DE102008002704A1 - Method for manufacturing composite materials, involves submitting solid material, and polyurethane reaction mixture is applied on solid material - Google Patents

Abstract

Composite materials manufacturing involves submitting a solid material. A polyurethane reaction mixture is applied on the solid material. Another polyurethane reaction mixture is applied on the former polyurethane reaction mixture. The former polyurethane reaction mixture and latter polyurethane reaction mixture are hardened to a polyurethane and another polyurethane.

Description

The The present invention relates to a process for the preparation of Composites of polyurethane foam and solid materials, wherein the bulk material is in the application of the first polyurethane reaction mixture a temperature of 50 ° C and more, in which one i) presenting the massive material, ii) one on the massive material first polyurethane reaction mixture, iii) the first Polyurethane reaction mixture, a second polyurethane reaction mixture and iv) the first polyurethane reaction mixture and the second polyurethane reaction mixture to a first polyurethane and a second polyurethane, and wherein the first Polyurethane has a higher density than the second polyurethane. Further, the present invention relates to a composite available after such a procedure.

Further Embodiments of the present invention are the claims, the description and examples. It goes without saying that the above-mentioned and those still to be explained below Features of the subject invention not only in the specified combination, but also in others Combinations are usable without departing from the scope of the invention leave.

polyurethane foams have long been known and used in different fields applied. A typical use is as a shoe sole, for Example of street shoes, sports shoes, sandals and boots.

Next elastic polyurethane foams are used today for the production shoe soles also used compact elastomers. Which includes u. a. thermoplastic polyurethane (TPU) or compact 2-component PUR cast elastomers and rubber z. B. on NBR or SBR basis. Among the special advantages of compact elastomers over Foam counts the lower abrasion and the so associated long durability of soles made therefrom. sole made of rubber also have an excellent wet skid resistance. Among the special advantages of elastic polyurethane foams include the low density, good damping properties as well as excellent protection against cold.

Out the desire to take advantage of these two material classes too unite, so-called combination soles have been developed in recent years been made of an outsole, for example, rubber or TPU and elastic polyurethane foam as midsole, consist. As a result, the good mechanical properties of Rubber or thermoplastic polyurethane with the advantages of elastic Polyurethane foam combined.

The combination sole is made by connecting the rubber or TPU outsole via direct polyurethane with the shoe upper. Here, a distinction can be made between two alternative methods. In process 1, the polyurethane reaction mixture is placed in a mold containing a rubber outsole prepared in a separate previous operation and closed by the shoe upper. The outsole material used can be stored for different lengths. In the more economical method 2, the production of the outsole and the Direktanspritzung takes place directly one after another on a rotary table system consisting of separate Anspritzaggregaten for the outsole and midsole material. An example of machinery of this kind can be found in Desma Today, 04-2005, pp. 4-5 (Source: http://www.desma.de/news/desma_today/pdf/DESMA_today_04_05_D.pdf ).

there The outsole is made of rubber or TPU from procedural economic Just before application of the polyurethane reaction mixture produced. The freshly produced rubber usually has temperatures of about 160 ° C. Freshly made TPU usually has Temperatures from 50 to 150 ° C. If such a rubber or TPU element with a polyurethane reaction mixture for production covered by polyurethane foams, receives often a composite material with reduced adhesion. Similar adhesion problems also occur in the application of polyurethane reaction mixtures on other hot materials, such as more Polymers or metals.

One way to improve adhesion is that the rubber sole used on the surface facing the polyurethane is chemically modified or provided with a layer of primer and adhesive to ensure adhesion to the polyurethane. Especially for safety shoes is in the EN ISO 20 345 specifies that the adhesion must be at least 4 N / mm in the case of stripping of the layers. In the case of a foam break, this value must be at least 3 N / mm.

To improve the adhesion between elastic polyurethane foams and hot rubber, various methods are known. So revealed EP-A-286 966 a process for the production of composite soles, in which subjecting the surface of a rubber-elastic material in a vacuum plasma treatment and then foaming a polyurethane foam layer by applying a polyurethane reaction mixture.

In the article Sci. Techn. 2005, 19 (1), 19-40 by CM Cepeda-Jiminez et al., "Surface Treatment of Vulcanized Latex for Improving its Adhesion Performance in Shoe Manufacturing". describes the need for pre-treatment of rubber by halogenation to achieve adhesion of polyurethane to rubber.

Next is out DE 19715551 a method is known in which in the manufacture of the rubber sole on the surface of a nonwoven fabric is vulcanized, which should increase the adhesion to the polyurethane.

disadvantage These methods are that for producing a combination sole with sufficient adhesion between rubber and polyurethane additional Work steps as well as an additional expenditure on production time and investments is necessary in machines. Next, these procedures can lead to corrosion of metal parts of the mold.

task The present invention was therefore a simple process for producing a composite material from a hot, to deliver solid material and polyurethane foams that too increased adhesion between polyurethane and solid Material in the composite material leads and which the shape of the Production of the composite material is not attacked.

These The object is achieved by a method in which i) presenting the massive material, ii) one on the massive material first polyurethane reaction mixture, iii) the first Polyurethane reaction mixture, a second polyurethane reaction mixture and iv) the first polyurethane reaction mixture and the second polyurethane reaction mixture to a first polyurethane and a second polyurethane, wherein the solid Material in the application of the first polyurethane reaction mixture a Temperature of 50 ° C and more, and the first polyurethane has a higher density than the second polyurethane.

Under a massive material in the sense of the invention are all massive Understand materials used in the production of composites with polyurethane foams a temperature of greater than 50 ° C, preferably from 100 to 200 ° C, particularly preferably from 110 to 180 ° C and especially from 140 to 180 ° C. to have. Preferably, the massive material is around freshly vulcanized rubber or TPU with these temperatures.

In the context of the invention, freshly vulcanized rubber is understood as meaning elastomers, for example butadiene rubber (BR), styrene-butadiene rubber (SBR), isoprene rubber (IR), styrene-isoprene-butadiene rubber (SIBR), acrylonitrile rubber. Butadiene rubber (NBR), chloroprene rubber (CR), isobutene-isoprene rubber (IIR), natural rubber (NR), which may be present in pure as well as in blends with each other with vulcanization accelerators and / or crosslinking agents on sulfur or Peroxide-based mixed and vulcanized according to standard practice. The elastomers optionally contain commercially available fillers, such as carbon blacks, silica, chalk, metal oxides, plasticizers, antioxidants, antiozonants and / or thermoplastic polymers, such as styrene-containing thermoplastics, for example polystyrene or polystyrene acrylonitrile (SAN), ethylene vinyl acetate (EVA), polyethylene, polypropylene, polycarbonate , thermoplastic polyurethane (TPU), polyvinyl chloride (PVC) or thermoplastic elastomers based on styrene-butadiene-styrene block copolymers or styrene-isoprene-styrene block copolymers or blends of said thermoplastics with one another. Such vulcanized rubber compounds are described, for example, in PA Ciullo, "The Rubber Formulary," Hoyes Publications, 1999, ISBN: 0-8155-1434-4 , Vulcanized rubber is particularly preferably rubber comprising butadiene rubber (BR), styrene-butadiene rubber (SBR), isoprene rubber (IR), styrene-isoprene-butadiene rubber (SIBR), acrylonitrile-butadiene rubber. Rubber (NBR), chloroprene rubber (CR), isobutene-isoprene rubber (IIR), and natural rubber (NR), or mixtures thereof, mixed with vulcanization accelerators and / or crosslinking agents based on sulfur or peroxide and vulcanized in accordance with standard practice. In particular, rubber vulcanized acrylonitrile butadiene rubber or styrene butadiene rubber is used.

The first polyurethane reaction mixture and the second polyurethane reaction mixture are obtainable by mixing a) organic polyisocyanates with b) at least one relatively high molecular weight Ver c) chain extenders and / or crosslinking agents, d) blowing agents and optionally e) catalysts and f) other auxiliaries and / or additives, wherein the first polyurethane reaction mixture can also contain no blowing agent d).

Preferably, polyurethane reaction mixtures are used, which are commonly used for the production of shoe soles. Such polyurethanes and polyurethane reaction mixtures are described, for example, in US Pat DE 2402734 . EP 463479 A1 and EP 358328 A1 ,

The for the preparation of the polyurethane composites of the invention used organic and / or modified polyisocyanates (a) include the known from the prior art aliphatic, cycloaliphatic and aromatic di- or polyfunctional isocyanates (component a-1) and any mixtures thereof. Examples are 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates and higher nuclear homologues of diphenylmethane diisocyanate (Polymeric MDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,4- or 2,6-toluene diisocyanate (TDI) or mixtures of said isocyanates.

Prefers 4,4'-MDI is used. The preferred 4,4'-MDI can 0 to 20% by weight 2,4 'MDI and small amounts, up to about 10% by weight, allophanate or uretonimine modified polyisocyanates. There may also be small amounts of polyphenylene polymethylene polyisocyanate (Polymer-MDI) are used. The total amount of these highly functional Polyisocyanates should not exceed 5% by weight of the isocyanate used.

The Polyisocyanate component (a) is preferably in the form of polyisocyanate prepolymers used. These polyisocyanate prepolymers are available in the above-described polyisocyanates (a-1), for example at temperatures of 30 to 100 ° C, preferably at about 80 ° C, with polyols (a-2) to be converted to the prepolymer.

polyols (a-2) are known in the art and described for example in the "Kunststoffhandbuch, Volume 7, Polyurethane", Carl Hanser Verlag, 3rd edition 1993, chapter 3.1.

Possibly are the said polyols in the preparation of Polyisocyanatprepolymere usual Chain extender or crosslinker added. Such Substances are described below under c). Especially preferred are used as chain extenders or crosslinkers dipropylene glycol or Tripropylene glycol used.

higher molecular weight Compounds b) having at least two isocyanate-reactive H atoms can be, for example, polyetherols or polyesterols be.

polyetherols are prepared by known methods, for example by anionic polymerization with alkali metal hydroxides or alkali metal alcoholates as catalysts and with the addition of at least one starter molecule, containing 2 to 3 reactive hydrogen atoms bound, or by cationic polymerization with Lewis acids, such as antimony pentachloride or borofluoride etherate of one or more Alkylene oxides having 2 to 4 carbon atoms in the alkylene radical. suitable Alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide and preferably ethylene oxide and 1,2-propylene oxide. Furthermore, as catalysts it is also possible to use multimetal cyanide compounds, so-called DMC catalysts can be used. The alkylene oxides can be singly, alternately one after the other or as mixtures be used. Preference is given to mixtures of 1,2-propylene oxide and ethylene oxide, wherein the ethylene oxide is present in amounts of from 10 to 50% is used as ethylene oxide endblock ("EO-cap"), so that the resulting polyols to over 70% primary OH end groups exhibit.

When Starter molecules are water or dihydric and trihydric alcohols, such as ethylene glycol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, glycerol or trimethylolpropane into consideration.

The Polyether polyols, preferably polyoxypropylene polyoxyethylene polyols, have a functionality of 2 to 3 and molecular weights from 1,000 to 8,000, preferably from 1,500 to 6,000 g / mol.

Polyester polyols may be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms, polyhydric alcohols, preferably diols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms. Suitable dicarboxylic acids are, for example: succinic acid, glutaric acid, adipic acid, Suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used both individually and in admixture with each other. Instead of the free dicarboxylic acids and the corresponding dicarboxylic acid derivatives, such as. As dicarboxylic acid esters of alcohols having 1 to 4 carbon atoms or dicarboxylic anhydrides are used. Preferably used dicarboxylic acid mixtures of succinic, glutaric and adipic acid in proportions of, for example, 20 to 35:35 to 50:20 to 32 parts by weight, and especially adipic acid. Examples of dihydric and polyhydric alcohols, in particular diols, are: ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10 -Decandiol, glycerol and trimethylolpropane. Preferably used are ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol. Can also be used polyester polyols from lactones, eg. B. ε-caprolactone or hydroxycarboxylic acids, eg. B. ω-hydroxycaproic acid.

to Preparation of the polyester polyols can be the organic, z. B. aromatic and preferably aliphatic polycarboxylic acids and / or derivatives, and polyhydric alcohols catalyst-free or preferably in the presence of esterification catalysts, suitably in an atmosphere of inert gas, at temperatures of 150 to 250 ° C, optionally under reduced pressure, be polycondensed. As esterification catalysts, for example Iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts into consideration. For the preparation of the polyester polyols, the organic Polycarboxylic acids and / or derivatives and polyhydric alcohols advantageously in the molar ratio of 1: 1 to 1.8, preferably 1: 1.05 to 1.2 polycondensed.

The polyester polyols obtained preferably have a functionality from 2 to 4, especially from 2 to 3, and a molecular weight from 480 to 3000, preferably 1000 to 3000 g / mol.

Also suitable as polyols are polymer-modified polyols, preferably polymer-modified polyesterols or polyetherols, particularly preferably graft polyether or graft polyesterols, in particular graft polyetherols. This is a so-called polymer polyol, which usually has a content of, preferably thermoplastic, polymers of 5 to 60 wt .-%, preferably 10 to 55 wt .-%, particularly preferably 30 to 55 wt .-% and in particular 40 to 50% by weight. Polymer polyesterols are for example in WO 05/098763 and EP-A-250351 and are usually prepared by free-radical polymerization of suitable olefinic monomers, for example styrene, acrylonitrile, (meth) acrylates, (meth) acrylic acid and / or acrylamide, in a graft-based polyesterol. The side chains are generally formed by transferring the radicals from growing polymer chains to polyesterols or polyetherols. In addition to the graft copolymers, the polymer polyol predominantly contains the homopolymers of the olefins dispersed in unchanged polyesterol or polyetherol.

In a preferred embodiment, acrylonitrile, styrene and acrylonitrile and styrene are used as monomers. The monomers are optionally polymerized in the presence of further monomers, a macromer, a moderator and using a radical initiator, usually azo or peroxide compounds, in a polyesterol or polyetherol as a continuous phase. This method is for example in DE 111 394 . US 3 304 273 . US 3,383,351 . US 3,523,093 . DE 1 152 536 and DE 1 152 537 described.

Of the Proportion of macromers is usually 1 to 20 wt .-%, based on the total weight of the preparation of the Polymerpolyols used monomers.

is in the higher molecular weight compound b) contain polymer polyol, this is preferably present together with other polyols, for example Polyetherols, polyesterols or mixtures of polyetherols and Polyesterols. Particularly preferred is the proportion of polymer polyol greater than 5 wt .-%, based on the total weight component (b).

As chain extenders and / or crosslinking agents (c) are substances having a molecular weight of preferably less than 500 g / mol, more preferably from 60 to 400 g / mol used, wherein chain extenders have 2 isocyanate-reactive hydrogen atoms and crosslinking agent 3 or more isocyanate-reactive hydrogen atoms , These can be used individually or preferably in the form of mixtures. Preference is given to using diols and / or triols having molecular weights of less than 400, more preferably from 60 to 300 and in particular from 60 to 150. For example, suitable are aliphatic, cycloaliphatic and / or araliphatic diols having 2 to 14, preferably 2 to 10 carbon atoms, such as ethylene glycol, 1,3-propanediol, 1,10-decanediol, 1,2-, 1,3-, 1, 4-dihydroxycyclohexane, diethylene glycol, dipropylene glycol and preferably monoethylene glycol, 1,4-butanediol, 1,6-hexanediol and bis (2-hydroxyethyl) hydroquinone, triols such as 1,2,4-, 1,3,5-trihydroxy cyclohexane, glycerol and trimethy lolpropane, and low molecular weight hydroxyl-containing polyalkylene oxides based on ethylene and / or 1,2-propylene oxide and the aforementioned diols and / or triols as starter molecules. Particularly preferred chain extenders (c) are monoethylene glycol, 1,4-butanediol and / or glycerol.

Provided Chain extenders, crosslinkers or mixtures apply it, these come expediently in amounts of 1 to 60 wt .-%, preferably 1.5 to 50 wt .-% and in particular 2 to 40 wt .-%, based on the weight of the components (b) and (c) are used.

As blowing agent (d) generally known chemically and / or physically acting compounds can be used. Chemical blowing agents are compounds which form gaseous products by reaction with isocyanate, such as, for example, water or formic acid. Physical blowing agents are understood as compounds which are dissolved or emulsified in the starting materials of polyurethane production and evaporate under the conditions of polyurethane formation. These are, for example, hydrocarbons, halogenated hydrocarbons, and other compounds, such as perfluorinated alkanes such as perfluorohexane, chlorofluorocarbons, and ethers, esters, ketones and / or acetals, for example (cyclo) aliphatic hydrocarbons having 4 to 8 carbon atoms, or hydrofluorocarbons as Solkane ^® 365 mfc from Solvay Fluorides LLC. In a preferred embodiment, the blowing agent employed is a mixture containing at least one of these physical blowing agents and water, in particular water as the sole blowing agent. If no water is used as blowing agent, preferably only physical blowing agents are used.

In Another preferred embodiment of the implementation the components (a), (b) and optionally (d) as additional Blowing agent hollow microspheres containing physical blowing agent, added. The hollow microspheres can also be mixed with the aforementioned additional chemical blowing agents and / or physical blowing agents.

The production of such hollow microspheres is for example in US Pat. No. 3,615,972 described. The hollow microspheres generally have a diameter of 5 to 50 microns. Examples of suitable hollow microspheres are available from Akzo Nobel under the trade name Expancell® ^®.

When Catalysts (e) for the production of polyurethane foams preferably uses compounds which the reaction of the hydroxyl groups containing compounds of component (b) and optionally (c) with the organic, optionally modified polyisocyanates (a) accelerate hard. Examples include amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tertiary amines, such as triethylamine, tributylamine, dimethylbenzylamine, N-methyl, N-ethyl, N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N'-tetramethylhexanediamine, penramethyl-diethylenetriamine, Tetramethyldiaminoethyl ether, bis (dimethylaminopropyl) urea, Dimethylpiperazine, 1,2-dimethylimidazole, 1-azabicyclo- (3,3,0) octane and preferably 1,4-diazabicyclo (2,2,2) octane and alkanolamine compounds, such as triethanolamine, triisopropanolamine, N-methyl- and N-ethyl-diethanolamine and dimethylethanolamine. Also contemplated are organic metal compounds, preferably organic tin compounds, such as tin (II) salts of organic carboxylic acids, eg. Tin (II) acetate, stannous (II) octoate, stannous (II) ethylhexoate and tin (II) laurate and the dialkyltin (IV) salts of organic Carboxylic acids, eg. Dibutyltin diacetate, dibutyltin dilaurate, Dibutyltin maleate and dioctyltin diacetate, as well as bismuth carboxylates, such as Bismuth (III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate or mixtures thereof. The organic metal compounds can alone or preferably in combination with strong basic amines be used.

Preferably be used 0.001 to 5 wt .-%, in particular 0.05 to 2 wt .-% Catalyst or catalyst combination, based on the weight component (b).

Of the Reaction mixture for the production of polyurethane foams Optionally, adjuvants and / or additives may also be used (f) are added. Mention may be made, for example, surface-active Substances, foam stabilizers, cell regulators, release agents, rubber vulcanization aids, Fillers, dyes, pigments, hydrolysis protectants, odor-absorbing substances and fungistatic and / or bacteriostatic acting substances.

Rubber vulcanization aids are to be understood as the vulcanization auxiliaries customary for the vulcanization of rubber. Specific examples include: vulcanizing agents, such as sulfur, peroxides, metal oxides, activators, such as metal oxides, eg. As the combination of zinc oxide and stearic acid, accelerators, such as thiorams, guanidines, thiazoles, sulfenamides and dithiocarbamates. These are for example, described in PA Ciullo, "The rubber formulation", Hoyes Publications, 1999, ISBN: 0-8155-1434-4 ,

Preferably, the first polyurethane reaction mixture further contains hyperbranched polymer (g). For the purposes of the invention, hyperbranched polymers (g) used are any polymers having a weight-average molecular weight of greater than 500 g / mol, the main chain of which is branched and having a degree of branching (DB) of greater than or equal to 0.05. Preference is given to hyperbranched polymers having a weight-average molecular weight of greater than 800 g / mol, particularly preferably greater than 1000 g / mol and in particular greater than 1500 g / mol and a degree of branching of 0.1 and greater. The degree of branching of the hyperbranched polymers according to the invention is particularly preferably 0.2 to 0.99 and in particular 0.3 to 0.95 and especially 0.35 to 0.75. To define the "Degree of Branching" is to H. Frey et al., Acta Polym. 1997, 48, 30 directed.

Preferred hyperbranched polymers (g) are those based on ethers, amines, esters, carbonates, amides, urethanes and ureas and their mixed forms, such as, for example, ester amides, amidoamines, ester carbonates and urea-urethanes. In particular, hyperbranched polyethers, polyesters, polyesteramides, polycarbonates or polyestercarbonates can be used as hyperbranched polymers. Such polymers and processes for their preparation are in EP 1141083 , in DE 102 11 664 , in WO 00/56802 , in WO 03/062306 , in WO 96/19537 , in WO 03/54204 , in WO 03/93343 , in WO 05/037893 , in WO 04/020503 , in DE 10 2004 026 904 , in WO 99/16810 , in WO 05/026234 and DE 10 2005 009 166 described.

In an embodiment, the inventive hyperbranched polymers have different functional groups on. Preferably, these functional groups are capable of Isocyanates and / or to react with reactive groups of the rubber or to interact with the rubber.

The functional groups that are reactive towards isocyanates are, for example, hydroxyl, amino, mercapto, epoxy, carboxyl or acid anhydride groups, preferably hydroxyl, amino, Mercapto or acid anhydride groups.

The functional groups that interact with the reactive groups of the gum For example, groups that are too radical are Are capable of polymerization, such as olefinic double bonds, Triple bonds or activated double bonds, such as Vinyl groups, (meth) acrylate groups, maleic or fumaric acid groups or their derivatives containing groups.

The functional groups that interact with the gum can, are units that are not covalent with the solid but interactions via positive or negative charged groups, via electronic donor or acceptor bonds, via Hydrogen bonds, via van der Waals bonds or exercise hydrophobic interactions.

hydrogen- or donor and acceptor bond forming units for example, hydroxyl, amino, amide, urea, urethane, mercapto, Epoxy, carboxyl or acid anhydride groups, carbonyl groups, Ester groups, ether groups, olefinic double bonds, conjugated Double bonds, triple bonds, activated double bonds, for example (meth) acrylate groups or maleic or fumaric acid or their derivatives containing groups.

Van der Waals bonds or hydrophobic interactions generating molecule regions may be, for example, linear or branched alkyl, alkenyl or alkynyl radicals of chain length C ₁ -C ₁₂₀ or aromatic systems having 1-10 ring systems which may also be reacted with heteroatoms, such as nitrogen, Phosphorus, oxygen or sulfur may be substituted. Also suitable are linear or branched polyether molecular regions based on ethylene oxide, propylene oxide, butylene oxide, styrene oxide or mixtures thereof, as well as polyethers based on tetrahydrofuran or butanediol.

In a preferred embodiment, the inventive hyperbranched polymers (g) both with isocyanate-reactive groups as well as rubber reacting or interacting Groups on, for example, the link the monomers obtained ester, ether, amide and / or carbonate structures as well as hydroxyl groups, carboxyl groups, amino groups, acid anhydride groups, (Meth) acrylic double bonds, maleinic double bonds, vinyl groups and / or long-chain linear or branched alkyl radicals.

Particularly suitable hyperbranched polymers (g) are, for example, in the earlier application with the application number EP 06121514.1 disclosed. The hyperbranched polymers (g) further have a hydroxyl number according to the rule DIN 53240 , Part 2 from 1 to 500, preferably from 10 to 500 and particularly preferably from 10 to 400 mg KOH / g.

Further have the hyperbranched polymers according to the invention (g) usually a glass transition temperature (measured according to ASTM method D3418-03 with DSC) of less than 100 ° C, preferably from -30 to 80 ° C.

In a preferred embodiment are for the first polyurethane reaction mixture and the second polyurethane reaction mixture the same components (a), (b), (c), and (f) are used, wherein the proportions of the components (a), (b), (c) and (f) to each other for the first and second polyurethane reaction mixtures are the same.

apart optionally in the first polyurethene reaction mixture contained component (g), the first polyurethane reaction mixture differ and the second polyurethane reaction mixture in the blowing agent (d), whereby the different densities of the first and the second Polyurethane can be adjusted. It contains preferably the first polyurethane reaction mixture is not an additional one Propellant (d). This will be traces of water up to a total amount of 0.1% by weight, based on the total weight of the components (a) bis (f) of the first polyurethane reaction mixture, for example the natural water content of component (b) or (c) not regarded as propellant (d).

contains the first polyurethane reaction mixture blowing agent is preferably hollow microspheres or endothermic propellants, which absorb heat during gas release. Such endothermic Propellants are, for example, bicarbonates and carbonates the alkali and alkaline earth metals such. For example, sodium bicarbonate.

In a preferred embodiment contains the second polyurethane reaction mixture as blowing agent (d) preferably Water in an amount of 0.1 to 2 wt .-%, preferably 0.2 to 1.5 Wt .-%, particularly preferably 0.3 to 1.2 wt .-%, in particular 0.4 to 1% by weight, based on the total weight of components (a) to (f) of the second polyurethane reaction mixture.

The Components (a) to (g) or (a) to (f) are used for the production the first and the second polyurethane reaction mixture in such Quantities mixed together that the equivalence ratio of NCO groups of the polyisocyanates (a) to the sum of the reactive hydrogen atoms of components (b), (c), (d) and (g) 1: 0.8 to 1: 1.25, preferably 1: 0.9 to 1: 1.10. Within the scope of the invention the mixture of components (a) to (g) or (a) to (f) in reaction conversions less than 90%, based on the isocyanate groups, as the reaction mixture designated.

The Composite materials according to the invention are preferably according to the oneshot method with the help of low-pressure or high-pressure technology in closed, suitably tempered Molds containing fresh vulcanized rubber. The molds are usually made of metal, for. B. Aluminum or steel. These procedures are for example described by Piechota and Röhr in "integral foam", Carl-Hanser-Verlag, Munich, Vienna, 1975, or in the "Plastics Handbook", volume 7, Polyurethane, 3rd edition, 1993, chapter 7. In this case, the rubber be used without any pretreatment. Next can for further Improvement of the adhesion of rubber also by known methods, such as halogenation or plasma treatment, are pretreated.

The starting components (a) to (g) of the first polyurethane reaction mixture are for this purpose preferably mixed at a temperature of 15 to 90 ° C, more preferably from 25 to 55 ° C and optionally introduced the reaction mixture under elevated pressure in the closed mold. The mixing can be carried out mechanically by means of a stirrer or a stirring screw or under high pressure in the so-called countercurrent injection method. The mold temperature is expediently 20 to 160 ° C, preferably 30 to 120 ° C, particularly preferably 30 to 60 ° C, wherein the surface of the solid material is greater than 50 ° C, preferably from 50 to 200 ° C, more preferably from 110 to 180 ° C and in particular from 140 to 180 ° C. Preferably, the first polyurethane reaction mixture covers 20% or more, more preferably 30% or more, of the surface of the bulk material to be covered with polyurethane. Subsequently, the starting components (a) to (f) of the second polyurethane reaction mixture are also preferably at a temperature of 15 to 90 ° C, particularly be preferably mixed from 25 to 55 ° C and introduced the second reaction mixture optionally under elevated pressure in the closed mold. Again, the mixing can be performed mechanically by means of a stirrer or a stirring screw or under high pressure in the so-called Gegenstrominjektionsverfahren. It is not necessary that the first polyurethane reaction mixture is already cured to the first polyurethane in the application of the second polyurethane reaction mixture. The weight ratio of the components (a) to (g) of the first polyurethane reaction mixture and the second polyurethane reaction mixture to rubber is preferably 1: 0.01 to 1:10, more preferably 1: 0.1 to 1: 2.

The amount of blowing agent and the amount of the reaction mixture introduced into the mold is preferably such that the first polyurethane has a density of 800 kg / m ³ or greater, preferably 900 to 1200 kg / m ³ and particularly preferably 950 to 1050 kg / m ³ , and the second polyurethane has a density of 80 to 700 kg / m ³ , preferably from 120 to 600 kg / m ³ . The densities indicating the ratio of theoretically maximum expansion volume to the expansion volume of the first polyurethane and the second polyurethane are from 1.1 to 8.5, preferably from 2.1 to 7.0, for the preparation of the polyurethane foams.

One Composite material according to the invention is preferably used as a shoe sole. It can be used to make the shoe the composite material according to the invention after its Production on the shoe upper, for example by sewing or gluing, to be attached. Alternatively, an inventive Shoe manufactured by direct injection method. It will the polyurethane reactive mixture is placed in a mold containing an outsole made of rubber and completed by the shoe upper becomes.

Composite materials of the invention exhibit pronounced adhesion between the polyurethane and the bulk material, preferably rubber. The adhesive tensile strength is after 24 hours of storage at room temperature after ( EN ISO 20345 in the case of a stripping of the layers, preferably at least 4.0, particularly preferably at least 4.5 and in particular at least 5.0 N / mm, in the case of a foam crack, the adhesion is preferably at least 3.0, more preferably at least 3.5 and in particular at least 4.0 N / mm.

In order to are advantages of a composite material according to the invention improved adhesion between polyurethane and solid material. This can be done without the use of expensive, harmful or for corrosion of metal parts leading methods for Improvement of liability can be achieved.

In the following the invention will be explained by means of examples. Starting Materials: Polyol 1 linear polyesterol (OHZ 55 mg KOH / mg and functionality 2) based on adipic acid and monoethylene glycol / diethylene glycol Polyol 2 highly branched polyesterol (OH number 350 mg KOH / mg) based on adipic acid, maleic acid and trimethylolpropane Catalyst 1 triethylenediamine Connected 1 triethanolamine Chain extender 1 monoethylene glycol Foam stabilizer 1 (DC 5169 ^® Dow Corning silicone-based) Propellant Center 1 water Isocyanate 1 Prepolymer (55 parts by weight of 4,4 'diisocyanatodiphenylmethane (pure MDI), 4 parts by weight of uretonimine-modified pure MDI, 30 parts by weight of a branched polyesterol (OHZ 60 mg KOH / mg and functionality 2.7) Base of adipic acid and ethylene glycol / trimethylolpropane, 11 parts by weight of a linear polyesterol (OHZ 55 mg KOH / mg and functionality 2) based on adipic acid and ethylene glycol / butanediol)

According to the composition given in Table 1, the polyol components A1 to A4 were prepared: Table 1 A1 (parts by weight) A2 (parts by weight) A3 (parts by weight) A4 (parts by weight) Polyol 1 86 86 82.3 82.3 Polyol 2 4.6 4.6 Catalyst 1 0.7 0.7 0.7 0.7 Connected 1 0.6 0.6 0.6 0.6 Chain extender 1 12 12 11.6 11.6 Foam stabilizer 1 0.2 0.2 0.2 0.2 Propellant 1 0.5 0.5

Tries:

Reaction mixture 1:

100 Parts by weight of the polyol component A1 and 130 parts by weight of isocyanate 1 were at 23 ° C for 5 s by means of Vollrathrührer (600 Rpm) mixed intensively into the reaction mixture 1.

Reaction mixture 2:

100 Parts by weight of the polyol component A2 and 143 parts by weight of isocyanate 1 were at 23 ° C for 5 s by means of Vollrathrührer (600 Rpm) is mixed intensively with the reaction mixture 2.

Reaction mixture 3:

100 Parts by weight of the polyol component A3 and 130 parts by weight of isocyanate 1 were at 23 ° C for 5 s by means of Vollrathrührer (600 Rpm) mixed intensively into the reaction mixture 1.

Reaction mixture 4:

100 Parts by weight of the polyol component A4 and 130 parts by weight of isocyanate 1 were at 23 ° C for 5 s by means of Vollrathrührer (600 Rpm) mixed intensively into the reaction mixture 1.

The Production of the composite body was carried out in a metal mold with the dimensions 20 × 20 × 1 cm. In this metal form was a NBR rubber (9 × 4 × 0.3 cm) with a Surface temperature of 160 ° C given. The others Production of the composite parts was carried out as described below.

Trial 1 (V1):

immediate after the preparation of the reaction mixture 1, 60 grams of this Reaction mixture on the rubber pad in the mold with a surface temperature given by 160 ° C. 10 seconds after Reaction Mixture I The gum was added, 220 g of the reaction mixture 2 were also immediately after its preparation, added to the 60 g of the reaction mixture 1 and the mold is closed.

Trial 2 (V2):

It was carried out analogously to experiment 1, with the difference that the Reaction mixture 2 20 seconds after reaction mixture I on the gum was added to the reaction mixture 1.

Comparative Experiment 1 (VG1):

It was similar to experiment 1 procedure with the difference that instead the 60 grams of reaction mixture 1 and 220 grams of the reaction mixture 2 280 grams of the reaction mixture 1 were used.

Trial 3 (V3):

Of the Sample body was prepared according to experiment 1 and measured, wherein instead of reaction mixture 1 reaction mixture 3 and instead of reaction mixture 2 reaction mixture 4 was used.

Trial 4 (V4):

Of the Sample body was prepared according to experiment 2 and measured, wherein instead of reaction mixture 1 reaction mixture 3 and instead of reaction mixture 2 reaction mixture 4 was used.

Comparative experiment 2 (VG2):

Of the Sample body was according to comparative experiment 1, wherein instead of reaction mixture 1 reaction mixture 3 was used.

From the composite bodies obtained, test specimens of dimensions 70 × 10 × 7 mm were cut, on which deduction measurements according to DIN EN 20345 were carried out. The values determined by the adhesion tensile measurements are given in Table 2. Table 2 V1 V2 VG1 V3 V4 VG2 Adhesion value N / mm 1.9 2.1 1.4 3.8 4.8 3.6

The experiments indicated that both by a compact advance as well as by the addition of hyperbranched polymers the adhesion properties between polyurethane and rubber can be improved.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 286966 A [0009]
• DE 19715551 [0011]
• - DE 2402734 [0018]
• EP 463479 A1 [0018]
• - EP 358328 A1 [0018]
• WO 05/098763 [0031]
• - EP 250351 A [0031]
• DE 111394 [0032]
• US 3304273 [0032]
• - US 3383351 [0032]
• US 3523093 [0032]
• - DE 1152536 [0032]
• - DE 1152537 [0032]
• - US 3615972 [0039]
• - EP 1141083 [0045]
• - DE 10211664 [0045]
• WO 00/56802 [0045]
• WO 03/062306 [0045]
• WO 96/19537 [0045]
• WO 03/54204 [0045]
• WO 03/93343 [0045]
• WO 05/037893 [0045]
• WO 04/020503 [0045]
• - DE 102004026904 [0045]
• WO 99/16810 [0045]
• WO 05/026234 [0045]
• - DE 102005009166 [0045]
• - EP 06121514 [0053]

Cited non-patent literature

• - Desma Today, 04-2005, p. 4-5 [0006]
• - http://www.desma.de/news/desma_today/pdf/DESMA_today_04_05_E.pdf [0006]
• - EN ISO 20 345 [0008]
• Sci. Techn. 2005, 19 (1), 19-40 by CM Cepeda-Jiminez et al. [0010] "Surface treatment of latex vulcanized to improve its adhesion performance in shoe manufacturing".
• - "The rubber formulation", Hoyes Publications, 1999, ISBN: 0-8155-1434-4 [0016]
• - PA Ciullo, "The rubber formulation", Hoyes Publications, 1999, ISBN: 0-8155-1434-4 [0043]
• - "Degree of Branching" is applied to H. Frey et al., Acta Polym. 1997, 48, 30 [0044]
• - DIN 53240 [0053]
• - EN ISO 20345 [0064]
• - DIN EN 20345 [0079]

Claims (14)

A method of making composites of polyurethane foam and bulk materials, wherein the bulk material has a temperature of 50 ° C and higher at the application of the first polyurethane reaction mixture comprising: i) introducing the bulk material, ii) a first polyurethane reaction mixture on the bulk material iii) applying a second polyurethane reaction mixture to the first polyurethane reaction mixture and, iv) curing the first polyurethane reaction mixture and the second polyurethane reaction mixture into a first polyurethane and a second polyurethane, characterized in that the first polyurethane has a higher density than the second polyurethane. Method according to claim 1, characterized in that that the first polyurethane reaction mixture and the second polyurethane reaction mixture are available by mixing a) organic Polyisocyanates with b) at least one higher molecular weight Compound having at least two reactive hydrogen atoms, c) Chain extenders and / or crosslinkers, d) Propellants and optionally e) catalysts and f) other aids and / or additives, the first one Polyurethane reaction mixture also no propellant d) included can. Method according to claim 2, characterized in that that the first polyurethane and the second polyurethane elastic Polyurethanes are. Method according to Claims 1 to 3, characterized that the first reaction mixture of the further g) hyperbranched Contains polymer. A method according to claim 1 to 4, characterized in that the first polyurethane has a density of greater than 800 kg / m ³ . A method according to claim 1 to 5, characterized in that the second polyurethane has a density of 80 to 700 kg / m ³ . Method according to Claims 1 to 6, characterized the first polyurethane reaction mixture is not a blowing agent d) having. Method according to Claims 1 to 7, characterized that the first polyurethane reaction mixture before applying the second polyurethane reaction mixture not yet cured is. Method according to Claims 1 to 8, characterized that the first polyurethane reaction mixture on the solid material is applied in such an amount and manner that the solid material to at least 20% of the surface with the first polyurethane reaction mixture is covered. Method according to Claims 1 to 9, characterized that is the first polyurethane reaction mixture and the second polyurethane reaction mixture in step iv) in a closed mold to the first polyurethane and the second polyurethane cured. Method according to claims 1 to 10, characterized in that that the temperature of the massive material when applying the first polyurethane reaction mixture 100 ° C to 200 ° C is. Process according to claims 1 to 11, characterized in that that the massive material is vulcanized rubber. Method according to Claims 1 to 12, characterized that the composite of polyurethane foam and solid materials a shoe sole is. Shoe sole, available after a procedure according to claim 13.