WO2022122120A1 - Matériau en feuille textile - Google Patents

Matériau en feuille textile Download PDF

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Publication number
WO2022122120A1
WO2022122120A1 PCT/EP2020/084981 EP2020084981W WO2022122120A1 WO 2022122120 A1 WO2022122120 A1 WO 2022122120A1 EP 2020084981 W EP2020084981 W EP 2020084981W WO 2022122120 A1 WO2022122120 A1 WO 2022122120A1
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WO
WIPO (PCT)
Prior art keywords
textile fabrics
vinyl
polymers
group
binder compositions
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PCT/EP2020/084981
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German (de)
English (en)
Inventor
Thomas Lehotkay
Johanna HRGOVIC
Original Assignee
Wacker Chemie Ag
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Filing date
Publication date
Application filed by Wacker Chemie Ag filed Critical Wacker Chemie Ag
Priority to PCT/EP2020/084981 priority Critical patent/WO2022122120A1/fr
Priority to US18/265,526 priority patent/US20240026583A1/en
Priority to EP20823765.1A priority patent/EP4259869A1/fr
Publication of WO2022122120A1 publication Critical patent/WO2022122120A1/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
    • D04H1/58—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
    • D04H1/641—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 characterised by the chemical composition of the bonding agent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • 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

Definitions

  • the invention relates to processes for the production of textile fabrics, the textile fabrics obtainable in this way, and binder compositions for the production of textile fabrics.
  • Textile fabrics are based on fiber material that can be woven (wovens), knitted (knitwear) or laid (nonwovens) and is reinforced with binders, such as nonwovens or felt.
  • Nonwovens are usually produced by airlay, wetlay or spunlay processes.
  • Polymers of ethylenically unsaturated monomers are often used as binders to strengthen the textile fabrics and are applied to the fiber material, for example in the form of aqueous dispersions, followed by subsequent drying.
  • the task was to produce textile fabrics using binder compositions that contain natural, renewable raw materials and lead to textile fabrics whose application-related property profile comes close to that of textile fabrics conventionally produced exclusively with petrochemical polymers as binders.
  • the binder compositions should be able to be applied by established methods and be compatible with otherwise conventional formulation components and result in stable mixtures that do not tend to separate.
  • textile fabrics should also be provided that are biodegradable to the greatest possible extent.
  • the textile fabrics should preferably also have advantageous mechanical strengths.
  • Biopolymers are used, for example, in technologies that are far removed from textile fabrics.
  • WO 9222606A1 describes hot-melt adhesives made from meltable polysaccharides and ethylene-vinyl acetate copolymers
  • WO9742271A1 describes adhesives made from synthetic polymers in combination with dextrin (derivatives).
  • WO2008003043A2 teaches matrices made from degradable and non-degradable polymers for the incorporation of therapeutically active compounds.
  • WO2010/133560 or also WO2004/085533 disclose thermoplastically processable mixtures based on synthetic polymers and flour or starch for the extrusion of shaped bodies.
  • WO2019 / 043134 are generally plastic products based on polyesters, such as Lactic acid or terephthalic acid, and for example polysaccharides can be removed.
  • One subject of the invention is a method for producing textile fabrics by applying one or more binder compositions to fibers, characterized in that binder compositions contain one or more polysaccharides and one or more polymers of vinyl esters.
  • Another object of the invention are textile fabrics obtainable by the process of the invention.
  • binder compositions for textile fabrics containing one or more polysaccharides and one or more polymers on one or more vinyl esters and one or more ethylenically unsaturated monomers, the carboxyl, anhydride, silane, isocyanate -, amide, hydroxyl, epoxy or NH groups (crosslinking monomers), based.
  • binder compositions it is possible in particular to further improve the mechanical strength, such as wet tensile strength, of the textile fabric.
  • the polymers of vinyl esters are preferably based on vinyl esters of unbranched or branched alkyl carboxylic acids having 1 to 18 carbon atoms, such as 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 5 to 15 carbon atoms, for example Veo-Va9 R or VeoValO R (trade name from Shell). Vinyl acetate is preferred.
  • Preferred vinyl ester polymers are based at 50 to 100% by weight, more preferably 60 to 94% by weight and most preferably 70 to 90% by weight of vinyl esters based on the total weight of the vinyl ester polymers.
  • the vinyl ester polymers are also based on one or more monomers selected from the group comprising acrylic esters or methacrylic esters of branched or unbranched alcohols having 1 to 15 carbon atoms, dienes, olefins, vinyl aromatics and vinyl halides. Olefins are preferred here.
  • the vinyl ester polymers are preferably based on from 1 to 45% by weight, more preferably from 5 to 30% by weight and most preferably from 15 to 25% by weight of such additional monomers, based on the total weight of the vinyl ester polymers.
  • Suitable monomers from the group of esters of acrylic acid or methacrylic acid are esters of unbranched or branched alcohols having 1 to 15 carbon atoms.
  • Preferred methacrylic esters or acrylic esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate.
  • Methyl acrylate, methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate and norbornyl acrylate are particularly preferred.
  • dienes 1,3-butadiene and isoprene.
  • copolymerizable olefins are ethene and propene.
  • Styrene and vinyl toluene for example, can be copolymerized as vinyl aromatics.
  • Vinyl chloride is preferred as the vinyl halide.
  • the vinyl ester polymers are preferably also based on one or more ethylenically unsaturated monomers which also carry carboxyl, anhydride, silane, isocyanate, amide, hydroxyl, epoxy or NH groups (crosslinking monomers). Crosslinking monomers bearing NH groups are preferred here. Vinyl ester polymers containing crosslinking monomer units lead to textile fabrics with higher strengths, such as dry strength, and in particular wet strength and solvent strength.
  • carboxy-functional comonomers are ethylenically unsaturated mono- and dicarboxylic acids having 2 to 10 carbon atoms, preferably acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid and maleic acid.
  • anhydride-functional comonomers are maleic anhydride or ethylenically unsaturated succinic anhydride derivatives, such as alkenyl succinic anhydrides, in particular having 2 to 25 carbon atoms in the alkenyl radical.
  • silicon-functional comonomers are acryloxypropyltri(alkoxy)- and methacryloxypropyltri(alkoxy)-silanes, vinyltrialkoxysilanes and vinylmethyldialkoxysilanes, it being possible for ethoxy groups, for example, to contain ethoxy and ethoxypropylene glycol ether radicals.
  • hydroxy-functional comonomers are hydroxyalkyl acrylates and hydroxyalkyl methacrylates with a C 1 -C 8 alkyl radical, preferably hydroxyethyl acrylate and methacrylate, hydroxypropyl acrylate and methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.
  • Examples of epoxy functional comonomers are glycidyl acrylate and glycidyl methacrylate.
  • Examples of NH-functional comonomers are acrylamide, methacrylamide, N-alkylol-functional comonomers with C to C4-alkylol residue, preferably N-methylol residue, such as N-methylolacrylamide (NMA), N-methylolmethacrylamide, N -Methylolallylcarbamate, C i- to C4-alkyl ethers of N-methylolacrylamide, N-methylolmethacrylamide and N-methylolallylcarbamate, for example their isobutoxyethers, and C i- to C4-alkyl esters of N-methylolacrylamide and N-methylolmethacrylamide and the N-methylolallyl carbamate.
  • NMA N-methylolacrylamide
  • NMA N-methylolmethacrylamide
  • crosslinking monomers are N-methylol functional monomers, most preferred are N-methylolacrylic amide, N-methylolmethacrylamide, N-methylolallylcarbamate, C- to C4-alkyl ethers of N-methylolacrylamide, such as the isobutoxyether.
  • the vinyl ester polymers are preferably based on 0 to 10 wt. -%, particularly preferably 0.1 to 5 wt. -% and most preferably 0.5 to 2 wt. -% on crosslinking monomers, based on the total weight of the vinyl ester polymers.
  • vinyl ester polymers in which the abovementioned crosslinking monomers can optionally also be polymerized, preferably in the abovementioned amounts: vinyl acetate polymers; vinyl ester-ethylene copolymers, such as vinyl acetate-ethylene copolymers; Vinyl acetate copolymers with one or more copolymerizable vinyl esters such as vinyl laurate, vinyl pivalate, vinyl 2-ethylhexanoic acid ester, vinyl ester of an alpha-branched carboxylic acid having 5 to 15 carbon atoms, in particular versatic acid vinyl ester (Veo-Va9R, VeoVal OR) which may also contain ethylene; Vinyl ester-ethylene-vinyl chloride copolymers, vinyl acetate and/or vinyl propionate and/or one or more copolymerizable vinyl esters such as vinyl laurate, vinyl pivalate, vinyl-2-ethylhexanoic acid ester, vinyl ester of an alpha
  • Vinyl acetate polymers vinyl acetate-ethylene copolymers, vinyl acetate-ethylene-vinyl chloride copolymers, vinyl ester-acrylic acid ester copolymers are particularly preferred. in particular with vinyl acetate and butyl acrylate and/or 2-ethylhexyl acrylate, in which optionally N-methylol-functional monomers can also be polymerized, preferably in the amounts mentioned above.
  • N-methylol functional vinyl ester polymers such as vinyl acetate-N-methylolacrylamide copolymers and vinyl acetate-ethylene-N-methylolacrylamide copolymers and combinations thereof.
  • the selection of the monomers or the selection of the proportions by weight of the comonomers is carried out in such a way that the polymers have a glass transition temperature Tg of -50.degree. C. to +120.degree. C., preferably -35.degree. C. to +45.degree.
  • the glass transition temperature Tg of the polymers can be determined in a known manner by means of differential scanning calorimetry (DSC).
  • Tgn glass transition temperature in Kelvin of the homopolymer of monomer n. Tg values for homopolymers are listed in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).
  • the binder compositions preferably contain from 1 to 90% by weight, more preferably from 10 to 85% by weight, even more preferably from 15 to 80% by weight, particularly preferably from 20 to 75% by weight and most preferably from 30 to 70% by weight vinyl ester polymers based on the dry weight of the binder compositions.
  • protective colloid-stabilized vinyl ester polymers particularly preferably to emulsifier-stabilized vinyl ester polymers and most preferably to vinyl ester polymers stabilized with nonionic emulsifiers, or combinations thereof.
  • the vinyl ester polymers are preferably not protective colloid-stabilized ted. The object according to the invention can be achieved even better with these measures.
  • protective colloids are polyvinyl alcohols, polyvinyl acetals, polyvinylpyrrolidones, copolymers of (meth)acrylates with carboxyl-functional comonomer units, poly(meth)acrylamide, polyvinylsulfonic acids and their copolymers, melamine formaldehyde sulfonates, naphthalene formaldehyde sulfonates, styrene maleic acid and vinyl ether maleic acid copolymers.
  • Preferred protective colloids are partially hydrolyzed polyvinyl alcohols, preferably with a degree of hydrolysis of 80 to 95 mol%, in particular 85 to 92 mol% and preferably a Höppler viscosity in 4% aqueous solution of 1 to 30 mPas, in particular 3 to 15 mPas (method according to Höppler at 20°C, DIN 53015) .
  • the protective colloids mentioned can be obtained by methods known to those skilled in the art.
  • the vinyl ester polymers are generally not stabilized with polysaccharides.
  • the polysaccharides contained in the binder compositions generally do not function as protective colloids.
  • the polysaccharides and the vinyl ester polymers, in particular the protective colloid and/or emulsifier stabilized vinyl ester polymers, are preferably present side by side.
  • the proportion of protective colloid is preferably 0 to 30% by weight, particularly preferably 0.5 to 25% by weight and most preferably 1 to 20% by weight, based on the total weight of the vinyl ester polymers.
  • Anionic, cationic or nonionic emulsifiers or combinations thereof can be used.
  • Anionic emulsifiers are preferred, and nonionic emulsifiers are particularly preferred.
  • anionic emulsifiers are alkyl sulfates, sulfonates or carboxylates with a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates, sulfonates or carboxylates with 8 to 18 carbon atoms in the hydrophobic radical and up to 40 ethylene or Propylene oxide units, alkyl or alkylaryl sulfonates having 8 to 18 carbon atoms, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or phosphates, ether phosphates, phosphonates and ether phosphonates and combinations thereof.
  • nonionic emulsifiers are alkyl polyglycol ethers or alkylaryl polyglycol ethers with 8 to 40 ethylene oxide units or ethylene oxide/propylene oxide block copolymers with 2 to 40 EO or PO units or generally EO-PO copolymers, and also alkyl polyglycosides with 1 to 20 C Atoms and ether alkyl polyglycosides with 2 to 40 EO or PO units or their.
  • the proportion of emulsifier is preferably 0 to 15% by weight, particularly preferably 0.1 to 5% by weight and most preferably 0.5 to 3% by weight, based on the total weight of the vinyl ester polymers.
  • the vinyl ester polymers can be prepared by means of known free-radically initiated polymerization processes, for example by means of aqueous suspension polymerization or preferably aqueous emulsion polymerization, as described, for example, in WO2015/067621.
  • the vinyl ester polymers are preferably present in the form of aqueous dispersions with a solids content of preferably 10 to 70% by weight, particularly preferably 40 to 60% by weight.
  • the Brookfield viscosity of the aqueous dispersions of the vinyl ester polymers is preferably 50 to 10,000 mPas, particularly preferably 100 to 2000 mPas (determined using a Brookfield viscometer at 23° C. and 20 rpm with a solids content of the dispersions of 49 to 51% by weight). %) .
  • the vinyl ester polymers can also be in the form of water-redispersible powders (polymer powder).
  • polymer powders can be obtained, for example, by spray drying aqueous polymer dispersions. Additives such as flame retardants, plasticizers, fillers and complexing agents can optionally be added during drying. Dispersing such polymer powders again leads to vinyl ester polymers in the form of aqueous dispersions.
  • the polysaccharides can be, for example, starch, glycogen, cellulose, cellulose derivatives such as chitosan and chitin, hyaluronic acid, glycosaminoglycans, alginates, galactans, cane sugar, maltodextrin or the products obtained by enzymatic or chemical cleavage or chemical modification of the aforementioned polysaccharides, or polysaccharides based on the monomers glucose, sucrose, fructose, galactose, lactose, maltose, mannose or the respective tautomeric structures or combinations thereof.
  • the polysaccharides can also be modifications with polymers based on protein structure or amino acids, such as glycoproteins or their derivatives.
  • Typical sources of polysaccharides are grain, tubers, roots, legumes, fruit starch, hybrid starch, corn, pea, potato, yam, wheat, barley, rice, sorghum or tapioca.
  • the polysaccharides have molecular weights of preferably 300 to 2,700,000 g/mol.
  • the polysaccharides are preferably based on 2 to 15,000 glucose molecules. The object according to the invention can be achieved even better with the preferred polysaccharides.
  • the binder compositions preferably contain from 5 to 95% by weight, more preferably from 15 to 90% by weight, even more preferably from 20 to 80% by weight, particularly preferably from 25 to 70% by weight and most preferably from 30 to 60% by weight polysaccharides based on the dry weight of the binder compositions.
  • the binder compositions preferably contain one or more crosslinkers, such as chemical crosslinkers, electrostatic crosslinkers or van der Waals crosslinkers and combinations thereof.
  • alkyl ureas such as methyl ureas and derivatives thereof, in particular dimethyl ethylene urea and derivatives thereof, for example ARKOFIX® NZF (trade name from Archroma); Melamine crosslinking agents and derivatives thereof, such as MADURIT® MW 125 (trade name from INEOS) or KNITTEX® CHN (trade name from Huntsman); aliphatic polycarboxylic acids such as butane-1,2,3,4-tetracarboxylic acid, polyisocyanates; Citric acid, protected polyisocyanates, epoxides, halogenated hydrocarbons such as bromine or chlorine hydrocarbons, in particular chloroform or trichloromethane, or alkoxylated silanes or combinations thereof.
  • alkyl ureas such as methyl ureas and derivatives thereof, in particular dimethyl ethylene urea and derivatives thereof, for example ARKOFIX® NZF (trade name from Archroma)
  • Electrostatic crosslinkers generally contain ionic groups or groups that form hydrogen bonds, such as CN-, C- 0, HN, HO, HS groups or ionic substances with cationic or anionic functional groups.
  • electrostatic crosslinkers with groups that form hydrogen bonds are polyacrylamides (PAM) and their derivatives.
  • Substances with cationic functional groups are, for example, quaternary ammonium compounds or protonatable amine compounds, such as monoammonium or polyammonium compounds, for example polyamidoamine-epichlorohydrin resins (PAE, trade name KYMENE® from Solenis); or partially or fully protonated chitosans or their reaction products, for example with epichlorohydrins, and combinations thereof.
  • Substances with anionic functional groups are, for example, mono- or poly-carboxylates, such as carboxymethyl cellulose (CMC), sulfonates, sulfinates or sulfides, and also copolymers of polyacrylamides with carboxy groups or combinations thereof.
  • CMC carboxymethyl cellulose
  • sulfonates such as carboxymethyl cellulose (CMC)
  • sulfinates such as sulfinates or sulfides
  • copolymers of polyacrylamides with carboxy groups or combinations thereof are, for example, mono- or poly-carboxylates, such as carboxymethyl cellulose (CMC), sulfonates, sulfinates or sulfides, and also copolymers of polyacrylamides with carboxy groups or combinations thereof.
  • Van der Waals crosslinkers are, for example, high-molecular nanocomposites such as nanocellulose or synthetic nanoplastics.
  • the binder compositions contain preferably 0 to 40% by weight, more preferably 0.1 to 35% by weight, particularly preferably 1 to 25% by weight and most preferably 2 to 15% by weight of crosslinking agent, based on the dry weight of the binder compositions.
  • binder compositions may contain one or more additives, such as emulsifiers, protective colloids such as polyvinyl alcohols, polyurethanes, polyacrylates and derivatives thereof, catalysts, wetting agents or dispersing agents, dyes, matting agents, fillers such as inorganic salts (e.g.
  • optical brighteners Based on, for example, stilbene compounds, free-radical scavengers or color stabilizers, antioxidants such as butylated hydroxytoluene, hydroxybenzophenone, salicylic acid esters, complexing agents such as water softeners based on ethylene tetraacetate salts, also superabsorbent polymers, grip-enabling components such as plasticizers, hydrophobing agents such as fluorocarbons, silicones, natural and synthetic waxes (e.g. paraffins, and polyethylenes), resins, flame retardant additives, antistatic additives, biocides, rheology additives, foam regulators or retention additives.
  • stilbene compounds free-radical scavengers or color stabilizers
  • antioxidants such as butylated hydroxytoluene, hydroxybenzophenone, salicylic acid esters
  • complexing agents such as water softeners based on ethylene tetraacetate salts
  • grip-enabling components such as
  • Preferred additives are emulsifiers and, in particular, catalysts.
  • the binder compositions preferably contain from 0 to 40% by weight, more preferably from 0.1 to 30% by weight and most preferably from 1 to 20% by weight of additives, based on the dry weight of the binder compositions.
  • emulsifiers are fatty alcohol ethoxylates with low degrees of ethoxylation, in particular 2 to 5 ethoxy units, di-isotridecyl sulfosuccinate or their salts, in particular sodium salts, or combinations thereof.
  • the binder compositions preferably contain from 0 to 15% by weight, more preferably from 0.1 to 5% by weight and most preferably from 0.5 to 3% by weight of emulsifiers, based on the dry weight of the binder compositions.
  • secondary properties such as hydrophilicity, soiling behavior, wettability or yellowing of the textile fabric can be influenced with emulsifiers.
  • acidic catalysts such as ammonium chloride, carboxylic acids such as citric acid, acetic acid, malic acid, formic acid, tartaric acid, oxalic acid, in particular hydroxy or dicarboxylic acids, sulfuric acid, phosphoric acid or, in general, stedt acids .
  • carboxylic acids such as citric acid, acetic acid, malic acid, formic acid, tartaric acid, oxalic acid, in particular hydroxy or dicarboxylic acids
  • sulfuric acid phosphoric acid or, in general, stedt acids .
  • a pH of preferably 0 to 5 and particularly preferably 2 to 4 is set.
  • Acid catalysts are preferably added in amounts of 0 to 3% by weight, preferably 0.1 to 2% by weight, based on the dry weight of the binder compositions.
  • the fibers are generally based on natural or synthetic, especially organic, materials.
  • synthetic fibers are viscose, polyester, polyamide, polypropylene or polyethylene fibers or their mixtures or their co-extrudates, which are also referred to, for example, as "BiCo_Fibers".
  • natural fibers are wood pulp - (Pulp), leather, fur, wool, cotton, jute, flax, hemp, coconut, ramie, sisal and cellulose fibers
  • Cellulosic fibers such as viscose, modal, lyocell and acetate are preferred , triacetate, cupro, rayon and cellulose fibers from cellulose.
  • Fiber mixtures which preferably contain several of the aforementioned fibers, are particularly preferred.
  • the fibers are preferably not based on inorganic materials.
  • the fibers are therefore preferably no ceramic fibers or mineral fibers and in particular no glass fibers. Such Fibers can be made conventionally and are commercially available.
  • the fibers can be of any length, such as lengths from 1 mm to infinite length, preferably 5 mm to 100 mm, more preferably 7 mm to 75 mm and most preferably 10 mm to 60 mm.
  • the fibers have diameters of preferably 0.1 ⁇ m to 1 mm, particularly preferably 0.5 ⁇ m to 100 ⁇ m and most preferably 1 ⁇ m to 50 ⁇ m.
  • the fibers can be loose or in the form of bundles or woven textiles, yarns or preferably in the form of nonwovens such as fleece, felt, scrims or knitted fabrics, or woven fabrics. be used on floors or carpets.
  • the nonwovens can optionally be thermally or mechanically preconsolidated, for example needled or hydroentangled.
  • Binder compositions can, for example, be in solid form, preferably in liquid form, in particular in aqueous form. Binder compositions in solid form can be converted into aqueous form by adding water.
  • the binder compositions in aqueous form have a solids content of preferably 1 to 80% by weight, particularly preferably 10 to 70% by weight and most preferably 20 to 60% by weight.
  • the vinyl ester polymers, polysaccharides, any crosslinking agents and any additives are mixed with one another.
  • polysaccharides in solid or aqueous form can be mixed with vinyl ester polymers in the form of water-redispersible powders, and water can optionally be added at the same time or at a later point in time.
  • the polysaccharides are preferably introduced in aqueous form and the vinyl ester polymers in the form of aqueous dispersions.
  • the polysaccharides are preferably stirred into water under high shear.
  • Hot-water-soluble polysaccharides are preferably stirred into hot water or diluted with hot water after pre-melting.
  • Cold-water-soluble polysaccharides are preferably stirred into water at room temperature, for example 20 to 30° C., with stirring, for example with a paddle stirrer, preferably until optical homogeneity.
  • Vinyl ester polymers are then preferably added in the form of aqueous dispersions.
  • the fibers can be mixed with the binder compositions and the resulting mixture laid out by conventional methods of nonwoven technology, for example using air-laying, wet-laying, direct spinning or carding devices, and then optionally solidified will.
  • the fibers can also be spread out flat and, if appropriate before or after solidification, the binder compositions can be applied.
  • the fibers can be laid out, for example, by means of an air-laying, wet-laying, direct spinning or carding device.
  • the binder composition prior to application of the binder composition, it can also be mechanically consolidated, for example by cross-laying, needling or hydro-entanglement.
  • the binder compositions can be applied, for example, in the form of a sheet, in spots or in a pattern over the entire area or partial areas of the fibers.
  • the application can take place, for example, by compulsory application, such as spraying, padding (padding, padding), coating, brushing, dipping or by means of foam application, or by non-compulsory applications, such as the exhaust method, or by combined methods, for example the overflow jet method.
  • the product thus obtained can then be treated for drying, solidifying, fixing or binding, for example by applying elevated temperatures and/or pressure, for example at 120 to 220° C., preferably for 20 seconds to 5 minutes.
  • elevated temperatures and/or pressure for example at 120 to 220° C., preferably for 20 seconds to 5 minutes.
  • Air, circulating air, air flow or infrared drying (LR drying) can also be used.
  • the binder compositions are also suitable for producing laminates, in which case two fiber layers are bonded together, or a fiber layer is bonded to another substrate. will stick.
  • the procedure can be such that a fiber layer is laid out, with the binder composition being mixed beforehand or applied after laying out, and a further fiber layer being laid on, for example by air laying.
  • another substrate for example a plastic film, can also be placed on top. Bonding then takes place through the application of temperature and, if necessary, pressure. With this procedure, for example, insulating materials, for example made of recycled cotton, are accessible, which are permanently laminated, for example, with a fiber fleece as a cover fleece.
  • the aqueous binder composition is used in an amount of preferably 1 to 50% by weight, more preferably 5 to 30% by weight and most preferably 10 to 25% by weight, based in each case on the total weight of the Fibers (dry/dry) .
  • Vinyl ester polymers are used in an amount of preferably 1 to 50% by weight, more preferably 5 to 30% by weight and most preferably 10 to 25% by weight, based on the total weight of the fibers (dry/dry).
  • the proportion of fibers is preferably 40 to 99% by weight, particularly preferably 50 to 90% by weight and most preferably 60 to 80% by weight, based in each case on the total weight of the textile fabric.
  • the textile fabrics produced according to the invention are preferably nonwovens, in particular tissues, felts, waddings or coarse-meshed, loose wovens, knitted fabrics or warp-knitted fabrics.
  • the textile fabrics can be used, for example, in the automotive sector, for household products such as tablecloths, hygiene items such as toilet paper, in the clothing industry, for medical textiles or geotextiles.
  • the binder compositions are also suitable for the production of voluminous nonwovens or wadding, which are used, for example, as semi-finished products for the production of molded parts from fiber materials or as padding, insulation and filter wadding.
  • the binder compositions can be applied to the fibers and solidified by increasing the temperature, preferably in a mold.
  • binder compositions according to the invention which contain vinyl ester polymers in addition to polysaccharides, are surprisingly stable and do not tend to separate, not even in the plants and process conditions in the production of textile fabrics.
  • the binder compositions can be applied as binders for textile fabrics by established methods.
  • the textile fabrics produced according to the invention have the desired performance properties, such as mechanical properties, and permanently fix the fibers, which represents a particular challenge when using binders containing biopolymer components.
  • textile fabrics with advantageous strength such as dry strength or even wet strength, or improved solvent resistance, are accessible using polysaccharides in binders, which have the desired resistance to mechanical stress without compromising the integrity and elasticity of the s textile fabric significantly to influence sen.
  • the polysaccharides (hereinafter abbreviated as "PSC") were stirred into water under high shear.
  • hot-water-soluble polysaccharides were stirred in with hot water under high shear or diluted with hot water by pre-melting.
  • Vinyl ester polymers (abbreviated to “VAE”) were then added in the form of an aqueous dispersion, and stirring was continued for 5 minutes using a paddle stirrer.
  • binder compositions of Examples 1 to 3 a) : VAc : vinyl acetate; E: ethylene; NMA: N-methylolacrylamide;
  • PSC 2 dextrin with 6000 to 7000 glucose units (obtained from Avebe). Testing of the compatibility and storage stability of the binder compositions:
  • binder compositions were based on 50 wt. -% (dry) on the polysaccharides (PSC) and aqueous emulsifier or polyvinyl alcohol-stabilized vinyl ester polymer dispersions (VAE) given in Table la and were stored for one month after their preparation at room temperature and according to the table 1b given periods of time on their storage stability or. Separation checked. The results are summarized in Table 1b.
  • Table 1b Storage stability of the binder compositions of Examples 1 to 3:
  • the binder compositions with the emulsifier-stabilized vinyl ester polymer dispersions of Examples 1 and 2 were more stable than the analogs of Example 3 stabilized with the protective colloid polyvinyl alcohol.
  • binder systems are usually applied to biodegradable reference materials.
  • 25% by weight of the binder compositions (solid/solid) given in Table 2 were applied to cellulose powder and examined for aerobic biodegradability in accordance with ISO 14855-1.
  • the test results are summarized in Table 2.
  • the binder compositions of Examples 5 and 6 show significantly higher degradability and thus meet the requirement for biodegradability of >90%.
  • the strip samples were each stored in water for 1 minute before the measurement.
  • the wet and dry strengths were determined analogously to DIN EN 29073 (Part 3: Test methods for nonwovens, 1992) and the measurement samples were measured using a maximum tensile force measurement on a Zwick® 1445 testing machine (100 N load cell) with TestXpert® software version 11.02 (company . Zwick Roell) with a clamping length of 10011 mm, a clamping width of 1511 mm and at a deformation rate of 150 mm/min.
  • the formaldehyde content was determined according to ISO 14184-1.
  • the nonwovens of Examples 8, 9, 11 and 12 come surprisingly close to the strengths of the nonwovens of Comparative Examples 7 and 10. This is surprising because otherwise biopolymers usually lead to a considerable deterioration in strength.
  • the nonwovens of Examples 8, 9, 11 and 12 are surprisingly soft despite the polysaccharides themselves having a hardening effect and also show good elasticity (elongation).
  • nonwovens of Examples 8, 9, 11 and 12 have a lower formaldehyde content than the nonwovens of Comparative Examples 7 and 10, which has a positive effect on the toxicological profile of the nonwovens.
  • Table 3 Dry strength of nonwovens, without crosslinker: a) : VAE 1: vinyl ester polymer from example 1;
  • VAE 2 vinyl ester polymer from Example 2
  • BSC 1 polysaccharide from example la;
  • PSC 2 polysaccharide from example 1b; b) : Based on the dry weight of binder composition and fleece.
  • Table 4 Dry and wet strength of nonwovens, also with crosslinkers: a) : VAE 1: vinyl ester polymer from example 1;
  • VAE 2 vinyl ester polymer from Example 2
  • PSC 1 polysaccharide from example la;
  • PSC 2 polysaccharide from example 1b; b) Crosslinker 1: ARKOFIX® NZF (trade name of Archroma);
  • Crosslinker 2 KNITTEX® CHN (trade name from Huntsman); catalyst: citric acid; the data in % refer to wt. % dry matter; c) : Based on the dry weight of binder composition and fleece.
  • Table 5 Dry and wet strength of nonwovens, also with crosslinkers: a) : VAE 1: vinyl ester polymer from example 1; VAE 2: vinyl ester polymer from Example 2;
  • PSC 1 polysaccharide from example la;
  • PSC 2 polysaccharide from example 1b; b): Crosslinker 1: Arkofix NZF (trade name of Archroma);
  • Crosslinker 2 Knittex CHN (trade name from Huntsman); catalyst: citric acid; the data in % relate to % by weight of dry substance; c) : Based on the dry weight of binder composition and fleece.
  • Table 6 Dry and wet strength of nonwovens, also with crosslinkers: a) : VAE 1: vinyl ester polymer from example 1; VAE 2: vinyl ester polymer from Example 2;
  • PSC 1 polysaccharide from example la;
  • PSC 2 polysaccharide from example 1b; b): Crosslinker 1: Arkofix NZF (trade name of Archroma);
  • Crosslinker 2 Knittex CHN (trade name from Huntsman);
  • Crosslinker 3 KYMENE 217 LXE (trade name of Solenis)
  • catalyst citric acid
  • the data in % relate to % by weight of dry substance
  • c) Based on the dry weight of binder composition and fleece.
  • the nonwovens obtained were pleasantly soft despite the polysaccharides, which had a hardening effect per se, and also when crosslinking agents were used, and they also showed good elasticity (elongation).
  • the formaldehyde content of the nonwovens could be significantly reduced, even when using crosslinking agents, which has a positive effect on the toxicological profile of the nonwovens. Only in the case of crosslinker 2 are the formaldehyde values significantly higher, since this splits off formaldehyde during crosslinking.

Abstract

L'invention concerne, entre autres, des procédés de production de matériaux en feuille textiles par application d'une ou de plusieurs compositions de liant sur des fibres, caractérisé en ce que les compositions de liant contiennent un ou plusieurs polysaccharides et un ou plusieurs polymères d'esters vinyliques.
PCT/EP2020/084981 2020-12-08 2020-12-08 Matériau en feuille textile WO2022122120A1 (fr)

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WO1997042271A1 (fr) 1996-05-06 1997-11-13 National Starch And Chemical Investment Holding Corporation Adhesifs a base de maltodextrine
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