EP1828298A2 - Utilisation de liants aqueux sans formaldehyde sur des substrats - Google Patents

Utilisation de liants aqueux sans formaldehyde sur des substrats

Info

Publication number
EP1828298A2
EP1828298A2 EP05819208A EP05819208A EP1828298A2 EP 1828298 A2 EP1828298 A2 EP 1828298A2 EP 05819208 A EP05819208 A EP 05819208A EP 05819208 A EP05819208 A EP 05819208A EP 1828298 A2 EP1828298 A2 EP 1828298A2
Authority
EP
European Patent Office
Prior art keywords
formaldehyde
free
aqueous
acid
aqueous binders
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.)
Withdrawn
Application number
EP05819208A
Other languages
German (de)
English (en)
Inventor
Kathrin Michl
Matthias Gerst
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.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1828298A2 publication Critical patent/EP1828298A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/32—Macromolecular compounds or prepolymers obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/34—Condensation polymers of aldehydes, e.g. with phenols, ureas, melamines, amides or amines
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C03C25/28—Macromolecular compounds or prepolymers obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C03C25/285—Acrylic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • 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
    • D04H1/4209—Inorganic fibres
    • 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
    • D04H1/4209—Inorganic fibres
    • D04H1/4218—Glass fibres
    • 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
    • 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
    • D04H1/645—Impregnation followed by a solidification process
    • 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
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • 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
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer
    • 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]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31645—Next to addition polymer from unsaturated monomers
    • 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]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31645—Next to addition polymer from unsaturated monomers
    • Y10T428/31649—Ester, halide or nitrile of addition polymer
    • 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]
    • Y10T428/3167—Of cork
    • 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
    • Y10T428/31895—Paper or wood
    • Y10T428/31906—Ester, halide or nitrile of addition polymer

Definitions

  • the present invention relates to the use of formaldehyde-free, aqueous, wide molecular weight distribution binders for substrates containing
  • the invention relates to the binder itself, as well as their use for z.
  • mats or plates in particular for fibrous and granular substrates such as nonwoven fabrics, glass fibers, rock wool, tear cotton, natural fibers or Kunststofffa- fibers.
  • nonwoven fabrics The solidification of sheet-like fiber structures, so-called nonwoven fabrics, takes place, for example, purely mechanically by needling or hydroentanglement of a wet or air-laid nonwoven or by chemical solidification of the nonwovens with a polymeric binder.
  • the binder application is usually carried out by impregnation, spraying or coating.
  • binders which contain formaldehyde-releasing crosslinkers are often used.
  • formaldehyde emissions the skilled person endeavors to provide alternatives to the previously known binders.
  • No. 6,221,973 discloses a formaldehyde-free, crosslinkable aqueous composition of a polyacid, a polyol and a phosphorus-containing reaction accelerator for use as a binder for heat-resistant nonwovens, eg. Eg glass fibers.
  • EP 990 727 discloses binders for mineral fibers of a low molecular weight polycarboxylic polymer and a polyol, wherein the pH of the binder is not greater than 3.5.
  • No. 5,932,665 discloses polycarboxy-polymer-based binders, which system can be cured by adjusting the molecular weight and the copolymer composition at lower temperatures than comparable homopolyacrylic acid systems.
  • EP 882 074 describes formaldehyde-free, aqueous binders of an ethylenically unsaturated acid anhydride or of an ethylenically unsaturated dicarboxylic acid and an alkanolamine as coating agent, impregnating agent and binder for fiber webs.
  • the object of the present invention was therefore to provide such binders for use with substrates such as moldings, mats or plates, which have good strength and at the same time good flowability.
  • aqueous polymer dispersion (D) produces binders with particularly good binder properties, in particular with regard to wet strength.
  • the high molecular weight fractions of the binder ensure high strengths of the substrates and the low molecular weight fractions simultaneously ensure a good flow behavior of the binder on the substrate.
  • the aqueous binder according to the invention contains a polymer A) which contains from 0 to 100% by weight, preferably from 5 to 50% by weight, particularly preferably from 10 to 40% by weight, of an ethylenically unsaturated acid anhydride or of an ethylenically unsaturated dicarboxylic acid Carboxylic groups can form an anhydride group is constructed.
  • dicarboxylic acid anhydrides are preferred.
  • Suitable ethylenically unsaturated dicarboxylic acids are generally those having carboxylic acid groups on adjacent carbon atoms.
  • the carboxylic acid groups may also be present in the form of their salts.
  • Preferred monomers A) are maleic acid, fumaric acid, maleic anhydride, itaconic acid, 1,2,3,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic anhydride, their alkali metal and ammonium salts or mixtures thereof. Particularly preferred are maleic acid and maleic anhydride.
  • monomers B can be used, for example:
  • Cio-monocarboxylic acids such as.
  • acrylic acid methacrylic acid, ethylacrylic acid, allylacetic acid, crotonic acid, vinylacetic acid, maleic monoesters such as monomethyl maleate, their mixtures or their alkali metal and ammonium salts.
  • oligopropene, oligohexene and oligooctadecene prepared by cationic polymerization olefins with high ⁇ -olefin content, such as.
  • B. polyisobutene prepared by cationic polymerization olefins with high ⁇ -olefin content
  • monomers b 3 such as methyl vinyl ether, ethyl vinyl
  • Acrylamides and alkyl-substituted acrylamides (monomers b 4 ), such as. Acrylamide, methacrylamide, N-tert-butylacrylamide, N-methyl (meth) acrylamide.
  • Sulfo group-containing monomers such as. B. allylsulfonic acid, methallylsulfonic acid, styrenesulfonate, vinylsulfonic acid, allyloxybenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, their corresponding alkali metal or ammonium salts or mixtures thereof.
  • Vinyl and allyl esters of C 1 to C 30 monocarboxylic acids (monomers b 8 ), such as. Vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl 2-ethylhexanoate, vinyl nonanoate, vinyl decanoate, vinyl pivalate, vinyl palmitate, vinyl stearate, vinyl laurate.
  • Other monomers b 9 are: N-vinylformamide, N-vinyl-N-methylformamide, styrene, ⁇ -methylstyrene, 3-methylstyrene, butadiene, N-vinylpyrrolidone, N-vinylimidazole, 1-vinyl-2-methylimidazole, 1-vinyl-2-methyl-imidazoline, N-vinylcaprolactam, acrylonitrile, methacrylonitrile, allyl alcohol, 2-vinylpyridine, 4-vinylpyridine, diallyldimethylammonium chloride, vinylidene chloride, vinyl chloride, acrolein, methacrolein and vinylcarbazoi or mixtures thereof.
  • the polymer preferably also contains monomers (B) in amounts of from 50 to 95, particularly preferably from 60 to 90,% by weight.
  • Preferred monomers are acrylic acid, methacrylic acid, esters of acrylic or methacrylic acid (for example methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate) ethene, propene, butene, isobutene, cyclopentene, methyl vinyl ether, Ethyl vinyl ether, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, vinyl acetate, styrene, butadiene, acrylonitrile, monomethyl monomethyl ester or mixtures thereof.
  • acrylic acid for example methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate) ethene, propene, butene, isobutene, cyclopentene, methyl vinyl ether, Ethyl vinyl ether, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid
  • acrylic acid methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ethene, acrylamide, styrene and acrylonitrile, monomethyl maleate or mixtures thereof.
  • acrylic acid methacrylic acid and methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, monomethyl maleate or mixtures thereof.
  • the polymers can be prepared by conventional polymerization, for. B. by substance, emulsion, suspension, dispersion, precipitation or solution. In the polymerization processes mentioned, it is preferable to operate with the exclusion of oxygen, preferably in a stream of nitrogen.
  • the usual equipment is used, for. B. stirred tank, stirred tank cascades, autoclaves, tubular reactors and kneaders.
  • the method of solution, emulsion, precipitation or suspension polymerization is used. Particularly preferred are the methods of solution and emulsion polymerization.
  • the polymerization can be carried out in solvents or diluents, such as.
  • water or optionally with proportions of up to 60% by weight of alcohols or glycols is used as the solvent or diluent. Particular preference is given to using water.
  • the polymerization can be carried out at temperatures of from 20 to 300, preferably from 60 to 200 ° C. Depending on the choice of polymerization conditions can be weight average molecular weights z. B. from 800 to 5 000 000, in particular from 1 000 to 1 000 000 set.
  • the weight-average molecular weights M w are above 3000. Weight-average molecular weights of from 3,000 to 600,000 are particularly preferred. M w is determined by gel permeation chromatography (detailed description in Examples).
  • the polymerization is preferably carried out in the presence of free-radical-forming compounds.
  • free-radical-forming compounds up to 30, preferably 0.05 to 15, particularly preferably 0.2 to 8,% by weight, based on the monomers used in the polymerization, are required.
  • the above weights are based on the sum of the components.
  • Suitable polymerization initiators are, for example, peroxides, hydroperoxides, peroxydisulfates, percarbonates, peroxyesters, hydrogen peroxide and azo compounds.
  • initiators which may be water-soluble or water-insoluble are hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxydicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl peroxide, acetylacetone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl pemeodecanoate, tert-amyl perpivalate tert-butylperpivalate, tert-butylperneohexanoate, tert-butylper-2-ethylhexanoate, tert-butyl perbenzoate, lithium, sodium, potassium and ammonium
  • the initiators can be used alone or mixed with each other, for. B. mixtures of hydrogen peroxide and sodium peroxydisulfate. Water-soluble initiators are preferably used for the polymerization in aqueous medium.
  • the known redox initiator systems can also be used as polymerization initiators.
  • Such redox initiator systems contain at least one peroxide-containing compound in combination with a redox coinitiator z.
  • sulfur compounds such as bisulfites, sulfites, thiosulfates, dithionites and tetrathionates of alkali metals and ammonium compounds. So you can combine use of peroxodisulfates with alkali metal or ammonium hydrogen sulfites, z. For example, ammonium peroxydisulfate and ammonium disulfite.
  • the amount of the peroxide-containing compound to the redox coinitiator is 30: 1 to 0.05: 1.
  • transition metal catalysts may additionally be used, for. Salts of iron, cobalt, nickel, copper, vanadium and manganese. Suitable salt are, for. Ferrous sulfate, cobalt II chloride, nickel II sulfate, copper I chloride. Based on monomers, the reducing transition metal salt is used in a concentration of 0.1 ppm to 1 000 ppm. So you can use combinations of hydrogen peroxide with iron-Il salts, such as 0.5 to 30% hydrogen peroxide and 0.1 to 500 ppm Mohr's salt.
  • redox coinitiators and / or transition metal catalysts eg. As benzoin, dimethylaniline, ascorbic acid and organically soluble complexes of heavy metals such as copper, cobalt, iron, manganese, nickel and chromium.
  • the amounts of redox coinitiators or transition metal catalysts usually used here are usually about 0.1 to 1000 ppm, based on the amounts of monomers used.
  • reaction mixture is polymerized at the lower limit of the temperature range of interest for the polymerization and then polymerized at a higher temperature, it is expedient to use at least two different initiators which decompose at different temperatures, so that one at each temperature interval sufficient concentration of radicals is available.
  • the initiator may also be added in stages, or the rate of initiator addition may be varied over time.
  • regulators may be used for this purpose, for example compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert-butylmercaptan, n-octylmercaptan, n-dodecylmercaptan and tert-dodecylmercaptan, C 1 - to C 4 -aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, hydroxylammonium salts such as hydroxylammonium sulfate, formic acid, sodium bisulfite, hypophosphorous acid or salts thereof or isopropanol.
  • organic SH groups such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert-butylmercaptan, n-octylmercaptan, n-dodecylmercaptan and ter
  • the polymerization onsregler are generally used in amounts of 0.1 to 20 wt .-%, based on the monomers. Also by the choice of the appropriate solvent can be influenced on the average molecular weight. This is how the polymerization leads in the presence of diluents with benzylic H atoms, or in the presence of secondary alcohols such as. B. isopropanol to a reduction of the average molecular weight by chain transfer.
  • Low molecular weight polymers are also obtained by: varying the temperature and / or the initiator concentration.
  • crosslinkers are compounds having two or more ethylenically unsaturated groups, such as diacrylates or dimethacrylates of at least dihydric saturated alcohols, e.g.
  • Ethylene glycol diacrylate ethylene glycol dimethacrylate, 1,2-propylene glycol diacrylate, 1,2-propylene glycol dimethacrylate, butanediol-1,4-diacrylate, 1,4-butanediol, hexanediol diacrylate, hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methylpentanediol diacrylate and 3-methylpentanediol dimethacrylate.
  • the acrylic acid and methacrylic acid esters of alcohols having more than 2 OH groups can also be used as crosslinking agents, eg.
  • Trimethylolpropane triacrylate or trimethylolpropane trimethacrylate Trimethylolpropane triacrylate or trimethylolpropane trimethacrylate.
  • Another class of crosslinkers are diacrylates or dimethacrylates of polyethylene glycols or polypropylene glycols having molecular weights of from 200 to 9,000, respectively.
  • Polyethylene glycols or polypropylene glycols used for the preparation of the diacrylates or dimethacrylates preferably have a molecular weight of from 400 to 2,000, respectively It is also possible to use block copolymers of ethylene oxide and propylene oxide or copolymers of ethylene oxide and propylene oxide which contain the ethylene oxide and propylene oxide units randomly distributed in the homopolymers of the ethylene oxide or propylene oxide.
  • the oligomers of ethylene oxide or propylene oxide are suitable for the preparation of crosslinking agents, for.
  • crosslinking agents for example, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate and / or tetraethylene glycol dimethacrylate.
  • crosslinking agents are vinyl acrylate, vinyl methacrylate, vinyl itaconate, divinyl dianinyl ether, butanediol divinyl ether, trimethylolpropane trivinyl ether, allyl acrylate, allyl methacrylate, pentaerythritol triallyl ether, triallyl sucrose, pentaallylsucrose, pentaallylsucrose, methylenebis (meth) acrylamide, divinylethyleneurea, divinylpropylurea, divinylbenzene, divinyldioxane, triallylcyanurate, tetraallylsilane , Tetravinylsi- lan and bis or polyacrylic siloxanes (eg Tegomereä Th. Goldschmidt AG).
  • the crosslinkers are preferably used in amounts of 10 ppm to 5 wt .-%, based on the monomers to be polymerized.
  • emulsifiers or protective colloids are used for this purpose.
  • anionic, nonionic niche, cationic and amphoteric emulsifiers into consideration.
  • Anionic emulsifiers are, for example, alkylbenzenesulfonic acids, sulfonated fatty acids, sulfosuccinates, fatty alcohol sulfates, alkylphenol sulfates and fatty alcohol ether sulfates.
  • nonionic emulsifiers which can be used are alkylphenol ethoxylates, primary alcohol ethoxylates, fatty acid ethoxylates, alkanolamide ethoxylates, fatty amine ethoxylates, EO / PO block copolymers and alkyl polyglucosides.
  • cationic or amphoteric emulsifiers used are: quaternized aminal alkoxylates, alkyl betaines, alkylamidobetaines and sulfobetaines.
  • Typical protective colloids are, for example, cellulose derivatives, polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, polyvinyl acetate, polyvinyl alcohol, polyvinyl ethers, starch and starch derivatives, dextran, polyvinylpyrrolidone, polyvinylpyridine, polyethyleneimine, polyvinylimidazole, polyvinylsuccinimide, polyvinyl-2-one. methyl succinimide, polyvinyl-1, 3-oxazolidone-2, polyvinyl-2-methylimidazoline and maleic acid or maleic anhydride-containing copolymers, as described, for. B. in DE 2 501 123 are described.
  • the emulsifiers or protective colloids are usually used in concentrations of 0.05 to 20 wt .-%, based on the monomers.
  • the monomers can be completely or partially neutralized by bases before or during the polymerization.
  • bases for example, alkali or alkaline earth compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, sodium carbonate; Ammonia; primary, secondary and tertiary amines, such as ethylamine, propylamine, monoisopropylamine, monobutylamine, hexylamine, ethanolamine, dimethylamine, diethylamine, di-n-propylamine, tributylamine, triethanolamine, dimethoxyethylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, dimethylethanolamine, Diisopropanolamine or morpholine in question.
  • bases for example, alkali or alkaline earth compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, sodium carbonate; Ammonia; primary, secondary and tertiary amines, such as
  • polybasic amines can be used for neutralization, such as.
  • ammonia for the partial or complete neutralization of the ethylenically unsaturated carboxylic acids before or during the polymerization, ammonia, triethanolamine and diethanolamine are used.
  • the ethylenically unsaturated carboxylic acids are not neutralized before and during the polymerization.
  • no neutralizing agent is added after the polymerization, except for alkanolamine C).
  • the polymerization can be carried out continuously or batchwise in a variety of variants. It is customary to pass some of the monomers, if appropriate in a suitable diluent or solvent and if appropriate in the presence of an emulsifier, a protective colloid or further auxiliaries, to render them inert, and to increase the temperature until the desired polymerization temperature is reached. However, it may also be submitted only a suitable diluent. Within a defined period of time, the radical initiator, other monomers and other auxiliaries, such as. B. regulators or crosslinkers are optionally added in each case in a diluent.
  • the feed times can be chosen to be different. For example, you can choose a longer feed time for the Initiatorzulauf than for the monomer feed.
  • the broad molecular weight distribution polymers can also be prepared in situ in one step by first synthesizing the low molecular weight fraction (at a particular initiator concentration / temperature) and after 0-100% addition of the monomers, lowering the initiator concentration in the reaction mixture, and / or Temperature is reduced (gradually or continuously); or the multimodal polymers can be prepared in situ in one step by first synthesizing the high molecular weight moiety (at a particular initiator concentration / temperature) and after adding the monomers to 100-0%, increasing the initiator concentration in the reaction mixture and / or raising the temperature becomes.
  • the polymer is obtained by the process of a solution polymerization in water, usually no separation of the solvent is necessary. Nevertheless, if there is a desire to isolate the polymer, z. B. be carried out a spray drying.
  • the solvent can be separated off by passing in steam so as to obtain an aqueous solution or dispersion.
  • the polymer can also be separated from the organic diluent by a drying process.
  • the polymers of A) and B) are preferably in the form of an aqueous dispersion or solution having solids contents of preferably from 10 to 80% by weight, in particular from 40 to 65% by weight.
  • Polymer A) can also be obtained by grafting maleic acid or maleic anhydride or a maleic acid or maleic anhydride-containing monomer mixture onto a grafting base.
  • Suitable graft bases are, for example, monosaccharides, oligosaccharides, modified polysaccharides and alkylpolyglycosides. ether.
  • Such graft polymers are described, for example, in DE 4 003 172 and EP 116 930.
  • the polyfunctional crosslinkers of component C) are, for example, alkanolamines having at least two OH groups. Alkanolamines of the formula I are preferred
  • R 1 is an H atom, an alkyl group or a CiC 10 CiC is 10 hydroxyalkyl group
  • R 2 and R 3 represent a CrC ⁇ o-hydroxyalkyl group.
  • R 2 and R 3 independently of one another are a C 2 -C 5 -hydroxyalkyl group and R 1 is an H atom, a C 1 -C 5 -alkyl group or a C 2 -C 5 -hydroxyalkyl group.
  • Diethanolamine triethanolamine, diisopropanolamine, triisopropanolamine, methyldiethanolamine, butyldiethanolamine and methyldiisopropanolamine. Particularly preferred is triethanolamine.
  • Polyfunctional crosslinkers C) can also be difunctional or polyfunctional alcohols, for example, for example, glycerol, methylolated melamines or phenols.
  • polyfunctional crosslinkers which can be used as component C) are described in EP 902 796, for example trimethylolpropane, pentaerythritol, neopentyl glycol, glucose, sorbitol, hexanediol, lysine, polyvinyl alcohol.
  • Alkanolamines are preferably used as component C, in particular preferably triethanolamine.
  • the aqueous polymer dispersion D) is understood as meaning, for example, pure acrylate dispersions, styrene-acrylate, XSB dispersions, polyurethane dispersions or a dispersion containing a modified polycarboxylic acid with alcohol as crosslinker component.
  • the polymer dispersion D is preferably understood to mean a dispersion containing modified polycarboxylic acid with a crosslinker component comprising dispersing polymer particles of at least one polymer A1 obtainable by free-radical emulsion polymerization in the presence of a polymer A2 which is composed of From 50 to 99.5% by weight of at least one ethylenically unsaturated mono- and / or dicarboxylic acid,
  • ethylenically unsaturated compound selected from the esters of ethylenically unsaturated monocarboxylic acids and the half-esters and diesters of ethylenically unsaturated dicarboxylic acids having an amine having at least one hydroxyl group,
  • alkyl below preferably straight-chain or branched CrC 22 -alkyl radicals, in particular C 1 -C 12 - and particularly preferably C r C 6 alkyl such as methyl, ethyl, n-propyl, n- Butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-dodecyl or n-stearyl.
  • C 1 -C 12 - and particularly preferably C r C 6 alkyl such as methyl, ethyl, n-propyl, n- Butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-dodecyl or n-stearyl.
  • Hydroxyalkyl is preferably hydroxyCrC ⁇ -alkyl, where the alkyl radicals may be straight-chain or branched, and in particular 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2-methyl-2-hydroxypropyl and 4-hydroxybutyl.
  • Cycloalkyl is preferably C 5 -C 7 cyclohexyl, in particular cyclopentyl and cyclohexyl.
  • Aryl is preferably phenyl or naphthyl.
  • the polymer A1 represents a free-radical emulsion polymer.
  • the polymer is composed of
  • the main monomer is preferably selected from
  • esters are in particular methyl, ethyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and 2-ethylhexyl acrylate and / or methacrylate; vinyl aromatic compounds, preferably styrene, ⁇ -methylstyrene, o-chlorostyrene, vinyltoluenes and mixtures thereof;
  • Vinyl esters of CrCl 8 mono- or dicarboxylic acids such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl aurate and / or vinyl stearate;
  • linear 1-olefins such as. Ethene, propene, butene, isobutene, pentene, cyclopentene, hexene or
  • Cyclohexene Furthermore, metallocene-catalyzed O-ligoolefins with terminal double bond, such as. B. Oligopropen or oligohexhexen suitable;
  • Particularly preferred major monomers are styrene, methyl methacrylate, n-butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, vinyl acetate, ethene and butadiene.
  • the comonomer is preferably selected from
  • ethylenically unsaturated mono- or dicarboxylic acids or their anhydrides preferably acrylic acid, methacrylic acid, methacrylic anhydride, maleic acid, maleic anhydride, fumaric acid and / or itaconic acid;
  • Acrylamides and alkyl-substituted acrylamides such as. Acrylamide, methacrylamide, N, N-dimethylacrylamide, N-methylolmethacrylamide, N-tert-butylacrylamide, N-methylmethacrylamide and mixtures thereof;
  • sulfo-containing monomers such as. B. allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, allyloxybenzenesulfonic acid, their corresponding alkali metal or ammonium salts or mixtures thereof and sulfopropyl and / or sulfopropyl methacrylate; C 1 -C 4 -Hydroxyalkylestem of C 3 -C 6 -mono- or dicarboxylic acids, in particular of acrylic acid, methacrylic acid or maleic acid, or their with 2 to 50 moles of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof alkoxylated derivatives or esters of 2 to 50 mol of ethylene oxide, propylene oxide, butylene oxide or mixtures thereof alkoxylated C r Ci 8 alcohols with the mentioned acids
  • hydroxyethyl acrylate hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, butanediol 1, 4-monoacrylate, ethyl diglycol acrylate, methyl polyglycol acrylate (11 EO), (meth) acrylic acid ester of reacted with 3,5,7,10 or 30 MoI ethylene oxide C 13 / C 15 -oxo alcohol or mixtures thereof;
  • N-vinyl compounds such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylpyrrolidone, N-vinylimidazole, 1-vinyl-2-methylimidazole, 1-vinyl-2-methylimidazoline, 2-vinylpyridine, 4-vinylpyridine , N-vinylcarbazole and / or N-vinylcaprolactam;
  • 1, 3-diketo groups containing monomers such as. Acetoacetoxyethyl (meth) acrylate or diacetone acrylamide, urea group-containing monomers such as ureidoethyl (meth) acrylate, acrylamidoglycolic acid, methacrylamide methyl glycol ether;
  • Silyl-containing monomers such as. B. trimethoxysilylpropyl methacrylate;
  • Glycidyl-containing monomers such as. B. glycidyl methacrylate.
  • Particularly preferred comonomers are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate and mixtures thereof. Very particular preference is given to hydroxyethyl acrylate and hydroxyethyl methacrylate, in particular in amounts of from 2 to 20% by weight, based on the total monomer Al
  • the polymer A2 contains from 50 to 99.5% by weight, preferably from 70 to 99% by weight, of those structural elements which are derived from at least one ethylenically unsaturated mono- or dicarboxylic acid. If desired, these acids may also be partially or completely present in the form of a salt in the polymer. The acidic form is preferred.
  • the polymer A2 is more than 10 g / l (at 25 C) soluble in water.
  • carboxylic acids are C 3 - to C 10 -monocarboxylic acids and C 4 - to C 8 -dicarboxylic acids, in particular acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid and / or itaconic acid. Particularly preferred are acrylic acid, methacrylic acid, maleic acid and mixtures thereof.
  • anhydrides such as maleic anhydride, acrylic acid or methacrylic anhydride.
  • the polymer A2 further contains 0.5 to 50 wt .-%, preferably 1 to 30 wt .-%, of at least one ethylenically unsaturated compound which is selected from the esters of ethylenically unsaturated monocarboxylic acids and the half esters and diesters of ethylenically unsaturated dicarboxylic acids at least one hydroxyl-containing amine, in copolymerized form.
  • the polymer A2 is preferably present as a comb polymer with covalently bound amine side chains.
  • Monocarboxylic acids suitable as a component of the esters are the aforementioned C 3 to C 10 monocarboxylic acids, in particular acrylic acid, methacrylic acid, crotonic acid, and mixtures thereof.
  • Dicarboxylic acids suitable as a component of the half-esters and diesters are the abovementioned C 4 - to C 8 -dicarboxylic acids, in particular fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, and mixtures thereof.
  • the amine having at least one hydroxyl group is selected from secondary and tertiary amines containing at least one C 6 to C 22 alkyl, C 6 to C 22 alkenyl, aryl C 6 to C 22 alkyl, or Aryl-C 6 - have up to C 22 -alkenyl, wherein the alkenyl group may have 1, 2 or 3 non-adjacent double bonds.
  • the amine is hydroxyalkylated and / or alkoxylated.
  • Alkoxylated amines preferably have one or two alkylene oxide radicals with terminal hydroxyl groups.
  • the alkylene oxide radicals preferably have from 1 to 100, preferably from 1 to 50, identical or different alkylene oxide units, randomly distributed or in the form of blocks.
  • Preferred alkylene oxides are ethylene oxide, propylene oxide and / or butylene oxide. Particularly preferred is ethylene oxide.
  • the polymer A2 preferably contains an unsaturated compound based on an amine component which comprises at least one amine of the general formula
  • R c contains NR a R b , where
  • R c is C 6 - to C 22 -alkyl, C 6 - to C 22 -alkenyl, aryl-C 6 -C 22 -alkyl or aryl-C 6 -C 22 -alkenyl, where the alkenyl radical is 1, 2 or 3 may have non-adjacent double bonds,
  • R a is hydroxy-C, -C 6 -alkyl or a radical of the formula II
  • the sequence of the alkylene oxide units is arbitrary and x and y independently of one another are an integer from 0 to 100, preferably 0 to 50, where the sum of x and y is> 1,
  • R b is hydrogen, C 1 - to C 22 -alkyl, hydroxyC r C 6 -alkyl, C 6 - to C 22 -alkenyl, aryl-C 6 -C 22 -alkyl, aryl-C 6 -C 22 - alkenyl or C 5 - to C 8 -cycloalkyl, where the alkenyl radical may have 1, 2 or 3 non-adjacent double bonds, or R b is a radical of the formula III
  • the sequence of the alkylene oxide units is arbitrary and v and w independently of one another are an integer from 0 to 100, preferably 0 to 50, stand.
  • R c is preferably C 8 - to C 20 -alkyl or C 8 - to C 20 -alkenyl, where the alkenyl radical may have 1,2 or 3 non-adjacent double bonds.
  • R c is the hydrocarbon radical of a saturated or mono- or polyunsaturated fatty acid.
  • Preferred radicals R c are z. N-octyl, ethylhexyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, palmityl, margarinyl, stearyl, palmitoleinyl, oleyl and linolyl.
  • the amine component is particularly preferably an alkoxylated fatty amine or an alkoxylated fatty amine mixture.
  • Particularly preferred are the ethoxylates.
  • alkoxylates of amines based on naturally occurring fatty acids are used, such as.
  • tallow fatty amines which contain predominantly saturated and unsaturated C 14 -, C 16 - and C 18 -alkyl amines or coconut amines which contain saturated, mono- and diunsaturated C 6 -C 22 -, preferably C 12 -C 14 -alkylamines
  • For alkoxylation suitable amine mixtures are, for. B. various Armeen® brands of the company Akzo or Noram® brands of the company. Ceca.
  • Suitable, commercially available alkoxylated amines are, for. B. the Noramox® brands from. Ceca, preferably ethoxylated oleyl amines, such as Noramox® 05 (5 EO units), as well as the marketed under the brand name Lutensol ⁇ FA products of BASF AG.
  • the copolymerization of the abovementioned esters, monoesters and diesters generally results in pronounced stabilization of the polymer dispersion D.
  • the polymer dispersion reliably maintains the colloidal stability of the latex particles when diluted with water or with dilute electrolytes or surfactant solutions.
  • esters, half esters and diesters described above takes place by customary methods known to the person skilled in the art.
  • the free acids or suitable derivatives such as anhydrides, halides, eg. As chlorides, and (Ci- to C 4 ) alkyl esters are used.
  • the preparation of half esters of unsaturated dicarboxylic acids is preferably carried out starting from the corresponding dicarboxylic anhydrides.
  • the reaction is carried out in the presence of a catalyst, such as.
  • a catalyst such as.
  • a dialkyl titanate or an acid such as sulfuric acid, toluenesulfonic acid or methanesulfonic acid.
  • the reaction generally takes place at reaction temperatures of 60 to 200 ° C. According to a suitable embodiment, the reaction takes place in the presence of an inert gas, such as nitrogen. Water formed in the reaction can be removed from the reaction mixture by suitable means, such as distillation. If desired, the reaction can be carried out in the presence of customary polymerization inhibitors.
  • the esterification reaction can be carried out substantially completely or only up to a partial conversion. If desired, one of the ester components, preferably the hydroxyl-containing amine, may be used in excess. The proportion of ester formation can be determined by means of infrared spectroscopy.
  • the preparation of the unsaturated esters, half-esters or diesters and their further reaction to the polymers A2 used according to the invention takes place without intermediate isolation of the esters and preferably in succession in the same reaction vessel.
  • the polymer A2 may contain from 0 to 20% by weight, preferably from 0.1 to 10% by weight, of other monomers in copolymerized form.
  • Useful monomers are the monomers mentioned in connection with the polymer A1, vinylaromatics, such as styrene, olefins, for example ethylene, or (meth) acrylic esters, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl ( meth) acrylate, 2-ethylhexyl (meth) acrylate and mixtures thereof are particularly preferred.
  • the preparation of the polymers A2 is preferably carried out by radical polymerization in bulk or in solution.
  • Suitable solvents for the solvent polymerization are z.
  • water water-miscible organic solvents such as alcohols and ketones, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, acetone, methyl ethyl ketone, etc., and mixtures thereof.
  • Suitable polymerization initiators are, for example, peroxides, hydroperoxides, peroxodisulfates, percarbonates, peroxoesters, hydrogen peroxide and azo compounds, as described in more detail below for the preparation of the polymer dispersions of the invention.
  • the polymers A2 can be prepared separately and isolated and / or purified by the usual method.
  • the polymers A2 are preferably prepared immediately before the preparation of the polymer dispersions according to the invention and used without dispersion for the dispersion polymerization.
  • the preparation of the polymers A2 can advantageously also be carried out by polymer-analogous reaction.
  • a polymer which contains 80 to 100% by weight of at least one ethylenically unsaturated mono- and / or dicarboxylic acid and 0 to 20% by weight of the abovementioned other polymers can be reacted with at least one hydroxyl-containing amine.
  • Suitable ethylenically unsaturated mono- and dicarboxylic acids are those mentioned above as the component of the polymers A1 and A2.
  • Suitable amines which have at least one hydroxyl group are likewise those mentioned above.
  • the acids may be present in the polymer used for polymer-analogous reaction, if desired, partially or completely in the form of a derivative, preferably a C 1 to C 6 alkyl ester.
  • the preparation of the polymers A2 by polymer-analogous reaction is preferably carried out in a suitable non-aqueous solvent or in bulk.
  • the amine component may optionally be used in excess to serve as a solvent.
  • the reaction is carried out in the presence of an esterification catalyst, as described above.
  • the reaction temperature is preferably in a range of 100 to 200 C. Water formed in the reaction may be removed by suitable means such as. B. distilling off.
  • the weight ratio of polymer A1 to polymer A2, on a solids basis, is preferably in the range from 7: 1 to 1: 7, in particular 3: 1 to 1: 3.
  • the latices according to the invention may contain from 0 to 50% by weight, preferably from 0.1 to 40% by weight, based on the polymer A2, of at least one surface-active, alkoxylated, preferably ethoxylated or propoxylated alkylamine contain.
  • Preferred alkylamines are the alkylamines of the formula R ° NR a R b , as defined above, which are also present in the polymer A2, wherein alkylamines of the formula ⁇ (EO / PO) m R - N
  • R represents an alkyl, alkenyl or alkylvinyl radical having at least 6 carbon atoms and m and n independently of one another are> 1, are particularly preferred.
  • Preferred radicals R have 8 to 22 carbon atoms.
  • the alkoxylated alkylamines contained in the polymer A2 and the additional alkylamine crosslinkers may be the same or different compounds.
  • the polymer dispersion according to the invention may also contain further crosslinkers, for example an amine or amide crosslinker having at least two hydroxyl groups.
  • Suitable crosslinkers are, in particular, the alkanolamines disclosed in DE 197 29 161, which are hereby incorporated by reference into the disclosure content of the present invention.
  • crosslinkers are ⁇ -hydroxyalkylamines of the formula
  • R 1 is an H atom, a C 1 to C 10 alkyl group, a C 1 to C 10 hydroxyalkyl group or a radical of the formula IV
  • the sequence of the alkylene oxide units is arbitrary and x and y independently of one another are an integer from 0 to 100, the sum of x and y being> 1 and R 2 and R 3 independently of one another being a C 1 - to C 10 - hydroxyalkyl group.
  • R 2 and R 3 are each independently a C 2 - to C 5 - hydroxyalkyl group, and R 1 is a hydrogen atom, a C 1 - to C 5 alkyl group or a C 2 - to C ⁇ hydroxyalkyl group.
  • ⁇ -hydroxyalkylamines are the amines disclosed in DE 196 21 573 as component A, which are hereby incorporated by reference into the disclosure content of the present invention. These include preferably linear or branched aliphatic compounds having at least two amino-functional groups of type (a) or (b) per molecule, wherein R is hydroxyalkyl and R 'is alkyl, preferably a compound of formula I.
  • A is C 2 -C 8 -alkylene which is optionally substituted by one or more groups independently selected from alkyl, hydroxyalkyl, cycloalkyl, OH and NR 6 R 7 , wherein R 6 and R 7 are independently H 1 is hydroxyalkyl or alkyl, and which is optionally interrupted by one or more oxygen atoms and / or NR 5 groups, wherein R 5 is H, hydroxyalkyl, (CH 2 ) n NR 6 R 7 , where n is 2 to 5 and R 6 and R 7 have the meanings given above, or alkyl which in turn is interrupted by one or more NR 5 groups, wherein R 5 has the meanings given above, and / or substituted by one or more NR 6 R 7 groups R 6 and R 7 may be as defined above;
  • o, q and s are independently 0 or an integer from 1 to 6
  • p and r are independently 1 or 2 and t is 0.1 or 2
  • cycloaliphatic radicals can also be substituted by 1, 2 or 3 alkyl radicals and R 1 , R 2 and R 3 and R 4 independently of one another are H, hydroxyalkyl, alkyl or cycloalkyl.
  • Preferred higher-functionality .beta.-hydroxyalkylamines are in particular at least doubly ethoxylated amines having a molar weight of less than 1 000 g / mol, such as.
  • R 1 is hydrogen, a short-chain alkyl group or HO (R 3 ) 2 C (R 2 ) 2 C-, n and n 'are each 1, -A- - - (CH 2 ) 2 - 2 ) m group, m is 0 to 8, preferably 2 to 8, R 2 are each hydrogen, and one of the R 3 groups are each hydrogen and the other hydrogen or CrC ⁇ alkyl.
  • R 1 is hydrogen, a short-chain alkyl group or HO (R 3 ) 2 C (R 2 ) 2 C-, n and n 'are each 1, -A- - - (CH 2 ) 2 - 2 ) m group, m is 0 to 8, preferably 2 to 8, R 2 are each hydrogen, and one of the R 3 groups are each hydrogen and the other hydrogen or CrC ⁇ alkyl.
  • BiS [N, N-di (2-hydroxyethyl)] adipamide.
  • the addition of the crosslinker generally causes a better curing of the compositions of the invention at a given curing temperature or a cure at low temperature for a given curing time.
  • the proportion by weight of the crosslinker relative to the sum of polymer A1 and A2 is from 0 to 30% by weight, preferably from 0.1 to 15% by weight.
  • a reaction accelerator can be added to the polymer dispersions D.
  • phosphorus-containing compounds in particular hypophosphorous acid and their alkali metal and alkaline earth metal salts or alkali metal tetrafluoroborates.
  • salts of Mn (II), Ca (II), Zn (II), Al (III), Sb (III) or Ti (IV) or strong acids such as para-toluenesulfonic acid, trichloroacetic acid and chlorosulfonic acid can be added as a reaction accelerator .
  • the proportion by weight of the reaction accelerator relative to the sum of polymer A1 and A2 is from 0.1 to 5% by weight, preferably from 0.1 to 2% by weight.
  • compositions of the polymer dispersions D are particularly preferred.
  • the preparation of the aqueous polymer dispersion D) is carried out as described in EP 1 240 205.
  • the dispersion is used in amounts of 1 to 80 wt .-%, preferably from 10 to 75 wt .-%, particularly preferably from 20 to 50 wt .-%.
  • the polymer from A) and B) and component C) are preferably used in such a ratio to one another that the molar ratio of carboxyl groups of components A) and B) and of the hydroxyl groups of component C) is 20: 1 to 1: 1, preferably 8: 1 to 5: 1 and more preferably 5: 1 to 1, 7: 1 (the anhydride groups are calculated here as 2 carboxyl groups).
  • the production of formaldehyde-free, aqueous binder according to the invention is carried out z. B. simply by adding the components C) and D) to the aqueous dispersion or solution of the polymers of A) and B).
  • the polymer dispersion D) can also be prepared in the presence of the other components.
  • the binders according to the invention preferably contain less than 1.0% by weight, more preferably less than 0.5% by weight and most preferably less than 0.3% by weight, in particular less than 0.1% by weight. , based on the sum of A), B), C) and D) of a phosphorus-containing reaction accelerator.
  • Phosphorus-containing reaction accelerators are in EP 651 088 and EP 583 086, DE 196 21523, EP 826 710 and mentioned. These are in particular alkali metal hypophosphites, phosphites, polyphosphates, dihydrogen phosphates, polyphosphoric acid, hypophosphoric acid, phosphoric acid, alkyl phosphinic acid or oligomers or polymers of these salts and acids.
  • the binders according to the invention preferably contain no phosphorus-containing reaction accelerators or no amounts of a phosphorus-containing compound which are effective for accelerating the reaction.
  • the binders of the invention may contain an esterification catalyst, such as. As sulfuric acid or p-toluenesulfonic acid.
  • the binders according to the invention can be used as impregnating agent or coating agent.
  • the binders according to the invention may be the sole constituent of the impregnating agent or coating agent. However, the impregnating or coating agents may also contain other suitable additives for the particular intended use. In consideration come z.
  • adhesion promoters eg., Alkoxysilanes, such as ⁇ -aminopropyltriethoxysilane, Fa. Witco: SiI Quest A-1100 silane
  • reducing agents and transesterification catalysts or fire retardants such as aluminum silicates , Aluminum hydroxides, borates or phosphates
  • melamine / formaldehyde resins melamine / formaldehyde resins
  • dispersions acrylates, styrene-butadiene dispersions
  • epoxy resins polyurethane resins
  • emulsifiers ionic, nonionic
  • water repellents sicones
  • the binders of the invention have, after drying (at 5O 0 C, duration
  • the cured films are stored in water at 23 ° C. for 48 hours. Soluble fractions remain in the water.
  • the film is then dried at 50 ° C. to constant weight and weighed.
  • the weight corresponds to the gel content, the gel content is calculated in wt .-%, based on the weight before separating the soluble fractions. Weight constancy is achieved when the weight loss over a period of 3 hours is less than 0.5, in particular less than 0.1 wt .-%.
  • the binders of the invention are suitable as binders for substrates such.
  • substrates such as for the production of moldings from fibers, chips or shavings, mats or plates, preferably for fibrous and granular substrates.
  • fiber webs z.
  • aramid carbon, polyacrylonitrile, polyester, mineral, PVC or glass fibers.
  • the binders of the invention z.
  • the following additives include: silicates, silicones, boron-containing compounds, lubricants, wetting agents.
  • the unbonded fiber webs (raw fiber webs), in particular of glass fibers, are bound by the binder according to the invention, d. H. solidified.
  • the binder according to the invention preferably in the weight ratio fiber / binder (solid) of 40: 1 to 1: 1, preferably 25: 1 to 2: 1 to the raw fiber mat z. B. applied by coating, spraying, impregnation, watering.
  • the binder according to the invention is preferably used in the form of a dilute aqueous preparation with 95 to 40 wt .-% water.
  • the binder according to the invention After application of the binder according to the invention on the raw fiber nonwoven generally takes place drying preferably at 100 to 400, in particular 130 to 28O 0 C, most preferably 130 to 230 0 C over a period of preferably 10 seconds to 10 minutes, in particular of 10 seconds up to 3 minutes.
  • the resulting bonded nonwoven fabric has a high strength in the dry and wet state. A yellowing of the bonded nonwoven fabric after drying is not or hardly observed.
  • the novel binders allow, in particular, short drying times and also low drying temperatures.
  • the bonded fiber webs in particular glass fiber webs are suitable for use as or in roofing membranes, as support materials for wallpaper or as inliner or support material for floor coverings z.
  • PVC floor coverings which have been produced using glass fiber vlies and PVC plastisols solidified with the binders according to the invention have only a slight yellowing tendency.
  • the bonded fiber webs are generally coated with bitumen.
  • the binders according to the invention can furthermore be used as binders for insulating materials made from the abovementioned fibers, in particular inorganic fibers such as mineral fibers and glass fibers.
  • binders based on phenol-formaldehyde condensation resins which have hitherto been customary in practice have the disadvantage that not insignificant amounts of phenol, formaldehyde and low molecular weight condensation products thereof volatilize in the production of the insulating materials. The restraint of these environmentally harmful substances is associated with great effort. Furthermore, formaldehyde may be released from the finished insulating products, which is undesirable in particular when used in residential buildings.
  • Fibers for insulating materials are technically produced on a large scale by spinning melts of the corresponding mineral raw materials (see, for example, EP 567 480).
  • the aqueous binder solution is preferably already sprayed on the freshly prepared, still hot fibers in the production of insulating materials.
  • the water evaporates predominantly and the resin remains essentially uncured as a viscous "high-solid" material to adhere to the fibers.
  • Fiber-binding binders are produced from the fibers and transported by suitable conveyor belts through a curing oven. There, the resin cures at oven temperatures of about 150 to 35O 0 C. After the curing oven, the insulating mats are assembled in a suitable manner, ie cut into a shape suitable for the end user.
  • the binders may contain common auxiliaries and additives in the practice of insulation production. Examples of these are water repellents such. For example, silicone oils, alkoxysilanes such. As 3-aminopropyltriethoxysilane as a coupling agent, soluble or emulsifiable oils as lubricants and dust binders and wetting agents.
  • the majority of the mineral or glass fibers used in the insulating materials has a diameter between 0.5 and 20 microns and a length between 0.5 and 10 cm.
  • Typical applications of the insulating materials are rectangular or triangular insulating panels as well as rolled insulating material webs.
  • the thickness and density of the insulating materials can be varied within wide limits, which can produce products with the desired insulation effect. Usual thicknesses are between 1 and 20 cm, common densities in the range between 5 and 300 kg / m 3 .
  • the insulating effect is characterized by the thermal conductivity lambda (in mW / mK).
  • the insulation boards have a high dry and wet strength.
  • the binders according to the invention are also suitable for the production of abrasive vats, eg. B. scourers or pot scratches based on bonded fiber webs.
  • Suitable fibers are natural fibers and synthetic fibers (eg nylon).
  • the solidification of the fiber webs is preferably carried out by spraying.
  • the binders are also suitable for the production of wood materials such as HoIz chipboard and wood fiber boards (see Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition 1976, Volume 12, pp. 709-727), which are obtained by gluing cut wood such. B. wood chips and wood fibers can be produced.
  • the water resistance of wood-based materials can be increased by adding to the binder a commercially available aqueous paraffin dispersion or other water repellents, or adding these water repellents before or after the fibers, chips or shavings.
  • chips whose average chip thickness is on average 0.1 to 2 mm, in particular 0.2 to 0.5 mm, and which contains less than 6% by weight of water.
  • the binder is applied as evenly as possible to the wood chips, wherein the weight ratio BindemittekHolzs Georgne based on the solid (calculated as A) + B)) is preferably 0.02: 1 to 0.3: 1.
  • a uniform distribution can be achieved, for example, by spraying the binder in finely divided form on the chips.
  • the glued wood chips are then spread to form a layer with as uniform a surface as possible, the thickness of the layer being determined by the desired thickness of the finished chipboard.
  • the litter layer is at a temperature of z. B. 100 to 250 0 C 1 preferably from 140 to 225 0 C by applying pressures of usually 10 to 750 bar compressed to a dimensionally stable plate.
  • the required pressing times can vary within a wide range and are generally between 15 seconds to 30 minutes.
  • the wood fibers of suitable quality required for the production of medium-density fibreboard (MDF) from the binders can be produced from bark-free wood chips by grinding in special mills or so-called refiners at temperatures of about 18O 0 C.
  • the wood fibers are generally fluidized with an air stream and the binder injected into the fiber stream thus generated ("blow-line” method).
  • the ratio of wood fibers to binder based on the dry content or solids content is usually 40: 1 to 3: 1, preferably 20: 1 to 4: 1.
  • the glued fibers are in the fiber stream at temperatures of z. B. 130 to 18O 0 C dried, spread to a nonwoven fabric and pressed at pressures of 20 to 40 bar to plates or moldings.
  • the glued wood fibers can also, such. As described in DE-OS 2 417 243, are processed into a transportable fiber mat. This semi-finished can then in a second, temporally and spatially separate step to plates or moldings, such as. B. interior door trim of motor vehicles to be further processed.
  • the binders according to the invention are furthermore suitable for the production of plywood and blockboard according to the generally known production methods.
  • plastic fibers e.g. As polypropylene, polyethylene, polyester, polyamides or polyacrylonitrile can be used. These plastic fibers can also act as co-binders in addition to the binder according to the invention.
  • the proportion of plastic fibers is preferably less than 50 wt .-%, in particular less than 30 wt .-% and most preferably less than 10 wt .-%, based on all chips,
  • Chips or fibers The processing of the fibers can be carried out according to the method practiced in fibreboards. However, preformed natural fibers sermats are impregnated with the binders of the invention, optionally with the addition of a wetting aid. The impregnated mats are then in the wettable or pre-dried state z. B. at temperatures between 100 and 25O 0 C and pressures between 10 and 100 bar to plates or moldings pressed.
  • the moldings obtained according to the invention have a low water absorption, a low thickness swelling after storage in water, a good strength and are formaldehyde-free. They can be used, inter alia, in the automotive industry.
  • a further application of the binders of the invention is the use in the production of abrasive materials, in particular of abrasive papers, abrasive fabrics, nonwovens or abrasive articles used. It may be advisable to adjust the aqueous polymer solutions to a pH of from 3 to 8, in particular from 3 to 5, before application to the corresponding paper or fabric or the corresponding body by addition of various inorganic or organic bases.
  • Suitable bases include i.a. Ammonia, organic mono- or polyfunctional amines, alcoholates and metal alkyl compounds, but also inorganic bases such as sodium hydroxide or soda.
  • the abrasive materials likewise obtainable in this manner have conventional abrasive granules, for example based on corundum, quartz, garnet, pumice, triple, silicon carbide, emery, aluminum oxides, zirconium oxides, kieselguhr, sand, gypsum, boron carbide, borides, carbides, nitrides, cerium oxide or silicates.
  • the abrasive materials of the invention may i.a. be prepared by first on the appropriate paper, fabric or the corresponding body, the aqueous polymer solution, optionally modified with z. As dispersions, then adds the selected abrasive granules and finally still re- large amounts of the aqueous polymer solution, optionally modified with z. B. dispersions added as so-called capping.
  • aqueous polymer solution leads to improved abrasive materials, which can i.a. characterized by high flexibility, toughness, tear strength and elongation at break, have a favorable abrasion behavior and in which the abrasive granules are well integrated.
  • a further use according to the invention of the binders is the use for the production of filter materials, in particular filter papers or filter cloths.
  • Tissue materials can be, for example, cellulose, cotton, polyester, polyamide, PE, PP, glass fleece, glass wool.
  • Suitable bases include triethanolamine, diethanolamine, monoethanolamine, hydroxyalkylamines, ammonia, organic mono- or polyfunctional amines, alcoholates and Metallalkylverbin- fertilize, but also inorganic bases such as sodium hydroxide or potassium hydroxide.
  • the application of the polymer solution to be used according to the invention to the filter materials is preferably carried out by the so-called impregnation method or by spraying.
  • the aqueous polymer solutions are applied by gluing onto the filter materials. It is recommended that after the gluing of the filter material with the aqueous polymer solutions, these still 0.1 to 60 minutes to anneal in particular 1 to 60 minutes at temperatures of 100 to 25O 0 C, in particular from 110 to 22O 0 C, ie cure.
  • the inventive use of the aqueous polymer solution as a binder for filter materials has the consequence that the treated filter materials u. a. have an increased mechanical stability (higher tensile strength and bursting strength), especially after storage in a humid climate and at elevated temperature. Furthermore, the inventive use of the aqueous binder causes the resulting filter materials u.a. are characterized by a high chemical resistance, for example to solvents, without affecting the permeability (pore size) of the filter material.
  • the aqueous polymer solutions By using the aqueous polymer solutions, it is also observed that these impart high strength to the filter materials already after drying (dry tensile strength), but the filter materials are still good at deformation below the curing temperature of the aqueous polymer solutions even after deformation by folding, creasing or Undergo pleating. After the subsequent thermal curing (tempering), the polymer solutions give the resulting filter materials according to the invention, essentially filter papers or filter cloths, a high dimensional stability. This property enables the production of semi-finished products and thus the separation of the manufacturing process into individual decoupled production steps.
  • a further use according to the invention is the use of the aqueous polymer solutions as binders for cork, nonwovens, mats or boards.
  • the polymers with a broad molecular weight distribution can be prepared in situ in one step by first synthesizing the low molecular weight fraction (at a specific initiator concentration / temperature) and after 0-100%) adding the monomers, lowering the initiator concentration in the reaction mixture and / or or the temperature is reduced (gradually or continuously); or the multimodal polymers can be prepared in situ in one step by first synthesizing the high molecular weight moiety (at a particular initiator concentration / temperature) and after adding the monomers to 100-0%, increasing the initiator concentration in the reaction mixture and / or raising the temperature becomes.
  • the polymers having a broad molecular weight distribution can be prepared by mixing
  • Polymers are prepared with different molecular weights.
  • the broad molecular weight distribution polymers can be prepared by synthesizing a low and high molecular weight polymer, respectively, in the presence of a second high and low molecular weight polymer, respectively.
  • the eluent used was 0.008 m TRIS buffer (tris (hydroxymethyl) aminomethane, Merck, Darmstadt) at pH 7 in distilled water with the addition of 0.15 mol / L NaCl and 0.01 mol / L NaN 3 .
  • the flow rate was 0.5 mL / min.
  • the plate count of the column combination at this flow rate was 37,000.
  • the detector used was a ERC 7510 differential refractometer from ERMA.
  • the binder solution is added about 1 wt .-% ⁇ -aminopropyltriethoxysilane with respect to the sum of all components.
  • the raw nonwovens of 32 cm length and 28 cm width are first passed through a continuous PES screen belt in the longitudinal direction through a 20% binder liquor and then via a suction device.
  • the belt speed is 0.6 m / min.
  • the adjustable thickness of the suction unit doses the wet application. In the case of a wet application of about 100% is obtained with a liquor concentration of the binder of 20%, a dry application of 20% + - 2%.
  • the impregnated nonwovens are cured for 2 minutes at 200 ° C. on a PES store as support in a Mathis dryer (hot air is set to maximum).
  • the size of the fleece is for
  • Clamping length for testing the tear resistance "dry”, “wet” and “hot” 200mm The take-off speed is set to 25 mm / min.
  • the tensile strengths are weight corrected to 60g / m 2 (calculation formula: F max * 60 [g / m 2 ] / "Is weight” [g / m 2 ]).
  • test sections measuring 10 x 10 cm are cut from the fabric patterns and dried for 10 minutes at 130 ° C, weighed and placed for 15 minutes in boiling condensed water and dried at 130 0 C followed by 1 h, cooled in a desiccator and weighed.
  • the weight loss is given in% based on bonded nonwoven.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Dispersion Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne l'utilisation de liants aqueux sans formaldéhyde à large distribution de poids moléculaire sur des substrats, lesquels liants contiennent (A) 0 à 100 % en poids d'un anhydride d'acide éthyléniquement insaturé ou d'un acide dicarboxylique éthyléniquement insaturé, dont les groupes acide carboxylique peuvent former un groupe anhydride, ou de mélanges de ces derniers, (B) 100 à 0 % en poids d'un composé éthyléniquement insaturé, (C) au moins un agent de réticulation polyfonctionnel ou des mélanges de ce dernier ainsi que (D) 1 à 80 % en poids d'une dispersion polymère aqueuse, les polymères de A) et B), obtenus par polymérisation radicalaire et classés dans un système de coordonnées en fonction de leur poids moléculaire moyen Mw et de leurs valeurs de polydispersité, se trouvant dans une zone située au-dessus d'une droite définie par l'équation de droite y = 1,25x + 20 000 et ayant été déplacée de façon parallèle dans le sens des y d'au moins + 3 000, l'axe des x désignant le poids moléculaire moyen en poids et l'axe des y la polydispersité multipliée par 10 000. Cette invention concerne également les liants eux-mêmes ainsi que leur utilisation sur, p. ex, des corps moulés, des nattes ou des panneaux, en particulier pour des substrats fibreux ou granuleux, tels que des non-tissés, des fibres de verre, de la laine minérale, du coton effiloché, des fibres naturelles ou des fibres synthétiques.
EP05819208A 2004-12-16 2005-12-14 Utilisation de liants aqueux sans formaldehyde sur des substrats Withdrawn EP1828298A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200410061144 DE102004061144A1 (de) 2004-12-16 2004-12-16 Verwendung formaldehydfreier wässriger Bindemittel für Substrate
PCT/EP2005/013404 WO2006063802A2 (fr) 2004-12-16 2005-12-14 Utilisation de liants aqueux sans formaldehyde sur des substrats

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US (1) US20090252962A1 (fr)
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DE102004061144A1 (de) 2006-06-22
US20090252962A1 (en) 2009-10-08

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