DE102009001121A1 - Multi-layer composite material, useful for manufacture of decorative material and automotive interior parts, comprises substrate, connecting layer and polyurethane layer having capillaries that extend over its entire thickness - Google Patents

Abstract

Multi-layer composite material comprises at least one substrate, at least one connecting layer and at least one polyurethane layer having capillaries that extend over its entire thickness. The polyurethane layer exhibits at least one pigment P. The multi-layer composite material exhibits a reflection of maximum up to 50% in the range of visible light with wavelengths of 380-720 nm and a reflection of at least 40% in the range of near infrared light with a wavelength of 720-1500 nm. An independent claim is also included for the manufacture of the multilayer composite material, comprising producing pigment containing polyurethane layer with the help of a matrix, applying at least one organic adhesive completely or partially on textile fabric and/or on polyurethane layer and connecting the polyurethane layer with the substrate in an intermittently, strip or flat manner.

Description

• (A) mindestens ein Substrat,
• (B) mindestens eine Verbindungsschicht,
• (C) mindestens eine Polyurethanschicht, die Kapillaren aufweist, die über die gesamte Dicke der Polyurethanschicht gehen,

wobei Polyurethanschicht (C) mindestens ein Pigment P aufweist,
und wobei das mehrschichtige Verbundmaterial im Bereich des sichtbaren Lichts mit Wellenlängen im Bereich von 380 bis 720 nm gemittelt eine Reflexion bis maximal 50% und im Bereich des nahen Infrarotlichts mit Wellenlängen im Bereich von 720 nm bis 1500 nm gemittelt eine Reflexion von mindestens 40% aufweist.The present invention relates to multilayer composite materials comprising

• (A) at least one substrate,
• (B) at least one tie layer,
• (C) at least one polyurethane layer having capillaries that run the full thickness of the polyurethane layer,

wherein polyurethane layer (C) has at least one pigment P,
and wherein the multilayer composite in the range of visible light having wavelengths in the range of 380 to 720 nm averaged a reflection to a maximum of 50% and in the range of near infrared light having wavelengths in the range of 720 nm to 1500 nm averaged reflection of at least 40% ,

Farther The present invention relates to a process for the preparation the composite materials according to the invention and their Use.

Multilayer composites, such as coated leather, coated textile, or coated cellulosic fiber-containing products, are becoming increasingly popular. In particular, with polyurethane coated composite body, as for example in WO 2005/047549 are described, have a wide range of applications due to the combination of many quite different properties. They combine the mechanical properties of leather with breathability, a pleasing appearance and a pleasant feel (feel).

It turns out, however, that the properties of coated substrates, which after the in WO 2005/047549 described methods are to be improved for some applications. Thus, it would be desirable if such substrates did not heat up so much in sunlight. In particular, in automotive applications, such heating effects may be detrimental, for example, on leather-clad dashboards or on steering wheels.

In EP 1 311 631 B1 planar elements are disclosed which have a dark surface and reduced solar absorption. They comprise a coating consisting of one or more pigments and a binder, wherein the coating can be applied to the substrate in one or more layers.

Applying a coating in one or more layers to a substrate results in a continuous film which can not be breathable. On the other hand, it is imperative that the coated substrates after EP 1 311 631 are coated throughout.

It So the task was to provide composite materials, on the one hand have a pleasing appearance and on the other do not heat up in the light, for example sunlight.

Accordingly were the multilayer composite materials defined above found.

• (A) mindestens ein Substrat,
• (B) mindestens eine Verbindungsschicht, und
• (C) mindestens eine Polyurethanschicht, die Kapillaren aufweist, die über die gesamte Dicke der Polyurethanschicht gehen,

wobei Polyurethanschicht (C) mindestens ein Pigment P aufweist,
und wobei das mehrschichtige Verbundmaterial im Bereich des sichtbaren Lichts mit Wellenlängen im Bereich von 380 bis 720 nm gemittelt eine Reflexion bis maximal 50% und im Bereich des nahen Infrarotlichts mit Wellenlängen im Bereich von 720 nm bis 1500 nm gemittelt eine Reflexion von mindestens 40% aufweist.Multilayer composite materials according to the invention may comprise three or more layers, for example four or five. Preferably, multilayer composites contain substantially three layers,

• (A) at least one substrate,
• (B) at least one tie layer, and
• (C) at least one polyurethane layer having capillaries that run the full thickness of the polyurethane layer,

wherein polyurethane layer (C) has at least one pigment P,
and wherein the multilayer composite in the range of visible light having wavelengths in the range of 380 to 720 nm averaged a reflection to a maximum of 50% and in the range of near infrared light having wavelengths in the range of 720 nm to 1500 nm averaged reflection of at least 40% ,

inventive multilayer composite material has in the range of light Wavelengths in the range of 380 to 720 nm averaged one Reflection up to a maximum of 50%, preferably up to a maximum of 40%.

The multilayer composite material according to the invention has in the range of near infrared light Wavelengths in the range of 720 to 1500 nm averaged a reflection of at least 40%, preferably at least 50%.

there is averaged under each understood that over the said wavelength range on average of the above determined maximum or minimum value for the reflection becomes. However, it does not have to cover the entire area of the minimum or maximum value can be achieved. For example, it can be observed be that for one or more sub-intervals in the field of visible light, a reflection of over 40% is observed when in the other subintervals of visible light the reflection is well below 40% or if in wider others Subareas, the reflection is well below 40%. For the reflection in subintervals of the near infrared light applies accordingly, that one can observe that for one or more subintervals in the range of the near infrared light a reflection of under 40% is observed when in the other subintervals of near infrared light the reflection is clearly greater than 40% or if in wider other areas the reflection is significantly larger than 40%.

In the context of the present invention, the reflection is preferably after ASTM G 159-98 determined, in a PVC matrix with a concentration of pigment P of 1 wt .-%.

When Substrate (A) are basically all substrates suitable the one with a visually and haptically appealing surface design wants to provide. Exemplary are: cellulose-containing Material, such as paper, cardboard, cardboard, wood, chipboard, Composite materials of natural fibers and plastic, Textile fabrics, leather, artificial leather, foams, preferably synthetic foams, thermoplastics, which may be formed as films or as injection-molded parts, thermosetting plastics, rigid materials, such as stone, Minerals, concrete, glass, enamel and ceramics, with glass and stones are preferred.

at Cellulosic material may be different types of act cellulosic materials. This includes in the For the purposes of the present invention, the term cellulose also includes hemicellulose and lignocellulose.

For example, cellulose-containing material may be cardboard, cardboard or paper. Paper in the sense of the present application may be uncoated or preferably coated or equipped according to methods known per se. In particular, paper may be bleached paper. Paper may contain one or more pigments, for example chalk, kaolin or TiO ₂ , and paper, paperboard or cardboard may be uncoloured (natural) or colored. Paper, cardboard and cardboard for the purposes of the present applications can be unprinted or printed.

In an embodiment of the present invention paper is kraft paper.

In An embodiment of the present invention may be in paper equipped with polyacrylate dispersion Act paper.

In another embodiment of the present invention Cellulose-containing material is wood or chipboard. For example, wood can be painted or unpainted Wood act, and wood in the sense of the present invention can be equipped biocide. Also veneer belongs to wood in the context of the present invention.

In An embodiment of the present invention may be Cellulose-containing material is a composite material (composite material) made of natural fibers and plastic that act on English also as Wood Plastic Composite or generally short as WPC is called.

there Among natural fibers, cellulose fibers are preferable or lignocellulosic fibers. examples are Fibers of flax, sisal, hemp, coconut, of abaca (so-called Manila hemp), but also rice husks, bamboo, straw and peanut shells. Preferred examples for cellulose fibers are wood fibers. It can be to trade fibers of freshly obtained wood in wood fibers of old wood. Furthermore, wood fibers can be fibers of different types Species such as softwoods of z. B. spruce, pine, fir or larches and hardwoods of z. B. Book and Oak trees act. Also wood waste such as wood shavings, Sawdust or sawdust are suitable. The wood fiber composition may in its constituents such as cellulose, Hemicellulose and lignin vary.

As plastic, especially thermoplastics for the production of composite material from natural Fibers and plastic chosen, which may be new or recycled from old thermoplastic polymers. Preference is given to plastic for composite material made of natural fibers and plastic polyolefins, preferably polyethylene, especially HDPE, polypropylene, in particular isotactic polypropylene, and polyvinyl chloride (PVC), in particular rigid PVC, polyvinyl acetate or mixtures of polyethylene and polypropylene selected.

composite For example, from natural fibers and plastic be processed by extrusion.

The Layer thickness of substrate of cellulosic material can in it varies depending on the species of the cellulose-containing material. Paper layers can for example, in the range of 50 to 150 microns thick, especially in the range of 80 to 120 microns. Cardboard and cardboard can span several layers of paper and have a thickness in the range from 0.1 mm to 5 cm, preferably 1 mm to 1 cm. Wood, chipboard and composite material of natural fibers and plastic can be in the range of 0.5 mm to 10 cm thick, with in the case of veneer, only the actual wood layer is considered shall be.

When Textile fabrics, in the context of the present invention also called textiles for short, are for example fabric, felt, knitwear (Knitwear), knitted fabrics, nonwovens, wadding, scrims and microfiber fabrics suitable.

Preferably Textiles are woven, knitted or crocheted Nonwovens (nonwovens).

textiles can be made of linen, strings, Ropes, yarns or threads. Textiles can be natural Origin, such as 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, further polyester microfibers and glass fiber fabric. Very particularly preferred are polyester, cotton and Polyolefins such as polyethylene and polypropylene as well selected blended fabrics selected from cotton-polyester blended fabrics, Polyolefin-polyester blend and polyolefin-cotton blend.

textiles may be untreated or treated, for example bleached or dyed. Preferably, textiles are on coated on one side only, or they are not coated.

textiles can be equipped, in particular they are easy-care and / or flameproof.

Textiles may have a basis weight in the range of 10 to 500 g / m ² , preferably 50 to 300 g / cm ² .

In An embodiment of the present invention will be substrate (A) chosen from leather or artificial leather, for example leather, Split leather, artificial leather and leather fibers (Lefa, English "bonded leather ").

Of the The term leather includes tanned in the context of the present invention Animal skins which are dressed or preferably untreated could be. Tanning can be done by a variety of methods done, for example, with chrome tanning agents, other mineral Tannins such as aluminum compounds or zirconium compounds, with polymer tanning agents, for example homopolymers or copolymers of (meth) acrylic acid, with aldehydes, especially with glutaraldehyde, with synthetic Tannins such as condensation products of aromatic Sulfonic acids with aldehydes, in particular with formaldehyde, or with other carbonyl group-containing compounds such as Condensation products of aromatic sulfonic acids with Urea. Other suitable leathers are those containing vegetable tannins and / or enzymatically tanned. Even leather that with a mixture are tanned from two or more of the aforementioned tanning agents, are suitable.

leather For the purposes of the present invention may further one or more have passed through the known work steps, for example Hydrophobing, fats, retanning and dyeing.

leather For example, it can be made from skins of cattle, pigs, Goats, sheep, fish, snakes, wild animals or birds be prepared.

leather may have a thickness in the range of 0.2 to 2 mm. Preferably it is grain leather. Leather can be free from rawhide flaws be, but also such leather, the Rohhautfehler has, for example barbed wire injuries, fighting between animals or insect bites is suitable.

In an embodiment of the present invention Leather is split or split leather.

In an embodiment of the present invention it is leather suede or split suede.

In one embodiment of the present invention, substrate (A) is artificial leather. For the purposes of the present invention, synthetic leathers also include precursors for synthetic leather, specifically those in which the uppermost layer, that is to say one or the outer layer, is missing. In the context of the present invention, artificial leather is plastic-coated, preferably textile fabrics with or without a cover layer, the cover layer, if present, having a leather-like appearance. Examples of artificial leather are fabric synthetic leather, fleece artificial leather, fiber artificial leather, foil artificial leather and foamed artificial leather. Also products with two outer layers such as non-woven artificial leather fall under the term artificial leather. Particularly preferred artificial leather are breathable synthetic leather based on polyurethane, as z. B. are described in Harro Träubel, New Materials Permeable to Water Vapor, Springer Verlag 1999 , Further preferred are support materials in which an open-cell polyurethane foam is applied to a textile support, for. B. as a foam or by direct Hinterschäumung.

at Foam can be different types of foams act. Preferably, they are synthetic foams.

Foam is after DIN 7726 defined as a material with cells distributed throughout the mass and a bulk density lower than the density of the framework.

Foamed material may be closed-cell, but in the context of the present invention is preferably largely open-celled. In one embodiment of the present invention, 50% of all lamellae are open, preferably 60 to 100%, and more preferably 65 to 99.9%, determined according to DIN ISO 4590 , An open lamella (cell) is defined as a cell that communicates with other cells via the gas phase.

The density of foam is preferably between 5 to 1000 kg / m ³ , preferably 6 to 300 kg / m ³ and particularly preferably in the range of 7 to 250 kg / m ³ .

In an embodiment of the present invention Foam an elongation at break greater than 100%.

In One embodiment of the present invention may include foam a mean pore diameter (number average) in the range of 1 micron to 1 mm, preferably 50 to 500 microns, determined by evaluation microscopic images of sections.

In a specific embodiment of the present invention, foam has a sound absorption level greater than 0.5 as measured DIN 52212 at a frequency of 2000 Hz and a layer thickness of the foam in question of 40 mm.

foam may be of natural or synthetic origin. For example foam made of natural sponges can be chosen as used for example as a cleaning article.

Examples for synthetic foams are polystyrene foams, also known as expanded polystyrene, polyurethane foams, Butadiene-styrene block copolymer foams, polyester foams and aminoplast foams.

Examples for aminoplast foams are foams based of urea-formaldehyde resins, foams based on phenol-formaldehyde resins and in particular aminoplast-formaldehyde resins, in particular melamine-formaldehyde resins, the latter in the context of the present invention also as melamine foams be designated.

at Polyurethane foams can be rigid polyurethane foams, Flexible polyurethane foams, so-called semi-rigid foams and viscoelastic polyurethane foams.

The production of the above-mentioned foams and in particular melamine foams is known per se, the latter and polyurethane foams are for example in WO 2005/103107 described in detail.

In an embodiment of the present invention the foam layer has a thickness in the range of 100 microns to 10 cm, preferred is a thickness of 1 mm to 1 cm.

Examples for rigid materials are stone, minerals, concrete, glass, Enamel and ceramics, with glass and stones being preferred.

Another Examples of rigid materials are thermosets and thermoplastics, for example, polycarbonates, polystyrene as homopolymers or copolymers, Polyamides, polyesters, polyolefins such as polyethylene or polypropylene, Polyether, each alone or in combination, in particular as a laminate.

Further Examples of rigid materials are metals that are not are processed into films, for example steel, soft iron, cast iron, wherein the metal in question may be painted or unpainted.

The Thickness of the layer of rigid material can vary within wide limits. For example, stone, minerals, concrete, glass, enamel and ceramics a layer thickness of 1 mm to 10 cm. The aforesaid metallic For example, rigid materials can range from 0.5 mm to 10 cm thick, preferably 1 mm to 1 cm. above mentioned thermosets and thermo paste as rigid materials can for example, 1 mm to 5 cm thick.

Also metals processed into foils, also called metal foils for short, or plastics, in particular thermoplastics, in short also plastic films called, are suitable as substrate (A).

Under Plastic or metal foils are understood in the context of the present Invention sheet metal or natural or preferably synthetic polymer having a thickness of 0.5 μm to 1 mm, preferably 1 μm to 0.5 mm, and more preferably may have up to 0.15 mm. Plastic and metal foils are in the context of the present invention also under the term Films subsumed.

Preferably Film is manually bendable, that is without assistance a tool.

Under Metals for films are silver, tin and in particular Aluminum preferred.

Under Plastics for films are polyolefins such as polyolefins such as polyethylene and polypropylene, furthermore polyester, polyamide, Polycarbonate, polyvinylchloride, polymethylmethacrylate and polystyrene preferably, wherein among polyolefins such as polyethylene and polypropylene not only the respective ethylene and propylene homopolymers, but also copolymers with other olefins such as acrylic acid or 1-olefins are to be understood. So are among polyethylene in particular Ethylene copolymers having 0.1 to less than 50 wt .-% of one or more 1-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-dodecene, wherein propylene, 1-butene and 1-hexene are preferred. Under polypropylene are in particular also propylene copolymers with from 0.1 to less than 50% by weight of ethylene and / or one or more 1-olefins such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-dodecene to understand, with ethylene, 1-butene and 1-hexene are preferred. Polypropylene is preferably substantially isotactic polypropylene to understand.

films made of polyethylene can be made of HDPE or LDPE or LLDPE become. Among polyamide films, those are preferred derive from nylon 6. Polyester films include polybutylene terephthalate and in particular of polyethylene terephthalate (PET). Under Polycarbonate films are preferably those derived from polycarbonates derived using bisphenol A. Among films of polyvinyl chloride are those made of hard polyvinyl chloride or soft polyvinyl chloride, where soft polyvinyl chloride also copolymers of vinyl chloride with vinyl acetate and / or acrylates includes.

Plastic films For the purposes of the present invention, composite films may also be used include, for example, films which are one of the above Include films and a metal foil or paper.

Prefers substrate (A) is selected from leather, artificial leather, thermoplastic Plastics, paper and textile.

inventive Multilayer composite material furthermore has at least one Connecting layer (B). In one embodiment of the present invention comprises according to the invention multilayer composite material at least two interconnecting layers (B), which differ, for example, by various additives can. Examples of such additives may be Pigments P, for example, organic pigments P1 and / or inorganic Be pigments P2, still hollow microspheres. Pigments P1 and P2 and hollow microspheres are further described below.

at Connecting layer (B) may be a perforated, that is not full-surface, pronounced layer, preferably a cured organic adhesive.

In an embodiment of the present invention Connecting layer (B) on a non-full-surface pattern. In another embodiment of the present invention Bonding layer (B) is a full-surface film.

In an embodiment of the present invention connecting layer (B) is a punctiform, strip-shaped or latticed, for example in the form of diamonds, rectangles, squares or a honeycomb structure brought up layer. Then comes polyurethane layer (C) with substrate (A) in contact at the gaps of the bonding layer (B).

In an embodiment of the present invention Bonding layer (B) is a layer of cured one organic adhesive, for example based on polyvinyl acetate, Polyacrylate or in particular polyurethane, preferably of polyurethanes with a glass transition temperature below 0 ° C.

there For example, curing of the organic adhesive may thermally, by actinic radiation or by aging be.

In a preferred embodiment, the organic Adhesive in the range of 0.1 to 10% of a water-dispersible Polyisocyanates added in addition to the organic adhesive can network. Water-dispersible polyisocyanates are z. B. isocyanurates, Biurets, allophanates or urethanes, preferably of aliphatic polyisocyanates such as As hexamethylene diisocyanates or isophorone diisocyanate derived and contain at least one hydrophilic group per molecule, the z. B. may be ionic or nonionic, z. B. sulfonate groups or carboxylate groups as examples of ionic groups or polyethylene glycol groups as examples of nonionic hydrophilic groups.

In another embodiment of the present invention Bonding layer (B) is an adhesive net.

In an embodiment of the present invention Bonding layer (B) has a maximum thickness of 100 μm, preferably 50 .mu.m, particularly preferably 30 .mu.m, completely more preferably 15 μm.

In an embodiment of the present invention the minimum thickness of the bonding layer (B) is 5 μm, preferably 15 μm, especially 25 μm.

In An embodiment of the present invention may be tie layer (B) contain hollow microspheres. Under hollow microspheres are in the frame of the present invention spherical particles having a middle Diameter in the range of 5 to 20 microns of polymeric material, especially halogenated polymer such as polyvinyl chloride or polyvinylidene chloride or copolymer of vinyl chloride with vinylidene chloride, to understand. Hollow microspheres may 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.

inventive Multilayer composite material also contains a Polyurethane layer (C) having capillaries which over go the entire thickness of the poly urethane layer, in short as a polyurethane layer (C). In this case, polyurethane layer (C) at least one Pigment P on.

In an embodiment of the present invention Polyurethane layer (C) has an average thickness in the range of 15 to 300 μm, preferably from 20 to 150 μm, especially preferably from 25 to 80 microns.

In a preferred embodiment of the present invention has polyurethane layer (C) on capillaries, over the total thickness (cross section) of the polyurethane layer (C) go.

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

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

In an embodiment of the present invention are the Capillaries evenly over polyurethane layer (C) distributed. In a preferred embodiment of However, the present invention, the capillaries are uneven about the polyurethane layer (C) distributed.

In an embodiment of the present invention are the Capillaries are essentially bent. In another embodiment In the present invention, the capillaries have a substantially straight course on.

The capillaries impart air and water vapor permeability to the polyurethane layer (C) without the need for perforation. In one embodiment of the present invention, the water vapor permeability of the polyurethane layer (C) may be above 1.5 mg / cm ² .h, measured after DIN 53333 , Thus, it is possible that moisture such as perspiration may migrate through the polyurethane layer (C).

In one embodiment, the multilayer composite material according to the invention has a water vapor permeability after DIN 53333 of over 1.5 mg / cm ² h.

In an embodiment of the present invention Polyurethane layer (C) in addition to the capillaries yet Pores that do not exceed the entire thickness of the polyurethane layer (C) go.

In In one embodiment, polyurethane layer (C) has a Muster on. The pattern can be arbitrary and, for example reproduce the pattern of a leather or a wooden surface. In one embodiment of the present invention can the pattern is a nubuck leather.

In an embodiment of the present invention Polyurethane layer (C) has a velvety appearance.

In an embodiment of the present invention, the Pattern of a velvet surface correspond, for example with hairs with a mean length of 20 to 500 μm, preferably 30 to 200 μm and especially preferably 60 to 100 microns. The hairs can for example, have a circular diameter. In a particular embodiment of the present invention the hairs have a conical shape.

In an embodiment of the present invention Polyurethane layer (C) hairs on, which in a middle Distance from 50 to 350, preferably 100 to 250 microns to each other are arranged.

For the case where the polyurethane layer (C) has hairs, the data on the average thickness refer to the Polyurethane layer (C) without the hairs.

polyurethane layer (C) is preferably at least one with substrate (A) Connecting layer (B) connected.

In an embodiment of the present invention Polyurethane layer (C) hollow microspheres.

In one embodiment of the present invention, polyurethane layer (C) may contain one or more additives, for example one or more fillers, for example talc, SiO ₂ , mica or ZnO, or one or more gripping agents, e.g. B. silicone-based.

polyurethane layer has at least one pigment P. Pigment P is closer in the following described.

pigment P can be chosen from organic pigments P1 and inorganic Pigments P2.

In the context of the present invention, pigments P are virtually insoluble finely divided organic colorants as defined in US Pat DIN 55944 to understand.

Exemplary selected pigments P1
Monoazo pigments: CI Pigment Brown 25; CI Pigment Orange 5, 13, 36 and 67; CI Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 52: 1 , 52: 2, 53, 53: 1, 53: 3, 57: 1, 63, 112, 146, 170, 184, 210, 245 and 251;
Disazo pigments, especially CI Pigment Orange 16, 34 and 44; CI Pigment Red 144, 166, 214 and 242; CI Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188;
Anthranthrone pigments, in particular CI Pigment Red 168;
Anthrachinonpigmente, in particular CI Pigment Yellow 147 and 177; CI Pigment Violet 31;
Anthrapyrimidine pigments, in particular CI Pigment Yellow 108;
Quinacridone pigments, in particular CI Pigment Red 122, 202 and 206; CI Pigment Violet 19;
Quinophthalone pigments, in particular CI Pigment Yellow 138;
Dioxazine pigments, especially CI Pigment Violet 23 and 37;
Indanthrone pigments, in particular CI Pigment Blue 60 and 64;
Isoindoline pigments, in particular CI Pigment Orange 69; CI Pigment Red 260; CI Pigment Yellow 139 and 185;
Isoindolinone pigments, in particular CI Pigment Orange 61; CI Pigment Red 257 and 260; CI Pigment Yellow 109, 110, 173 and 185;
β-naphthol pigments, naphthol AS pigments, laked pigments, isoviolanthrone pigments, in particular CI Pigment Violet 31;
Metal complex pigments, in particular CI Pigment Yellow 117, 150 and 153; CI Pigment Green 8;
Perinone pigments, in particular CI Pigment Orange 43; CI Pigment Red 194;
Perylene pigments, in particular CI Pigment Black 31 and 32; CI Pigment Red 123, 149, 178, 179, and 224; CI Pigment Violet 29;
Phthalocyanine pigments, especially CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; CI Pigment Green 7 and 36;
Pyranthrone pigments, in particular CI Pigment Orange 51; CI Pigment Red 216;
Thioindigo pigments, especially CI Pigment Red 88 and 181; CI Pigment Violet 38;
Triaryl carbonium pigments, in particular CI Pigment Blue 1, 61 and 62; CI Pigment Green 1; CI Pigment Red 81, 81: 1 and 169; CI Pigment Violet 1, 2, 3 and 27; CI Pigment Black 1 (aniline black);
CI Pigment Brown 22.

Preferably Pigment P is selected from dark pigments, in particular from black pigments.

In an embodiment of the present invention Polyurethane layer (C) at least one pigment P, and pigment P has in the range of light with wavelengths in the range of 380 a reflection up to 720 nm averaged to a maximum of 50%, preferably to maximum 40%.

In one embodiment, pigment P averaged in the wavelength range of 720 nm to 1500 nm has a reflection of at least 40%, measured z. B. after ASTM G 159-98 ). For embodiments in which it is desired to use mixtures of at least two pigments P, the pigment mixture in question averaged in the wavelength range of 720 nm to 1500 nm, a reflection of at least 40%, measured, for. B. after ASTM G 159-98 ).

In a particularly preferred embodiment of the present invention Invention pigment P is selected from perylene pigments and Dioxazine.

In another embodiment has polyurethane layer (C), optionally in combination with compound layer (B), in Wavelength range from 720 nm to 1500 nm, a permeability (Transparency) of at least 45%, preferably at least 40%. The transparency can be measured by the same methods as the Reflection, for example, spectroscopically. In such embodiments has substrate (A) a relatively high reflection, so that for the entire invention multilayer composite material a reflection of at least 45%, preferably at least 50%, in the wavelength range of 720 nm is given to 1500 nm.

In one embodiment of the present invention, substrate (A) is selected from white pigment filled materials such as polymers, fibers, fabrics or foams, with TiO _{2 being} a particularly well-suited white pigment. Further suitable substrates are sheets of aluminum, in particular sheets provided with TiO ₂ -containing coatings made of aluminum.

In an embodiment of the present invention chooses one pigment P from inorganic pigments P2, in the following also briefly called pigment P2. Preference is given to inorganic black pigments.

When For example, inorganic pigments are insoluble in water (i.e., at 20 ° C, a maximum of 100 mg / l dissolve, preferably maximum 10 mg / l) oxides, hydroxides, carbonates, sulfides or sulfates of divalent, trivalent or tetravalent metals, and mixed oxides and to call silicates. Mixed forms are also suitable, for example basic oxides and basic carbonates. Suitable metals can For example: nickel, cobalt, aluminum, zinc, copper, chromium, Antimony and especially iron. Spinels may also be suitable be. Inorganic pigments P2 can be corresponding oxides, Hydroxides, carbonates, sulfides or sulfates in pure form, d. H. when Pure substance, its or even contaminated in natural form or artificially endowed. For example, doping is suitable Zinc, chromium, manganese, titanium, cerium, germanium and lanthanum.

Particularly preferred inorganic pigments P2 are hematites, which may be synthetic or natural. Hematite is understood in the case of the present invention α-Fe ₂ O ₃ , which may contain up to 10 wt .-% Al ₂ O ₃ .

In one embodiment of the present invention, hematite is α-Fe ₂ O ₃ containing up to 1% by weight of germanium.

In one embodiment of the present invention, hematite is α-Fe ₂ O ₃ , which may contain up to 20% by weight of iron oxide in one or more other modifications, for example as γ-Fe ₂ O ₃ .

In one embodiment of the present invention, hematite is α-Fe ₂ O ₃ containing traces of titanium.

Further preferred inorganic pigments P2 are selected from TiO ₂ (white pigment), (Nb, Sb) TiO ₂ (yellow pigment), (Cr, Sb) TiO ₂ (beige pigment), (Mn, Sb) TiO ₂ (brown pigment), (Sn , Zn) TiO ₂ (orange pigment), furthermore CI Pigment Brown 29 and CrFeO (chrome-iron brown).

In an embodiment of the present invention Polyurethane layer (C) in the range of 0.1 to 10 wt .-%, preferably in the range of 0.2 to 5% by weight of pigment P.

In an embodiment of the present invention Polyurethane layer (C) several different pigments P, for example two or three. In another embodiment of the present invention Invention contains polyurethane layer (C) exactly one pigment P.

In an embodiment of the present invention in addition to polyurethane layer (C) and compound layer (B) at least a pigment P.

In an embodiment of the present invention Bonding layer (B) and polyurethane layer (C) on average 0.1 to 10% by weight of pigment P, preferably 0.2 to 5% by weight.

In An embodiment of the present invention is pigment P in bonding layer (B) and pigment P in polyurethane layer (C) each different. In a preferred embodiment of the present invention are Pigment P in tie layer (B) and polyurethane layer (C) are the same.

In an embodiment of the present invention Connecting layer (B) and polyurethane layer (C) each have an inorganic Pigment P2, which may be different or preferably the same.

In another embodiment of the present invention contains neither bonding layer (B) nor polyurethane layer (C) an inorganic pigment P2.

In one embodiment of the present invention, polyurethane layer (C) contains in the range of 0.1 to 10 wt .-% of pigment P2, preferably 0.2 to 5 wt .-%.

In an embodiment of the present invention Polyurethane layer (C) several different pigments P2, for example two or three. In another embodiment of the present invention Polyurethane layer (C) contains exactly one pigment P2.

In an embodiment of the present invention in addition to polyurethane layer (C) and compound layer (B) at least a pigment P2. In another embodiment of the present invention Invention contains compound layer (B) at least one Pigment P2, but no pigment P1.

The Morphology of pigment P is free to choose. So can Pigment P for example in the form of needles, cube-shaped Particles, leaflets or cuboids are present.

One Another object of the present invention is a method for the production of multilayered according to the invention Composite materials, in the context of the present invention also short called manufacturing process according to the invention. In one embodiment of the invention Manufacturing process one proceeds in such a way that one with the help of a Forming a polyurethane layer (C), at least one organic Adhesive all over or partially on substrate (A) and / or on polyurethane layer (C) and then polyurethane layer (C) with substrate (A) punctiform, strip-like or flat combines.

In an embodiment of the present invention one according to the invention multilayer composite material by a coating process ago by first a polyurethane film (C ') provides at least one substrate (A) or the polyurethane film (C) or both on one surface each partially, for example patterned, with organic Adhesive provides, for example, sprayed or brushed and then bring the two surfaces into contact. Then you can still press the system so available together or thermally treat or press together with heating.

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

you brings an aqueous polyurethane dispersion on a die The preheated water allows the water to evaporate and then transferred to the thus forming polyurethane film (C ') on substrate (A).

The Applying aqueous polyurethane dispersion on the Template can be made by methods known per se, in particular by spraying, for example with a spray gun.

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

• 1) Aufbringen eines flüssigen Bindemittels, das gegebenenfalls Zusatz- und/oder Hilfsstoffe enthält, auf eine gemusterte Oberfläche, beispielsweise eine andere Matrize oder ein Originalmuster,
• 2) Aushärten des Bindemittels, beispielsweise durch thermisches Aushärten, Strahlungshärtung oder durch Alternlassen,
• 3) Trennen der so erhältlichen Matrize und gegebenenfalls Aufbringen auf einen Träger, beispielsweise eine Metallplatte oder einen Metallzylinder.

In one embodiment of the present invention, a die is provided which comprises 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 auxiliaries, to a patterned surface, for example another matrix or an original sample,
• 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 carrier, for example a metal plate or a metal cylinder.

In An embodiment of the present invention is used so before you give up a liquid silicone on a pattern, the silicone age and thus harden and then deduct. The silicone film is then placed on an aluminum carrier glued.

In a preferred embodiment of the present invention one prepares a die, which is a laser-engravable layer or a layer composite comprising a laser-engravable Layer on a support, wherein the laser-engravable layer a binder and optionally further additives and auxiliaries includes. The laser engravable layer is also preferable elastomeric.

• 1) Bereitstellen einer lasergravierbaren Schicht oder eines Schichtverbunds, umfassend eine lasergravierbare Schicht auf einem Träger, wobei die lasergravierbare Schicht ein Bindemittel sowie vorzugsweise Zusatz- und Hilfsstoffe umfasst,
• 2) thermochemische, photochemische oder aktinische Verstärkung der lasergravierbaren Schicht,
• 3) Eingravieren einer der Oberflächenstruktur der oberflächenstrukturierten Beschichtung entsprechenden Oberflächenstruktur in die lasergravierbare Schicht mit einem Laser.

In a preferred embodiment, the provision of a die 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 carrier, preferably, they are present on a carrier. Examples suitable supports include fabrics and films polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Polybutylene terephthalate (PBT), polyethylene, polypropylene, polyamide or polycarbonate, preferably PET or PEN films. Also as Carriers are papers and knitted fabrics, for example made of cellulose. As carrier can also conical or cylindrical tubes of the said materials, so-called Sleeves, are used. Sleeves are also suitable Glass fiber fabrics or composites of glass fibers and polymers Materials. Further suitable carrier materials are metallic carriers such as solid or tissue-shaped, planar or cylindrical supports of aluminum, steel, magnetizable Spring steel or other iron alloys.

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

The The laser-engravable layer comprises at least one binder may be a prepolymer, which in the course of a thermochemical Reinforcement to a polymer reacts. Suitable binders You can choose depending on the desired properties of the laser engravable Layer or die, for example with regard to hardness, Elasticity or flexibility. Suitable binders can be subdivided essentially into 3 groups, without the binders should be limited thereto.

The The first group includes those binders that are over ethylenic have unsaturated groups. The ethylenic unsaturated groups are photochemical, thermochemical, by means of electron beams or with any combination These processes can be networked. In addition, a mechanical Reinforcement be done by means of Füllstof fen. Such binders are, for example, those which are 1,3-diene monomers as isoprene or 1,3-butadiene in copolymerized form. The ethylenic unsaturated group can be used as a chain building block of the polymer (1,4-incorporation), or it may be a side-group (1,2-incorporation) to be bound to the polymer chain. As examples are 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 called with ethylenically unsaturated groups.

Other examples include thermoplastic elastomeric block copolymers of alkenylaromatics and 1,3-dienes. The block copolymers may be either linear block copolymers or radial block copolymers. Typically, they are ABA-type triblock copolymers, but they may also be AB-type diblock polymers or those having multiple alternating elastomeric and thermoplastic blocks, e.g. B. 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 ^®.

Further Examples of binders with ethylenically unsaturated Groups include modified binders in which crosslinkable Groups by grafting reactions in the polymeric molecule be introduced.

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 , -OC ( O) NHR ¹ , -SO ₃ H or -CO-. Examples of binders include Si likonelastomere, 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 polyester. Here, 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 An embodiment of the present invention can be Use binders that contain both ethylenically unsaturated Groups as well as functional groups. Examples include functional silicone addition-curing silicone elastomers 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 from butadiene and 4-hydroxystyrene.

The The third group of binders includes those that do not have any ethylenically unsaturated groups still functional Groups. To name here are, for example, polyolefins or ethylene / propylene elastomers or by hydrogenation of diene units obtained products such as SEBS rubbers.

Polymer layers, the binders without ethylenically unsaturated or functional Groups usually have to be mechanical, with Using high-energy radiation or a combination thereof, to an optimal sharp-edged structuring by laser too enable.

you can also use mixtures of two or more binders, wherein these are both binders from only one of the described Groups can act or to mixtures of binders from two or all three groups. The combination options are limited only insofar as the suitability of the polymer layer for the laser structuring process and the molding process should not be negatively affected. Advantageously, for example a mixture of at least one elastomeric binder which has no functional groups, with at least one other Binder, which functional groups or ethylenically unsaturated Groups has to be used.

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

In one embodiment of the present invention, polyurethane film (C ') is formed by means of a silicone die. 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.

optional For example, the elastomeric layer or laser-engravable layer can be reactive low molecular weight or oligomeric compounds. oligomers Compounds generally do not have a molecular weight more than 20,000 g / mol. Reactive low molecular weight and oligomeric Compounds are referred to below as monomers for the sake of simplicity be designated.

monomers On the one hand can be added to the speed photochemical or thermochemical crosslinking or crosslinking by means of high-energy radiation, if desired becomes. When using binders from the first and second Group is the addition of monomers for acceleration in general not mandatory. For binders from the third group the addition of monomers is generally recommended, without that this is absolutely 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. Preferably, the boiling point of suitable monomers is at least 150 ° C. Particularly suitable are amides of acrylic acid or methacrylic acid with mono- or polyfunctional alcohols, amines, amino alcohols or hydroxy ethers and esters, styrene or substituted styrenes, esters of Fu maric 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, tripropylene glycol diacrylate, dioctyl fumarate, N-dodecylmaleimide and triallyl isocyanurate.

Especially suitable for 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 for example, 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 It is also possible to use monomers which are both ethylenic have unsaturated groups such as 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 It is also possible to use mixtures of different monomers provided the properties of the elastomeric layer are not adversely affected by the mixture. As a rule is the amount of added monomers 0 to 40 wt .-% with respect to the amount of all constituents of the elastomeric Layer or the relevant laser-engravable layer, preferably 1 to 20 wt .-%.

In In one embodiment, one or more monomers use with one or more catalysts. So it is possible Silicone matrices by adding one or more acids or by organotin compounds, the step 2) of providing to accelerate the die. Suitable organotin compounds can di-n-butyltin dilaureate, 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 can continue Additives and auxiliaries such as IR absorbers, dyes, Dispersing aids, antistatic agents, plasticizers or abrasive particles include. The amount of such additives and auxiliaries should as a rule 30 wt .-% with respect to the amount of all components of the elastomeric Do not exceed the layer or the relevant laser-engravable layer.

The elastomeric layer or the laser-engravable layer may consist of several Single layers are built. These single layers can of equal, approximately equal or different material composition be. The thickness of the laser-engravable layer or all individual layers together, as a rule, between 0.1 and 10 mm, preferably 0.5 to 3 mm. The thickness can be dependent on application technology and mechanical process parameters the laser engraving process and the molding process.

The elastomeric layer or the laser-engravable layer may optionally furthermore, a top layer having a thickness of not more than 300 μm exhibit. The composition of such a top layer can be seen in Regard to optimal engraving and mechanical stability select while the composition of the underneath lying layer with regard to optimum hardness or elasticity is selected.

In an embodiment of the present invention is the Upper layer itself laser engravable or in the course of laser engraving removable together with the underlying layer. The upper class comprises at least one binder. You can still use an absorber for laser radiation or even monomers or auxiliaries include.

In an embodiment of the present invention the silicone die is one with the help of laser engraving textured silicone matrix.

Of very particular advantage thermoplastic elastomeric binders or silicone elastomers are used for the process according to the invention. When thermoplastic elastomeric binders are used, the production preferably takes place by extrusion between a carrier film and a cover film or cover element followed by calendering, as for example for flexographic printing elements in US Pat EP-A 0 084 851 disclosed. In this way, even thicker layers can be produced in a single operation. Multilayer elements can be produced by coextrusion.

wishes To structure the matrix by means of laser engraving is so it prefers to laser-engrave the layer before laser engraving Heating (thermochemical), by irradiation with UV light (photochemically) or by irradiation with high-energy radiation (actinic) or any combination thereof.

Subsequently is the laser-engravable layer or the composite layer on a cylindrical (temporary) carrier, 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 applied and engraved as described above. Alternatively, the plane layer or the layer composite as well engraved above. Optional will be during laser engraving the laser engravable layer with a round washer or a continuous washer with a cleaning agent for removal Washed by gravure residues.

On The described manner may be the die as a negative die or be prepared as a positive die.

In In a first variant, the die has a negative structure, so that the textile (A) connectable coating directly through Applying a liquid plastic material to the surface the template and then solidification of the polyurethane can be obtained.

In In a second variant, the matrix has a positive structure, so that first a negative die by impression of the laser-structured positive template is produced. Of this Negative die can be used with a flat backing connectable coating then by applying a liquid plastic material on the surface the negative matrix and subsequent consolidation of the Plastic material can be obtained.

Preferably be in the matrix structural elements with dimensions in the range engraved from 10 to 500 microns. The structural elements can be formed as surveys 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 be a regular or make an irregular grid. examples are a classical dot screen or a stochastic screen, for example a frequency modulated grid.

In an embodiment of the present invention operates to structure the matrix with the help of a laser cell into the die, which has a mean depth in the range of 50 to 250 microns and a center distance in the range of 50 to 250 μm.

For example can you engrave the matrix so that it "cups" (depressions) having a diameter in the range of 10 to 500 microns have on the surface of the die. Preferably the diameter at the surface of the die 20 to 250 microns and more preferably 30 to 150 μm. The distance of Cup may, for example, 10 to 500 microns, preferably 20 to 200 .mu.m, particularly preferably up to 80 microns.

In an embodiment of the present invention the template is preferably adjacent to a surface coarse structure still a surface fine structure. Both coarse as well also fine structure can be generated by laser engraving. The fine structure may, for example, a micro-roughness with a Roughness amplitude in the range of 1 to 30 microns and a Roughness frequency of 0.5 to 30 microns. Preferably lie the dimensions of the microroughness in the range of 1 to 20 μm, more preferably 2 to 15 microns and more preferably 3 to 10 μm.

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 (532 nm) or frequency-tripled (355 nm) Nd-YAG laser can be used, or else an excimer laser (eg 248 nm). 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-YAG 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.

in the As a rule, the template obtained after production directly be used. If desired, the obtained Die still to be cleaned. By such a cleaning step will be detached, but may not be complete removed from the surface removed layer components. in the The rule is simple treatment with water, water / surfactant, alcohols or inert organic detergents, preferably are low in swelling.

In another step brings an aqueous formulation of polyurethane on the die. The application may preferably done by spraying. The matrix should be heated when applying the formulation of polyurethane, for example to temperatures of at least 80 ° C, preferably at least 90 ° C. The water from the aqueous formulation Polyurethane vaporizes and forms capillaries in itself solidifying polyurethane layer.

Under becomes watery in connection with the polyurethane dispersion understood that it contains water, but less than 5 Wt .-%, based on the dispersion, preferably less than 1 wt .-% organic solvent. Particularly preferred no volatile organic solvent prove. Under volatile organic solvents are used in the present invention, such organic solvents understood that at normal pressure a boiling point of up to 200 ° C. exhibit.

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

The aqueous polyurethane dispersion further contains at least one pigment P1 and optionally also at least one Pigment P2.

Polyurethane (PU) are well known, commercially available and generally comprise a soft phase of higher molecular weight Polyhydroxyl compounds, for. As polycarbonate, polyester or Polyether segments, and a urethane hard phase, formed from low molecular weight Chain extenders and di- or polyisocyanates.

• (a) Isocyanaten, bevorzugt Diisocyanaten mit
• (b) gegenüber Isocyanaten reaktiven Verbindungen, üblicherweise mit einem Molekulargewicht (M_w) von 500 bis 10.000 g/mol, bevorzugt 500 bis 5.000 g/mol, besonders bevorzugt 800 bis 3.000 g/mol, und
• (c) Kettenverlängerungsmitteln mit einem Molekulargewicht von 50 bis 499 g/mol gegebenenfalls in Gegenwart von
• (d) Katalysatoren
• (e) und/oder üblichen Zusatzstoffen hergestellt.

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

• (a) isocyanates, preferably diisocyanates with
• (b) isocyanate-reactive compounds, usually having a molecular weight (M _w ) of 500 to 10,000 g / mol, preferably 500 to 5,000 g / mol, particularly 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'-dimethyldiphenyl 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. Preference is given to polyether polyols, for example those based on well-known starter substances and conventional Alkylene oxides, for example ethylene oxide, 1,2-propylene oxide and / or 1,2-butylene oxide, preferably polyetherols based on polyoxytetramethylene (poly-THF), 1,2-propylene oxide and ethylene oxide. Polyetherols have the advantage that they have a higher stability to hydrolysis than polyesterols, and are preferred as component (b), in particular for the preparation of soft polyurethanes polyurethane (PU1).

When Polycarbonate diols are in particular aliphatic polycarbonate diols to name, for example, 1,4-butanediol polycarbonate and 1,6-hexanediol polycarbonate.

When Polyester diols are to be mentioned by polycondensation of at least one primary diol, preferably at least a primary aliphatic diol, for example ethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol or particularly preferred 1,4-dihydroxymethylcyclohexane (as mixture of isomers) or mixtures of at least two of the abovementioned 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 especially isophthalic acid.

polyetherols are preferred 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 to triols such as glycerol, in the presence produced by highly active catalysts. Such highly active Catalysts are, for example, cesium hydroxide and dimetal cyanide catalysts, also referred to as DMC catalysts. A frequently used one DMC catalyst is the 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 can also be mixtures of different polyols be used.

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

When Chain extenders (c) are known 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 with exactly two functional groups Groups per molecule, used, for example, diamines and / or alkanediols having 2 to 10 C atoms in the alkylene radical, in particular 1,3-propanediol, Butanediol-1,4, 1,6-hexanediol and / or di-, tri-, tetra-, penta-, Hexa, hepta, octa, nona and / or Dekaalkylenglykole with 3 to 8 carbon atoms per molecule, preferably corresponding Oligo- and / or polypropylene glycols, with mixtures of chain extenders (c) can be used.

Especially The components (a) to (c) are preferably difunctional Compounds, d. H. Diisocyanates (a), difunctional polyols, preferred 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 per se known tertiary amines, such as. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo- (2,2,2) octane ("DABCO") and similar tertiary amines, and especially organic metal compounds such as titanic acid esters, iron compounds such as. 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 incorporated in amounts of from 0.0001 to 0.1 parts by weight per 100 parts by weight of component (b) puts.

Besides catalyst (d), auxiliaries and / or additives (e) can also be added to components (a) to (c). Mention may be made, for example, blowing agents, antiblocking agents, surface-active substances, fillers, for example nanoparticle-based fillers, in particular fillers based on CaCO ₃ , furthermore nucleating agents, lubricants, dyes and pigments, antioxidants, eg. Against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers, metal deactivators. In a preferred embodiment, component (e) also includes hydrolysis protectants such as, for example, polymeric and low molecular weight carbodiimides. Preferably, the soft polyurethane contains triazole and / or triazole derivative and antioxidants in an amount of 0.1 to 5 wt .-% based on the total weight of the relevant soft polyurethane. As antioxidants are generally suitable substances which inhibit or prevent unwanted oxidative processes in the plastic to be protected. In general, antioxidants are commercially available. Examples of antioxidants are hindered phenols, aromatic amines, thiosynergists, trivalent phosphorus organophosphorus compounds, and hindered amine light stabilizers ("HALS"). 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-S. 121 , Examples of aromatic amines can be found in [1] pp. 107-108. Examples of thiosynergists are given in [1], pp. 104-105 and pp. 112-113. Examples of phosphites can be found in [1], pp. 109-112. Examples of HALS are given in [1], pp. 123-136. For use in the antioxidant mixture are preferably phenolic antioxidants. 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 ° C. Furthermore, antioxidants are preferably used which are amorphous or liquid. Also, as component (e), mixtures of two or more antioxidants may be used.

Next the said components (a), (b) and (c) and optionally (d) and (e) may also be chain regulators (chain terminators), usually having a molecular weight of from 31 to 3000 g / mol. Such chain regulators are compounds that are only one opposite Isocyanates have reactive functional group, such as. B. monofunctional Alcohols, monofunctional amines and / or monofunctional polyols. By such chain regulator can flow behavior, in particular For soft polyurethanes, targeted. chain regulators may generally be in an amount of 0 to 5, preferably 0.1 to 1 parts by weight, based on 100 parts by weight of the component (b) are used and fall by definition the component (c).

Next the said components (a), (b) and (c) and optionally (d) and (e) may also include crosslinking agents having two or more toward isocyanate-reactive groups towards the end of Build-up reaction can be used, for example, hydrazine hydrate.

to Adjustment of the hardness of polyurethane (PU) can the components (b) and (c) in relatively broad molar ratios to get voted. Proven molar ratios have proven of component (b) to total chain extenders to be used (c) from 10: 1 to 1:10, in particular from 1: 1 to 1: 4, wherein the hardness of the soft polyurethanes increases with increasing content of (c). The implementation for the production of polyurethane (PU) can at a Code 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 respectively. The key figure is defined by the ratio the total amount of isocyanate groups used in the reaction Component (a) to the isocyanate-reactive groups, d. H. the active hydrogens, components (b) and optionally (C) and optionally monofunctional towards isocyanates reactive components as chain terminators such. B. monoalcohols.

The Production of polyurethane (PU) can according to known methods continuously, for example according to one-shot or the prepolymer method, or discontinuously according to the known prepolymer process respectively. In these methods, the reaction coming components (a), (b), (c) and optionally (d) and / or (e) are mixed sequentially or simultaneously with each other, wherein the reaction starts 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-methyl is removed pyrrolidone or N-ethylpyrrolidone.

In an embodiment of the present invention aqueous dispersions according to the invention two different polyurethane polyurethane (PU1) and polyurethane (PU2), of which polyurethane (PU1) is a so-called soft Polyurethane, which is constructed as described above as polyurethane (PU), and at least one hard polyurethane (PU2).

hard Polyurethane (PU2) can basically be used analogously to soft polyurethane (PU1), but you choose others opposite Isocyanate-reactive compounds (b) or other mixtures of opposite Isocyanate-reactive compounds (b), within the scope of the present invention Invention also as isocyanate-reactive compounds (b2) or abbreviated to compound (b2).

Examples for compounds (b2) are in particular 1,4-butanediol, 1,6-hexanediol and neopentyl glycol, either in mixture with each other or in mixture with polyethylene glycol.

In A variant of the present invention is selected as Diisocyanate (a) and polyurethane (PU2) in each case mixtures of diisocyanates, For example, mixtures of HDI and IPDI, wherein for the preparation of hard polyurethane (PU2) larger shares IPDI chooses to produce 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, wherein the Shore A hardness after DIN 53505 was determined after 3 s.

In an embodiment of the present invention Polyurethane (PU) has an average particle diameter in the range from 100 to 300 nm, preferably 120 to 150 nm, determined by Laser light scattering.

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

In an embodiment of the present invention Polyurethane (PU2) has an average particle diameter in the range in the range of 100 to 300 nm, preferably 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. Particularly suitable are crosslinkers based on trimeric diisocyanates, in particular based on aliphatic diisocyanates such as hexamethylene diisocyanate. Very particular preference is given to crosslinkers, as they are known in WO 2008/113755 are described.

Aqueous polyurethane dispersions may contain other ingredients, for example
(f) a silicone compound having reactive groups,
in the context of the present invention also called silicone compound (f).

Examples for reactive groups related to silicone compounds (f) are, for example, carboxylic acid groups, carboxylic acid derivatives such as carboxylic acid methyl esters or carboxylic acid anhydrides, especially succinic anhydride groups, and especially preferably carboxylic acid groups.

Examples of reactive groups are furthermore primary and secondary amino groups, for example NH (iso-C ₃ H ₇ ) groups, NH (nC ₃ H ₇ ) groups, NH (cyclo-C ₆ H ₁₁ ) groups and NH (nC ₄ H ₉ ) groups, in particular NH (C ₂ H ₅ ) groups and NH (CH ₃ ) groups, and very particularly preferably NH ₂ groups.

Furthermore, aminoalkylamino groups are preferred, for example
-NH-CH ₂ -CH ₂ -NH ₂ groups, -NH-CH ₂ -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 with 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, especially para-toluylene, and C ₂ -C ₁₈ -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 ) ₁₀ -, - (CH ₂ ) ₁₂ -, - (CH ₂ ) ₁₄ -, - (CH ₂ ) ₁₆ - and - (CH ₂ ) ₁₈ -.

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.

Very particular preference is given to silicone compounds having reactive groups (f) as described in US Pat WO 2008/113755 are described.

In one embodiment of the present invention, aqueous polyurethane dispersion further 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 polydialkylsiloxane (g) or Polydimethylsiloxane (g) called.

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

Very particular preference is given to polydialkylsiloxanes (g) and in particular polydimethylsiloxanes (g), as described in US Pat WO 2008/113755 are described.

In one embodiment of the present invention, aqueous polyurethane dispersion contains
total in the range of 20 to 30% by weight of polyurethane (PU), or in total in the range of 20 to 30% by weight of polyurethanes (PU1) and (PU2),
in total in the range from 0.15 to 20% by weight, preferably in the range from 0.5 to 12% by weight (pigment (s) P,
optionally in the range of 1 to 10, preferably 2 to 5 wt .-% hardener,
optionally in the range of 1 to 10% by weight of silicone compound (f),
in the range of zero to 10, preferably 0.5 to 5 wt .-% polydialkylsiloxane (g).

In one embodiment of the present invention, aqueous polyurethane dispersion contains
in the range of 10 to 30 wt .-% soft polyurethane (PU1) and
in the range of zero to 20 wt .-% hard polyurethane (PU2).

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

there in% by weight, in each case the active ingredient or solid and are based on the sum of the solids of aqueous polyurethane dispersion based.

In an embodiment of the present invention aqueous polyurethane dispersion at least one additive (h) selected from pigments, matting agents, sunscreens, Antistatic agents, antisoil, anticancer, thickening agents, in particular Thickeners based on polyurethanes, and hollow microspheres.

In an embodiment of the present invention aqueous polyurethane dispersion in total up to 20% by weight on additives (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 tetraglycols and di- or preferably monohydric glycols, diglycols, triglycols or tetraglycols 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"). Another object of the present invention is the use of inventive multilayer composite materials as or for the production of decorative material and the decorative materials thus produced. Another object of the present invention is a method for the production of decorative material using multilayer composite materials according to the invention. Examples of decorative materials are garlands and laminations.

One Another object of the present invention is the use of multilayer composite materials according to the invention as or for the production of vehicle interior parts and the so produced Vehicle interior parts. Another object of the present invention is a method for producing vehicle interior parts under Use of multi-layered according to the invention Composite materials. Exemplary for vehicle interior parts are seats, for example, for boats, ships, aircraft, Railway cars and in particular automobiles, but also for Seating or reclining furniture. Another item of the present invention are seats, seating and reclining furniture, prepared using inventive multilayer composite materials. Other automotive interior parts are, for example, steering wheels, door panels, Center consoles and hat racks.

The Invention will be further explained by working examples.

I. Preparation of the starting materials

I.1 Preparation of an aqueous Polyurethane Dispersion Disp. 1

6 Gew.-% einer 65 Gew.-% wässrigen Dispersion der Silikonverbindung nach Beispiel 2 aus EP-A 0 738 747 (f.1)
2 Gew.-% Perylenpigment P1.1, hergestellt nach US 7,416,601 , Beispiel 1 b),
0,5 Gew.-% eines Verdickungsmittels auf Polyurethanbasis,
1 Gew.-% Mikrohohlkugeln aus Polyvinylidenchlorid, gefüllt mit Isobutan, Durchmesser 20 μm, kommerziell erhältlich z. B. als Expancel^® der Fa. Akzo Nobel.In a stirred vessel was mixed with stirring:
7% by weight of an aqueous dispersion (particle diameter: 125 nm, solids content: 40%) of a soft polyurethane (PU1.1) prepared from hexamethylene diisocyanate (a1.1) and isophorone diisocyanate (a1.2) in a ratio by weight of 13: 10 as diisocyanates and as diols a polyesterdiol (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), and also 3% by weight of monomethylated polyethylene glycol (c.1) and 3% by weight of H ₂ N-CH ₂ CH ₂ -NH-CH ₂ CH ₂ -COOH, wt .-% in each case 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 (1.1),

6 wt .-% of a 65 wt .-% aqueous dispersion of the silicone compound of Example 2 from EP-A 0 738 747 (F.1)
2 wt .-% perylene pigment P1.1, prepared according to US 7,416,601 Example 1 b)
0.5% by weight of a polyurethane-based thickener,
1 wt .-% hollow microspheres of polyvinylidene chloride, filled with isobutane, diameter 20 microns, commercially available z. B. as Expancel ^® the Fa. Akzo Nobel.

Aqueous dispersion Disp. 1 with a solids content of 35% and a kinematic viscosity of 25 sec. At 23 ° C, determined by DIN EN ISO 2431, as of May 1996 ,

I.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 (a1.1) and isophorone diisocyanate (a1.2) in the ratio by weight 13 : 10 as diisocyanates and as diols a polyester diol (b1.1) with a Molekularge 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) , 3 wt .-% monomethylated polyethylene glycol (c.1) and 3 wt .-% H ₂ N-CH ₂ CH ₂ -NH-CH ₂ CH ₂ -COOH, wt .-% each based on polyester diol (b1.1 )
Softening point of 62 ° C, softening starts at 55 ° C, Shore hardness A 54,
65% by weight of an aqueous dispersion (particle diameter: 150 nm) of a hard polyurethane (a2.2) obtainable by reacting isophorone diisocyanate (a1.2), 1,4-butanediol (PU1.2), 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% by weight of a 70% by weight solution (in propylene carbonate) of compound (V.1), NCO content 12%,
2 wt .-% perylene pigment P1.1, prepared according to US 7,416,601 , Example 1 b).

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

II. Preparation of a matrix

One Liquid silicone was poured onto a pad that the pattern of a full-grain calfskin had. It was allowed to cure, by adding a solution of di-n-butylbis (1-oxoneodecyloxy) stannane as 25 wt .-% solution in tetraethoxysilane as an acidic hardener and received an average 2 mm silicone rubber layer, which served as a template. The die was made to a 1.5 mm thick Glued aluminum carrier.

III. Application of aqueous Polyurethane dispersions on die from II.

The template from II. Was placed on a heatable surface and heated to 91 ° C. Subsequently, through a spray disp. 1 sprayed, 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 ° C until the surface was no longer sticky.

The Spray nozzle was at a height of 20 cm from the continuous base in the same direction arranged mobile and moved transversely to the direction of movement the underlay. The pad had the spray nozzle after about 14 seconds happened and had a temperature of 59 ° C. To an approximately two-minute exposure to dry, 85 ° C warm air was the thus prepared, reticulated-looking polyurethane film (C.1) almost anhydrous.

In an analogous arrangement immediately after the thus coated die 50 g / m ² wet of Disp. 2 applied as a bonding layer (B.1) and then allowed to dry.

you obtained one with polyurethane film (C.1) and bonding layer (B.1) coated die.

A with a dye mixture (70 parts by weight of dye EP-B 0 970 148 , Example 2.18, 30 parts by weight Acid Brown 75 (iron complex), Color Index 1.7.16.) Dyed grain leather (A.1) was mixed with Disp. 2 sprayed, with 30 g / m ² (wet) on the grain side. The so sprayed leather was allowed to dry for several minutes.

IV. Production of an Inventive multilayer composite material MSV.1

you put leather (A.1) with the sprayed side on the still warm bonding layer (B.1), which together with polyurethane film (C.1) on the matrix, and compressed in a press 4 bar and 110 ° C for 15 seconds. Subsequently took out the thus obtained inventive multilayer composite MSV.1 from the press and removed the matrix.

The Reflection is determined according to the above mentioned rule and is averaged over the wavelength range from 380 to 720 nm 25%. The reflection is averaged over the wavelength range from 720 to 1500 nm, averaged 60%.

The thus obtained multilayer composite material according to the invention MSV.1 was characterized by a pleasant feel, an appearance, which was identical to a high quality leather surface, as well as breathability.

V. Preparation of a comparison material

you proceeded as described in Examples I to IV, but replaced in disp. 1 and Disp. 2 Perylenpigment P1.1 each by a same amount of soot.

you received V-MSV.2. The multilayer composite material thus obtained V-MSV.2 was characterized by a pleasant feel, an appearance, which was identical to a high quality leather surface, as well as breathability.

VI. Determination of warming under light irradiation

From each of MSV.1 and V-MSV.2, a 10 × 10 cm test piece was cut out and irradiated the specimens with a 100 W incandescent bulb at a distance of 10 cm, to the side of the respective one Polyurethane layer (C). Using a thermocouple (Ebro CTX 1300) was measured over the period of 30 minutes each of the heating, each on the meat side and on the grain side. The results are shown in Table 1. Table 1: heating of inventive and non-inventive multilayer composite material Duration [min] MSV.1 grain side [° C] MSV.1 meat side [° C] V-MSV.2 grain side [° C] V-MSV.2 meat side [° C] 0 25.6 25.8 24.5 25.2 5 45.1 51.7 51.2 63.2 10 46.2 52.8 57.4 67.9 15 46.4 52.8 57.3 68.2 20 46.4 53.2 57.1 68.4 25 46.8 53.6 57.6 68.9 30 46.8 52.5 56.9 68.2

QUOTES INCLUDE IN THE DESCRIPTION

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

Cited patent literature

• WO 2005/047549 [0003, 0004]
• - EP 1311631 B1 [0005]
• - EP 1311631 [0006]
• WO 2005/103107 [0050]
• - EP 0084851 A [0156]
• - WO 2008/113755 [0198, 0205, 0208]
• EP 0738747A [0218]
• - US 7416601 [0218, 0220]
• - EP 0970148 B [0227]

Cited non-patent literature

• ASTM G 159-98 [0013]
• - Harro Träubel, New Materials Permeable to Water Vapor, Springer Verlag 1999 [0038]
• - DIN 7726 [0040]
• - DIN ISO 4590 [0041]
• - DIN 52212 [0045]
• - DIN 53333 [0082]
• - DIN 53333 [0083]
• - DIN 55944 [0095]
• ASTM G 159-98 [0099]
• ASTM G 159-98 [0099]
• - Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Munich, 2001 ([1]), pp. 98-107 and pp. 116-S. 121 [0184]
• - DIN 53505 [0194]
• - DIN EN ISO 2431, as of May 1996 [0219]
• - DIN EN ISO 2431, as of May 1996 [0221]

Claims (17)

Multilayer composite material comprising (A) at least one substrate, (B) at least one tie layer, (C) at least one polyurethane layer having capillaries which over go the entire thickness of the polyurethane layer, being polyurethane layer (C) has at least one pigment P, and wherein the multilayered Composite material in the range of visible light with wavelengths in the range of 380 to 720 nm a reflection averaged up to a maximum 50% and near infrared with wavelengths a reflection of at least averaged in the range of 720 nm to 1500 nm 40%. Multilayer composite material according to claim 1, characterized in that the polyurethane layer (C) at least one Contains pigment P. Multilayer composite material according to claim 1 or 2, characterized in that connecting layer (B) at least contains a pigment P. Multilayer composite material according to one of the claims 1 to 3, characterized in that pigment P in connecting layer (B) and polyurethane layer (C) are the same. Multilayer composite material according to one of the claims 1 to 4, characterized in that polyurethane layer (C) at least contains a pigment P and that the pigment-containing polyurethane layer (C) in the range of near-infrared light with wavelengths a reflection of at least averaged in the range of 720 nm to 1500 nm 40%. Multilayer composite material according to one of the claims 1 to 5, characterized in that substrate (A) is selected is made of leather, synthetic leather, thermoplastics, paper and textile. Multilayer composite material according to one of the claims 1 to 6, characterized in that connecting layer (B) a full-surface film is or a non-full-surface Pattern has. Multilayer composite material according to one of the claims 1 to 7, characterized in that pigment P is selected is made of perylene pigments and hematite. Multilayer composite material according to one of the claims 1 to 8, characterized in that neither connecting layer (B) polyurethane layer (C) have an inorganic pigment P2. Multilayer composite material according to one of the claims 1 to 9, characterized in that the content of pigment P in Polyurethane layer (C) or in polyurethane layer (C) and bonding layer (B) in the range of 0.1 to 5 wt .-% is. Multilayer composite material according to one of the claims 1 to 10, characterized in that it has a velvety appearance having. Process for producing multilayer composite materials according to one of claims 1 to 11, characterized that with the help of a template, a pigment-containing polyurethane layer (C) forms, at least one organic adhesive over the entire surface or partially on textile fabric (A) and / or on Applying polyurethane layer (C) and then polyurethane layer (C) with substrate (A) punctiform, strip-like or flat combines. Method according to claim 12, characterized in that polyurethane layer (C) is formed by means of a silicone matrix. Method according to claim 12 or 13, characterized that the die is a laser engraved one Silicone matrix is trading. Method according to one of claims 12 to 14, that you can structure the template with the help of a laser Wells into the matrix incorporating a medium Have depth in the range of 50 to 250 microns and a Center distance in the range of 50 to 250 μm. Use of multilayer composite materials according to any one of claims 1 to 10 as or for the production of decoration material. Use of multilayer composite materials according to any one of claims 1 to 10 as or for the production of vehicle interior parts.