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EP0781359B1 - Utilisation d'un liant textile resistant aux solvants - Google Patents

Utilisation d'un liant textile resistant aux solvants Download PDF

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Publication number
EP0781359B1
EP0781359B1 EP19950932751 EP95932751A EP0781359B1 EP 0781359 B1 EP0781359 B1 EP 0781359B1 EP 19950932751 EP19950932751 EP 19950932751 EP 95932751 A EP95932751 A EP 95932751A EP 0781359 B1 EP0781359 B1 EP 0781359B1
Authority
EP
European Patent Office
Prior art keywords
weight
copolymer
alkoxymethyl
vinyl
vinyl acetate
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.)
Expired - Lifetime
Application number
EP19950932751
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German (de)
English (en)
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EP0781359A1 (fr
Inventor
Andreas Lumpp
Gerhard KÖGLER
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Wacker Chemie AG
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Wacker Chemie AG
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Publication of EP0781359A1 publication Critical patent/EP0781359A1/fr
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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 for Improve the solvent resistance of the equipment and solidification of fiber materials, as well as a process for the production of solvent-resistant fiber structures.
  • aqueous copolymer dispersions as binders for solidifying and coating fiber structures such as fabrics, fleeces and wadding made of textile fibers or textile yarns.
  • Copolymer dispersions are common of (meth) acrylate or vinyl ester copolymers used, which self-crosslinking to improve strength Comonomer units with N-methylol or N-methylol ether functions contain. Usually up to 10 % By weight of N-methylol- (meth) acrylamide (NMA or NMMA) copolymerized.
  • NMA or NMMA N-methylol- (meth) acrylamide copolymerized.
  • the disadvantage of these binders is the release of formaldehyde by hydrolytic cleavage of the N-methylol function as well as the low solvent resistance of the solidified or coated materials.
  • the improvement the resistance to solvents by incorporating pre-crosslinking, polyethylenically unsaturated comonomer units is known. However, this measure often leads
  • EP-B 205862 relates to textile binders based on vinyl acetate-ethylene copolymers, which is 1 to 5% by weight of N-methylol (meth) acrylamide units or their ethers contain. To improve wet strength when using a copolymer binder with a low NMA content is suggested additionally use melamine formaldehyde resins.
  • EP-A 261378 teaches the heat resistance of functional with N-methylol Copolymers bound fiber mats to improve that such copolymers as binders are used in which the N-methylol functions are wholly or partially etherified.
  • textile binders are based described of vinyl acetate / ethylene copolymer emulsions, which instead of reducing formaldehyde release of N-methylol (meth) acrylamide units exclusively N- (n-butoxymethyl) acrylamide units contain.
  • EP-A 86889 (AU-A 8310718) relates to a method for Production of a textile coating agent, which under Exposure to water, no white swelling and no whitening shows.
  • the coating agent consists of an aqueous Copolymer emulsion, which by emulsion copolymerization obtained from (meth) acrylates with N-methylol- (meth) acrylamide be, with the N-methylol (meth) acrylamides at least 20 mol% are etherified with an alcohol and the Emulsion polymerization in the presence of a fatty alcohol 10 to 20 carbon atoms.
  • the solvent resistance textile binders are not discussed.
  • the invention was based on the task of binders Based on aqueous copolymer dispersions or copolymer powders to provide those equipped with it In addition to high dry and wet strength, textiles also have a high level Give solvent resistance.
  • 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 a mixture of monomer units composed of N- (alkoxymethyl) acrylamides or N- (alkoxymethyl) methacrylamides with a C 1 -C 6 -alkyl radical with N-methylolacrylamide ( NMA) and / or N-methylol methacrylamide (NMMA).
  • NMA N-methylolacrylamide
  • NMMA N-methylol methacrylamide
  • copolymers which, in the weight percentages 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 of 5: 1 up to 1:10 included.
  • copolymers which contain 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, in particular of 1: 1 to 1: 5 included.
  • vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate, vinyl pivalate and vinyl esters of ⁇ -branched monocarboxylic acids with 9 to 10 C atoms, for example VeoVa9 R or VeoVa10 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 methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate. Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate and 2-ethylhexyl acrylate.
  • the vinyl 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 acrylic acid esters or methacrylic acid esters of alcohols with 1 to 12 carbon atoms, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate and / or ethylenically unsaturated dicarboxylic acid esters or their derivatives, such as diisopropyl fumarate, diethyl dumarate, the dimethyl dibutyl ether contain the maleic acid or fumaric
  • 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 monomers mentioned is preferably made so that copolymers with a glass transition temperature T g of -30 ° C. to + 30 ° C. are obtained.
  • the vinyl ester copolymers and the (meth) acrylic ester copolymers still 0.05 to 3.0 %
  • one or more auxiliary monomers from the group of the ethylenic unsaturated carboxylic acids preferably acrylic acid or methacrylic acid, from the group of the ethylenically unsaturated Carboxamides, preferably acrylamide and 2-acrylamidopropanesulfonic acid, from the group of ethylenically unsaturated Sulfonic acids or their salts, preferably vinyl sulfonic acid, and / or from the group of multiple ethylenic unsaturated comonomers, for example divinyl adipate, 1,9-decadiene, allyl methacrylate, triallyl cyanurate and crosslinking comonomers such as acrylamidoglycolic acid (AGA), methyl acrylamidoglycolic acid methyl ester (AGA), methyl acrylamidoglycolic acid methyl ester (A
  • the production of the vinyl ester copolymers or (Meth) acrylic ester copolymers are preferably carried out after the emulsion polymerization process.
  • the polymerization can be discontinuous or continuous, with or without the use of seed latices, with presentation of all or individual components of the reaction mixture, or below partial submission and subsequent dosing of the or individual components of the reaction mixture, or according to the dosing process be done without submission. All dosages preferably take place to the extent of the consumption of the respective Component.
  • the polymerization takes place in a temperature range of 40 ° C up to 80 ° C and with those for emulsion polymerization methods usually used.
  • the Initiation takes place by means of the usual water-soluble radical formers, which are preferably in amounts of 0.01 to 1.0 % By weight, based on the total weight of the monomers will. Examples include ammonium and potassium persulfate, Alkyl hydroperoxides such as tert-butyl hydroperoxide; Hydrogen peroxide.
  • the radicals mentioned Initiators also in a known manner with 0.01 to 0.5% by weight, based on the total weight of the monomers, of reducing agents be combined.
  • anionic surfactants are suitable, 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 residue and up to 40 ethylene or propylene oxide units, Alkyl or alkylarylsulfonates with 8 to 18 C atoms, esters and half esters of sulfosuccinic acid monohydric alcohols or alkylphenols.
  • Suitable non-ionic Examples of surfactants are alkyl polyglycol ethers or Alkylaryl polyglycol ether with 8 to 40 ethylene oxide units.
  • protective colloids preferably in quantities of up to 4% by weight, based on the total weight of the monomers.
  • examples include vinyl alcohol / vinyl acetate copolymers grading 80 to 100 Mol% vinyl alcohol units, polyvinyl pyrrolidones with one Molecular weight from 5000 to 400000, hydroxyethyl celluloses with a degree of substitution range of 1.5 to 3.
  • the desired pH range for the polymerization which in the is generally between 3 and 7, in a known manner by acids, bases or conventional buffer salts, such as alkali phosphates or alkali carbonates.
  • acids, bases or conventional buffer salts such as alkali phosphates or alkali carbonates.
  • buffer salts such as alkali phosphates or alkali carbonates.
  • mercaptans, Aldehydes and chlorinated hydrocarbons can be added.
  • the solids content of the aqueous dispersions is preferably 30 to 65% by weight.
  • the dispersion is used to produce the dispersion powder dried, preferably spray-dried or freeze-dried, particularly preferably spray-dried. This can on the known devices, such as spraying through multi-component nozzles or with the disc, in one if necessary heated dry gas flow. In general, temperatures above 250 ° C are not used. The optimal temperature of the dry gas can be in a few Attempts to be identified; often temperatures have Particularly proven over 60 ° C.
  • 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 contain still 0 to 30% by weight, particularly preferably 1 to 15 % By weight, based on the base polymer, with polyvinyl alcohol a degree of hydrolysis of 85 to 94 mol%, and / or 0 to 10 % By weight of vinyl alcohol copolymers with 5 to 35% by weight of 1-methylvinyl alcohol units, and / or 0 to 30% by weight, particularly preferred 4 to 20 wt.%, Based on the total weight of polymer Ingredients, antiblocking agents and possibly up to 2% by weight, based on the base polymer, defoamer.
  • the aqueous copolymer dispersions or the redispersible ones Dispersion powders are suitable for finishing and solidification of natural or synthetic fiber materials.
  • Examples include wood fiber, cellulose fiber, wool, Cotton, mineral fibers, ceramic fibers, synthetic fibers on the Basis of fiber-forming polymers such as viscose, polyethylene, Polypropylene, polyester, polyamide, polyacrylonitrile or carbon fiber, fibers of homo- or copolymers vinyl chloride or fibers of homo- or copolymers of tetrafluoroethylene.
  • They are particularly suitable aqueous copolymer dispersions or the dispersion powder for finishing and strengthening cellulose fiber materials.
  • the fibers are spread out over a large area.
  • the processes for this are known and primarily from the application in which the solidified fiber material goes, dependent.
  • the fibers can be air-laid, wet-laid, Direct spinning or carding device can be designed.
  • the flat structures can be hardened are mechanically solidified with binder, for example by cross-laying, needles or hydroentangling.
  • the aqueous copolymer dispersions in the usual way by impregnation, Foam impregnation, spraying, splashing, painting or Printed applied. If necessary after removing the excess binder by, for example, squeezing, the textile structures at temperatures of 80 up to 200 ° C, preferably between 120 and 180 ° C, dried. Depending on the area of application, this is for the solidification of the Amount of binder required between 5 and and 50% by weight of binder, based on the weight of the fiber.
  • copolymer powder If copolymer powder is used, it becomes powder Binder in a manner known per se on the, if necessary mechanically pre-consolidated, sprinkled with fiber material, sprinkled in (for example with carded wadding), shaken or mixed directly with the fiber.
  • the textile structures are at temperatures of 80 to 200 ° C, preferably between 120 and 180 ° C, dried. Depending on the area of application lies the necessary for the consolidation of the fiber material Amount of binder between 5 and 50% by weight of binder, based on the fiber weight.
  • the solvent-resistant textile binder is preferably suitable for the consolidation of nonwovens, for example in Household and hygiene areas and for industrial wipes. Another area of application is sliding equipment of tissues.
  • a cellulose fiber fleece was used to manufacture the nonwovens using a full bath impregnation with 20% by weight copolymer dispersion (Solid based on fiber) solidified.
  • the excess Binder was squeezed between two rollers and the fleece Dried in a tumble dryer at 150 ° C for 3 minutes.
  • HZK maximum tensile force
  • the maximum tensile force was measured with a Zwick tensile testing machine, where the tension measurement with a constant Expansion speed of 100 mm / min took place. With everyone Measurement, the maximum tensile force is determined and the measurement ends when the force drops to 40% of the maximum tractive force is. 5 non-woven strips per sample were combined clamped. It was the average of two series of measurements certainly.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention a pour objet l'utilisation de liants textiles N-(alcoxyméthyl)-(méth)acrylamide fonctionnels afin d'améliorer la résistance aux solvants lors du finissage et de la consolidation de matériaux fibreux au moyen de liants textiles. L'invention est caractérisée en ce que le liant textile utilisé est une dispersion aqueuse de copolymères ou une poudre de copolymères pouvant être de nouveau dispersée, les copolymères présentant une température de transition vitreuse (Tg) comprise entre -60 et +60 °C, contenant (a) au moins un motif monomère du groupe des esters de vinyle d'acides carboxyliques ramifiés ou non, comprenant 1 à 12 atomes de carbone, des esters d'acide acrylique et d'acide méthacrylique avec des alcools ramifiés ou non, comportant 1 à 12 atomes de carbone, des aromates de vinyle, des halogénures de vinyle et de l'α-oléfine et (b) 0,3 à 10 % en poids, par rapport au poids total du copolymère, d'au moins un N-(alcoxyméthyl)acrylamide ou un N-(alcoxyméthyl)méthacrylamide comportant un radical alkyle C1-C6, ou des mélanges de ces N-(alcoxyméthyl)-(méth)acrylamides avec un N-méthylolacrylamide et/ou un N-méthylolméthacrylamide dans un rapport en poids entre le composé de N-méthylol et le composé de N-(alcoxyméthyle) d'au maximum 5:1.

Claims (7)

  1. Utilisation de liants textiles à fonctions N-(alcoxyméthyl) (méth)acrylamide pour l'amélioration de la résistance aux solvants lors du finissage et de la consolidation de matériaux fibreux avec des liants textiles, caractérisée en ce que le liant textile utilisé est une dispersion aqueuse de copolymères ou une poudre de copolymères redispersible formée de copolymères ayant une Tg de -60°C à +60°C, contenant:
    a) une ou plusieurs unités de monomères du groupe des esters vinyliques d'acides carboxyliques non ramifiés ou ramifiés ayant de 1 à 12 atomes C, des esters de l'acide acrylique et de l'acide méthacrylique avec des alcools non ramifiés ou ramifiés avec 1 à 12 atomes C, des vinylaromatiques, des halogénures de vinyle et des α-oléfines, et
    b) 0,3 à 10% en poids, par rapport au poids total du copolymère, d'un mélange d'unités monomères d'un ou plusieurs N-(alcoxyméthyl)acrylamides ou N-(alcoxyméthyl)méthacrylamides, avec un radical alcoyle en C1-6, avec le N-méthylolacrylamide et/ou le N-méthylolméthacrylamide en un rapport pondéral du composé N-méthylol au composé N-(alcoxyméthyl) de 5:1 au plus.
  2. Utilisation suivant la revendication 1, caractérisée en ce que 0,5 à 3,0% en poids, par rapport au poids total du copolymère, des mélanges du N-(alcoxyméthyl) (méth)acrylamide et du N-méthylolacrylamide ou du N-méthylolméthacrylamide sont présents dans un rapport pondéral du composé N-méthylol au composé N-(alcoxyméthyl) de 5:1 à 1:10.
  3. Utilisation suivant la revendication 1 ou 2, caractérisée en ce que les N-(alcoxyméthyl) (méth)acrylamides contenus sont le N-(isobutoxyméthyl)acrylamide (IBMA), le N-(isobutoxyméthyl)méthacrylamide (IBMMA), le N- (n-butoxyméthyl)acrylamide (NBMA) et/ou le N- (n-butoxyméthyl)méthacrylamide (NBMMA).
  4. Utilisation suivant la revendication 3, caractérisée en ce que 0,5 à 3,0% en poids, par rapport au poids total du copolymère, d'un mélange de NMA et de IBMA (IBMMA) sont présents en un rapport pondéral NMA/IBMA (IBMMA) de 3:1 à 1:5.
  5. Utilisation suivant l'une quelconque des revendications 1 à 4, caractérisée en ce que l'on utilise des copolymères d'esters vinyliques qui contiennent comme unités comonomères a), dans chaque cas par rapport au poids total du copolymère,
    90 à 99,7% en poids d'ester vinylique, en particulier d'acétate de vinyle,
    ou
    49,7 à 89,7% en poids d'ester vinylique, en particulier d'acétate de vinyle, et 10 à 50% en poids d'α-oléfine, en particulier d'éthylène,
    ou
    50 à 75% en poids d'acétate de vinyle, 1 à 30% en poids d'ester vinylique d'un acide carboxylique α-ramifié, en particulier VeoVa9R et/ou VeoVa10R, ainsi que 10 à 40% en poids d'éthylène,
    ou
    70 à 98,7% en poids d'acétate de vinyle et 1 à 30% en poids d'ester vinylique d'un acide carboxylique α-ramifié, en particulier VeoVa9R et/ou VeoVa10R,
    ou
    70 à 98,7% en poids d'ester vinylique, en particulier d'acétate de vinyle, et 1 à 30% en poids d'ester de l'acide acrylique, en particulier d'acrylate de n-butyle ou d'acrylate de 2-éthylhexyle,
    ou
    50 à 75% en poids d'acétate de vinyle, 1 à 30% en poids d'ester de l'acide acrylique, en particulier d'acrylate de n-butyle ou d'acrylate de 2-éthylhexyle, ainsi que 10 à 40% en poids d'éthylène,
    ou
    30 à 75% en poids d'acétate de vinyle, 1 à 30% en poids d'ester vinylique d'un acide carboxylique α-ramifié, en particulier VeoVa9R et/ou VeoVa10R, 1 à 30% en poids d'ester de l'acide acrylique, en particulier d'acrylate de n-butyle ou d'acrylate de 2-éthylhexyle, ainsi que 10 à 40% en poids d'éthylène.
  6. Utilisation suivant l'une quelconque des revendications 1 à 4, caractérisée en ce que l'on utilise des copolymères d'esters de l'acide (méth)acrylique qui contiennent , comme unités comonomères a), dans chaque cas par rapport au poids total du copolymère,
    90 à 99,7% en poids d'acrylate de n-butyle, et/ou d'acrylate de 2-éthylhexyle,
    ou
    40 à 59,7% en poids de méthacrylate de méthyle, 59,7 à 40% en poids d'acrylate de n-butyle et/ou d'acrylate de 2-éthylhexyle,
    ou
    40 à 59,7% en poids de styrène et 59,7 à 40% en poids d'acrylate de n-butyle et/ou d'acrylate de 2-éthylhexyle.
  7. Procédé de préparation d'un produit fibreux résistant aux solvants, caractérisé en ce que l'on applique une dispersion aqueuse de copolymères ou une poudre de copolymères redispersibles formée de copolymères ayant une Tg de -60°C à +60°C, contenant:
    a) une ou plusieurs unités de monomères du groupe des esters vinyliques d'acides carboxyliques non ramifiés ou ramifiés ayant de 1 à 12 atomes C, des esters de l'acide acrylique et de l'acide méthacrylique avec des alcools non ramifiés ou ramifiés avec 1 à 12 atomes C, des vinylaromatiques, des halogénures de vinyle et des α-oléfines, et
    b) 0,3 à 10% en poids, par rapport au poids total du copolymère, d'un mélange d'un ou plusieurs N-(alcoxyméthyl)acrylamides ou N- (alcoxyméthyl)méthacrylamides, avec un radical alcoyle en C1-6, avec le N-méthylolacrylamide et/ou le N-méthylolméthacrylamide en un rapport pondéral du composé N-méthylol au composé N-(alcoxyméthyl) de 5:1 au plus,
    en une quantité de 5 à 50% en poids de liant, par rapport au poids du produit fibreux, sur le matériau fibreux étalé en nappe et en ce qu'on la sèche à une température de 80 à 200°C.
EP19950932751 1994-09-15 1995-09-14 Utilisation d'un liant textile resistant aux solvants Expired - Lifetime EP0781359B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4432945 1994-09-15
DE19944432945 DE4432945A1 (de) 1994-09-15 1994-09-15 Lösungsmittelfester Textilbinder
PCT/EP1995/003623 WO1996008597A1 (fr) 1994-09-15 1995-09-14 Liant textile resistant aux solvants

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EP0781359A1 EP0781359A1 (fr) 1997-07-02
EP0781359B1 true EP0781359B1 (fr) 1998-05-06

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US (1) US5763022A (fr)
EP (1) EP0781359B1 (fr)
DE (2) DE4432945A1 (fr)
ES (1) ES2118623T3 (fr)
FI (1) FI971068A (fr)
WO (1) WO1996008597A1 (fr)

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DE19631935A1 (de) * 1996-08-08 1998-02-12 Wacker Chemie Gmbh Lösungsmittelfestes Textilbindemittel
DE19716352A1 (de) * 1997-04-18 1998-10-22 Wacker Chemie Gmbh Hartes und hydrophobes Binde- und Beschichtungsmittel für textile Flächengebilde
US6638319B2 (en) 2001-04-04 2003-10-28 Healthtex Apparel Corp. Polymer for printed cotton
US6645255B2 (en) 2001-04-04 2003-11-11 Healthtex Apparel Corp. Polymer-grafted stretchable cotton
US6645256B2 (en) 2001-04-04 2003-11-11 Healthtex Apparel Corp. Polymer grafted cotton
DE10332621A1 (de) † 2003-07-17 2005-02-03 Wacker Polymer Systems Gmbh & Co. Kg Verfahren zur Herstellung von Polyvinylalkohol-freien, wässrigen Polymerdispersionen
US7264377B2 (en) * 2004-02-10 2007-09-04 Halo Sun, Llc Sensor-activated audible story lamp
US7649067B2 (en) 2005-10-19 2010-01-19 Wacker Polymers, L.P. Process of making a vinyl ester based polymer latex composition
DE102012202843A1 (de) 2012-02-24 2013-08-29 Wacker Chemie Ag Verfahren zur Herstellung von Vinylester-Ethylen-Acrylsäureamid-Mischpolymerisaten
WO2016055128A1 (fr) 2014-10-06 2016-04-14 Siniat International Mat perfectionné et plaques de plâtre associées appropriés pour des zones humides
WO2019115392A1 (fr) 2017-12-13 2019-06-20 Heiq Materials Ag Formulations antisalissure pour applications textiles
WO2021155932A1 (fr) * 2020-02-06 2021-08-12 Wacker Chemie Ag Composition de liant sans formaldéhyde

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BE539963A (fr) * 1954-07-23
NL252972A (fr) * 1959-06-24
FR1260307A (fr) * 1959-06-24 1961-05-05 Bayer Ag Dispersions aqueuses de copolymères autoréticulants
FR2003769A1 (fr) * 1968-03-13 1969-11-14 Basf Ag
DE2512589C2 (de) * 1975-03-21 1990-07-12 Wacker-Chemie GmbH, 8000 München Thermisch selbstvernetzende Copolymere
US4044197A (en) * 1975-03-21 1977-08-23 Wacker-Chemie Gmbh Thermally self-cross-linkable ethylene/vinyl acetate copolymers
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DE3205904A1 (de) * 1982-02-19 1983-09-01 Chemische Fabrik Pfersee Gmbh, 8900 Augsburg Verfahren zur emsulsionscopolymerisation, die nach dem verfahren hergestellten emulsionscopolymerisate und deren verwendung
JPS59125972A (ja) * 1983-01-07 1984-07-20 伴　実 絹繊維の改質処理方法
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US4859508A (en) * 1986-09-26 1989-08-22 National Starch And Chemical Corporation Heat resistant binders
JPH01168971A (ja) * 1987-12-23 1989-07-04 Nisshin Kagaku Kogyo Kk 繊維用弾性加工剤及び風合改良剤
CA2073693A1 (fr) * 1990-11-14 1992-05-15 David B. Farmer Materiaux fibreux non tisses

Also Published As

Publication number Publication date
WO1996008597A1 (fr) 1996-03-21
EP0781359A1 (fr) 1997-07-02
FI971068A0 (fi) 1997-03-14
ES2118623T3 (es) 1998-09-16
DE59502125D1 (de) 1998-06-10
FI971068A (fi) 1997-03-14
US5763022A (en) 1998-06-09
DE4432945A1 (de) 1996-03-21

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