nose. 5) Polyamine as a built-in bond extender. Such materials include, for example, 6) the polyamines discussed. 3a) The diamine-functional hydrophilic agent in question is also suitable as the chain extender to be incorporated. 6) Polyamine crosslinker. While such materials may also employ trifunctional polyamines or polyfunctional polyamines to achieve specific properties, it is preferred to use aliphatic or cycloaliphatic diamines. In general, polyamines containing additional functional groups such as, for example, OH groups can be used. The polyamine crosslinker which is not incorporated into the polymer backbone at normal or slightly elevated ambient temperatures, e.g., 20 to 60 °C, is mixed immediately during the preparation of the reactive dispersion or at subsequent time points. Examples of suitable aliphatic polyamines are ethylenediamine, 1,2- and 1,3-propanediamine, 1,4-tetradecyldiamine, 1,6-hexamethylenediamine, 2,2,4- and 9 201215738 2,4,4·trimethylene hexamethylenediamine isomer mixture, 2—mercaptopentamethylenediamine and diethylenetriamine. In another preferred embodiment, the dispersion contains at least one coagulant in addition to the polyurethane carboxylic acid. The coagulant is a salt or an acid such as an ammonium salt of an organic acid which initiates agglomeration of the polyurethane under specific conditions such as, for example, a specific temperature. Such materials include acid generating chemicals which are substances which are not acids at room temperature but which become acid upon warming. Specific examples of such compounds include ethylene glycol diacetate, ethylene glycol phthalate, diethylene glycol phthalate, triethyl citrate, citric acid monomethyl hydrazine, and organic acid . The coagulant is preferably present in the composition in an amount of from 1 to 1 Torr based on the solid content of the dispersion B. The polyamino phthalate present in the dispersion enthalpy is preferably an anionic and/or nonionic hydrophilized polyurethane which can be obtained by: Α) preparing an isocyanate-functional pre-form from the following Polymer Α 1) organic polyisocyanate Α 2) polymeric polyol having a number average molecular weight of from 400 to 8000 g/mole, preferably from 400 to 6000 g/mole, particularly preferably from 6 to 3000 g/mol. And 15 to 6 'preferably 1.8 to 3, particularly good 1.9 to 2 ΟΗ ΟΗ functionality and A3) as the case may have a molecular weight of 32 to 400 g / mol of the thiol-functional compound and 201215738 4) as the case may be Isocyanate-reactive anion or potential anion and/or optionally non-ionic hydrophilic agent, B) all or part of free NC thiol

Bl) optionally reacts with a compound having a molecular weight of from 32 to 400 g/mol of amino group and/or B2) isocyanate, preferably an amine-functional, anionic or potentially anionic hydrophilic agent ▲ followed by a chain extender The reaction and the resulting prepolymer are dispersed in water after the threshold of step B). Any potential soil present therein is converted into an ionic form by partial or complete reaction with the neutralizing agent. / In order to achieve anionic hydrophilization, it is necessary to carry out A4) and/or B2) using a hydrophilic agent, wherein the hydrophilic agent comprises at least a group reactive with an NCO group, such as an amine group, a hydroxyl group or a thiol group and additionally comprising - C0 (J-ϋ or ρ〇3 as an anion or a fully or partially protonated acid form thereof as a potential anionic group. The anionic polyaminoacetic acid vinegar dispersion (1) has a low hydrophilic anionic group, preferably per 100 g of solids Resin 01 to equivalent. In order to obtain good deposition stability, the number average particle diameter of the tert-amine-based f-ester dispersion by laser correlation spectroscopy is preferably less than 75 G nm. Preferably, the system is less than a nanometer, and the extremely preferred system is less than 400 nanometers. During the preparation of the NCO-functional prepolymer, the component of the octagonal compound is compounded in the NCO group of 201215738 to the compound of the components A2) to A4). NCO reactive groups, such as amine, hydroxyl or thiol groups, 〇 5 to 3.5, preferably 1.2 to 3.0, particularly preferably 1.3 to 2.5 °, the amount of the amine-functional compound of step B) To make the isocyanate-reactive amine groups in these compounds free in the prepolymer The equivalent ratio of the isocyanate groups is from 40 to 150%, preferably from 50 to 125%, particularly preferably from 60 to 120%. Suitable polyisocyanates of component A1) are aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates which are known per se by the skilled artisan having an NCO functionality of 2. Examples of suitable polyisocyanates of this type are 1,4-tert-butyl diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2, 2, 4- and / Or 2,4,4-tridecylhexamethylenediisocyanate, isomeric bis(4,4'-isocyanatocyclohexyl)methane or a mixture thereof with any desired isomer content, 1,4 - cyclohexyl diisocyanate, 1,4-phenylene diisocyanate, 2,4- and/or 2,6-nonylphenylene diisocyanate, 1,5-anaphthyl diisocyanate, 2,2'- And/or 2,4'- and/or 4,4'-diphenylmethane diisocyanate, 1,3- and/or 1,4-bis(2-isocyanatopropan-2-yl)benzene ( TMXDI), 1,3-bis(isocyanatodecyl)benzene (XDI) and 2,6-diisocyanatohexanoic acid vinegar (Isoic acid diisocyanate) containing CrC8-alkyl. In addition to the above polyisocyanate, it is also possible to use a ureidodione, a trimeric isocyanate, an amino phthalate, a ureido phthalate, a biuret, an imine oxadiamine and/or an oxa compound. The lignin structure is proportional to 12 201215738 Modified diisocyanate and unmodified polyisocyanate containing more than 2 NCO groups per molecule, such as 4-isocyanatodecyloctane 1,8-diisocyanate (decane three) Isocyanate) or triphenyldecane 4,4',4''-triisocyanate. Preference is given to polyisocyanates or poly-types of the abovementioned types which contain only aliphatic and/or cycloaliphatic bonded isocyanate groups and have an average NCO functionality of from 2 to 4, preferably from 2 to 2.6, particularly preferably from 2 to 2.4. A mixture of isocyanic acid. Particularly preferred in A1) is 1,6-hexamethylene diisocyanate, isophorone diisocyanate, isomeric bis(4,4'-isocyanatocyclohexyl)decane, and mixtures thereof. A polymer polyol having a number average molecular weight Mn of from 400 to 8000 g/mole, preferably from 400 to 6000 g/mole, and particularly preferably from 600 to 3000 g/mole, is used in A2). Preferably, it has an OH functionality of from 1.5 to 6, particularly preferably from 1.8 to 3, and very preferred from 1.9 to 2.1. Polyester polyols, polyacrylate polyols, polyamine phthalate polyols, polycarbonate polyols, polyether polyols known per se in this type of polymeric polyol based polyamine phthalate coating technology Polyester polyacrylic acid from polyhydric alcohol, polyamino phthalic acid S, polyacrylic acid S, polyhydric alcohol, polyamino phthalate polyester polyol, polyamine phthalate polyether polyol, polyamine Base phthalate polycarbonate polyols and polyester polycarbonate polyols. They can be used in A2) individually or in any desired mixture. Polyester polyols of this type are known per se - and optionally 3 13 201215738 and a polycondensate of a tetrahydric alcohol with a di- and optionally a tricarboxylic acid or a hydroxycarboxylic acid or a lactone. It is also possible to use a corresponding polyglycolic acid for the preparation of a lower alcohol of a polyester or a corresponding polyglycolic acid to replace the free polyphenolic acid. Examples of suitable glycols are ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, and 1,2-propanediol, U3-propanediol, iota, 3 -butanediol, iota, 4-butanediol, 1,6-hexanediol and isomers, neopentyl glycol or neopentyl glycol hydroxytrimethyl acetate, of which 1,6-hexane It is preferred to be drunk and isomers, neodecanediol, and neodymium. Further, a polyhydric alcohol such as trimethylpropane, glycerin, erythritol, pentaerythritol, trihydroxydecylbenzene or trisylethyltrimeric isocyanate may also be used. Dicarboxylic acid phthalic acid, isophthalic acid, p-dodecanoic acid, tetrahydrophthalic acid, hexahydrodibenzoic acid, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, hydrazine Diacid, glutaric acid, tetraxanthenil, maleic acid, fumaric acid, isaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3_two Ethyl glutaric acid and / or 2,2 • dimethyl succinic acid. The corresponding anhydride can also be used as the acid source. Average Functionality of Polyol to be Esterified>2 厶 , 丄丄 _ 〆, ¥ | Ί Color Use monocarboxylic acids such as benzoic acid and hexane formic acid. = Acid is an aliphatic or aromatic acid of the above type. The best is the second, the dicarboxylic acid and 1,2,4-stupic tricarboxylic acid as the case may be. The reaction is used as an acid or a money system (for example, ketohexanoic acid, butyl phthalic acid, stearyl stearic acid, and the like. Suitable 201215738 is intended to be a homologue, preferably a vinegar having a number average molecular weight of from 400 to 8000 g/mole, preferably from 600 to 3000 g/mol of a hydroxyl-containing polycarbonate, preferably a polycarbonate binary. Alcohols can also be used in A2). Such materials can be obtained by reacting a carbonic acid derivative such as diphenyl carbonate, dimercaptocarbonate or phosgene with a polyol, preferably a glycol. Examples of this type of glycol are ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octane Alcohol, neopentyl glycol, 1,4-bishydroxydecylcyclohexane, 2-methyl1,3-propanediol, 2,2,4-tridecyl-1,3-pentanediol, dipropylene glycol, Polypropylene glycol, dibutylene glycol, polytetramethylene glycol, bisphenol A, and a lactone modified by a lactone of the above type. The polycarbonate diol preferably comprises 40 to 100% by weight of hexanediol, preferably 1,6-hexanediol and/or hexanediol derivative. This type of hexanediol derivative is based on hexanediol and additionally contains an ester or ether group in addition to the terminal OH group. Derivatives of this type can be obtained by the reaction of hexanediol with an excess of caprolactone or by the etherification of hexanediol with itself to obtain di- or trihexanediol. Instead of or in addition to the pure polycarbonate diol, a polyether polycarbonate diol can also be used in A2). The hydroxyl group-containing polycarbonate preferably has a linear structure. Polyether polyols are also useful in A2). Suitable polyether polyols are, for example, those found in the polyurethane chemistry which are known per se by cationic ring opening to polymerize tetrahydrofuran. 15 201215738 Polybutadiene diol polyether. Also suitable polyether polyols are known per se as products of styrene, ethylene oxide, propylene oxide, butylene oxide and/or surface gas alcohol addition on di- or polyfunctional starter molecules. It is also possible to use, as component A4) (nonionic hydrophilic agent), a polyether polyol which is at least proportionally added to the di- or polyfunctional starting molecule based on ethylene oxide. Suitable starting compounds are all compounds known from the prior art, such as, for example, water, butyl diglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, sorbitol , ethylene diamine, triethanolamine, 1,4-butanediol. Preferred starting molecules are water, ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol and butyldiethylene glycol. A particularly preferred embodiment of the polyaminophthalic acid ester dispersion (1) comprises a mixture of a polycarbonate polyol and a polybutanediol polyol as component A2), wherein the proportion of the polycarbonate polyol in the mixture is 20 The ratio to 80% by weight, and the polybutanediol polyol is 80 to 20% by weight. The polybutanediol polyol in a ratio of 30 to 75% by weight and the polycarbonate polyol in a ratio of 25 to 70% by weight are preferred. It is particularly preferred to use a polybutanediol polyol in a ratio of from 35 to 70% by weight and a polycarbonate polyol in a proportion of from 30 to 65% by weight, in each case conditional polycarbonate polyol and polybutadiene The total weight percentage of the diol polyol is 100% and the ratio of the sum of the polycarbonate polyol and the polybutanediol polyol in the component A2) is at least 50% by weight, preferably 60% by weight, particularly preferably It is at least 70% by weight. 201215738 The compound of component A3) has a molecular weight of 62 to 400 g/mole. Polyhydric alcohol having up to 2 carbon atoms in the molecular weight range, such as ethylene glycol, diethylene glycol, triethylene glycol, hydrazine, 2 - propylene glycol, 1,3-propanediol, 1, 4 may be used in A3). -butanediol, 1,3-butanediol, cyclohexanol, 1,4-cyclohexane, dihydrogen, 1,6-hexanediol, neopentyl glycol, gas geminal dihydroxyethyl ether, Bisphenolphthalein (2,2·bis(4-hydroxyphenyl)propane), hydrogenated bisphenolphthalein (2,2-bis(4-hydroxycyclohexyl)propane), trishydroxypropylpropane, glycerin, neopentyl Tetraol and any desired mixture of each other. Also suitable for ester diols in the molecular weight range, such as α-transpyridyl-ε-per hexanoic acid S, ω-pyridyl-γ-pyridic acid, β-hydroxyethyl Adipate or β-hydroxyethyl terephthalate. Further, a monofunctional isocyanate-reactive hydroxyl-containing compound can also be used in A3). Examples of monofunctional compounds of this type are ethanol, n-butanol, ethylene glycol monobutyl ether, diethylene glycol monomethyl shrine, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol Monomethyl ether, dipropylene glycol monodecyl ether, tripropylene glycol monodecyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl shunt, tripropylene glycol monobutyl shout, 2-ethyl Hexanol, 1-octanol, 1_12th hospital alcohol, 1-hexadecanol. Preferred compounds of component A3) are 1,6-hexanediol, 1,4-butanediol, neopentyl glycol and trimethylolpropane. The anionic or potentially anionic hydrophilic compound of component Α4) means all compounds comprising at least one isocyanate-reactive group, such as a hydroxyl group and at least 17 201215738, such as (for example, χοσΜ+, _s〇3-M+, _pQp) M+ is, for example, a metal cation, H+, NH + / NHR3+, wherein R can in each case be Crc]2-alkyl, c_4C_cycloalkyl and/or cvcv-based, which interact with the aqueous medium 5 is used for the second time to enter the pH-dependent dissociation equilibrium and can be negatively charged or neutral in this way. Suitable anionic or potentially anionic hydrophilic compounds are mono- and di-basic, mono- and di-(four) and single and two County linonic acid and its salts. Examples of anionic or potentially anionic hydrophilic agents of this type are dimercaptopropionic acid, bis-butyric acid, trans-trimethylacetic acid, frequency acid, citric acid, glycolic acid, lactic acid and 2-propoxylated adduct of butanediol and NaHs〇3, as described in DE-A 2 446 440, pp. 5-9, formula I-III. Preferred anion or potential of component A4) Anionic hydrophilic agents are those in which the above type contains a carboxylate or a carboxylic acid group and/or a sulfonate group. Preferred anionic or potentially anionic hydrophilic agents Α4) are those which contain carboxylate or carboxylic acid groups as ionic or potentially ionic groups, such as dihydroxymethyl propionic acid, dimethylol butyric acid and hydroxytrimethylacetic acid or salts thereof Suitable nonionic hydrophilic compounds of component Α4), for example, comprise at least a hydroxyl group or an amine group, preferably a polyoxyalkylene group of at least one hydroxyl group. Examples are statistically averaged from 5 to 70 per molecule, Preferably, from 7 to 55 ethylene oxide units of monohydroxy-functional polyalkylene oxide polyether alcohols are obtained in a manner known per se by alkoxylation of suitable starting molecules (for example in Ullmann Encyclop Sdie der technischen) 201215738

Chemie [Ullm Discussion, s Encycl〇pedia # Industdal

Chemistry], 4th edition, Volume 19, Verlag chemje,

Weinheim, pp. 31-38). It is a combination of pure oxygen oxyethylene bakes, which comprises at least 30 mole %, preferably at least 4 mole % of ethylene oxide units, based on the % of oxygen burned. 40 ^100 Epoxy epoxy (10) units of monofunctional alcohol, non-: hydrophilic agent, suitable for starting molecules, saturated units of alcohol, hydrazine, n-propanol, isopropanol, n-butanol, iso Butanol, = alcohol isomeric pentane, octanol and decyl alcohol, n-decane alcohol, cyclohexanol, ri-n-tetradecyl alcohol, hexadecanol, n-octadeca 3-ethyl-3-mercapto Methyl dimethyl hexanol or transmethyl hexanone, single appearance test such as (example ==?-alcohol, diethylene glycol decyl alcohol, 1,1·di & ether, unsaturated alcohol , such as isomerase or methoxy: alkenyl alcohol or oleyl alcohol, aromatic alcohol 'such as phenol, mellow alcohol or eugenol, such as benzene f-alcohol, big bacteria dipropylamine, diisopropyl-fluorenyl Amine, diethylamine, amine, N-methyl- and heart amine: ?(2-ethyl·hexyl) secondary amine, such as beer, _ trobens or monocyclohexylamine and heterozygous or one = 卞 上 上 上 上 - - - - - - - diol diol diol diol diol diol diol diol diol diol diol diol diol diol diol diol diol diol diol diol diol diol Any desired order or also in the form of a mixture for burning oxidation It is possible to use di- or polyamines, such as 1,2-ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6- Isomer mixture of diaminohexane, isophoronediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, 2-mercaptopentamethylenediamine , diethylenetriamine, triamine decane, 1,3- and 1,4-decyldiamine, α,α,α',α'-tetradecyl-1,3- and -1, 4-decyldiamine and 4,4-diaminodicyclohexyldecane and/or dimercaptoethylenediamine as component Β1). You can also use 肼 or 醯肼, such as 醯肼. Preferred are isophorone diamine, 1,2-ethylenediamine, 1,4-diaminobutane, anthracene and diethylenetriamine. Further, a compound containing a secondary amino group in addition to the primary amine group or a thiol group in addition to the amine group (primary or secondary) can also be used as the component Β1). Examples thereof are primary/secondary amines such as diethanolamine, 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexyl Aminopropane, 3-amino-1-indenylaminobutane, alkanolamines such as anthraquinone-aminoethylethanolamine, ethanolamine, 3-aminopropanol, neopentylamine. In addition, monofunctional isocyanate-reactive amine based compounds such as, for example, methylamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isodecyloxy can also be used. Propylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, fluorenyl-mercaptopropylamine, diethyl(fluorenyl)aminopropylamine, morphine , piperidine or its 20 201215738 suitable for substituted derivatives, guanamine amines made from diprimary amines and monocarboxylic acids, monoimines of secondary amines, primary/third Amine such as N,N-dimethylaminopropylamine as component B1). Preferred compounds of component B1) are 1,2-ethylenediamine, i,4-diaminobutane and isophoronediamine. The anionic or potentially anionic hydrophilic compound of component B2) means that all comprise at least one isocyanate-reactive group, preferably an amine group and at least one functionality, such as, for example, -COCTM+, -SCVM+, -Ρ0 (0·Μ +) a compound of 2, wherein M1 is, for example, a metal cation, H+, NH4+, NHR3+, wherein R may in each case be a Cl_Cl2_alkyl, a burnt and/or a C2-C4-carbyl group, which is associated with an aqueous medium The interaction enters a pH-dependent dissociation equilibrium and can be negatively charged or neutral in this manner. Suitable anionic or potentially anionic hydrophilic compounds are mono- and diaminocarboxylic acids, mono- and diaminosulfonic acids, and mono- and diaminophosphonic acids and salts thereof. Examples of anionic or potentially anionic hydrophilic agents of this type are N-(2-aminoethyl)-β-alanine, 2-(2-aminoethylamino)-benzine acid, ethylenediamine-propyl Base- or butyl acid, 1,2- or 1,3-propanediamine-β-ethyl acid, glycine, alanine, bovine acid, lysine, 3,5-diamine Benzoic acid and the addition reaction product of IPDA and acrylic acid (ερ_α 0 916 647, Example 1). Further, cyclohexylaminopropenic acid (CAPA) known from WO-A 01/88006 can be used as an anionic or latent anionic hydrophilic agent. 21 201215738 Preferred anionic or potentially anionic hydrophilic compounds of component B2) are those of the above type containing carboxylate or carboxylic acid groups and/or sulfonate groups such as N-(2-aminoethyl)-0-alanine , 2·(2·Aminoethylamino)diethyl sulfonate or a salt of an addition reaction product of IPDA and acrylic acid (ΕΡ-Α 0 916, example 1). The hydrophilization can also be carried out using a mixture of an anionic or potentially anionic hydrophilic agent and a nonionic hydrophilic agent. In the preferred embodiment for preparing a particular polyaminophthalate dispersion, 'the following amounts of components Α1' to Α4) and Β1) to Β2) are used, wherein the sum of the individual amounts is always 100% by weight: 5 to 40 % by weight of component Α1), 55 to 90% by weight of component Α2), 0.5 to 20% by weight of component A3) and Β1), 0.1 to 25% by weight of component Α4) and Β2) Wherein from 0.1 to 5% by weight, based on the total of the components Α1) to Α4) and Β1) to Β2), an anionic or potentially anionic hydrophilic agent selected from the group consisting of Α4) and/or Β2). In a particularly preferred embodiment for the preparation of a particular polyamine phthalate dispersion, the following amounts of components Α1) to Α4) and Β1) to Β2) are used, wherein the sum of the individual amounts is always % by weight: 5 to 35 weight % of component Α1), 60 to 90% by weight of component Α2), 0.5 to 15% by weight of component A3) and Β1), sum of 0.1 to 15% by weight of component Α4) and Β2), Wherein an anionic or potentially anionic hydrophilic agent selected from the group consisting of A4) and/or B2) is used in an amount of from 0.2 to 4, 22, 15,15, and 2, based on the total of the components Α1) to Α4) and Β1) to Β2). In a very preferred embodiment for the preparation of a specific polyamine phthalate dispersion, the following amounts of components A1) to A4) and B1) to B2) are used, wherein the sum of the individual amounts is always 100% by weight: 10 to 30% by weight of component A1) '65 to 85% by weight of component A2), 0.5 to 14% by weight of component A3) and B1), 0.1 to 13.5% by weight of component A4) and B2) The sum, wherein from 0.5 to 3.0% by weight, based on the total of components A1) to A4) and B1) to B2), an anionic or potentially anionic hydrophilic agent selected from the group consisting of A4) and/or B2). The preparation of the anionically hydrophilized polyurethane dispersion (I) can be carried out in one or more steps in a homogeneous or multi-step reaction, and partly in a dispersed phase. After the complete or partial polyaddition of A1) to A4), a dispersion, emulsification or dissolution step is carried out. If necessary, another polyaddition or modification is then carried out in the dispersed phase. All methods known from the prior art can be utilized herein, such as, for example, prepolymer blending, acetone or melt dispersion. Preferably, the acetone method is used. For the preparation by the acetone method, the components A2) to A4) and the polyisocyanate component A1) are usually introduced in whole or in part to prepare an isocyanate-functional polyaminophthalate prepolymer and, if appropriate, water-miscible but The isocyanate group is diluted with an inert solvent and then heated to a temperature ranging from 50 to 120 °C. In order to accelerate the isocyanate addition reaction, 23 201215738 uses a catalyst known in polyurethane chemistry. Suitable solvents are solvents which are customary in the aliphatic ketone function, such as acetone, 2-butanone, which can be added at the beginning of the preparation and, if necessary, later. Preferred are acetone and 2-butanone. Other solvents may be additionally used, such as diphenylbenzene, toluene, cyclohexane, butyl acetate, methoxypropyl acetate, N-methylpyrrolidone, N-ethyl beta than ketamine, and The solvent of the ether or g unit may be completely or partially distilled or completely left in the dispersion in the case of N-fluorenyl ketone and N-ethyl η than slightly ketone. However, it is preferred not to use other solvents which are not customary aliphatic ketone functional solvents. Next, any component that has not been added at the beginning of the reaction in Α1) to Α4) is metered. When the polyaminophthalate prepolymer is prepared from Α1) to Α4), the isocyanate-reactive isocyanate-reactive group has a molar ratio of from 1.05 to 3.5, preferably from 1.2 to 3.0, particularly preferably from 1.3 to 2.5. The components Α1) to Α4) are converted into part or all of the prepolymer system, but are preferably all carried out. Therefore, the polyaminophthalate prepolymer containing a free isocyanate group is obtained in a solid form or in a solution form. The partial or complete conversion of the latent anionic group to the anionic group is used in a stepwise manner, such as a tertiary amine, such as 1 to 12 C atoms, preferably 1 to 6 C atoms in each of the alkyl groups. Up to 3 C atoms of a trialkylamine or an alkali metal base, such as a corresponding gas oxide. Examples thereof are tridecylamine, triethylamine, decyldiethylamine, tripropylamine, Ν-methylmorpholine, decyldiisopropylamine, ethyldi-24 201215738 isopropylamine And monoisopropylethylamine. The alkyl group may also have, for example, a hydroxyl group such as a dialkyl monoalkanolamine, an alkyl dialkanolamine, and a trialkanolamine. The neutralizing agent can also be an inorganic base if necessary, such as an aqueous ammonia solution or sodium hydroxide or potassium hydroxide. Preferred are ammonia, triethylamine, triethanolamine, tridecylethanolamine or monoisopropylethylamine, and sodium hydroxide and potassium hydroxide, particularly sodium hydroxide and potassium hydroxide. The molar amount of the base is from 5 Å to 125 mol%, preferably from 70 to 1 mol%, of the molar amount of the acid group to be neutralized. If the dispersed water already contains neutralizing agent, it can be neutralized simultaneously with the dispersion. In a further processing step, the resulting prepolymer is then dissolved by means of an aliphatic ketone such as acetone or 2-butanone, if this has not been done or only partially. In the chain extension of step B), the NH2- and/or NH-functional components are partially or completely reacted with the remaining isocyanate groups in the prepolymer. Chain extension/termination is preferably carried out prior to dispersion in water. For the termination of the bond 'usually an amine B1 containing an isocyanate-reactive group, such as mercaptoamine, ethylamine, propylamine, butylamine, octylamine, laurylamine, stearylamine, isomethoxypropyl Amine, dimethylamine, monoethylamine, dipropylamine, dibutylamine, N-decylaminopropylamine, monoethyl(decyl)aminopropylamine, morphine, piperazine Pyridine or a substituted derivative thereof, a mercaptoamine prepared from a dibasic amine and a monodecanoic acid, a monoimine of a primary amine, a primary/ tertiary amine such as N,N-dimethyl Aminopropylamine. 25 201215738 If partial or complete chain elongation is carried out using an anion or potential anionic hydrophilic agent containing NH2 or NH groups as defined in Definition B2), the chain elongation of the prepolymer is preferably carried out prior to dispersion. The amine components B1) and B2) may optionally be used in the process according to the invention, either individually or in the form of a mixture, by water or by solvent dilution, any of which is in principle feasible. If water or an organic solvent is used in combination as a diluent, the content of the diluent in the component for chain elongation in B) is preferably from 70 to 95% by weight. Dispersion is preferably carried out after the chain has been elongated. For this purpose, the dissolved and chain-extended polyurethane polymer is optionally subjected to high shear, such as, for example, vigorous stirring into the dispersed water or, conversely, the dispersed water is stirred into the chain-extended polyamine group. In the formic acid polymer solution. Preferably, water is added to the polyamine silicate polymer having dissolved chain elongation. The solvent still present in the dispersion after the dispersion step is usually removed by distillation. Removal during dispersion is equally feasible. The residual content of the organic solvent in the polyurethane dispersion (1) is generally less than 1.0% by weight based on the entire dispersion. The pH of the polyamine phthalate dispersion (1) which is indispensable in the present invention is generally less than 9.0, preferably less than 8.5 Å, and less than 8 to 6.0 to 7.5. f The polyamine phthalic acid vinegar dispersion (I) has a solid content of 4 to 7% by weight, preferably 50 to 65% by weight, particularly preferably 55 to 65 by weight in another preferred towel, dispersion B also contains a coagulant (II) in addition to the hydrated polyurethane. 26 201215738 The coagulant (π) which can be used in the composition is all organic compounds containing at least 2 cationic groups. Preferably, all of the cationic flocculants and precipitants known from the prior art, such as poly [2-(N) ,Kr,N>>trimethylamino)ethyl acrylate], polyethylenimine, poly[N-(dimethylamine^methyl)-propenylamine], substituted acrylamide, Substituted sulfhydryl groups, N-vinyl decylamine, N-vinylacetamide, ethyl ruthenium sulphate, 2-vinyl "pyridyl or 4-ethyl acridine salts" Cationic homopolymer or copolymer. Preferably, the coagulant (Π) is a cationic copolymer comprising a structural unit of the formula (2), wherein the structural unit of the formula (1) and the structural unit of the formula (2) Cationic copolymer of acrylamide: ! =0 | nh2 H3C-N-CH3 CH3X- Formula (1) Formula (2) wherein R is C=0, -COO(CH2)2- or -COO(CH2)3- and X&quot Halide ion, preferably chloride, cationic coagulant (II) used especially for this type of polymer having a number average molecular weight of 500,000 to 50,000,000 g/mole. This type of coagulant (II) A flocculant as a sewage sludge is sold, for example, under the trade name Praestol® (Degussa Stockhausen, Krefeld, DE). The preferred coagulant of the Praestol® type is Praestol® 27 201215738 K111L, K122L, K133L, BC 270L, K144L, K166L, BC 55L, 185K, 187K, 190K, K222L, K232L, K233L, K234L, K255L, K332L, K333L, K334L , E 125, E 150 and mixtures thereof. Very good coagulant is praest〇i8ΐ85κ, 187K and 190K and mixtures thereof. Dispersion B preferably comprises at least one pigment. The manner in which it is precipitated in or on the textile substrate is largely dependent on the chemical composition of dispersion B used in accordance with the present invention and is particularly dependent upon the type of coagulant present. For example, precipitation can be carried out by condensation or by agglomeration of a salt, an acid or an electrolyte.

In general, precipitation is achieved by an increase in temperature. For example, the fabric substrate can be briefly heat treated by steam, for example, at 1 Torr to 1 1 〇〇C for 1 to 10 seconds. This is especially preferred if an ammonium salt or an organic acid is used as the coagulant. On the other hand, if the above-mentioned acid generating chemical substance is used as a coagulating agent, it is preferable to carry out the method as described in Us 5 916 636, US ice 8,597, still 5,952,413 and still 6_, 39'3. Alternatively, the coacervate is caused by > 5: into the salt solution. Preferably, the coagulation is carried out using an inorganic salt selected from the group consisting of metal salts and soil metal salts. The inorganic salt is particularly selected from the group consisting of a metal tooth, an alkali metal nitrate, an alkali metal phosphate, an alkali metal sulfate, an alkali metal carbonate, an alkali metal argon salt, an alkaline earth metal tooth, and a soil metal salt. 28, a group of soil-measuring metal salts, soil-salting metal sulfates, alkaline earth metal carbonates and alkaline earth metal carbonates. 201215738 Salt: The inorganic salt is particularly excellent in gasification, potassium carbonate, sodium carbonate, potassium sulfate, potassium carbonate, sodium hydrogencarbonate, hydrogencarbonate unloading, chemical town, sulfur, chlorinated 35 or sulfur gorge. The unexpanded f calcium or magnesium chloride. f' wind The inorganic salt is preferably in an amount of 25% by weight based on the total amount of the salt solution, particularly preferably 1 to 15% by weight, and particularly preferably 1 to 10% by weight in the salt solution. in. After the precipitation in step c), other drying or condensation is carried out as necessary. %, the fabric substrate used is preferably a woven fabric, a knitted fabric or a non-woven fabric based on natural and/or human k fibers. The woven substrate is particularly preferably a non-woven fabric (staple nonwoven, microfiber non-woven or the like). The fabric substrate is preferably made of polyester, nylon (6 or 66), cotton, cotton/cotton blend, wool, sesame, elastic yarn, glass, thermoplastic polyamine-based (TPU), thermoplastic olefin (TPO). Or a fiber composition of the analog. The fabric substrate can have a joined/mesh (woven), woven or non-woven construction. °Heil fabric substrate can be dyed, colorant N 粗 τ 吸收 吸收 absorber, plasticizer, soil redeposition agent, lubricating secondary antioxidant, flame retardant, rheological agent and the like before or after coating. Treat 'but it's better to do this before coating. The non-woven fabric defined by t is subjected to a general coloring process by impregnation and agglomeration of the elastomeric polymer to obtain a synthetic leather having a good color developing property. 29 201215738 The invention thus further relates to coated fabrics obtained according to the process of the invention, preferably synthetic leather. [Embodiment] Example Dispersion A has the following composition:

Ca(N03)2 80 pbw thiol cellulose water 0.4 pbw 920 pbw Dispersion B1 for salt coacervation has the following composition:

Impranil 1380 1000 pbw water 5000 pbw The process for preparing coated fabrics by salt agglomeration is described in the figure 分散 Dispersion B2 for thermal coacervation has the following composition:

Impranil DLU 100 pbw coagulant WS 20 pbw EmulvinWA 20 pbw water 5000 pbw Process for preparing coated fabrics by thermal coacervation is described in the drawing 〇201215738 The process has been carried out without the substrate in contact with the dispersion A Very hard touch. Conversely. The substrate which has been treated in accordance with the present invention exhibits a pleasant soft rounded touch. When the obtained substrate is subsequently coated, the difference between the substrate treated by the dispersion A and the untreated substrate is also apparent, and the crease of the sharp and/or foaming is revealed in the case of the untreated coagulant. fold). The substrate treated in accordance with the present invention exhibits a round, optically perfect crease. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a method of preparing a coated fabric by salt agglomeration. Figure 2 is a method of making a coated fabric using thermal coagulation. [Main component symbol description] None

Claims (1)

201215738 VII. Scope of Application: 1. A method of making a coated fabric comprising at least the following steps: a) contacting a textile substrate with an aqueous dispersion A comprising at least one inorganic salt and at least one modified cellulose b) contacting the textile substrate with an aqueous dispersion B comprising a polyurethane, and c) precipitating the polyamino phthalate in or on the textile substrate. 2. The method of claim 1, wherein the inorganic salt is selected from the group consisting of an alkali metal salt and an alkaline earth metal salt. 3. The method according to claim 2, wherein the alkali metal The salt is selected from the group consisting of a metal halide, a metal salt, a metal salt, a metal sulfate, a metal carbonate, and a metal hydrogencarbonate. 4. The method of claim 2, wherein the alkaline earth metal salt is selected from the group consisting of alkaline earth metal halides, soil test metal acid salts, soil test metal acid salts, soil test metal sulfates, soil test metal carbonates And a salt of the group consisting of alkaline earth metal hydrogencarbonate. The method of claim 1, wherein the inorganic salt is present in the dispersion A in an amount of from 0.01 to 25% by weight based on the total amount of the dispersion A. 6. The method of claim 1, wherein the modified cellulose is selected from the group consisting of mercapto cellulose, ethyl cellulose, propyl cellulose, hydroxydecyl cellulose, hydroxyethyl cellulose, and hydroxyl groups. A compound of the group consisting of propylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxyethylcellulose, and carboxypropylcellulose. 7. The method of claim 1, wherein the modified cellulose is present in the dispersion A in an amount of from 1 ppm to 5% by weight based on the total amount of the dispersion A. 8. The method of claim 1, wherein the fabric substrate used is a woven fabric, a knitted fabric or a non-woven fabric based on natural and/or artificial fibers. 9. Process according to item 1 of the patent application, characterized in that the polyamine phthalate is precipitated in the aqueous bath of step c) or at a temperature ranging from 80 to 120 °C. 10. A coated fabric obtainable by the method of claims 1 to 9 according to claim 33 201215738. 11. The coated fabric of claim 10, wherein the coated fabric is a synthetic leather. 34