TW200528503A - Aqueous adhesive dispersions - Google Patents

Abstract

Aqueous polymer dispersions based on polyurethanes that include (a) at least one polyurethane dispersion having a mean particle size of from 60 to 350 nm, and (b) at least one polychloroprene dispersion having a mean particle size of from 60 to 300 nm, and (c) at least one aqueous silicon dioxide dispersion having a particle diameter of the SiO2 particles of from 1 to 400 nm. The dispersion can be prepared by admixing a mixture of (b) and (c) with (a). The dispersions can be used in adhesive compositions.

Description

200528503 IX. Description of the invention: Relevant specialties 1 Application for claiming phase y Thousand calls This patent application claims the priority of German Patent Application No. 103 43 676.6 filed on September 18, 2003, according to U.S., C. §119. [Technical field to which the invention belongs] The present invention relates to an aqueous polymer dispersion liquid based on a polyurethane and a polybutadiene, and a method for producing the same and its use. [Prior art] The adhesive based on polyurethane is mainly a solvent-containing adhesive, which is applied to two substrates to be bonded and dried. By bonding the two substrates successively under the pressure of RT or after thermal activation, a bonding force with high initial strength can be obtained immediately after the bonding operation. For ecological reasons, there is a growing need for suitable aqueous adhesive dispersions that can be processed into corresponding aqueous adhesive formulations. These systems have the disadvantage that the adhesive layer must be dried after application, and the substrates can only be joined together after the dried adhesive film has been thermally activated in advance. It is not possible to join the substrates together at room temperature. On the other hand, it is possible to manufacture a mixture which can be combined with a substrate at room temperature while being moist, by using a polybutadiene diluent, and by combining an aqueous dioxide hair dispersion. However, it has been discovered that many substrates (such as plasticized PVC) that can be successfully bonded through a polyurethane dispersion adhesive after thermal activation, can only pass waterborne polybutadienes unacceptably at room temperature. Diene 200528503 dispersion combined. However, it is currently impossible to prepare and utilize aqueous formulations using polyurethane and polybutadiene dispersions together, because polybutadiene dispersions are generally strongly alkaline polymer dispersions ( In water). Under these conditions, the polyurethanes are hydrolyzed, and the polymer chains are hydrolyzed & even after the pH of the formulation is lowered using a suitable agent (e.g. aminoacetic acid), these mixtures are unstable because A small amount of HC1 was separated from the butadiene during storage, which also caused degradation of the polyurethane chain. The object of the present invention is to provide an aqueous polyurethane adhesive composition, which is applied to the substrates to be bonded and after bonding, exhibits ancient strength, especially when wet (wet strength), And it's stable for water ::. [Summary of the invention] The present invention relates to an aqueous polymer dispersion, which comprises a) at least one fluorenyl formamide having an average particle size of 60 to 350 nm. 〇 Nano-based polybutadiene dispersion, and 〇 At least one with a particle size! &Amp; 02 particles to 400 nm. The present invention also relates to a method for preparing the above polymer dispersion liquid = by Dinger Sanling of Lingxian County) and aqueous dioxane dispersion liquid = additives that need to be selected as cohesive auxiliary substances, and mixed with amino formic acid S for dispersion The liquid mixture of (b) and (b) and (b) of the present invention further relates to the adhesive group 200528503 with the above polymer dispersion. The present invention further relates to a substrate 'which is bonded together through the above polymer dispersion, especially when the substrate is a structural component of a shoe or a shoe.发明 Details # Except in the operation examples or otherwise mentioned, it should be understood that in all cases, all numbers used in the specification and the scope of patent application or the terms indicating the amount of ingredients, reaction conditions, etc. are modified by the word "about", It was found that 'by appropriately combining a polyurethane dispersion, an aqueous polybutadiene dispersion (stable for HC1 separation), and an aqueous silicon dioxide dispersion, manufacturing can exhibit a high degree of binding after being combined. Initial strength, wet strength, and stable adhesives are possible .... Silic acid products are known in many applications from prior art. Although solid SiO2 products are widely used to control rheological properties, as fillers, or as adsorption Agent, but silicon dioxide dispersion (silica sol) is mainly used as an adhesive for many inorganic materials, as a polishing compound for semiconductors, or as a cohesive partner in colloidal reactions. For example, the European patent Ep_A 〇3 ^ 928 is disclosed in the presence of silica sol using polybutadiene latex as the impregnating layer in the process of fireproofing components. The pyrogenic silicic acid system is disclosed in French patents 341 537 and FR-A 2 210 699 (combined polybutadiene latex for the manufacture of flame-resistant foaming trimming or asphalt coating) and in Japanese patent Jp_A = 256 738 (combined polybutadiene-acrylic copolymer). High solid content The tempering effect of the polybutadiene dispersion is known from the prior art. European patent EP_A0 857 741 reveals that the product passes through 50 ° 200528503. Ming = Γ: Scattered Γ isocyanate has good reactivity. For adhesives !: J 6 is a polymer dispersion containing coagulum during storage or during the preparation period, === An Erqi :: r high stability. The low storage of the dispersion The present invention provides aqueous A polymer dispersion comprising at least one) a polyurethane dispersion having an average particle size of 60 to 350 nm, preferably 70 f 300 nm (measured by laser correlation spectroscopy), and b) at least one Having an average particle size of 60 to 300 nm, preferably 60 to 200 nm, more preferably 60 to 150 nm, and most preferably 60 to 120 nm (measured by laser correlation spectroscopy) Polygas butadiene dispersion, and, e) at least one having a particle size i to 400 nm, preferably 5 to 100. Nanometer ’is particularly preferred for Si02 particles of 8 to 60 nanometers (through GN · Sears,

Measured by the method of Analytical Chemistry Vol. 28, N. 12, 1981-1983 (December 1956), and its relevant parts are incorporated in this case for reference) aqueous silica dispersion. The polyurethane dispersion (a) to be used according to the present invention comprises polyurethane (A), which is a reaction product of the following components: 200528503 λ

Al) Polyisocyanate, A2) Polymeric polyols and / or polyamines with an average molar weight of 400 to 8000, ^ A3) Choose monohydric alcohols or polyols or monoamines or polyamines with a molar weight of up to 400 as required An amine or amino alcohol, a compound selected from the group consisting of A4) a compound having at least one ionic or potentially ionic group and / or A5) which has become hydrophilic non-ionic compounds. A potential ionic group within the scope of the present invention is a group that can form an ionic group. Polyurethane (A) preferably uses 7 to 45% by weight of A1), 50 to 91% by weight of A2), 0 to 15% by weight of A5), 0 to 12% by weight of ions or potential The ionic compound A4) and A3) are selected from 0 to 30% by weight, where the sum of A4) and A5) is 0.1 to 27% by weight 0/0, and the total of the ingredients is 100% by weight. Polyurethane (A) is particularly preferably from 10 to 30% by weight of A1), 65 to 90% by weight of A2), 0 to 10% by weight of A5), 3 to 9% by weight of ions or potential The ionic compound A4) and A3) are selected from 0 to 10% by weight, where the sum of A4) and A5) is 0.1 to 19% by weight, and the total of the ingredients is 100% by weight. Polyurethane (Α) is particularly preferably used from 8 to 27% by weight of A1), 65 to 85% by weight of A2), 0 to 8% by weight of A5), 3 to 8% by weight of ions or potential Anionic compound A4) and A3) selected from 0 to 8% by weight 200528503 as required, wherein the sum of A4) and A5) is 0 · ΐ to 16% by weight 0 / o, and the total of the ingredients is 100% by weight %. Suitable polyisofluorates (A1) are aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates. It is also possible to use mixtures of these polyisocyanates. Examples of suitable polyisocyanates are butyl diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4-trimethylhexamethylene diisocyanate Isomers of isocyanates and / or 2,4,4-trimethylhexamethylene diisocyanate, bis (4,4'_isocyanatecyclohexyl) methane or mixtures thereof having any desired isomer content , Isocyanate-methyl 丨, octane diisocyanate, 1,4-cyclohexyl diisocyanate, phenylene diisocyanate, 2,4-tolyl diisocyanate, and / or 2,6 • tolyl diisocyanate Isocyanate, 1,5-naphthyl diisocyanate, 2,4, _diphenylmethane diisocyanate or 4,4'_diphenylmethane diisocyanate, triphenylmethane 4,4,4,4, _triphenylmethane Isocyanates or their derivatives and mixtures thereof having a urethane, isocyanurate, biuret, biuret, uretdione, iminogeminodione structure. Preferred are the isomers of hexamethylene diisocyanate, isophor-diisocyanate, bis (4,4-isocyanate cyclohexyl) methylbenzene, and mixtures thereof. Preferred are polyisocyanates or polyisocyanate mixtures of the type described above having isohelium-based rings having only aliphatic and / or cycloaliphatic bonding. It is very well known that the starting ingredient (A1) is a polyisocyanate or a polyisocyanate mixture based on Satoshi, Noodle, and / or 4,4, _diisocyanase di = hexyl methylbenzene. Also suitable as polyisocyanate g (A1) are those with uric acid vinegar ', carbamic acid, biuret, biuret, imine; two: cyanide network and (or ~ __ triketone structure Any desired species of polyisocyanate r has been prepared by modification of simple materials, cyclic compounds, diisocyanates, and / or diisocyanuric acids ^ 200528503 'and is made of at least two species such as j. Prakt. Chem. 336 (1994), composed of diisocyanates as described on pages 185-200. Suitable polymeric polyols or polyamines (A2) have an OH functionality of at least 1.5 to 4, such as polyacrylates, polyesters, polyimides Esters, polyethers, polycarbonates, polyester carbonates, polyacetals, polyolefins, and polysiloxanes. Molars with OH functionality 2 to 3 and weight ranges from 600 to 2500 are preferred. Polyols. Suitable hydroxy group-containing polycarbonates are prepared by reacting a carbonic acid derivative (such as diphenyl carbonate, dimethyl carbonate, or phosgene) with a diol. A suitable diol is, for example, ethyl Diols, 1,2-propanediol and 13-propanediol, 1,3-butanediol and ι, 4-butanediol, ι, 6-hexanediol, ι, 8 -Octanediol, neopentyl Alcohol, 1,4-bishydroxymethylcyclohexane, 2-methyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, bicondensation Propylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, bisphenol A, tetrabromobisphenol A, and lactone modified diols. The diol component preferably contains 40 to 100% by weight of hexane. Burned diols, preferably 1,6-hexanediol and / or hexanediol derivatives, preferably those containing mysterious or ester groups and terminal OH groups, for example according to German patent DE-A 1 770 245 Through the reaction of 1 mol hexanediol with at least 1 mol (preferably 1 to 2 mol) caprolactone, or through the etherification reaction of hexane diol with itself to form a bisection Products made from hexanediol or dihexylene glycol. For example, the preparation of these derivatives is known from German patent DE-A 1 570 540. It is also possible to use those disclosed in German patent DE_A3 717 060 Polyol-polycarbonate glycol. The polyether esters should preferably be linear. However, by combining polyfunctional ingredients (especially low molecular weight polyols), they can be slightly branched as appropriate. Suitable for this purpose For example, glycerol, trimethylolpropane, ^ 6- 11 200528503 hexanetriol, 1,2,4-butanetriol, trimethylolpropane, pentaerythritol, quinitol, mannitol, and sorbitol Alcohols, glucosides, 134,6 • dihydrohexitols. Suitable polyether polyols are polytetramethylene glycol polyethers known per se in polyurethane chemistry, which can, for example, pass through tetrahydrofuran It is prepared by the polymerization reaction (via cationic ring-opening). Other suitable polyether polyols are polyethers, such as styrene oxide, propylene oxide, butylene oxide, or epoxy propane, which are prepared using starter molecules. (Especially propylene oxide) polyols. Suitable polyester polyols are, for example, the reaction products of multiproton (preferably diproton and optionally triproton) alcohols with polyvalent (preferably divalent) carboxylic acids. Instead of free polycarboxylic acids, it is also possible to use corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters or mixtures of lower carbon alcohols during the preparation of the polyester. The polycarboxylic acid may have an aliphatic, cycloaliphatic, aromatic and / or heterocyclic nature and may be optionally substituted by, for example, a halogen atom and / or unsaturated. The component (A3) is suitable for capping a polyurethane prepolymer. The purpose of monofunctional alcohols and monoamines should be considered here. Preferred monohydric alcohols are aliphatic monohydric alcohols having 1 to carbon atoms, such as ethanol, n-butanol, ethylene glycol, monomethyl ether, 2-ethylhexanol, 1-octanol, 1-12 Alcohol or 1-hexadecanol. Preferred monoamines are aliphatic monoamines such as diethylamine, dibutylamine, ethanolamine, methylethanolamine or N, N-diethanolamine and amines of the jeffamin® μ series (Huntsman Corp. Europe, Belgium) Or amine-functional polyethylene oxide and polypropylene oxide. Also suitable as component (A3) are polyols, amine polyols and polyamines with a molecular weight of less than 400 (most of which are described in the literature). 200528503 Preferred ingredients (A3) are, for example, a) alkane-diols and alkane-triols, such as ethanediol, 1,2-propanediol and 1,3-propanediol, 1,4-butane Diols and 2,3-butanediol, 1,5-pentanediol, 1,3-dimethylpropanediol, 1,6-hexanediol, neopentyl glycol, 1,4- Cyclohexanedimethanol, 2-methyl-1,3-propanediol, 2-ethyl-2-butanediol, trimethylpentanediol, regioisomeric diethyloctanediol , 1,2-cyclohexyldiol and 1,4-cyclohexyldiol, 2,2-dimethyl-3-mercaptopropionic acid (2,2-dimethyl-3-hydroxypropyl ester ), Hydrogenated bisphenol A [2,2-bis (4-hydroxycyclohexyl) propane], trimethylolethane, trimethylolpropane, or glycerol, b) ether glycols, such as bis Ethylene glycol, diethylene glycol, tetraethylene glycol, dipropylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol or hydrogen-quinone-dihydroxyethyl ether, c) (I) and (II) ester diols H0- (CH2) x-C0-0- (CH2) y-0H (I), H0- (CH2) x-0_C0-R-C0-0 (CH2) x_0H (II), wherein R is an alkylene or aryl group having 1 to 10 carbon atoms (preferably 2 to 6 carbon atoms), and X is 2 to 6, And y is 3 to 5, for example, δ-acylbutyl-ε-hydroxy • hexanoate, ω-acylhexyl-γ-acylbutyrate, adipic acid (β-hydroxyethyl) ester, and Phthalic acid (β-hydroxyethyl) esters, and 200528503 d) diamines and polyamines, such as 1,2-diaminoethane, ι, 3-diaminopropane, 1,6-diaminohexane , 1,3-phenylenediamine and ι, 4-phenylenediamine, 4,4, -diphenylmethanediamine, isophoronediamine, 2,2,4-trimethylhexamine Isomeric mixture of methylene diamine and 2,4,4-trimethylhexamethylene diamine, 2-methyl-pentamethylene diamine, dimethyl ethyl triamine, 1,3- Phenyldimethyldiamine and 1,4-Phenylenediamine, α, α, α ,, α, _tetramethyl 4,3-Phenylenediamine and α, α, α ', Α'_tetramethyl_ι, 4-phenylenedimethyldiamine, 4,4-diaminodicyclohexylmethane, amine-functional polyethylene oxide or polypropylene oxide (under the name Jeffamin® , D series (available from Huntsman Corp. Europe, Belgium), diethylene triamine and triethylene tetramine. Suitable diamines within the scope of the present invention are also hydrazine, hydrazine hydrate and substituted hydrazine (such as N-methylphosphonium, N, N, · dimethylhydrazine and its homologs), and acid dihydrazine, Adipic acid, p-methyl adipic acid, sebacic acid, 3-hydroxypropionic acid, and terephthalic acid, hemaziridinyl hydrazine (e.g., hemihydrazinohydrazine propionate hydrazine (as disclosed in German patent DE_A1 77). 591)), semi-battery-based stilt-based flavor hydrazine (for example, 2-cobazine ethylclibamate (as disclosed in German patent DE: A 1 918 504)) or amine hemihydrazine compound (E.g. β-aminoethylhemahydrazino-carbonate (as disclosed in German patent DE-A 1 902 931)). Ingredient (A4) contains an ionic group which can be a rider or a Yinxuan. Compounds with cation and anion dispersing properties are, for example, osmium, ammonium, sodium carbonate, phosphonium sulfonium, or can be converted to the above-mentioned groups through salt formation (latent ten®) and can be present via isocyanate Reactive groups that are incorporated into macromolecules. Preferred suitable isonitro 200528503 acid ester reactive groups are hydroxyl and amine groups φ Suitable ionic or potential ionic compounds (A4) are, for example, monoacids and dihydroxycarboxylic acids, monoaminocarboxylic acids and diamines Carboxylic acid, monohydroxysulfonic acid and dihydroxysulfonic acid, monoaminosulfonic acid and diaminosulfonic acid, and monodicarboxylic acid and monohydroxyphosphonic acid, or monoaminophosphonic acid and diaminophosphonic acid , And its = class, such as dimethylolpropanoic acid, dimethylolbutanoic acid, hydroxyvaleric acid, qinaminoethyl) -β-alanine, 2- (2-amino-ethylamino) -Ethanesulfonic acid, ethylenediamine-propyl-sulfonic acid or ethylenediamine-butyl-sulfonic acid, 1,2-propylenediamine · β-ethylsulfonic acid, or 1,3 _Dipropylamine-β-ethylsulfonic acid, malic acid, citric acid, glycolic acid, lactic acid, glycine, alanine, taurine, lysine, 3,5 · diaminobenzoic acid Addition of ipdi and acrylic acid (European patent EP-A0 916 647, Example 1) and its basic and / or ammonium salts; addition of sodium bisulfite and 2.butane-1,4-diol Materials, polyether tank acid brewing, propoxylation of 2-butanyl alcohol and NaHS〇3 Adducts (for example, disclosed in German Patent DE_A2 446 440 (pages 5-9, formula ΙΙΙΙΙ)) and components which can be converted into cationic groups (such as N-methyl · diethylene glycol amine) as hydrophilic Structural composition. Preferred ionic or potentially ionic compounds are those having a carboxyl or acidate and / or sulfonate group and / or an ammonium group. Particularly preferred ionic compounds are those containing carboxyl and / or acid groups as ionic or potential ionic groups, such as N-N- (2-aminoethyl) -β-alanine salts, 2- ( 2. Amine-Ethylamino) Salts of acetic acid or the addition products of IPDI and acrylic acid (European Patent EP-A 0916 647, Example 1) and dimethylolpropionic acid salt

A suitable compound (A5) having a nonionic hydrophilic effect is, for example, a polyoxyalkylene ether containing at least one hydroxyl or amine group. These polyethers contain 15 200528503% by weight of components derived from ethylene oxide. Of the linear structure_ and the general formula (m) has a content of 30% to 100% and a suitable compound having a functionality of 1 to 3

HO

m wherein R and R each independently represent a divalent aliphatic, cycloaliphatic or aromatic group having 1 to 18 carbon atoms, which can insert oxygen and / or nitrogen atoms, and R3 represents an alkoxy group Polyoxyethylene group. Compounds having a non-ionic hydrophilic effect are also, for example, ethylene oxide units having a statistical average of 5 to 70 (preferably 7 to 55) ethylene oxide units per molecule and permeated through suitable initiator molecules in a manner known per se. Proton polyepoxy alcohol polyether alcohol (for example, Ullmanns Encyclopadie der technischen Chemie, 4th edition, Verlag Chemie, Weinheim, pages 31_38). Suitable starter molecules are, for example, saturated monohydric alcohols (e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, pentanol, hexanol, octanol, and nonanol). Isomers, n-decanol, n-undecanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol 'methylcyclohexanol or hydroxymethylcyclohexane Isomers, 3-ethyl-3_hydroxymethyl-oxetanol or tetrazolium methyl alcohol), one shrink --r · ethylene-alcohol " ~ alkanyl bond (for example a 16 200528503 Diethylene glycol monobutyl ether), unsaturated alcohols (such as allyl alcohol, dimethyl allyl alcohol, or oleyl alcohol), aromatic alcohols (such as the isomerization of phenol, cresol, and methoxyphenol) Materials), aryl fatty alcohols (such as benzyl alcohol, mycanol, or cinnamyl alcohol), secondary monoamines such as mono-f-amine, mono-ethylamine, dipropylamine, diisopropylamine, dibutylamine, bis _ (2_ethylhexyl) -amine, N_methyl_cyclohexylamine, and ethyl_cyclohexylamine or dicyclohexylamine) and heterocyclic secondary amines (eg, morpholine, pyrrolidine =, Hydropyridine or 1-H-pyrazole). A preferred starter molecule is a saturated monohydric alcohol. Particularly preferred is the use of diethylene glycol monobutyl ether as a starter molecule.

Suitable alkylene oxides for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in the alkoxylation reaction in any desired order or externally as a mixture. The polyalkylene oxide polyether alcohol is a pure polyoxyethylene polyether, or a mixed polyalkylene oxide polyether containing at least 30 mole% (preferably at least 40 mole%) ethylene oxide units. A preferred non-ionic compound is a functionally mixed polyepoxy fired polyether containing at least 40 mole% ethylene oxide units and not more than 60 mole% propylene oxide units. b The combination of nonionic (A4) and ionic (A5) hydrophilic agents is preferably used to prepare polyurethane (A). Particularly preferred is a combination of non-ionic and ionic hydrophilic agents. The preparation of the aqueous polyurethane (A) can be carried out in one or more steps in a homogeneous phase, or in the case of a multi-step reaction, partly in a dispersed phase. After the full or partial polyaddition reaction, a dispersing, emulsifying or decomposing step is performed. Thereafter, as appropriate, another polyaddition reaction or modification is performed in the dispersed phase. In order to prepare polyurethane sulfonium, any method known from the prior art can be used, such as emulsifier shear, Lai, prepolymer miscibility 17 200528503 bulk emulsification, ketimine and solids Spontaneous dispersion method or its derivative method. A summary of this method can be found in] Viethoden der organischen Chemie (Methods of Organic Chemistry) (Houben_Weyl, Supplement or Supplement to Fourth Edition, Volume E20, H. Bartl and J. Falbe, Stuttgart, New York, Thiemel 987, 167M682). Preferred are melt emulsification, prepolymer mixing, and acetone. The acetone method is particularly preferred. In order to prepare a polyurethane prepolymer, some or all of the components (A2) to (A5) (without primary or secondary amine groups) and polyisocyanate (A1) are usually placed in a reactor And, if appropriate, diluted with a solvent (which is water-miscible, but inert to the isocyanate ring) (but preferably no solvent is used), and heated to a relatively high temperature (preferably in the range of 50 to 120 ° C) ). Suitable solvents are, for example, acetone, methyl ethyl ketone, tetrahydrosmell, dizaki, 6 nitrile, dipropylene glycol dimethyl ether, and 1β > methyl-2_pyrrolidone (not only added at the beginning of the preparation, but also visible Situations are added in batches later). Acetone and methyl ethyl ketone are preferred. The reaction may occur under normal pressure and pressure, for example, at a normal pressure boiling point exceeding the solvent (such as acetone). It is also possible to use catalysts known to accelerate the isocyanate addition reaction (such as triethylamine, 14-diπacetate?) Octane, dibutyltin oxide, tin dioctanoate or Dibutyltin dilaurate, 'bis_ (2_ethylhexanoic acid) _ > or other organometallic compounds are placed in the reactor or metered in later. Dibutyltin dilaurate is more preferred. Components (A), (Α2) added at the beginning of the reaction, and any one of (A3) and (A4) and / or (A5) may be used as needed (these components do not include primary or secondary Amine group). In the process of preparing the polyurethane prepolymer, the ratio of isocyanate group to isocyanate reactive group is 18 200528503 0.90 to 3, preferably 0.95 to 2.5, particularly preferably 1 〇5,

To (A5), which does not contain a part of a primary or secondary amine group, j · 0. (A2) is better to be complete) The total amount of isocyanate-reactive groups is me or complete (but? (A1) becomes (A5). The conversion effect is usually monitored closely by the standard NCO content of the component. For this purpose, the amount of the reaction mixture (for example, infrared or near-infrared spectroscopy, refractive index measurement, and chemical analysis (such as titration) of the spectroscopy measurement. Cut and remove the sample formate. Solvent form or in solution ^ diamidine I This amine is prepared from (A1) and (A2) to (A5)

, With anion and cation dispersion; u is or any full salt formation (if it has not been performed in the starting molecule). In the example of anionic groups, 'Analytical species can be used for this purpose, 7 columns such as ammonia, ammonium carbonate or ammonium bicarbonate, trimethylamine, triethylamine, tributylamine, diisopropylethylamine , Dimethylethanolamine, diethylethanolamine, triethanolamine, potassium hydroxide or sodium carbonate, preferably triethylamine, triethanolamine, dimethylethanolamine or monoisopropylethylamine. The test content is 50 to 100% of the content of the anionic group, preferably 60 to 90%. In the example of the cationic group, monomethyl sulfate or succinic acid is used. If only the non-ionic hydrophilic compound (A5) having an ether group is used, the neutralization step is omitted. If the water used for the dispersing action already contains a neutralizing agent, it can also be neutralized simultaneously with the dispersing action. 0 Possible amine components are (A2), (A3), and (A4) which can be used to convert the remaining isocyanate groups. ). This chain extension can be performed in a solvent (before dispersion, during dispersion) or in water (after dispersion). When an amine component is used as (A4), it is preferable to perform a chain extension effect before dispersion. 19 200528503 Amine components (A2), (A3) and (A4) can be added to the reaction mixture diluted with organic solvents and / or water. It is preferred to use 70 to 95% by weight of a solvent and / or water. If more than one amine component is present, the conversion can be performed sequentially or simultaneously by adding the mixture in any desired order. For the purpose of preparing the polyurethane dispersion (A), a polyurethane prepolymer (selectable shear force if necessary, such as vigorous stirring) is introduced into the water for dispersion, or vice versa Next, water for dispersion is added to the prepolymer with stirring. Next, if it is not carried out in the homogeneous phase, an increase in the molar mass can be achieved by reacting any of the isocyanate groups present with the components (A2) and (A3). The content of the polyamines (A2) and (A3) used depends on the content of the unconverted isocyanate group Q isocyanate group, which is 50 to 100%, preferably 75 to 95%, and is preferably a polyamine ( A2), (A3) transformation. If necessary, remove the organic solvent. The dispersion has a solid content of 10 to 70% by weight, preferably 25 to 65% by weight, and particularly preferably 30 to 60% by weight. The coating system according to the present invention can be used alone or in combination with adhesives, auxiliary substances and additives known in coating technology (especially light stabilizers (such as UV absorbers) and sterically hindered amines (HALS) and Oxidants, fillers and coating aids (e.g. anti-settling agents, anti-foaming agents and / or wetting agents), flow aids, reactive diluents, plasticizers, catalysts, auxiliary solvents and / or thickeners And additives (such as dispersions, pigments, colorants or mattifying agents)). In particular, combinations with other adhesives, such as polyurethane dispersions or polyacrylate dispersions (which may also be hydroxy-functional, as the case may be), are also possible without difficulty. Additives can be added to the coating system according to the invention immediately before processing. However, it is also possible to add at least some of the additives before or during the dispersing action of the adhesive or adhesive. The selection and measurement of these substances (which can be added to individual ingredients and / or to the mixture as a whole) are known to those skilled in the art. Polybutadiene production has been known for a long time; it is carried out through an emulsion polymerization reaction in an alkaline aqueous medium. Please refer to, Ullmanns

Encyclopadie der technischen Chemie ", Volume 9, page 366,

Verlag Urban and Schwarzenberg, Munich-Berlin 1957 ;, Encyclopedia of Polymer Science and Technology ", Vol. 3, pp. 705-730, John Wieley, New York 1965 ;, Methoden der # organischen Chemie" (Houben_Weyl) XIV / l, p. 738, George Thieme Verlay Stuttgart 1961. Consider any compound and mixture of emulsifiers that are theoretically effective in stabilizing emulsions, such as water-soluble salts (especially long-chain fatty acids, turpentine and turpentine derivatives, sodium, potassium, and money salts), higher molecular weight Alcohol sulfates, aryl sulfonic acids, formaldehyde condensation products of aryl sulfonic acids, non-ionic emulsifiers based on polyethylene oxide and polypropylene oxide, and polymers with an emulsifying effect (such as polyvinyl alcohol) (German patent DE- A 2 307 811, DE-A 2 426.012, DE-A2 514 666, DE-A2 527 320, DE-A2 755 074, DE-A 3 246 748, DE-A 1 271 405, DE-A 1 301 502, US patent US-A2,234,215, Japanese patent jp_A60 031 51〇). Therefore, the purpose is to provide an aqueous polygas butadiene dispersion. The difference lies in long storage stability, that is, its pH does not change significantly during storage. '' This objective is achieved by providing an aqueous polybutadiene dispersion, which is obtained by continuous or discontinuous polymerization of airbutadiene in aqueous emulsification 21 200528503, with or without the addition of only a small amount Conditioners, removal of residual monomers, and storage under special conditions, where it is possible to establish the desired polymer structure in a targeted manner. Therefore, the polybutadiene dispersion used according to the present invention is permeated in a basic medium of gasbutadiene and 0 to 20 parts by weight of an ethylenically unsaturated monomer (which can be copolymerized with gasbutadiene). Prepared by polymerization. Suitable copolymerizable monolithic systems are disclosed, for example, in "Methoden der organischen Chemie" (Houben-Weyl) XIV / 1, page 738 or less, George Thieme Verlay Stuttgart 1961. It is preferred to have 3 to 12 carbons per molecule Atoms and 1 or 2 copolymerizable C = C double bond compounds. Examples of preferred copolymerizable monomers are 2,3-dichlorobutadiene and 1-chlorobutadiene. The polygas butadiene dispersion of the present invention is prepared by emulsion polymerization at a temperature of 0 to 70 ° C (preferably at 5 to 45 ° C) and a pH value of 10 to 14 (preferably pH 11 to PH 13). ). The activation is affected by conventional activators or activator systems. Polybutadiene dispersions have a particle size of 60 to 300 nm, preferably 60 to 200 nm, and more preferably 60 to 150 nm, preferably 60 to 120 nm. The following are examples of activators and activator systems that can be mentioned: Formamidine sulfinic acid, potassium peroxodisulfate, potassium peroxodisulfate are The redox system of the substrate and silver salt (Na salt of anthraquinone β-acetic acid) are selected as needed. Among them, such as formamidinesulfinic acid, hydroxymethyl Compounds such as Na salt of sodium sulfinic acid, sodium sulfite, and sodium dithionite are suitable for use as redox complexes. Peroxide and nitrogen peroxide-based redox systems are also suitable for D continuous or 22 200528503, _ discontinuous The preparation of the polygas butadiene according to the present invention is preferably carried out by continuous polymerization. In order to adjust the viscosity of the polychloroprene according to the present invention, conventional chain transfer agents such as mercaptans (as disclosed in, for example, Germany) can be used. Patent DE_A3 711, British patent GB-A 1 048 235, French patent fr_A2073 106) or xanthogen monosulfide (as disclosed in, for example, German patents de-A 1 186 215, DE-A2 156 453, DE-A2 306 610 and DE-A3 044 811, European patent EP-A 0 053 319, British patent GB-A 512 458, GB-A 952 156 and US patents US_A2,321,693 and US-A2 567 117). _ Very good The chain transfer agent is n-dodecyl mercaptan and xanthogen disulfide used according to German patents DE-A3 044 8U, DE-A2 306 610 and DE-A2 156 453. The polymerization reaction is usually 50% to 95% (Preferably 60% to 80%) termination at monomer conversion 'wherein Agents, such as phlodon, tertiary butyl catechol, or diethylhydroxylamine. In this group emulsion polymerization reaction, a single system at different positions merges into growing polymer bonds, such as in polymerization At a reaction temperature of 42 ° C, 92.5% is at the anti-1,4 position, 5.2% is at the cis-1, 2 Φ position, 1.2% is at the 1,2-position, and 1.1% is at the 3,4_ position (W. Obrecht at Houben-Weyl: Methoden der organischen Chemie, Vol. 20, Part 3, Makromolekulare Stoffe, (1987), p. 845), where the monomers incorporated at the 1,2-position contain unstable, easily split gas atoms. This is an active material that undergoes a sulfurization reaction with a metal oxide. After the polymerization reaction, the residual gas-butadiene monomer is removed by steam distillation. It is as disclosed in W. Obrecht in Houben · Weyl: Methoden der organischen Chemie, Volume 20, Part 3 ’Makromolekulare 23 200528503

Stoffe, () 卯 7) on page 852. The low-monomer polybutadiene dispersion prepared in this way was then stored at the south temperature. During this period, some unstable gas atoms are separated and a polygas butadiene network (gel) is formed which is insoluble in organic solvents. In the other step, the solid content of the dispersion is increased by a creaming procedure. For example, this creaming is performed by adding alginate (as disclosed in "Neoprene Latices, John C. Cad, EI Du Pont 1964, p. 13,"). Therefore, the present invention also relates to Preparation of a storable polybutadiene dispersion:-in the presence of 0 to 1 mole (based on 100 grams of monomers), preferably 0 to 025 moles, at a temperature of 0 ° C To 7 (rc, preferably 5 to 45C, particularly preferably 1G ° C to 25 ° C, the polymerization reaction of gas butadiene is carried out, wherein the dispersion has a fraction insoluble in organic solvents. % By weight, preferably 0.5 to 5% by weight (based on polymer),-removal of residual unpolymerized monomer by steam distillation,-storage of the dispersion at a temperature of 5 (TC to 11 (rc, preferably _ To 100 ° C in spring, particularly good is 7 (rc to 9 (rc, in which the fraction (gel part) insoluble in organic solvents) is increased to i wt% to 6G wt%, which lasts for 3 hours to 14 days, And it is determined by the positioning preparatory test ^-By the creaming procedure, the solid content is increased to 50 to 64 weight, preferably 52 to 59 weight%, Dispersions with extremely low salt content, especially low gas ion content (less preferably less than 500 ppm). 24200528503 Aqueous dispersions of silicon dioxide have been known for a long time. Depending on the preparation method, they have different structures. Silica sol, silica gel, fumed silicic acid, or precipitated silicic acid or mixtures thereof can be used as the basis to prepare the silicon dioxide dispersion b) suitable for the present invention. Silicic acid sol is an amorphous silicon dioxide in water The colloidal solution, which is also known as Shixi and Gujiao, is usually referred to as Shixisol. Shijixi is in the form of spherical particles that have been hydroxylated on the surface. The particle size of the gelatinous particles is usually 1 To 200 nm, specific BET surface area related to particle size (through GN · Sears, φ

Measured by the method of Analytical Chemistry Vol. 28, Ν · 12, 1981-1983 (December 1956), the relevant part of which is incorporated in this case for reference) is ΐ5 to 2000 m 2 / g. The surface of the SiO2 particles has an electric charge that is compensated by the corresponding counter ions, thus causing the stabilization of the colloidal solution. The alkali-stabilized silica sol has a pH value of 7 to U.5, and contains, for example, a small amount of Na2O, K2O, LhO, ammonia, organic nitrogen test, tetrahydrogen ammonium hydroxide or alkali aluminate or ammonium aluminate as Alkalizing agent. The silica sol can also be in the form of a weak acid, which becomes a semi-stable gel solution. It is also possible to prepare cation-adjusted Shixisol by coating the surface with A12 (〇H) 5C1. The solid content of the hair sol is 5 to 60% by weight of Si02. By ion exchange, the establishment and stabilization of Si02 particles of the desired particle size (distribution), the establishment of the desired Si02 concentration, and the surface modification of Si02 particles as appropriate (for example, using A12 (0H) 5C1), the preparation method of silica sol substantially eliminates the test through the manufacturing steps of water glass. In any of these steps, the SiO2 particles do not leave a colloidal dissolved state. This explanation exists for example the existence of separate primary particles with high adhesion efficacy. 25 200528503 It should be understood that silicone is a colloidal shaped or unformed silicic acid with a loose to dense pore structure with elastic to solid consistency. Silicic acid is in the form of highly condensed polysilicic acid. Siloxane and / or silanol groups are located on the surface. Silicone is made from water glass by reaction with mineral acids. Furthermore, a distinction is made between pyrogenic silicic acid and precipitated silicic acid. During the preparation process, water is put into a container, and then water glass and an acid (for example, H2SO4) are added simultaneously. This produces colloidal primary particles which agglomerate as the reaction proceeds and grow together to form agglomerates. The specific surface area is 30 to 800 square meters / gram (DIN 66131), and the primary particle diameter is 5 to 100 nanometers. These primary particles of silicic acid in solid form are tightly crosslinked to form secondary agglomerates. By flame hydrolysis or assisted by the arc method, fumed silicic acid can be prepared. The main synthesis method of pyrogenic silicic acid is flame hydrolysis, in which tetrakisparite is burned in a hydrogen-oxygen flame to decompose. The resulting acid is therefore non-crystalline to x-rays. The ignited dream acid has significantly fewer OH groups on the almost non-porous surface than the precipitated silicic acid. The pyrogenic silicic acid prepared by flame hydrolysis has a specific surface area of 50 to 600 m 2 / g φ (DIN 66131) and a primary particle size of 5 to 50 nm; the silicic acid prepared by the arc method It has a specific surface area of 25 to 300 square meters per gram (DIN 66131) and a primary particle size of 5 to 500 nm. Additional information on the synthesis and properties of silicic acid in solid form can be found in, for example, K · Η · Bttchel, Η · _Η · Moretto, P · Woditsch "Industrielle Anorganische Chemie 'Wiley-VCH Verlag 1999, Chapter 5.8. If presented The isolated solid form of the SiO2 raw material (such as fumed or precipitated silicic acid) is used in the polymer dispersion according to the present invention, which is converted into an aqueous SiO2 dispersion through 26 200528503 dispersion. Dispersion of previous techniques The machine is used to make a silicon dioxide dispersion, preferably a high shear rate disperser or a diffuser plate.) It is preferred to use Si02 particles with a primary particle size of i to 400 nm ( It is preferably 5 to 100 nanometers, more preferably 8 to 60 nanometers), and it is an aqueous dispersion of oxidized hair. When using acid, it is ground into powder by grinding particles.

The polymer dispersion liquid preferably obtained according to the present invention is one in which the Si02 particles of the silicon dioxide dispersion liquid b) are separated uncrosslinked primary particles. It is also preferred that the Si02 particles on the particle surface have a hydroxyl group. Particularly preferred is the use of an aqueous silicic acid sol as an aqueous silica dispersion. 1. = According to the properties of the silicic acid according to the present invention, it is a thickened side in the miscellaneous dispersion of polyurethane and polybutadiene j. The result is self-refinement and easy separation. ) The adhesive produced can hold -1 treatment, and has high security even for porous substrates to be combined.

For this purpose, the thickening agent is accelerated by additives, and these add oxides. Zinc zinc or other metal with amphoteric nature and partial hydrolysates are examples of the polymer residues produced according to the present invention. The ratio of individual ingredients makes the resulting dispersion liquid with a dispersed polymer content of 99%. The content of the polyurethane dispersion (a) is 55 to% 'and the content of the silicon dioxide dispersion (b) is 1 to 45% by weight. 27 200528503 = The fraction is based on the weight of the non-volatile component The polymer dispersion liquid according to the present invention as a reference and a total weight of ιιο weight preferably contains a compound amount of 7% to 7%, and a weight of 0 to 7% and 20% of Λ to 7% of weight. "A mixture of liquid dispersion (b), the weight of the genital component is based on 100% by weight in total. ', Non-volatile in the polyurethane and polybutadiene according to the present invention: =. The content of the dispersion is *: acid ====== ene-butadiene dispersion (content up to 30% by weight).

The polymer dispersion according to the present invention contains other additives and an optional adhesion auxiliary substance as required. For example, you can add fillers such as stone powder, quartz sand, barite powder, calcium carbonate, chalk, dolomite or talc, and optionally wetting agents (such as polylinate, such as sodium hexametaphosphate) , Naphthalene acid, polyacrylic acid or sodium salt) 'wherein the filler is added in an amount of 10 to 60% by weight, compared to ㈣20 i 50% by weight, and the wetting agent is added in an amount of 0.2 to 0.6% by weight, all Figures are based on non-volatile components. For the manufacture of highly transparent adhesive films, for example, an epoxy (Ruetapox® 0164; bisphenol A epichlorohydrin resin, MW > 700), viscosity: 8000-13000 mPas' Supplier: BakeliteAG, Varzinger Str. 49, 47138 Duisburg-Meiderich). It is preferred to use 28 200528503, * zinc oxide or magnesium oxide as an additive, and use a small amount of hydrogenated hydrogen gas that can be separated from the polymer of succinic acid as the acceptor. Based on the non-volatile component, it is added in an amount of 0.1 to 10% by weight, preferably i to 5% by weight, and it can be partially hydrolyzed in the presence of polybutadiene dispersion liquid ⑷, or Contains hydrolysable components. In this way, the viscosity of the polymer dispersion can be increased and adjusted to a desired level. This hydrolysis is directed to Zn0 and is disclosed, for example, in Gmelins Handbuch der anorganische Chemie ", 8th edition, 1924, Verlag Chemie Leipzig, Vol. 32, pages 134/135, and supplemental Vol. 32, Verlag Chemie, 1956, Pages 1001 to 1003. · For MgO, § 'The line is disclosed in, for example, "Gmeiing [Handbuch der anorganische Chemie, 8th edition, 1939, Verlag Chemie Berlin, Volume 27, pages 12/13, 47_50, 62-64 . Other suitable auxiliary substances that may be used are, for example, organic thickeners (based on non-volatile components) in an amount of 0.01 to 1% by weight, such as cellulose derivatives, alginates, starches, starch derivatives, polymer Urethane thickener or polyacrylic acid, or inorganic thickener (based on non-volatile components), such as bentonites, in an amount of 0.05 to 5% by weight. _ For the purpose of preservation, fungicides can also be added to the adhesive composition according to the invention. These fungicides are used in an amount of 0.02 to 1% by weight based on the non-volatile components. Suitable fungicides are, for example, phenols and cresol derivatives or organotin compounds. It is also possible to tackify resins in a dispersed form (such as unmodified or modified natural resins such as turpentine esters, hydrocarbon resins, or synthetic resins) such as phthalate resins (see, for example, "Klebharze" R. Jordan R. Hinterwaldner, pp. 75-115, Hinterwaldner Verlag Munich 29 200528503 1994)) is added to the polymer dispersion according to the invention. Alkyl phenol resins and terpene resin dispersions with a softening point greater than 70 (preferably greater than 110) are preferred. Organic solvents (such as toluene, acetone, xylene, butyl acetate, formazan) may also be used. Ethyl ketone, ethyl acetate, dipurinane, or mixtures thereof) or plasticizers (based on adipic acid esters, phthalic acid esters, or phosphate esters), based on non-volatile components' 0.5 to 10 parts by weight. The present invention also provides a method for preparing a polymer dispersion according to the present invention, 'characterized in that the polybutadiene dispersion is mixed with the silicon dioxide dispersion (b)' and then a polyamine group is added Formate dispersion, in which the viscosity of the polybutadiene-silicon dioxide mixture is reduced. Conventional adhesion aids and additives may be added as appropriate. The adhesion formulation of the present invention may be added in a known manner, such as by spraying. Cloth coating, pouring, knife coating, spraying, roller coating or dipping. Drying of adhesive films at room temperature or at temperatures up to 220 ° C. Adhesive formulations can be used as a single component , Or as known Accompanied by the use of a cross-linking agent. By heating at a temperature of 150 to 18 ° C for a short time (seconds to minutes), the adhesive layer may be cured as appropriate. Compared to the conventional polybutadiene adhesive, according to the present invention The adhesive of the invention additionally exhibits a significantly reduced yellowing tendency. It adheres to plasticized PVC without activation, and it exhibits good wet adhesion properties on difficult-to-bond artificial leather (Mesh). Because it is not subject to hydrolysis Due to the effect of destruction, the combination maintains its high quality. The polymer dispersion according to the present invention can be used as an adhesive, for example, 200528503 for adhesively bonding any desired substrate of the same type or different types, such as wood, paper, Plastics, textiles, leather, rubber or inorganic materials (such as ceramics, stoneware, fiberglass or cement). [Embodiment] The substances used in Example 1, 1 Table 1: Polyurethane and polybutadiene dispersion liquid

Dispersion product supplier A Dispercoll® C VPLS 2325 5 8% Water-soluble poly-2-gasbutadiene with a significant tendency to crystallize (1, 3) Dispersion pH about 13 (according to DIN 53606) Bayer MaterialScience AG B Dispercoll® U 54 50% dispersion of aliphatic hydroxy-polyester polyurethane; particle size 200 nm minimum activation temperature: 45-55 ° C pH 6.0-9.0 Bayer MaterialScience AG Table 2: Silicon dioxide products Supplier Supply Form Type Dispercoll® S5005 Bayer MaterialScience AQ Lev ”DE silica sol dispersion, 50%, BET 50 m2 / g, pH 9, particle size 50 nm silica sol Dispercoll® Bayer silica sol dispersion, 30% , Silica sol 31 200528503 S3030 MaterialScience AQ BET 300 m² / g, Lev., DE pH 10, Preparation of a polybutadiene dispersion with a particle size of 9 nm: Examples (Dispercoll® C VPLS 2325, A1 polymerization reaction Through the measurement and adjustment device, the aqueous phase (w), monomer phase (M), and activator phase (A) are introduced into the polymerization cascade (consisting of 7 identical reactors), each of which has a specific product. 50 liters) Anti each «^ 25 2,650,714 persons in the (number of recommendations for each of the single parts by weight (M) = dan wooden cargo boat DE-A: 100.0 parts by weight 0.5 parts by weight 〇.〇3 005 parts by weight

Chlorobutene n-dexyl thiol, thiothiophene (W) = aqueous phase: demineralized water 115.0 parts by weight sodium salt of disproportionated abietic acid 2.6 parts by weight potassium hydroxide 1.0 parts by weight 32 200528503% '«(A) = Activator phase: 1 ° / 〇Aqueous formamidine sulfinic acid solution 0.05 parts by weight potassium persulfate 0.05 parts by weight anthraquinone-2-sulfonic acid Na salt 0.005 At an internal temperature of 15 ° C. by weight, the reaction was slightly started. The released polymerization heat was dissipated by external cooling, and the reaction temperature was maintained at 10 ° C. At a monomer conversion of 80%, the reaction was terminated by adding diethylhydroxylamine. Residual monomer was removed by steam distillation. The solid content was 38% by weight, the gel content was 4% by weight, and the pH was 12.8. After a polymerization time of 120 hours, the polymerization reaction line was slowed down. A2) Tempering of the dispersion liquid After steam distillation, the dispersion liquid was tempered in an insulated storage tank at a temperature of 80 ° C for 2 days, and the temperature was adjusted by additional heating as appropriate. The latex is then cooled and becomes milk fat (A3). A3) Creaming procedure Solid alginate (Manutex) was dissolved in deionized water and a 2% by weight alginate solution was prepared. 200 grams of the polygas butadiene dispersion was placed into each of eight 250 ml glass bottles, and 6 to 20 grams (in a 2 gram gradient) of the pharmacy salt solution was added with stirring. After a storage time of 24 hours, the amount of whey that had formed above the thick latex was measured. Multiply the alginate content in the sample with the most significant whey formation by 5 and get the optimal alginate content for the pore lipidation of 1 kg of polybutadiene 33 200528503 dispersion. 1.2 Measurement method 1.2.1 Determination of peel strength of plasticized pVC at room temperature The test was performed according to EN 1392. Two plasticized PVC samples (30% dioctyl dioctanoate, dop) (measured in nanometers) were roughened with an abrasive paper (roughness = 80), and the dispersion was applied to the powder through a brush On both sides, apply to rough surface and dry at room temperature for 60 minutes. The specimens were then placed in two and pressed in a press (10 seconds; 4 bar line pressure). A tear test was performed at room temperature on a commercially available tensile tester. The intensity values were determined immediately after binding and immediately after p. The samples were stored at 23 ° C and 50% relative humidity. Application of Adhesive ...-Use a knife to apply the adhesive as a single component (200 μg) 1.3 Production of adhesive components · In order to make a formulation, place the polybutadiene dispersion in a peeling beaker . Then add the antioxidant Rhenofit® DDA-50OM (N-phenylaniline, styrene-treated 'solid content 50%, pH 8-10, manufacturer Rhein Chemie Rheinau GmbH), the oxidation form Borchers® 9802 (Aqueous paste based on activated zinc oxide, essentially viscous white paste, pigment content 50% by weight, density about 166 g / cm3, viscosity at 10.3 l / s is 3500 mPas; the supplier is 34 200528503

Borchers GmbH, Alfred Nobel Str., 50, 40765 Monheim) and finally chopped sol. After a reaction time of 30 minutes, essentially viscous agglomerates were formed through the gelation of silica sol (CR (organic) _silica dioxide / silica sol- (inorganic) -hybrid system), by adding polyamines The urethane dispersion is adjusted to a desired viscosity. 30% plasticizer bound to PVC (non-activation bonding) Γ 2 * 3 4 5 6 7 * Dispercoll® C 2325 100 100 100 100 100 100 Dispercoll® U 54 _ mm 25 50 75 100 100 Dispercoll® S 3030 _ 20 20 20 20 20 Zinc oxide Borchers® 9802 4 4 4 4 4 4 Rhenofit® DDA-50 EM 2 2 2 2 2 2 Peel strength [Newton / mm] Immediate 0.1 0.2 1.1 1.5 0.7 0.5 0 Peel strength [Newton / mm] 1 0.2 03 1.5 1.5 0.6 0.5 0 * Compared with No. 4 adhesive combined with artificial leather (mesh) Artificial leather contains a PUR top layer with a textile side of polyethylene terephthalate substrate. On the textile side, apply MESH with an adhesive, and 35 200528503-without any reaction time, after a specific time (minutes), press it together manually (at the fingertips) (textile side to textile side, Called Umbugg method)-After 90 seconds in a 65 ° C circulating air oven, after a specific time (minutes), press them together manually (with fingertips) (textile side to textile side, called Umbugg method) ).

Storage at RT (minutes) 0 4 6 8 10 12 15 Formulation 4 = CCCCBBA Formulation 2 according to the invention 2 = CCCCCCC stored at 65 ° C for 90 seconds 0 4 6 8 10 12 15 Formulation 4 = According to the invention AAAAAAA formulation 2 = comparative CCCCCCC

A: Good strength B: Medium strength _ C: Inappropriate strength, bad combination Although the present invention has been described in detail above for the purpose of illustration, it should be understood that this detail is only for the purpose of illustration and the case should be familiar to the art Those who make changes do not depart from the spirit and scope of the present invention, and are limited only by the scope of patent application as attached. 36

Claims (1)

200528503 10. Scope of patent application: 1_ An aqueous polymer dispersion, which includes the following: Ϊ less; a kind of polyurethane having an average particle size of 60 to 350 nanometers b) at least one having an average particle size of 60 to 300 μm The polymerization gas, the liquid dispersion, and the olefinic component C) are at least one SiO2 oxidized stone dispersion having a particle size of 1 to 400 nm. Property II U: An aqueous polymer dispersion according to item 1 of the patent, wherein the 102 particles have a particle size of 5 to 100 nm. 3. The aqueous polymer dispersion according to item 1 of the patent scope, wherein the 102 particles have a particle size of 8 to 60 nm. 4. ί: The aqueous polymer dispersion of item 1 of the patent, in which 詨 12 particles are in the form of separated, uncrosslinked primary particles. The aqueous polymer dispersion according to item 1, wherein the particles have a hydroxyl group at the surface of the particles. 6: The aqueous polymer dispersion of item 1 in the scope of claim 1, wherein the water, the silicon oxide dispersion C) is an aqueous silicic acid sol. The water-based polymer dispersion of the first item of the chemical industry is Huafangba, w L This gas is gathered for the second-year Sanshou) and the water-based dioxin is used as a liquid dispersion, and if necessary, it is selected as an adhesive auxiliary substance: The 8-adhesive composition of (b) and (8) is mixed with the polyurethane dispersion liquid, and the polymer dispersion liquid includes the polymer dispersion liquid as described in item 1 of the patent application range. Sigh 37 200528503. _ 9. A substrate, which is bonded together through a polymer dispersion such as the one in the scope of patent application. 10. If the base material of item 9 of the patent application scope, wherein the base material is a structural component of a shoe or a shoe. 11. The aqueous polymer dispersion according to item 2 of the patent application, wherein the SiO 2 particles are in the form of separated, uncrosslinked primary particles. 12. The aqueous polymer dispersion of claim 3, wherein the SiO 2 particles are in the form of separated, uncrosslinked primary particles. 13. The aqueous polymer dispersion according to item 2 of the patent application, wherein the SiO2 particles have a hydroxyl group at the surface of the particles. 14. The aqueous polymer dispersion of claim 3, wherein the SiO 2 particles have a hydroxyl group at the surface of the particles. 15. The aqueous polymer dispersion according to item 2 of the application, wherein the aqueous silica dispersion c) is an aqueous silicic acid sol. 16. The aqueous polymer dispersion according to item 3 of the application, wherein the aqueous silica dispersion c) is an aqueous silicic acid sol. 38 200528503 VII. Designated Representative Map: (1) The designated representative map in this case is: (). C number J (2) Brief description of the component symbols in this representative figure: None 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None 4