WO2009106501A1

WO2009106501A1 - Multi-layer composite material, production and use thereof

Info

Publication number: WO2009106501A1
Application number: PCT/EP2009/052111
Authority: WO
Inventors: Carl Jokisch; Jürgen WEISER; Peter Rudolf
Original assignee: Basf Se
Priority date: 2008-02-27
Filing date: 2009-02-23
Publication date: 2009-09-03

Abstract

The invention relates to a multi-layer composite material which comprises the following components: (A) a sheet material, (B) a material which is capable of absorbing water or aqueous liquids, (C) optionally at least one connecting layer, (D) a polyurethane layer having capillaries that extend through the entire thickness of the polyurethane layer, (E) and at least one intermediate layer between the combination of sheet material (A) and absorbent material (B) and the polyurethane layer (D), the intermediate layer (E) being selected from textile, paper, nonwovens, synthetic leather and open-cell foam.

Description

Multilayer composite material, its manufacture and use

The present invention relates to a multilayer composite material comprising as components: (A) a sheet,

(B) a material which can absorb water or aqueous liquids,

(C) optionally at least one tie layer,

(D) a polyurethane layer having capillaries extending the full thickness of the polyurethane layer, (E) and at least one intermediate layer between the combination of fabric (A) and absorbent material (B) on the one hand and polyurethane layer (D) on the other, with intermediate layer (E) is selected from textile, paper, nonwovens, artificial leather and open-cell foam.

Furthermore, the present invention relates to a method for producing multilayer composite materials according to the invention. Moreover, the present invention relates to the use of multilayer composite materials according to the invention, for example in the interior of vehicles, for the production of seats and for room climate management.

Cellulose cloths can in many cases absorb water or aqueous liquids well. An even more versatile use than today, however, fails in many cases because moist cellulose cloths are unsightly and have only a very low mechanical strength.

Superabsorbents, known in their form as superabsorbent polymers (SAP), are used in numerous products intended to absorb large quantities of liquid, in particular body fluid, for example in diapers. However, many of these products have the disadvantage that they do not look pleasing from the outside. They can quickly become dirty, for example, by dusting, and then look grubby. Many of these products are disposable.

Another argument against a permanent use of superabsorbers is that they do not have a pleasing appearance in many variants.

It was therefore the object to provide a material that combines good fluid-absorbing properties with a pleasing appearance. In addition, the material should be good to clean externally.

Accordingly, the above-defined multilayer composite materials were found. Multilayer composite materials according to the invention comprise as component

(A) a sheet, for example in the form of a film, in particular a plastic film, or a foam. Suitable plastic films are for example made of polyethylene, polyamide, preferably polyester or block copolymers of styrene and 1, 3-butadiene. Suitable foams are produced, for example, by foaming polypropylene, polyurethane, polystyrene, in each case with or without one or more additives, for example particles of graphite.

Sheet (A) is preferably a textile fabric, in the context of the present invention also referred to as a textile fabric (A) or, for short, as a textile (A). For the purposes of the present invention, textile (A) is understood as meaning, for example, fabrics such as felts, woven fabrics, knitted fabrics, knits, nonwovens and wadding. Textile (A) may be of natural origin, for example cotton, wool or flax, or synthetic, for example polyamide, polyester, modified polyester, polyester blend, polyamide blend, polyacrylonitrile, triacetate, acetate, polycarbonate, polyolefins such as polyethylene and polypropylene, polyvinyl chloride, furthermore microfibers and micro hollow fibers such as polyester microfibers and glass fiber fabrics. Particularly preferred are polyesters, cotton and polyolefins such as polyethylene and polypropylene, as well as selected blended fabrics selected from cotton-polyester blended fabrics, polyolefin-polyester blend fabrics, and polyolefin-cotton blended fabrics. Especially preferred embodiments of textile (A) are polyester fabrics and nonwovens.

Multilayer composite materials according to the invention furthermore comprise

(B) a material which can absorb water or aqueous liquids, which in the context of the present application is also referred to as absorptive material (B) for short. Examples of absorbent materials (B) are pulp or cotton textile. If you want to choose cotton textile as absorbent material (B), you choose as fabric (A) another material than cotton.

Under water and aqueous liquids is in particular water in the gaseous state of matter to understand, for example, as moisture, most preferably atmospheric humidity.

In a preferred embodiment of the present invention, absorbent material (B) is a superabsorbent, which is also referred to as superabsorber (B) in the context of the present invention. Superabsorbent (B) in the context of the present invention is a substance which is many times its own weight, for example up to a thousand times, of liquid liquids, in particular aqueous liquids, for example, aqueous body fluids such as blood, urine or sweat and of course water.

Preferably, superabsorbent (B) is a synthetic organic copolymer having superabsorbent properties. Synthetic organic copolymers with superabsorbent properties, hereinafter also referred to as superabsorbent polymers (SAP) or superabsorbent copolymers (B), are preferably copolymers which are prepared by copolymerization of at least two SAPs or SAP-forming monomers.

For the purposes of the present application, superabsorbent or SAP-forming monomers are to be understood as meaning polymerizable compounds which contribute to the absorbency of the copolymers formed therefrom. Examples are monoethylenically unsaturated compounds or compounds having a polymerizable double bond with at least one hydrophilic radical, such as carboxyl, carboxylic anhydride, carboxylic acid salt, sulfonic acid, sulfonic acid salt, hydroxyl, ether, amide, amino or quaternary ammonium salt groups , Suitable superabsorbent or SAP-forming monomers are, for example:

1. carboxyl group-containing monomers: monoethylenically unsaturated mono- or polycarboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, sorbic acid and itaconic acid;

2. carboxylic acid anhydride group-containing monomers: monoethylenically unsaturated polycarboxylic anhydrides such as maleic anhydride;

3. Carboxylic acid salt-containing monomers: water-soluble salts (alkali salts, ammonium salts, amine salts, etc.) of monoethylenically unsaturated mono- or polycarboxylic acids, such as sodium (meth) acrylate, trimethylamine (meth) acrylate, triethanolamine (meth) acrylate, sodium maleate, methylamine maleate;

4. monomers containing sulfonic acid groups: aliphatic or aromatic vinylsulfonic acids such as vinylsulfonic acid, allylsulfonic acid, vinyltoluenesulfonic acid, styrenesulfonic acid), (meth) acrylic sulfonic acid, sulfopropyl (meth) acrylate, 2-hydroxy-3-

(Meth) acryloxy-propylsulphonic);

5. monomers containing sulfonic acid salt groups: alkali salts, ammonium salts, amine salts of sulfonic acid group-containing monomers as mentioned above;

6. hydroxyl-containing monomers: monoethylenically unsaturated alcohols, such as (meth) allyl alcohol, monoethylenically unsaturated ethers or esters of polyols, for example, alkylene glycols, glycerol, polyoxyalkylene polyols such as hydroxyethyl (meth) acrylate, triethylene glycol (meth) acrylate, poly (oxyethyleneoxypropylene) glycol mono (meth) allyl ethers, wherein the hydroxy groups are optionally etherified or esterified;

7. amide group-containing monomers: vinylformamide, (meth) acrylamide, N-alkyl (meth) acrylamides such as N-methacrylamide, N-hexylacrylamide, furthermore N, N-dialkyl (meth) acrylamides such as N, N-dimethylacrylamide or N, N-di n-propylacrylamide, N-hydroxyalkyl (meth) acrylamides such as N-methylol (meth) acrylamide or N-hydroxyethyl (meth) acrylamide, N, N-dihydroxyalkyl (meth) acrylamides such as N, N

Dihydroxyethyl (meth) acrylamide] vinyl lactams such as N-vinylpyrrolidone;

8. Amino group-containing monomers: Amino group-containing esters, e.g. Dialkylaminoalkyl esters, dihydroxyalkylaminoalkyl esters, morpholinoalkyl esters, monoethylenically unsaturated mono- or dicarboxylic acids, such as dimethylaminoethyl (meth) acrylate,

Diethylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate or dimethylaminoethyl fumarate, heterocyclic vinyl compounds such as vinylpyridines, e.g. 2-vinylpyridine, 4-vinylpyridine, N-vinylpyridine, also N-vinylimidazole; such as

9. quaternary ammonium salt groups-containing monomers: for example, N ₁ N ₁ N-trialkyl-N- (meth) acryloyloxyalkylammoniumsalze such as N ₁ N ₁ NT rimethyl-N- (meth) acryloyl-oxyethylammoniumchlorid ₁ N, N, N-triethyl-N- ( meth) acryloyloxyethylammonium chloride, 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride, and monomers according to GB-PS 1, 034,296.

Monomers which are suitable for use in place of or in combination with the SAP-forming monomers and which become water-soluble by hydrolysis include monoethylenically unsaturated compounds having at least one hydrolyzable group, such as esters, amide and nitrile groups. Such monomers having an ester group include, for example, C 1 -C 4 -alkyl esters of monoethylenically unsaturated carboxylic acids, such as methyl (meth) acrylate and ethyl (meth) acrylate, and furthermore 2-ethylhexyl (meth) acrylate and esters of monoethylenically unsaturated alcohols [vinyl ester, (Meth allyl ester, etc.] such as vinyl acetate and (meth) allyl acetate. Suitable nitrile group-containing monomers include (meth) acrylonitrile.

In one embodiment of the present invention, SAP-forming monomers are water-soluble monomers which, for example, at 20 ^° C., may have a solubility of at least 5 g / l in distilled water.

Among these water-soluble or hydrolysis-water-soluble monomers are water-soluble monomers which do not require hydrolysis after polymerization, due to the ease of processing in the production of absorbent MA. materials (B) are preferred. Further, as water-soluble monomers, by way of preparation, absorbent materials (B) having high water absorption include monomers containing carboxyl groups, such as (meth) acrylic acid and maleic anhydride; carboxylic acid salt group-containing monomers such as sodium (meth) acrylate, trimethylamine (meth) acrylate and triethanolamine (meth) acrylate and quaternary ammonium salt group-containing monomers such as N, N, N-trimethyl-N- (meth) acryloyloxyethylammonium chloride preferred.

Very particularly preferred superabsorbent monomers include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, sorbic acid, itaconic acid, cinnamic acid, vinylsulfonic acid, allylsulfonic acid, vinyltoluenesulfonic acid, styrenesulfonic acid, sulfo (meth) acrylate, sulfopropyl (meth) acrylate, 2-acrylamide 2-methylpropanesulfonic acid, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, their sodium, potassium and ammonium salts, maleic anhydride and combinations thereof, for example as free acid or at least partially neutralized, preferably from 1 to 100 mol% , Particularly preferably 10 to 80 mol% and most preferably 15 to 75 mol% is neutralized. Most preferably, the superabsorbent-forming monomer is neutralized acrylic acid.

Superabsorber (B) is preferably in the form of particles.

Superabsorbents (B) in particulate form, also referred to as SAP particles in the context of the present invention, are lightly crosslinked polymers in particulate form, which are prepared from at least one of the abovementioned SAP-forming monomers and at least one internal crosslinker , the polymers thus available are highly absorbent. Preferred SAP particles are, on average, sufficiently small that they can easily be prepared by spray-drying or by spraying, preferably with a diameter of less than 150 μm, more preferably less than 100 μm. Such a morphology can be obtained directly as a result of the polymerization process, or the high-absorbency polymers can also be brought to the desired average particle size of the SAP particles by sieving, milling, pulverizing, rubbing or a combination thereof. The average diameter of the SAP particles is, for example, in the range of 10 to 130 μm, preferably 15 to 100 μm, and most preferably 40 to 90 μm.

In order to produce particles of superabsorbent (B), in many embodiments at least one SAP-forming monomer is copolymerized with at least one crosslinker.

The production of particles of superabsorbent (B) is carried out from one or more SAP-forming monomer and at least one internally crosslinking compound, also referred to as internal crosslinker, wherein the particles of superabsorbent (B) preferably from 50 to 99.9 mole percent of SAP-forming monomer or SAP-forming monomers are formed. The additional use of internal crosslinker gives particles of superabsorbent (B) which comprise a slightly crosslinked polymer.

The crosslinking takes place essentially uniformly over the entire particle of superabsorber (B). Suitable internal crosslinkers are those compounds having two or more groups reactive with the monoethylenically unsaturated monomers which are at least partially soluble or dispersible in water or an aqueous monomer mixture. The internal crosslinker may be selected from an unsaturated monomer such as divinylbenzene, a compound having at least two functional groups reactive toward a monoethylenically unsaturated monomer such as ethylenediamine, a compound having at least one unsaturated bond and at least one reactive functional group such as glycidyl (meth) acrylate.

Exemplary internal crosslinkers are: tetraallyloxyethane, N, N'-methylenebisacrylamide, N, N'-methylenebismethacrylamide, triallylamine, trimethylolpropane triacrylate, glycerol propoxytriacrylate, divinylbenzene, N-methylolacrylamide, N-methylolmethacrylamide, glycidyl methacrylate, polyethylene polyamines, ethylenediamine, ethylene glycol and glycerol , Preferred internal crosslinkers are those having at least two allyl groups, very particularly preferably three or four allyl groups. Preferred internal crosslinkers are tetraallyloxyethane and the triallyl ether of pentaerythritol. The amount of internal crosslinker used according to the invention depends on the internal crosslinker and the polymerization process. Typically, the amount of internal crosslinker is from about 0.005 to about 1.0 mole percent, based on moles of the SAP-forming monomer.

Components optionally used in the production of particles of superabsorbent (B) are water-soluble hydroxyl-containing polymers such as polysaccharides and vinyl or acrylic polymers. Examples of water-soluble polysaccharides are starches, water-soluble celluloses and polygalactomannans. Suitable starches include the native starches such as sweet potato starch, potato starch, wheat starch, corn starch, rice starch, tapioca starch and the like. Also suitable are refined or modified starches, such as dialdehyde starch, starch etherified with alkyl alcohols, in particular methanol-etherified starch, allyl-etherified starch, oxyalkylated starch, aminoethyl etherified starch and cyanomethyl-etherified starch. Also suitable are polyvinyl alcohol and polyvinyl alcohol copolymers.

Suitable water-soluble cellulose is cellulose obtained from such sources as wood, stems, bast, seed fluff and the like, which is then derivatized to hydroxyalkylcellulose, carboxymethylcellulose, methylcellulose and the like. Suitable polygalactomannans are guar gum and locust bean gum as well as their hydroxyalkyl, carboxyalkyl and aminoalkyl derivatives. Water-soluble vinyl and acrylic polymers include polyvinyl alcohol and polyhydroxyethyl acrylate. Preferred polysaccharide is native starch, such as wheat starch, corn starch and alpha starch. These optionally prefabricated hydroxy-containing polymers can be used in an amount of 1 to 15 wt .-%, preferably from 1 to 10 wt .-% and most preferably 5 wt .-%, based on solids content of absorbent material (B).

Particles of superabsorbent (B) can be prepared by known polymerization. The polymerization takes place in the presence of, for example, redox initiators and thermal initiators. It is possible to work primarily with the redox initiators, with the thermal polymerization initiators optionally being used only to suppress the residual monomer content of the final polymerization product to below 0.1 percent by weight. Optionally, thermal initiators or redox initiators can be used as the sole initiator system. Examples of various initiator systems can be found in US 4,497,930, which describes a two-component initiator system of persulfate and hydroperoxide, and in US 5,145,906, which discloses a three component initiator system, i. Redox system plus thermal initiator disclosed.

Particles of superabsorbent (B) may be prepared by the solution or reverse-suspension polymerization method or by a suitable bulk polymerization method. The solution polymerization and reverse polymerization processes are known per se in the art, see, for example, U.S. Patents 4,076,663; 4,286,082; 4,654,039 and 5,145,906, in which the Lösungspolymerisati- onsverfahren is described, and US Pat. Nos. 4,340,706; 4,497,930; 4,666,975; 4,507,438 and 4,683,274, which describe the reverse-suspension polymerization process.

In one embodiment of the present invention, absorbent material (B) and in particular superabsorbent (B) are physically or chemically bonded to fabric (A). In this case, one can choose the type of physical or chemical combination of absorbent material (B) and in particular superabsorbent (B) with fabric (A) according to the geometric dimensions of absorbent material (B) and in particular superabsorbent (B). Thus it is possible, for example, to design absorbent material (B) in the form of cellulose wipes, which is adhered or glued to the fabric (A). In another variant, absorbent material (B) and in particular superabsorbent (B) in the form of particles, for example granular or spherical particles, with a mean diameter (number average) in the range of 1 .mu.m to 1 cm, preferably 10 .mu.m to 1 mm, and stores them in the pores of sheets. In a their variant is designed absorptive material (B) and in particular superabsorber (B) in the form of particles, such as granular or spherical particles, with a mean diameter (number average) in the range of 1 .mu.m to 1 cm, preferably 10 .mu.m to 1 mm , and fixes them to sheet (A) with the aid of a binder or an adhesive.

In a preferred variant of the present invention, superabsorbent (B) can be prepared in the presence of fabrics (A), in particular of textile fabric (A). In one embodiment of the present invention, it is possible to polymerize superabsorber (B) onto sheets (A), for example by carrying out the (co) polymerization completely or temporarily in the presence of sheet (A). For example, it is possible to prepare a mixture of one or more SAP-forming monomers with water and one or more initiators and apply them to a textile fabric. Thereafter, the (co) polymerization is initiated. In another embodiment of the present invention, a mixture of one or more SAP-forming monomers, water and one or more initiators is first prepared and then the (co) polymerization is initiated. After a certain time, one then adds sheet (A) or applies the reacting mixture to textile fabric and then completes the (co) polymerization.

In a preferred variant of the present invention, it is possible to finish superabsorbent (B) in the presence of flat structures (A), in particular of textile fabric (A). For this purpose it is possible, for example, to mix a mixture of one or more SAP-forming monomers with superabsorbent (B) in particulate form, water and one or more initiators and to apply them to a textile fabric. Thereafter, the (co) polymerization is initiated.

This can be done, for example, by applying a polymerization mixture containing particles of superabsorbent (B) with SAP-forming monomer, water and one or more initiators on sheet (A), for example, sprayed, paddled or poured, and then triggers the polymerization ,

Particles of superabsorbent (B) are preferably contained in the polymerization mixture at about 1 to 20% by weight, preferably at 2 to 15% by weight and most preferably at 5 to 10% by weight. It has been found that if the content of SAP particles is too high, premature polymerization may occur in the polymerization mixture in some cases.

In one embodiment of the present invention, the polymerization mixture has a viscosity of at least 20 mPas measured at 20 ^° C. in the Brookfield Viscometer, spindle 02, 20 rpm. The polymerization mixture may additionally contain a crosslinking agent and / or a plasticizer and / or at least one odor-controlling agent and / or a skin care agent, such as panthotenol, aloe vera, having a pH range corresponding to that of the skin. Alternatively, the SAP particles contained in the polymerization mixture may contain at least one odor-controlling agent and / or one skin care agent, such as panthotenol, aloe vera, having a pH range corresponding to that of the skin.

For example, the acquisition layer and the storage layer of the absorbent body have a pH of from 2.0 to 7.5, and preferably from 4.0 to 6.5. According to a preferred embodiment of the invention, the acquisition layer and the storage layer have a different pH. Thus, e.g. the pH of the acquisition layer is 4.0 to 6.5, and preferably 4.2 to 4.5 and that of the storage layer is 5.0 to 6.0.

According to another preferred embodiment of the invention, the SAP particles consist of MBIE SAP particles or multi-zone compositions of SAP particles, e.g. in WO 99/25393, preferably having a ratio of SAP anionic to cationic of from about 5: 1 to about 1: 5.

Further variants by which superabsorbent (B) can be combined with textile fabric (A) are described in the publications WO 03/053487, EP 0 764 223, US Pat. No. 7,115,321 and EP 1 178 149 WO 2004/039493.

In a variant, the combination of textile fabric (A) and absorbent material (B) comprises fibers of superabsorbent (B), which are processed together with fibers of other material to form a nonwoven fabric, as described in WO 2004/039493.

In another variant of the present invention, the combination of textile fabric (A) and absorbent material (B) is a foamy superabsorber which is fixed on textile.

In one embodiment of the present invention, sheet (A) and absorbent material (B) together have an average thickness in the range of 100 μm to 10 mm, preferably 1 mm.

Multilayer composite material according to the invention furthermore comprises (D) at least one polyurethane layer which has capillaries which extend over the entire thickness of the polyurethane layer, in the context of the present invention also referred to as polyurethane layer (D) for short. In one embodiment of the present invention, polyurethane layer (D) has an average thickness in the range from 15 to 300 μm, preferably from 20 to 150 μm, particularly preferably from 25 to 80 μm.

Polyurethane layer (D) has capillaries that go over the entire thickness (cross section) of the polyurethane layer (D).

In one embodiment of the present invention, polyurethane layer (D) has on average at least 100, preferably at least 250 capillaries per 100 cm ² .

In one embodiment of the present invention, the capillaries have an average diameter in the range of 0.005 to 0.05 mm, preferably 0.009 to 0.03 mm.

In one embodiment of the present invention, the capillaries are evenly distributed over polyurethane layer (D). In a preferred embodiment of the present invention, however, the capillaries are unevenly distributed over the polyurethane layer (D).

In one embodiment of the present invention, the capillaries are substantially bent. In another embodiment of the present invention, the capillaries have a substantially straight course.

The capillaries impart air and water vapor permeability to the polyurethane layer (D) without the need for perforation. In one embodiment of the present invention, the water vapor permeability of the polyurethane layer (D) can be above 1.5 mg / cm ² -h, measured according to DIN 53333. Thus it is possible for moisture, such as sweat, to migrate through the polyurethane layer (D) and of absorbent material (B). If the environment is very dry, absorbent material can release the moisture.

In one embodiment of the present invention, polyurethane layer (D), in addition to the capillaries, still has pores which do not extend over the entire thickness of the polyurethane layer (D).

In one embodiment, polyurethane layer (D) has a pattern. The pattern can be arbitrary and, for example, the pattern of a leather or a wooden surface play. In one embodiment of the present invention, the pattern may reflect a nubuck leather. In one embodiment of the present invention, polyurethane layer (D) has a velvet-like appearance.

In one embodiment of the present invention, the pattern may correspond to a velvet surface, for example with hairs having an average length of 20 to 500 μm, preferably 30 to 200 μm and particularly preferably 60 to 100 μm. The hairs may, for example, have a circular diameter. In a particular embodiment of the present invention, the hairs have a conical shape.

In one embodiment of the present invention, polyurethane layer (D) has hairs which are arranged at an average distance of 50 to 350, preferably 100 to 250 microns to each other.

In the event that the polyurethane layer (D) has hair, the information on the average thickness on the polyurethane layer (D) without the hairs refer.

In one embodiment of the present invention, the multilayer composite material according to the invention may comprise a tie layer (C), which will be explained in more detail below. Bonding layer (C) may have a uniform or uneven thickness, wherein the bonding layer (C) ensures a total air permeability.

In another embodiment of the present invention composite material according to the invention contains no bonding layer (C). The combination of combination of fabrics (A) and absorbent material (B) can then be made, for example, by welding, in particular by ultrasonic welding, for example at frequencies in the range of 19 to 25 kHz or in the range of 40 to 70 kHz.

Bonding layer (C) may be a perforated layer, that is to say not the entire surface, of a distinct layer, preferably a hardened organic adhesive.

In one embodiment of the present invention, tie layer (C) is a layer in the form of dots, stripes or lattices, for example in the form of diamonds, rectangles, squares or a honeycomb structure. Then, polyurethane layer (D) comes in contact with sheet (A) or absorbent material (B) at the gaps of bonding layer (C). In one embodiment of the present invention, tie layer (C) is a layer of a cured organic adhesive, for example based on polyvinyl acetate, polyacrylate or, in particular, polyurethane, preferably of polyurethanes with a glass transition temperature below 0 ° C.

The curing of the organic adhesive may be effected, for example, thermally, by actinic radiation or by aging.

In another embodiment of the present invention, bonding layer (C) is an adhesive net.

In one embodiment of the present invention, the bonding layer (C) has a maximum thickness of 100 μm, preferably 50 μm, more preferably 30 μm, most preferably 15 μm.

In one embodiment of the present invention, tie layer (C) may include hollow microspheres. For the purposes of the present invention, hollow microspheres are spherical particles having an average diameter in the range from 5 to 20 μm of polymeric material, in particular of halogenated polymer such as, for example, polyvinyl chloride or polyvinylidene chloride or copolymer of vinyl chloride with vinylidene chloride. Hollow microspheres can be empty or preferably filled with a substance whose boiling point is slightly lower than the room temperature, for example with n-butane and especially with isobutane.

In one embodiment of the present invention, polyurethane layer (D) may be bonded to sheet (A) or absorbent material (B) via at least two tie layers (C) having the same or different composition, such that the polyurethane layer (D ) comes into direct contact with fabric (A) or with absorbent material (B) at at least one location. Thus, one bonding layer (C) may contain one pigment and the other bonding layer (C) may be pigment-free.

In one variant, one connecting layer (C) may contain hollow microspheres and the other connecting layer (C) may not.

In one embodiment of the present invention, the multilayer composite material according to the invention can have no further layers. In another embodiment of the present invention, the multilayer composite material according to the invention comprises at least one intermediate layer (E) between absorbent material (B) and bonding layer (C), between bonding layer (C) and polyurethane layer (D) or between two bonding layers (C). , which may be the same or different, lies. Intermediate layer (E) is selected from tex- til, paper, nonwovens, nonwovens of synthetic materials such as polypropylene or polyurethane, in particular nonwoven thermoplastic polyurethane, synthetic leather and open-cell foam, for example melamine-formaldehyde foam or polyurethane foam.

In an embodiment of the present invention, intermediate layer (E) may have an average diameter (thickness) in the range of 0.05 mm to 5 cm, preferably 0.1 mm to 0.5 cm, particularly preferably 0.2 mm to 2 mm.

Preferably, intermediate layer (E) has a water vapor permeability in the range of greater than 1, 5 mg / cm ² -h, measured according to DIN 53333.

Multilayer composite materials according to the invention have a high mechanical strength and fastness properties. Furthermore, they have a high water vapor permeability. In addition, multilayer composite materials according to the invention have a pleasing appearance and a very pleasant soft feel. In addition, if desired, the combination of fabric (A) and absorbent material (B) is easily replaced, for example, by severing and then attaching a new combination of fabric (A) and absorbent material (B). Advantageously, the application of inventive multilayer composite material, for example, in seats for means of transport such as boats, automobiles, aircraft, railways, trams, buses and especially in child seats. Also in other areas in the interior of vehicles, multilayer composite material according to the invention can advantageously be used, for example in steering wheels, armrests, headliners, interior trim pieces, center consoles, parcel shelves and dashboards. Furthermore, multilayer composite material according to the invention can advantageously be used for room climate management. The room climate management is effected by the fact that multi-layer composite materials according to the invention absorb (absorb) moisture in a humid environment and release (desorb) in a dry environment, thus being able to ensure a uniformly humid climate.

Another use of multilayer composite materials according to the invention are sports articles, for example sports bags, rucksacks, rackets such as, for example, tennis or hockey sticks, sports shoes and the inside of helmets. Another use of multilayer composites of the invention are electrical devices and their packaging, such as mobile phones and mobile phone cases, game consoles, computer keyboards. Another use for multilayer composite materials according to the invention are furniture, such as sofas, reclining furniture such as chairs, armchairs and chairs. Another use for composite materials according to the invention are elements for the Interior of buildings, such as curtains, curtains and wall coverings.

A further subject of the present invention is a process for the production of multilayer composite materials according to the invention, also referred to in the context of the present invention as a production process according to the invention. In one embodiment of the production process according to the invention, the procedure is such that material (B) which can absorb water or aqueous liquids, also referred to as absorbent material (B) for short, is joined to a fabric (A), preferably to a textile fabric (A) in that a polyurethane layer (D) is formed by means of a matrix, at least one organic adhesive is applied over all or part of the sheet (A) and / or polyurethane layer (D) bonded to the absorbent material (B), and then polyurethane layer (D) is applied the area combined with material (B) sheet (A) connects point-like, strip-like or flat.

Definition and preparation of absorbent material (B) and of sheet (A) are described above. Preferably, absorbent material (B) is a superabsorbent (B). Sheet (A) is preferably a textile fabric (A).

In one embodiment of the present invention, the multilayer composite material of the present invention is prepared by a coating process by first preparing a combination of sheet (A) and absorbent material (B), further providing a polyurethane film (D), at least the combination of absorbent material (B ) and sheet (A) or the polyurethane film (D) or both on each surface partially, for example, pattern-coated, with organic adhesive and then brings the two surfaces into contact. Then you can still press the system so available together or thermally treated or pressed together with heating.

The polyurethane film (D) forms the later polyurethane layer (D) of the multilayer composite material according to the invention. The polyurethane film (D) can be prepared as follows.

An aqueous polyurethane dispersion is applied to a die which is preheated, allowing the water to evaporate, and thereafter transferring the resulting polyurethane film (D) to the combination of sheet (A) and absorbent material (B). The application of aqueous polyurethane dispersion on the die can be carried out by methods known per se, in particular by spraying, for example with a spray gun.

The matrix may have a pattern, also called structuring, which is produced for example by laser engraving or by molding.

In one embodiment of the present invention, a die is provided which has an elastomeric layer or a layer composite comprising an elastomeric layer on a support, wherein the elastomeric layer comprises a binder and optionally further additives and auxiliaries. The provision of a template may then include the following steps:

1) applying a liquid binder, optionally containing additives and / or adjuvants, on a patterned surface, for example another

Die or an original pattern,

2) curing the binder, for example by thermal curing, radiation curing or by aging,

3) separating the thus obtainable template and optionally applying to a support, for example a metal plate or a metal cylinder.

In one embodiment of the present invention, the procedure is to apply a liquid silicone to a pattern that ages and thus hardens silicone and then peels it off. The silicone film is then glued on an aluminum carrier.

In a preferred embodiment of the present invention, a die is provided which has a laser-engravable layer or a layer composite comprising a laser-engravable layer on a support, wherein the laser-engravable layer comprises a binder and optionally further additives and auxiliaries. The laser-engravable layer is also preferably elastomeric.

In a preferred embodiment, the provision of a template comprises the following steps:

1) providing a laser-engravable layer or a layer composite comprising a laser-engravable layer on a support, wherein the laser-engravable layer comprises a binder and preferably additives and auxiliaries,

2) thermochemical, photochemical or actinic amplification of the laser-engravable layer, 3) engraving a surface structure corresponding to the surface structure of the surface-structured coating into the laser-engravable layer with a laser.

The laser-engravable layer, which is preferably elastomeric, or the layer composite can be present on a support, preferably they are present on a support. Examples of suitable supports include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polyethylene, polypropylene, polyamide or polycarbonate fabrics and films, preferably PET or PEN films.

Also suitable as a carrier papers and knitted fabrics, such as cellulose. Conical or cylindrical tubes made of the said materials, so-called sleeves, can also be used as the carrier. Also suitable for sleeves are glass fiber fabrics or composite materials made of glass fibers and polymeric materials. Further suitable carrier materials are metallic carriers such as, for example, solid or tissue-shaped, flat or cylindrical carriers made of aluminum, steel, magnetizable spring steel or other iron alloys.

In one embodiment of the present invention, the support may be coated with an adhesive layer for better adhesion of the laser-engravable layer. In another embodiment of the present invention, no adhesive layer is required.

The laser-engravable layer comprises at least one binder, which may be a prepolymer, which reacts to a polymer in the course of a thermochemical reinforcement. Suitable binders can be selected depending on the desired properties of the laser-engravable layer or the matrix, for example with regard to hardness, elasticity or flexibility. Suitable binders can be subdivided essentially into 3 groups, without the binders being intended to be limited thereto.

The first group includes such binders having ethylenically unsaturated groups. The ethylenically unsaturated groups can be crosslinked photochemically, thermochemically, by means of electron beams or with any combination of these processes. In addition, a mechanical reinforcement can be made by means of fillers. Such binders are, for example, those which comprise copolymerized 1,3-diene monomers, such as isoprene or 1,3-butadiene. The ethylenically unsaturated group can function once as a chain building block of the polymer (1, 4-incorporation), or it can be bound as a side group (1, 2-incorporation) to the polymer chain. Examples include natural rubber, polybutadiene, polyisoprene, styrene-butadiene rubber, nitrile-butadiene rubber, acrylonitrile-butadiene-styrene (ABS) copolymer, butyl rubber, styrene-isoprene rubber, polychloroprene, polynorbornene rubber, ethylene Propylene-diene rubber (EPDM) or polyurethane elastomers having ethylenically unsaturated groups. Other examples include thermoplastic elastomeric block copolymers of alkenyl aromatics and 1,3-dienes. The block copolymers may be either linear block copolymers or radial block copolymers. These are usually ABA-type triblock copolymers, but they can also be AB-type diblock polymers, or those having a plurality of alternating elastomeric and thermoplastic blocks, eg ABABA. It is also possible to use mixtures of two or more different block copolymers. Commercially available triblock copolymers often contain certain proportions of diblock copolymers. Diene units can be 1, 2, or 1, 4 linked. Both block copolymers of styrene-butadiene and of styrene-isoprene type can be used. They are available, for example under the name Kraton ^® commercially. Furthermore possible to employ thermoplastic-elastomeric block copolymers having end blocks of styrene and a random styrene-butadiene middle block, which are available under the name Styroflex ^®.

Other examples of ethylenically unsaturated binder include modified binders in which crosslinkable groups are introduced into the polymeric molecule by grafting reactions.

The second group includes such binders having functional groups. The functional groups can be thermochemically crosslinked by means of electron beams, photochemically or with any combination of these processes. In addition, a mechanical reinforcement can be made by means of fillers. Examples of suitable functional groups include -Si (HR ¹ ) O-, -Si (R ¹ R ² ) O-, -OH, -NH ₂ , -NHR ¹ , -COOH, -COOR ¹ , -COHN ₂ , -O- C (O) NHR ¹ , -SO ₃ H or -CO-. Examples of binders include silicone elastomers, acrylate rubbers, ethylene-acrylate rubbers, ethylene-acrylic acid rubbers or ethylene-vinyl acetate rubbers and their partially hydrolyzed derivatives, thermoplastic elastomeric polyurethanes, sulfonated polyethylenes or thermoplastic elastomeric polyesters. R ¹ and, if present, R ^{2 are} different or preferably identical and selected from organic groups and in particular C ¹ -C 6 -alkyl.

In one embodiment of the present invention, it is possible to use binders which have both ethylenically unsaturated groups and functional groups. Examples include addition-crosslinking silicone elastomers having functional and ethylenically unsaturated groups, copolymers of butadiene with (meth) acrylates, (meth) acrylic acid or acrylonitrile, and also copolymers or block copolymers of butadiene or isoprene with functionalized styrene derivatives, for example block copolymers of butadiene and hydroxystyrene. The third group of binders includes those which have neither ethylenically unsaturated groups nor functional groups. These include, for example, polyolefins or ethylene / propylene elastomers or products obtained by hydrogenation of diene units, such as, for example, SEBS rubbers.

Polymer layers which contain binders without ethylenically unsaturated or functional groups generally have to be reinforced mechanically, with the aid of high-energy radiation or a combination thereof, in order to enable optimum sharp-edged structuring by means of laser.

It is also possible to use mixtures of two or more binders, which may be both binders from in each case only one of the groups described, or mixtures of binders from two or all three groups. The possible combinations are limited only insofar as the suitability of the polymer layer for the laser structuring process and the molding process must not be adversely affected. For example, a mixture of at least one elastomeric binder which has no functional groups can advantageously be used with at least one further binder which has functional groups or ethylenically unsaturated groups.

In one embodiment of the present invention, the proportion of the binder (s) in the elastomeric layer or laser-engravable layer is from 30% by weight to 99% by weight relative to the sum of all the constituents of the elastomeric layer or laser-engravable layer concerned, preferably 40 to 95 wt .-%, and most preferably 50 to 90 wt .-%.

In one embodiment of the present invention, polyurethane layer (D) is formed by means of a silicone matrix. For the purposes of the present invention, silicone matrices are those matrices which are prepared using at least one binder which has at least one, preferably at least three O-Si (R ¹ R ² ) -O- groups per molecule, the variables being as defined above are.

Optionally, the elastomeric layer or laser-engravable layer may comprise reactive low molecular weight or oligomeric compounds. Oligomeric compounds generally have a molecular weight of not more than 20,000 g / mol. Reactive low molecular weight and oligomeric compounds will hereinafter be referred to as monomers for the sake of simplicity.

On the one hand, monomers can be added in order to increase the rate of photochemical or thermochemical crosslinking or crosslinking by means of high-energy radiation, if desired. When using binders from the first and second groups, the addition of monomers to the Acceleration generally not mandatory. In the case of binders from the third group, the addition of monomers is generally recommended, without this necessarily being necessary in every case.

Regardless of the crosslink speed issue, monomers can also be used to control the crosslink density. Depending on the nature and amount of the low molecular weight compounds added, further or narrower networks are obtained. As monomers on the one hand known ethylenically unsaturated monomers can be used. The monomers should be substantially compatible with the binders and have at least one photochemically or thermochemically reactive group. They should not be volatile. The boiling point of suitable monomers is preferably at least 150 ^° C. Particularly suitable are amides of acrylic acid or methacrylic acid with monofunctional or polyfunctional alcohols, amines, aminoalcohols or hydroxyethers and esters, styrene or substituted styrenes, esters of fumaric or maleic acid or allyl compounds. Examples include n-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, dipropylene glycol diacrylate, tripropyric acid. glycol diacrylate, dioctyl fumarate, N-dodecyl maleimide and triallyl isocyanurate.

Particularly suitable for the thermochemical reinforcement monomers include reactive low molecular weight silicones such as cyclic siloxanes, Si-H-functional siloxanes, siloxanes with alkoxy or ester groups, sulfur-containing siloxanes and silanes, dialcohols such as 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, diamines such as 1, 6-hexanediamine, 1, 8-octanediamine, amino alcohols such as ethanolamine, diethanolamine, butylethanolamine, dicarboxylic acids such as 1, 6-hexanedicarboxylic acid, terephthalic acid , Maleic acid or fumaric acid.

It is also possible to use monomers which have both ethylenically unsaturated groups and functional groups. As examples of its ω-hydroxyalkyl (meth) acrylates, such as ethylene glycol mono (meth) acrylate, 1, 4-butanediol mono (meth) acrylate or 1, 6-hexanediol mono (meth) acrylate.

Of course, mixtures of different monomers can be used, provided that the properties of the elastomeric layer are not adversely affected by the mixture. In general, the amount of added monomers 0 to 40 wt .-% with respect to the amount of all components of the elastomeric layer or the laser-engravable layer concerned, preferably 1 to 20 wt .-%.

In one embodiment, one or more monomers may be employed with one or more catalysts. So it is possible to make silicone matrices by adding one or more acids or by organotin compounds to accelerate the step 2) of providing the template. Suitable organotin compounds may be: di-n-butyltin dilaurate, di-n-butyltin diactanoate, di-n-butyltin di-2-ethylhexanoate, di-n-octyltin di-2-ethylhexanoate and di-n-butylbis (1-oxoneodecyloxy) stannane.

The elastomeric layer or the laser-engravable layer may further comprise additives and auxiliaries, for example IR absorbers, dyes, dispersing aids, antistatic agents, plasticizers or abrasive particles. The amount of such additives and auxiliaries should as a rule not exceed 30% by weight with respect to the amount of all components of the elastomeric layer or the relevant laser-engravable layer.

The elastomeric layer or the laser-engravable layer can be constructed from a plurality of individual layers. These individual layers can be of the same, approximately the same or different material composition. The thickness of the laser-engravable layer or all individual layers together is generally between 0.1 and 10 mm, preferably 0.5 to 3 mm. The thickness can be suitably selected depending on application and machine process parameters of the laser engraving process and the molding process.

The elastomeric layer or the laser-engravable layer may optionally further comprise a top layer having a thickness of not more than 300 μm. The composition of such a topsheet can be selected for optimal engravability and mechanical stability while selecting the composition of the underlying layer for optimum hardness or elasticity.

In one embodiment of the present invention, the topsheet itself is laser engravable or can be removed by laser engraving together with the underlying layer. The topsheet comprises at least one binder. It may further comprise an absorber for laser radiation or even monomers or auxiliaries.

In one embodiment of the present invention, the silicone matrix is a laser-engraved silicone matrix.

Of very particular advantage thermoplastic elastomeric binders or silicone elastomers are used for the process according to the invention. When using thermoplastically elastomeric binders, the preparation is preferably carried out by extrusion between a carrier film and a cover film or a cover element followed by calendering, as disclosed, for example, for flexographic printing elements in EP-A 0 084 851. In this way even thicker layers can be produced in a single work make a gear. Multilayer elements can be produced by coextrusion.

If it is desired to pattern the template by means of laser engraving, it is preferable to apply the laser-engravable layer before laser engraving by heating (thermochemically), by irradiation with UV light (photochemically) or by irradiation with energy ( actinic) or any combination thereof.

Subsequently, the laser-engravable layer or the layer composite is applied to a cylindrical (temporary) support, for example made of plastic, glass fiber reinforced plastic, metal or foam, for example by means of adhesive tape, negative pressure, clamping devices or magnetic force, and engraved as described above. Alternatively, the plane layer or the layer composite can also be engraved as described above. Optionally, during the laser engraving process, the laser engravable layer is washed with a round washer or a continuous washer with a debris removal cleaner.

In the manner described, the die can be produced as a negative die or as a positive die.

In a first variant, the matrix has a negative structure, so that the coating connectable to the sheet (A) and absorbent material (B) can be obtained directly by applying a liquid plastic material to the surface of the matrix and then solidifying the polyurethane ,

In a second variant, the die has a positive structure, so that first a negative die is produced by molding of the laser-structured positive die. The coating which can be bonded to a flat support can then be obtained from this negative die by applying a liquid plastic material to the surface of the negative die and then solidifying the plastic material.

Preferably, structural elements having dimensions in the range from 10 to 500 μm are engraved into the matrix. The structural elements may be formed as elevations or depressions. Preferably, the structural elements have a simple geometric shape and are, for example, circles, ellipses, squares, diamonds, triangles and stars. The structural elements can form a regular or irregular grid. Examples are a classical dot matrix or a stochastic screen, for example a frequency-modulated screen. In one embodiment of the present invention, for structuring the template by means of a laser, cells are introduced into the matrix having an average depth in the range from 50 to 250 μm and a center distance in the range from 50 to 250 μm.

For example, the die may be engraved to have "cups" (depressions) having a diameter in the range of 10 to 500 microns at the surface of the die Preferably, the diameter at the die surface is 20 to 250 microns and more particularly The spacing of the wells may be, for example, 10 to 500 μm, preferably 20 to 200 μm, particularly preferably up to 80 μm. The tone values of the grid are generally between 3% and 50%.

In one embodiment of the present invention, the die preferably still has a surface fine structure in addition to a surface coarse structure. Both coarse and fine structure can be produced by laser engraving. The fine structure may be, for example, a microroughness with a roughness amplitude in the range of 1 to 30 μm and a roughness frequency of 0.5 to 30 μm. The dimensions of the microroughness are preferably in the range from 1 to 20 .mu.m, more preferably from 2 to 15 .mu.m, and particularly preferably from 3 to 10 .mu.m.

Laser engraving is especially suitable for IR lasers. However, it is also possible to use lasers with shorter wavelengths, provided the laser has sufficient intensity. For example, a frequency doubled (532nm) or frequency tripled (355nm) Nd-Y AG laser can be used, or even an excimer laser (e.g., 248nm). For laser engraving, for example, a CO 2 laser with a wavelength of 10640 nm can be used. Particular preference is given to using lasers having a wavelength of 600 to 2000 nm. For example, Nd-Y AG lasers (1064 nm), IR diode lasers or solid-state lasers can be used. Particularly preferred are Nd / YAG lasers. The image information to be engraved is transmitted directly from the lay-out computer system to the laser apparatus. The lasers can be operated either continuously or pulsed.

As a rule, the template obtained can be used directly after production. If desired, the resulting template can still be cleaned. By such a cleaning step detached, but not yet completely removed from the surface layer components are removed. As a rule, simple treatment with water, water / surfactant, alcohols or inert organic cleaning agents is sufficient, which are preferably low in swelling.

In a further step, an aqueous formulation of polyurethane is applied to the matrix. The application can preferably be effected by spraying. The The matrix should be heated when applying the formulation of polyurethane, for example to temperatures of at least 80 ⁰ C, preferably at least 90 ⁰ C. The water from the aqueous formulation of polyurethane evaporates and forms the capillaries in the solidifying polyurethane layer.

By aqueous, in connection with the polyurethane dispersion, is meant that it contains water, but less than 5% by weight, based on the dispersion, preferably less than 1% by weight of organic solvent. Most preferably, no volatile organic solvent can be detected. Volatile organic sol- vents are understood to be organic solvent in the present invention, which have a boiling point of up to 200 ⁰ C at atmospheric pressure.

The aqueous polyurethane dispersion may have a solids content in the range from 5 to 60 wt .-%, preferably 10 to 50 wt .-% and particularly preferably 25 to 45 wt .-%.

Polyurethanes (PU) are well known, commercially available and generally consist of a soft phase of higher molecular weight polyhydroxyl compounds, e.g. polycarbonate, polyester or polyether segments, and a urethane

Hard phase, formed from low molecular weight chain extenders and di- or polyisocyanates.

Processes for the preparation of polyurethanes (PU) are well known. In general, polyurethanes (PU) are converted by reaction of

(a) isocyanates, preferably diisocyanates with

(b) isocyanate-reactive compounds, usually having a molecular weight (Mw) of 500 to 10,000 g / mol, preferably 500 to 5,000 g / mol, more preferably 800 to 3,000 g / mol, and (c) chain extenders having a molecular weight of 50 to 499 g / mol, optionally in the presence of

(d) catalysts

(e) and / or customary additives.

In the following, by way of example, the starting components and processes for the preparation of the preferred polyurethanes (PU) are set forth. The components (a), (b), (c) and optionally (d) and / or (e) usually used in the preparation of the polyurethanes (PU) are described below by way of example:

As isocyanates (a) it is possible to use generally known aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, for example tri-, tetra-, penta-, hexa-, hepta- 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- isocyanato-methyl-cyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4-cyclohexane diisocyanate, 1-methyl-2,4- and / or -2, 6-cyclohexane diisocyanate and / or 4,4'-, 2,4'- and 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-toluene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethyl-diphenyl-diisocyanate, 1, 2 Diphenylethane diisocyanate and / or phenylene diisocyanate. Preferably, 4,4'-MDI is used. Also preferred are aliphatic diisocyanates, in particular hexamethylene diisocyanate (HDI), and particularly preferred are aromatic diisocyanates such as 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) and mixtures of the above-mentioned isomers.

As isocyanate-reactive compounds (b) it is possible to use the generally known isocyanate-reactive compounds, for example polyesterols, polyetherols and / or polycarbonatediols, which are usually also grouped under the term "polyols", with molecular weights (M _w ) in the region of 500 and 8,000 g / mol, preferably 600 to 6,000 g / mol, in particular 800 to 3,000 g / mol, and preferably an average functionality to isocyanates of 1, 8 to 2.3, preferably 1, 9 to 2.2, in particular 2. Polyether polyols are preferably used, for example those based on generally known starter substances and customary alkylene oxides, for example ethylene oxide, 1,2-propylene oxide and / or 1,2-butylene oxide, preferably polyetherols based on polyoxytetramethylene (polyTHF), 1 , 2-propylene oxide and ethylene oxide.Polyetherols have the advantage that they have a higher hydrolytic stability than polyesterols, and are preferably as component (b), in particular for the production of soft polyurethanes polyurethane (PU 1).

Particularly suitable polycarbonate diols are aliphatic polycarbonate diols, for example 1,4-butanediol polycarbonate and 1,6-hexanediol polycarbonate.

As the polyester diols are those mentioned by polycondensation of at least one primary diol, preferably at least one primary aliphatic diol, for example ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol or more preferably 1, 4-dihydroxymethylcyclohexane (as Mixture of isomers) or mixtures of at least two of the aforementioned diols on the one hand and at least one, preferably at least two dicarboxylic acids or their anhydrides on the other hand. Preferred dicarboxylic acids are aliphatic dicarboxylic acids such as adipic acid, glutaric acid, succinic acid and aromatic dicarboxylic acids such as phthalic acid and in particular isophthalic acid. Polyetherols are preferably by addition of alkylene oxides, in particular ethylene oxide, propylene oxide and mixtures thereof, of diols such as ethylene glycol, 1, 2-propylene glycol, 1, 2-butylene glycol, 1, 4-butanediol, 1, 3-propanediol, or at Triols such as glycerin, prepared in the presence of highly active catalysts. Such highly active catalysts include cesium hydroxide and dimetal cyanide catalysts, also referred to as DMC catalysts. A frequently used DMC catalyst is zinc hexacyanocobaltate. The DMC catalyst can be left in the polyetherol after the reaction, preferably it is removed, for example by sedimentation or filtration.

Instead of a polyol, it is also possible to use mixtures of different polyols.

To improve the dispersibility can be used as isocyanate-reactive compounds (b) proportionately one or more diols or diamines having a carboxylic acid group or sulfonic acid group (b '), in particular alkali metal or ammonium salts of 1, 1-dimethylolbutanoic, 1, 1-dimethylolpropionic or

Chain extenders (c) used are aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 to 499 g / mol and at least two functional groups, preferably compounds having exactly two functional groups per molecule, known per se - For example, diamines and / or alkanediols having 2 to 10 carbon atoms in the alkylene radical, in particular 1, 3-propanediol, butanediol-1, 4, hexanediol-1, 6 and / or di-, tri-, tetra-, penta-, Hexa, hepta, octa, nona and / or Dekaalkylenglykole having 3 to 8 carbon atoms per molecule, preferably corresponding oligo- and / or polypropylene glycols, whereby mixtures of chain extenders (c) can be used.

More preferably, components (a) to (c) are difunctional compounds, i. Diisocyanates (a), difunctional polyols, preferably polyetherols (b) and difunctional chain extenders, preferably diols.

Suitable catalysts (d), which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the synthesis components (b) and (c), are known per se tertiary amines, such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine , N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo- (2,2,2) octane ("DABCO") and the like tertiary amines, and in particular organic metal compounds such as titanic acid esters, iron compounds such. For example, iron (III) acetylacetonate, tin compounds, e.g. As tin diacetate, tin dioctoate, tin dilaurate or Zinndialkylsalze aliphatic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate or the like. The catalysts are usually used in amounts of from 0.0001 to 0.1 parts by weight per 100 parts by weight of component (b).

Besides catalyst (d), auxiliaries and / or additives (e) can also be added to components (a) to (c). Examples which may be mentioned are blowing agents, anti-blocking agents, surface-active substances, fillers, for example nanoparticle-based fillers, in particular fillers based on CaCC 3, nucleating agents, lubricants, dyes and pigments, antioxidants, for example against hydrolysis, light, heat or discoloration In a preferred embodiment, component (e) also includes hydrolysis stabilizers such as, for example, polymeric and low molecular weight carbodiimides Preferably, the soft polyurethane contains triazole and / or triazole derivative and antioxidants in one From 0.1 to 5% by weight, based on the total weight of the relevant soft polyurethane, antioxidants are generally suitable substances which inhibit or prevent undesired oxidative processes in the plastic to be protected commercially available. Examples of antioxidants are hindered phenols, aromatic amines, thiosynergists, trivalent phosphorus organophosphorus compounds, and hindered amine light stabilizers. Examples of sterically hindered phenols can be found in Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Munich, 2001 ([1]), pp. 98-107 and pp.116-p121 aromatic amines can be found in [1] pp. 107-108. Examples of thiosynergists are given in [1], p.104-105 and p.112-1 13. Examples of phosphites can be found in [1], p.109-112. Examples of hindered amine light stabilizers are given in [1], p.123-136. For use in the antioxidant mixture, phenolic antioxidants are preferred. In a preferred embodiment, the antioxidants, in particular the phenolic antioxidants, have a molecular weight of greater than 350 g / mol, more preferably greater than 700 g / mol and a maximum molecular weight (M _w ) of at most 10,000 g / mol, preferably up to a maximum of 3,000 g / mol on. Furthermore they preferably have a melting point of at most 180 ⁰ C. In addition, advertising the preferred antioxidants used which are amorphous or liquid. Also, as component (e), mixtures of two or more antioxidants may be used.

In addition to the stated components (a), (b) and (c) and optionally (d) and (e), it is also possible to use chain regulators (chain terminators), usually having a molecular weight of from 31 to 3000 g / mol. Such chain regulators are compounds which have only one isocyanate-reactive functional group. such as monofunctional alcohols, monofunctional amines and / or monofunctional polyols. By means of such chain regulators, a flow behavior, in particular in the case of soft polyurethanes, can be adjusted in a targeted manner. Chain regulators can generally be used in an amount of 0 to 5, preferably 0.1 to 1, parts by weight, based on 100 parts by weight of component (b), and fall by definition under component (c).

In addition to the stated components (a), (b) and (c) and optionally (d) and (e) it is also possible to use crosslinking agents having two or more isocyanate-reactive groups towards the end of the synthesis reaction, for example hydrazine hydrate.

To adjust the hardness of polyurethane (PU), components (b) and (c) can be selected in relatively wide molar ratios. Molar ratios of component (b) to total chain extenders (c) of 10: 1 to 1:10, in particular from 1: 1 to 1: 4, have proven useful, the hardness of the soft polyurethanes increasing with increasing content of (c ) increases. The reaction for the preparation of polyurethane (PU) may be at a ratio of 0.8 to 1, 4: 1, preferably at a ratio of 0.9 to 1, 2: 1, more preferably at a ratio of 1, 05 to 1 , 2: 1. The index is defined by the ratio of the total isocyanate groups used in the reaction of component (a) to the isocyanate-reactive groups, i. the active hydrogens, the components (b) and optionally (c) and optionally monofunctional isocyanate-reactive components as chain terminators such as e.g. Monoalcohols.

The production of polyurethane (PU) can be carried out continuously by processes known per se, for example by one-shot or the prepolymer process, or batchwise by the prepolymer process known per se. In these processes, the reacting components (a), (b), (c) and optionally (d) and / or (e) may be mixed together successively or simultaneously with the reaction starting immediately.

Polyurethane (PU) can be dispersed in water by methods known per se, for example by dissolving polyurethane (PU) in acetone or preparing it as a solution in acetone, adding water and then removing the acetone, for example by distilling off. In one variant, polyurethane (PU) is prepared as a solution in N-methylpyrrolidone or N-ethylpyrrolidone, water is added and the N-methylpyrrolidone or N-ethylpyrrolidone is removed.

In one embodiment of the present invention, aqueous dispersions according to the invention comprise two different polyurethanes polyurethane (PU 1) and polyurethane (PU 2), of which polyurethane (PU 1) is a so-called soft polyurethane is, which is constructed as described above as polyurethane (PU), and at least one hard polyurethane (PU2).

Hard polyurethane (PU2) can in principle be prepared analogously to soft polyurethane (PU 1), but other isocyanate-reactive compounds (b) or other mixtures of isocyanate-reactive compounds (b) are also used in the context of the present invention Isocyanate-reactive compounds (b2) or abbreviated to compound (b2).

Examples of compounds (b2) are in particular 1, 4-butanediol, 1, 6-hexanediol and neopentyl glycol, either in admixture with one another or in admixture with polyethylene glycol.

In one variant of the present invention, mixtures of diisocyanates, for example mixtures of HDI and IPDI, are selected as the diisocyanate (a) and polyurethane (PU2), larger amounts of IPDI being selected for the preparation of hard polyurethane (PU2) than for production of soft polyurethane (PU1).

In one embodiment of the present invention, polyurethane (PU2) has a Shore A hardness in the range of more than 60 to a maximum of 100, the Shore hardness A according to DIN 53505 being determined after 3 seconds.

In one embodiment of the present invention, polyurethane (PU) has a mean particle diameter in the range of 100 to 300 nm, preferably 120 to 150 nm, determined by laser light scattering.

In one embodiment of the present invention, soft polyurethane (PU1) has an average particle diameter in the range of 100 to 300 nm, preferably 120 to 150 nm, determined by laser light scattering.

In one embodiment of the present invention, polyurethane (PU2) has a mean particle diameter in the range from 100 to 300 nm, preferably from 120 to 150 nm, determined by laser light scattering.

The aqueous polyurethane dispersion may further comprise at least one curing agent, which may also be referred to as a crosslinker. Suitable hardeners are compounds which can crosslink a plurality of polyurethane molecules with one another, for example during thermal activation. Crosslinking agents based on trimeric diisocyanates, in particular based on aliphatic diisocyanates such as hexamethylene diisocyanate, are particularly suitable. Very particular preference is given to crosslinkers of the formula Ia or Ib, in the context of the present invention also referred to as compound (V), O-V, N-, O, N .0

^ N N, NH HN,

I a

wherein R ³ , R ⁴ and R ^{5 may be} different or preferably the same and are selected from A ¹ -NCO and A ¹ -NH-CO-X, wherein

A ^{1 is} a spacer having 2 to 20 carbon atoms, selected from arylene, unsubstituted or substituted by one to four C 1 -C 4 -alkyl groups, alkylene and cycloalkylene, for example 1, 4-cyclohexylene. Preferred spacers A ¹ are phenylene, in particular para-phenylene, furthermore toluene, especially para-toluylene, and C ₂ -C 12 -alkylene, such as ethylene (CH ₂ CH ₂ ), furthermore - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ -, - (CH ₂ ) ₈ -, - (CH ₂ ) io-,

X is chosen 0 (AO) _x R ⁶ , where

AO is C ₂ -C 4 -alkylene oxide, for example butylene oxide, in particular ethylene oxide (CH ₂ CH ₂ O) or propylene oxide (CH (CH ₃ ) CH ₂ O) or (CH ₂ CH (CH ₃ ) O),

x is an integer in the range of 1 to 50, preferably 5 to 25, and

R ⁶ is selected from hydrogen and C 1 -C 30 -alkyl, in particular C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl , n-nonyl, n-decyl, more preferably C1-C4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl.

Particularly preferred compounds (V) are those in which R ³ , R ⁴ and R ^{5 are} each the same (CH ₂ ) ₄ -NCO, (CH ₂ ) ₆ -NCO or (CH ₂ ) i ₂ -NCO.

Aqueous polyurethane dispersions may contain other ingredients, for example

(f) a silicone compound having reactive groups, also called silicone compound (f) in the present invention. Examples of reactive groups in connection with silicone compounds (f) are, for example, carboxylic acid groups, carboxylic acid derivatives such as, for example, carboxylic acid methyl esters or carboxylic anhydrides, in particular succinic anhydride groups, and particularly preferably carboxylic acid groups.

Examples of reactive groups are further primary and secondary amino groups, for example NH (iso-C3H ₇₎ groups, NH (n-C3H ₇₎ groups, NH (cyclo-C6Hn) - groups, and NH (n-C4H9) groups, particularly NH (C2H ₅₎ groups, and NH (CH ₃₎ - groups, and most preferably NH 2 groups.

Furthermore, aminoalkylamino preferably such as -NH-CH ₂ -CH ₂ -NH ₂ groups, -NH-CH2-CH ₂ -CH 2 NH ₂ groups, -NH-CH ₂ -CH ₂ -NH (C ₂ H ₅ ) Groups, -NH-CH ₂ -CH ₂ -CH ₂ -NH (C ₂ H ₅ ) groups, -NH-CH ₂ -CH ₂ -NH (CH ₃ ) groups, -NH-CH ₂ -CH ₂ -CH ₂ -NH (CH ₃ ) groups.

The reactive group (s) are bonded to silicone compound (f) either directly or preferably via a spacer A ² . A ² is selected from arylene, unsubstituted or substituted by one to four C 1 -C 4 -alkyl groups, alkylene and cycloalkylene such as 1, 4-cyclohexylene. Preferred spacers A ² are phenylene, in particular para-phenylene, furthermore toluene, in particular para-toluylene, and C ₂ -C 18 -alkylene, such as ethylene (CH ₂ CH ₂ ), furthermore - (CH ₂ ) ₃ -, - (CH ₂ ) 4-, - _(CH2) S-, - (CH ₂ J ₆ -, - (CH ₂₎ S-, - _(CH2) io-, - _(CH2) i2-, - (CH ₂₎ i ₄ -, - (CH ₂ ) ₁₆ - and - (CH ₂ ) i ₈ -.

In addition to the reactive groups, silicone compound (f) contains non-reactive groups, in particular di-C 1 -C 10 -alkyl-SiO ₂ groups or phenyl-C 1 -C 10 -alkyl-SiO ₂ -

Groups, in particular dimethyl-SiO ₂ groups, and optionally one or more Si (CH ₃ ) ₂ -OH groups or Si (CH ₃ ) ₃ groups.

In one embodiment of the present invention, silicone compound (f) has on average one to four reactive groups per molecule.

In a specific embodiment of the present invention, silicone compound (f) has on average one to four COOH groups per molecule.

In another specific embodiment of the present invention, silicone compound (f) has on average one to four amino groups or aminoalkylamino groups per molecule.

Silicone compound (f) has catenated or branched Si-O-Si units. In one embodiment of the present invention, silicone compound (f) has a molecular weight M _n in the range of 500 to 10,000 g / mol, preferably up to 5,000 g / mol.

If silicone compound (f) has a plurality of reactive groups per molecule, these reactive groups may be bonded directly or via spacer A ² via several Si atoms or in pairs via the same Si atom to the Si-O-Si chain.

The reactive groups or the reactive group can be bonded to one or more of the terminal Si atoms of silicone compound (f) - directly or via spacer A ² . In another embodiment of the present invention, the reactive group or groups are bonded to one or more of the non-terminal Si atoms of silicone compound (f) - directly or via spacer A ² -.

In one embodiment of the present invention, aqueous polyurethane dispersion furthermore comprises a polydi-C 1 -C 4 -alkylsiloxane (g) which has neither amino groups nor COOH groups, preferably a polydimethylsiloxane, in the context of the present invention also briefly polydialkylsiloxane (g) or polydimethylsiloxane ( g) called.

In this case, C 1 -C ₄ -alkyl in polydialkylsiloxane (g) can be different or preferably identical and selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl where unbranched C 1 -C 4 -alkyl is preferred, particularly preferred is methyl.

Polydialkylsiloxane (g) and preferably polydimethylsiloxane (g) are preferably unbranched polysiloxanes with Si-O-Si chains or those polysiloxanes which have up to 3, preferably at most one branch per molecule.

Polydialkylsiloxane (D) and in particular polydimethylsiloxane (g) may have one or more Si (C 1 -C 4 -alkyl) ₂ -OH groups.

In one embodiment of the present invention, aqueous polyurethane dispersion contains in total in the range from 20 to 30% by weight of polyurethane (PU) or in total in the range from 20 to 30% by weight of polyurethanes (PU1) and (PU2), optionally in the range from 1 to 10, preferably from 2 to 5,% by weight of hardener, optionally in the range of from 1 to 10% by weight of silicone compound (f), in the range from zero to 10, preferably from 0.5 to 5,% by weight of polydialkylsiloxane ( G).

In one embodiment of the present invention, aqueous polyurethane dispersion contains in the range of 10 to 30 wt .-% soft polyurethane (PU 1) and in the range of zero to 20 wt .-% hard polyurethane (PU2).

In one embodiment of the present invention, aqueous polyurethane dispersion has a total solids content of 5 to 60% by weight, preferably 10 to 50% by weight and more preferably 25 to 45% by weight.

In this case, statements in% by weight each denote the active ingredient or solid and are based on the total aqueous polyurethane dispersion. The remainder to 100 wt .-% missing remainder is preferably continuous phase, for example water or a mixture of one or more organic solvents and water.

In one embodiment of the present invention, aqueous polyurethane dispersion contains at least one additive (h) selected from pigments, matting agents, light stabilizers, antistatic agents, antisoil, anticancer resin, thickening agents, in particular polyurethane-based thickeners, and hollow microspheres.

In one embodiment of the present invention, aqueous polyurethane dispersion contains a total of up to 20% by weight of additive (h).

Aqueous polyurethane dispersion may also contain one or more organic solvents. Suitable organic solvents are, for example, alcohols such as ethanol or isopropanol and in particular glycols, diglycols, triglycols or tetra-glycols and di- or preferably monohydric glycols, diglycols, triglycols or tetraglycols which are etherified with C 1 -C ₄ -alkyl. Examples of suitable organic solvents are ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, 1,2-dimethoxyethane, methyltriethylene glycol ("methyltriglycol") and triethylene glycol n-butyl ether ("butyltriglycol").

For the preparation of aqueous polyurethane dispersions, polyurethane (PU), hardener and silicone compound (f) can be mixed with water and optionally one or more of the abovementioned organic solvents. Furthermore, if desired, it is mixed with polydialkylsiloxane (g) and additives (h). The mixing can be carried out, for example, by stirring. The order of addition of polyurethane (PU), hardener, silicone compound (f) and water and optionally one or more of the abovementioned organic solvents and - if desired - polydialkylsiloxane (g) and additives (h) is arbitrary.

Preference is given to starting from a dispersed in water or a mixture of water and organic solvent polyurethane (PU) or dispersed soft polyurethane (PU 1) and hard polyurethane (PU2) and are, preferably with stirring, curing agent and silicone compound (f ) and, if desired, polydialkylsiloxane (g) and optionally one or more organic solvents. However, it is preferable to omit the addition of organic solvent.

In a specific embodiment, thickening agent is added last as an example of an additive (h) and thus sets the desired viscosity of the aqueous polyurethane dispersion.

After the polyurethane layer (D) has cured, it is separated from the matrix, for example by peeling, to obtain a polyurethane film (D) which forms the polyurethane layer (D) in the multilayer composite material according to the invention.

In a further operation of the manufacturing process according to the invention is preferably applied to organic adhesive on polyurethane film (D) or the combination of fabric (A) and absorbent material (B), and not on the entire surface, for example in the form of dots or stripes. In a variant of the present invention, a preferably organic adhesive is applied to the polyurethane film (D) and a preferably organic adhesive to the combination of fabric (A) and absorbent material (B), the two adhesives differing, for example by one or more adhesives several additives or in that it is chemically different preferably organic adhesives. Subsequently, polyurethane film (D) and the combination of fabric (A) and absorbent material (B) are joined so that the layer (s) of adhesive between polyurethane film (D) and the combination of fabric (A) and absorbent material (B) come to rest. The adhesive or adhesives are cured, for example thermally, by actinic radiation or by aging, and obtains a multilayer composite material according to the invention.

In one embodiment of the present invention, an intermediate layer (E) is placed between absorbent material (B) and tie layer (C), between tie layer (C) and polyurethane layer (D) or between two tie layers (C).

The intermediate layer (E) is as defined above.

Placement can be manual or mechanical, continuous or discontinuous.

A further subject of the present invention is the use of multilayer composite materials according to the invention for producing seats. Seats are for example seats for means of transport such as boats, automobiles, aircraft, railways, trams, buses and especially in child seats. Another object of the present invention is a method for producing seats under Use of multilayer composite materials according to the invention. Another object of the present invention are seats, comprising a multilayer composite material according to the invention. On surfaces of seats according to the invention, only little sweat is deposited, moisture and other liquids are absorbed.

Also in other areas in the interior of vehicles, multilayer composite material according to the invention can advantageously be used, for example in steering wheels, armrests, headliners, interior trim pieces, center consoles, parcel shelves and dashboards. Furthermore, multilayer composite material according to the invention can advantageously be used for room climate management. The room climate management is brought about by the fact that multi-layer composite materials according to the invention absorb (absorb) moisture in a moist environment and release (desorb) again in a dry environment, thus being able to ensure a uniformly humid climate. Another object of the present invention is thus the use of multilayer composite materials according to the invention for room climate management.

Another object of the present invention is the use of inventive multilayer composite materials in sports articles, such as sports bags, backpacks, rackets such as tennis or hockey sticks, sports shoes and the inside of helmets. Another object of the present invention is the use of multilayer composite materials according to the invention in electrical appliances and their packaging, for example mobile telephones and cases for mobile phones, game consoles, keyboards for computers. Another object of the present invention is the use of multilayer composite materials according to the invention for the production of furniture, such as sofas, reclining furniture such as chairs, armchairs and chairs. Another object of the present invention is the use of composite materials according to the invention as or for the production of elements for the interior of buildings, such as curtains, curtains and wall coverings.

The invention will be further explained by working examples.

I. Preparation of the starting materials

1.1 Preparation of an Aqueous Polyurethane Dispersion Disp.1

7% by weight of an aqueous dispersion (particle diameter 125 nm, solids content: 40%) of a soft polyurethane (PU1.1), prepared from hexamethylene diisocyanate (a 1.1) and isophorone diisocyanate (a1.2), were mixed with stirring in a stirred vessel. in the weight ratio 13:10 as diisocyanates and as diols a polyester diol (b1.1) having a molecular weight M _w of 800 g / mol, prepared by polycondensation of isophthalic acid, adipic acid and 1, 4-dihydroxymethylcyclohexane (mixture of isomers) in a molar ratio of 1: 1: 2, 5 wt. % 1, 4-butanediol (b1.2), and 3 wt .-% monomethylated polyethylene glycol (c.1) and 3 wt .-% H2N-CH2CH2-NH-CH2CH2-COOH, wt .-% each based on polyester diol (b1.1),

Softening point of soft polyurethane (PU1.1): 62 ° C, softening starts at 55 ° C, Shore hardness A 54,

65 wt .-% of an aqueous dispersion (particle diameter: 150 nm) of a hard polyurethane (PU2.2), obtainable by reacting isophorone diisocyanate (a1.2), 1, 4-butanediol, 1, 1-dimethylolpropionic acid, hydrazine hydrate and polypropylene glycol with a molecular weight M _w of 4200 g / mol, softening point of 195 ° C., Shore hardness A 86, 3.5% by weight of a 70% by weight solution (in propylene carbonate) of compound (V.1),

(CH ₂ ) ₆ NCO

, N O

T (V.1)

OCN- (CH ₂ ) ^ Y ^ (CH ₂ ) ₆ NCO O

6 wt .-% of a 65 wt .-% aqueous dispersion of the silicone compound according to Example 2 of EP-A 0 738 747 (f.1) 2 wt .-% carbon black,

0.5% by weight of a polyurethane-based thickener,

1 wt .-% hollow microspheres of polyvinylidene chloride, filled with isobutane, diameter

20 μm, commercially available for. B. as Expancel® the Fa. Akzo Nobel.

This gave aqueous dispersion Disp.1 having a solids content of 35% and a kinematic viscosity of 25 seconds at 23 ° C, determined according to DIN EN ISO 2431, as of May 1996.

1.2 Preparation of an Aqueous Formulation Disp.2

In a stirred vessel was mixed with stirring:

7 wt .-% of an aqueous dispersion (particle diameter: 125 nm), solids content: 40%) of a soft polyurethane (PU1.1), prepared from hexamethylene diisocyanate (a 1.1) and isophorone diisocyanate (a1.2) in a ratio by weight 13: 10 as diisocyanates and as diols a polyester diol (b1.1) having a molecular weight M _w of 800 g / mol, prepared by polycondensation of isophthalic acid, adipic acid and 1, 4-dihydroxymethylcyclohexane (mixture of isomers) in a molar ratio of 1: 1: 2 , 5% by weight of 1,4-butanediol (b1.2), 3% by weight of simply methylated polyethylene glycol (c.1) and 3% by weight of H ₂ N-CH ₂ CH ₂ -NH-CH ₂ CH ₂ -COOH,% by weight, based in each case on polyether diol (b1.1),

Softening point of 62 ° C, softening starts at 55 ° C, Shore A 54 hardness, 65 wt .-% of an aqueous dispersion (particle diameter: 150 nm) of a hard polyurethane (α2.2), obtainable by reacting isophorone diisocyanate (a1. 2), 1, 4-butanediol (PU 1.2), 1, 1-dimethylolpropionic acid, hydrazine hydrate and polypropylene glycol having a molecular weight M _w of 4200 g / mol (b1.3), polyurethane (PU2.2) had a softening point of 195 ° C, Shore hardness A 90,

3.5 wt .-% of a 70 wt .-% solution (in propylene carbonate) of compound (V.1), NCO content 12%, 2 wt .-% carbon black.

This gave a polyurethane dispersion Disp.2 having a solids content of 35% and a kinematic viscosity of 25 sec., Determined after at 23 ° C according to DIN EN ISO 2431, as of May 1996.

1.3 Production of a combination of textile fabric (A) and superabsorbent (B)

On a polyethylene terephthalate nonwoven (A.1) having a basis weight of 70 g / m ² , a monomer solution was sprayed on and cured by UV radiation for 2 minutes. It was then dried for 5 minutes at 90 ^° C. in a countercurrent dryer.

The monomer solution contained 19.6 kg of a 37.5% by weight aqueous sodium acrylate solution (corresponding to 24.5% by weight).

% Sodium acrylate in the entire monomer solution),

435 g of acrylic acid (8.5% by weight),

900 g of polyethylene glycol diacrylate (diacrylate of a polyethylene glycol with a middle

Molecular weight M _n of 400 g / mol) (3% by weight) as crosslinker, 66 g of 2-hydroxy-1- [4- (hydroxyethoxy) phenyl] -2-methyl-1-propanone (0.22% by weight). %) when

Initiator,

1500 g of glycerol [5 wt .-%) and

7500 g of a 25% by weight aqueous sodium chloride solution (6.25% by weight NaCl).

The amount of monomer solution was chosen so that the loading of the polyethylene terephthalate nonwoven (A.1) with polymerized water-absorbing polymer (B.1) was 160 g / m ² , in short also "combination of textile fabric (A.1). and superabsorbers (B.1) "called.

II. Preparation of a matrix A liquid silicone was poured onto a pad having the pattern of a full-grain calfskin. The mixture was allowed to cure by adding thereto a solution of di-n-butylbis (1-oxoneodecyloxy) stannane as a 25% by weight solution in tetraethoxysilane as an acidic hardener to obtain an average 2 mm thick silicone rubber layer which served as the template. The die was glued to a 1.5 mm thick aluminum support.

III. Application of Aqueous Polyurethane Dispersions to Matrices from II.

The template from II. Was placed on a heatable pad and heated to 91 ⁰ C. The mixture was then sprayed through a spray nozzle Disp.1, namely 88 g / m ² (wet). The application was carried out without admixing air with a spray nozzle having a diameter of 0.46 mm, at a pressure of 65 bar. It was allowed to solidify at 91 ⁰ C until the surface was no longer sticky.

The spray nozzle was mobile at a height of 20 cm from the continuous base in the direction of movement thereof and moved transversely to the direction of movement of the base. The pad had passed the spray nozzle after about 14 seconds and had a temperature of 59 ° C. After about two minutes exposure to dry, 85 ° C warm air, the net-looking polyurethane film (D.1) thus prepared was nearly anhydrous.

In an analogous assembly was immediately subsequent to the thus coated die 50 g / m ² wet from Disp.2 as a bonding layer (C.1) and was subsequently allowed to dry. The bonding layer (C.1) was not closed.

A die coated with polyurethane film (D.1) and tie layer (C.1) was obtained.

IV. Production of a Multilayer Composite Material According to the Invention

A non-woven polyurethane (E.1), 300 μm thick, 150 g / m ² basis weight, was sprayed with a spray nozzle having a nozzle diameter of 0.52 mm under a spray angle exiting the spray nozzles from 60 ° Disp.2 to. The application amount was 15 g / m ² wet. The mixture was allowed to dry for three minutes and was given a combination of bonding layer (C.2) and intermediate layer (E.1).

Subsequently, the combination of textile fabric (A.1) and super absorber (B.1) was placed on the sprayed side on that of bonding layer (C.2) and intermediate layer (E.1). Thereafter, the thus obtained composite with the intermediate layer (E.1) was applied to the still-warm bonding layer (C.1), which was on the matrix together with polyurethane film (D.1), and pressed in a press at 4 bar and 110 ⁰ C for 15 seconds. Subsequently, the composite multilayer composite material MSV.1 according to the invention thus obtained was removed from the press and the die was removed.

The multilayer composite material MSV.1 according to the invention thus obtained was distinguished by a pleasant feel, optics that were identical to the look of a leather surface, and breathability.

Claims

claims

1. Multilayer composite material comprising as components:

(A) a sheet, (B) a material which can absorb water or aqueous liquids,

(C) optionally at least one tie layer,

(D) a polyurethane layer having capillaries that run the full thickness of the polyurethane layer, (E) and at least one intermediate layer between the combination of fabric (A) and absorbent material (B) on the one hand and polyurethane layer (D) on the other hand Interlayer (E) is selected from textile, paper, nonwovens, artificial leather and open-cell foam.

2. Multilayer composite material according to claim 1, characterized in that the fabric (A) is a textile fabric.

3. Multilayer composite material according to claim 2, characterized in that it is in the fabric (A) to a fabric or a

Nonwoven fabric made of polyester.

4. Multilayer composite material according to one of claims 1 to 3, characterized in that material (B) which can absorb water or aqueous liquids is a superabsorber (B).

5. Multilayer composite material according to one of claims 1 to 4, characterized in that it is the superabsorbent (B) is an organic copolymer, which is grafted onto sheets (A).

6. Multilayer composite material according to one of claims 1 to 5, characterized in that the bonding layer (C) is a layer of a cured organic adhesive.

7. Multilayer composite material according to one of claims 1 to 6, characterized in that the polyurethane layer (D) has a pattern.

8. Multilayer composite material according to one of claims 1 to 7, characterized in that the polyurethane layer (D) has a velvet-like appearance.

9. Multilayer composite material according to one of claims 1 to 8, characterized in that it is the connecting layer to a perforated layer of a cured organic adhesive.

10. A process for producing multilayer composite materials according to any one of claims 1 to 8, characterized in that a material (B), which can absorb water or aqueous liquids, with a sheet (A) connects, using a die a polyurethane layer ( D), applying at least one organic adhesive over its entire surface or partially to fabrics (A) joined to absorptive material (B) and / or to polyurethane layer (D) and then to polyurethane layer (D) with the fabric combined with absorbent material (B) (A) connects point-like, strip-like or flat.

1 1. A method according to claim 10, characterized in that one forms polyurethane layer (D) by means of a Silikonmatrize.

12. The method according to claim 10 or 1 1, characterized in that it is the silicone die is a structured by means of laser engraving silicone matrix.

13. The method according to any one of claims 10 to 12, that for the structuring of the matrix by means of a laser cups incorporated in the die, which have an average depth in the range of 50 to 250 microns and a center distance in the range of 50 to 250 microns.

14. The method according to any one of claims 10 to 13, characterized in that an intermediate layer (E) between absorbent material (B) and bonding layer (C), between bonding layer (C) and polyurethane layer (D) or between two bonding layers ( C).

15. Use of multilayer composite materials according to one of claims 1 to 9 for the production of seats.

16. A method for producing seats using multilayer composite materials according to any one of claims 1 to 9.

A seat comprising a multilayer composite according to any one of claims 1 to 9.

18. Use of multilayer composite materials according to one of claims 1 to 9 for room climate management.

19. Use of multilayer composite materials according to one of claims 1 to 9 in the interior of vehicles.

20. Vehicles containing in the interior at least one multilayer composite material according to one of claims 1 to 9.