WO2020161110A1

WO2020161110A1 - In-mould coating for cellasto midsoles

Info

Publication number: WO2020161110A1
Application number: PCT/EP2020/052692
Authority: WO
Inventors: Ulrich Holwitt; Ingo Windeler; Steffen Richter; Maike GREVER
Original assignee: Basf Polyurethanes Gmbh
Priority date: 2019-02-05
Filing date: 2020-02-04
Publication date: 2020-08-13
Also published as: CN113412294A

Abstract

The present invention relates to a method for producing a moulded body comprising a polyurethane elastomer, comprising applying a composition (Z) containing a release agent, a carrier agent (T), a compound (V1) selected from the group made up of flame retardants and dyes, and a polyurethane, or a reaction mixture which is suitable for forming a polyurethane, to at least part of the surface (OF) of a mould, at least partially removing the carrier agent (T) and introducing a mixture (M1) into the mould. The method also comprises reacting the mixture (M1) to obtain the moulded body comprising a polyurethane elastomer. The present invention also relates to a moulded body that can be or is obtained using a method of this kind, and to the use of a moulded body according to the invention as a damping element, shock absorber or jounce bumper, or as part of a shoe or part of a shoe sole, for example an insole or a midsole.

Description

In-mold coating for Cellasto midsoles

The present invention relates to a process for the production of a molded body comprising a polyurethane elastomer, comprising the application of a composition (Z) containing a release agent, a carrier (T), a compound (V1) selected from the group of flame retardants and dyes and a polyurethane or a Reaction mixture which is suitable for forming a polyurethane contains the at least partial removal of the carrier by means of (T)) and the introduction of a mixture (M 1) into the mold. The method further comprises the reaction of the mixture (M1) to give the molded body comprising a polyurethane elastomer. The present invention further relates to a molded body obtainable or obtained by such a method and the use of a molded body according to the invention as a damping element, shock absorber or stop buffer or as part of a shoe or a shoe sole, for example an insole or midsole.

Elastomers based on polyisocyanate polyadducts and their preparation are generally known and widely described, for example in EP-A 62 835, EP-A 36 994, EP-A 250 969, DE-A 195 48 770 and DE-A 195 48 771, EP 1, 379,568 B1. Compact and microcellular materials are known.

Molded parts made of microcellular polyurethane are often used as damping elements in the automotive sector, where they have to withstand high mechanical loads for years and at the same time should have good hydrolysis resistance. The use as a shoe sole or part of a shoe sole is also known per se.

For many applications it is advantageous to produce moldings that are coated with active components or also colored. The application of such a coating requires additional process steps which make the production of shaped bodies more complex.

It was therefore an object of the present invention to provide a simple process for the production of moldings comprising polyurethane elastomers which, in addition to good mechanical and dynamic properties, also have a coating with an active substance or a dye.

According to the invention, this object is achieved by a method for producing a molded body comprising a polyurethane elastomer, at least comprising steps (i) to (vi):

(i) providing a shape with a surface (OF);

(ii) Application of a composition (Z) containing a release agent, a carrier (T), a compound (V1) selected from the group consisting of flame retardants and dyes and a polyurethane or a reaction mixture which is suitable for a polyurethane form, on at least part of the surface (OF), comprising the steps (iia) and (ü):

(iia) applying a composition (Z1) containing a release agent and a carrier agent (T1) to at least part of the surface (OF);

(iib) applying a composition (Z2) to at least part of the surface (OF) coated with the release agent, the composition (Z2) being a carrier (T2), a compound (V1) selected from the group consisting of flame retardants and Contains dyes and a polyurethane or a reaction mixture which is suitable to form a polyurethane;

(iii) at least partial removal of the carrier means (T);

(iv) Introducing a mixture (M 1) into the mold, comprising

(A) at least one prepolymer containing isocyanate groups,

(b) at least one chain extender (KV);

(v) allowing the mixture (M 1) to react to completion to give a molded body comprising a polyurethane elastomer;

(vi) removing the molded article obtained from the mold.

According to a further aspect, the present invention also relates to a shaped body, obtainable or obtained by a method at least comprising steps (i) to (vi):

(i) providing a shape with a surface (OF);

(ii) Applying a composition (Z) containing a release agent, a carrier (T), a compound (V1) selected from the group consisting of flame retardants and dyes and a polyurethane or a reaction mixture which is suitable to form a polyurethane on at least a part of the surface (OF), comprising the steps (iia) and (iib):

(iii) At least partial removal of the carrier means (T);

(iv) Introducing a mixture (M1) into the mold, comprising

(A) at least one prepolymer containing isocyanate groups,

(b) at least one chain extender (KV);

(v) allowing the mixture (M1) to react to completion to give a molded body comprising a polyurethane elastomer;

(vi) removing the molded article obtained from the mold.

The method according to the invention comprises at least steps (i) to (vi). The method can also include further steps, for example further shaping steps or a temperature treatment.

Surprisingly, it has been found that molded bodies comprising polyurethane elastomers with a permanent coating can be produced by the method according to the invention, the shape and type or distribution of the coating on the molded body being able to be easily adapted.

According to the invention, a composition (Z) is first introduced and the mixture (M1) is introduced in the course of the process. In the context of the present invention, the components of the composition (Z) are applied gradually in the form of a composition (Z1) and a composition (Z2).

According to the invention, according to step (i), a mold with a surface (OF) is provided. In the context of the present invention, all suitable forms can be used for the production of polyurethane elastomers. Suitable forms are known per se to the person skilled in the art.

The shapes that are the negative of the molded parts are generally customary shapes, for example metal molds, and which, due to their shape and composition, ensure the three-dimensional shape of the molded parts according to the invention.

According to step (ii), the composition (Z) comprising a release agent, a carrier (T), a compound (V1) is selected from the group consisting of flame retardants and dyes and a polyurethane or a reaction mixture which is suitable to form a polyurethane is applied to at least part of the surface (OF).

The surface (OF) is usually at least 90% wetted with the composition (Z). The release agents used preferably contain surface-active substances that help the release agent spread over the surface, so that after the release agent droplets have been sprayed on, the droplets can spread and form a closed covering layer with one another. Suitable methods for applying the composition (Z) are known per se to the person skilled in the art. The composition (Z) can, for example, be sprayed on or painted on.

After step (ii), the carrier (T) can be partially or completely removed, for example by evaporation.

Step (ii) here comprises at least the substeps of step (iia) and step (iib), it being possible for the components of the composition (Z) to be applied gradually. According to the invention, step (ii) can comprise further substeps.

In this case, according to step (iia), the composition (Z1) containing a release agent and a carrier agent (T1) is first applied to at least part of the surface (OF).

The surface (OF) is usually at least 90% wetted with the composition (Z1). Suitable methods for applying the composition (Z1) are known per se to the person skilled in the art. The composition (Z1) can, for example, be sprayed on or painted on.

The composition (Z) or (Z1) contains a release agent and a carrier agent (T1) as carrier agents are solvents or water. Suitable release agents are known per se to the person skilled in the art. For example, release agents based on wax and / or silicone are suitable. Additives such as Teflon powder or liquid, solid or pasty organofluorine compounds are also suitable as separating substances. Such release agents are usually combined with surface-active substances.

After step (iia) the carrier (T1) can be partially or completely removed, for example by evaporation.

According to step (iib), a composition (Z2) is applied to at least part of the surface (OF) coated with the release agent, the composition (Z2) being a carrier (T2), a compound (V1) selected from the group consisting of flame retardants and Dyes and a polyurethane or a reaction mixture which is suitable to form a polyurethane contains. The composition (Z2) contains a carrier (T2). Solvents or else water are suitable as carriers. The carrier means (T2) can be identical to or different from the carrier means (T1).

The composition (Z) or the composition (Z2) furthermore contains a compound (V1) selected from the group consisting of flame retardants and dyes. Suitable connec tions (V1) are known per se to the person skilled in the art.

The compounds used, in particular dyes, can be present in the composition (Z) or in the composition (Z2) in dissolved form or also in suspension.

The proportion of pigment after evaporation of the carrier is usually in the range from 1 to 60%, preferably in the range from 5 to 30%.

Accordingly, according to a further embodiment, the present invention relates to a method as described above, wherein the compound (V1) is contained in the composition (Z2) in an amount in the range from 0.3 to 8% by weight, preferably in the range from 0, 5 to 4% by weight.

Suitable mixtures are known per se to the person skilled in the art.

Accordingly, according to a further embodiment, the present invention relates to a method as described above, wherein the composition (Z2) is applied to the upper surface (OF) in an amount such that a layer with a thickness in the range from 5 μm to 0.5 mm is obtained.

Organic dyes such as nigrosine, pigments such as e.g. Titanium dioxide, cadmium sulfide, zinc sulfide, cadmium sulfide selenide, phthalocyanines, ultramarine blue or carbon black can be added.

The amount of dye used and the concentration of the dye in the composition (Z2) can vary within wide limits. The amount or concentration of the dye used can be adjusted in order to adjust the color intensity. The dye is preferably used in the composition (Z2) in an amount in the range from 0.1 to 60% by weight, more preferably in the range from 1 to 30% by weight, particularly preferably in the range from 2 to 30% by weight preferably in the range from 5 to 30% by weight, based in each case on the entire composition (Z2).

In the context of the present invention, metal complex dyes, for example, which have good solubility in polar solvents, for example neozapon dyes, can be used as dyes. Cationic dyes, which have good solubility in alcohols and glycol ethers, can also be used. Suitable dyes are, for example, basonyl dyes. Commercially available dyes are also suitable, for example under the trade names Neozapon Black X55, Neozapon Black X51, Neozapon Red 335, Neozapon Yellow 141, Neozapon Red 471, Neozapon Blue 807, Neozapon Orange 251, Basonyl Green 830 liquid, Basonyl Blue 644 liquid, Basonyl Red 545 liquid, Basonyl Red 555 liquid, Basonyl Green 830 liquid, Basonyl Blue 636, Basantol Yellow 099 liquid, Basantol Black X82 liquid, Neptun Yellow 075, Heliogen Blue L 6930, Basacid Orange 282 liquid, Basacid Yellow 093 liquid, Isopur SU 12021/911 or Reaktint Yellow X15.

In the context of the present invention, dyes are preferably selected from the group consisting of Neozapon Black X55, Neozapon Red 335, Neozapon Orange 251, Basonyl Green 830 liquid, Basonyl Blue 644 liquid, Basonyl Red 545 liquid, Basonyl Red 555 liquid, Basonyl Green 830 liquid, Basonyl Blue 636, and Neptun Yellow 075 are used. A dye selected from the group consisting of Basonyl Blue 644, Basonyl Red 545, Basonyl Green 830 and Neozapon black X55, and Neptun Yellow 075 is also used before given.

The composition (Z2) further contains a polyurethane or a reaction mixture which is suitable for forming a polyurethane. Suitable compounds are known per se to the person skilled in the art. Suitable compounds are described, for example, in EP 2035517 A1. The polyurethane or the reaction mixture which is suitable for forming a polyurethane preferably comprises aliphatic or cycloaliphatic diisocyanates. According to the invention, trimers of the diisocyanates can also be used. Compounds which react with the isocyanates are polyether polyols, polyester polyols, polyether ester polyols, hydroxyalkyl-modified acrylates, polyacrylic acid esters, polyacrylic acid esters whose acid function is only partially esterified, and / or other resins which contain OH groups and / or crosslinkable double bonds Commitment.

The carrier (T) contained in the composition (Z) or the carrier (T1) contained in the composition (Z1) and / or the carrier (T2) contained in the composition (Z2) are at least partially in accordance with step (iii) away.

In the context of the present invention, the carrier (T) contained in the composition (Z) or the carrier (T1) contained in the composition (Z1) and / or the carrier (T2) contained in the composition (Z2) are according to Step (iii) removed preferably from 20 to 100%, more preferably from 50 to 100%.

According to step (iv) of the method according to the invention, a mixture (M1) is then introduced into the mold, the mixture (M1) comprising components (a) and (b):

(A) at least one prepolymer containing isocyanate groups,

(b) at least one chain extender (KV). According to the invention, the mixture can be produced directly when it is introduced into the mold or before it is introduced into the mold. The components of the mixture (M 1) react in the mold to form a polyurethane elastomer. The process according to the invention further comprises step (v), according to which the mixture (M 1) can fully react with a polyurethane elastomer to obtain a molded body.

The mixture (M 1) is introduced into the mold in an amount corresponding to the desired density of the molded part. The moldings are usually hardened after 2 minutes to 60 minutes and can therefore be removed from the mold.

The molded body obtained is then removed from the mold in step (vi).

The mixture (M 1) contains the components (a) and (b) and can contain further components. For example, it is possible that the mixture (M 1) also selects a compound (V2) from the group of flame retardants and dyes contains. This can be added to one or both of components (a) and (b) or fed separately to the mixture.

According to a further embodiment, the present invention accordingly relates to a method as described above, the mixture (M 1) containing at least one compound (V2) selected from the group consisting of flame retardants and dyes.

The prepolymer and the chain extender (KV) are reacted, with optionally further polyols or further chain extenders and optionally catalyst, optionally blowing agent and / or crosslinking agent and optionally additives and / or additives, provided they are not added or only partially added in the first step can be added.

Accordingly, in a further embodiment, the present invention relates to a method as described above, the mixture (M 1) having at least one further component selected from the group consisting of polyols, blowing agents, water, chain extenders and / or crosslinking agents, catalysts, other auxiliaries and additives. According to the invention, the mixture (M 1) can also contain release agents.

The equivalence ratio of NCO groups to the sum of the reactive hydrogen atoms in the mixture (M 1) is usually in the range from 0.8: 1 to 1.5: 1, preferably 1: 1 to 1.3: 1 and in particular 1.02 : 1 to 1, 15: 1. A ratio of 1: 1 corresponds to an isocyanate index of 100. In the context of the present invention, the isocyanate index is understood to mean the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups, multiplied by 100.

Suitable prepolymers and chain extenders (KV) containing isocyanate groups are known per se to the person skilled in the art. These react to form a polyurethane elastomer. In the context of the present invention, the isocyanate-terminated prepolymer preferably has an NCO content of 2 to 20% by weight. The prepolymer containing isocyanate groups is preferably obtained by reacting an isocyanate composition (ZI) with the polyol composition (ZP).

The polyol composition (ZP) contains at least one polyol. In the context of the present invention, preference is given to polyol compositions (ZP) comprising a poly-e-caprolactone polyol and an α-hydro-m-hydroxypoly (oxytetramethylene) polyol. Also preferred are polyol compositions (ZP), the condensation products of adipic acid and individual or more diols selected from the group of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5 Pentanediol, diethylene glycol and 1,6-hexanediol contained.

The polyol composition (ZP) preferably contains a poly-s-caprolactone polyol and an α-hydro-γ) -hydroxypoly (oxytetramethylene) polyol and can contain further components, in particular further substances which are reactive toward isocyanates, for example further polyols. Suitable polyols are known per se to the person skilled in the art. For example, polyethers, polyesters or polycarbonates are suitable.

According to the invention, all poly-s-caprolactone polyols can be used, in particular those with a number average molecular weight in the range from 1500 to 2500 g / mol. Poly-s-caprolactone diols are preferably used, i.e. those poly-s-caprolactone polyol which are obtained or obtainable using a difunctional starter. Starters suitable for the purposes of the present invention are, for example, diols with a number average molecular weight in the range from 80 to 1500 g / mol, for example polyether polyols or polyester polyols. In particular, polyether polyols are suitable, especially long-chain polyether diols such as, for example, α-hydro-m-hydroxypoly (oxytetramethylene) diols.

According to a further embodiment, the present invention also relates to a method as described above, wherein the poly-s-caprolactone polyol used is obtainable or is obtained by reacting e-caprolactone and a starter molecule which is selected from the group consisting of a- Hydro-m-hydroxypoly (oxytetramethylene) diols, polyethylene glycols and polypropylene glycols.

According to a further embodiment, the present invention therefore also relates to a method as described above, wherein the poly-s-caprolactone polyol used is obtainable or is obtained by reacting e-caprolactone and a starter molecule which is selected from the group consisting of diols with a molecular weight in the range from 80 to 1500 g / mol.

Suitable starter molecules are selected in particular from the group consisting of neopentyl glycol (NPG), 1,4-butanediol (BDO), 1,6-hexanediol (HDO) and long-chain polyether diol len with a number average molecular weight in the range from 800 to 1200 g / mol, preferably 900 to 1,100 g / mol.

In the context of the present invention, the number average molecular weights are obtained by determining the OH number, unless stated otherwise. Suitable measurement conditions are known to those skilled in the art.

The polyol composition (ZP) can furthermore contain an α-hydro-m-hydroxypoly (oxytetramethylene) polyol. Suitable α-hydro-m-hydroxypoly (oxytetramethylene) polyols are known per se. Hydro-w-hydroxypoly (oxytetramethylene) polyols with a number average molecular weight in the range from 1500 to 2500 g / mol are preferably suitable for the purposes of the present invention. In the context of the present invention, mixtures of two or more hydro-m-hydroxypoly (oxytetramethylene) polyols with different molecular weights can also be used.

The composition of the polyol composition (ZP) can vary within wide ranges. In the context of the present invention, preference is given to the proportion of α-Hydro-w-hydroxypoly (oxytetramethylene) polyol in the polyol composition (ZP) in the range from 0.1 to 50% by weight, preferably in the range from 10 to 35% by weight , particularly preferably in the range from 15-30% by weight. According to a preferred embodiment, the polyol composition (ZP) consists of the poly-s-caprolactone polyol and the a-hydro-w-hydroxypoly (oxytetramethylene) polyol.

The isocyanate composition (ZI) contains one or more polyisocyanates. Suitable polyisocyanates are known per se to the person skilled in the art. According to the invention, organic isocyanates are preferred as isocyanates, aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates are further preferred, diisocyanates are further preferred. Preferred diisocyanates are tri-, tetra-, penta-, flexa-, flepta- and / or octamethylene diisocyanate, 2-methylpentamethylene diisocyanate-1,5, 2-ethyl-butylene-diisocyanate-1,4, pentamethylene diisocyanate 1, 5, butylene diisocyanate-1, 4, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate (IPDI), 1, 4- and / or 1, 3-bis ( isocyanatomethyl) cyclohexane (FHXDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or-2,6-cyclohexane diisocyanate, 4,4'-, 2,4'- and / or 2,2 '- dicyclohexylmethane diisocyanate, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI),

1,5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), o-tolidine diiso cyanate (TODI), p-phenyl diisocyanate (PPDI), 1,2-diphenylethane diisocyanate and / or pheny - Lene diisocyanate, 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate (Fl 12 MDI), 2,4-paraphenylene diisocyanate (PPDI), 2,4-tetramethylene xylene diisocyanate (TMXDI), preferably 2.2 '-,

2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) and / or 1,6-flexamethylene diisocyanate (HDI).

1,5-Naphthylene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (MDI), p-phenyl diisocyanate (PPDI) and / or o-tolidine diisocyanate (TODI) are particularly preferred. 1,5-Naphthylene diisocyanate (NDI) is further preferred. According to a further embodiment, the present invention also relates to a method as described above, the polyisocyanate composition being an isocyanate selected from the group consisting of 1,5-naphthylene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (MDI), p-phenyl diisocyanate (PPDI) ) and o-Tolidinediisocyanate (TODI), or mixtures thereof.

The mixture (M 1) can contain further components. For example, propellants can be used according to the invention. These propellants can also contain water. In addition to water, generally known chemically and / or physically acting compounds can also be used as blowing agents.

Chemical blowing agents are compounds that react with isocyanate to form gaseous products, such as water or formic acid. Physical blowing agents are compounds that are dissolved or emulsified in the starting materials for polyurethane production and that evaporate under the conditions of polyurethane formation.

Suitable propellants in the context of the present invention are, for example, low-boiling liquids which evaporate under the influence of the exothermic polyaddition reaction. Liquids which are inert towards the organic polyisocyanate and have boiling points below 100 ° C. are particularly suitable. Examples of such, preferably used liquids are halogenated, preferably fluorinated hydrocarbons, such as. B. methylene chloride and dichloromonofluoromethane, per- or partially fluorinated hydrocarbons, such as. B. trifluoromethane, difluoromethane, difluoroethane, tetrafluoroethane and heptafluoropropane and 1, 1, 1, 4,4,4-hexafluoro-2-butene, hydrocarbons, such as. B. n- and iso-butane, n- and iso-pentane and the technical mixtures of these hydrocarbons, propane, propylene, hexane, heptane, cyclobutane, cyclopentane and cyclohexane, dialkyl ethers, preferably e.g. Dimethyl ether, diethyl ether and furan, carboxylic acids such as formic acid, carboxylic acid esters, preferably e.g. Methyl and ethyl formate, ketones, preferably e.g. B. acetone, and / or fluorinated and / or perfluorinated, tertiary alkylamines, preferably z. B. perfluoro-dimethyl-iso-propylamine.

Mixtures of these low-boiling liquids with one another and / or with other substituted or unsubstituted hydrocarbons can also be used. The most appropriate amount of propellant to be used depends on the density that you want to achieve chen, and on the amount of water preferably used with. In general, amounts of 1% by weight to 15% by weight, preferably 2% by weight to 11% by weight, based on the polyol composition (ZP), are suitable.

In a preferred embodiment, the propellant used is a mixture containing at least one of these propellants and water, particularly preferably no physical propellants are used, and particularly preferably water is used as the sole propellant. According to the invention, it is also possible to additionally add hollow microspheres which contain physical propellants. The hollow microspheres can also be used as a mixture with the aforementioned blowing agents.

The hollow microspheres usually consist of a shell made of thermoplastic polymer and their core is filled with a liquid, low-boiling substance based on alkanes. The production of such hollow microspheres is described in US Pat. No. 3,615,972, for example. The hollow microspheres generally have a diameter of 5 to 50 mΐti. Examples of suitable hollow microspheres are available under the trade name Expancell® ^® from Akzo Nobel.

The hollow microspheres are generally added in an amount of 0.5 to 5% by weight, based on the total weight of the polyols used. In a particularly preferred embodiment, the blowing agent used is a mixture of microholes and water, with no further physical blowing agents being included.

It is particularly preferred to use exclusively water as the blowing agent. In the context of the present invention, water is also suitable as a chain extender. Thus, in the context of the present invention, water can also be used as a chain extender, the added water, taking into account the other starting materials, being used in an amount that the NCO / OH ratio is between 0.85 and 1.30, particularly preferably between 0 .95 and 1.20.

Since the water functions both as a crosslinker with the formation of urea groups and as a blowing agent due to the reaction with isocyanate groups with the formation of carbon dioxide, it is listed separately from any other crosslinkers and / or blowing agents.

The chain extenders and / or crosslinking agents used are preferably alkanediols with 2 to 12 carbon atoms, preferably with 2, 4 or 6 carbon atoms, more preferably ethanediol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1, 10-decanediol and preferably 1,4-butanediol. Further preferred chain extenders and / or crosslinking agents are dialkylene glycols having 4 to 8 carbon atoms, preferably diethylene glycol and dipropylene glycol and / or di-, tri or tetrafunctional polyoxyalkylene polyols.

Further preferred chain extenders and / or crosslinkers are branched-chain and / or unsaturated alkanediols with preferably no more than 12 carbon atoms, preferably 1,2-propanediol, 2-methyl-, 2,2-dimethyl-propanediol-1,3,2-butyl -2-ethylpropanediol-1, 3, butene-2-diol-1, 4 and butyn-2-diol-1, 4, diesters of terephthalic acid with glycols with 2 to 4 carbon atoms, preferably terephthalic acid-bis-ethylene glycol or - 1,4-butanediol, hydroxyalkylene ethers of hydroquinone or resorcinol, such as 1,4-di- (β-hydroxyethyl) -hydroquinone or 1,3-di- (β-hydroxyethyl) resorcinol, alkanolamines with 2 to 12 carbon atoms, such as prefers Ethanolamine, 2-aminopropanol and 3-amino-2,2-dimethylpropanol, N-alkyldi-alkanolamines, such as, for example, N-methyl- and N-ethyl-diethanolamine.

In the context of the present invention, chain extenders preferably used are selected from the group consisting of water, diols with a molecular weight in the range from 50 to 500 g / mol, triols with a molecular weight in the range from 50 to 500 g / mol, and diamines with a Molecular weight in the range from 50 to 500 g / mol. Further preferred chain extenders are selected from the group consisting of water, diols with a molecular weight in the range from 50 to 200 g / mol, triols with a molecular weight in the range from 50 to 200 g / mol, and diamines with a molecular weight in the range of 50 up to 200 g / mol.

According to a further embodiment, the present invention also relates to a method as described above, wherein the chain extender (KV) is selected from the group consisting of water, diols with a molecular weight in the range from 50 to 500 g / mol, triols with a molecular weight of Range from 50 to 500 g / mol, and diamines with a molecular weight in the range from 50 to 500 g / mol.

According to the invention, the amounts of the individual components used can vary. Ge quantities suitable for the production of polyurethane elastomers are known per se to the person skilled in the art.

To accelerate the reaction of the starting materials, a catalyst, for example, can be added to the mixture (M1).

Customary auxiliaries and / or additives can also be used. Auxiliaries and / or additives are present as a single substance or as a mixture of at least two auxiliaries and / or additives. Examples include surface-active substances, fillers, flame retardants, nucleating agents, oxidation stabilizers, lubricants and demoulding aids, dyes and pigments, optionally stabilizers, preferably against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and / or Plasticizers.

Stabilizers in the context of the present invention are additives that protect a plastic or a plastic mixture against harmful environmental influences. Examples are primary and secondary antioxidants, hindered amine light stabilizers, UV absorbers, Hydrolyseschutzmit tel, quenchers and flame retardants. Examples of commercial stabilizers are given in Plastics Additive Handbook, 5th Edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001 ([1]), pp.98-S136.

Suitable surface-active substances are, for example, compounds which serve to support the homogenization of the starting materials and are optionally also suitable for regulating the cell structure. Examples include emulsifiers, such as, for example Sodium salts of castor oil sulfates or of fatty acids and salts of fatty acids with amines, for example oleic diethylamine, stearic diethanolamine, ricinolic acid diethanolamine, salts of sulfonic acids, for example alkali or ammonium salts of dodecylbenzene or dinaphthyl methane disulfonic acid; Foam stabilizers, such as siloxane-oxalkylene copolymers and other organosiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, Turkish red oil and peanut oil and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes. Oligomeric polyacrylates with polyoxyalkylene and fluoroalkane radicals as side groups are also suitable for improving the emulsifying effect, the cell structure and / or their stabilization. The surface-active Substan zen are usually used in amounts of 0.01 parts by weight to 5 parts by weight, based on 100 parts by weight of the polyol composition (ZP).

Fillers, in particular reinforcing fillers, are to be understood as meaning the customary organic and inorganic fillers, reinforcing agents and weighting agents known per se. Specifically, the following may be mentioned by way of example: inorganic fillers such as silicate minerals, for example sheet silicates such as antigorite, serpentine, tinsel, amphiboles, chrysotile, talc; Metal oxides such as kaolin, aluminum oxides, aluminum silicate, titanium oxides and iron oxides, metal salts such as chalk, barite and inorganic pigments such as cadmium sulphide, zinc sulphide and glass particles. Examples of organic fillers are: carbon black, melamine, expandable graphite, rosin, cyclopentadienyl resins, graft polyols and graft polymers.

Fibers, for example carbon fibers or glass fibers, are preferably used as reinforcing fillers, especially when a high heat resistance or very high rigidity is required, it being possible for the fibers to be equipped with flake agents and / or sizes.

The inorganic and organic fillers can be used individually or as mixtures and are usually added to the reaction mixture in amounts of 0.5% by weight to 50% by weight, preferably 1% by weight to 30% by weight, based on the weight the polyol composition (ZP) and the isocyanate composition (ZI) added.

Suitable flame retardants are, for example, tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (1,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate and tetrakis ( 2-chloroethyl) ethylene diphosphate.

In addition to the halogen-substituted phosphates already mentioned, inorganic flame retardants such as red phosphorus, aluminum oxide hydrate, antimony trioxide, arsenic trioxide, ammonium polyphosphate and calcium sulfate or cyanuric acid derivatives, such as melamine or mixtures of at least two flame retardants, such as ammonium phosphates and melamine and optionally starch and / or Expandable graphite can be used to make the polyurethane elastomers produced according to the invention flame resistant. In general, it has proven to be expedient to use 5 parts by weight to 50 parts by weight, preferably 5 parts by weight to To use 25 parts by weight of the flame retardants or mixtures mentioned for each 100 parts by weight of the structural components (a) and (b).

As the nucleating agent, e.g. Talc, calcium fluoride, sodium phenyl phosphinate, aluminum oxide and finely divided polytetrafluoroethylene in amounts of up to 5% by weight, based on the total weight of the polyol composition (ZP) and the isocyanate composition (ZI) are used.

Suitable oxidation retarders and heat stabilizers which can be added to the polyurethane elastomers according to the invention are, for example, halides of metals from group I of the periodic table, e.g. Sodium, potassium, lithium halides, optionally in connection with copper (I) halides, e.g. Chlorides, bromides or iodides, sterically hindered phenols, hydroquinones, and substituted compounds of these groups and mixtures thereof, which are preferably used in concentrations of up to 1% by weight based on the weight of the polyol composition (ZP) and the isocyanate composition (ZI) .

Examples of hydrolysis protection agents are various substituted carbodiimides, such as, preferably, 2,2 ', 6,6'-tetraisopropyldiphenylcarbodiimide or carbodiimides based on 1,3-bis- (1-methyl-1-isocyanato-ethyl) -benzene such as, for example in the documents DE 19821668 A1,

US 6,184,410, DE 10004328 A1, US 6,730,807, EP 0 940 389 B1 or US 5,498,747 are described, which are generally in amounts of up to 4.0% by weight, preferably 1.5% by weight to 2.5% by weight .-% based on the weight of the polyol composition (ZP) and the Isocyanatzusam composition (ZI) are used.

Lubricants and mold release agents, which are usually also added in amounts of up to 1% by weight, based on the weight of the polyol composition (ZP) and the isocyanate composition (ZI), are stearic acid, stearyl alcohol, stearic acid esters and amides and the fatty acid esters of pentaerythritol.

More detailed information on the abovementioned auxiliaries and additives can be found in the specialist literature, e.g. from Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Munich, 2001, pp.98-S136.

(i) providing a shape with a surface (OF);

(iii) At least partial removal of the carrier means (T);

(iv) Introducing a mixture (M 1) into the mold, comprising

(A) at least one prepolymer containing isocyanate groups,

(b) at least one chain extender (KV);

(vi) removing the molded article obtained from the mold.

With regard to the compounds used and preferred proportions, reference is made to the above embodiments.

Microcellular polyurethane elastomers according to the invention have, for example, a density according to DIN EN ISO 845 of 0.1 × 10 ³ kg / m ³ to 1.2 × 10 ³ kg / m ³ , preferably 0.2 × 10 ³ kg / m ³ to 0.8 x 10 ³ kg / m ³ , preferably with a tensile strength according to DIN EN ISO 1798 of more than 2 N / mm ² , preferably 2 N / mm ² to 8 N / mm ² , an elongation according to DIN EN ISO 1798 of more than 300%, preferably 300% to 700% and a tear strength according to DIN ISO 34, B (b) of more than 8 N / mm, preferably 8 N / mm to 25 N / mm.

Furthermore, within the scope of the present invention, preferred microcellular polyurethane elastomers have, for example, a diameter of the cells of 0.05 mm to 0.5 mm, more preferably 0.05 mm to 0.15 mm.

The present invention encompasses various embodiments which differ, for example, by the manufacturing process and the properties of the polyurethanes obtained; for example, by setting a different isocyanate index in the manufacturing process, materials of different density can be obtained. Furthermore, according to a further aspect, the present invention also relates to the use of a shaped body as described above or a shaped body obtainable or obtained according to a method as described above as a damping element, shock absorber or stop buffer or as part of a shoe or a shoe sole, for example an insole or midsole.

The present invention also relates to molded articles. Preferred molded bodies are, for example, a damping element, a shock absorber or stop buffer, for vehicle construction, before given to aircraft construction, watercraft construction or land vehicle construction, particularly preferably for land vehicle construction, preferably as additional springs, stop buffers, wishbone bearings, rear axle chassis bearings, stabilizer bearings, longitudinal strut bearings , Strut support bearings, shock absorber bearings, bearings for wishbones and / or as a temporary spare wheel located on the rim, which in the case of a tire damage, for example, ensures that the vehicle continues to drive and remains controllable.

Furthermore, according to a further aspect, the present invention also relates to a molded body, the molded body preferably being a damping element, shock absorber or stop buffer or part of a shoe or a shoe sole, for example an insole or midsole.

For example, the shoe soles or shoe sole parts can be formed from a molded body obtained according to the invention, for example by cutting, punching, peeling and / or thermoforming, optionally together with other materials, such as optionally further polyurethane foams or ethylene vinyl acetate.

The polyurethane shoe soles according to the invention are preferably used as a midsole, for example for street shoes, sports shoes, sandals and boots. In particular, the polyurethane shoe soles according to the invention are used as midsoles for sports shoes. Furthermore, a shoe sole according to the invention also includes shoe sole parts, for example heel parts or ball parts. Shoe soles according to the invention can also be used as insert soles or combination soles.

A method according to the invention leads to polyurethane shoe soles with excellent mechanical properties. In particular, the polyurethane shoe soles according to the invention show high rebound resilience with high hardnesses and low densities. It is also advantageous that, particularly when using polyols with a maximum functionality of 2.2 and when crosslinking agents are not used, the polyurethane shoe soles obtained can be thermally reshaped. It is also possible to recycle the polyurethane shoe soles produced by melting and thermoplastic processing, for example together with thermoplastic polyurethane. Finally, the use of hybrid materials is advantageous. Here, a polyurethane element according to a method according to the invention with others Materials, for example EVA, combined in such a way that a structure is obtained in which one or more layers consisting of the polyurethane according to the invention are located below, above or between layers of other materials.

Polyurethane shoe soles in the sense of the invention include one-piece shoe soles, so-called combination soles, midsoles, insoles or shoe sole parts, such as heel parts or ball parts. Insoles are understood to mean inserts for the forefoot, inserts over the entire foot or footbeds. Further, shoe soles in the sense according to the invention include polyurethane hybrid shoe soles which, in addition to the polyurethane according to the invention, contain other materials such as further polyurethanes and / or ethylene vinyl acetate.

In particular, the polyurethane shoe soles according to the invention are outer soles, midsoles, or sole parts such as heel parts, ball parts, inserts for the forefoot, inserts over the entire foot or footbeds.

Further embodiments of the present invention can be found in the claims and the Beispie sources. It goes without saying that the features mentioned above and those explained below of the subject matter / method / uses according to the invention can be used not only in the respectively specified combination but also in other combinations without departing from the scope of the invention. So is z. B. also implicitly includes the combination of a preferred feature with a particularly preferred feature, or a feature not further characterized with a particularly preferred feature, etc. even if this combination is not expressly mentioned.

Exemplary embodiments of the present invention are listed below, but these do not limit the present invention. In particular, the present invention also includes those embodiments that result from the references given below and thus combinations. In particular, when a range of embodiments is mentioned below, for example the expression “the method according to one of embodiments 1 to 4” is to be understood as meaning that any combination of the embodiments in this area is explicitly disclosed to the person skilled in the art, i.e. the expression is to be understood as a synonym for “The method according to one of embodiments 1, 2, 3 and 4”.

1. A method for producing a molded article comprising a polyurethane elastomer, at least comprising steps (i) to (vi):

(i) providing a shape with a surface (OF);

(ii) Applying a composition (Z) containing a release agent, a carrier (T), a compound (V1) selected from the group consisting of flame retardants and dyes and a polyurethane or a reaction mixture which is suitable to form a polyurethane on at least one Part of the surface (OF), comprising the steps (iia) and (iib): (iia) applying a composition (Z1) containing a release agent and a carrier agent (T1) to at least part of the surface (OF);

(iib) applying a composition (Z2) to at least part of the with

Release agent-coated surface (OF), the composition (Z2) containing a carrier (T2), a compound (V1) selected from the group consisting of flame retardants and dyes, and a polyurethane or a reaction mixture which is suitable for forming a polyurethane;

(iii) At least partial removal of the carrier means (T);

(iv) Introducing a mixture (M1) into the mold, comprising

(A) at least one prepolymer containing isocyanate groups,

(b) at least one chain extender (KV);

(vi) removing the molded article obtained from the mold.

2. The method according to embodiment 1 or 2, wherein the mixture (M1) contains at least one compound (V2) selected from the group consisting of flame retardants and dyes.

3. The method according to any one of embodiments 1 to 2, wherein the compound (V1) is contained in an amount in the range from 0.3 to 5% by weight in the composition (Z2).

4. The method according to any one of embodiments 1 to 3, wherein the composition (Z2) is applied to the surface (OF) in an amount such that a layer with a thickness in the range from 5 μm to 0.5 mm is obtained.

5. The method according to any one of embodiments 1 to 4, wherein the mixture (M1) contains at least one further component selected from the group consisting of polyols, blowing agents, water, chain extenders and / or crosslinking agents, catalysts, other auxiliaries and additives.

6. The method according to one of embodiments 1 to 5, wherein the polyisocyanate composition is an isocyanate selected from the group consisting of 1,5-naphthylene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (MDI), p-phenyl diisocyanate (PPDI) and o-Tolidinediisocyanate (TODI), or mixtures thereof. Process according to one of embodiments 1 to 6, wherein the chain extender (KV) is selected from the group consisting of water, diols with a molecular weight in the range from 50 to 500 g / mol, triols with a molecular weight in the range from 50 to 500 g / mol, and diamines with a molecular weight in the range from 50 to 500 g / mol. Moldings, obtainable or obtained by a process at least comprising steps (i) to (vi):

(i) providing a shape with a surface (OF);

(ii) Applying a composition (Z) containing a release agent, a carrier (T), a compound (V1) selected from the group consisting of flame retardants and dyes and a polyurethane or a reaction mixture which is suitable to form a polyurethane on at least one Part of the surface (OF), comprising the steps (iia) and (iib):

(iib) applying a composition (Z2) to at least part of the surface (OF) coated with the release agent, the composition (Z2) being a carrier (T2), a compound (V1) selected from the group consisting of flame retardants and dyes and a polyurethane or a reaction mixture which is suitable to form a polyurethane contains;

(iii) At least partial removal of the carrier means (T);

(iv) Introducing a mixture (M1) into the mold, comprising

(A) at least one prepolymer containing isocyanate groups,

(b) at least one chain extender (KV);

(vi) removing the molded article obtained from the mold. Shaped body according to embodiment 8, wherein the mixture (M1) contains at least one compound (V2) selected from the group of flame retardants and dyes. 10. Shaped body according to one of embodiments 8 to 9, wherein the compound (V1) is contained in an amount in the range from 0.3 to 5% by weight in the composition (Z2).

1 1. Shaped body according to one of embodiments 8 to 10, the composition (Z2) being applied to the surface (OF) in an amount such that a layer with a thickness in the range from 5 μm to 0.5 mm is obtained.

12. Shaped body according to one of embodiments 8 to 11, wherein the mixture (M 1) contains at least one further component selected from the group consisting of polyols, blowing agents, water, chain extenders and / or crosslinking agents, catalysts, other auxiliaries and additives .

13. Shaped body according to one of embodiments 8 to 12, wherein the polyisocyanate composition is an isocyanate selected from the group consisting of 1,5-naphthylene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (MDI), p-phenyl diisocyanate (PPDI) and o-Tolidinediisocyanate (TODI), or mixtures thereof.

14. Shaped body according to one of embodiments 8 to 13, wherein the chain extender (KV) is selected from the group consisting of water, diols with a molecular weight in the range from 50 to 500 g / mol, triols with a molecular weight in the range from 50 to 500 g / mol, and diamines with a molecular weight in the range from 50 to 500 g / mol.

15. Use of a molded body obtainable or obtained according to a method according to one of the embodiments 1 to 7 or a molded body according to one of the embodiments 8 to 14 as a damping element, shock absorber or stop buffer or as part of a shoe or a shoe sole, for example an insole or midsole .

In the following, the invention is to be explained in more detail using examples, without restricting the subject matter of the invention.

Examples

1. Production of a molded article coated with in-mold coating 1.1 Production of a prepolymer containing isocyanate groups

1000 parts by weight (0.5 mol) of a polycaprolactone polyol with an average molecular weight of 2000 g / mol were heated to 140 ° C. and at this temperature with 240 parts by weight (1.14 mol) of solid NDI (1,5-naphthylene diisocyanate) are added with vigorous stirring.

An NCO-terminated prepolymer with an NCO content of 4.09% by weight and a viscosity at 90 ° C. of 3000 mPas (measured with a rotational viscometer from Rheometrics Scientific) was obtained.

Production of the crosslinking component

The crosslinking component was produced by mixing the following components:

32.7 parts by weight of a 50% strength aqueous solution of a fatty acid sulfonate

16.4 parts by weight of water

28 parts by weight of a carbodiimide based on 1,3-bis (1-isocyanato-1-methylethyl) benzene (TMXDI) ()

18.1 parts by weight of a fatty acid polyglycol ester

4.2 parts by weight of a mixture of fatty acid polyglycol esters and amine salts of alkyl benzene sulfonates

0.6 parts by weight of a mixture of:

30 wt .-% pentamethyl diethylenetriamine and

70 wt .-% N-methyl-N ’- (dimethylaminoethyl) piperazine Manufacture of molded articles

A lockable, metallic mold heated to 70 ° C was treated with a release agent (e.g. Acmosil 36-5324, Stahl) and then with a paint system (binder and hardener, e.g. Permutex RP-39-528 and Permutex XR-5577, Fa. Stahl) be sprayed and allowed to dry (120 s).

100 parts by weight of the prepolymer containing isocyanate groups, heated to 90 ° C., were intensively stirred for about 10 seconds with the crosslinking component (2.52 parts by weight) heated to 50 ° C. The reaction mixture was then poured into the mold pretreated with the paint system and heated to 70 ° C., the mold was closed and the reaction mixture was allowed to harden. After 20 minutes, the coated molding was removed from the mold and post-cured thermally at 110 ° C. for 16 hours. Cited literature

EP 62 835 A1

EP 36 994 A1

EP 250 969 A1

DE 195 48 770 A1

DE 195 48 771 A1

EP 1 379 568 B1

U.S. 3,615,972

Plastics Additive Handbook, 5th Edition, H. Zweifel, ed., Hanser Publishers, Munich, 2001 ([1]), pp.98-p.136

DE 19821668 A1

U.S. 6,184,410

DE 10004328 A1

U.S. 6,730,807

EP 0 940 389 B1

U.S. 5,498,747

Claims

(i) providing a shape with a surface (OF);

(iib) applying a composition (Z2) to at least part of the with

(iii) At least partial removal of the carrier means (T);

(iv) Introducing a mixture (M1) into the mold, comprising

(A) at least one prepolymer containing isocyanate groups,

(b) at least one chain extender (KV);

(vi) removing the molded article obtained from the mold.

2. The method according to claim 1, wherein the mixture (M 1) contains at least one compound (V2) selected from the group consisting of flame retardants and dyes.

3. The method according to any one of claims 1 to 2, wherein the compound (V1) is contained in a Men ge in the range of 0.3 and 5% by weight in the composition (Z2).

4. The method according to any one of claims 1 to 3, wherein the composition (Z2) is applied to the surface (OF) in an amount such that a layer with a thickness in the range from 5 μm to 0.5 mm is obtained.

5. The method according to any one of claims 1 to 4, wherein the mixture (M1) contains at least one further component selected from the group consisting of polyols, propellants, water, chain extenders and / or crosslinking agents, catalysts, other auxiliaries and additives.

6. The method according to any one of claims 1 to 5, wherein the polyisocyanate composition is an isocyanate selected from the group consisting of 1, 5-naphthylene diisocyanate (NDI), 4,4'-diphenylmethane diisocyanate (MDI), p-phenyl diisocyanate (PPDI) and o-Tolidinediisocyanate (TODI), or mixtures thereof.

7. The method according to any one of claims 1 to 6, wherein the chain extender (KV) is selected from the group consisting of water, diols with a molecular weight in the range from 50 to 500 g / mol, triols with a molecular weight in the range from 50 to 500 g / mol, and diamines with a molecular weight in the range from 50 to 500 g / mol.

8. Shaped bodies obtainable or obtained by a process at least comprising the

Steps (i) to (vi):

(i) providing a shape with a surface (OF);

(iii) At least partial removal of the carrier means (T);

(iv) Introducing a mixture (M1) into the mold, comprising (A) at least one prepolymer containing isocyanate groups,

(b) at least one chain extender (KV); (v) allowing the mixture (M1) to react to completion to give a molded body comprising a polyurethane elastomer;

(vi) removing the molded article obtained from the mold.

9. Use of a molded body obtainable or obtained according to a method according to one of claims 1 to 7 or a molded body according to claim 8 as a damping element, shock absorber or stop buffer or as part of a shoe or a shoe sole, for example an insole or midsole.