WO2008122297A1 - Composition adhésive comprenant une dispersion de polymère contenant une charge, son procédé de production et d'utilisation - Google Patents

Composition adhésive comprenant une dispersion de polymère contenant une charge, son procédé de production et d'utilisation Download PDF

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Publication number
WO2008122297A1
WO2008122297A1 PCT/EP2007/003082 EP2007003082W WO2008122297A1 WO 2008122297 A1 WO2008122297 A1 WO 2008122297A1 EP 2007003082 W EP2007003082 W EP 2007003082W WO 2008122297 A1 WO2008122297 A1 WO 2008122297A1
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WIPO (PCT)
Prior art keywords
particles
filler
weight
water
adhesive composition
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PCT/EP2007/003082
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English (en)
Inventor
Matthias Passmann
Horst Beck
Aranguiz Roberto Antonio Pavez
Original Assignee
Henkel Ag & Co. Kgaa
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Priority to PCT/EP2007/003082 priority Critical patent/WO2008122297A1/fr
Publication of WO2008122297A1 publication Critical patent/WO2008122297A1/fr

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    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • Adhesive Composition comprising a Filler-containing Polymer Dispersion, Method for its Production and its Use
  • This invention relates to an adhesive composition
  • an adhesive composition comprising a filler-containing polymer dispersion which contains water, particles of an inorganic filler and particles of an organic polymer polymerized in the presence of the filler particles.
  • DE 199 59 916 A1 discloses a filler-containing polymer dispersion which contains organic or inorganic filler particles and particles of at least one synthetic organic polymer polymerized in the presence of the filler particles, the ratio of the particle size of the filler particles to the particle size of the polymer particles being in the range from 1.1 :1 to 20:1.
  • the polymer dispersion can be used as an adhesive or a surface coating.
  • Polymer particles with a diameter of about 0.01 to about 30 ⁇ m play an important role in many areas of plastics technology.
  • Adhesives or coating compositions containing polymer particles with diameters in this range are frequently used in particular for bonding articles or for coating surfaces. Examples of the range of applications include decorative surface coatings in the form of paint coatings or other coatings and the bonding of two surfaces having identical or different properties with adhesives of the type frequently encountered in the field of bonding.
  • the polymer particles mentioned are generally produced by polymerization of olefinically unsaturated monomers of which the properties can be modified by the polymerization of mixtures of various monomers, for example by co- or terpolymerization.
  • the modified properties of a single polymer particle are generally transferred as a collective property to a surface coating or bond prepared with the aid of such polymer particles.
  • Collective properties which are often subject to an application-related modification include, for example, hardness, elasticity and - above all in adhesive applications - bond strength, open time or early adhesion.
  • compositions used to prepare the coating or the bond are just as important.
  • viscosity, flow behavior or residual monomer content are often modified in dependence upon the desired application.
  • Inorganic or organic fillers are often added to a surface coating composition or an adhesive containing polymer particles to modify the above-mentioned properties of a surface coating or a bond.
  • Inorganic fillers reduce the level of organic polymer material in the coating and thus contribute to greater hardness of the coating and to protection of the environment and raw materials through a lower content of organic polymers.
  • Organic fillers are capable of imparting certain combined properties of the filler and polymer particles present therein, for example to a polymer dispersion.
  • Another problem addressed by the invention was to provide a filler-containing polymer dispersion which could be used as a high-strength adhesive, particularly on wood.
  • a further problem addressed by the invention was to provide a filler-containing polymer dispersion with a low residual monomer content.
  • Yet another problem addressed by the invention was to provide an adhesive which would have an adequate open time, high early adhesion and a low viscosity coupled with excellent flow behavior.
  • a final problem addressed by the invention was to provide a process for the production of such filler-containing polymer dispersions.
  • an adhesive comprising a filler-containing polymer dispersion which contains inorganic filler particles and particles of at least one synthetic organic polymer polymerized in the presence of the filler particles, the filler particles having a low diameter and a low BET surface area.
  • the present invention relates to an adhesive composition
  • an adhesive composition comprising a filler-containing polymer dispersion which contains water, particles of an inorganic filler and particles of an organic polymer polymerized in the presence of the filler particles characterized in that the filler particles at least partly are SiO 2 particles having a primary particle diameter (d50) of 0.01 to 30 ⁇ m and a BET surface area of
  • the BET surface area of the SiO 2 particles is 40 to 60 m 2 /g.
  • the adhesive composition comprises 10 to 70 percent by weight of an organic polymer, 1 to 70 percent by weight of SiO 2 particles and 20 to 89 percent by weight of water, the total of organic polymer, SiO 2 particles and water being 100 percent by weight.
  • the adhesive according to the invention in addition to the SiO 2 particles optionally contains either other inorganic filler particles of one type or organic filler particles of one type, other inorganic filler particles of one type and organic filler particles of one type or inorganic filler particles of two or more different types or organic filler particles of two or more different types or inorganic filler particles of one type and organic filler particles of two or more different types or organic filler particles of one type and inorganic filler particles of two or more different types or inorganic filler particles of two or more different types or inorganic filler particles of two or more different types and organic filler particles of two or more different types.
  • the organic filler particles and the (likewise organic) polymer particles differ to the extent that the organic polymer particles are formed in the presence of the filler particles, i.e. the polymerization of the polymer particles takes place in the presence of the filler particles.
  • the effect according to the invention is obtained even when the organic filler particles and the polymer particles have substantially the same monomer composition. In one preferred embodiment of the invention, however, the organic filler particles and the polymer particles have different monomer compositions.
  • the term "primary particle size” is understood to be the "d50" value, i.e. the value at which about 50% of the particles have a smaller diameter and about 50% of the particles have a larger diameter. In principle, this value may be determined by any particle measuring techniques, for example measuring techniques based on the principle of light diffraction.
  • the particle size data appearing in the present specification were obtained with a MASTERSIZER X from Malvern Instruments, Herrsching, Germany (version 1.2b). The mode of operation of this instrument is based on the diffraction of a light beam, the particle size being correlated with the diffraction angle.
  • Other techniques for determining particle sizes include, for example, granulometry in which a uniform suspension of a small quantity of the powder to be investigated is prepared in a suitable dispersion medium and is then exposed to sedimentation. The percentage distribution of the particle sizes can be estimated from the correlation between size and density of the spherical particles and their sedimentation rate as determined by Stokes 1 law and the sedimentation time.
  • Other methods for determining particle size include microscopy, electron microscopy, sieve analysis, sedimentation analysis, determination of the surface density and the like.
  • Polymer particles in the context of the present invention are understood to be dispersed particles of a substantially water-insoluble synthetic organic polymer polymerized in the presence of an inorganic or organic filler particle or a mixture of two or more of such filler particles, as described above.
  • suitable filler particles to be used in addition to the SiO 2 particles are any organic or inorganic particles which have a primary particle size (as defined above) of about 0.033 to about 10 ⁇ m, for example about 0.05 to about 5 ⁇ m or about 0.1 to about 4 ⁇ m or 0.2 to about 3 ⁇ m or about 0.5 to about 1.0 ⁇ m.
  • particle size classification is based on the size of the primary particles.
  • a “primary particle” in the context of the present invention is understood to be a particle which is held together by primary ionic or covalent forces, for example in the form of a crystal lattice.
  • “secondary particles” are understood to be agglomerates of two or more primary particles which adhere to one another at the outer surfaces or boundaries of the primary particles under the effect of weak ionic forces, other polarity-based forces, or van-der-Waals forces and which can be broken up into the primary particles with minimal energy, for example by simple mechanical dispersion and/or by addition of a dispersant which breaks up the particles by eliminating or reducing the weak binding forces between the primary particles.
  • Filler particles suitable for the purposes of the invention and to be used in addition to the SiO 2 particles are, for example, inorganic materials which are inert to the at least one organic polymer and during the production of the filler-containing polymer dispersion under the prevailing reaction conditions.
  • suitable inorganic materials are aluminium silicates, for example andalusite, sillimanite, kyanite, mullite, pyrophyllite or imogolite.
  • compounds based an sodium aluminium or calcium silicates are also suitable.
  • suitable inorganic materials are minerals, such as silica, silica flour, silica gel, barium sulfate, metal oxides, such as zinc oxide, titanium dioxide, zeolites, kaophilite, leucite, potash feldspar, biotite, the group of soro-, cyclo-, ino-, phyllo- and tecto-silicates, the group of soluble or poorly soluble sulfates, such as gypsum, anhydrite or heavy spar, and calcium minerals, such as talcum or chalk (CaCO 3 ).
  • the inorganic materials mentioned may be used individually, i.e. as filler particles of a single type, for the purposes of the present invention. However, a mixture of two or more types of the filler particles mentioned may equally well be used.
  • organic filler particles suitable for the purposes of the invention and to be used in addition to the SiO 2 particles are organic filler particles in the presence of which the polymerization of the polymer particles may take place.
  • Suitable organic filler particles are, for example, polyvinyl acetate and copolymers of polyvinyl acetate with one or more polymerizable compounds, polystyrene, polyethylene, polypropylene, waxes, such as polyethylene wax, polybutylene, polybutadiene, copolymers of butadiene and styrene, polyacrylonitrile, resins, such as rosin or hydrocarbon resins, polyacrylate esters or polymethacrylate esters with linear or branched aliphatic, aromatic or cycloaliphatic alcohols, such as methanol, ethanol, propanol, isopropanol, the isomeric butanols and higher homologs of the alcohols mentioned containing up to about 22 carbon atoms, cyclohexan
  • the organic filler particles contain as organic filler filler particles containing polyvinyl acetate or copolymers of polyvinyl acetate with one or more polymerizable compounds, polystyrene, polyethylene, polypropylene, waxes, polybutylene, polybutadiene, copolymers of butadiene and styrene, polyacrylonitrile, resins, polyacrylate esters or polymethacrylate esters or polymers containing silyl groups.
  • the organic filler particles consist of the polymers mentioned.
  • the filler-containing polymer dispersion contains less than five different types of filler particles, for example four, three or two different types.
  • the polymer dispersion according to the invention contains filler particles of only one type.
  • the filler particles usable in accordance with the present invention may have smooth, rough or porous surfaces. In one preferred embodiment, the filler particles have a rough surface or a porous surface.
  • the filler-containing polymer dispersions according to the invention contain particles of chalk (CaCO 3 ), gypsum (CaSO 4 ) as anhydrite, hemihydrate or dihydrate, silica flour, silica gel, titanium dioxide, silica flour, talcum or a layer silicate as filler in addition to the SiO 2 particles.
  • the filler-containing polymer dispersion contains polymer particles consisting of an organic polymer or of a mixture of two or more organic polymers.
  • Suitable organic polymers are any organic polymers obtainable by radical polymerization of olefinically unsaturated and radical-polymerizable monomers.
  • Olefinically unsaturated monomers accessible to emulsion polymerization are particularly suitable for the production of the polymer particles.
  • Suitable polymers are, for example, vinyl ester polymers of which the basic monomeric unit is a vinyl ester of a linear or branched carboxylic acid containing about 2 to about 10 carbon atoms.
  • the vinyl ester polymers are used not only as homopolymers or copolymers of vinyl ester monomers; in another embodiment of the invention, a copolymer of vinyl acetate and ethylene (EVA copolymer) is used as the organic polymer.
  • EVA copolymer vinyl acetate and ethylene
  • Other suitable organic polymers emanate from the group of styrene/butadiene rubbers (SBRs). Rubbers such as these are produced by copolymerization of styrene and butadiene and generally contain the two monomers in a ratio by weight of about 23.5 : 76.5 or about 40 : 60.
  • SBRs are normally 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 homo- and copolymers.
  • a radical polymerization of ethylene is carried out, for example, in the high-pressure polymerization to LDPE under pressures of about 1 ,400 to 3,500 bar and at temperatures of 150 to 350 0 C. The reaction is initiated by oxygen or peroxides.
  • Suitable comonomers are linear or branched ⁇ , ⁇ -unsaturated olefins.
  • polyacrylates or the polymethacrylates or the copolymers of acrylates and methacrylates thereof are the polyacrylates or the polymethacrylates or the copolymers of acrylates and methacrylates thereof.
  • the polymers mentioned may optionally have a free acid content which corresponds to 20 - 25 ml of 0.1 N KOH solution.
  • 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.
  • This polymer may be obtained by polymerization of vinylidene fluoride and may be adapted in regard to chemical and mechanical properties, for example by copolymerization with suitable monomers, such as ethylene, acrylonitrile, acrylate esters, methacrylate esters and the like.
  • polyvinyl chlorides obtainable by suspension polymerization (S-PVC), micro- suspension polymerization or emulsion polymerization (E-PVC) are also suitable.
  • the polymers mentioned may be present in the filler- containing polymer dispersion according to the invention both individually and in the form of mixtures of two or more thereof.
  • the filler-containing polymer dispersion contains polyvinyl acetate or polyacrylate, more particularly polybutyl acrylate, or a mixture of polyvinyl acetate and polyacrylate as polymer particles.
  • the percentage content of filler in the polymer dispersion as a whole may be between about 5 and about 55% by weight. In one preferred embodiment of the invention, the percentage content is between about 5 and about 50% by weight, for example between about 10 and about 35% by weight.
  • the content of filler particles may be about 15, 20, 25 or 30% by weight or may assume an intermediate value.
  • the filler-containing polymer dispersion according to the invention may optionally contain at least one water-soluble organic polymer with a molecular weight of more than about 600 and an HLB value determined according to the method of Griffin of at least 15, for example more than about 16 or more than about 17 or more than about 18. This is preferred particularly when at least partly inorganic filler particles are present as filler particles in the polymer dispersion according to the invention.
  • a compound suitable as a water-soluble organic polymer is, for example, polyvinyl alcohol which may be up to about 99% hydrolyzed, for example between about 70 and about 95% or between about 80 and about 88% hydrolyzed, the acetic acid groups of the chain being replaced by OH groups which are preferably distributed statistically over the entire polymer chain.
  • the polyvinyl alcohol preferably has a degree of polymerization of more than 100 and, more particularly, more than about 2,000. Particularly good results can be obtained, for example, with polyvinyl alcohol having a degree of polymerization of about 1 ,000 to about 2,000.
  • the polyvinyl alcohol preferably has an HLB value of at least about 19 or at least about 20, for example about 21 to about 26, for example about 22 to about 24.
  • Suitable polyvinyl alcohols are obtainable from Clariant, for example under the names of Mowiol 40/88, Mowiol 26/88, Mowiol 8/88 or Mowiol 4/88 and other polyvinyl alcohols having different hydrolysis degrees.
  • water-soluble organic polymers suitable for use in accordance with the invention consist, for example, of the cellulose ethers, carboxymethyl celluloses, hydroxyethyl celluloses, casein, sodium or potassium alginates, polyurethanes, etc.
  • the ratio of the mean specific surface of organic polymers to organic or inorganic filler particles is about 5:1.
  • the total specific surface corresponding to the inorganic fillers, based on the organic water-soluble polymers, in the dispersion according to the invention is about 5% to about 35% of the total surface of the dispersion.
  • the fillers increase the mean total specific surface of the dispersion.
  • the filler-containing polymer dispersion contains at least one ionic surfactant with an HLB value of 1 to 10.
  • the ionic surfactant has a molecular weight of less than about 600.
  • Anionic, cationic or ampholytic surfactants or mixtures of two or more thereof may be present.
  • suitable anionic surfactants are alkyl sulfates, more particularly those with a chain length of about 8 to about 18 carbon atoms, alkyl and alkaryl ether sulfates containing about 8 to about 18 carbon atoms in the hydrophobic part and 1 to about 10 ethylene oxide (EO) or propylene oxide (PO) units or mixtures thereof in the hydrophilic part of the molecule, sulfonates, more particularly alkyl sulfonates, containing about 8 to about 18 carbon atoms, alkylaryl sulfonates containing about 8 to about 18 carbon atoms, taurides, esters and semiesters of sulfosuccinic acid with monohydric alcohols or alkylphenols containing 4 to about 15 carbon atoms, which may optionally be ethoxylated with 1 to about 20 EO units, alkali metal and ammonium
  • alkyl or alkaryl phosphates or alkyl or alkaryl sulfates containing about 8 to about 22 carbon atoms in the organic moiety alkyl ether or alkaryl ether phosphates or alkyl ether or alkaryl ether sulfates containing about 8 to about 22 carbon atoms in the alkyl or alkaryl moiety and 1 to about 10 EO units or a mixture of two or more thereof are used as anionic surfactants.
  • an alkyl or alkaryl sulfate containing about 8 to about 22 carbon atoms in the organic moiety or an alkyl ether or alkaryl ether sulfate containing about 8 to about 22 carbon atoms in the alkyl or alkaryl moiety and 1 to about 10 EO units or a mixture of two or more thereof is used as anionic surfactant.
  • cationic surfactants are salts of primary, secondary or tertiary fatty amines containing about 8 to about 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid or phosphoric acids, quaternary alkyl and alkyl benzene ammonium salts, more particularly those of which the alkyl groups contain about 6 to about 24 carbon atoms, more particularly the halides, sulfates, phosphates or acetates or mixtures of two or more thereof, alkyl pyridinium, alkyl imidazolinium or alkyl oxazolidinium salts, more particularly those of which the alkyl chain contains 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-dimethyl ammonium salts with a C 8 . 18 acyl group or alkyl imidazolium betaines.
  • the alkali metal salts are used: the alkali metal salts, more particularly the Na salt, of C 12/14 fatty alcohol ether sulfates, alkyl phenyl ether sulfates, more particularly the alkali metal or NH 4 salts thereof, Na-n-dodecyl sulfate, di-K-oleic acid sulfonate (C 18 ), Na-n-alkyl- (C 10 C 13 )-benzene sulfonate, Na-2-ethyl hexyl sulfate, NH 4 lauryl sulfate (C 8/14 ), Na lauryl sulfate (C 12/14 ), Na lauryl sulfate (C 12/16 ), Na lauryl sulfate (C 12/18 ), Na cetyl stearyl sulfate (C 16718 ), Na oleyl cetyl sulfate
  • the adhesive according to the invention contains ionic surfactants, they are present in a preferred embodiment of the invention in a quantity of up to about 1 % by weight or less, for example in a quantity of up to about 0.8% by weight or about 0.5% by weight or less, based on the dispersion as a whole. Smaller quantities of ionic surfactant, for example up to about 0.2% by weight or less, for example about 0.1 % by weight, 0.05% by weight or 0.02% by weight, may also be present. In another preferred embodiment of the invention, the ratio of ionic surfactant to organic water- soluble polymer is about 0.1 % to about 3.0%.
  • the filler-containing polymer dispersion contains at least one nonionic surfactant with an HLB value of 13 to 20.
  • the nonionic surfactant has a molecular weight of less than about 600.
  • nonionic surfactants are alkyl polyglycol ethers, preferably those containing about 8 to about 20 EO units and alkyl groups with about 8 to about 20 carbon atoms, alkylaryl polyglycol ethers, preferably those containing about 8 to about 40 EO units and about 8 to about 20 carbon atoms in the alkyl or aryl groups, ethylene oxide/propylene oxide (EO/PO) block copolymers, preferably those containing about 8 to about 40 EO units and the same number of PO units, addition products of alkyl amines containing alkyl groups with about 8 to about 22 carbon atoms with ethylene oxide or propylene oxide, fatty and resin acids containing about 6 to about 32 carbon atoms, alkyl polyg
  • the adhesives according to the invention contain, for example, nonyl phenol ethoxylates, octyl phenol ethoxylates, C 12/14 fatty alcohol ethoxylates, oleyl cetyl ethoxylates, C 16/18 fatty alcohol ethoxylates, cetyl stearyl ethoxylates, ethoxylated triglycerides, sorbitan monolaurate, sorbitan monooleate, sorbitan-20EO-monooleate, sorbitan-20EO-monostearate or a mixture of two or more thereof as nonionic surfactant.
  • the adhesive according to the invention contains nonionic surfactants, they are present in a preferred embodiment of the invention in a quantity 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 dispersion as a whole.
  • Small quantities of nonionic surfactant for example up to about 0.2% by weight or less, for example about 0.1% by weight, 0.05% by weight or 0.02% by weight, may also be present.
  • the ratio of nonionic surfactant(s) to organic water-soluble polymers (based on weight) is about 0.01 to about 1.0%.
  • the ratio of nonionic surfactant(s) to anionic surfactant(s) (based on weight) in one preferred embodiment of the invention is about 5:1 to about 1 :5, for example about 3:1 to about 1 :3 or about 2:1 to about 1 :2. In another preferred embodiment of the invention, the ratio by weight of nonionic surfactant to anionic surfactant is about 1.2:1 to about 1 :1.2 or about 1 :1.
  • the adhesive contains up to about 30% by weight, based on the adhesive as a whole, of additives.
  • additives include, for example, stabilizers, defoamers, antioxidants, photostabilizers, pigment dispersants, fillers, pH adjusters, plasticizers and the like.
  • Suitable plasticizers are, for example, esters, such as abietic acid ester, adipic acid ester, azelaic acid ester, benzoic acid ester, butyric acid ester, acetic acid ester, esters of higher fatty acids containing about 8 to about 44 carbon atoms, esters of OH-functional or epoxidized fatty acids, fatty acid esters and fats, glycolic acid esters, phosphoric acid esters, phthalic acid esters, linear or branched alcohols containing 1 to 12 carbon atoms, 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 ester, adipic acid ester, azelaic acid ester, benzoic acid ester, butyric acid ester, acetic acid ester, esters of higher fatty acids
  • asymmetrical esters of dibasic aliphatic dicarboxylic acids for example the esterification product of adipic acid monooctyl ester with 2-ethyl hexanol (Edenol DOA, a product of Cognis Deutschland GmbH, D ⁇ sseldorf), are particularly suitable.
  • plasticizers are the pure or mixed ethers of monohydric, linear or branched C 4 .., 6 alcohols or mixtures of two or more different ethers of such alcohols, for example dioctyl ethers (obtainable as Cetiol OE from Cognis Deutschland GmbH, D ⁇ sseldorf).
  • end-capped polyethylene glycols for example polyethylene or polypropylene glycol di-C ⁇ -alkyl ethers, more particularly the dimethyl or diethyl ethers of diethylene glycol or dipropylene glycol and mixtures of two or more thereof, are used as plasticizers.
  • An adhesive may contain up to about 10% by weight of typical tackifiers.
  • Suitable tackifiers are, for example, resins, terpene oligomers, coumarone/indene resins, aliphatic petrochemical resins and modified phenolic resins.
  • the adhesive according to the invention may contain up to about 2% by weight and preferably about 1 % by weight of UV stabilizers.
  • UV stabilizers are the so-called hindered amine light stabilizers (HALS).
  • HALS hindered amine light stabilizers
  • the filler-containing polymer dispersion contains about
  • the filler-containing polymer dispersion is prepared by emulsion polymerization.
  • emulsion polymerization is understood to be a polymerization process in which monomers insoluble or poorly soluble in water are emulsified in water using emulsifiers and polymerized using water-soluble initiators. Suitable emulsion polymerization processes are described, for example, in Comprehensive Polymer Chemistry, 4, 171-218, Elias (5th Edition), 2, 93 et seq; in Encyclopaedia of Polymer Science and Engineering, 12, 512 et seq and in Encyclopaedia of Polymer Science and Technology, 5, 801 et seq.
  • the dispersion of the filler particles is carried out in such a way that any agglomerates of filler particles present are separated at least substantially, i.e. to a level of at least about 80 or 90% by weight, into their primary particles.
  • This separation into the primary particles is generally promoted by the presence of emulsifiers or dispersants, as used in emulsion or suspension polymerization.
  • any other form of separation of any filler particle agglomerates into the primary particles is also possible in the context of the process according to the invention, including for example ultrasonic deagglomeration, flotation or electrokinetic techniques.
  • the filler-containing polymer dispersion is prepared by emulsion polymerization.
  • a dispersion of the filler particles in water is preferably first produced.
  • an aqueous solution of an ionic surfactant is first prepared, the ionic surfactant used preferably being the surfactant which, subsequently, is also used in the emulsion polymerization.
  • an aqueous solution of an organic water-soluble polymer with a molecular weight of at least about 600 and an HLB value of at least about 15 is first prepared.
  • an aqueous solution containing both an ionic surfactant and a water-soluble polymer with a molecular weight of at least about 600 and an HLB value of at least about 15 may also first be prepared.
  • the dispersion of the filler particles is prepared in a preferred embodiment of the present invention.
  • the filler particles are dispersed in one of the above-mentioned solutions, the dispersion being stirred until any filler agglomerates present have been largely dispersed.
  • the dispersion of the filler particles and the dispersion of any agglomerates present may simply be followed by several successive measurements of the particle size distribution during the dispersion process. Separation into the primary particles is achieved when the particle size distribution differs only slightly, if at all, in two successive measurements.
  • the dispersion of the agglomerates may optionally be influenced by influencing the temperature, the stirring speed or the emulsifier or mixture of two or more emulsifiers used.
  • the effects of the proposed measures may readily be monitored and optimized for individual cases by measurement of the particle size distribution.
  • the emulsion polymerization is continued. This is done, for example, by dissolving a polymerization initiator in the dispersion, heating the dispersion to a suitable temperature and then starting the polymerization reaction by dropwise addition of monomers.
  • this procedure may also be replaced by any other procedure by which the emulsion polymerization can be carried out in the filler particle dispersion.
  • a preliminary emulsion containing the monomers or the monomer mixture and the filler dispersion may also be prepared by the procedure described above.
  • This preliminary emulsion which may optionally contain a polymerization initiator, may be added dropwise or in portions at a temperature suitable for the polymerization reaction.
  • the present invention also relates to a process for the production of an adhesive composition
  • a filler-containing polymer dispersion which contains water, particles of an inorganic filler and particles of an organic polymer characterized in that a radical-polymerizable monomer is subjected to emulsion polymerization in an aqueous phase using a polymerization initiator, the aqueous phase containing filler particles characterized in that the filler particles are SiO 2 particles having a primary particle diameter (d50) of 0.01 to 30 ⁇ m and a BET surface area of 20 to 100 m 2 /g.
  • the aqueous phase additionally contains a nonionic surfactant, suitable nonionic surfactants having already been described in the foregoing.
  • a water-soluble polymerization initiator more particularly a peroxo compound of an organic or inorganic acid
  • Suitable polymerization initiators are water-soluble initiators, such as tert-butyl hydroperoxide, sodium peroxodisulfate, peroxodisulfuric acid, cumene hydroperoxide, hydrogen peroxide, sodium or potassium percarbonate; azo compounds, such as diazoisobutyrodinitrile or benzoyl peroxide.
  • Redox initiators i.e. systems consisting of oxidizing and reducing agents, are also suitable.
  • water-soluble redox initiators contain transition metals, for example Fe/HO (I), although other basic components, for example the systems peroxysulfates/metabisulfates, peroxysulfates/thiosulfates or peroxides/thiosulfates, may also be used.
  • transition metals for example Fe/HO (I)
  • other basic components for example the systems peroxysulfates/metabisulfates, peroxysulfates/thiosulfates or peroxides/thiosulfates, may also be used.
  • sodium persulfate, potassium persulfate or ammonium persulfate is used as the polymerization initiator.
  • the quantity of polymerization initiator used is generally between about 0.01 and about 0.5% by weight, based an the dispersion as a whole. In one preferred embodiment of the invention, the total amount of polymerization initiator used is between about 0.03 and about 0.2% by weight, for example between about 0.05 and about 0.15% by weight.
  • the total quantity of polymerization initiator may be present in the dispersion of the filler particles at the beginning of the polymerization process.
  • the polymerization initiator is added in at least two batches at different stages of the polymerization reaction.
  • part of the total quantity of polymerization initiator may be added before the monomer(s), the remainder being added in portions or continuously during or after addition of the monomer(s).
  • the process according to the invention is carried out in at least two successive stages, a dispersion containing
  • ionic surfactant with an HLB value of 1 to 10 or a nonionic surfactant with an HLB value of 13 to 20 or a mixture of two or more thereof
  • inorganic filler with a particle size of primary particles (d50) of 0.01 to 0.5 ⁇ m
  • polymerization initiator at least one water-soluble organic polymer with a molecular weight of more than 600 and an HLB value of more than 15
  • the organic or inorganic filler particles or a mixture thereof are/is added before the polymerization initiator.
  • the organic filler or the inorganic filler or a mixture thereof is present substantially in the form of its primary particles before the polymerization.
  • the polymerization temperature applied in the process according to the invention depends upon the choice of the monomers used and the polymerization process applied.
  • the polymerization temperature in one preferred embodiment of the invention is in the range from about 80 to 90 0 C.
  • the present invention also relates to the use of the adhesive composition for bonding wood, paper or paperboard.
  • Dispersion with SiO 2 particles having a BET surface area of 50 m 2 /g and a primary particle size d50 of 10 ⁇ m (Dura-Sil from DuraPact GmbH, Haan, Germany) 1.1 38.75 g vinyl acetate monomer were filled into a monomer container.
  • the pre-mix was heated to 80 °C and 90 % of the catalyst solution were added. The mixture was homogenized by stirring for 5 minutes. 1.6 Thereafter, the vinyl acetate monomer was added over a period of 3.5 to 4 hours.
  • Dispersion with SiO 2 particles having a BET surface area of 50 m 2 /g and a primary particle size d50 of 40 nm (Aerosil OX 50 from Degussa AG, Frankfurt, Germany)
  • the pre-mix was heated to 80 0 C and 90 % of the catalyst solution were added.
  • the mixture was homogenized by stirring for 5 minutes.
  • Adhesives comprising the filler-containing polymer dispersions of Example 1 and 2 solve the problems of the invention, i.e. the provision of an adhesive that can be used for the production of high-quality bonds having superior wet-strength, particularly on wood.
  • the filler-containing polymer dispersions have a low residual monomer content.
  • Adhesives prepared with the filler-containing polymer dispersions show an adequate open time, high early adhesion, a low viscosity and excellent flow behavior.
  • the viscosity of the dispersions is affected by increasing the values at same conditions.
  • the moisture resistance of the film is promoted, where the best case is through polymerization.

Abstract

L'invention concerne une composition adhésive comprenant une dispersion de polymère contenant une charge qui contient de l'eau, des particules d'une charge inorganique et des particules d'un polymère organique polymérisé en présence des particules de la charge caractérisée en ce que les particules de la charge sont au moins en partie des particules de SiO2 ayant un diamètre de particule principal (d50) de 0,1 à 30 µm et une surface spécifique BET de 20 à 100 m2/g, son procédé de fabrication et d'utilisation.
PCT/EP2007/003082 2007-04-05 2007-04-05 Composition adhésive comprenant une dispersion de polymère contenant une charge, son procédé de production et d'utilisation WO2008122297A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014090775A1 (fr) 2012-12-14 2014-06-19 Henkel Ag & Co. Kgaa Procédé de fabrication d'une dispersion de polyacétate de vinyle

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19959916A1 (de) * 1998-12-30 2000-07-20 Henkel Chile Sa Füllstoffhaltige Polymerdispersion, Verfahren zu deren Herstellung und deren Verwendung
US20050085584A1 (en) * 2003-09-18 2005-04-21 Rudiger Musch Aqueous adhesive dispersions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19959916A1 (de) * 1998-12-30 2000-07-20 Henkel Chile Sa Füllstoffhaltige Polymerdispersion, Verfahren zu deren Herstellung und deren Verwendung
US20050085584A1 (en) * 2003-09-18 2005-04-21 Rudiger Musch Aqueous adhesive dispersions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014090775A1 (fr) 2012-12-14 2014-06-19 Henkel Ag & Co. Kgaa Procédé de fabrication d'une dispersion de polyacétate de vinyle
RU2652689C2 (ru) * 2012-12-14 2018-04-28 Хенкель Аг Унд Ко. Кгаа Способ получения поливинилацетатной дисперсии

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