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WO2003046065A2 - Dispersion de polymeres marquee et adhesifs produits a partir de celle-ci - Google Patents

Dispersion de polymeres marquee et adhesifs produits a partir de celle-ci Download PDF

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Publication number
WO2003046065A2
WO2003046065A2 PCT/EP2002/013128 EP0213128W WO03046065A2 WO 2003046065 A2 WO2003046065 A2 WO 2003046065A2 EP 0213128 W EP0213128 W EP 0213128W WO 03046065 A2 WO03046065 A2 WO 03046065A2
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WO
WIPO (PCT)
Prior art keywords
polymer
polymer dispersion
weight
water
mixture
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Application number
PCT/EP2002/013128
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German (de)
English (en)
Other versions
WO2003046065A3 (fr
Inventor
Bernhard Grünewälder
Thomas Empt
Birgit Ness
Werner Haller
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP02799725A priority Critical patent/EP2099872A2/fr
Publication of WO2003046065A2 publication Critical patent/WO2003046065A2/fr
Publication of WO2003046065A3 publication Critical patent/WO2003046065A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives based on 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 acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/14—Amylose derivatives; Amylopectin derivatives
    • C08L3/16—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a polymer dispersion comprising water, at least one polymer which can be prepared by emulsion polymerization and at least one element selected from the group consisting of Li, B, Co, Cu, Mo, Ni, Pb or Sn or a salt of such an element or a mixture from two or more of them.
  • Dispersion adhesives with water-dispersible polymers such as are obtainable, for example, by emulsion polymerization of ethylenically unsaturated monomers in the aqueous phase, are frequently used in this area.
  • the quality of the adhesives themselves comes to the fore.
  • manufacturers rely on the adhesives used to meet all the required standards, so that pieces of furniture do not show any quality defects due to low-quality adhesives.
  • adhesives are mixed with fluorescent markers, for example. This is to ensure that a bond is to be subsequently checked to see whether it was carried out with the adhesive actually intended for this bond.
  • the object is achieved by a polymer dispersion comprising water, at least one water-dispersible polymer and at least one element selected from the group consisting of Li, B, Co, Cu, Mo, Ni, Pb or Sn or a salt thereof Contains elements or a mixture of two or more thereof.
  • the invention therefore relates to a polymer dispersion comprising water, at least one water-dispersible polymer and at least one element selected from the group consisting of Li, B, Co, Cu, Mo, Ni, Pb or Sn or a salt of such an element or a mixture from two or more of them.
  • a “polymer dispersion” is understood to mean a dispersion of particulate polymer particles in the aqueous phase.
  • the size of the polymer particles is in a range that is usually observed when carrying out polymerizations by means of emulsion polymerization. Exemplary sizes within the scope of the present invention are in a range from approximately 0.001 to approximately 0.2 mm.
  • water-dispersible in the context of the present invention includes, for example, all polymers which are self-dispersible in water, ie without the addition of emulsifiers or with the addition of only small amounts of emulsifier, for example up to about 1 or up to about 0.5% by weight. % or up to about 0.2% by weight or less form a stable dispersion in water or an aqueous environment.
  • polymers are suitable which have a sufficient number of hydrophilic groups, for example quaternary amino groups, carboxyl groups or polyether groups.
  • water-dispersible as used in the context of the present text, are polymers which are not themselves dispersible in water, but which form stable dispersions in water with the addition of emulsifiers. These include, for example, those polymers that can be prepared by emulsion polymerization.
  • the polymer dispersions according to the invention can contain water which comes from any source.
  • the water used in the polymer dispersions according to the invention is tap water, as is generally available from corresponding supply sources. It is however, it is equally possible to use groundwater, process water, process water or any other form of water recovered from a cycle in the polymer dispersions according to the invention, provided that the pH and the salt content allow stable polymer dispersions to be maintained.
  • olefinically unsaturated monomers are suitable, which are accessible to emulsion polymerization.
  • Suitable polymers for producing the dispersions according to the invention are, for example, vinyl ester polymers, the monomeric basic building block of which is a vinyl ester of a linear or branched carboxylic acid having about 2 to about 44, for example about 3 to about 15, carbon atoms.
  • Monomers for these homo- or polymeric polyvinyl esters are vinyl formate, vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl esters of saturated branched monocarboxylic acids with 9 to about 15 carbon atoms in the acid residue, vinyl esters of longer-chain saturated or unsaturated fatty acids Vinyl laurate, vinyl stearate or vinyl ester of benzoic acid and substituted derivatives of benzoic acid such as vinyl p-tert-butylbenzoate in question.
  • the vinyl esters mentioned can each be present individually or as a mixture of two or more of the vinyl esters mentioned in the polyvinyl ester. In the context of a preferred embodiment of the invention, the proportion of such vinyl esters in the entire polymer is at least about 50% by weight, for example at least about 75% by weight.
  • polymers which also have other comonomers in addition to one of the abovementioned vinyl esters or a mixture of two or more of the abovementioned vinyl esters can also be present in the polymer dispersion.
  • ethylenically unsaturated monomers which can be copolymerized with the abovementioned vinyl esters are, for example, acrylic acid, methacrylic acid and their esters with primary and secondary saturated monohydric alcohols having 1 to about 28 carbon atoms, such as methanol, ethanol, propanol, butanol, 2-ethylhexyl alcohol, cycloaliphatic Alcohols such as cyclohexanol, hydroxymethylcyclohexane or Hydroxyethylcyclohexan.
  • the esters of the above-mentioned, ethylenically unsaturated acids with longer-chain fatty alcohols are also suitable.
  • comonomers are ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid or citraconic acid and their mono- or diesters with saturated monohydric aliphatic alcohols having 1 to about 28 carbon atoms.
  • the proportion of such comonomers in the polymers present in the polymer dispersion according to the invention can be up to about 25% by weight, for example about 0.1 to about 15% by weight.
  • comonomers are simple ethylenically unsaturated hydrocarbons such as ethylene or ⁇ -olefins having about 3 to about 28 carbon atoms, for example propylene, butylene, styrene, vinyl toluene, vinyl xylene and halogenated unsaturated aliphatic hydrocarbons such as vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride and the like , Such comonomers can have a proportion of the polymer used in the dispersions according to the invention of up to about 50% by weight or less, for example about 0.5 to about 25% by weight.
  • Multi-ethylenically unsaturated monomers can also be used as comonomers in the context of the present invention.
  • monomers are diallyl phthalates, diallyl maleate, triallyl cyanurate, tetraallyloxyethane, divinylbenzene, butanediol-1,4-dimethacrylate, triethylene glycol dimethacrylate,
  • the proportion of such comonomers in the polymers produced by emulsion polymerization in the dispersions according to the invention is up to about 10% by weight, for example about 0.01 to about 5% by weight.
  • ethylenically unsaturated compounds with N-functional groups include, for example, acrylamide, methacrylamide, allyl carbamate, acrylonitrile, N-methylolacrylamide, N-methyloImethacrylamide, N-methylolallyl carbamate and the N-methyl esters, alkyl ethers or Mannich bases of N-methylol acrylamide or N-methylol methacrylamide or N-methylolallyl carbamate, acrylamidoglyomethylester, acrylamidoglymethylester, acrylamidoglyomethylester, acrylamidoglymethylester, acrylamidoglyomethylester, acrylamidoglyomethylester, acrylamidoglyomethylester, acrylamidoglyomethylester, acrylamidoglyomethylester, acrylamidoglyomethylester, acrylamidoglyomethylester, acrylamidooglycolic acid, acrylamidoglyomethylester, acrylamid
  • Ethylimidazolidone methacrylate N-vinylformamide, N-vinylpyrrolidone and the like.
  • SBR styrene-butadiene rubbers
  • SBR styrene-butadiene rubbers
  • Such rubbers are produced by copolymerization of styrene and butadiene and generally contain the two monomers in a weight ratio of about 23.5 to 76.5 or about 40 to 60.
  • the SBR are usually produced by emulsion polymerization in water.
  • polyvinyl acetates are thermoplastic polymers of vinyl acetate.
  • the polymerization is generally carried out by suspension or emulsion polymerization.
  • Another suitable group of polymers are the polyethylene homopolymers and copolymers.
  • a radical polymerization of ethylene is carried out, for example, as part of the high-pressure polymerization to LDPE at pressures of about 1,400 to 3,500 bar at temperatures of 150 to 350 ° C. The reaction is started by oxygen or peroxides.
  • Linear or branched ⁇ , ⁇ -unsaturated olefins are suitable as comonomers.
  • Another group of suitable polymers are the polyacrylic acid esters or the methacrylic acid esters or copolymers of polyacrylic acid esters and polymethacrylic acid esters. If appropriate, the polymers mentioned can still have small proportions (up to about 10%) of free acrylic acid or methacrylic acid groups.
  • polyvinylidene chloride is polyvinylidene chloride.
  • the polymer is preferably obtained by emulsion polymerization of 1,1-dichloroethylene. Copolymers of 1,1-dichloroethylene with acrylates, methacrylates, vinyl chloride or acrylonitrile are particularly suitable.
  • polyvinylidene fluoride is polyvinylidene fluoride.
  • the polymer can be obtained by polymerizing vinylidene fluoride and can be adapted in terms of chemical and mechanical properties, for example by copolymerization with suitable monomers such as ethylene, acrylonitrile, acrylate esters, methacrylate esters and the like.
  • E-PVC emulsion polymerization
  • the polymers mentioned can be present in the polymer dispersion according to the invention both individually and in a mixture of two or more thereof.
  • a copolymer of vinyl acetate and ethylene (EVA copolymer) is used as the organic polymer.
  • the polymer dispersion contains polyvinyl acetate or polyacrylate, in particular polybutyl acrylate or a mixture of polyvinyl acetate and polyacrylate.
  • the polymer dispersion according to the invention contains the above Emulsion polymerizable polymers in an amount of at least about 30 wt .-%.
  • the proportion of such polymers is at least about 35 or at least about 40% by weight.
  • the content of such polymers can also be higher, for example at least about 45% by weight or at least about 50% by weight or higher, for example at least about 55 or at least about 60% by weight.
  • a polymer dispersion according to the invention also contains at least one element selected from the group consisting of Li, B, Co, Cu, Mo, Ni, Pb or Sn or a salt of such an element or a mixture of two or more thereof.
  • the elements and compounds used for marking are not a natural component of the substrate (wood) to be glued or adhesives usually used for gluing. To determine this, samples of wood from different origins commonly used in furniture construction were examined for their content of different elements.
  • the above-mentioned elements are present in the polymer dispersion according to the invention in the form of one of their inorganic or organic salts or in the form of a mixture of two or more of their salts, that is to say in ionized form.
  • all anions which do not adversely affect the properties of the polymer dispersion are suitable as anions for the corresponding salts.
  • Compounds which have non-toxic anions are preferably used.
  • the concentration of the abovementioned compounds is preferably in a range which, on the one hand, permits the easiest possible detection and, on the other hand, has no negative influence on the properties of the polymer dispersion.
  • Suitable concentrations are preferably within a range, the lower limit of which is determined by the detection limit of the respective element using available analytical methods, for example currently approximately 1 ppm, and the upper limit of which is approximately 1000 ppm, preferably at most approximately 500 ppm.
  • the concentration of one of the abovementioned compounds in a polymer dispersion according to the invention or a mixture of two or more of the abovementioned compounds covers about 2 to about 400 ppm, for example about 5 to about 300 or about 10 to about 200 ppm.
  • chlorides or nitrates in particular are used as salts.
  • the scope of a further preferred embodiment of the present invention is used to label a polymer dispersion according to the invention lithium chloride.
  • the polymer dispersion according to the invention can also contain at least one protective colloid or a mixture of two or more protective colloids.
  • Suitable protective colloids are, for example, etherified cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.
  • polyvinylpyrrolidone or polycarboxylic acids such as polyacrylic acid or polymethacrylic acid, if appropriate in the form of their copolymers with esters of acrylic acid or methacrylic acid optionally carrying OH groups, and copolymers of maleic acid or maleic anhydride with other ethylenically unsaturated compounds such as methyl vinyl ether or styrene.
  • polyvinyl alcohol for example polyvinyl alcohol, with a degree of hydrolysis of about 30 to about 100% by weight, for example about 60 to about 98% by weight or about 70 to about 88% by weight, is used as the protective colloid.
  • a polymer dispersion according to the invention contains a protective colloid carrying OH groups.
  • the polymer dispersion contains polyvinyl alcohol as a protective colloid.
  • the total proportion of the protective colloid or protective colloids in the total polymer dispersion according to the invention is about 0 to about 20, for example about 0.5 to about 15 or about 1 to about 10% by weight.
  • the polymer dispersion according to the invention can also contain a water-soluble, acidic metal salt to improve the water resistance.
  • Suitable salts are, for example, the nitrates, chlorides, oxychlorides or sulfates of aluminum, iron, chromium, titanium, zirconium or vanadium.
  • the salts of aluminum, chromium or zirconium for example aluminum chloride, aluminum nitrate, chromium chloride or zirconium oxychloride, are used in particular.
  • the acidic metal salts mentioned can each be used alone or as a mixture of two or more thereof.
  • the corresponding salts are present in an amount of about 0.05 to about 20% by weight, based on the total polymer dispersion, for example about 0.1 to about 10% by weight or about 0.2 to about 5% by weight. , used.
  • a solution of the corresponding metal salts is advantageously stirred into the polymer dispersion.
  • the corresponding metal salts or a mixture of two or more of the corresponding metal salts is added in an amount such that the pH of the polymer dispersion is about 1 to about 5. In a further preferred embodiment of the invention, the pH of the polymer dispersion is about 2 to about 4. If the pH of the polymer dispersion is to remain stable over a long period of time, it has proven to be advantageous if a buffer system is added to the polymer dispersion. Suitable buffer systems for the dispersion are, for example:
  • the polymer dispersion according to the invention may also contain a crosslinking resin or a mixture of two or more crosslinking resins.
  • Suitable crosslinking of the present invention for example, phenol-formaldehyde resins, or 1, 3 are suitable in the context of dimethylol-4,5-dihydroxyimidazolidon (4,5-dihydroxy-N, N '-dimethylolethylenharn- material) or dihydroxymethyl, dihydroxymethyl or dihydroxymethyl their thio derivatives or self-condensation products thereof or mixtures of two or more thereof.
  • Suitable phenol-formaldehyde resins can be obtained by reacting phenol or phenol derivatives with formaldehyde or formaldehyde derivatives with an increase in molecular weight.
  • the production of such phenol-formaldehyde resins follows the general rules of inorganic chemistry and is known to the person skilled in the art.
  • Phenol-formaldehyde resins suitable in the context of the invention have, after crosslinking in a preferred embodiment of the invention, a softening point (ring and ball) of approximately 80 to approximately 130 ° C., for example approximately 90 to approximately 120 ° C.
  • Phenol-formaldehyde resins which are suitable in the context of the present invention have OH groups on the aromatic phenol units.
  • phenol-formaldehyde resins can be used which have an OH number of 100 or less, for example about 80, about 60 or about 40 or less, for example about 20 or about 10.
  • Suitable phenol-formaldehyde resins have, for example, less than 10% by weight of free methyl groups, for example less than 8% by weight, less than 6% by weight or less than 4% by weight or less.
  • Suitable phenol-formaldehyde resins are themselves dispersible in water and are stable as a dispersion over a longer period, for example for a period of 4 weeks or more.
  • Phenol-formaldehyde resins whose phenol units are substituted in the p-position to the OH group can also be used in the context of the present invention.
  • Linear or branched, saturated or unsaturated alkyl chains with 1 to about 22 C atoms are suitable as substituents.
  • the phenol-formaldehyde resins suitable for the purposes of the present invention are usually sold as aqueous emulsions with a solids content of up to about 60% by weight.
  • emulsions which have a viscosity of about 50 to about 100 poise with a solids content of about 45 to about 55% by weight and a pH of about 6.5 to about 7, 5 have.
  • Suitable phenol-formaldehyde resins are available, for example, under the name Resin XR 14277 A (manufacturer: CECA / ELF-Atochem).
  • It is an aqueous emulsion of a reactive phenolic resin with a low free formaldehyde content (less than 0.1%). It is a milky, white to slightly yellowish product with a viscosity in the range from 60 to 80 poise and a pH in the range from 7 to 7.5, which has a solids content of 49 to 52% by weight.
  • crosslinking resins of the types HRJ and SP for example SP-8025, which are sold by Schenectady International, in particular the resins:
  • HRJ-11112 (terpene / phenol base) with a Brookfield viscosity of 300-750, a particle size of about 0.5 to about 3.0 ⁇ m, a solids content of about 39 to about 47% and a pH value of about 9-10
  • HRJ-10416 (alkyl / phenol base) with a Brookfield viscosity of 1200-2750, a particle size of about 1.0 to about 5.0 ⁇ m , a solids content of about 51 to about 57% and a pH of about 4.5 - 6.5.
  • Vernetzerharztypen to crosslinking resins are based on hydroxymethyl-substituted imidazolidinones, such as 1, 3-dimethylol-4,5-dihydroxyimidazolidinone (4,5-dihydroxy-N, N '-dimethylolethylenharnstoff)
  • Crosslinker resins of this type are commercially available, for example, under the names Fixapret, Stabitex, Permafresh, Sarcoset, Sumitex, Prox, Knittex, Cassurit, Neuperm or Depremol.
  • the compounds of the Fixapret series can be used as crosslinking resins, for example Fixapret C-PX, Fixapret COC, Fixapret CP 40 IGD, Fixapret CPK IGD, Fixapret CPNS IGD, Fixapret CP IGD or Fixapret CPN IGD.
  • the compounds mentioned are usually used as aqueous emulsions or solutions with a solids content of between about 30 and 50% by weight.
  • Fixapret C-PX is a polycondensation product of glyoxal urea formaldehyde (dimethylglyoxal urine) in water, with a pH of 8.0 to 8.5, a solids content of 40 to 42% by weight, a content of free formaldehyde of less than 1.1% by weight, a density of 1.03 to 1.06 g / cm 3 , an apha color of at most 50 which does not cause precipitation in the presence of MgCl.
  • crosslinking resins are commercially available, for example, in the product range marketed under the name Stabitex (manufacturer: BASF). Basically, all products are sold under the above name used. In a preferred embodiment of the present invention, however, Stabitex ZF or Stabitex GFA is used as the crosslinking resin.
  • the compounds mentioned are usually used as aqueous emulsions or solutions with a solids content of between about 30 and 50% by weight.
  • the polymer dispersions according to the invention can contain the crosslinking resin in an amount of 0 to about 5% by weight, for example in an amount of 0.05 to about 4% by weight or 0.1 to about 3% by weight.
  • a polymer dispersion according to the invention can also contain an ionic surfactant or a mixture of two or more ionic surfactants.
  • such ionic surfactants have a molecular weight of less than about 600.
  • Anionic, cationic or ampholytic surfactants can be present.
  • suitable anionic surfactants are alkyl sulfates, in particular those with a chain length of about 8 to about 18 carbon atoms, alkyl and alkaryl ether sulfates with about 8 to about 18 carbon atoms in the hydrophobic radical and 1 to about 10 ethylene oxide (EO) or propylene oxide (PO) units, or a mixture thereof, in the hydrophilic part of the molecule, sulfonates, in particular alkyl sulfonates, with about 8 to about 18 carbon atoms, alkylarylsulfonates with about 8 to about 18 carbon atoms, taurides, esters and half esters of sulfosuccinic acid with monovalent Alcohols or alkylphenols with 4 to about 15 C atoms, which can optionally be ethoxylated with 1 to about 20 EO units, alkali and ammonium salts of
  • a polymer dispersion according to the invention contains alkyl and alkaryl phosphates with about 8 to as anionic surfactants about 22 carbon atoms in the organic radical, alkyl ether or alkaryl ether phosphates with about 8 to about 22 carbon atoms in the alkyl or alkaryl radical and 1 to about 10 EO units.
  • cationic surfactants are salts of primary, secondary or tertiary fatty amines with about 8 to about 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid or phosphoric acids, quaternary alkyl and alkylbenzene ammonium salts, especially those whose alkyl groups have about 6 to about 24 carbon atoms have, in particular the halides, sulfates, phosphates or acetates, or mixtures of two or more thereof, alkylpyridinium, alkylimidazolinium or alkyloxazolidinium salts, in particular those whose alkyl chain has up to about 18 carbon atoms, for example the halides, sulfates, phosphates or Acetates, or mixtures of two or more thereof.
  • ampholytic surfactants are long-chain substituted amino acids such as N-alkyl-di (aminoethyl) glycine or N-alkyl-2-aminopropionic acid salts, betaines such as N- (3-acylamidopropyl) -N, N-dimethylammonium salts with a C 8 . 18 acyl radical or alkylimidazolium betaines.
  • the alkali metal salts in particular the Na salt of the C 12/14 fatty alcohol ether sulfates, alkylphenol ether sulfates, in particular their alkali metal or NH 4 salts, Na-n-dodecyl sulfate, Di -K-oleic acid sulfonate (C ⁇ 8 ), Na-n-alkyl- (C ⁇ oC 13 ) -benzenesulfonate, Na-2-ethylhexyl sulfate, NH4-lauryl sulfate (C 8 / ⁇ 4 ), Na-lauryl sulfate (C 12 / ⁇ 4 ), Na lauryl sulfate (C12 / 16), Na lauryl sulfate (C12 / 18), Na cetyl stearyl sulfate (Ci6 / ⁇ ).
  • the alkali metal salts in particular the Na salt of the C 12/14 fatty
  • Na-Oleylcetylsulfat (C 16/18), Sulfobernsteinkladi-Na salt, Fettalkoholsulfosuccinat-di-Na salt, dialkylsulfosuccinate-Na-salt or di-Na sulfosuccinamate or mixtures of two or more thereof.
  • the polymer dispersion according to the invention contains ionic surfactants, they are in a preferred embodiment of the invention in an amount of up to about 1% by weight or less, for example up to about 0.8% by weight or about 0.5% by weight or less, based on the total dispersion , contain. If appropriate, smaller amounts of ionic surfactant can also be present, for example up to about 0.2% by weight or below, for example about 0.1% by weight, 0.05% by weight or 0.02% by weight ,
  • the filler-containing polymer dispersion can contain at least one nonionic surfactant with a molecular weight of less than about 600.
  • nonionic surfactants are alkyl polyglycol ethers, preferably those with about 8 to about 20 EO units and alkyl radicals with about 8 to about 20 C atoms, alkylaryl polyglycol ethers, preferably those with about 8 to about 40 EO units and about 8 to about 20 C.
  • ethylene oxide / propylene oxide (EO / PO) block copolymers preferably those with about 8 to about 40 EO or PO units
  • natural products and their derivatives such as lecithin, lanolin or sarcosine, linear organo (poly) siloxanes containing polar groups, in particular especially those with alkoxy groups with up to about 10 C atoms and up to about 20 EO or PO groups.
  • nonionic surfactants are nonylphenol ethoxylates, octylphenol ethoxylates, C 12/14 fatty alcohol ethoxylates, oleyl cetyl ethoxylates, C 16/18 -
  • the dispersion according to the invention contains, for example in addition to or instead of a buffer system, one or more compounds which are required to react with a strong mineral acid, such as, for example, when using the acidic metal salts in the context of present invention can be released, neutralizing the same.
  • Amines are suitable for this purpose, for example, which can be reacted with a mineral acid under protonation.
  • Suitable amines are, for example, primary, secondary or tertiary amines, which may also have one or more functional groups.
  • Amines which have one or more OH functionalities for example ethanolamine, diethanolamine or in particular triethanolamine, are particularly suitable.
  • compounds with at least one epoxy group which are also suitable for this purpose.
  • epoxidized natural fats or fatty acids such as those sold by the Henkel company under the name Edenol®, are particularly suitable.
  • a polymer dispersion according to the invention contains up to about 30% by weight, based on the total dispersion, of additives.
  • the additives include, for example, stabilizers, defoamers, antioxidants, photo stabilizers, pigment distributors, fillers, pH regulators, plasticizers and the like.
  • Suitable plasticizers are, for example, esters such as abietic acid esters, adipic acid esters, azelaic acid esters, benzoic acid esters, butyric acid esters, acetic acid esters, esters of higher fatty acids with about 8 to about 44 carbon atoms, esters with OH groups or epoxidized fatty acids, fatty acid esters and fats, glycolic acid esters, phosphoric acid esters, phthalic acid esters , from 1 to 12 carbon atoms containing linear or branched alcohols, propionic acid esters, sebacic acid esters, sulfonic acid esters, thiobutyric acid esters, trimellitic acid esters, citric acid esters, and mixtures of two or more thereof.
  • esters such as abietic acid esters, adipic acid esters, azelaic acid esters, benzoic acid esters, butyric acid esters, acetic acid esters, esters of higher fatty acids
  • asymmetric esters of difunctional, aliphatic or aromatic dicarboxylic acids are particularly suitable, for example the esterification product of mono-octyl adipate with 2-ethylhexanol (Edenol DOA, Henkel, Dusseldorf) or the esterification product of phthalic acid with butanol.
  • plasticizers are the pure or mixed ethers of monofunctional, linear or branched C 4.16 alcohols or mixtures of two or more different ethers of such alcohols, for example dioctyl ether (available as Cetiol OE, from Henkel, Düsseldorf).
  • end group-capped polyethylene glycols are used as plasticizers.
  • plasticizers polyethylene or polypropylene glycol di-C 1-4 alkyl ether, in particular the dimethyl or diethyl ether of diethylene glycol or dipropylene glycol, and mixtures of two or more thereof.
  • the preparation according to the invention can contain up to about 10% by weight of conventional tackifiers.
  • Suitable tackifiers are, for example, resins, terpene oligomers, coumarone / linden resins, aliphatic, petrochemical resins and modified phenolic resins.
  • the preparation according to the invention can contain up to about 2% by weight, preferably about 1% by weight, of UV stabilizers.
  • UV stabilizers can contain up to about 2% by weight, preferably about 1% by weight, of UV stabilizers.
  • HALS hindered amine light stabilizers
  • UV stabilizers are particularly suitable as UV stabilizers.
  • a water-dispersible in particular a polymer which can be prepared by emulsion polymerization, or a mixture of two or more thereof
  • a polymer dispersion according to the invention can in principle be produced in any manner by mixing a dispersion of a water-dispersible polymer or a mixture of two or more such polymers in water or in an aqueous environment with one of the elements already mentioned, in particular in its salt form.
  • the present invention therefore relates to a method for producing a polymer dispersion according to the invention, in which a dispersion of a water-dispersible polymer with an element selected from the group consisting of Li, B, Co, Cu, Mo, Ni, Pb or Sn or a salt such an element or a mixture of two or more thereof.
  • the polymer dispersion according to the invention is produced by emulsion polymerization.
  • emulsion polymerization is understood to mean a polymerization process in which monomers which are insoluble or poorly soluble in water are emulsified in water with the aid of emulsifiers and polymerized using water-soluble initiators. Suitable processes for emulsion polymerization are described, for example, in Comprehensive Polymer Chemistry, 4, 171-218, Elias (5th edition), 2, 93ff. Encyclopaedia of Polymer Science and Engineering, 12, 512ff. or Encyclopaedia of Polymer Science and Technology, 5, 801 ff.
  • Both water-soluble and oil-soluble polymerization initiators can be used as polymerization initiators in the preparation of the polymer dispersions according to the invention.
  • Particularly suitable polymerization initiators are water-soluble initiators such as tert-butyl hydroperoxide, sodium peroxodisulfate, peroxodisulfuric acid, cumene hydroperoxide, azo compounds such as
  • Redox initiators ie systems which consist of oxidizing and reducing agents, are also suitable.
  • water-soluble redox initiators contain transition metals, e.g. B. Fe / HO (I), but other basic components can also be present, e.g. B. the systems peroxysulfates / metabisulfates, peroxysulfates / thiosulfates or
  • sodium persulfate, potassium persulfate or ammonium persulfate are used as polymerization initiators.
  • the amount of polymerization initiator used in the context of the present invention is generally from about 0.01 to about 0.5% by weight, based on the total dispersion. In a preferred embodiment of the invention, the total amount of polymerization initiator used is about 0.03 to about 0.2% by weight, for example about 0.05 to about 0.15% by weight.
  • the total amount of the polymerization initiator can already be present in the reaction mixture at the start of the polymerization. In a preferred embodiment of the invention, however, the polymerization initiator is added in at least two batches at different times in the polymerization reaction. So z. B. the addition of part of the total amount of the polymerization initiator before the monomer addition, while the addition of the remaining amount can be done in portions or continuously during the monomer addition, or after the monomer addition has ended.
  • the elements or salts provided for marking the polymer dispersion in the context of the present invention can also be added before, during or after the polymerization reaction. It is also included in the scope of the present invention that corresponding adhesives are formulated, for example, as two-component systems and that the resin and hardener are only mixed by the user. In these cases it is possible that the element used for marking is in the hardener. In a preferred embodiment, however, the corresponding salts are added to the relation mixture after the polymerization reaction and are homogeneously distributed in the polymer dispersion by appropriate homogenization processes, for example by stirring. It has turned out to be preferred if salts are used to mark the polymer dispersion which are completely soluble in the polymer dispersions.
  • the present invention therefore also relates to a process for producing a polymer dispersion according to the invention, in which an element selected from the group consisting of Li, B, Co, Cu, Mo, Ni, before, during or after an emulsion polymerisation for producing a polymer which can be prepared by emulsion polymerisation , Pb or Sn or a salt of such an element or a mixture of two or more thereof is added.
  • the further constituents contained in the polymer dispersion for example protective colloids, surfactants and additives, can, if the presence of such additives in a polymer dispersion according to the invention is desired, be added before, during or after the emulsion polymerization.
  • the crosslinking resins can also be added before, during or after the emulsion polymerization.
  • the addition can take place, for example, shortly before the start or at the start of the polymerization reaction. It has been shown that the addition of the crosslinking resin before or during the polymerization process leads to products whose storage stability at high temperatures, for example at about 30 to about 50 ° C., is increased compared to products in which the crosslinking resin has been added after the polymerization ,
  • the invention thus also relates to a process for the preparation of a polymer dispersion comprising water, by emulsion polymerization polymer which can be prepared, a protective colloid, a water-soluble acidic metal salt and at least one crosslinking resin, in which a crosslinking resin based on hydroxymethyl-substituted imidazolidinones, hydroxymethyl-substituted pyrimidinones or hydroxymethyl-substituted triazinones is used before or during an emulsion polymerization to prepare a polymer which can be prepared by emulsion polymerization the self-condensation products or mixed condensates of two or more of the compounds mentioned or a mixture of two or more thereof is added to the reaction mixture.
  • 1,3-dimethylol-4,5-dihydroxyimidazolidinone 4,5-dihydroxy-N, N ' - dimethylolethyleneurea
  • dihydroxymethylethyleneurea, dihydroxymethylpropyleneurea or dihydroxymethyluron or their thio derivatives can be used as crosslinking resins either in the form of respective specified compounds whose
  • Self-condensation products or mixed condensates of two or more of the compounds mentioned or mixtures of two or more of the compounds or condensates mentioned are added.
  • the emulsion polymerization is carried out in the presence of a protective colloid or a mixture of two or more protective colloids.
  • the polymer dispersions according to the invention are suitable for surface coating or for bonding identical or different substrates, it being possible to coat or glue both substrates with a smooth surface and substrates with rough or porous surfaces.
  • natural or artificial substrates are suitable, for example floor coverings, felt, wood, wood-based materials and the like.
  • the polymer dispersions according to the invention are used for coating or bonding substrates based on natural raw materials, for example for bonding wood, Wood materials, paper or cardboard are used.
  • the present invention therefore also relates to the use of the polymer dispersions according to the invention in adhesives or surface coating compositions such as lacquers, emulsion paints, glues, adhesives or other surface coatings.
  • Another object of the invention is therefore also an adhesive or a surface coating composition containing a polymer dispersion according to the invention or a polymer dispersion produced according to a method according to the invention.
  • Another object of the present invention relates to the use of an element selected from the group consisting of Li, B, Co, Cu, Mo, Ni, Pb or Sn or a salt of such an element or a mixture of two or more thereof for marking dispersion adhesives ,
  • test specimen was then trimmed on the circular saw and then the test specimen was planed evenly on both sides of the thickness planer. 3.5 mm were planed from each side. A test specimen was produced which was 3 mm thick and had an adhesive joint in the middle. For the analytical processing, chips with a thickness of 0.2 mm on the narrow side, parallel to the fiber, were planed using a hand plane. The samples thus obtained were digested and then analyzed analytically with AAS.
  • test panels were exposed to practical exposure to the weather for a period of 6 months and then prepared and analyzed by the same method.
  • the properties of the marked adhesive were then examined and compared with the unmarked basic dispersion.
  • the marked adhesive was also subjected to a storage test.
  • the measurement is carried out on conditioned, undamped solid beech (Fagus sylvatica) with a wood moisture content of 8-10% and an adhesive application of 150 ⁇ and 200 ⁇ .
  • the measurement is carried out under constant climatic conditions at 23 ° C and 50% rh, the adhesive to be tested, stored at 23 ° C, with a 150 ⁇ and 200 ⁇ Spiral squeegee applied.
  • the adhesive film is tested for skin formation at intervals of one minute. If skin formation can be seen, one minute is deducted from the determined value. An average of 150 and 200 ⁇ is formed.
  • the information is given in minutes.
  • the test is carried out on butt-glued solid, undamped and planed beech (Fagus sylvatica) stored at 23 ° C and 50% relative humidity with a wood moisture content of 8 to 9%.
  • the individual beechwoods are each 24 mm deep at the head end, cut off at an angle of 20 °, so that when the individual parts are glued together, an isosceles wedge cutout with a total angle of both legs of 40 ° is formed, which is 24 mm deep and a wide shoulder Has 18.5 mm. This creates a wedge cutout of 2 cm in width at each adhesive joint.
  • test timbers Before the test, the test timbers must be conditioned for at least 2 weeks under constant conditions at 23 ° C 50% RH to ensure that a balance wood moisture between 8 and 9% is reached.
  • the wooden parts are bonded under defined climatic conditions at 23 ° C and 50% RH, whereby the adhesive itself should also have a temperature of 23 ° C.
  • the adhesive is applied on one side with a 150 ⁇ spiral squeegee.
  • the parts are joined after a flash-off time of 1 minute after application of the adhesive.
  • a pressure between 0.6 and 0.7 N / mm 2 is applied. After a pressing time of 10 min. the tensioned parts are relaxed and checked immediately afterwards.
  • the measurement itself is carried out on a mechanical tearing machine in which a force deflection mechanism has been attached, in which the testing machine can be converted from a tensile testing machine to a compression testing machine.
  • a solid, polished aluminum wedge with a flank angle of 20 ° was fitted to the force absorption, which fits exactly into the notch of the test specimen without touching the flank base.
  • the aluminum wedge was then driven into the notch of the wooden test specimen at a constant speed and the force in N was determined which was necessary to split the adhesive joint.
  • the four adhesive joints are split every 10 seconds.
  • the arithmetic mean is then calculated from the four determined values of the four glue lines.
  • thermoplastic wood adhesives for non-load-bearing applications
  • the stress group D3 was tested (minimum requirement: 2.0 N / mm 2 )
  • the adhesive to be tested is stored in a 250 ml glass bottle with a water vapor impermeable closure at 40 ° C + -1 ° C for a period of three months. After this time, the characteristics are checked.

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

Abstract

L'invention concerne une dispersion de polymères contenant de l'eau, au moins un polymère produit par polymérisation en émulsion et au moins un élément choisi dans le groupe constitué de Li, B, Co, Cu, Mo, Ni, Pb, Sn ou un de ses sels ou un mélange de deux éléments ou plus.
PCT/EP2002/013128 2001-11-30 2002-11-22 Dispersion de polymeres marquee et adhesifs produits a partir de celle-ci WO2003046065A2 (fr)

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DE10158839.9 2001-11-30
DE10158839A DE10158839A1 (de) 2001-11-30 2001-11-30 Markierte Polymerdispersion und daraus erhältliche Klebstoffe

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WO2003046065A3 WO2003046065A3 (fr) 2003-09-18

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004106451A1 (fr) * 2003-05-27 2004-12-09 Henkel Kommanditgesellschaft Auf Aktien Dispersion polymere marquee et adhesifs obtenus a partir de ladite dispersion
WO2011073354A1 (fr) 2009-12-18 2011-06-23 Construction Research & Technology Gmbh Procédé d'identification qualitative et quantitative de marchandises pondéreuses
WO2020098897A1 (fr) 2018-11-15 2020-05-22 Ocean Team Group A/S Procédé de décolmatage pulsé à contre-courant de tuyaux obstrués, par exemple dans un système de tuyaux hydrauliques

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10343262A1 (de) * 2003-09-17 2005-04-21 Franz Josef Landen Kaltleimklebebinder für Leimviskositäten bis maximal 6000 mpas/sekunde

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Publication number Priority date Publication date Assignee Title
IT1256783B (it) * 1992-01-27 1995-12-15 Alberto Gilli Procedimento per la realizzazione di un prodotto verniciante a dispersione particellare totalmente a base acquosa e prodotto verniciante ottenibile mediante tale procedimento.
DE19548038A1 (de) * 1995-12-21 1997-06-26 Basf Ag Verfahren zur Herstellung von Polymerisaten durch Emulsionspolymerisation
US6060154A (en) * 1997-09-30 2000-05-09 Sumitomo Metal Mining Co., Ltd. Coating liquid for selective permeable membrane, selective permeable membrane and selective permeable multilayered membrane
DE19818115B4 (de) * 1998-04-23 2005-07-21 Kiesel Bauchemie Gmbh & Co. Kg Lösemittelarmer oder lösemittelfreier Verlegewerkstoff zum Verlegen von Bodenbelägen
DE19900459A1 (de) * 1999-01-08 2000-07-13 Basf Ag Polymerdispersion

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004106451A1 (fr) * 2003-05-27 2004-12-09 Henkel Kommanditgesellschaft Auf Aktien Dispersion polymere marquee et adhesifs obtenus a partir de ladite dispersion
WO2011073354A1 (fr) 2009-12-18 2011-06-23 Construction Research & Technology Gmbh Procédé d'identification qualitative et quantitative de marchandises pondéreuses
US8575240B2 (en) 2009-12-18 2013-11-05 Construction Research & Technology Gmbh Method for qualitatively and quantitatively identifying bulk goods
WO2020098897A1 (fr) 2018-11-15 2020-05-22 Ocean Team Group A/S Procédé de décolmatage pulsé à contre-courant de tuyaux obstrués, par exemple dans un système de tuyaux hydrauliques

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DE10158839A1 (de) 2003-06-26
EP2099872A2 (fr) 2009-09-16
WO2003046065A3 (fr) 2003-09-18

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