WO1997017387A1 - Starch-containing polymer dispersions and their use as laminate adhesives - Google Patents

Starch-containing polymer dispersions and their use as laminate adhesives Download PDF

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Publication number
WO1997017387A1
WO1997017387A1 PCT/EP1996/004581 EP9604581W WO9717387A1 WO 1997017387 A1 WO1997017387 A1 WO 1997017387A1 EP 9604581 W EP9604581 W EP 9604581W WO 9717387 A1 WO9717387 A1 WO 9717387A1
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WO
WIPO (PCT)
Prior art keywords
polymer
weight
diisocyanate
groups
feed
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PCT/EP1996/004581
Other languages
German (de)
French (fr)
Inventor
Gerald Wildburg
Jürgen BARWICH
Renate WÜSTEFELD
Hans-Joachim Fricke
Gerd Rehmer
Original Assignee
Basf Aktiengesellschaft
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Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP96934780A priority Critical patent/EP0858469A1/en
Priority to AU72972/96A priority patent/AU7297296A/en
Publication of WO1997017387A1 publication Critical patent/WO1997017387A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers

Definitions

  • the invention relates to a dispersion of a free-radically polymerized polymer containing a polyisocyanate as crosslinking agent, characterized in that the polymer is obtainable by emulsion polymerization of ethylenically unsaturated monomers in the presence of a protective colloid containing hydroxyl groups or primary or secondary amino groups.
  • laminating adhesives can be used universally, i.e. they are equally intended for the lamination of different polymer films, e.g. made of polyethylene (PE), oriented propylene (OPP), polyamide (PA) or polyethylene terephthalate (PETP) with one another and also suitable for laminating polymer films with paper or in particular also with aluminum films.
  • PE polyethylene
  • OPP oriented propylene
  • PA polyamide
  • PETP polyethylene terephthalate
  • the lamination adhesives should have good adhesion to all of these substrates and, after lamination, have a high strength in the film composites obtained.
  • the laminating adhesives must also be free of fine coagulate, resistant to aging light and low-foaming.
  • US Pat. No. 4,609,690 discloses dispersions of free-radically polymerized polymers which contain polyisocyanates as crosslinking agents. They are used as adhesives for the production of plywood.
  • DE-A-40 36 927 describes special polyisocyanates which are used as crosslinking agents in polymer dispersions.
  • the polymer dispersions are also used to bond polymer films.
  • DE-A-4 133 193 has already disclosed the preparation of polymer dispersions by radical polymerization of ethylenically unsaturated monomers in the presence of starch.
  • EP-A-206 059 describes the addition of polyisocyanates to aqueous polymer dispersions. These polymer dispersions can, among other things, be used as thickeners. starch can also be added. The dispersions are used as adhesives.
  • the object of the present invention was therefore a polymer dispersion which can be used as a laminating adhesive for a wide variety of substrates, e.g. Polymer foils or aluminum foils are suitable and meet the requirements described above to a high degree.
  • the dispersion of the free-radically polymerized polymer can be obtained by free-radical polymerization of ethylenically unsaturated monomers in the presence of a protective colloid containing hydroxyl groups.
  • the obtained polymer is preferably made of so-called main monomers selected from C1-C2 0 alkyl (meth) acrylates, Vinylestern of up to 20 carbon atoms-containing carboxylic acids, vinyl aromatics with up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides , non-aromatic hydrocarbons with at least 2 conjugated double bonds or mixtures of these monomers.
  • main monomers selected from C1-C2 0 alkyl (meth) acrylates, Vinylestern of up to 20 carbon atoms-containing carboxylic acids, vinyl aromatics with up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides , non-aromatic hydrocarbons with at least 2 conjugated double bonds or mixtures of these monomers.
  • the above monomers can e.g. to 60 to
  • 100% by weight preferably 80 to 100% by weight, can be contained in the polymer.
  • Examples include (Meth) acrylic acid alkyl esters with a Ci-Cio-alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • Vinyl esters of carboxylic acids with 1 to 20 C atoms are, for example, vinyl laurate, stearate, vinyl propionate, vinyl versatic acid and vinyl acetate.
  • Suitable vinyl aromatic compounds are vinyl toluene, ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chlorine, fluorine or bromine-substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • butadiene, isoprene and chloroprene may be mentioned as non-aromatic hydrocarbons having 2 to 8 carbon atoms and at least two olefinic double bonds.
  • the polymer particularly preferably consists of at least 60% by weight of (meth) acrylic alkyl acid esters and mixtures thereof.
  • Further monomers which can be present in the polymer for example from 0 to 40% by weight, preferably from 0 to 20% by weight, are in particular Ci-Cio-hydroxyalkyl (meth) acrylates, (meth) acrylamide and its am Nitrogen with C 1 -C 4 -alkyl-substituted derivatives.
  • the polymer can also contain ethylenically unsaturated monomers with carboxylic acid groups such as (meth) acrylic acid, maleic acid, ethylenically unsaturated acid anhydrides or half esters, such as maleic anhydride or maleic acid or fumaric acid semiesters.
  • carboxylic acid groups such as (meth) acrylic acid, maleic acid, ethylenically unsaturated acid anhydrides or half esters, such as maleic anhydride or maleic acid or fumaric acid semiesters.
  • the glass transition temperature of the polymer can be determined by conventional methods such as differential thermal analysis or differential scanning calorimetry (see e.g. ASTM 3418/82, so-called “midpoint temperature”).
  • the glass transition temperature of the polymer is preferably below 60 ° C, in particular it is -50 to + 60 ° C, particularly preferably -30 to + 40 ° C and very particularly preferably -30 to + 20 ° C.
  • the polymer is preferably produced by emulsion polymerization.
  • the emulsion polymerization can be carried out batchwise, with or without the use of seed latices, with presentation of all or individual components of the reaction mixture, or preferably with partial delivery and subsequent metering of the or individual components of the reaction mixture, or by the dosing method without a template.
  • the monomers can be polymerized in the emulsion polymerization, as usual, in the presence of a water-soluble initiator and an emulsifier at preferably 30 to 95 ° C.
  • Suitable initiators are, for example, sodium, potassium and ammonium persulfate, tert. -Butyl hydroperoxides, water-soluble azo compounds or redox initiators such as H 2 0 2 / ascorbic acid.
  • Other suitable emulsifiers are reaction products of alkylene oxides, in particular ethylene or propylene oxide, with fatty alcohols, fatty acids or phenol, or alkylphenols.
  • the amount of emulsifiers is in particular 0 to 10% by weight, preferably 0.05 to 5% by weight and particularly preferably 0.05 to 2% by weight, based on the polymer.
  • Regulators can be used in the polymerization to adjust the molecular weight. Suitable are e.g. -SH-containing compounds such as mercaptoethanol, mercaptopropanol, thiophenol, thioglycerin, ethyl thioglycolate, methyl thioglycolate and tert-dodecyl mercaptan.
  • -SH-containing compounds such as mercaptoethanol, mercaptopropanol, thiophenol, thioglycerin, ethyl thioglycolate, methyl thioglycolate and tert-dodecyl mercaptan.
  • the emulsion polymerization is carried out in the presence of a protective colloid which contains hydroxyl groups or primary or secondary amino groups.
  • the protective colloid can be introduced during the emulsion polymerization, partly introduced and metered in, or added entirely during the emulsion polymerization.
  • the polymerization batch advantageously contains at least half of the total amount of protective colloid.
  • the total amount of protective colloid is particularly preferably introduced during the polymerization.
  • the total amount of the protective colloid is preferably 0.1 to 50% by weight, particularly preferably 1 to 20% by weight and very particularly preferably 2 to 10% by weight, based on the polymer.
  • the protective colloid can contain only hydroxyl groups, only primary or only secondary amino groups. However, the protective colloid can also contain hydroxyl groups as well as primary or second contain amino groups.
  • the amount by weight of the total hydroxyl groups, primary or secondary amino groups (hydroxyl groups as OH and primary or secondary amino groups are both calculated as NH) is preferably 0.1 to 60% by weight, preferably 2 to 50% by weight. %, based on the protective colloid.
  • Protective colloids are e.g. Polysaccharides such as starches or celluloses, polyvinyl alcohol or gelatin.
  • the weight-average molecular weight of the protective colloids is preferably from 500 to 50,000 and particularly preferably from 1,000 to 25,000, which can be measured by gel chromatography.
  • Preferred protective colloids are polysaccharides, starches are particularly preferred.
  • the polysaccharides can be of vegetable or animal origin, soluble in water or only dispersible therein. Suitable are, among other things, the so-called swelling starches, which can be obtained, for example, by hydrothermal treatment of native starch. Thin-boiling starches are also suitable. These are starches that have been slightly degraded with acids or enzymes or that have been oxidized with mild oxidizing agents. Even in higher concentrations, when boiling with water, they do not produce viscous paste, but rather relatively thin liquids. Acid-modified starches which are obtained by heating an aqueous starch suspension below the gelatinization temperature in the presence of small amounts of acid are also suitable. Oxidatively modified starches are also suitable.
  • Chromic acid, permanganate, hydrogen peroxide, nitrogen dioxide, hypochlorite or periodic acid can be used as the oxidizing agent.
  • all native starches such as cereal starches (e.g. corn, wheat, rice or millet), tuber and root starches (e.g. potatoes, tapioca roots or arrowroot) or sago starches are suitable as starting starches.
  • roasted dextrins as described, for example, in EP-A 408 099 and in EP-A 334 515. They can be obtained by heating moist-dry starch, usually in the presence of small amounts of acid.
  • Typical roasted dextrins are, for example, commercially available white and yellow dextrins; these also include dextrins, which are sold under the trademarks Noredux ® and Tackidex ® .
  • dextrin is used here generally for starch breakdown products.
  • the radical emulsion polymerization is carried out with very particular advantage in the presence of saccharified starches. This is a starch degradation product obtainable by hydrolysis in the aqueous phase. This gives aqueous polymer dispersions which, in addition to high mechanical and thermal stability, also have good rheological properties even after storage. More detailed information on the production of the starches and starch derivatives mentioned can be found in G.
  • starches and starch derivatives mentioned can be used according to the invention in a form which is chemically modified, for example, by etherification or esterification become.
  • This chemical modification can be carried out on the starch before it is broken down or afterwards. Esterifications are possible with both inorganic and organic acids, their anhydrides or chlorides. Phosphated and acetylated derivatives are of particular interest.
  • the most common method of etherification is treatment with organic halogen compounds, epoxides or sulfates in an aqueous alkaline solution.
  • Particularly suitable ethers are alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers and allyl ethers. Cyanoalkylated derivatives and reaction products with 2,3-epoxypropyltrimethylammonium chloride are also suitable.
  • chemically unmodified products are preferred. Degradation products of cellulose, for example cellobiose and its oligomers, are also suitable.
  • the sugared starches to be used with particular preference in accordance with the invention are commercially available as such (for example the C * PUR products 01906, 01908, 01910, 01912, 01915, 01921, 01924, 01932 or 01934 from Cerestar).
  • Such saccharified starches differ chemically from the roasted dextrins in that hydrolytic degradation in an aqueous medium (usually suspensions or solutions), which as a rule at a solids content of 10 to 30% by weight and preferably acid or enzyme catalysis is carried out, the possibility of recombination and branching is essentially not given, which is not least expressed in other molecular weight distributions.
  • sugared starches which have a bimodal molecular weight distribution have proven to be particularly advantageous according to the invention.
  • the production of sugared starches is generally known and is described, inter alia, in G. Tegge, Starch and Starch Derivatives, Behr's Verlag, Hamburg 1984, p. 173 and p. 220 ff., And in EP-A 441 197.
  • the saccharified starches are normally completely soluble in water at room temperature, the solubility limit generally being above 50% by weight, which has proven to be particularly advantageous for the preparation of the aqueous polymer dispersions.
  • the proportion by weight of the saccharified starches, which has a molecular weight below 1000 is at least 10% by weight, but not more than 70% by weight.
  • aqueous polymer dispersions are obtained in their property profile when using saccharified starches, the 40 wt .-% aqueous solutions at 25 ° C and a shear rate of 75 s -1 one according to DIN 53 019 determined dynamic viscosity ⁇ 40 [Pa-sl from 0.005 to 0.06, preferably from 0.005 to 0.03.
  • the solids content of the polymer dispersions obtained is preferably 40 to 80, particularly preferably 45 to 75% by weight.
  • the dispersion of the free-radically polymerized polymer contains a polyisocyanate as a crosslinking agent.
  • Crosslinking occurs with the hydroxyl groups of the protective colloid.
  • the polyisocyanate Due to the crosslinking reaction that occurs, the polyisocyanate is only added before the later use of the dispersion, e.g. as an adhesive, in particular laminating adhesive. Sufficient time remains after the addition of the polyisocyanate, generally more than 48 hours for processing.
  • the polyisocyanates are in particular (cyclo) aliphatic or aromatic diisocyanates or higher functional polyisocyanates which are derived from the diisocyanates.
  • the polyisocyanates used are, for example, linear or branched C 4 -C 4 -alkylene diisocyanates, cycloaliphatic diisocyanates with a total of 6 to 12 C atoms, aromatic diisocyanates with a total of 8 to 14 C atoms, polyisocyanates containing isocyanurate groups, uretdione diisocyanates, and polyurides containing biuret groups ⁇ cyanates, polyisocyanates containing urethane or allophanate groups, polyisocyanates containing oxadiazinetrione groups, uretonimine-modified polyisocyanates or mixtures thereof.
  • diisocyanates a) include Tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octarethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1,4-diisocyanate, such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diis
  • polyisocyanates are multinuclear homologs of the aromatic diisocyanates mentioned above.
  • the corresponding isocyanato-isocyanurates based on hexamethylene diisocyanate and isophorone diisocyanate are particularly preferred.
  • the present isocyanurates are, in particular, simple tris-isocyanatoalkyl or tris-isocyantocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologues containing more than one isocyanurate ring.
  • the isocyanato-isocyanurates generally have an NCO content of 10 to 30% by weight, in particular 15 to 25% by weight, and an average NCO functionality of 3 to 4.5.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • polyisocyanates containing biuret groups with aromatic, preferably aliphatically bound, isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues are polyisocyanates containing biuret groups with aromatic, preferably aliphatically bound, isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues.
  • These biuret groups containing polyisocyanates generally have an NCO content of 18 to 22% by weight and an average NCO functionality of 3 to 3.5 or 4.5.
  • polyisocyanates containing urethane and / or allophanate groups with aromatic, preferably aliphatic or cycloaliphatic, bonded isocyanate groups such as, for example, by reacting excess amounts of hexamethylene diisocyanate or of isophorone diisocyanate with simple polyhydric alcohols such as, for example, Trimethylolpropane,
  • Glycerin, 1,2-dihydroxypropane or mixtures thereof can be obtained.
  • These polyisocyanates containing urethane and / or allophanate groups generally have an NCO content of 12 to 20% by weight and an average NCO functionality of 2.5 to 3.
  • Polyisocyanates containing oxadiazinetrione groups preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Such polyisocyanates containing oxadiazinetrione groups can be prepared from diisocyanate and carbon dioxide.
  • the polyisocyanates a) to f) can also be used in a mixture, if appropriate also in a mixture with diisocyanates.
  • Aliphatic or cycloaliphatic polyisocyanates or diisocyanates are preferred.
  • Hydrophilically modified polyisocyanates which are self-dispersible in water are particularly preferred.
  • the polyisocyanates described above are reacted with compounds which have at least one, preferably a hydrophilic group, which can be ionic or nonionic, and at least one, preferably one, isocyanate-reactive groups, for example one Have hydroxyl, mercapto or primary or secondary amino group (NH group for short).
  • the hydrophilic group can e.g. are an ionic group or a group which can be converted into an ionic group.
  • Anionic or convertible groups are e.g. Carboxylic acid or sulfonic acid groups.
  • Suitable compounds are e.g. Hydroxycarboxylic acids, such as hydroxypivalic acid or dimethylolpropionic acid or hydroxy or amine sulfonic acids.
  • Cationic or convertible groups are e.g. quaternary ammonium groups or tertiary amino groups.
  • Groups which can be converted into ionic groups are preferably converted into ionic groups before or during the dispersion of the mixture according to the invention in water.
  • inorganic and / or organic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydrogen carbonate, ammonia or primary, secondary and particularly tertiary amines, e.g. Triethylamine or dimethylamino propanol can be used.
  • Ammonium groups are inorganic or organic acids, e.g. Hydrochloric acid, acetic acid, fumaric acid, maleic acid, lactic acid, tartaric acid, oxalic acid or phosphoric acid or as quaternizing agent, e.g. Methyl chloride, methyl iodide, dimethyl sulfate, benzyl chloride, chloroacetate or bromoacetamide are suitable.
  • Other suitable neutralizing and quaternizing agents are e.g. in U.S. Patent No. 3,479,310, column 6.
  • the content of the ionic groups or groups which can be converted into ionic groups is preferably 0.1 to 3 mol per kg of the self-dispersible polyisocyanates.
  • Nonionic groups are, for example, polyalkylene ether groups, in particular those with 10 to 80 alkylene oxide units.
  • Polyethylene ether groups or polyalkylene ether groups are preferred which, in addition to other alkylene oxide units, for example propylene oxide, contain at least 10 ethylene oxide units.
  • Suitable compounds are, for example, polyalkylene ether alcohols.
  • the content of the hydrophilic nonionic groups, in particular the polyalkylene ether groups, is preferably 0.5 to 20, particularly preferably 1 to 15% by weight, based on the self-dispersible polyisocyanates.
  • the preparation of the self-dispersible polyisocyanates is known from DE-A-35 21 618, DE-A-40 01 783 and DE-A-42 03 510.
  • the compounds having at least one hydrophilic group and at least one isocyanate-reactive group can be reacted with part of the polyisocyanate and the hydrophilic modified polyisocyanates obtained can then be mixed with the other polyisocyanates.
  • the preparation can also be carried out by adding the compounds to the total amount of the polyiscoyanates and then carrying out the reaction "in situ".
  • Preferred water-emulsifiable polyisocyanates are those with hydrophilic, nonionic groups, in particular polyalkylene ether groups.
  • the water emulsifiability is preferably achieved solely by the hydrophilic nonionic groups.
  • the amount of the polyisocyanates is preferably 0.1 to
  • the dispersion according to the invention is particularly suitable as an adhesive, preferably as a laminating adhesive, for large-area bonding of substrates.
  • the dispersion can contain other conventional additives, e.g. Contain wetting agents, thickeners, protective colloids, light stabilizers, biocides.
  • the dispersion according to the invention is preferably applied to the large-area substrates with a layer thickness of 0.1 to 20, particularly preferably 2 to 7 g / m 2, for example by knife coating, brushing, etc.
  • the coated substrate can then be laminated with a second substrate, the temperature being, for example, 20 to 200, preferably 20 to 70 ° C. and the pressure, for example 1 to 30 , preferably 3 to 20 N / m 2 .
  • Suitable substrates are e.g. Polymer films, especially made of polyethylene, oriented polypropylene, polyamide, polyethylene terephthalate, polyacetate, cellophane etc., or also paper or metal foils, especially made of aluminum.
  • the polymer films are glued to one another (composite film lamination) or also transparent polymer films with paper (glossy film lamination), in particular polymer films or paper with metal foils, e.g. Aluminum foils to be glued.
  • the bonded composites also show high resistance to boiling water.
  • the dispersions according to the invention are also free of fine coagulate and are therefore also suitable for producing transparent film composites.
  • Solids content of the aqueous polymer dispersion (measured according to DIN 53 189): 54.2% by weight.
  • a mixture of 311.11 g of water and 30 g of maltodextrin C * PUR 01915 is heated to 85 ° C. and 10% by weight of feed 1 and 10% by weight of feed 2 are added. It is polymerized for 15 minutes at 85 ° C. and then the metering of the remaining amounts of feeds 1 and 2 is started. The addition takes place continuously over 3 hours (feed 1) and 3.5 hours (feed 2). The mixture is then polymerized at 85 ° C for 1 hour.
  • Feed 1 150 g of water 8 g of sodium lauryl sulfonate (15% in water)
  • Feed 2 50 g of water
  • Solids content of the aqueous polymer dispersion (measured according to DIN 53 189): 55.1% by weight.
  • Feed 2 50 g of water
  • Solids content of the aqueous polymer dispersion (measured according to DIN 53 189): 54.9% by weight.
  • a mixture of 311.11 g of water and 30 g of maltodextrin C * PUR 01915 is heated to 85 ° C. and mixed with 10% by weight of feed 1 and 10% by weight of feed 2. It is polymerized for 15 minutes at 85 ° C. and then the metering of the remaining amounts of feeds 1 and 2 is started. The addition takes place continuously over 3 hours (feed 1) and 3.5 hours (feed 2). The mixture is then polymerized at 85 ° C for 1 hour.
  • Feed 1 150 g of water
  • Feed 2 50 g of water and 1.8 g of sodium peroxodisulfate
  • Solids content of the aqueous polymer dispersion (measured in accordance with DIN 53 189): 54% by weight.
  • Feed 2 50 g of water
  • Feed 3 50 g of water
  • Feed 4 100 g of water
  • Solids content of the aqueous polymer dispersion 51% by weight.
  • 262 g of demineralized water, 35 g of feed 1 (see below) and 20 g of feed 2 are placed in a reaction vessel with stirrer and two feed vessels (feed 1 and feed 2) and heated to 85.degree. After 15 minutes, feed 1 is uniformly added to the reaction vessel over the course of 2 h and feed 2 is uniformly added over the course of 2.5 h. After the last addition of initiator (feed 2), the dispersion is stirred at 85 ° C. for 1 hour. After the polymerization, 50 g of a 20 wt. -% solution of the emulsifier p-isononylphenol polyoxyethylene (4) sodium sulfate was added to the dispersion and stirred.
  • Feed 1 (this feed is stirred during the polymerization)
  • Feed 2 100 g of demineralized water and 5 g of sodium persulfate.
  • the film composites obtained were then stored for 7 days at room temperature and normal climate and then cut into strips 2 cm wide. These strips were then peeled off at 23 ° C at an angle of 180 ° at a speed of 100 m / min. The peeling force in N was determined for the 15 mm wide strips. Results can be found in Table 1.
  • the film composites obtained according to the above procedure were stored at room temperature for 7 days and then boiled for 30 minutes.

Abstract

Described are dispersions of radical-polymerized polymers, the dispersions containing a polyisocyanate as the crosslinking agent. The dispersions are characterized in that the polymer is obtained by the emulsion polymerization of ethylenically unsaturated monomers in the presence of a protective colloid containing hydroxyl groups.

Description

Stärkehaltige Polymerdispersionen und ihre Verwendung als KaschierklebstoffStarch-containing polymer dispersions and their use as laminating adhesives
Beschreibungdescription
Die Erfindung betrifft eine Dispersion eines radikalisch polyme- risierten Polymeren, enthaltend ein Polyisocyanat als Vernetzer, gekennzeichnet dadurch, daß das Polymer durch Emulsionspolymeri- sation von ethylenisch ungesättigten Monomeren in Gegenwart eines Hydroxylgruppen oder primäre oder sekundäre Aminogruppen ent¬ haltenden Schutzkolloids erhältlich ist.The invention relates to a dispersion of a free-radically polymerized polymer containing a polyisocyanate as crosslinking agent, characterized in that the polymer is obtainable by emulsion polymerization of ethylenically unsaturated monomers in the presence of a protective colloid containing hydroxyl groups or primary or secondary amino groups.
An Kaschierklebstoffe werden in der Praxis eine Vielzahl von un- terschiedlichen Anforderungen gestellt. Insbesondere ist ge¬ wünscht, daß Kaschierklebstoffe universell einsetzbar sind, d.h. sie sollen sich gleichermaßen für die Kaschierung von unter¬ schiedlichen Polymerfolien, z.B. aus Polyethylen (PE) , orientier¬ tem Propylen (OPP) , Polyamid (PA) oder Polyethylenterephthalat (PETP) miteinander und auch für Kaschierung von Polymerfolien mit Papier oder insbesondere auch mit Aluminiumfolien eignen.A large number of different requirements are placed on laminating adhesives in practice. In particular, it is desired that laminating adhesives can be used universally, i.e. they are equally intended for the lamination of different polymer films, e.g. made of polyethylene (PE), oriented propylene (OPP), polyamide (PA) or polyethylene terephthalate (PETP) with one another and also suitable for laminating polymer films with paper or in particular also with aluminum films.
Dementsprechend sollen die Kaschierklebstoffe zu all diesen Sub¬ straten eine gute Haftung aufweisen und nach der Kaschierung eine hohe Festigkeit der erhaltenen Folienverbunde bewirken.Accordingly, the lamination adhesives should have good adhesion to all of these substrates and, after lamination, have a high strength in the film composites obtained.
Da die Folienverbunde oft transparent sind, müssen die Kaschier¬ klebstoffe auch frei sein von feinem Koagulat sowie alterungs- lichtbeständig und schaumarm sein.Since the film composites are often transparent, the laminating adhesives must also be free of fine coagulate, resistant to aging light and low-foaming.
Die Verarbeitung in den Kaschieranlagen setzt eine hohe Scher- Stabilität und gute Fließeigenschaften voraus. Darüberhinaus sind zur Vermeidung von Lösemittelabfällen und -emissionen grundsätz¬ lich wäßrige Systeme gewünscht.Processing in the laminating plants requires high shear stability and good flow properties. In addition, in order to avoid solvent wastes and emissions, aqueous systems are generally desired.
Aus der US-A-4 609 690 sind Dispersionen von radikalisch polyme- risierten Polymeren, welche Polyisocyanate als Vernetzer enthal¬ ten, bekannt. Sie werden als Klebstoffe zur Herstellung von Sperrholz verwendet.US Pat. No. 4,609,690 discloses dispersions of free-radically polymerized polymers which contain polyisocyanates as crosslinking agents. They are used as adhesives for the production of plywood.
In der DE-A-40 36 927 werden spezielle Polyisocyanate beschrie¬ ben, welche als Vernetzer in Polymerdispersionen Verwendung fin¬ den. Die Polymerdispersionen werden auch zur Verklebung von Polymerfolien eingesetzt. Aus der DE-A-4 133 193 war bereits die Herstellung von Polymer¬ dispersionen durch radikalische Polymerisation von ethylenisch ungesättigten Monomeren in GEgenwart von Stärke bekannt.DE-A-40 36 927 describes special polyisocyanates which are used as crosslinking agents in polymer dispersions. The polymer dispersions are also used to bond polymer films. DE-A-4 133 193 has already disclosed the preparation of polymer dispersions by radical polymerization of ethylenically unsaturated monomers in the presence of starch.
In der EP-A-206 059 wird der Zusatz von Polyisocyanaten zu wäßrigen Polymerdispersionen beschrieben. Diesen Polymer- dispersionen kann als Verdickungsmittel u.a. auch Stärke zuge¬ setzt werden. Die Dispersionen werden als Klebstoffe verwendet.EP-A-206 059 describes the addition of polyisocyanates to aqueous polymer dispersions. These polymer dispersions can, among other things, be used as thickeners. starch can also be added. The dispersions are used as adhesives.
Die eingangs beschriebenen Anforderungen an Kaschierklebstoffe werden von keiner der voranstehenden Polymerdispersionen im ge¬ wünschten Ausmaß erfüllt.The requirements described above for laminating adhesives are not met to the desired extent by any of the above polymer dispersions.
Aufgabe der vorliegenden Erfindung war daher eine Polymer- dispersion, die sich als Kaschierklebstoff für unterschiedlichste Substrate, z.B. Polymerfolien oder Aluminiumfolien eignet und die oben beschriebenen Anforderungen im hohen Maße erfüllt.The object of the present invention was therefore a polymer dispersion which can be used as a laminating adhesive for a wide variety of substrates, e.g. Polymer foils or aluminum foils are suitable and meet the requirements described above to a high degree.
Demgemäß wurde die oben beschriebene Polymerdispersion und ihre Verwendung als Kaschierklebstoff gefunden.Accordingly, the polymer dispersion described above and its use as a laminating adhesive have been found.
Die Dispersion des radikalisch polymerisierten Polymeren ist er¬ hältlich durch radikalische Polymerisation von ethylenisch ungesättigten Monomeren in Gegenwart eines Hydroxylgruppen ent- haltenden Schutzkolloids.The dispersion of the free-radically polymerized polymer can be obtained by free-radical polymerization of ethylenically unsaturated monomers in the presence of a protective colloid containing hydroxyl groups.
Das erhaltene Polymer besteht vorzugsweise aus sogenannten Haupt- monomeren, ausgewählt aus C1-C20-Alkyl(meth)acrylaten, Vinylestern von bis zu 20 C-Atome enthaltenden Carbonsäuren, Vinylaromaten mit bis zu 20 C-Atomen, ethylenisch ungesättigten Nitrilen, Vinylhalogeniden, nicht aromatischen Kohlenwasserstoffen mit mindestens 2 konjugierten Doppelbindungen oder Mischungen dieser Monomeren.The obtained polymer is preferably made of so-called main monomers selected from C1-C2 0 alkyl (meth) acrylates, Vinylestern of up to 20 carbon atoms-containing carboxylic acids, vinyl aromatics with up to 20 C atoms, ethylenically unsaturated nitriles, vinyl halides , non-aromatic hydrocarbons with at least 2 conjugated double bonds or mixtures of these monomers.
Die vorstehend genannten Monomeren können z.B. zu 60 bisThe above monomers can e.g. to 60 to
100 Gew.-%, vorzugsweise 80 bis 100 Gew. -%, im Polymer enthalten sein.100% by weight, preferably 80 to 100% by weight, can be contained in the polymer.
Zu nennen sind z.B. (Meth)acrylsäurealkylester mit einem Ci-Cio-Alkylrest, wie Methylmethacrylat, Methylacrylat, n-Butyl¬ acrylat, Ethylacrylat und 2-Ethylhexylacrylat.Examples include (Meth) acrylic acid alkyl esters with a Ci-Cio-alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
Insbesondere sind auch Mischungen der (Meth)acrylsäurealkylester geeignet. Vinylester von Carbonsäuren mit 1 bis 20 C-Atomen sind z.B. Vinyllaurat, -stearat, Vinylpropionat, Versaticsäurevinylester und Vinylacetat.Mixtures of the (meth) acrylic acid alkyl esters are also particularly suitable. Vinyl esters of carboxylic acids with 1 to 20 C atoms are, for example, vinyl laurate, stearate, vinyl propionate, vinyl versatic acid and vinyl acetate.
Als vinylaromatische Verbindungen kommen Vinyltoluol, α- und p-Methylstyrol, α-Butylstyrol, 4-n-Butylstyrol, 4-n-Decylstyrol und vorzugsweise Styrol in Betracht. Beispiele für Nitrile sind Acrylnitril und Methacrylnitril.Suitable vinyl aromatic compounds are vinyl toluene, α- and p-methylstyrene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene. Examples of nitriles are acrylonitrile and methacrylonitrile.
Die Vinylhalogenide sind mit Chlor, Fluor oder Brom substituierte ethylenisch ungesättigte Verbindungen, bevorzugt Vinylchlorid und Vinylidenchlorid.The vinyl halides are chlorine, fluorine or bromine-substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
Als nicht aromatische Kohlenwasserstoffe mit 2 bis 8 C-Atomen und mindestens zwei olefinischen Doppelbindungen seien Butadien, Isopren, und Chloropren genannt.Butadiene, isoprene and chloroprene may be mentioned as non-aromatic hydrocarbons having 2 to 8 carbon atoms and at least two olefinic double bonds.
Besonders bevorzugt besteht das Polymer zu mindestens 60 Gew. -% aus (Meth)acrylalkylsäureester und deren Mischungen.The polymer particularly preferably consists of at least 60% by weight of (meth) acrylic alkyl acid esters and mixtures thereof.
Weitere Monomere, die z.B. von 0 bis 40 Gew. -%, vorzugsweise von 0 bis 20 Gew.-% im Polymer enthalten sein können, sind ins¬ besondere Ci-Cio-Hydroxyalkyl (meth)acrylate, (Meth)acrylamid sowie dessen am Stickstoff mit Cι-C4-Alkyl substituierten Derivaten.Further monomers which can be present in the polymer for example from 0 to 40% by weight, preferably from 0 to 20% by weight, are in particular Ci-Cio-hydroxyalkyl (meth) acrylates, (meth) acrylamide and its am Nitrogen with C 1 -C 4 -alkyl-substituted derivatives.
Desweiteren können z.B. auch ethylenisch ungesättigte Monomere mit Carbonsäuregruppen wie (Meth)acrylsaure, Maleinsäure, ethylenisch ungesättigte Säureanhydride oder Halbester, wie Maleinsäureanhydrid oder Maleinsäure- bzw. Fumarsäurehalbester im Polymer enthalten sein.Furthermore, e.g. The polymer can also contain ethylenically unsaturated monomers with carboxylic acid groups such as (meth) acrylic acid, maleic acid, ethylenically unsaturated acid anhydrides or half esters, such as maleic anhydride or maleic acid or fumaric acid semiesters.
Die Glasübergangstemperatur des Polymeren läßt sich nach üblichen Methoden wie Differentialthermoanalyse oder Differential Scanning Calorimetrie (s. z.B. ASTM 3418/82, sog. "midpoint temperature") bestimmen.The glass transition temperature of the polymer can be determined by conventional methods such as differential thermal analysis or differential scanning calorimetry (see e.g. ASTM 3418/82, so-called "midpoint temperature").
Die Glasübergangstemperatur des Polymeren liegt bevorzugt unter 60°C, insbesondere beträgt sie -50 bis +60°C, besonders bevorzugt -30 bis +40°C und ganz besonders bevorzugt -30 bis +20°C.The glass transition temperature of the polymer is preferably below 60 ° C, in particular it is -50 to + 60 ° C, particularly preferably -30 to + 40 ° C and very particularly preferably -30 to + 20 ° C.
Die Herstellung des Polymeren erfolgt vorzugsweise durch Emul' sionspolymerisation.The polymer is preferably produced by emulsion polymerization.
Die Emulsionspolymerisation kann diskontinuierlich, mit oder ohne Verwendung von Saatlatices, unter Vorlage aller oder einzelner Bestandteile des Reaktionsgemisches, oder bevorzugt unter teil¬ weiser Vorlage und Nachdosierung der oder einzelner Bestandteile des Reaktionsgemisches, oder nach dem Dosierverfahren ohne Vor¬ lage durchgeführt werden.The emulsion polymerization can be carried out batchwise, with or without the use of seed latices, with presentation of all or individual components of the reaction mixture, or preferably with partial delivery and subsequent metering of the or individual components of the reaction mixture, or by the dosing method without a template.
Die Monomeren können bei der Emulsionspolymerisation wie üblich in Gegenwart eines wasserlöslichen Initiators und eines Emul¬ gators bei vorzugsweise 30 bis 95°C polymerisiert werden.The monomers can be polymerized in the emulsion polymerization, as usual, in the presence of a water-soluble initiator and an emulsifier at preferably 30 to 95 ° C.
Geeignete Initiatoren sind z.B. Natrium-, Kalium- und Ammonium¬ persulfat, tert. -Butylhydroperoxide, wasserlösliche Azover- bindungen oder auch Redoxinitiatoren wie H202/Ascorbinsäure.Suitable initiators are, for example, sodium, potassium and ammonium persulfate, tert. -Butyl hydroperoxides, water-soluble azo compounds or redox initiators such as H 2 0 2 / ascorbic acid.
Als Emulgatoren dienen z.B. Alkalisalze von längerkettigen Fett¬ säuren, Alkylsulfate, Alkylsulfonate, alkylierte Arylsulfonate oder alkylierte Biphenylethersulfonate. Des weiteren kommen als Emulgatoren Umsetzungsprodukte von Alkylenoxiden, insbesondere Ethylen- oder Propylenoxid mit Fettalkoholen, -säuren oder Phenol, bzw. Alkylphenolen in Betracht.E.g. serve as emulsifiers Alkali salts of longer-chain fatty acids, alkyl sulfates, alkyl sulfonates, alkylated aryl sulfonates or alkylated biphenyl ether sulfonates. Other suitable emulsifiers are reaction products of alkylene oxides, in particular ethylene or propylene oxide, with fatty alcohols, fatty acids or phenol, or alkylphenols.
Die Menge der Emulgatoren beträgt insbesondere 0 bis 10 Gew. -%, bevorzugt 0,05 bis 5 Gew. -% und besonders bevorzugt 0,05 bis 2 Gew. -%, bezogen auf das Polymer.The amount of emulsifiers is in particular 0 to 10% by weight, preferably 0.05 to 5% by weight and particularly preferably 0.05 to 2% by weight, based on the polymer.
Zur Einstellung des Molekulargewichts können bei der Polymerisa¬ tion Regler eingesetzt werden. Geeignet sind z.B. -SH enthaltende Verbindungen wie Mercaptoethanol, Mercaptopropanol, Thiophenol, Thioglycerin, Thioglykolsäureethylester, Thioglykolsäuremethyl- ester und tert.-Dodecylmercaptan.Regulators can be used in the polymerization to adjust the molecular weight. Suitable are e.g. -SH-containing compounds such as mercaptoethanol, mercaptopropanol, thiophenol, thioglycerin, ethyl thioglycolate, methyl thioglycolate and tert-dodecyl mercaptan.
Die Emulsionspolymerisation wird in Gegenwart eines Schutz- kolloids vorgenommen, welches Hydroxylgruppen oder primäre oder sekundäre Aminogruppen enthält.The emulsion polymerization is carried out in the presence of a protective colloid which contains hydroxyl groups or primary or secondary amino groups.
Das Schutzkolloid kann bei der Emulsionspolymerisation vorgelegt werden, zum Teil vorgelegt und zudosiert oder ganz während der Emulsionspolymerisation zudosiert werden. Vorteilhafterweise ent¬ hält der Polymerisationsansatz bei einem erreichten Umsatz von 80 % der zu polymerisierenden Monomeren mindestens die Hälfte der gesamten Schutzkolloidmenge. Besonders bevorzugt wird die gesamte Schutzkolloidmenge bei der Polymerisation vorgelegt.The protective colloid can be introduced during the emulsion polymerization, partly introduced and metered in, or added entirely during the emulsion polymerization. When the conversion of 80% of the monomers to be polymerized is reached, the polymerization batch advantageously contains at least half of the total amount of protective colloid. The total amount of protective colloid is particularly preferably introduced during the polymerization.
Die Gesamtmenge des Schutzkolloids beträgt vorzugsweise 0,1 bis 50 Gew. -%, besonders bevorzugt 1 bis 20 Gew.-% und ganz besonders bevorzugt 2 bis 10 Gew. -%, bezogen auf das Polymer.The total amount of the protective colloid is preferably 0.1 to 50% by weight, particularly preferably 1 to 20% by weight and very particularly preferably 2 to 10% by weight, based on the polymer.
Das Schutzkolloid kann nur Hydroxylgruppen, nur primäre oder nur sekundäre Aminogruppen enthalten. Das Schutzkolloid kann jedoch auch sowohl Hydroxylgruppen als auch primäre bzw. als auch sekun- däre Aminogruppen enthalten. Die Gewichtsmenge der insgesamt ent¬ haltenen Hydroxylgruppen, primären oder sekundären Aminogruppen (wobei Hydroxylgruppen als OH und primäre oder sekundäre Amino¬ gruppen beide als NH berechnet werden) beträgt vorzugsweise 0,1 bis 60 Gew. -%, vorzugsweise 2 bis 50 Gew.-%, bezogen auf das Schutzkolloid.The protective colloid can contain only hydroxyl groups, only primary or only secondary amino groups. However, the protective colloid can also contain hydroxyl groups as well as primary or second contain amino groups. The amount by weight of the total hydroxyl groups, primary or secondary amino groups (hydroxyl groups as OH and primary or secondary amino groups are both calculated as NH) is preferably 0.1 to 60% by weight, preferably 2 to 50% by weight. %, based on the protective colloid.
Als Schutzkolloide zu nennen sind z.B. Polysaccharide wie Stärken oder Cellulosen, Polyvinylalkohol oder Gelatine.Protective colloids are e.g. Polysaccharides such as starches or celluloses, polyvinyl alcohol or gelatin.
Das gewichtsmittlere Molgewicht der Schutzkolloide beträgt vor¬ zugsweise 500 bis 50000 und besonders bevorzugt von 1000 bis 25000, meßbar durch Gelpermentionschromatographie.The weight-average molecular weight of the protective colloids is preferably from 500 to 50,000 and particularly preferably from 1,000 to 25,000, which can be measured by gel chromatography.
Bevorzugte Schutzkolloide sind Polysaccharide, besonders bevor¬ zugt sind Stärken.Preferred protective colloids are polysaccharides, starches are particularly preferred.
Die Polysaccharide können pflanzlichen oder tierischen Ursprungs, in Wasser löslich oder nur darin dispergierbar sein. Geeignet sind u.a. die sogenannten Quellstärken, die beispielsweise durch hydrothermische Behandlung von nativer Stärke erhältlich sind. Ferner eignen sich dünnkochende Stärken. Es handelt es dabei um mit Säuren oder Enzymen geringfügig abgebaute oder mit milden Oxidationsmitteln oxidierte Stärken, die auch in höheren Konzen- trationen beim Kochen mit Wasser keine viskosen Kleister, sondern relativ dünne Flüssigkeiten ergeben. Außerdem sind säuremodifi¬ zierte Stärken geeignet, die durch Erwärmen einer wäßrigen Stärkesuspension unterhalb der Verkleisterungstemperatur in Gegenwart geringer Säuremengen gewonnen werden. Weiterhin kommen oxidativ modifizierte Stärken in Betracht. Als Oxidationsmittel können z.B. Chromsäure, Permanganat, Wasserstoffperoxid, Stick¬ stoffdioxid, Hypochlorit oder Perjodsäure herangezogen werden. Als Ausgangsstärken sind prinzipiell alle nativen Stärken wie Getreidestärken (z.B. Mais, Weizen, Reis oder Hirse), Knollen- und Wurzelstärken (z.B. Kartoffeln, Tapiokawurzeln oder Arrow- root) oder Sagostärken geeignet. Vorteilhaft ist die Verwendung von Röstdextrinen, wie sie z.B. in der EP-A 408 099 sowie in der EP-A 334 515 beschrieben sind. Sie sind durch Erhitzen von feuchttrockner Stärke, meist in Anwesenheit geringer Mengen Säure, erhältlich. Typische Röstdextrine sind z.B. im Handel erhältliche Weiß- und Gelbdextrine; ferner zählen dazu Dextrine, die unter dem Warenzeichen Noredux® und Tackidex® vertrieben werden. Der Begriff Dextrin wird hier ganz generell für Stärke- abbauprodukte verwendet. Mit ganz besonderem Vorteil wird jedoch die radikalische Emul¬ sionspolymerisation in Gegenwart von verzuckerten Stärken durch¬ geführt. Hierbei handelt es sich um ein durch Hydrolyse in wä߬ riger Phase erhältliches Stärkeabbauprodukt. Hierbei werden wäß- rige Polymerdispersionen erhalten, die neben hoher mechanischer und thermischer Stabilität auch gute rheologische Eigenschaften auch nach Lagerung aufweisen. Detailliertere Angaben zur Her¬ stellung der genannten Stärken und Stärkederivate findet man in G. Tegge, Stärke und Stärkederivate, Behr's Verlag, Hamburg 1984. Selbstverständlich können die genannten Stärken und Stärkederi¬ vate in z.B. durch Veretherung oder Veresterung chemisch modi¬ fizierter Form erfindungsgemäß angewendet werden.The polysaccharides can be of vegetable or animal origin, soluble in water or only dispersible therein. Suitable are, among other things, the so-called swelling starches, which can be obtained, for example, by hydrothermal treatment of native starch. Thin-boiling starches are also suitable. These are starches that have been slightly degraded with acids or enzymes or that have been oxidized with mild oxidizing agents. Even in higher concentrations, when boiling with water, they do not produce viscous paste, but rather relatively thin liquids. Acid-modified starches which are obtained by heating an aqueous starch suspension below the gelatinization temperature in the presence of small amounts of acid are also suitable. Oxidatively modified starches are also suitable. Chromic acid, permanganate, hydrogen peroxide, nitrogen dioxide, hypochlorite or periodic acid can be used as the oxidizing agent. Basically, all native starches such as cereal starches (e.g. corn, wheat, rice or millet), tuber and root starches (e.g. potatoes, tapioca roots or arrowroot) or sago starches are suitable as starting starches. It is advantageous to use roasted dextrins, as described, for example, in EP-A 408 099 and in EP-A 334 515. They can be obtained by heating moist-dry starch, usually in the presence of small amounts of acid. Typical roasted dextrins are, for example, commercially available white and yellow dextrins; these also include dextrins, which are sold under the trademarks Noredux ® and Tackidex ® . The term dextrin is used here generally for starch breakdown products. However, the radical emulsion polymerization is carried out with very particular advantage in the presence of saccharified starches. This is a starch degradation product obtainable by hydrolysis in the aqueous phase. This gives aqueous polymer dispersions which, in addition to high mechanical and thermal stability, also have good rheological properties even after storage. More detailed information on the production of the starches and starch derivatives mentioned can be found in G. Tegge, Starch and Starch Derivatives, Behr's Verlag, Hamburg 1984. Of course, the starches and starch derivatives mentioned can be used according to the invention in a form which is chemically modified, for example, by etherification or esterification become.
Diese chemische Modifizierung kann bereits an der Ausgangsstärke vor deren Abbau oder danach durchgeführt werden. Veresterungen sind sowohl mit anorganischen als auch mit organischen Säuren, deren Anhydriden oder Chloriden möglich. Von besonderem Interesse sind phosphatierte und acetylierte Derivate. Die gängigste Methode zur Veretherung ist die Behandlung mit organischen Halo- genverbindungen, Epoxiden oder Sulfaten in wäßriger alkalischer Lösung. Besonders geeignete Ether sind Alkylether, Hydroxyalkyl- ether, Carboxyalkylether und Allylether. Ferner kommen cyanalky- lierte Derivate sowie Umsetzungsprodukte mit 2,3-Epoxipropyl- trimethylammoniumchlorid in Betracht. Chemisch nicht modifizierte Produkte sind jedoch bevorzugt. Geeignet sind auch Abbauprodukte der Cellulose, beispielsweise Cellobiose und ihre Oligomeren.This chemical modification can be carried out on the starch before it is broken down or afterwards. Esterifications are possible with both inorganic and organic acids, their anhydrides or chlorides. Phosphated and acetylated derivatives are of particular interest. The most common method of etherification is treatment with organic halogen compounds, epoxides or sulfates in an aqueous alkaline solution. Particularly suitable ethers are alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers and allyl ethers. Cyanoalkylated derivatives and reaction products with 2,3-epoxypropyltrimethylammonium chloride are also suitable. However, chemically unmodified products are preferred. Degradation products of cellulose, for example cellobiose and its oligomers, are also suitable.
Die erfindungsgemäß ganz besonders bevorzugt anzuwendenden ver¬ zuckerten Stärken sind als solche im Handel erhältlich (z.B. die C* PUR Produkte 01906, 01908, 01910, 01912, 01915, 01921, 01924, 01932 oder 01934 der Fa. Cerestar) . Derartige verzuckerte Stärken sind von den Röstdextrinen u.a. dadurch chemisch verschieden, daß bei einem hydrolytischen Abbau in wäßrigem Medium (üblicherweise Suspensionen oder Lösungen), der in der Regel bei Feststoffgehal- ten von 10 bis 30 Gew.% sowie vorzugsweise säure- oder enzymkata¬ lysiert vorgenommen wird, die Möglichkeit der Rekombination und Verzweigung im wesentlichen nicht gegeben ist, was sich nicht zuletzt auch in anderen Molekulargewichtsverteilungen äußert. So haben sich verzuckerte Stärken, die eine bimodale Molekular- gewichtsverteilung aufweisen, erfindungsgemäß als besonders vor¬ teilhaft erwiesen. Die Herstellung verzuckerter Stärken ist allgemein bekannt und u.a. in G. Tegge, Stärke und Stärkederi¬ vate, Behr's Verlag, Hamburg 1984, S. 173 und S. 220 ff., sowie in der EP-A 441 197 beschrieben. Die verzuckerten Stärken sind normalerweise bei Raumtemperatur in Wasser vollständig löslich, wobei die Löslichkeitsgrenze in der Regel oberhalb von 50 Gew.-% liegt, was sich für die Herstellung der wäßrigen Polymerisatdispersionen als besonders vorteilhaft erweist.The sugared starches to be used with particular preference in accordance with the invention are commercially available as such (for example the C * PUR products 01906, 01908, 01910, 01912, 01915, 01921, 01924, 01932 or 01934 from Cerestar). Such saccharified starches differ chemically from the roasted dextrins in that hydrolytic degradation in an aqueous medium (usually suspensions or solutions), which as a rule at a solids content of 10 to 30% by weight and preferably acid or enzyme catalysis is carried out, the possibility of recombination and branching is essentially not given, which is not least expressed in other molecular weight distributions. For example, sugared starches which have a bimodal molecular weight distribution have proven to be particularly advantageous according to the invention. The production of sugared starches is generally known and is described, inter alia, in G. Tegge, Starch and Starch Derivatives, Behr's Verlag, Hamburg 1984, p. 173 and p. 220 ff., And in EP-A 441 197. The saccharified starches are normally completely soluble in water at room temperature, the solubility limit generally being above 50% by weight, which has proven to be particularly advantageous for the preparation of the aqueous polymer dispersions.
Ferner ist es von Vorteil, wenn der Gewichtsanteil der verzucker¬ ten Stärken, der ein Molekulargewicht unterhalb von 1000 auf¬ weist, wenigstens 10 Gew.-%, jedoch nicht mehr als 70 Gew.-% beträgt.It is also advantageous if the proportion by weight of the saccharified starches, which has a molecular weight below 1000, is at least 10% by weight, but not more than 70% by weight.
Darüber hinaus ist es empfehlenswert, solche verzuckerten Stärken anzuwenden, deren Dextroseäquivalent DE 5 bis 40 beträgt. Der DE-Wert charakterisiert das Reduktionsvermögen bezogen auf das Reduktionsvermögen von wasserfreier Dextrose und wird nachIn addition, it is recommended to use sugared starches whose dextrose equivalent DE is 5 to 40. The DE value characterizes the reducing power based on the reducing power of anhydrous dextrose and is
DIN 10 308 Ausgabe 5.71, des Normenausschusses Lebensmittel und landwirtschaftliche Produkte, bestimmt (vgl. auch Günther Tegge, Stärke und Stärkederivate, Behr's Verlag, Hamburg 1984, S. 305).DIN 10 308 Edition 5.71, of the Standards Committee for Food and Agricultural Products (see also Günther Tegge, Starch and Starch Derivatives, Behr's Verlag, Hamburg 1984, p. 305).
Außerdem hat es sich gezeigt, daß in ihrem Eigenschaftsprofil besonders günstige wäßrige Polymerisatdispersionen dann erhalten werden, wenn man verzuckerte Stärken einsetzt, deren 40 gew.-%ige wäßrige Lösungen bei 25°C und einem Schergefälle von 75 s-1 eine nach DIN 53 019 bestimmte dynamische Viskosität η40 [Pa-sl von 0,005 bis 0,06, vorzugsweise von 0,005 bis 0,03, aufweisen.In addition, it has been shown that particularly favorable aqueous polymer dispersions are obtained in their property profile when using saccharified starches, the 40 wt .-% aqueous solutions at 25 ° C and a shear rate of 75 s -1 one according to DIN 53 019 determined dynamic viscosity η 40 [Pa-sl from 0.005 to 0.06, preferably from 0.005 to 0.03.
Der Feststoffgehalt der erhaltenen Polymerdispersionen beträgt vorzugsweise 40 bis 80, besonders bevorzugt 45 bis 75 Gew.-%.The solids content of the polymer dispersions obtained is preferably 40 to 80, particularly preferably 45 to 75% by weight.
Die Dispersion des radikalisch polymerisierten Polymeren enthält ein Polyisocyanat als Vernetzer.The dispersion of the free-radically polymerized polymer contains a polyisocyanate as a crosslinking agent.
Die Vernetzung tritt dabei mit den Hydroxylgruppen des Schutz- kolloids ein.Crosslinking occurs with the hydroxyl groups of the protective colloid.
Der Zusatz des Polyisocyanats erfolgt aufgrund der eintretenden Vernetzungsreaktion erst vor der späteren Verwendung der Disper¬ sion, z.B. als Klebstoff, insbesondere Kaschierklebstoff. Nach Zusatz des Polyisocyanats bleibt ausreichend Zeit, im allgemeinen mehr als 48 Stunden zur Verarbeitung.Due to the crosslinking reaction that occurs, the polyisocyanate is only added before the later use of the dispersion, e.g. as an adhesive, in particular laminating adhesive. Sufficient time remains after the addition of the polyisocyanate, generally more than 48 hours for processing.
Bei den Polyisocyanaten handelt es sich um insbesondere (cyclo)aliphatische oder aromatische Diisocyanate oder höher¬ funktionelle Polyisocyanate, welche sich von den Diisocyanaten ableiten. Als Polyisocyanate kommen z.B. geradlinige oder verzweigte C4-Cι4-Alkylendiisocyanate, cycloaliphatische Diisocyanate mit insgesamt 6 bis 12 C-Atomen, aromatische Diisocyanate mit insge¬ samt 8 bis 14 C-Atomen, Isocyanuratgruppen aufweisende Polyiso- cyanate, Uretdiondiisocyanate, Biuretgruppen aufweisende Polyiso¬ cyanate, Urethan- oder Allophanatgruppen aufweisende Polyiso¬ cyanate, Oxadiazintriongruppen enthaltende Polyisocyanate, Uretonimin-modifizierte Polyisocyanate oder deren Gemische in Betracht.The polyisocyanates are in particular (cyclo) aliphatic or aromatic diisocyanates or higher functional polyisocyanates which are derived from the diisocyanates. The polyisocyanates used are, for example, linear or branched C 4 -C 4 -alkylene diisocyanates, cycloaliphatic diisocyanates with a total of 6 to 12 C atoms, aromatic diisocyanates with a total of 8 to 14 C atoms, polyisocyanates containing isocyanurate groups, uretdione diisocyanates, and polyurides containing biuret groups ¬ cyanates, polyisocyanates containing urethane or allophanate groups, polyisocyanates containing oxadiazinetrione groups, uretonimine-modified polyisocyanates or mixtures thereof.
Als Diisocyanate a) genannt seien z.B. Tetramethylendiisocyanat, Hexamethylendiisocyanat(1,6-Diisocyanatohexan) , Octarnethylendi- isocyanat, Decamethylendiisocyanat, Dodecamethylendiisocyanat, Tetradecamethylendiisocyanat, Trimethylhexandiisocyanat oder Tetramethylhexandiisocyanat, cycloaliphatische Diisocyanate wie 1,4-, 1,3- oder 1,2-Diisocyanatocyclohexan, 4, 4' -Di (isocyanato- cyclohexyl)methan, l-Isocyanato-3, 3, 5-trimethyl-5- (isocyanato- methyl)cyclohexan (Isophorondiisocyanat) oder 2,4- oder 2,6-Diisocyanato-l-methylcyclohexan oder aromatische Diisocyanate wie 2,4-Diisocyanatotoluol, 2, 6-Diisocyanatotoluol, Tetramethyl- xylylendiisocyanat, 1,4-Diisocyanatobenzol, 4,4' - und 2,4-Diiso- cyanatodiphenyIrrtethan, p-Xylylendiisocyanat, sowie Isopropenyldi- methyltoluylendiisocyanat.Examples of diisocyanates a) include Tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octarethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1,4-diisocyanate, such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate such as 1,4-, 1,3-diisocyanate, such as 1,4-diisocyanate, such as 1,4-diisocyanate, 1,4-diisocyanate, such as 1,4-diisocyanate, such as 1,4-diisocyanate, 1,4-diisocyanate, such as 1,4-diisocyanate, 1,4-diisocyanate, such as 1,4-diisocyanate, 1,4-diisocyanate, such as 1,4-diisocyanate, 1,4-diisocyanate, such as 1,4-diisocyanate (isocyanato-cyclohexyl) methane, l-isocyanato-3, 3, 5-trimethyl-5- (isocyanato-methyl) cyclohexane (isophorone diisocyanate) or 2,4- or 2,6-diisocyanato-l-methylcyclohexane or aromatic diisocyanates such as 2 , 4-diisocyanatotoluene, 2, 6-diisocyanatotoluene, tetramethyl-xylylene diisocyanate, 1,4-diisocyanatobenzene, 4,4'- and 2,4-diisocyanate-diphenyirrtethane, p-xylylene diisocyanate, and isopropenyldimethyltoluenediisocyanate.
Als Polyisocyanate seien z.B. mehrkernige Homologe der vorstehend genannten aromatischen Diisocyanate genannt.Examples of polyisocyanates are multinuclear homologs of the aromatic diisocyanates mentioned above.
Weiterhin genannt seien:May also be mentioned:
a) Isocyanuratgruppen aufweisende Polyisocyanate von aromati¬ schen, vorzugsweise aliphatischen und/oder cycloaliphatischen Diisocyanaten. Besonders bevorzugt sind hierbei die entspre¬ chenden Isocyanato-Isocyanurate auf Basis von Hexamethylen¬ diisocyanat und Isophorondiisocyanat. Bei den vorliegenden Isocyanuraten handelt es sich insbesondere um einfache Tris- isocyanatoalkyl- bzw. Tris-isocyantocycloalkyl-Isocyanurate, welche cyclische Trimere der Diisocyanate darstellen, oder um Gemische mit ihren höheren, mehr als einen Isocyanuratring aufweisenden Homologen. Die Isocyanato-Isocyanurate haben im allgemeinen einen NCO-Gehalt von 10 bis 30 Gew. -%, ins¬ besondere 15 bis 25 Gew. -% und eine mittlere NCO-Funktionali¬ tät von 3 bis 4,5. b) Uretdiondiisocyanate mit aromatischen, vorzugsweise alipha- tisch und/oder cycloaliphatisch gebundenen Isocyanatgruppen, vorzugsweise von Hexamethylendiisocyanat oder Isophorondiiso¬ cyanat abgeleitet. Bei Uretdiondiisocyanaten handelt es sich um cyclische Dimerisierungsprodukte von Diisocyanaten.a) polyisocyanates containing isocyanurate groups of aromatic, preferably aliphatic and / or cycloaliphatic diisocyanates. The corresponding isocyanato-isocyanurates based on hexamethylene diisocyanate and isophorone diisocyanate are particularly preferred. The present isocyanurates are, in particular, simple tris-isocyanatoalkyl or tris-isocyantocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologues containing more than one isocyanurate ring. The isocyanato-isocyanurates generally have an NCO content of 10 to 30% by weight, in particular 15 to 25% by weight, and an average NCO functionality of 3 to 4.5. b) uretdione diisocyanates with aromatic, preferably aliphatic and / or cycloaliphatic, bonded isocyanate groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
c) Biuretgruppen aufweisende Polyisocyanate mit aromatischen, vorzugsweise aliphatisch gebundenen Isocyanatgruppen, ins¬ besondere Tris(6-isocyanatohexyl)biuret oder dessen Gemische mit seinen höheren Homologen. Diese Biuretgruppen aufweisen¬ den Polyisocyanate weisen im allgemeinen einen NCO-Gehalt von 18 bis 22 Gew.-% und eine mittlere NCO-Funktionalität von 3 bis 3,5 bzw. 4,5 auf.c) Polyisocyanates containing biuret groups with aromatic, preferably aliphatically bound, isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues. These biuret groups containing polyisocyanates generally have an NCO content of 18 to 22% by weight and an average NCO functionality of 3 to 3.5 or 4.5.
d) Urethan- und/oder Allophanatgruppen aufweisende Polyiso¬ cyanate mit aromatischen, vorzugsweise aliphatisch oder cycloaliphatisch gebundenen Isocyanatgruppen, wie sie bei¬ spielsweise durch Umsetzung von überschüssigen Mengen an Hexamethylendiisocyanat oder an Isophorondiisocyanat mit ein- fachen mehrwertigen Alkoholen wie z.B. Trimethylolpropan,d) polyisocyanates containing urethane and / or allophanate groups with aromatic, preferably aliphatic or cycloaliphatic, bonded isocyanate groups, such as, for example, by reacting excess amounts of hexamethylene diisocyanate or of isophorone diisocyanate with simple polyhydric alcohols such as, for example, Trimethylolpropane,
Glycerin, 1,2-Dihydroxypropan oder deren Gemischen erhalten werden können. Diese Urethan- und/oder Allophanatgruppen auf¬ weisenden Polyisocyanate haben im allgemeinen einen NCO-Ge¬ halt von 12 bis 20 Gew. -% und eine mittlere NCO-Funktionali- tat von 2,5 bis 3.Glycerin, 1,2-dihydroxypropane or mixtures thereof can be obtained. These polyisocyanates containing urethane and / or allophanate groups generally have an NCO content of 12 to 20% by weight and an average NCO functionality of 2.5 to 3.
e) Oxadiazintriongruppen enthaltende Polyisocyanate, vorzugs¬ weise von Hexamethylendiisocyanat oder Isophorondiisocyanat abgeleitet. Solche Oxadiazintriongruppen enthaltenden Poly- isocyanate sind aus Diisocyanat und Kohlendioxid herstellbar.e) Polyisocyanates containing oxadiazinetrione groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such polyisocyanates containing oxadiazinetrione groups can be prepared from diisocyanate and carbon dioxide.
f) Uretonimin-modifizierte Polyisocyanate.f) Uretonimine-modified polyisocyanates.
Die Polyisocyanate a) bis f) können auch im Gemisch, gegebenen- falls auch im Gemisch mit Diisocyanaten, eingesetzt werden.The polyisocyanates a) to f) can also be used in a mixture, if appropriate also in a mixture with diisocyanates.
Bevorzugt sind aliphatische bzw. cycloaliphatische Polyiso¬ cyanate, bzw. Diisocyanate.Aliphatic or cycloaliphatic polyisocyanates or diisocyanates are preferred.
Besonders bevorzugt sind hydrophil modifizierte Polyisocyanate, welche selbstdispergierbar in Wasser sind.Hydrophilically modified polyisocyanates which are self-dispersible in water are particularly preferred.
Zur Herstellung der selbstdispergierbaren Polyisocyanate werden die oben bezeichneten Polyisocyanate umgesetzt mit Verbindungen, die mindestens eine, vorzugsweise eine hydrophile Gruppe, welche ionisch oder nichtionisch sein kann, und mindestens eine, vor¬ zugsweise eine mit Isocyanat reaktive Gruppen, z.B. eine Hydroxy-, Mercapto- oder primäre oder sekundäre Aminogruppe (kurz NH-Gruppe) aufweisen.To produce the self-dispersible polyisocyanates, the polyisocyanates described above are reacted with compounds which have at least one, preferably a hydrophilic group, which can be ionic or nonionic, and at least one, preferably one, isocyanate-reactive groups, for example one Have hydroxyl, mercapto or primary or secondary amino group (NH group for short).
Bei der hydrophilen Gruppe kann es sich z.B. um eine ionische oder in eine ionische Gruppe überführbare Gruppe handeln.The hydrophilic group can e.g. are an ionic group or a group which can be converted into an ionic group.
Anionische bzw. in anionische Gruppen überführbare Gruppen sind z.B. Carbonsäure- oder Sulfonsäuregruppen.Anionic or convertible groups are e.g. Carboxylic acid or sulfonic acid groups.
Geeignete Verbindungen sind z.B. Hydroxycarbonsauren, wie Hydroxypivalinsäure oder Dimethylolpropionsäure oder Hydroxy- bzw. Aminsulfonsäuren.Suitable compounds are e.g. Hydroxycarboxylic acids, such as hydroxypivalic acid or dimethylolpropionic acid or hydroxy or amine sulfonic acids.
Kationische bzw. in kationische Gruppen überführbare Gruppen sind z.B. quarternäre Ammoniumgruppen bzw. tertiäre Aminogruppen.Cationic or convertible groups are e.g. quaternary ammonium groups or tertiary amino groups.
In ionische Gruppen überführbare Gruppen werden vorzugsweise vor oder während der Dispergierung der erfindungsgemäßen Mischung in Wasser in ionische Gruppen überführt.Groups which can be converted into ionic groups are preferably converted into ionic groups before or during the dispersion of the mixture according to the invention in water.
Zur Überführung z.B. von Carbonsäuregruppen oder Sulfonsäure¬ gruppen in anionische Gruppen können anorganische und/oder orga¬ nische Basen wie Natriumhydroxid, Kaliumhydroxid, Kaliumcarbonat, Natriumhydrogencarbonat, Ammoniak oder primäre, sekundäre und be- sonders tertiäre Amine, z.B. Triethylamin oder Dimethylamino- propanol eingesetzt werden.For transfer e.g. of carboxylic acid groups or sulfonic acid groups in anionic groups, inorganic and / or organic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydrogen carbonate, ammonia or primary, secondary and particularly tertiary amines, e.g. Triethylamine or dimethylamino propanol can be used.
Zur Überführung von tertiären Aminogruppe in die entsprechenden Kationen, z.B. Ammoniumgruppen, sind als Neutralisationsmittel anorganische oder organische Säuren, z.B. Salzsäure, Essigsäure, Fumarsäure, Maleinsäure, Milchsäure, Weinsäure, Oxalsäure oder Phosphorsäure oder als Quarternierungsmittel, z.B. Methylchlorid, Methyliodid, Dimethylsulfat, Benzylchlorid, Chloressigethylester oder Bromacetamid geeignet. Weitere geeignete Neutralisations- und Quarternierungsmittel sind z.B. in der US-PS 3 479 310, Spalte 6, beschrieben.To convert tertiary amino group into the corresponding cations, e.g. Ammonium groups are inorganic or organic acids, e.g. Hydrochloric acid, acetic acid, fumaric acid, maleic acid, lactic acid, tartaric acid, oxalic acid or phosphoric acid or as quaternizing agent, e.g. Methyl chloride, methyl iodide, dimethyl sulfate, benzyl chloride, chloroacetate or bromoacetamide are suitable. Other suitable neutralizing and quaternizing agents are e.g. in U.S. Patent No. 3,479,310, column 6.
Der Gehalt der ionischen Gruppen bzw. in ionische Gruppen über¬ führbare Gruppen beträgt vorzugsweise 0,1 bis 3 mol pro kg der selbstdispergierbaren Polyisocyanate.The content of the ionic groups or groups which can be converted into ionic groups is preferably 0.1 to 3 mol per kg of the self-dispersible polyisocyanates.
Nichtionische Gruppen sind z.B. Polyalkylenethergruppen, ins¬ besondere solche mit 10 bis 80 Alkylenoxideinheiten. Bevorzugt sind Polyethylenethergruppen oder Polyalkylenethergruppen, die neben anderen Alkylenoxideinheiten, z.B. Propylenoxid, mindestens 10 Ethylenoxideinheiten enthalten. Geeignete Verbindungen sind z.B. Polyalkylenetheralkohole.Nonionic groups are, for example, polyalkylene ether groups, in particular those with 10 to 80 alkylene oxide units. Polyethylene ether groups or polyalkylene ether groups are preferred which, in addition to other alkylene oxide units, for example propylene oxide, contain at least 10 ethylene oxide units. Suitable compounds are, for example, polyalkylene ether alcohols.
Der Gehalt der hydrophilen nichtionischen Gruppen, insbesondere der Polyalkylenethergruppen beträgt vorzugsweise 0,5 bis 20, besonders bevorzugt 1 bis 15 Gew.-%, bezogen auf die selbst¬ dispergierbaren Polyisocyanate.The content of the hydrophilic nonionic groups, in particular the polyalkylene ether groups, is preferably 0.5 to 20, particularly preferably 1 to 15% by weight, based on the self-dispersible polyisocyanates.
Die Herstellung der selbstdispergierbaren Polyisocyanate ist aus der DE-A-35 21 618, DE-A-40 01 783 und DE-A-42 03 510 bekannt.The preparation of the self-dispersible polyisocyanates is known from DE-A-35 21 618, DE-A-40 01 783 and DE-A-42 03 510.
Bei der Herstellung der selbstdispergierbaren Polyisocyanate können die Verbindungen mit mindestens einer hydrophilen Gruppe und mindestens einer gegenüber Isocyanat reaktiven Gruppe mit einem Teil des Polyisocyanats umgesetzt und die erhaltenen hydro- phil modifizierten Polyisocyanate dann mit den übrigen Polyiso¬ cyanaten gemischt werden. Die Herstellung kann aber auch so erfolgen, daß die Verbindungen zur Gesamtmenge der Polyisco- cyanate zugesetzt wird und dann die Umsetzung "in situ" durchge¬ führt wird.In the preparation of the self-dispersible polyisocyanates, the compounds having at least one hydrophilic group and at least one isocyanate-reactive group can be reacted with part of the polyisocyanate and the hydrophilic modified polyisocyanates obtained can then be mixed with the other polyisocyanates. However, the preparation can also be carried out by adding the compounds to the total amount of the polyiscoyanates and then carrying out the reaction "in situ".
Bevorzugte wasseremulgierbare Polyisocyanats sind solche mit hydrophilen, nichtionischen Gruppen, insbesondere Polyalkylen¬ ethergruppen. Vorzugsweise wird dabei die Wasseremulgierbarkeit allein durch die hydrophilen nichtionischen Gruppen erreicht.Preferred water-emulsifiable polyisocyanates are those with hydrophilic, nonionic groups, in particular polyalkylene ether groups. The water emulsifiability is preferably achieved solely by the hydrophilic nonionic groups.
Die Menge der Polyisocyanate beträgt vorzugsweise 0,1 bisThe amount of the polyisocyanates is preferably 0.1 to
10 Gew. -%, besonders bevorzugt 2 bis 5 Gew.-% bezogen auf das10% by weight, particularly preferably 2 to 5% by weight, based on the
Polymer.Polymer.
Die erfindungsgemäße Dispersion eignet sich insbesondere als Klebstoff, vorzugsweise als Kaschierklebstoff zum großflächigen Verkleben von Substraten.The dispersion according to the invention is particularly suitable as an adhesive, preferably as a laminating adhesive, for large-area bonding of substrates.
Der Dispersion kann für die Verwendung als Klebstoff, ins- besondere Kaschierklebstoff weitere übliche Zusatzstoffe, z.B. Netzmittel, Verdicker, Schutzkolloide, Lichtschutz-Stabilisato¬ ren, Biozide enthalten.For use as an adhesive, in particular laminating adhesive, the dispersion can contain other conventional additives, e.g. Contain wetting agents, thickeners, protective colloids, light stabilizers, biocides.
Bei der Verwendung als Kaschierklebstoff wird die erfindungs- gemäße Dispersion auf die großflächigen Substrate vorzugsweise mit einer Schichtdicke von 0,1 bis 20, besonders bevorzugt 2 bis 7 g/m2 z.B. durch Rakeln, Streichen etc. aufgetragen. Nach kurzer Zeit zur Ablüftung der Dispersionswasser (vorzugs¬ weise nach 1 bis 60 Sekunden kann die das beschichtete Substrat dann mit einem zweiten Substrat kaschiert werden, wobei die Temperatur z.B. 20 bis 200, vorzugsweise 20 bis 70°C und de rDruck z.B. 1 bis 30, vorzugsweise 3 bis 20 N/m2 betragen kann.When used as a lamination adhesive, the dispersion according to the invention is preferably applied to the large-area substrates with a layer thickness of 0.1 to 20, particularly preferably 2 to 7 g / m 2, for example by knife coating, brushing, etc. After a short time for venting the dispersion water (preferably after 1 to 60 seconds, the coated substrate can then be laminated with a second substrate, the temperature being, for example, 20 to 200, preferably 20 to 70 ° C. and the pressure, for example 1 to 30 , preferably 3 to 20 N / m 2 .
Als Substrate eignen sich z.B. Polymerfolien, insbesondere aus Polyethylen, orientiertem Polypropylen, Polyamid, Polyethylen- terephthalat, Polyacetat, Zellglas etc., oder auch Papier oder Metallfolien, insbesondere aus Aluminium.Suitable substrates are e.g. Polymer films, especially made of polyethylene, oriented polypropylene, polyamide, polyethylene terephthalate, polyacetate, cellophane etc., or also paper or metal foils, especially made of aluminum.
Es können z.B. die Polymerfolien miteinander verklebt werden (Verbundfolienkaschierung) oder auch transparente Polymerfolien mit Papier (Glanzfolienkaschierung) , insbesondere können auch Polymerfolien bzw. Papier mit Metallfolien, z.B. Aluminiumfolien, verklebt werden.For example, the polymer films are glued to one another (composite film lamination) or also transparent polymer films with paper (glossy film lamination), in particular polymer films or paper with metal foils, e.g. Aluminum foils to be glued.
Es ist ein Vorteil der Erfindung, daß unterschiedlichste Substrate miteinander verklebt, d.h. kaschiert werden können, wo- bei die erfindungsgemäße Dispersion eine gute Haftung an den Sub¬ straten aufweist und eine hohe Festigkeit des verklebten Verbun¬ des bewirkt.It is an advantage of the invention that a wide variety of substrates glue together, i.e. can be laminated, whereby the dispersion according to the invention has good adhesion to the substrates and brings about a high strength of the bonded bond.
Insbesondere zeigen die verklebten Verbünde auch eine hohe Koch- wasserfestigkeit.In particular, the bonded composites also show high resistance to boiling water.
Die erfindungsgemäßen Dispersionen sind darüberhinaus auch frei von feinem Koagulat und eignen sich daher auch zur Herstellung transparenter Folienverbunde.The dispersions according to the invention are also free of fine coagulate and are therefore also suitable for producing transparent film composites.
BeispieleExamples
Beispiel 1example 1
Ein Gemisch aus 674,3 g Wasser und 120 g Maltodextrin C*PURA mixture of 674.3 g water and 120 g maltodextrin C * PUR
01915, ein Stärkederivat, wird auf 85°C erhitzt und mit 5 Gew. -% von Zulauf 1 und 20 Gew. -% von Zulauf 2 versetzt. Es wird 15 Mi¬ nuten bei 85°C anpolymerisiert und anschließend mit der Dosierung der Restmengen der Zuläufe 1 und 2 begonnen. Die Zugabe erfolgt kontinuierlich über 3 Stunden (Zulauf 1) und 3,5 Stunden (Zu¬ lauf 2). Danach wird 1 Stunde bei 85°C nachpolymerisiert. Zulauf 1: 300 g Wasser01915, a starch derivative, is heated to 85 ° C. and 5% by weight of feed 1 and 20% by weight of feed 2 are added. Polymerization is carried out for 15 minutes at 85 ° C. and the metering of the remaining amounts of feeds 1 and 2 is then started. The addition takes place continuously over 3 hours (feed 1) and 3.5 hours (feed 2). The mixture is then polymerized at 85 ° C for 1 hour. Feed 1: 300 g of water
696 g Butylacrylat696 g butyl acrylate
444 g Styrol444 g styrene
60 g Hydroxyethylacrylat60 g of hydroxyethyl acrylate
16 g Natriumlaurylsulfonat (15 %ig in Wasser, Steinapol NLS)16 g sodium lauryl sulfonate (15% in water, Steinapol NLS)
Zulauf 2: 100 g WasserFeed 2: 100 g of water
7,2 g Natriumperoxodisulfat7.2 g sodium peroxodisulfate
Feststoffgehalt der wäßrigen Polymerdispersion (gemessen nach DIN 53 189) : 54,2 Gew.-%.Solids content of the aqueous polymer dispersion (measured according to DIN 53 189): 54.2% by weight.
Beispiel 2Example 2
Ein Gemisch aus 311,11 g Wasser und 30 g Maltodextrin C*PUR 01915 wird auf 85°C erhitzt und mit 10 Gew.-% von Zulauf 1 und 10 Gew. -% von Zulauf 2 versetzt. Es wird 15 Minuten bei 85°C anpolymerisiert und anschließend mit der Dosierung der Restmengen der Zuläufe 1 und 2 begonnen. Die Zugabe erfolgt kontinuierlich über 3 Stunden (Zulauf 1) und 3,5 Stunden (Zulauf 2). Danach wird 1 Stunden bei 85°C nachpolymerisiert.A mixture of 311.11 g of water and 30 g of maltodextrin C * PUR 01915 is heated to 85 ° C. and 10% by weight of feed 1 and 10% by weight of feed 2 are added. It is polymerized for 15 minutes at 85 ° C. and then the metering of the remaining amounts of feeds 1 and 2 is started. The addition takes place continuously over 3 hours (feed 1) and 3.5 hours (feed 2). The mixture is then polymerized at 85 ° C for 1 hour.
Zulauf 1: 150 g Wasser 8 g Natriumlaurylsulfonat (15 %ig in Wasser)Feed 1: 150 g of water 8 g of sodium lauryl sulfonate (15% in water)
30 g Ethylacrylat 222 g Methylmethacrylat 348 g n-Butylacrylat30 g ethyl acrylate 222 g methyl methacrylate 348 g n-butyl acrylate
Zulauf 2: 50 g WasserFeed 2: 50 g of water
1,8 g Natriumperoxodisulfat1.8 g sodium peroxodisulfate
Feststoffgehalt der wäßrigen Polymerdispersion (gemessen nach DIN 53 189) : 55,1 Gew. -%.Solids content of the aqueous polymer dispersion (measured according to DIN 53 189): 55.1% by weight.
Beispiel 3Example 3
Ein Gemisch aus 309,17 g Wasser und 30 g Maltodextrin C*PUR 01915 wird auf 85°C erhitzt und mit 5 Gew. -% von Zulauf 1 und 10 Gew.-% von Zulauf 2 versetzt. Es wird 15 Minuten anpolymerisiert und an¬ schließend mit der Dosierung der Restmengen der Zuläufe 1 und 2 begonnen. Die Zugabe erfolgt kontinuierlich über 3 Stunden (Zu¬ lauf 1) und 3,5 Stunden (Zulauf 2). Danach wird 1 Stunde nach¬ polymerisiert. Zulauf 1 150 g WasserA mixture of 309.17 g of water and 30 g of maltodextrin C * PUR 01915 is heated to 85 ° C. and 5% by weight of feed 1 and 10% by weight of feed 2 are added. Polymerization is carried out for 15 minutes and the metering of the remaining amounts of feeds 1 and 2 is then started. The addition takes place continuously over 3 hours (inlet 1) and 3.5 hours (inlet 2). The mixture is then polymerized for 1 hour. Inlet 1 150 g of water
8 g Natriumlaurylsulfonat (15 %ig in Wasser) 60 g Methylenethacrylatacrylat 540 g Ethylacrylat 10,7 g Natrium-Dodecylphenoxybenzendisulfonsäure, 45 %ig in Wasser (Dowfax 2A1)8 g sodium lauryl sulfonate (15% in water) 60 g methylene ethacrylate acrylate 540 g ethyl acrylate 10.7 g sodium dodecylphenoxybenzene disulfonic acid, 45% in water (Dowfax 2A1)
Zulauf 2: 50 g WasserFeed 2: 50 g of water
1,8 g Natriumperoxodisulfat1.8 g sodium peroxodisulfate
Feststoffgehalt der wäßrigen Polymerdispersion (gemessen nach DIN 53 189) : 54,9 Gew. -%.Solids content of the aqueous polymer dispersion (measured according to DIN 53 189): 54.9% by weight.
Beispiel 4Example 4
Ein Gemisch aus 311,11 g Wasser und 30 g Maltodextrin C*PUR 01915 wird auf 85°C erhitzt und mti 10 Gew. -% von Zulauf 1 und 10 Gew. -% von Zulauf 2 versetzt. Es wird 15 Minuten bei 85°C anpolymerisiert und anschließend mit der Dosierung der Restmengen der Zuläufe 1 und 2 begonnen. Die Zugabe erfolgt kontinuierlich über 3 Stunden (Zulauf 1) und 3,5 Stunden (Zulauf 2). Danach wird 1 Stunde bei 85°C nachpolymerisiert.A mixture of 311.11 g of water and 30 g of maltodextrin C * PUR 01915 is heated to 85 ° C. and mixed with 10% by weight of feed 1 and 10% by weight of feed 2. It is polymerized for 15 minutes at 85 ° C. and then the metering of the remaining amounts of feeds 1 and 2 is started. The addition takes place continuously over 3 hours (feed 1) and 3.5 hours (feed 2). The mixture is then polymerized at 85 ° C for 1 hour.
Zulauf 1: 150 g WasserFeed 1: 150 g of water
8 g Steinapol NLS (15 %ig in Wasser)8 g Steinapol NLS (15% in water)
30 g Ethylacrylat30 g of ethyl acrylate
222 g Styrol222 g styrene
348 g n-Butylacrylat348 g of n-butyl acrylate
Zulauf 2: 50 g Wasser 1,8 g NatriumperoxodisulfatFeed 2: 50 g of water and 1.8 g of sodium peroxodisulfate
Feststoffgehalt der wäßrigen Polymerdispersion (gemessen nach DIN 53 189) : 54 Gew. -%.Solids content of the aqueous polymer dispersion (measured in accordance with DIN 53 189): 54% by weight.
Beispiel 5Example 5
226 g Wasser werden auf 85°C erhitzt und mit 5 Gew. -% von Zulauf 1 und 20 Gew. -% von Zulauf 2 versetzt. Es wird 15 min anpoly- merisiert und anschließend mit der Dosierung der Zuläufe 1, 2, 3 und 4 begonnen. Die Zugabe verläuft kontinuierlich über 3 Stunden (Zuläufe 1, 3 und 4) und 3,5 Stunden (Zulauf 2). Danach wird 1 Stunde nachpolymerisiert. Zulauf 1: 150 g Wasser226 g of water are heated to 85 ° C. and 5% by weight of feed 1 and 20% by weight of feed 2 are added. The mixture is polymerized for 15 minutes and then metering in of feeds 1, 2, 3 and 4 is started. The addition runs continuously over 3 hours (feeds 1, 3 and 4) and 3.5 hours (feed 2). Then polymerization is continued for 1 hour. Feed 1: 150 g of water
8 g Steinapol NLS (15 %ig in Wasser)8 g Steinapol NLS (15% in water)
30 g Ethylacrylat30 g of ethyl acrylate
220 g Styrol220 g styrene
348 g n-Butylacrylat348 g of n-butyl acrylate
Zulauf 2: 50 g WasserFeed 2: 50 g of water
3,6 g Natriumperoxodisulfat3.6 g sodium peroxodisulfate
Zulauf 3: 50 g WasserFeed 3: 50 g of water
24 g Natronlauge (25 %ig)24 g sodium hydroxide solution (25%)
Zulauf 4: 100 g WasserFeed 4: 100 g of water
30 g Gelatine (Gelitabol D)30 g gelatin (Gelitabol D)
Feststoffgehalt der wäßrigen Polymerdispersion: 51 Gew. -%.Solids content of the aqueous polymer dispersion: 51% by weight.
Vergleichsbeispiel 1Comparative Example 1
Zum Vergleich wurde eine Dispersion ohne Schutzkolloid herge¬ stellt.For comparison, a dispersion without a protective colloid was produced.
In einem Reaktionsgefäß mit Rührer und zwei Zulaufgefäßen (Zulauf 1 und Zulauf 2) werden 262 g entsalztes Wasser, 35 g des Zu- laufs 1 (siehe unten) und 20 g des Zulaufs 2 vorgelegt und auf 85°C erwärmt. Nach 15 Minuten wird innerhalb von 2 h gleichmäßig der Zulauf 1 sowie innerhalb von 2,5 h gleichmäßig der Zulauf 2 zum Reaktionsgefäß zugegeben. Nach der letzten Initiator-Zugabe (Zulauf 2) wird die Dispersion noch 1 Stunde bei 85°C gerührt. Nach der Polymerisation wird 50 g einer 20 gew. -%igen Lösung des Emulgators p-Isononylphenolpolyoxyethylen- (4) -Natriumsulfat z ur Dispersion zugegeben und verrührt.262 g of demineralized water, 35 g of feed 1 (see below) and 20 g of feed 2 are placed in a reaction vessel with stirrer and two feed vessels (feed 1 and feed 2) and heated to 85.degree. After 15 minutes, feed 1 is uniformly added to the reaction vessel over the course of 2 h and feed 2 is uniformly added over the course of 2.5 h. After the last addition of initiator (feed 2), the dispersion is stirred at 85 ° C. for 1 hour. After the polymerization, 50 g of a 20 wt. -% solution of the emulsifier p-isononylphenol polyoxyethylene (4) sodium sulfate was added to the dispersion and stirred.
Zulauf 1: (dieser Zulauf wird während der Polymerisation gerührt)Feed 1: (this feed is stirred during the polymerization)
82,5 g entsalztes Wasser 400 g Ethylacrylat 90 g Methylmethacrylat 10 g 20 gew.-%ige Lösung des Natriumsalzes vom82.5 g of demineralized water 400 g of ethyl acrylate 90 g of methyl methacrylate 10 g of a 20% by weight solution of the sodium salt of
Emulgator p-Dodecyldiphenyletherdisulfonat in WasserEmulsifier p-dodecyldiphenyl ether disulfonate in water
50 g 20 gew. -%ige Lösung vom Umsetzungsprodukt aus p-Isononylphenol mit 50 mol Ethylenoxid als Emulgator in Wasser50 g 20 wt. -% solution of the reaction product from p-isononylphenol with 50 mol of ethylene oxide as an emulsifier in water
Zulauf 2: 100 g entsalztes Wasser 5 g Natriumpersulfat. Anwendungs technische PrüfungFeed 2: 100 g of demineralized water and 5 g of sodium persulfate. Application technical testing
Herstellung der Verbundfolien und Bestimmung der SchälfestigkeitProduction of the composite films and determination of the peel strength
In die Dispersionen der Beispiele 1 bis 5 und des Vergleichs- beispiels wurden 3 Gew. -% (bezogen auf die Copolymerisat- dispersion) der Emulsion eines selbstemulgierbaren Polyisocyanats auf Basis Hexamethylendiisocyanat und Toluylendiisocyanat ein¬ gerührt und homogen verteilt. Anschließend wurden diese Zube- reitungen mit einer Trockenschichtdicke von 2-3 g/m2 auf ver¬ schiedene auf 50°C erwärmte Folien (Polyethylenterephthalat: PETP; Polyamid: PA; Polypropylen (coronavorbehandelt) : PP, Aluminium: Alu) geräkelt, und nach 20 Sekunden mit einer Polyethylenfolie (coronavorbehandelt) kaschiert. Anschließend wurden die erhaltenen Folienverbunde 7 Tage bei Raumtemperatur und Normal¬ klima gelagert und danach in 2 cm breite Streifen zerschnitten. Diese Streifen wurden dann bei 23°C im Winkel von 180° mit einer Geschwindigkeit von 100 m/min abgezogen. Es wurde die Schälkraft in N bei den 15 mm breiten Streifen bestimmt. Ergebnisse finden sich in Tabelle 1.3% by weight (based on the copolymer dispersion) of the emulsion of a self-emulsifiable polyisocyanate based on hexamethylene diisocyanate and tolylene diisocyanate was stirred into the dispersions of Examples 1 to 5 and of the comparative example and distributed homogeneously. These preparations were then knife-coated with a dry layer thickness of 2-3 g / m 2 onto various foils heated to 50 ° C. (polyethylene terephthalate: PETP; polyamide: PA; polypropylene (corona treated): PP, aluminum: aluminum), and after 20 seconds covered with a polyethylene film (corona treated). The film composites obtained were then stored for 7 days at room temperature and normal climate and then cut into strips 2 cm wide. These strips were then peeled off at 23 ° C at an angle of 180 ° at a speed of 100 m / min. The peeling force in N was determined for the 15 mm wide strips. Results can be found in Table 1.
Tabelle 1Table 1
Figure imgf000018_0001
Figure imgf000018_0001
KochwasserfestigkeitBoil water resistance
Die gemäß obiger Verfahrensweise erhaltenen Folienverbunde wurden 7 Tage bei Raumtemperatur gelagert und dann 30 Minuten gekocht.The film composites obtained according to the above procedure were stored at room temperature for 7 days and then boiled for 30 minutes.
Die Schälfestigkeit wurde wie oben nach Abkühlung der Folienver- bunde bestimmte (Tabelle 2) .The peel strength was determined as above after the film composites had cooled (Table 2).
Tabelle 2Table 2
Figure imgf000018_0002
Figure imgf000018_0002

Claims

Patentansprüche claims
1. Dispersion eines radikalisch polymerisierten Polymeren, ent¬ haltend ein Polyisocyanat als Vernetzer, gekennzeichnet da¬ durch, daß das Polymer durch Emulsionspolymerisation von ethylenisch ungesättigten Monomeren in Gegenwart eines Hydro¬ xylgruppen oder primäre oder sekundäre Aminogruppen ent¬ haltenden Schutzkolloids erhältlich ist.1. Dispersion of a free-radically polymerized polymer containing a polyisocyanate as crosslinking agent, characterized in that the polymer is obtainable by emulsion polymerization of ethylenically unsaturated monomers in the presence of a protective colloid containing hydroxyl groups or primary or secondary amino groups.
2. Dispersion gemäß Anspruch 1, dadurch gekennzeichnet, daß es sich bei dem Schutzkolloid um Stärke handelt.2. Dispersion according to claim 1, characterized in that the protective colloid is starch.
3. Dispersion gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Schutzkolloid in Mengen von 0,1 bis 50 Gew. -%, bezogen auf das Polymer, eingesetzt wird.3. Dispersion according to claim 1 or 2, characterized in that the protective colloid is used in amounts of 0.1 to 50% by weight, based on the polymer.
4. Dispersion gemäß einem der Ansprüche 1 bis 3, dadurch gekenn¬ zeichnet, daß das Polymer eine Glasübergangstemperatur unter 60°C aufweist.4. Dispersion according to one of claims 1 to 3, characterized gekenn¬ characterized in that the polymer has a glass transition temperature below 60 ° C.
5. Verwendung der Dispersion gemäß einem der Ansprüche 1 bis 4 als Klebstoff.5. Use of the dispersion according to one of claims 1 to 4 as an adhesive.
6. Verwendung der Dispersion gemäß einem der Ansprüche 1 bis 4 als Kaschierklebstoff.6. Use of the dispersion according to one of claims 1 to 4 as a laminating adhesive.
7. Verwendung der Dispersion gemäß einem der Ansprüche 1 bis 4 als Klebstoff für die Kaschierung von Polymerfolien miteinan- der, von Polymerfolien mit Papier oder Aluminiumfolien.7. Use of the dispersion according to one of claims 1 to 4 as an adhesive for the lamination of polymer films with one another, polymer films with paper or aluminum foils.
8. Kaschierte Substrate, erhältlich unter Verwendung einer Dis¬ persion gemäß einem der Ansprüche 1 bis 4. 8. Laminated substrates obtainable using a dispersion according to one of claims 1 to 4.
PCT/EP1996/004581 1995-11-03 1996-10-22 Starch-containing polymer dispersions and their use as laminate adhesives WO1997017387A1 (en)

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CN1329120C (en) * 2000-12-11 2007-08-01 巴斯福股份公司 Catalyst coating for hydrogenation of maleic anhyride and related compounds to give gamma-butyrolactone, tetrahyarofuran and derivatives thereof

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KR102324787B1 (en) 2014-12-12 2021-11-11 신쏘머 에스디엔. 비에이치디. Polymer latex composition for dip-molding applications
WO2016110367A1 (en) * 2015-01-08 2016-07-14 Basf Se Protective adhesive film
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US6800675B1 (en) 1999-10-19 2004-10-05 Südzucker Aktiengesellschaft Mannheim/Ochsenfurt Emulsion polymerization method
CN1329120C (en) * 2000-12-11 2007-08-01 巴斯福股份公司 Catalyst coating for hydrogenation of maleic anhyride and related compounds to give gamma-butyrolactone, tetrahyarofuran and derivatives thereof

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