EP0781359A1 - Use of solvent-resistant textile binders - Google Patents

Use of solvent-resistant textile binders

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Publication number
EP0781359A1
EP0781359A1 EP95932751A EP95932751A EP0781359A1 EP 0781359 A1 EP0781359 A1 EP 0781359A1 EP 95932751 A EP95932751 A EP 95932751A EP 95932751 A EP95932751 A EP 95932751A EP 0781359 A1 EP0781359 A1 EP 0781359A1
Authority
EP
European Patent Office
Prior art keywords
weight
vinyl
alkoxymethyl
copolymer
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP95932751A
Other languages
German (de)
French (fr)
Other versions
EP0781359B1 (en
Inventor
Andreas Lumpp
Gerhard KÖGLER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
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Wacker Chemie AG
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Publication of EP0781359A1 publication Critical patent/EP0781359A1/en
Application granted granted Critical
Publication of EP0781359B1 publication Critical patent/EP0781359B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425—Cellulose series
    • D04H1/4258—Regenerated cellulose series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • 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
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • 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
    • 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
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • 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
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
    • 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
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • the invention relates to the use of N- (alkoxymethyl) - (meth) acrylamide-functional textile binders to improve the solvent resistance in the finishing and strengthening of fiber materials, and to a method for producing solvent-resistant fiber structures.
  • aqueous copolymer dispersions as binders for solidifying and coating fiber structures such as fabrics, nonwovens and wadding made of textile fibers or textile yarns.
  • copolymer dispersions of (meth) acrylate or vinyl ester copolymers which contain self-crosslinking comonomer units with N-methylol or N-methylol ether functions to improve the strength, usually up to 10% by weight % N-methylol- (meth) acrylic id (NMA or NMMA) copolymerized.
  • NMA or NMMA N-methylol- (meth) acrylic id copolymerized.
  • a disadvantage of these binders is the release of formaldehyde by hydrolytic cleavage of the N-methylol function and the low solvent resistance of the materials solidified or coated with them. It is known to improve the resistance to solvents by incorporating pre-crosslinking, polyethylenically unsaturated comonomer units. However, this measure frequently leads to problems
  • thermally self-crosslinking copolymers which contain 2 to 10% by weight of N-Me- contain thylol- (meth) acrylamide or their N-methylol ether.
  • a disadvantage is that in the copolymers containing N-methylol-acrylamide used therein, the tempered copolymer films show good solvent resistance, but not the nonwovens bonded with them.
  • EP-B 205862 relates to textile binders based on vinyl acetate-ethylene copolymers which contain 1 to 5% by weight of N-methylol (meth) acrylamide units or their ethers.
  • N-methylol (meth) acrylamide units or their ethers In order to improve the wet strength when using a copolymer binder with a low NMA content, it is proposed to additionally use melamine formaldehyde resins.
  • EP-A 261378 teaches to improve the heat resistance of fiber mats bonded with N-methylol-functional copolymers by using copolymers in which the N-methylol functions are wholly or partly etherified as binders are.
  • WO-A 92/08835 describes textile binders based on vinyl acetate / ethylene copolymer emulsions which, instead of N-methylol- (meth) acrylamide units, exclusively N- (n-butoxymethy1) acrylamide to reduce the release of formaldehyde -Units included.
  • EP-A 86889 (AU-A 8310718) relates to a process for producing a textile coating composition which, under the action of water, shows no white swelling and no white break.
  • the coating agent consists of an aqueous copolymer emulsion which is obtained by emulsion copolymerization of (meth) acrylates with N-methylol- (meth) acrylamide, the N-methylol- (meth) crylamides being at least 20 Mol% are etherified with an alcohol and the emulsion polymerization takes place in the presence of a fatty alcohol having 10 to 20 carbon atoms.
  • the solvent resistance textile binders are not discussed.
  • the invention was based on the object of providing binders based on aqueous copolymer dispersions or copolymer powders which, in addition to high dry and wet strength, impart high solvent resistance to textiles finished therewith.
  • the invention relates to the use of N- (alkoxymethyl) - (meth) acrylamide-functional textile binders to improve the solvent resistance in the finishing and solidification of fiber materials with textile binders, characterized in that an aqueous copolymer dispersion or a redispersible material is used as the textile binder Copolymer powder of copolymers with a Tg of -60 * C to + 60 * C, containing a) one or more monomer units from the group of the vinyl esters of unbranched or branched carboxylic acids with 1 to 12 C atoms, the esters acrylic acid and methacrylic acid with unbranched or branched alcohols having 1 to 12 carbon atoms, vinyl aromatics, vinyl halides and ⁇ -olefins, and b) 0.3 to 10% by weight, based on the total weight of the copolymer, of one or more N.
  • Methylol methacrylamide in a weight ratio of N- Methylol compound to N- (alkoxymethyl) compound of at most 5: 1 is used.
  • N- (alkoxymethyl) - (meth) acrylamides are N- (isobutoxymethyl) acrylamide (IBMA), N- (isobutoxymethyl) methacrylamide (IBMMA), N- (n-butoxymethyl) acrylamide (NBMA) and N- (n-butoxymethyl) methacrylamide (NBMMA).
  • the copolymers preferably contain 0.5 to 3.0% by weight, based on the total weight of the copolymer, of N- (alkoxy-methyl) acrylamides or N- (alkoxymethyl) methacrylamides with a C ⁇ _- to Cg-alkyl radical or mixtures of these N- (alkoxy ⁇ methyl) - (meth) acrylamides with N-methylolacrylamide (NMA) and / or N-methylolmethacrylamide (NMMA).
  • NMA N-methylolacrylamide
  • NMMA N-methylolmethacrylamide
  • copolymers which, in the proportions by weight mentioned, mixtures of the N- (alkoxymethyl) - (meth) acrylamides with N-methylolacrylamide or N-methylolmethacrylamide in a weight ratio of N-methylol compound to N- (alkoxymethyl) compound from 5: 1 to 1:10 included.
  • copolymers in particular 0.5 to 3.0% by weight, based on the total weight of the copolymer, of a mixture of NMA and IBMA (IBMMA) in a weight ratio of NMA / IBMA (IBMMA) of 3: 1 to 1: 5 from 1: 1 to 1: 5 included.
  • vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, l-methyl vinyl acetate, vinyl pivalate and vinyl esters of a-branched monocarboxylic acids with 9 to 10 carbon atoms, for example VeoVa9 R or VeoVal0 R. Vinyl acetate is particularly preferred.
  • Preferred methacrylic acid esters or acrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl ethacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate.
  • Methyl acrylate, methyl methacrylate, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
  • the vinyl ester copolymers may optionally contain from 1.0 to 50% by weight, based on the total weight of the comonomer phase, of o-olefins such as ethylene or propylene and / or vinyl aromatics such as styrene and / or vinyl halides such as vinyl chloride and / or acrylic acid esters or methacrylic acid esters of alcohols 1 to 12 carbon atoms, such as methyl acrylate Methylmeth ⁇ , ethyl acrylate, ethyl methacrylate, Pr 'opylacrylat, pylmethacrylat product, n-butyl acrylate, n-butyl methacrylate, hexyl acrylate 2-ethyl and / or ethylenically unsaturated esters and their Dicarbonsau ⁇ Derivatives such as diisopropyl fumarate, which contain dimethyl, dibutyl and diethyl esters of maleic acid or
  • the (meth) acrylic ester copolymers may optionally contain 1.0 to 50% by weight, based on the total weight of the comonomer phase, of ⁇ -olefins such as ethylene or propylene and / or vinyl aromatics such as styrene and / or vinyl halides such as vinyl chloride and / or ethylenically unsaturated Dicarboxylic acid esters or their derivatives, such as diisopropyl fumarate, which contain dimethyl, dibutyl and diethyl esters of maleic acid or fumaric acid, or maleic anhydride.
  • the selection from the mentioned monomers is preferably made in such a way that copolymers with a glass transition temperature Tg of -30 ° C. to + 30 ° C. are obtained.
  • the vinyl ester copolymers and the (meth) acrylic ester copolymers may also contain 0.05 to 3.0% by weight, based on the total weight of the comonomer mixture, one or more auxiliary monomers from the group of ethylenically unsaturated carboxylic acids, preferably acrylic acid or methacrylic acid, from the group of ethylenically unsaturated carboxylic acid amides, preferably acrylamide and 2-acrylic amidopropanesulfonic acid, from the group of ethylenically unsaturated sulfonic acids or their Salts, preferably vinylsulfonic acid, and / or from the group of the polyethylenically unsaturated comonomers, for example divinyladipath, 1,9-decadiene, allyl methacrylate, triallyl cyanurate and crosslinking comonomers such as acrylamidoglycolic acid (AGA), methyl acrylamidoglycolic acid methyl ester (
  • Preferred vinyl ester copolymers contain as comonomer units a), in each case based on the total weight of the
  • vinyl ester in particular vinyl acetate, and 1 to 30% by weight of acrylic acid ester, in particular n-butyl acrylate or 2-ethylhexyl acrylate;
  • vinyl acetate 50 to 75% by weight of vinyl acetate, 1 to 30% by weight of acrylic acid ester, in particular n-butyl acrylate or 2-ethylhexyl acrylate, and
  • VeoVal0 R 1 to 30% by weight acrylic acid ester, especially n- Butyl acrylate or 2-ethylhexyl acrylate, and 10 to 40% by weight of ethylene;
  • Preferred (meth) acrylic acid ester copolymers contain as comonomer units a), in each case based on the total weight of the copolymer:
  • the vinyl ester copolymers or the (meth) acrylic ester copolymers are preferably prepared by the emulsion polymerization process.
  • the polymerization can be carried out batchwise or continuously, with or without the use of seed latices, with presentation of all or individual constituents of the reaction mixture, or with partial presentation and subsequent metering of the or individual constituents of the reaction mixture, or according to the metering process without presentation . All doses are preferably made to the extent of the consumption of the respective component.
  • comonomers a) 10 to 25% by weight are initially introduced and the remainder is metered in together with the comonomers b) in emulsion.
  • abs is preferably at a pressure of 20 to 100 bar. worked.
  • the polymerization is carried out in a temperature range from 40.degree. C. to 80.degree. C. and initiated using the methods usually used for emulsion polymerization.
  • the initiation is carried out using the customary water-soluble Ra Dical formers, which are preferably used in amounts of 0.01 to 1.0% by weight, based on the total weight of the monomers. Examples include ammonium and potassium persulfate, alkyl hydroperoxides, such as tert-butyl hydroperoxide; Hydrogen peroxide.
  • the radical initiators mentioned can also be combined in a known manner with 0.01 to 0.5% by weight, based on the total weight of the monomers, of reducing agents. For example, formaldehyde sulfoxylate salts, sodium bisulfite or ascorbic acid are suitable.
  • redox catalyst components are preferably metered in during the polymerization.
  • emulsifiers and protective colloids conventionally used in emulsion polymerization can be used as dispersants.
  • anionic surfactants such as alkyl sulfates with a chain length of 8 to 18 carbon atoms, alkyl and alkylaryl ether sulfates with 8 to 18 carbon atoms in the hydrophobic radical and up to 40 ethylene or propylene oxide units, alkyl or alkylaryl sulfonates are suitable with 8 to 18 carbon atoms, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols.
  • Suitable nonionic surfactants are, for example, alkyl polyglycol ethers or alkylaryl polyglycol ethers with 8 to 40 ethylene oxide units.
  • protective colloids preferably in amounts of up to 4% by weight, based on the total weight of the monomers.
  • examples of these are vinyl alcohol / vinyl acetate copolymers with a content of 80 to 100 mol% of vinyl alcohol units, polyvinyl pyrrolidones with a molecular weight of 5,000 to 400,000, hydroxyethyl celluloses with a degree of substitution range of 1.5 to 3.
  • the pH range desired for the polymerization which is generally between 3 and 7, can be set in a known manner using acids, bases or conventional buffer salts, such as alkali metal phosphates or alkali metal carbonates.
  • the regulators typically used for example mercaptans, aldehydes and chlorinated hydrocarbons, can be added during the polymerization.
  • the solids content of the aqueous dispersions is preferably 30 to 65% by weight.
  • the dispersion is dried, preferably spray-dried or freeze-dried, particularly preferably spray-dried.
  • Known devices such as spraying through multi-component nozzles or with the disk, in a possibly heated dry gas flow, can be used here. In general, temperatures above 250'C are not used. The optimum temperature of the drying gas can be determined in a few experiments; temperatures above 60 ° C. have often proven particularly useful.
  • antiblocking agents for example aluminum silicates, diatomaceous earth, calcium carbonate
  • defoamers for example based on silicone or hydrocarbons
  • spraying aids for example polyvinyl alcohols or water-soluble melamine-formaldehyde condensation products, can optionally be added to the dispersion.
  • the dispersion powders still contain 0 to 30% by weight, particularly preferably 1 to 15 % By weight, based on the base polymer, polyvinyl alcohol with a degree of hydrolysis of 85 to 94 mol%, and / or 0 to 10% by weight vinyl alcohol copolymers with 5 to 35% by weight 1-methyl-vinyl alcohol units, and / or 0 to 30% by weight, particularly preferably 4 to 20% by weight, based on the total weight of polymeric constituents, antiblocking agents and optionally up to 2% by weight, based on the base polymer, defoamer.
  • the aqueous copolymer dispersions or the redispersible dispersion powders are suitable for finishing and solidifying natural or synthetic " fiber materials.
  • fiber materials include wood fiber, cellulose fiber, wool, cotton, mineral fibers, ceramic fibers, synthetic fibers based on fiber-forming polymers such as Viscose fiber, polyethylene, polypropylene, polyester, polyamide, polyacrylonitrile or carbon fiber, fibers of homo- or copolymerizates of vinyl chloride or fibers of homo- or copolyme- risates of tetrafluoroethylene Copolymer dispersions or the dispersible polymer powders for finishing and solidifying cellulose fiber materials.
  • Another object of the invention is a process for the production of solvent-resistant fiber structures, characterized in that an aqueous copolymer dispersion or a redispersible copolymer powder of copolymers with a Tg of -60'C to + 60 * C, containing a) one or more monomer units from the Group of the vinyl esters of unbranched or branched carboxylic acids with 1 to 12 C atoms, the esters of acrylic acid and methacrylic acid with unbranched or branched alcohols with 1 to 12 C atoms, vinyl aromatics, vinyl halides and ⁇ -olefins and b ) 0.3 to 10% by weight, based on the total weight of the copolymer, one or more N- (alkoxymethyl) acrylamides or N- (alkoxymethyl) methacrylamides with a C 1 -C 6 -alkyl radical or mixtures of these N- (alkoxymethyl) - (meth) acrylamides with N-methylol
  • the fibers are spread out over a large area.
  • the methods for this are known and primarily depend on the application in which the solidified fiber material goes.
  • the fibers can be laid out by means of an air-laying, wet-laying, direct spinning or carding device. If necessary, the flat structures can be mechanically solidified with binding agent prior to solidification, for example by cross-laying, needling or water jet hardening.
  • the aqueous copolymer dispersions are customarily impregnated, foam-impregnated, sprayed, slapped. Brushed or printed applied. If necessary after separating off the excess binder by, for example, squeezing, the textile structures are dried at temperatures from 80 to 200 ° C., preferably between 120 and 180 ° C. Depending on the area of application, the amount of binder required to solidify the fiber material is between 5 and 50% by weight of binder, based on the weight of the fiber.
  • the powdered binder is sprinkled in a manner known per se onto the, if appropriate mechanically pre-consolidated, fiber material. sprinkled in (e.g. with carded wadding), shaken in or mixed directly with the fiber.
  • the textile structures at temperatures of 80 to 200 'C, preferably zwi ⁇ rule 120 and 180 * C and dried.
  • the amount of binder required to solidify the fiber material is between 5 and 50% by weight of binder, based on the weight of the fiber.
  • Pigments, antioxidants, dyes, plasticizers, film-forming aids, fillers, flame retardants, foam-forming aids, foam inhibitors, wetting agents, thermosensitizers, antistatic agents, biocides, grip improvers, additional crosslinking agents or catalysts to accelerate the crosslinking reaction, if necessary, can also be added to the binder according to the invention in the usual amounts for this purpose.
  • the solvent-resistant textile binder is preferably suitable for the consolidation of nonwovens, for example in the household and hygiene area and for industrial wipes. Another area of application is the anti-slip finishing of fabrics.
  • a cellulose fiber fleece was solidified by means of a full bath impregnation with 20% by weight copolymer dispersion (solid based on fiber). The excess binder was squeezed between two rollers and the fleece was dried for 3 minutes at 150 ° C. in a drum dryer.
  • Solvent resistance of the nonwovens was determined by measuring the maximum tensile force (HZK) of nonwoven strips with a width of 1.5 cm and a length of 15 cm.
  • the nonwovens were stored in a standard atmosphere at T-23'C and 50% RH (DIN 50014) for at least 24 hours.
  • the nonwovens were stored in water for 1 minute immediately before the measurement.
  • the nonwovens were stored in isopropanol for 1 minute immediately before the measurement.
  • the maximum tensile force was measured using a Zwick tensile testing machine, the tensile measurement being carried out at a constant rate of expansion of 100 mm / min. The maximum tensile force is determined for each measurement and the measurement ends when the force has dropped to 40% of the maximum tractive force. 5 non-woven strips per sample were clamped together. The average of two series of measurements was determined.

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Abstract

The invention pertains to the use of N-(alkoxymethyl)-meth(acrylamide-functional textile binders to improve resistance to solvents in finishing and stabilizing fiber materials with textile binders, characterized in that the textile binder used is an aqueous copolymer dispersion or a redispersible copolymer powder of copolymers with a Tg of -60 °C to +60 °C, containing (a) one or more monomer units from the group consisting of vinyl esters of unbranched or branched carboxylic acids with 1 to 12 carbon atoms, esters of acrylic acid and methacrylic acid with unbranched or branched alcohols with 1 to 12 carbon atoms, vinyl aromatics, vinyl halides and α-olefins, and (b) 0.3 to 10 wt %, relative to the total weight of the copolymer, of one or more N-(alkoxymethyl)-acrylamides or N-(alkoxymethyl)methacrylamides with a C1-C6 alkyl residue, or mixtures of these N-(alkoxymethyl)-meth(acrylamides with N-methylolacrylamide and/or N-methylolmethacrylamide in a weight ratio of N-methylol compound to N-(alkoxymethyl) compound of at most 5:1.

Description

Lösungsmittelfester Textilbinder Solvent resistant textile binder
Die Erfindung betrifft die Verwendung von N-(Alkoxymethyl)- (meth)acrylamid-funktionellen Textilbindemitteln zur Verbesserung der Lösungsmittelfestigkeit bei der Ausrüstung und Verfestigung von Fasermaterialien, sowie ein Verfahren zur Herstellung von lösungsmittelfesten Fasergebilden.The invention relates to the use of N- (alkoxymethyl) - (meth) acrylamide-functional textile binders to improve the solvent resistance in the finishing and strengthening of fiber materials, and to a method for producing solvent-resistant fiber structures.
Die Verwendung von wäßrigen Copolymerdispersionen als Binde¬ mittel zur Verfestigung und Beschichtung von Fasergebilden wie Geweben, Vliesen und Watten aus Textilfaser oder Textil- garnen ist bekannt. Häufig werden dabei Copolymerdispersio¬ nen von (Meth)acrylat- oder Vinylester-Copolymerisaten ein¬ gesetzt, welche zur Verbesserung der Festigkeit selbstver¬ netzende Comonomereinheiten mit N-Methylol- oder N-Methylol- ether-Funktionen enthalten, üblicherweise werden bis zu 10 Gew% N-Methylol-(Meth)acryla id (NMA bzw. NMMA) copolymeri- siert. Nachteilig bei diesen Bindemitteln ist die Formalde¬ hydfreisetzung durch hydrolytische Spaltung der N-Methylol- Funktion sowie die geringe Lösungsmittelbeständigkeit der damit verfestigten oder beschichteten Materialien. Die Ver¬ besserung der Lösungsmittelbeständigkeit durch Einbau von vorvernetzenden, mehrfach ethylenisch ungesättigten Comono- mer-Einheiten ist bekannt. Diese Maßnahme führt jedoch häu¬ fig zu Problemen bei der Herstellung der Copolymerisate.The use of aqueous copolymer dispersions as binders for solidifying and coating fiber structures such as fabrics, nonwovens and wadding made of textile fibers or textile yarns is known. Often, copolymer dispersions of (meth) acrylate or vinyl ester copolymers are used which contain self-crosslinking comonomer units with N-methylol or N-methylol ether functions to improve the strength, usually up to 10% by weight % N-methylol- (meth) acrylic id (NMA or NMMA) copolymerized. A disadvantage of these binders is the release of formaldehyde by hydrolytic cleavage of the N-methylol function and the low solvent resistance of the materials solidified or coated with them. It is known to improve the resistance to solvents by incorporating pre-crosslinking, polyethylenically unsaturated comonomer units. However, this measure frequently leads to problems in the preparation of the copolymers.
Aus der DE-A 2512589 (US-A 4044197) sind thermisch selbst¬ vernetzende Copolymere bekannt, welche 2 bis 10 Gew% N-Me- thylol-(meth)acrylamid oder deren N-Methylolether enthalten. Nachteilig ist, daß bei den darin verwendeten N-Methylol- acrylamid-haltigen Copolymeren zwar die getemperten Copoly- merfil e gute Lösungsmittelbeständigkeit zeigen, nicht aber die damit gebundenen Vliese.From DE-A 2512589 (US-A 4044197) thermally self-crosslinking copolymers are known which contain 2 to 10% by weight of N-Me- contain thylol- (meth) acrylamide or their N-methylol ether. A disadvantage is that in the copolymers containing N-methylol-acrylamide used therein, the tempered copolymer films show good solvent resistance, but not the nonwovens bonded with them.
Die EP-B 205862 betrifft Textilbinder auf der Basis von Vi- nylacetat-Ethylen-Copolymerisaten, welche 1 bis 5 Gew% N-Me¬ thylol(meth)acrylamid-Einheiten bzw. deren Ether enthalten. Zur Verbesserung der Naßfestigkeit, bei Verwendung eines Co- polymerbinders mit niederem NMA-Gehalt, wird vorgeschlagen zusätzlich Melaminformaldehyd-Harze einzusetzen.EP-B 205862 relates to textile binders based on vinyl acetate-ethylene copolymers which contain 1 to 5% by weight of N-methylol (meth) acrylamide units or their ethers. In order to improve the wet strength when using a copolymer binder with a low NMA content, it is proposed to additionally use melamine formaldehyde resins.
Die EP-A 261378 lehrt, die Hitzebeständigkeit von mit N-Me- thylol-funktionellen Copolymerisaten gebundenen Fasermatten dadurch zu verbessern, daß als Bindemittel solche Copoly e- risate eingesetzt werden, bei denen die N-Methylol-Funktio- nen ganz oder teilweise verethert sind.EP-A 261378 teaches to improve the heat resistance of fiber mats bonded with N-methylol-functional copolymers by using copolymers in which the N-methylol functions are wholly or partly etherified as binders are.
In der WO-A 92/08835 werden Textilbindemittel auf der Basis von Vinylacetat/Ethylen-Copolymeremulsionen beschrieben, welche zur Verminderung der Formaldehyd-Freisetzung anstelle von N-Methylol-(meth)acrylamid-Einheiten ausschließlich N- (n-butoxymethy1)-acrylamid-Einheiten enthalten.WO-A 92/08835 describes textile binders based on vinyl acetate / ethylene copolymer emulsions which, instead of N-methylol- (meth) acrylamide units, exclusively N- (n-butoxymethy1) acrylamide to reduce the release of formaldehyde -Units included.
Die EP-A 86889 (AU-A 8310718) betrifft ein Verfahren zur Herstellung eines Textilbeschichtungsmittels, welches unter Einwirkung von Wasser keine Weißquellung und keinen Wei߬ bruch zeigt. Das Beschichtungs ittel besteht aus einer wä߬ rigen Copolymeremulsion, welche durch Emulsionscopolymerisa- tion von (Meth)acrylaten mit N-Methylol-(meth)acrylamid er¬ halten werden, wobei die N-Methylol-(meth) crylamide zu min¬ destens 20 Mol% mit einem Alkohol verethert sind und die Emulsionspolymerisation in Gegenwart eines Fettalkohols mit 10 bis 20 C-Atomen erfolgt. Die Lösungsmittelbeständigkeit von Textilbindern wird nicht diskutiert.EP-A 86889 (AU-A 8310718) relates to a process for producing a textile coating composition which, under the action of water, shows no white swelling and no white break. The coating agent consists of an aqueous copolymer emulsion which is obtained by emulsion copolymerization of (meth) acrylates with N-methylol- (meth) acrylamide, the N-methylol- (meth) crylamides being at least 20 Mol% are etherified with an alcohol and the emulsion polymerization takes place in the presence of a fatty alcohol having 10 to 20 carbon atoms. The solvent resistance textile binders are not discussed.
Der Erfindung lag die Aufgabe zugrunde, Bindemittel auf der Basis von wäßrigen Copolymerdispersionen oder Copolymerpul- vern zur Verfügung zu stellen, welche damit ausgerüsteten Textilien neben hoher Trocken- und Naßfestigkeit eine hohe Lösungsmittelfestigkeit verleihen.The invention was based on the object of providing binders based on aqueous copolymer dispersions or copolymer powders which, in addition to high dry and wet strength, impart high solvent resistance to textiles finished therewith.
überraschenderweise ist dies dadurch gelungen, daß anstelle von N-Methylol-funktionellen Copolymerisaten solche verwen¬ det werden, in denen die N-Methylolfunktionen ganz oder vor¬ zugsweise teilweise verethert sind, wobei aufgrund des hy¬ drophoberen Charakters der N-Methylolether-haltigen Copoly- merisate eher der gegenteilige Effekt zu erwarten war.Surprisingly, this has been achieved by using, in place of N-methylol-functional copolymers, those in which the N-methylol functions are wholly or preferably partially etherified, with the N-methylol ether-containing copoly being due to the more hydrophobic nature of the copoly - Merisate rather the opposite effect was to be expected.
Gegenstand der Erfindung ist die Verwendung von N-(Alkoxy- methyl)-(meth)acrylamid-funktionellen Textilbindemitteln zur Verbesserung der Lösungsmittelfestigkeit bei der Ausrüstung und Verfestigung von Fasermaterialien mit Textilbindemit¬ teln, dadurch gekennzeichnet, daß als Textilbindemittel eine wäßrige Copolymerdispersion oder ein redispergierbares Copo- lymerp.ulver von Copolymeren mit einer Tg von -60*C bis +60*C, enthaltend a) ein oder mehrere Monomereinheiten aus der Gruppe der Vi- nylester von unverzweigten oder verzweigten Carbonsäuren mit 1 bis 12 C-Atomen, der Ester der Acrylsäure und Methacrylsäure mit unverzweigten oder verzweigten Alko¬ holen mit 1 bis 12 C-Atomen, Vinylaromaten, Vinylhaloge- nide und α-Olefine und b) 0.3 bis 10 Gew%, bezogen auf das Gesamtgewicht des Co¬ polymers, ein oder mehrere N-(Alkoxy ethyl)acrylamide oder N-(Alkoxymethyl)methacrylamide mit einem C^- bis Cg-Alkylrest oder Gemische dieser N-(Alkoxymethyl)- (meth)acrylamide mit N-Methylolacrylamid und/oder N-The invention relates to the use of N- (alkoxymethyl) - (meth) acrylamide-functional textile binders to improve the solvent resistance in the finishing and solidification of fiber materials with textile binders, characterized in that an aqueous copolymer dispersion or a redispersible material is used as the textile binder Copolymer powder of copolymers with a Tg of -60 * C to + 60 * C, containing a) one or more monomer units from the group of the vinyl esters of unbranched or branched carboxylic acids with 1 to 12 C atoms, the esters acrylic acid and methacrylic acid with unbranched or branched alcohols having 1 to 12 carbon atoms, vinyl aromatics, vinyl halides and α-olefins, and b) 0.3 to 10% by weight, based on the total weight of the copolymer, of one or more N. - (Alkoxy ethyl) acrylamides or N- (alkoxymethyl) methacrylamides with a C ^ - to Cg-alkyl radical or mixtures of these N- (alkoxymethyl) - (meth) acrylamides with N-methyl olacrylamide and / or N-
Methylolmethacrylamid in einem Gewichtsverhältnis von N- Methylolverbindung zu N-(Alkoxymethyl)-Verbindung von höchstens 5 : 1, verwendet wird.Methylol methacrylamide in a weight ratio of N- Methylol compound to N- (alkoxymethyl) compound of at most 5: 1 is used.
Bevorzugte N-(Alkoxymethyl)-(meth)acrylamide sind N-(isobut- oxymethyl)-acrylamid (IBMA) , N-(isobutoxymethyl)-methacryl- amid (IBMMA) , N-(n-butoxymethyl)-acrylamid (NBMA) und N-(n- butoxymethyl)-methacrylamid (NBMMA) .Preferred N- (alkoxymethyl) - (meth) acrylamides are N- (isobutoxymethyl) acrylamide (IBMA), N- (isobutoxymethyl) methacrylamide (IBMMA), N- (n-butoxymethyl) acrylamide (NBMA) and N- (n-butoxymethyl) methacrylamide (NBMMA).
Vorzugsweise enthalten die Copolymere 0.5 bis 3.0 Gew%, be¬ zogen auf das Gesamtgewicht des Copolymers, N-(Alkoxy¬ methyl)acrylamide oder N-(Alkoxymethyl)methacrylamide mit einem Cτ_- bis Cg-Alkylrest oder Gemische dieser N-(Alkoxy¬ methyl)-(meth)acrylamide mit N-Methylolacrylamid (NMA) und/oder N-Methylolmethacrylamid (NMMA) . Besonders bevorzugt werden Copolymere, welche in den genannten Gewichtsanteilen, Gemische der N-(Alkoxymethyl)-(meth)acrylamide mit N-Methy¬ lolacrylamid oder N-Methylolmethacrylamid in einem Gewichts¬ verhältnis von N- Methylolverbindung zu N-(Alkoxymethyl)- Verbindung von 5 : 1 bis 1 : 10 enthalten. Am meisten bevor¬ zugt werden Copolymere, welche 0.5 bis 3.0 Gewi, bezogen auf das Gesamtgewicht des Copolymers, eines Gemisches von NMA und IBMA (IBMMA) in einem Gewichtsverhältnis von NMA/IBMA (IBMMA) von 3 : 1 bis 1 : 5, insbesonders von 1 : 1 bis l : 5 enthalten.The copolymers preferably contain 0.5 to 3.0% by weight, based on the total weight of the copolymer, of N- (alkoxy-methyl) acrylamides or N- (alkoxymethyl) methacrylamides with a Cτ_- to Cg-alkyl radical or mixtures of these N- (alkoxy¬ methyl) - (meth) acrylamides with N-methylolacrylamide (NMA) and / or N-methylolmethacrylamide (NMMA). Particularly preferred are copolymers which, in the proportions by weight mentioned, mixtures of the N- (alkoxymethyl) - (meth) acrylamides with N-methylolacrylamide or N-methylolmethacrylamide in a weight ratio of N-methylol compound to N- (alkoxymethyl) compound from 5: 1 to 1:10 included. Most preferred are copolymers, in particular 0.5 to 3.0% by weight, based on the total weight of the copolymer, of a mixture of NMA and IBMA (IBMMA) in a weight ratio of NMA / IBMA (IBMMA) of 3: 1 to 1: 5 from 1: 1 to 1: 5 included.
Bevorzugte Vinylester sind Vinylacetat, Vinylpropionat, Vi- nylbutyrat, Vinyl-2-ethylhexanoat, Vinyllaurat, l-Methyl- vinylacetat, Vinylpivalat und Vinylester von a-verzweigten Monocarbonsäuren mit 9 bis 10 C-Atomen, beispielsweise VeoVa9R oder VeoVal0R. Besonders bevorzugt ist Vinylacetat.Preferred vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, l-methyl vinyl acetate, vinyl pivalate and vinyl esters of a-branched monocarboxylic acids with 9 to 10 carbon atoms, for example VeoVa9 R or VeoVal0 R. Vinyl acetate is particularly preferred.
Bevorzugte Methacrylsäureester oder Acrylsäureester sind Methylacrylat, Methylmethacrylat, Ethylacrylat, Ethylmeth- acrylat, Propylacrylat, Propyl ethacrylat, n-Butylacrylat, n-Butylmethacrylat, 2-Ethylhexylacrγlat. Besonders bevorzugt sind Methylacrylat, Methylmethacrylat , n-Butylacrylat und 2- Ethylhexylacrylat.Preferred methacrylic acid esters or acrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl ethacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate. Methyl acrylate, methyl methacrylate, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
Die Vinylester-Copolymerisate können gegebenenfalls 1.0 bis 50 Gew%, bezogen auf das Gesamtgewicht der Comonomerphase, o-Olefine wie Ethylen oder Propylen und/oder Vinylaromaten wie Styrol und/oder Vinylhalogenide wie Vinylchlorid und/oder Acrylsäureester bzw. Methacrylsäureester von Alko¬ holen mit 1 bis 12 C-Atomen, wie Methylacrylat, Methylmeth¬ acrylat, Ethylacrylat, Ethylmethacrylat, Pr'opylacrylat, Pro- pylmethacrylat, n-Butylacrylat, n-Butylmethacrylat, 2-Ethyl- hexylacrylat und/oder ethylenisch ungesättigte Dicarbonsau¬ reester bzw. deren Derivate wie Diisopropylfumarat, die Dimethyl-, Dibutyl- und Diethylester der Maleinsäure bzw. Fumarsäure, oder Maleinsäureanhydrid enthalten. Die Auswahl aus den genannten Monomeren wird dabei vorzugsweise so getroffen, daß Copolymerisate mit einer Glasübergangstempe¬ ratur Tg von -30*C bis +30*C erhalten werden.The vinyl ester copolymers may optionally contain from 1.0 to 50% by weight, based on the total weight of the comonomer phase, of o-olefins such as ethylene or propylene and / or vinyl aromatics such as styrene and / or vinyl halides such as vinyl chloride and / or acrylic acid esters or methacrylic acid esters of alcohols 1 to 12 carbon atoms, such as methyl acrylate Methylmeth¬, ethyl acrylate, ethyl methacrylate, Pr 'opylacrylat, pylmethacrylat product, n-butyl acrylate, n-butyl methacrylate, hexyl acrylate 2-ethyl and / or ethylenically unsaturated esters and their Dicarbonsau¬ Derivatives such as diisopropyl fumarate, which contain dimethyl, dibutyl and diethyl esters of maleic acid or fumaric acid, or maleic anhydride. The selection from the monomers mentioned is preferably made so that copolymers with a glass transition temperature Tg of -30 ° C. to + 30 ° C. are obtained.
Die (Meth) crylsäureester-Copolymerisate können gegebenen¬ falls 1.0 bis 50 Gew%, bezogen auf das Gesamtgewicht der Comonomerphase, α-Olefine wie Ethylen oder Propylen und/oder Vinylaromaten wie Styrol und/oder Vinylhalogenide wie Vinyl¬ chlorid und/oder ethylenisch ungesättigte Dicarbonsaureester bzw. deren Derivate wie Diisopropylfumarat, die Dimethyl-, Dibutyl- und Diethylester der Maleinsäure bzw. Fumarsäure, oder Maleinsäureanhydrid enthalten. Die Auswahl aus den ge¬ nannten Monomeren wird dabei vorzugsweise so getroffen, daß Copolymerisate mit einer Glasübergangstemperatur Tg von -30"C bis +30*C erhalten werden.The (meth) acrylic ester copolymers may optionally contain 1.0 to 50% by weight, based on the total weight of the comonomer phase, of α-olefins such as ethylene or propylene and / or vinyl aromatics such as styrene and / or vinyl halides such as vinyl chloride and / or ethylenically unsaturated Dicarboxylic acid esters or their derivatives, such as diisopropyl fumarate, which contain dimethyl, dibutyl and diethyl esters of maleic acid or fumaric acid, or maleic anhydride. The selection from the mentioned monomers is preferably made in such a way that copolymers with a glass transition temperature Tg of -30 ° C. to + 30 ° C. are obtained.
Gegebenenfalls enthalten die Vinylester-Copolymerisate und die (Meth)acrylsäureester-Copolymerisate noch 0.05 bis 3.0 Gew%, bezogen auf das Gesamtgewicht des Comonomergemisches, ein oder mehrere Hilfsmonomere aus der Gruppe der ethyle¬ nisch ungesättigten Carbonsäuren, vorzugsweise Acrylsäure oder Methacrylsäure, aus der Gruppe der ethylenisch ungesät¬ tigten Carbonsäureamide, vorzugsweise Acrylamid und 2-Acryl- amidopropansulfonsäure, aus der Gruppe der ethylenisch unge¬ sättigten Sulfonsäuren bzw. deren Salze, vorzugsweise Vinyl- sulfonsäure, und/oder aus der Gruppe der mehrfach ethyle¬ nisch ungesättigten Comonomeren, beispielsweise Divinyladi- pat, 1,9-Decadien, Allylmethacrylat, Triallylcyanurat und vernetzende Comonomere wie Acrylamidoglykolsäure (AGA) , Me- thylacrylamidoglykolsäuremethylester (MAGME) , Polyglykoldi- methacrylat.The vinyl ester copolymers and the (meth) acrylic ester copolymers may also contain 0.05 to 3.0% by weight, based on the total weight of the comonomer mixture, one or more auxiliary monomers from the group of ethylenically unsaturated carboxylic acids, preferably acrylic acid or methacrylic acid, from the group of ethylenically unsaturated carboxylic acid amides, preferably acrylamide and 2-acrylic amidopropanesulfonic acid, from the group of ethylenically unsaturated sulfonic acids or their Salts, preferably vinylsulfonic acid, and / or from the group of the polyethylenically unsaturated comonomers, for example divinyladipath, 1,9-decadiene, allyl methacrylate, triallyl cyanurate and crosslinking comonomers such as acrylamidoglycolic acid (AGA), methyl acrylamidoglycolic acid methyl ester (MAGME) , Polyglycol dimethacrylate.
Bevorzugte Vinylester-Copolymerisate enthalten als Comono- mereinheiten a) , jeweils bezogen auf das Gesamtgewicht desPreferred vinyl ester copolymers contain as comonomer units a), in each case based on the total weight of the
Copolymers:Copolymers:
90 bis 99.7 Gew% Vinylester, insbesonders Vinylacetat;90 to 99.7% by weight of vinyl ester, in particular vinyl acetate;
49.7 bis 89.7 Gew% Vinylester, insbesonders Vinylacetat sowie 10 bis 50 Gew% α-Olefin, insbesonders Ethylen;49.7 to 89.7% by weight of vinyl ester, in particular vinyl acetate and 10 to 50% by weight of α-olefin, in particular ethylene;
50 bis 75 Gew% Vinylacetat, 1 bis 30 Gew% Vinylester einer -verzweigten Carbonsäure, insbesonders VeoVa9R und/oder50 to 75% by weight of vinyl acetate, 1 to 30% by weight of vinyl ester of a branched carboxylic acid, in particular VeoVa9 R and / or
VeoVal0R, sowie 10 bis 40 Gew% Ethylen;VeoVal0 R and 10 to 40% by weight ethylene;
70 bis 98.7 Gew% Vinylacetat und 1 bis 30 Gew% Vinylester einer o-verzweigten Carbonsäure, insbesonders VeoVa9R und/oder VeoVal0R,70 to 98.7% by weight of vinyl acetate and 1 to 30% by weight of vinyl ester of an o-branched carboxylic acid, in particular VeoVa9 R and / or VeoVal0 R ,
70 bis 98.7 Gew% Vinylester, insbesonders Vinylacetat, und 1 bis 30 Gew% Acrylsäureester, insbesonders n-Butylacrylat oder 2-Ethylhexylacrylat;70 to 98.7% by weight of vinyl ester, in particular vinyl acetate, and 1 to 30% by weight of acrylic acid ester, in particular n-butyl acrylate or 2-ethylhexyl acrylate;
50 bis 75 Gew% Vinylacetat, 1 bis 30 Gew% Acrylsäureester, insbesonders n-Butylacrylat oder 2-Ethylhexylacrylat, sowie50 to 75% by weight of vinyl acetate, 1 to 30% by weight of acrylic acid ester, in particular n-butyl acrylate or 2-ethylhexyl acrylate, and
10 bis 40 Gew% Ethylen;10 to 40% by weight ethylene;
30 bis 75 Gew% Vinylacetat, 1 bis 30 Gew% Vinylester einer α-verzweigten Carbonsäure, insbesonders VeoVa9R und/oder30 to 75% by weight of vinyl acetate, 1 to 30% by weight of vinyl ester of an α-branched carboxylic acid, in particular VeoVa9 R and / or
VeoVal0R, 1 bis 30 Gew% Acrylsäureester, insbesonders n- Butylacrylat oder 2-Ethylhexylacrylat, sowie 10 bis 40 Gew% Ethylen;VeoVal0 R , 1 to 30% by weight acrylic acid ester, especially n- Butyl acrylate or 2-ethylhexyl acrylate, and 10 to 40% by weight of ethylene;
Bevorzugte (Meth)acrylsäureester-Copolymerisate enthalten als Comonomereinheiten a) , jeweils bezogen auf das Gesamtge¬ wicht des Copolymers:Preferred (meth) acrylic acid ester copolymers contain as comonomer units a), in each case based on the total weight of the copolymer:
90 bis 99.7 Gew% n-Butylacrylat und/oder 2-Ethylhexylacry- lat.90 to 99.7% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.
40 bis 59.7 Gew% Methylmethacrylat , 59.7 bis 40 Gew% n- Butylacrylat und/oder 2-Ethylhexylacrylat;40 to 59.7% by weight of methyl methacrylate, 59.7 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate;
40 bis 59.7 Gew% Styrol und 59.7 bis 40 Gew% n-Butylacrylat und/oder 2-Ethylhexylacrγlat.40 to 59.7% by weight of styrene and 59.7 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.
Die Herstellung der Vinylester-Copolymerisate bzw. der (Meth)acrylsäureester-Copolymerisate erfolgt vorzugsweise nach dem Emulsionspolymerisationsverfahren. Die Polymerisa¬ tion kann diskontinuierlich oder kontinuierlich, mit oder ohne Verwendung von Saatlatices, unter Vorlage aller oder einzelner Bestandteile des Reaktionsgemisches, oder unter teilweiser Vorlage und Nachdosierung der oder einzelner Be¬ standteile des Reaktionsgemisches, oder nach dem Dosier¬ verfahren ohne Vorlage durchgeführt werden. Alle Dosierungen erfolgen vorzugsweise im Maße des Verbrauchs der jeweiligen Komponente.The vinyl ester copolymers or the (meth) acrylic ester copolymers are preferably prepared by the emulsion polymerization process. The polymerization can be carried out batchwise or continuously, with or without the use of seed latices, with presentation of all or individual constituents of the reaction mixture, or with partial presentation and subsequent metering of the or individual constituents of the reaction mixture, or according to the metering process without presentation . All doses are preferably made to the extent of the consumption of the respective component.
In einer bevorzugten Ausführungsform werden 10 bis 25 Gew% der Comonomeren a) vorgelegt und der Rest zusammen mit den Comonomeren b) in Emulsion zudosiert. Bei der Copolymerisa- tion mit Ethylen wird vorzugsweise bei einem Druck von 20 bis 100 bar abs. gearbeitet.In a preferred embodiment, 10 to 25% by weight of the comonomers a) are initially introduced and the remainder is metered in together with the comonomers b) in emulsion. In the copolymerization with ethylene, abs is preferably at a pressure of 20 to 100 bar. worked.
Die Polymerisation wird in einem Temperaturbereich von 40"C bis 80'C durchgeführt und mit den für die Emulsionspolymeri¬ sation üblicherweise eingesetzten Methoden eingeleitet. Die Initiierung erfolgt mittels der üblichen wasserlöslichen Ra- dikalbildner, die vorzugsweise in Mengen von 0.01 bis 1.0 Gew%, bezogen auf das Gesamtgewicht der Monomeren, einge¬ setzt werden. Beispiele hierfür sind Ammonium- und Kalium¬ persulfat, Alkylhydroperoxide, wie tert.-Butylhydroperoxid; Wasserstoffperoxid. Gegebenenfalls können die genannten ra¬ dikalischen Initiatoren auch in bekannter Weise mit 0.01 bis 0.5 Gew%, bezogen auf das Gesamtgewicht der Monomeren, Re¬ duktionsmittel kombiniert werden. Geeignet sind zum Beispiel Formaldehydsulfoxylat-Salze, Natriumbisulfit oder Ascorbin- säure. Bei der Redoxinitiierung werden dabei vorzugsweise eine oder beide Redox-Katalysatorkomponenten während der Po¬ lymerisation dosiert.The polymerization is carried out in a temperature range from 40.degree. C. to 80.degree. C. and initiated using the methods usually used for emulsion polymerization. The initiation is carried out using the customary water-soluble Ra Dical formers, which are preferably used in amounts of 0.01 to 1.0% by weight, based on the total weight of the monomers. Examples include ammonium and potassium persulfate, alkyl hydroperoxides, such as tert-butyl hydroperoxide; Hydrogen peroxide. If appropriate, the radical initiators mentioned can also be combined in a known manner with 0.01 to 0.5% by weight, based on the total weight of the monomers, of reducing agents. For example, formaldehyde sulfoxylate salts, sodium bisulfite or ascorbic acid are suitable. In the case of redox initiation, one or both redox catalyst components are preferably metered in during the polymerization.
Als Dispergiermittel können alle üblicherweise bei der Emul¬ sionspolymerisation verwendeten Emulgatoren und Schutzkollo¬ ide eingesetzt werden. Vorzugsweise werden 1 bis 4 Gew%, be¬ zogen auf das Gesamtgewicht der Monomeren, an Emulgator ein¬ gesetzt. Geeignet sind beispielsweise anionische Tenside, wie Alkylsulfate mit einer Kettenlänge von 8 bis 18 C-Ato¬ men, Alkyl- und Alkylarylethersulfate mit 8 bis 18 C-Atomen im hydrophoben Rest und bis zu 40 Ethylen- oder Propylen- oxideinheiten, Alkyl- oder Alkylarylsulfonate mit 8 bis 18 C-Atomen, Ester und Halbester der Sulfobernsteinsäure mit einwertigen Alkoholen oder Alkylphenolen. Geeignete nichtio¬ nische Tenside sind beispielsweise Alkylpolyglykolether oder Alkylarylpolyglykolether mit 8 bis 40 Ethylenoxideinheiten.All emulsifiers and protective colloids conventionally used in emulsion polymerization can be used as dispersants. Preferably 1 to 4% by weight, based on the total weight of the monomers, of emulsifier is used. For example, anionic surfactants such as alkyl sulfates with a chain length of 8 to 18 carbon atoms, alkyl and alkylaryl ether sulfates with 8 to 18 carbon atoms in the hydrophobic radical and up to 40 ethylene or propylene oxide units, alkyl or alkylaryl sulfonates are suitable with 8 to 18 carbon atoms, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols. Suitable nonionic surfactants are, for example, alkyl polyglycol ethers or alkylaryl polyglycol ethers with 8 to 40 ethylene oxide units.
Gegebenenfalls können Schutzkolloide, vorzugsweise in Mengen von bis zu 4 Gew%, bezogen auf das Gesamtgewicht der Mono¬ meren, eingesetzt werden. Beispiele hierfür sind Vinylal- kohol/Vinylacetat-Copolymere mit einem Gehalt von 80 bis 100 Mol% Vinylalkoholeinheiten, Polyvinylpyrrolidone mit einem Molekulargewicht von 5000 bis 400000, Hydroxyethylcellulosen mit einem Substitutionsgradbereich von 1.5 bis 3. Der für die Polymerisation gewünschte pH-Bereich, der im allgemeinen zwischen 3 und 7 liegt, kann in bekannter Weise durch Säuren, Basen oder übliche Puffersalze, wie Alkali¬ phosphate oder Alkalicarbonate, eingestellt werden. Zur Mo¬ lekulargewichtseinstellung können bei der Polymerisation die üblicherweise verwendeten Regler, zum Beispiel Mercaptane, Aldehyde und Chlorkohlenwasserstoffe, zugesetzt werden.If necessary, protective colloids, preferably in amounts of up to 4% by weight, based on the total weight of the monomers, can be used. Examples of these are vinyl alcohol / vinyl acetate copolymers with a content of 80 to 100 mol% of vinyl alcohol units, polyvinyl pyrrolidones with a molecular weight of 5,000 to 400,000, hydroxyethyl celluloses with a degree of substitution range of 1.5 to 3. The pH range desired for the polymerization, which is generally between 3 and 7, can be set in a known manner using acids, bases or conventional buffer salts, such as alkali metal phosphates or alkali metal carbonates. To adjust the molecular weight, the regulators typically used, for example mercaptans, aldehydes and chlorinated hydrocarbons, can be added during the polymerization.
Der Feststoffgehalt der wäßrigen Dispersionen beträgt vor¬ zugsweise 30 bis 65 Gew%.The solids content of the aqueous dispersions is preferably 30 to 65% by weight.
Zur Herstellung der Dispersionspulver wird die Dispersion getrocknet, vorzugsweise sprühgetrocknet oder gefrierge¬ trocknet, besonders bevorzugt sprühgetrocknet. Hierbei kann auf die bekannten Vorrichtungen, wie zum Beispiel Versprühen durch Mehrstoffdüsen oder mit der Scheibe, in einem gegebe¬ nenfalls erhitzten Trockengasström, zurückgegriffen werden. Im allgemeinen werden Temperaturen über 250'C nicht ange¬ wandt. Die optimale Temperatur des Trockengases kann in we¬ nigen Versuchen ermittelt werden; oft haben sich Temperatu¬ ren über 60*C besonders bewährt.To prepare the dispersion powders, the dispersion is dried, preferably spray-dried or freeze-dried, particularly preferably spray-dried. Known devices, such as spraying through multi-component nozzles or with the disk, in a possibly heated dry gas flow, can be used here. In general, temperatures above 250'C are not used. The optimum temperature of the drying gas can be determined in a few experiments; temperatures above 60 ° C. have often proven particularly useful.
Zur Erhöhung der Lagerfähigkeit und um zum Beispiel bei Pul¬ vern mit niederer Glasübergangstemperatur Tg ein Verbacken und Verblocken zu verhindern, wird bei der Trocknung gegebe¬ nenfalls Antiblockmittel, beispielsweise Aluminiumsilikate, Kieselgur, Calciumcarbonat, zugegeben. Des weiteren können gegebenenfalls noch Entschäumer, beispielsweise auf Silikon¬ oder Kohlenwasserstoffbasis, oder Verdüsungshilfen, bei¬ spielsweise Polyvinylalkohole oder wasserlösliche Melamin- Formaldehyd-Kondensationsprodukte, der Dispersion zugegeben werden.To increase the shelf life and to prevent caking and blocking, for example in the case of powders with a low glass transition temperature Tg, antiblocking agents, for example aluminum silicates, diatomaceous earth, calcium carbonate, are added when drying. Furthermore, defoamers, for example based on silicone or hydrocarbons, or spraying aids, for example polyvinyl alcohols or water-soluble melamine-formaldehyde condensation products, can optionally be added to the dispersion.
In einer bevorzugten Ausführungsform enthalten die Disper¬ sionspulver noch 0 bis 30 Gew%, besonders bevorzugt 1 bis 15 Gew%, bezogen auf das Basispolymerisat, Polyvinylalkohol mit einem Hydrolysegrad von 85 bis 94 Mol%, und/oder 0 bis 10 Gew% Vinylalkoholcopolymerisate mit 5 bis 35 Gew% 1-Methyl- vinylalkoholeinheiten, und/oder 0 bis 30 Gew%, besonders be¬ vorzugt 4 bis 20 Gew%, bezogen auf das Gesamtgewicht polyme¬ rer Bestandteile, Antiblockmittel und gegebenenfalls bis zu 2 Gew%, bezogen auf das Basispolymerisat, Entschäumer.In a preferred embodiment, the dispersion powders still contain 0 to 30% by weight, particularly preferably 1 to 15 % By weight, based on the base polymer, polyvinyl alcohol with a degree of hydrolysis of 85 to 94 mol%, and / or 0 to 10% by weight vinyl alcohol copolymers with 5 to 35% by weight 1-methyl-vinyl alcohol units, and / or 0 to 30% by weight, particularly preferably 4 to 20% by weight, based on the total weight of polymeric constituents, antiblocking agents and optionally up to 2% by weight, based on the base polymer, defoamer.
Die wäßrigen Copoly erdispersionen bzw. die redispergierba- ren Dispersionspulver eignen sich zur Ausrüstung und Verfe¬ stigung von natürlichen oder synthetischen" Fasermaterialien. Beispiele hierfür sind Holzfaser, Cellulosefaser, Wolle, Baumwolle, Mineralfasern, Keramikf sern, Kunstfasern auf der Basis von faserbildenden Polymeren wie Viskosefaser, Poly- ethylen-, Polypropylen-, Polyester-, Polyamid-, Polyacryl- nitril- oder Carbonfaser, Fasern von Homo- oder Copolymeri¬ saten des Vinylchlorids oder Fasern von Homo- oder Copolyme¬ risaten des Tetrafluorethylens. Besonders geeignet sind die wäßrigen Copolymerdispersionen bzw. die Dispersionspulver zur Ausrüstung und Verfestigung von Cellulosefaser-Materia- lien.The aqueous copolymer dispersions or the redispersible dispersion powders are suitable for finishing and solidifying natural or synthetic " fiber materials. Examples include wood fiber, cellulose fiber, wool, cotton, mineral fibers, ceramic fibers, synthetic fibers based on fiber-forming polymers such as Viscose fiber, polyethylene, polypropylene, polyester, polyamide, polyacrylonitrile or carbon fiber, fibers of homo- or copolymerizates of vinyl chloride or fibers of homo- or copolyme- risates of tetrafluoroethylene Copolymer dispersions or the dispersible polymer powders for finishing and solidifying cellulose fiber materials.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung von lösungsmittelfesten Fasergebilden, dadurch gekennzeichnet, daß eine wäßrige Copolymerdispersion oder ein redispergierbares Copolymerpulver von Copolymeren mit einer Tg von -60'C bis +60*C, enthaltend a) ein oder mehrere Monomereinheiten aus der Gruppe der Vi¬ nylester von unverzweigten oder verzweigten Carbonsäuren mit 1 bis 12 C-Atomen, der Ester der Acrylsäure und Methacrylsäure mit unverzweigten oder verzweigten Alko¬ holen mit 1 bis 12 C-Atomen, Vinylaromaten, Vinylhaloge¬ nide und α-Olefine und b) 0.3 bis 10 Gew%, bezogen auf das Gesamtgewicht des Co¬ polymers, ein oder mehrere N-(Alkoxymethyl)acrylamide oder N-(Alkoxymethyl)methacrylamide mit einem Cι~ bis Cβ-Alkylrest oder Gemische dieser N-(Alkoxymethyl)- (meth)acrylamide mit N-Methylolacrylamid und/oder N- Methylolmethacryla id in einem Gewichtsverhältnis von N- Methylolverbindung zu N-(Alkoxymethyl)-Verbindung von höchstens 5 : 1, in einer Menge von 5 bis 50 Gew% Bindemittel, bezogen auf das Fasergewicht, auf das flächenhaft ausgebreitete Faser¬ material aufgetragen wird und bei einer Temperatur von 80 bis 200*C getrocknet wird.Another object of the invention is a process for the production of solvent-resistant fiber structures, characterized in that an aqueous copolymer dispersion or a redispersible copolymer powder of copolymers with a Tg of -60'C to + 60 * C, containing a) one or more monomer units from the Group of the vinyl esters of unbranched or branched carboxylic acids with 1 to 12 C atoms, the esters of acrylic acid and methacrylic acid with unbranched or branched alcohols with 1 to 12 C atoms, vinyl aromatics, vinyl halides and α-olefins and b ) 0.3 to 10% by weight, based on the total weight of the copolymer, one or more N- (alkoxymethyl) acrylamides or N- (alkoxymethyl) methacrylamides with a C 1 -C 6 -alkyl radical or mixtures of these N- (alkoxymethyl) - (meth) acrylamides with N-methylolacrylamide and / or N-methylol methacrylic acid in a weight ratio of N-methylol compound to N- ( Alkoxymethyl) compound of at most 5: 1, in an amount of 5 to 50% by weight of binder, based on the fiber weight, is applied to the fiber material which is spread out over a surface area and is dried at a temperature of 80 to 200 ° C.
Vor der Verfestigung werden die Fasern flächenhaft ausge¬ breitet. Die Verfahren hierzu sind bekannt und primär von der Anwendung, in die das verfestigte Fasermaterial geht, abhängig. Die Fasern können mittels einer Luftlege-, Na߬ lege-, Direktspinn- oder Krempelvorrichtung ausgelegt wer¬ den. Gegebenenfalls können die Flächengebilde vor der Verfe¬ stigung mit Bindemittel noch mechanisch verfestigt werden, beispielsweise durch Kreuzlegen, Nadeln oder Wasserstrahl¬ verfestigung.Before the consolidation, the fibers are spread out over a large area. The methods for this are known and primarily depend on the application in which the solidified fiber material goes. The fibers can be laid out by means of an air-laying, wet-laying, direct spinning or carding device. If necessary, the flat structures can be mechanically solidified with binding agent prior to solidification, for example by cross-laying, needling or water jet hardening.
Bei der erfindungsgemäßen Verwendung werden die wäßrigen Co¬ polymerdispersionen in üblicher Weise durch Imprägnieren, Schaumimprägnieren, Sprühen, Pflatschen. Streichen oder Bedrucken aufgetragen. Gegebenenfalls nach Abtrennen des überschüssigen Bindemittels durch beispielsweise Abquet¬ schen, werden die textilen Gebilde bei Temperaturen von 80 bis 200*C, vorzugsweise zwischen 120 und 180*C, getrocknet. Je nach Anwendungsbereich liegt die für die Verfestigung des Fasermaterials notwendige Menge an Bindemittel zwischen 5 und 50 Gew% Bindemittel, bezogen auf das Fasergewicht.In the use according to the invention, the aqueous copolymer dispersions are customarily impregnated, foam-impregnated, sprayed, slapped. Brushed or printed applied. If necessary after separating off the excess binder by, for example, squeezing, the textile structures are dried at temperatures from 80 to 200 ° C., preferably between 120 and 180 ° C. Depending on the area of application, the amount of binder required to solidify the fiber material is between 5 and 50% by weight of binder, based on the weight of the fiber.
Werden Copolymerpulver verwendet, wird das pulverförmige Bindemittel in an sich bekannter Weise auf das, gegebenen¬ falls mechanisch vorverfestigte, Fasermaterial aufgestreut, eingestreut (beispielsweise bei Krempelwatten) , eingerüttelt oder direkt mit der Faser vermischt. Die textilen Gebilde werden bei Temperaturen von 80 bis 200 ' C , vorzugsweise zwi¬ schen 120 und 180*C, getrocknet. Je nach Anwendungsbereich liegt die für die Verfestigung des Fasermaterials notwendige Menge an Bindemittel zwischen 5 und 50 Gew% Bindemittel, bezogen auf das Fasergewicht.If copolymer powder is used, the powdered binder is sprinkled in a manner known per se onto the, if appropriate mechanically pre-consolidated, fiber material. sprinkled in (e.g. with carded wadding), shaken in or mixed directly with the fiber. The textile structures at temperatures of 80 to 200 'C, preferably zwi¬ rule 120 and 180 * C and dried. Depending on the field of application, the amount of binder required to solidify the fiber material is between 5 and 50% by weight of binder, based on the weight of the fiber.
Zu dem erfindungsgemäßen Bindemittel können noch Pigmente, Antioxidantien, Farbstoffe, Weichmacher, Filmbildehilfsmit¬ tel, Füllstoffe, Flammschutzmittel, Schaumbildehilfsmittel, Schauminhibitoren, Netzmittel, Thermosensibilisierungsmit- tel, Antistatika, Biozide, Griffverbesserungsmittel, zusätz¬ liche Vernetzer oder Katalysatoren zur eventuell notwendigen Beschleunigung der Vernetzungsreaktion in dazu üblichen Men¬ gen zugegeben werden.Pigments, antioxidants, dyes, plasticizers, film-forming aids, fillers, flame retardants, foam-forming aids, foam inhibitors, wetting agents, thermosensitizers, antistatic agents, biocides, grip improvers, additional crosslinking agents or catalysts to accelerate the crosslinking reaction, if necessary, can also be added to the binder according to the invention in the usual amounts for this purpose.
Der lösungsmittelfeste Textilbinder eignet sich vorzugsweise für die Verfestigung von Vliesstoffen, beispielsweise im Haushalts- und Hygienebereich und für Industriewischtücher. Ein weiteres Anwendungsgebiet ist die Schiebefestausrüstung von Geweben.The solvent-resistant textile binder is preferably suitable for the consolidation of nonwovens, for example in the household and hygiene area and for industrial wipes. Another area of application is the anti-slip finishing of fabrics.
Die nachfolgenden Beispiele dienen zur weiteren Erläuterung der Erfindung:The following examples serve to further explain the invention:
Herstellung der Copolymerdispersionen:Preparation of the copolymer dispersions:
Beispiel 1:Example 1:
In einem Druckreaktor wurden 192 kg Wasser, 1.46 kg einer 10 %-igen wäßrigen Ameisensäurelösung, 14.7 kg einer wäßrigen Lösung eines Isotridecylethoxylats mit 15 EO-Einheiten(Gena- pol X150) und 2.02 kg einer 25 %-igen wäßrigen Lösung von Vinylsulfonat zusammen mit 27.3 kg Butylacrylat und 17.6 kg Vinylacetat vorgelegt. Es wurde auf 50*C aufgeheizt und Ethylen mit einem Druck von 60 bar aufgepreßt. Nach Errei¬ chen des Temperaturgleichgewichts wurden eine Lösung von 619 g Ammoniumpersulfat in 24.2 kg Wasser und eine Lösung von 309 g Ascorbinsäure in 24.5 kg Wasser zudosiert. Nach Auspo¬ lymerisation der Vorlage wurden 187 kg Vinylacetat zudo¬ siert. Nach Beendigung der Vinylacetat-Dosierung wurde ein Gemisch aus 12.6 kg Wasser, 10.5 kg einer 30 %-igen wäßrigen Acrylamid-Lösung, 2.4 kg N-Methylolacrylamid und 2.4 kg N- (isobutoxymethyl)-acrylamid zusammen mit einem Gemisch aus 16.7 kg Butylacrylat und 16.7 kg Vinylacetat zudosiert. Nach Beendigung der Polymerisation resultierte eine Disper¬ sion mit einem Feststoffgehalt von 53 Gew% und einer Copoly- merzusammensetzung von 11.0 % Ethylen, 72.0 % Vinylacetat, 14.2 % Butylacrylat, 1.0 % Acrylamid, 0.8 % N-Methylolacryl¬ amid und 0.8 % N-(isobutoxymethyl)-acrylamid und 0.2 % Vi- nylsulfonat.In a pressure reactor, 192 kg of water, 1.46 kg of a 10% aqueous formic acid solution, 14.7 kg of an aqueous solution of an isotridecyl ethoxylate with 15 EO units (Genapol X150) and 2.02 kg of a 25% aqueous solution of vinyl sulfonate were added together with 27.3 kg butyl acrylate and 17.6 kg Vinyl acetate submitted. It was heated to 50 * C and ethylene was injected at a pressure of 60 bar. After the temperature equilibrium had been reached, a solution of 619 g of ammonium persulfate in 24.2 kg of water and a solution of 309 g of ascorbic acid in 24.5 kg of water were metered in. After the original had been polymerized, 187 kg of vinyl acetate were added. After the vinyl acetate metering had ended, a mixture of 12.6 kg of water, 10.5 kg of a 30% strength aqueous acrylamide solution, 2.4 kg of N-methylolacrylamide and 2.4 kg of N- (isobutoxymethyl) acrylamide together with a mixture of 16.7 kg of butyl acrylate and 16.7 kg of vinyl acetate added. After the end of the polymerization, a dispersion with a solids content of 53% by weight and a copolymer composition of 11.0% ethylene, 72.0% vinyl acetate, 14.2% butyl acrylate, 1.0% acrylamide, 0.8% N-methylolacrylamide and 0.8% N- (isobutoxymethyl) acrylamide and 0.2% vinyl sulfonate.
Beispiel 2:Example 2:
Es wurde analog Beispiel 1 vorgegangen, mit dem Unterschied, daß anstelle des NMA/IBMA-Gemisches 4.8 kg N-(isobutoxy- methyl)-acrylamid copolymerisiert wurden.The procedure was analogous to Example 1, with the difference that 4.8 kg of N- (isobutoxymethyl) acrylamide were copolymerized instead of the NMA / IBMA mixture.
Nach Beendigung der Polymerisation resultierte eine Disper¬ sion mit einem Feststoffgehalt von 53 Gew% und einer Copoly- merzusammensetzung von 11.0 % Ethylen, 72.0 % Vinylacetat, 14.2 % Butylacrylat, 1.0 % Acrylamid, 1.6 % N-(isobutoxy- methyl)-acrylamid und 0.2 % Vinylsulfonat.After the end of the polymerization, a dispersion with a solids content of 53% by weight and a copolymer composition of 11.0% ethylene, 72.0% vinyl acetate, 14.2% butyl acrylate, 1.0% acrylamide, 1.6% N- (isobutoxymethyl) acrylamide and 0.2% vinyl sulfonate.
Beispiel 3 (Vergleichsbeispiel) :Example 3 (comparative example):
Es wurde analog Beispiel 1 vorgegangen mit dem Unterschied, daß nur N-Methylolmethacrylamid und kein N-(isobutoxyme- thyl)-acrylamid verwendet wurde.The procedure was analogous to Example 1, with the difference that only N-methylol methacrylamide and no N- (isobutoxymethyl) acrylamide was used.
Nach Beendigung der Polymerisation resultierte eine Disper¬ sion mit einem Feststoffgehalt von 53 Gew% und einer Copoly- merzusammensetzung von 11.0 % Ethylen, 72.0 % Vinylacetat, 14.2 % Butylacrylat, 1.0 % Acrylamid, 1.6 % N-Methylolacryl- amid und 0.2 % Vinylsulfonat.After the end of the polymerization, a dispersion with a solids content of 53% by weight and a copolymer composition of 11.0% ethylene, 72.0% vinyl acetate resulted, 14.2% butyl acrylate, 1.0% acrylamide, 1.6% N-methylol acrylamide and 0.2% vinyl sulfonate.
Beispiel 4:Example 4:
In einem Laborreaktor wurden 542 g Wasser, 0.5 g einer 10 %- igen wäßrigen Fe(II)sulfatlösung, 11.9 g einer wäßrigen Lö¬ sung eines Ethylenoxid-Propylenoxid-Blockcopolymers (Genapol PF40) und 3.1 g einer 25 %-igen wäßrigen Lösung von Vinyl¬ sulfonat zusammen mit 8.2 g Butylacrylat und 70.5 g Vinyl¬ acetat vorgelegt. Es wurde auf 45*C aufgeheizt. Nach Errei¬ chen des Temperaturgleichgewichts wurden eine Lösung von 9.8 g Ammoniumpersulfat in 187 g Wasser und eine Lösung von 4.9 g Rongalit in 192 g Wasser zudosiert. Nach Auspolymerisation der Vorlage wurden 776 g Vinylacetat und 39.6 g Butylacrylat zudosiert. Nach Beendigung der Vinylacetat/Butylacrylat-Do- sierung wurde ein Gemisch aus 86 g Wasser, 9.21 g Acrylsäu- re, 20.7 g N-Methylolacrylamid und 9.9 g N-(isobutoxy- methyl)-acrylamid zusammen mit 76.8 g einer 40 %-igen wäßri¬ gen Lösung eines Isotridecylethoxylats mit 15 EO-Einheiten (Genapol X150) und 21.9 g einer 28 %-igen wäßrigen Lösung, eines sulfatisierten Alkylethoxylats mit ca. 3 EO-Einheiten (Genapol ZRO) zudosiert.542 g of water, 0.5 g of a 10% strength aqueous Fe (II) sulfate solution, 11.9 g of an aqueous solution of an ethylene oxide-propylene oxide block copolymer (Genapol PF40) and 3.1 g of a 25% strength aqueous solution of Submitted vinyl sulfonate together with 8.2 g butyl acrylate and 70.5 g vinyl acetate. It was heated to 45 * C. After the temperature equilibrium had been reached, a solution of 9.8 g of ammonium persulfate in 187 g of water and a solution of 4.9 g of Rongalit in 192 g of water were metered in. After polymerization of the initial charge, 776 g of vinyl acetate and 39.6 g of butyl acrylate were metered in. After the vinyl acetate / butyl acrylate metering had ended, a mixture of 86 g of water, 9.21 g of acrylic acid, 20.7 g of N-methylolacrylamide and 9.9 g of N- (isobutoxymethyl) -acrylamide together with 76.8 g of a 40% strength was added aqueous solution of an isotridecyl ethoxylate with 15 EO units (Genapol X150) and 21.9 g of a 28% aqueous solution, a sulfated alkyl ethoxylate with about 3 EO units (Genapol ZRO).
Nach Beendigung der Polymerisation resultierte eine Disper¬ sion mit einem Feststoffgehalt von 50 Gew% und einer Copoly- merzusa mensetzung von 91.0 % Vinylacetat, 5.1 % Butylacry¬ lat, 1.7 % N-Methylolacrylamid, 0.8 % N-(isobutoxymethyl)- acrylamid, 1.0 % Acrylsäure und 0.01 % Vinylsulfonat.After the end of the polymerization, a dispersion with a solids content of 50% by weight and a copolymer composition of 91.0% vinyl acetate, 5.1% butyl acrylate, 1.7% N-methylolacrylamide, 0.8% N- (isobutoxymethyl) acrylamide, 1.0 resulted % Acrylic acid and 0.01% vinyl sulfonate.
Beispiel 5 (Vergleichsbeispiel) :Example 5 (comparative example):
Es wurde analog Beispiel 4 vorgegangen mit dem Unterschied, daß nur N-Methylolmethacrylamid und kein N-(isobutoxyme- thyl)-acrylamid verwendet wurde.The procedure was analogous to Example 4, with the difference that only N-methylol methacrylamide and no N- (isobutoxymethyl) acrylamide was used.
Nach Beendigung der Polymerisation resultierte eine Disper¬ sion mit einem Feststoffgehalt von 50 Gew% und einer Copoly- merzusammensetzung von 91.0 % Vinylacetat, 5.1 % Butylacry- lat, 2.5 % N-Methylolacrylamid, 1.0 % Acrylsäure und 0.01 % Vinylsulfonat.After the end of the polymerization, a dispersion with a solids content of 50% by weight and a copolymer composition of 91.0% vinyl acetate, 5.1% butyl acrylate resulted. lat, 2.5% N-methylolacrylamide, 1.0% acrylic acid and 0.01% vinyl sulfonate.
Anwendungstechnische Prüfung:Application test:
Herstellung der Vliese:Production of the fleeces:
Zur Herstellung der Vliesstoffe wurde ein Zellwollfaservlies mittels Vollbadimprägnierung mit 20 Gew% Copolymerdispersion (Feststoff bezogen auf Faser) verfestigt. Der überschüssige Binder wurde zwischen zwei Walzen abgequetscht und das Vlies 3 Minuten bei 150*C in einem Trommeltrockner getrocknet.To produce the nonwovens, a cellulose fiber fleece was solidified by means of a full bath impregnation with 20% by weight copolymer dispersion (solid based on fiber). The excess binder was squeezed between two rollers and the fleece was dried for 3 minutes at 150 ° C. in a drum dryer.
Bestimmung der Festigkeit der Vliese gemäß DIN 53857:Determination of the strength of the nonwovens according to DIN 53857:
Die Trockenfestigkeit, Naßfestigkeit undThe dry strength, wet strength and
Lösungsmittelfestigkeit der Vliese wurde mittels Vermessung der Höchstzugkraft (HZK) von Vliesstreifen mit einer Breite von 1.5 cm und einer Länge von 15 cm bestimmt.Solvent resistance of the nonwovens was determined by measuring the maximum tensile force (HZK) of nonwoven strips with a width of 1.5 cm and a length of 15 cm.
Vor der Messung wurden die Vliese mindestens 24 Stunden lang in Normklima bei T - 23'C und 50 % RLF (DIN 50014) gelagert.Before the measurement, the nonwovens were stored in a standard atmosphere at T-23'C and 50% RH (DIN 50014) for at least 24 hours.
Zur Bestimmung der Naßfestigkeit wurden die Vliese unmittelbar vor der Messung 1 Minute in Wasser gelagert. ZurTo determine the wet strength, the nonwovens were stored in water for 1 minute immediately before the measurement. to
Bestimmung der Lösungsmittelfestigkeit wurden die Vliese unmittelbar vor der Messung 1 Minute in Isopropanol gelagert.To determine the solvent resistance, the nonwovens were stored in isopropanol for 1 minute immediately before the measurement.
Die Messung der HöchstZugkraft erfolgte mit einer Zwick- Zugprüfmaschine, wobei die Zugmessung mit einer konstanten Dehnungsgeschwindigkeit von 100 mm/min erfolgte. Bei jeder Messung wird die Höchstzugkraft festgestellt und die Messung beendet, wenn die Kraft auf 40 % der Höchstzugkraft gefallen ist. Jeweils 5 Vliesstreifen pro Probe wurden gemeinsam eingespannt. Es wurde der Mittelwert aus zwei Meßreihen bestimmt.The maximum tensile force was measured using a Zwick tensile testing machine, the tensile measurement being carried out at a constant rate of expansion of 100 mm / min. The maximum tensile force is determined for each measurement and the measurement ends when the force has dropped to 40% of the maximum tractive force. 5 non-woven strips per sample were clamped together. The average of two series of measurements was determined.
Die Ergebnisse der Messungen sind in Tabelle 1 zusammengefaßt:The results of the measurements are summarized in Table 1:
Tabelle 1:Table 1:
Beispiel NMA IBMA HZK (N) HZK (N) HZK (N) (%) (%) trocken naß IsopropanolExample NMA IBMA HZK (N) HZK (N) HZK (N) (%) (%) dry wet isopropanol
1 0.8 0.8 20.4 9.5 8.51 0.8 0.8 20.4 9.5 8.5
2 0 1.6 19.1 8.4 8.12 0 1.6 19.1 8.4 8.1
3* 1.6 0 19.1 9.2 5.13 * 1.6 0 19.1 9.2 5.1
4 1.7 0.8 25.5 11.3 13.34 1.7 0.8 25.5 11.3 13.3
5* 2.5 0 23.0 10.2 10.05 * 2.5 0 23.0 10.2 10.0
= Vergleichsbeispiele = Comparative examples

Claims

Patentansprüche claims
1. Verwendung von N-(Alkoxymethyl)-(meth)acrylamid-funktio- nellen Textilbindemitteln zur Verbesserung der Lösungs¬ mittelfestigkeit bei der Ausrüstung und Verfestigung von Fasermaterialien mit Textilbindemitteln, dadurch gekenn¬ zeichnet, daß als Textilbindemittel eine wäßrige Copoly¬ merdispersion oder ein redispergierbares Copolymerpulver von Copolymeren mit einer Tg von -60*C bis +60*C, ent¬ haltend a) ein oder mehrere Monomereinheiten aus der Gruppe der Vinylester von unverzweigten oder verzweigten Carbon¬ säuren mit 1 bis 12 C-Atomen, der Ester der Acrylsäu- re und Methacrylsäure mit unverzweigten oder ver¬ zweigten Alkoholen mit 1 bis 12 C-Atomen, Vinylaroma¬ ten, Vinylhalogenide und α-Olefine und b) 0.3 bis 10 Gew%, bezogen auf das Gesamtgewicht des Copolymers, ein oder mehrere N-(Alkoxymethyl)acryl¬ amide oder N-(Alkoxymethyl)methacrylamide mit einem C^- bis Cg-Alkylrest oder Gemische dieser N-(Alkoxy¬ methyl)-(meth)acrylamide mit N-Methylolacrylamid und/oder N-Methylolmethacrylamid in einem Gewichts¬ verhältnis von N-Methylolverbindung zu N-(Alkoxy¬ methyl)-Verbindung von höchstens 5 : 1, verwendet wird.1. Use of N- (alkoxymethyl) - (meth) acrylamide-functional textile binders to improve the solvent resistance when finishing and solidifying fiber materials with textile binders, characterized in that an aqueous copolymer dispersion or a redispersible copolymer powder of copolymers with a Tg of -60 * C to + 60 * C, containing a) one or more monomer units from the group of vinyl esters of unbranched or branched carboxylic acids with 1 to 12 C atoms, the esters of Acrylic acid and methacrylic acid with unbranched or branched alcohols with 1 to 12 carbon atoms, vinyl aromatics, vinyl halides and α-olefins and b) 0.3 to 10% by weight, based on the total weight of the copolymer, of one or more N- (Alkoxymethyl) acrylamides or N- (alkoxymethyl) methacrylamides with a C 1- to C 6 -alkyl radical or mixtures of these N- (alkoxymethyl) - (meth) acrylamides with N-methylolacrylamide and / or N-methylol methacrylamide in a weight ratio of N-methylol compound to N- (alkoxy-methyl) compound of at most 5: 1 is used.
2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß 0.5 bis 3.0 Gew%, bezogen auf das Gesamtgewicht des Co¬ polymers, Gemische der N-(Alkoxymethyl)-(meth)acrylamide mit N-Methylolacrylamid oder N-Methylolmethacrylamid in einem Gewichtsverhältnis von N- Methylolverbindung zu N- (Alkoxymethyl)-Verbindung von 5 : 1 bis 1 : 10 enthalten sind. 2. Use according to claim 1, characterized in that 0.5 to 3.0% by weight, based on the total weight of the co-polymer, mixtures of the N- (alkoxymethyl) - (meth) acrylamides with N-methylolacrylamide or N-methylolmethacrylamide in a weight ratio of N-methylol compound to N- (alkoxymethyl) compound from 5: 1 to 1:10 are included.
3. Verwendung nach Anspruch l oder 2, dadurch gekennzeich¬ net, daß als N-(Alkoxymethyl)-(meth)acrylamide N-(iso- butoxymethy1)-acrylamid (IBMA) , N-(isobutoxymethyl)- methacrylamid (IBMMA), N-(n-butoxymethyl)-acrylamid (NBMA) und/oder N-(n-butoxymethyl)-methacrylamid (NBMMA) enthalten sind.3. Use according to claim 1 or 2, characterized in that the N- (alkoxymethyl) - (meth) acrylamides are N- (isobutoxymethy1) acrylamide (IBMA), N- (isobutoxymethyl) methacrylamide (IBMMA), N- (n-butoxymethyl) acrylamide (NBMA) and / or N- (n-butoxymethyl) methacrylamide (NBMMA) are included.
4. Verwendung nach Anspruch 3, dadurch gekennzeichnet, daß 0.5 bis 3.0 Gew%, bezogen auf das Gesamtgewicht des Copolymers, eines Gemisches von NMA und IBMA (IBMMA) in einem Gewichtsverhältnis von NMA/IBMA (IBMMA) von 3 : 1 bis l : 5 enthalten sind.4. Use according to claim 3, characterized in that 0.5 to 3.0% by weight, based on the total weight of the copolymer, of a mixture of NMA and IBMA (IBMMA) in a weight ratio of NMA / IBMA (IBMMA) of 3: 1 to 1: 5 are included.
5. Verwendung nach Anspruch 1 bis 4, dadurch gekennzeichnet daß Vinylester-Copolymerisate verwendet werden, welche als Comonomereinheiten a) , jeweils bezogen auf das Gesamtgewicht des Copolymers,5. Use according to claim 1 to 4, characterized in that vinyl ester copolymers are used which, as comonomer units a), in each case based on the total weight of the copolymer,
90 bis 99.7 Gew% Vinylester, insbesonders Vinylacetat, oder90 to 99.7% by weight of vinyl ester, in particular vinyl acetate, or
49.7 bis 89.7 Gew% Vinylester, insbesonders Vinylacetat sowie 10 bis 50 Gew% α-Olefin, insbesonders Ethylen, oder49.7 to 89.7% by weight of vinyl ester, in particular vinyl acetate and 10 to 50% by weight of α-olefin, in particular ethylene, or
50 bis 75 Gew% Vinylacetat, 1 bis 30 Gew% Vinylester ei¬ ner α-verzweigten Carbonsäure, insbesonders VeoVa9R und/oder VeoVal0R, sowie 10 bis 40 Gew% Ethylen, oder50 to 75% by weight of vinyl acetate, 1 to 30% by weight of vinyl ester of an α-branched carboxylic acid, in particular VeoVa9 R and / or VeoVal0 R , and 10 to 40% by weight of ethylene, or
70 bis 98.7 Gew% Vinylacetat und 1 bis 30 Gew% Vinyl¬ ester einer α-verzweigten Carbonsäure, insbesonders VeoVa9R und/oder VeoVal0R, oder70 to 98.7% by weight of vinyl acetate and 1 to 30% by weight of vinyl ester of an α-branched carboxylic acid, in particular VeoVa9 R and / or VeoVal0 R , or
70 bis 98.7 Gew% Vinylester, insbesonders Vinylacetat, und 1 bis 30 Gew% Acrylsäureester, insbesonders n-Butyl¬ acrylat oder 2-Ethylhexylacrylat, oder 50 bis 75 Gew% Vinylacetat, 1 bis 30 Gew% Acrylsäure- ester, insbesonders n-Butylacrylat oder 2-Ethylhexyl- acrylat, sowie 10 bis 40 Gew% Ethylen, oder70 to 98.7% by weight of vinyl ester, in particular vinyl acetate, and 1 to 30% by weight of acrylic acid ester, in particular n-butyl acrylate or 2-ethylhexyl acrylate, or 50 to 75% by weight of vinyl acetate, 1 to 30% by weight of acrylic acid esters, especially n-butyl acrylate or 2-ethylhexyl acrylate, and 10 to 40% by weight of ethylene, or
30 bis 75 Gew% Vinylacetat, 1 bis 30 Gew% Vinylester ei¬ ner α-verzweigten Carbonsäure, insbesonders VeoVa9R und/oder VeoVal0R, 1 bis 30 Gew% Acrylsäureester, insbe¬ sonders n-Butylacrylat oder 2-Ethylhexylacrylat, sowie 10 bis 40 Gew% Ethylen, enthalten.30 to 75% by weight of vinyl acetate, 1 to 30% by weight of vinyl ester of an α-branched carboxylic acid, in particular VeoVa9 R and / or VeoVal0 R , 1 to 30% by weight of acrylic acid ester, in particular n-butyl acrylate or 2-ethylhexyl acrylate, and 10 up to 40% by weight of ethylene.
6. Verwendung nach Anspruch 1 bis 4, dadurch gekennzeichnet daß (Meth)acrylsäureester-Copolymerisate verwendet wer¬ den, welche als Comonomereinheiten a) , jeweils bezogen auf das Gesamtgewicht des Copolymers,6. Use according to claim 1 to 4, characterized in that (meth) acrylic ester copolymers are used which, as comonomer units a), in each case based on the total weight of the copolymer,
90 bis 99.7 Gew% n-Butylacrylat und/oder 2-Ethylhexyl- acrylat, oder90 to 99.7% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate, or
40 bis 59.7 Gew% Methylmethacrylat, 59.7 bis 40 Gew% n- Butylacrylat und/oder 2-Ethylhexylacrylat, oder40 to 59.7% by weight of methyl methacrylate, 59.7 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate, or
40 bis 59.7 Gew% Styrol und 59.7 bis 40 Gew% n-Butyl¬ acrylat und/oder 2-Ethylhexylacrylat, enthalten.40 to 59.7% by weight of styrene and 59.7 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.
7. Verfahren zur Herstellung von lösungs ittelfesten Faser¬ gebilden, dadurch gekennzeichnet, daß eine wäßrige Copo¬ lymerdispersion oder ein redispergierbares Copolymerpul¬ ver von Copolymeren mit einer Tg von -60*C bis +60*C, enthaltend a) ein oder mehrere Monomereinheiten aus der Gruppe der Vinylester von unverzweigten oder verzweigten Carbon¬ säuren mit 1 bis 12 C-Atomen, der Ester der Acrylsäu- re und Methacrylsäure mit unverzweigten oder ver¬ zweigten Alkoholen mit 1 bis 12 C-Atomen, Vinylaroma¬ ten, Vinylhalogenide und α-Olefine und b) 0.3 bis 10 Gew%, bezogen auf das Gesamtgewicht des Copolymers, ein oder mehrere N-(Alkoxymethyl) cryl¬ amide oder N-(AlkoxymethylJ ethacrylamide mit einem Cι~ bis Cg-Alkylrest oder Gemische dieser N-(Alkoxy¬ methyl)-(meth)acrylamide mit N-Methylolacrylamid und/oder N-Methylolmethacrylamid in einem Gewichts¬ verhältnis von N-Methylolverbindung zu N-(Alkoxyme¬ thyl)-Verbindung von höchstens 5 : 1, in einer Menge von 5 bis 50 Gew% Bindemittel, bezogen auf das Fasergewicht, auf das flächenhaft ausgebreitete Fasermaterial aufgetragen wird und bei einer Temperatur von 80 bis 200*C getrocknet wird. 7. A process for the production of solvent-resistant fibers, characterized in that an aqueous copolymer dispersion or a redispersible copolymer powder of copolymers with a Tg of -60 ° C. to + 60 ° C., containing a) one or more monomer units from the group of the vinyl esters of unbranched or branched carboxylic acids with 1 to 12 C atoms, the esters of acrylic acid and methacrylic acid with unbranched or branched alcohols with 1 to 12 C atoms, vinyl aromas, vinyl halides and α - olefins and b) 0.3 to 10% by weight, based on the total weight of the copolymer, of one or more N- (alkoxymethyl) crylamides or N- (alkoxymethylJethacrylamides with a C 1 -C 6 -alkyl radical or mixtures of these N- (alkoxymethyl) - (Meth) acrylamides with N-methylolacrylamide and / or N-methylolmethacrylamide in a weight ratio of N-methylol compound to N- (alkoxymethyl) compound of at most 5: 1, in an amount of 5 to 50% by weight of binder , based on the weight of the fiber, to which fiber fiber is spread and dried at a temperature of 80 to 200 ° C.
EP19950932751 1994-09-15 1995-09-14 Use of solvent-resistant textile binders Expired - Lifetime EP0781359B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19944432945 DE4432945A1 (en) 1994-09-15 1994-09-15 Solvent resistant textile binder
DE4432945 1994-09-15
PCT/EP1995/003623 WO1996008597A1 (en) 1994-09-15 1995-09-14 Solvent-resistant textile binder

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US5763022A (en) 1998-06-09
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FI971068A0 (en) 1997-03-14
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ES2118623T3 (en) 1998-09-16
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EP0781359B1 (en) 1998-05-06

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