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EP2773809B1 - Procédé d'enduction de produits textiles. - Google Patents

Procédé d'enduction de produits textiles. Download PDF

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Publication number
EP2773809B1
EP2773809B1 EP12783579.1A EP12783579A EP2773809B1 EP 2773809 B1 EP2773809 B1 EP 2773809B1 EP 12783579 A EP12783579 A EP 12783579A EP 2773809 B1 EP2773809 B1 EP 2773809B1
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EP
European Patent Office
Prior art keywords
alkaline
process according
group
alkali metal
earth metal
Prior art date
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EP12783579.1A
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German (de)
English (en)
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EP2773809A1 (fr
Inventor
Rolf Irnich
Xuehui Zhao
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Covestro Deutschland AG
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Covestro Deutschland AG
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B21/00—Successive treatments of textile materials by liquids, gases or vapours
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
    • D06M11/65—Salts of oxyacids of nitrogen
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D06M11/71—Salts of phosphoric acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/02—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with cellulose derivatives
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/042—Acrylic polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/10—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with styrene-butadiene copolymerisation products or other synthetic rubbers or elastomers except polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/186—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials one of the layers is on one surface of the fibrous web and the other layer is on the other surface of the fibrous web
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2205/00—Condition, form or state of the materials
    • D06N2205/24—Coagulated materials
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2033—Coating or impregnation formed in situ [e.g., by interfacial condensation, coagulation, precipitation, etc.]

Definitions

  • 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 solution comprising at least one inorganic salt and at least one modified cellulose.
  • Synthetic leathers are employed, inter alia, as shoe upper materials, for articles of clothing, as bag-making material or in the upholstery sector, for example.
  • the main coating material used here is polyurethane.
  • the generally known principles of coating textiles with polyurethane are described in W. Schröer, Textilveredlung [Textile Finishing] 1987, 22 (12), 459-467 .
  • a description of the coagulation process is additionally found in " New Materials Permeable to Water Vapor", Harro T syndromebel, Springer Verlag, Berlin, Heidelberg, New York, 1999, ISBN 3-540-64946-8, pages 42 to 63 .
  • the main processes used in the production of synthetic leather are the direct coating process, the transfer coating process (indirect coating) and the coagulation (wet) process.
  • the coating in the transfer process is applied to a temporary support with a subsequent lamination step, in which the film is combined with the textile substrate and detached from the temporary support (release paper).
  • the transfer process is preferably employed with textile substrates, which do not permit high tensile stresses during coating, or with open fabrics which are not particularly dense.
  • a textile substrate is usually coated with a solution comprising polyurethane in DMF.
  • the coated substrate is passed through DMF/water baths, where the proportion of water is increased stepwise. Precipitation of the polyurethane and formation of a microporous film occur here.
  • Use is made here of the fact that DMF and water have excellent miscibility and DMF and water serve as a solvent/non-solvent pair for polyurethane.
  • Coagulated polyurethane coatings are employed, in particular, for high-quality synthetic leather, since they have comparatively good breathing activity and a leather feel.
  • the basic principle of the coagulation process is based on the use of a suitable solvent/nonsolvent pair for polyurethane.
  • the great advantage of the coagulation process is that microporous, breathing-active synthetic leather having an excellent leather feel can be obtained. Examples are, for example, the synthetic leather brands Clarino® and Alcantara®.
  • a disadvantage of the coagulation process is the necessity to use large amounts of DMF as an organic solvent. In order to minimize the exposure of employees to DMF emissions during production, additional design measures have to be taken, which represent a not inconsiderable increased outlay compared with simpler processes. Furthermore, it is necessary to dispose of or work up large amounts of DMF/water mixtures. This is problematical since water and DMF form an azeotrope and can therefore only be separated by distillation with increased effort.
  • JP 48 028043 B discloses a process wherein a non-woven material is coated with a mixture containing 10 to 70 wt.-% of a water insoluble pulverized material such as an anorganic metal salt of group Ha, Ilia, Iva elements, and a water soluble high molecular material, such as carboxy methyl cellulose.
  • a water insoluble pulverized material such as an anorganic metal salt of group Ha, Ilia, Iva elements
  • a water soluble high molecular material such as carboxy methyl cellulose.
  • the coated non-woven is then impregnated with a binder, such as a mixture of a polybutylene adipate and a polymer of 4,4'-diphenyl methylene Diisocyanate and ethyleneglycole.
  • a binder such as a mixture of a polybutylene adipate and a polymer of 4,4'-diphenyl methylene Diisocyanate and ethyleneg
  • One object of the present invention was therefore to develop a process for the coating of textile substrates which still enables coated textiles having good properties, such as, for example, good feel, to be obtained without the need to employ toxicologically unacceptable solvents, such as, for example, DMF.
  • the object has been achieved by a process for the production of coated textiles, comprising at least the steps of
  • the inorganic salt is preferably a salt selected from the group comprising alkali metal salts and alkaline-earth metal salts.
  • the inorganic salt is particularly preferably a salt selected from the group consisting of alkali metal halides, alkali metal phosphates, alkali metal nitrates, alkali metal sulfates, alkali metal carbonates, alkali metal hydrogen carbonates, alkaline-earth metal halides, alkaline-earth metal nitrates, alkaline-earth metal phosphates, alkaline-earth metal sulfates, alkaline-earth metal carbonates and alkaline-earth metal hydrogen carbonates.
  • the inorganic salt is very particularly preferably sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, magnesium chloride, magnesium sulfate, magnesium nitrate, calcium chloride, calcium nitrate or calcium sulfate.
  • the inorganic salt is even more preferably calcium nitrate, magnesium nitrate, calcium chloride or magnesium chloride.
  • the inorganic salt is preferably present in solution A in an amount of 0.01 to 25 % by weight, particularly preferably in an amount of 0.5 to 15 % by weight, and very particularly preferably in an amount of 0.5 to 10 % by weight, based on the total amount of dispersion A.
  • the chemically modified cellulose is preferably a compound selected from the group consisting of alkylated celluloses, hydroxyalkylated celluloses and carboxyalkylated celluloses.
  • the chemically modified cellulose is particularly preferably a compound selected from the group consisting of methylcellulose, ethylcellulose, propylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxyethylcellulose and carboxypropylcellulose.
  • the chemically modified cellulose is very particularly preferably methylcellulose or ethylcellulose.
  • the modified cellulose is preferably present in solution A in an amount of 10 ppm to 5 % by weight, particularly preferably in an amount of 100 ppm to 3 % by weight, very particularly preferably in an amount of 400 ppm to 1.5 % by weight, based on the total amount of dispersion A.
  • the textile substrate is preferably brought into contact with an aqueous solution A at room temperature for a period of 2 to 4 minutes, particularly preferably 1 to 2 minutes, very particularly preferably 0.2 to 1 minute.
  • bringing into contact means partial or complete immersion, preferably complete immersion, in a solution or application of the solution by means of a hand coater, printing or spraying.
  • the textile substrate After being brought into contact with a solution A, the textile substrate is preferably passed through a wringer device consisting of two rollers in order to remove the excess solution A.
  • the wringer device here should preferably be set in such a way that solution A remains in the textile substrate in an amount of 60 to 180 % by weight, particularly preferably 70 to 140 %, very particularly preferably 80 to 120 %, based on the weight per unit area of the substrate (liquor uptake), before the substrate is brought into contact with a dispersion B containing at least one polymer selected from the group consisting of polyacrylate and polybutadiene.
  • the textile substrate is preferably partially dried for a period of 2 to 10 minutes, particularly preferably 1 to 5 minutes, using air, infrared or hot cylinders before it can be brought into contact with a dispersion B containing at least one polymer selected from the group consisting of polyacrylate and polybutadiene.
  • the polyacrylate and polybutadiene present in dispersion B is not particularly restricted so long as they are soluble in water.
  • Polyacrylate polymers are prepared from monomers containing hydroxyl groups, "acidic” monomers, or monomers that contain neither acidic nor OH groups.
  • Suitable hydroxyl group-containing monomers include hydroxyalkyl esters of acrylic acid or methacrylic acid, preferably with 2 to 4 carbon atoms in the alkyl radical, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-or 3-hydroxypropyl acrylate and methacrylate, the isomeric hydroxybutyl acrylates and methacrylates and mixtures of these monomers.
  • Suitable "acidic" comonomers include olefinically unsaturated, polymerizable compounds that contain at least one carboxyl group and/or sulfonic acid group, such as olefinically unsaturated monocarboxylic or dicarboxylic acids having a molecular weight of 72 to 207.
  • olefinically unsaturated monocarboxylic or dicarboxylic acids having a molecular weight of 72 to 207.
  • examples include acrylic acid, methacrylic acid, maleic acid, itaconic acid and olefinically unsaturated compounds containing sulfonic acid groups, for example, 2-acrylamido-2-methylpropanesulfonic acid and mixtures of these olefinically unsaturated acids.
  • a third group of olefinically unsaturated monomers that may be jointly used in the production of polyacrylate polymers include olefinically unsaturated compounds that do not contain either acidic groups or hydroxyl groups.
  • examples include esters of acrylic acid or methacrylic acid with 1 to 18, preferably 1 to 8 carbon atoms in the alcohol radical, such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, n-stearyl acrylate, the methacrylates corresponding to these acrylates, styrene, alkyl-substituted styrenes, butadiene, isoprene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl stearate, and mixtures of these monomers.
  • Comonomers containing epoxy groups
  • aqueous dispersions containing polyacrylate and/or polybutadiene is carried out according to known free-radical polymerization methods, for example, solution polymerization, emulsion polymerization and suspension polymerization.
  • free-radical emulsion polymerization in an aqueous medium is preferred.
  • Continuous or discontinuous polymerization processes may be used. Examples of discontinuous processes are the batch process and feed process, the latter being preferred.
  • water is added alone or with part of the anionic emulsifier and optionally a non-ionic emulsifier, as well as with part of the monomer mixture, and is heated to the polymerization temperature.
  • the polymerization is started by free radicals and the remaining monomer mixture is metered in together with an initiator mixture and the emulsifier over a period of 1 to 10 hours, preferably 3 to 6 hours. If necessary, the reaction mixture is then post-activated in order to carry out the polymerization to a conversion of at least 99%.
  • the emulsifiers used are may be anionic and/or non-ionic.
  • Anionic emulsifiers are those containing carboxylate, sulfate, sulfonate, phosphate or phosphonate groups.
  • Emulsifiers are preferred that contain sulfate, sulfonate, phosphate or phosphonate groups.
  • the emulsifiers may have a low molecular weight or high molecular weight. The latter are described, for example, in DE-A 3 806 066 and DE-A 1 953 349 .
  • Preferred anionic emulsifiers are those that are built up from long-chain alcohols or substituted phenols and a polyether chain bonded to the hydroxyl group containing 2 to 100 ethylene oxide units as well as a sulfuric acid or phosphoric acid group bonded in the form of an ester unit. Ammonia or amines are preferred neutralizing agents for the unesterified acid groups.
  • the emulsifiers may be added to the emulsion batch individually or as mixtures.
  • Suitable as non-ionic emulsifiers which may be used in combination with the anionic emulsifiers, are reaction products of aliphatic, araliphatic, cycloaliphatic or aromatic carboxylic acids, alcohols, phenol derivatives and/or amines with epoxides, such as ethylene oxide.
  • Examples include reaction products of ethylene oxide with castor oil carboxylic acids and abietic acid; with long-chain alcohols such as oleyl alcohol, lauryl alcohol, stearyl alcohol; with phenol derivatives such as substituted benzyl phenols, phenyl phenols and nonyl phenols; and with long-chain amines such as dodecylamine and stearylamine.
  • the reaction products with ethylene oxide include oligoethers and/or polyethers with degrees of polymerization of 2 to 100, preferably 5 to 50.
  • emulsifiers are added in amounts of 0.1 to 10 wt. %, based on the mixture of the monomers.
  • Suitable co-solvents include water-soluble as well as water-insoluble solvents.
  • Suitable co-solvents include aromatic compounds such as benzene, toluene, xylene and chlorobenzene; esters such as ethyl acetate, butyl acetate, methyl glycol acetate, ethyl glycol acetate and methoxypropyl acetate; ethers such as butyl glycol, tetrahydrofuran, dioxane, ethyl glycol ether and ethers of diglycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; trichloromonofluoroethane; and cyclic amides such as N-methyl-pyrrolidone and N-methylcaprolactam
  • the free radical-initiated polymerization may be started by water-soluble and water-insoluble initiators or initiator systems whose radical decomposition half-lives at temperatures from 10° C. to 100° C. are 0.5 sec. to 7 hours.
  • the polymerization is carried out in aqueous emulsion in the aforementioned temperature range, preferably between 30° C. and 90° C., under a pressure of 10 3 to 2 ⁇ 10 4 mbar.
  • the exact polymerization temperature is determined according to the type of initiator.
  • the initiators are used in amounts of 0.05 to 6 wt. %, based on the total amount of monomers.
  • Suitable initiators include water-soluble and water-insoluble azo compounds such as azoisobutyrodinitrile or 4,4'-azo-bis-(4-cyanopentanoic acid); inorganic and organic peroxides such as dibenzoyl peroxide, t-butyl perpivalate, t-butyl-per-2-ethylhexanoate, t-butyl perbenzoate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, dicyclohexyl dicarbonate, dibenzyl peroxydicarbonate, the sodium, potassium and ammonium salts of peroxodisulfuric acid, and hydrogen peroxide.
  • water-soluble and water-insoluble azo compounds such as azoisobutyrodinitrile or 4,4'-azo-bis-(4-cyanopentanoic acid
  • inorganic and organic peroxides such as dibenzoyl peroxide
  • the peroxodisulfates and hydrogen peroxides may be used in combination with reducing agents, such as the sodium salt of formamidinesulfinic acid, ascorbic acid or polyalkylene polyamines. A significant reduction of the polymerization temperature is generally thereby achieved.
  • regulators In order to regulate the molecular weight of the polymers conventional regulators may be used, such as n-dodecylmercaptan, t-dodecylmercaptan, diisopropyl xanthogene disulfide, di(methylene-trimethylolpropane)xanthogene disulfide and thioglycol.
  • the regulators are added in amounts of at most 3 wt. %, based on the monomer mixture.
  • neutralizing agents are added to the polymers present in aqueous dispersion to obtain a degree of neutralization of 30 to 100%, preferably 50 to 100%.
  • Inorganic bases ammonia or amines are added as neutralizing agents. Examples include inorganic bases, such as sodium hydroxide and potassium hydroxide; and amines such as ammonia, trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine and triethanolamine.
  • the neutralizing agents may be used in substoichiometric or excess stoichiometric amounts, which results in the aforementioned contents of sulfonate and/or carboxylate groups, in particular carboxylate groups and the aforementioned acid numbers.
  • the result is an acid number of zero, such that the content of sulfonate and/or carboxylate groups corresponds to the original content of sulfonic acid groups and/or carboxyl groups.
  • the content of sulfonate and/or carboxylate groups corresponds to the amount of neutralizing agent that is employed.
  • the resulting aqueous dispersions have the aforementioned concentrations and viscosities.
  • the optional co-solvents may remain in the aforementioned amounts in the aqueous dispersion or may be removed by distillation after the polymerization reaction.
  • Preferred aqueous dispersions B comprising polyacrylates are dispersions sold under the brand name Primal® which are available from Rohm and Hass, Philadelphia, Pa., USA.
  • Preferred aqueous dispersions B comprising polybutadiene include Euderm®-Resin40B and Euderm®-Resin50B.
  • dispersion B comprises at least one coagulant besides at least one polymer selected from the group consisting of polyacrylate and polybutadiene.
  • a coagulant is a salt or acid, for example ammonium salts of organic acids, which causes coagulation of the at least one polymer selected from the group consisting of polyacrylate and polybutadiene under certain conditions, such as, for example, a particular temperature.
  • These substances include an acid-generating chemical agent, i.e. a substance which is not an acid at room temperature, but becomes an acid after warming.
  • Certain examples of such compounds include ethylene glycol diacetate, ethylene glycol formate, diethylene glycol formate, triethyl citrate, monostearyl citrate and an organic acid ester.
  • the coagulant is preferably present in the composition in an amount of 1 to 10 % by weight, based on the solids content of dispersion B.
  • the number average particle size of the specific polyacrylate dispersions and polybutadiene dispersions is preferably less than 750 nm, particularly preferably less than 500 nm and very particularly preferably less than 400 nm, determined by means of laser correlation spectroscopy.
  • the manner in which the precipitation in or on the textile substrate is accomplished depends to a large extent on the chemical composition of the dispersion B used in accordance with the invention and in particular on the type of coagulant, if present.
  • the precipitation can be carried out by evaporation coagulation or by salt, acid or electrolyte coagulation.
  • the precipitation is achieved by an increase in temperature.
  • the textile substrate can be subjected to brief heat treatment with steam, for example at 100 to 110 °C for 1 to 10 s. This is particularly preferred if ammonium salts or organic acids are used as coagulant. If, on the other hand, the above-mentioned acid-generating chemicals are used as coagulant, the precipitation is preferably carried out as described in US 5,916,636 , US 5,968,597 , US 5,952,413 and US 6,040,393 .
  • the coagulation is caused by dipping into a salt solution.
  • the coagulation is preferably carried out using an inorganic salt selected from the group consisting of alkali metal salts and alkaline-earth metal salts.
  • the inorganic salt is particularly preferably a salt selected from the group consisting of alkali metal halides, alkali metal nitrates, alkali metal phosphates, alkali metal sulfates, alkali metal carbonates, alkali metal hydrogen carbonates, alkaline-earth metal halides, alkaline-earth metal phosphates, alkaline-earth metal nitrates, alkaline-earth metal sulfates, alkaline-earth metal carbonates and alkaline-earth metal hydrogen carbonates.
  • the inorganic salt is very particularly preferably sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium sulfate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, magnesium chloride, magnesium sulfate, calcium chloride or calcium sulfate.
  • the inorganic salt is still more preferably calcium chloride or magnesium chloride.
  • the inorganic salt is preferably present in the salt solution in an amount of 1 to 25 % by weight, particularly preferably in an amount of 1 to 15 % by weight, very particularly preferably in an amount of 1 to 10 % by weight, based on the total amount of salt solution.
  • step c After the precipitation in step c), further steps, such as drying or condensation, are carried out if necessary.
  • the textile substrate employed is preferably a woven fabric, knitted fabric or nonwoven based on natural and/or synthetic fibers.
  • the textile substrate is particularly preferably a nonwoven (staple fiber nonwoven, microfiber nonwoven or the like).
  • the textile substrate can preferably be built up from fibers of polyester, nylon (6 or 6,6), cotton, polyester/cotton blends, wool, ramie, spandex, glass, thermoplastic polyurethane (TPU), thermoplastic olefins (TPO) or the like.
  • the textile substrate can have a linked/mesh-like (knitted), woven or nonwoven construction.
  • the textile substrate can be treated with dyes, colorants, pigments, UV absorbers, plasticizers, soil redeposition agents, lubricants, antioxidants, flame inhibitors, rheology agents and the like, either before coating or thereafter, but there is a preference for such additions before coating.
  • the present invention therefore furthermore relates to a coated textile, preferably synthetic leather, obtained by the process according to the invention.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Paints Or Removers (AREA)

Claims (11)

  1. Procédé de fabrication de textiles enduits, consistant au moins à :
    a) mettre un substrat textile en contact avec une solution aqueuse A comprenant au moins un sel inorganique et au moins une cellulose modifiée,
    b) mettre un substrat textile en contact avec une dispersion aqueuse B comprenant au moins un polymère choisi dans le groupe constitué par le polyacrylate et le polybutadiène et
    c) précipiter l'au moins un polymère choisi dans le groupe constitué par le polyacrylate et le polybutadiène dans ou sur le substrat textile.
  2. Procédé selon la revendication 1, dans lequel le sel inorganique est un sel sélectionné dans le groupe constitué de sels de métaux alcalins et de sels de métaux alcalino-terreux.
  3. Procédé selon la revendication 2, dans lequel le sel de métal alcalin est un sel sélectionné dans le groupe constitué d'halogénures de métaux alcalins, de nitrates de métaux alcalins, de phosphates de métaux alcalins, de sulfates de métaux alcalins, de carbonates de métaux alcalins et d'hydrogénocarbonates de métaux alcalins.
  4. Procédé selon la revendication 2, dans lequel le sel de métal alcalino-terreux est un sel sélectionné dans le groupe constitué d'halogénures de métaux alcalino-terreux, de nitrates de métaux alcalino-terreux, de phosphates de métaux alcalino-terreux, de sulfates de métaux alcalino-terreux, de carbonates de métaux alcalino-terreux et d'hydrogénocarbonates de métaux alcalino-terreux.
  5. Procédé selon la revendication 1, dans lequel le sel inorganique est présent dans la dispersion A dans une quantité de 0,01 % à 25 % en poids, relativement à la quantité totale de dispersion A.
  6. Procédé selon la revendication 1, dans lequel la cellulose modifiée est un composé sélectionné dans le groupe constitué de la méthylcellulose, de l'éthylcellulose, de la propylcellulose, de l'hydroxyméthylcellulose, de l'hydroxyéthylcellulose, de l'hydroxypropylcellulose, de l'hydroxypropylméthylcellulose, de la carboxyméthylcellulose, de la carboxyéthylcellulose et de la carboxypropylcellulose.
  7. Procédé selon la revendication 1, dans lequel la cellulose modifiée est présente dans la dispersion A dans une quantité de 10 ppm à 5 % en poids, relativement à la quantité totale de dispersion A.
  8. Procédé selon la revendication 1, caractérisé en ce que le substrat textile employé est un tissu tissé, un tissu tricoté ou un non-tissé à base de fibres naturelles et/ou synthétiques.
  9. Procédé selon la revendication 1, caractérisé en ce que l'au moins un polymère choisi dans le groupe constitué par le polyacrylate et le polybutadiène est précipité à l'étape c) dans un bain contenant de l'eau ou en utilisant une température de 80 °C à 120 °C.
  10. Textile enduit pouvant être obtenu par un procédé selon les revendications 1 à 9.
  11. Textile enduit selon la revendication 10, caractérisé en ce que le textile enduit est un cuir synthétique.
EP12783579.1A 2011-11-04 2012-11-02 Procédé d'enduction de produits textiles. Active EP2773809B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/CN2011/001862 WO2013063724A1 (fr) 2011-11-04 2011-11-04 Procédé pour l'enduction de textiles
PCT/EP2012/071695 WO2013064617A1 (fr) 2011-11-04 2012-11-02 Procédé d'enduction de produits textiles.

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EP2773809B1 true EP2773809B1 (fr) 2020-02-05

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EP (1) EP2773809B1 (fr)
JP (1) JP6295201B2 (fr)
KR (1) KR101981354B1 (fr)
BR (1) BR112014010817A2 (fr)
CA (1) CA2854257A1 (fr)
MX (1) MX2014005349A (fr)
TW (1) TWI589751B (fr)
WO (2) WO2013063724A1 (fr)

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CN107780230A (zh) * 2016-08-24 2018-03-09 科思创聚合物（中国）有限公司 织物涂覆方法

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DE1953349C3 (de) 1969-10-23 1975-07-03 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung wäßriger Dispersionen von Polymerisaten aus olefinisch ungesättigten Monomeren
JPS4828043B1 (fr) * 1970-08-14 1973-08-29
JPS5936713B2 (ja) * 1979-06-05 1984-09-05 東レ株式会社 寸法安定性に優れた皮革状シ−トの製造方法
DE3806066A1 (de) 1988-02-26 1989-09-07 Bayer Ag Verfahren zur herstellung von waessrigen polymerisatdispersionen, die so erhaeltlichen dispersionen und ihre verwendung zur herstellung von beschichtungen
US5518764A (en) * 1994-03-22 1996-05-21 Bayer Aktiengesellschaft Process for coating textiles
US5916636A (en) 1998-03-17 1999-06-29 Milliken & Company Method of making a polyurethane suede-like fabric/elastomer composite
US6380298B2 (en) * 1998-11-13 2002-04-30 Owens Corning Fiberglas Technology, Inc. Superabsorbent water-resistant coatings for fiber-reinforced articles
TW526304B (en) * 1999-03-30 2003-04-01 Kuraray Co Process for producing a leather-like sheet
JP2002249988A (ja) * 2001-02-20 2002-09-06 Toray Ind Inc 皮革様シート状物の製造方法
KR101289578B1 (ko) * 2002-12-20 2013-07-24 다우 글로벌 테크놀로지스 엘엘씨 합성 가죽의 제조방법 및 이러한 방법으로 제조된 합성가죽
JP4697737B2 (ja) * 2004-12-22 2011-06-08 三洋化成工業株式会社 皮革様シート材料の製造方法
WO2008077786A1 (fr) 2006-12-22 2008-07-03 Basf Se Procédé de fabrication de textiles enduits, notamment de cuir synthétique
GB0906727D0 (en) * 2009-04-20 2009-06-03 Midas Safety Inc Foamed polymer
CN102094319A (zh) * 2009-12-11 2011-06-15 国家纳米技术与工程研究院 一种纺织品抗菌剂及其制备与应用
DE102010011067B4 (de) * 2010-03-11 2014-02-20 Trans-Textil Gmbh Flexibles Flächenmaterial zur Begrenzung eines Matrixmaterial-Zuführraums und Verfahren zu dessen Herstellung
WO2013056391A1 (fr) * 2011-10-18 2013-04-25 Bayer Materialscience Ag Procédé pour l'enduction de textiles

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EP2773809A1 (fr) 2014-09-10
BR112014010817A2 (pt) 2017-04-18
JP2015501393A (ja) 2015-01-15
WO2013064617A1 (fr) 2013-05-10
KR20140093697A (ko) 2014-07-28
JP6295201B2 (ja) 2018-03-14
MX2014005349A (es) 2014-05-28
KR101981354B1 (ko) 2019-05-22
TWI589751B (zh) 2017-07-01
US20140370770A1 (en) 2014-12-18
WO2013063724A1 (fr) 2013-05-10
CA2854257A1 (fr) 2013-05-10
TW201333300A (zh) 2013-08-16

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