WO2014012719A1

WO2014012719A1 - Composite sheet material, method for the production and use thereof

Info

Publication number: WO2014012719A1
Application number: PCT/EP2013/062313
Authority: WO
Inventors: Andreas Gerken; Jürgen BÜHRING
Original assignee: Benecke-Kaliko Ag
Priority date: 2012-07-19
Filing date: 2013-06-14
Publication date: 2014-01-23
Also published as: DE102012106561A1; EP2875181A1

Abstract

The invention relates to a composite sheet material, comprising at least the following layers: a textile support layer (5), a laminating layer (4) which is connected to the textile support layer (5), a polyurethane intermediate layer (3) based on an unblocked high-solid polyurethane system, a polyurethane cover layer (2) and at least one lacquer layer based on polyurethane and/or acrylate polymers which is applied onto the polyurethane cover layer (2) and which faces outward. The invention further relates to a method for producing such a composite sheet material and the use of the composite sheet material. To achieve a high degree of service performance while reducing toxicity as much as possible, the polyurethane cover layer (2) is based on a solvent-free or solvent-poor high-solid polyurethane system which contains a) polyfunctional isocyanates and/or polyfunctional isocyanate prepolymers, b) at least one polyfunctional hydroxy-group-containing compound based on polytetra-, polypenta- and/or polyhexamethylene glycol, and c) at least one metal catalyst.

Description

Description Composite layer material, process for its preparation and use

The invention relates to a composite layer material comprising at least the following layers: a textile carrier layer, a laminating layer bonded to the textile carrier layer, a polyurethane intermediate layer based on an unblocked high-solid polyurethane system, a polyurethane topcoat and at least one outwardly facing lacquer layer applied to the polyurethane topcoat layer from

Polyurethane and / or acrylate polymers. Furthermore, the invention relates to a method for producing such a composite layer material and the use of the

Composite layer material.

Such composite layer materials are known for example from EP 1 059 379 B1 and z. B. used as leather-like cover materials for different applications. Special requirements are placed on the leather-like cover materials in the interior of vehicles.

Decorative leather-like covering materials in the interior of vehicles which are subjected to dynamic loads must, in addition to the required flexibility in the cold and in the heat, also be sufficiently usable for the end user. This means that the cover material must be abrasion resistant, resistant to aging and also easy to clean. This is especially true for seat cover materials that are constantly exposed to dynamic loads and are constantly in contact with the clothing of the passenger. Due to the constant friction between clothing and cover material and the constantly changing pressure loads, the cover material is constantly exposed to high stress. Excessive stress experienced cover materials in the seating area of a motor vehicle, in particular on the side cheeks of the backrest and the seat on the respective entry side, since the seat material is exposed when entering a combined high pressure and friction load. In addition, if a low ambient temperature, the risk of very large that the cover material after a short time cracks or other damage and the entire seat cover must be replaced.

Another requirement placed on cover materials used in the

Vehicle interior are to be used, is the absence of toxic or hazardous substances. Such substances may only be contained below lower limit values and are detected, for example, according to VDA 278.

The composite layer materials currently available on the market, known as

Covering materials are used with leather look meet the above

Requirements are not permanent.

Thus, for example, in reference materials based on PVC in the

Intermediate and top layers in the seat back area during entry and exit a constant superficial abrasion of plasticizers. From inside the PVC

Layers then migrates plasticizer back to the surface, as equilibrium sets in again. Thus, with the period of use, the PVC cover material, which is flexible in the original state and in particular cold-flexible, to

Softeners impoverish and consequently embrittle. The cover material is thereby less flexible, in particular less cold flexible, whereby the risk of cracking under load in the material increases.

Alternative cover materials on the basis of coagulated polyurethanes, such as Alcantara ^® frequently have the disadvantage that they are not sufficiently stable to abrasion in the seat cheek area. Furthermore, such coverings often have unacceptable soiling and cleaning behavior in use. In addition, will Such reference materials produced by means of polluting processes, since in the production of large amounts of toxic Ν, Ν-dimethylformamide are used.

Other cover materials use polyurethanes based on blocked isocyanates. As a rule, toxic diamines and blocked butanone oxime isocyanate prepolymers are used for the production of the cover materials. The isocyanates split in the production of the cover material when heated the reproductive toxic

Butanonoxim from which, however, remains in significant quantities in the reference material and endangers the user, which is constantly in contact with the cover material, especially in seating applications.

Other cover materials based on a combination of polyurethane films made from dissolved in solvents polyurethanes and so-called low-solvent or

solvent-free high-solid polyurethane systems - sold, for example, by the company Bayer - are usually not sufficient in the cold

(For example, at -10 ° C) flexible, especially since the built-up of the solvent in dissolved polyurethane layers do not have a sufficiently low glass transition temperature. Alternative polyurethane solvent systems with low

In turn, glass transition temperatures are too soft and therefore less resistant to abrasion.

At present, no cover material is commercially available which at the same time is abrasion-resistant, cold-flexible and essentially free of plasticizers and toxic solvents.

The invention is based on the object to provide a composite layer material which is characterized by a high degree of serviceability when used as a reference material and has the lowest possible toxicity.

The object is achieved in that the polyurethane cover layer (2) is based on a solvent-free or low-solvent high-solid polyurethane system which a) polyfunctional isocyanates and / or polyfunctional isocyanate prepolymers and b) at least one polyfunctional hydroxyl-containing compound based on Polytetra-, polypenta and / or polyhexamethylene glycol and c) has at least one metallic catalyst.

The polyurethane topcoat can therefore one or more polyfunctional

hydroxyl-containing compounds based on polytetra, polypenta and / or polyhexamethylene glycol. In addition to the aforementioned polyols, other polyols and / or polyfunctional H-acidic compounds capable of reacting with the isocyanate groups may be present in the high-solids polyurethane system. The composite sheet material may include further layers, such as others

Polyurethane layers within the composite or more on the

Polyurethane topcoat applied paint layers have.

It has surprisingly been found that the inventive

Composite layer material can be used excellently as a reference material, which is characterized by a high durability. The composite layer material is particularly abrasion-resistant and cold-flexible, the abrasion resistance z. B. with

Saddle abrasion tests and the cold flexibility z. B. with a so-called

Ballyfex test (DIN 53351) can be detected. It is there for the

Cold flexibility necessary that at least one polyfunctional hydroxyl-containing compound based on polytetra-, polypenta and / or polyhexamethylene glycol is present in the system.

From a toxic point of view, the composite layer material has a reduced risk because of the use of high-solids polyurethane systems, which are characterized by a solvent content of less than 20 percent by mass, as less volatile

Substances are contained in the composite layer material. The detection of volatile substances can be carried out via a test according to VDA 278 (VOC and Fog value). In addition, a material can be achieved with the composite layer material according to the invention, which meets the requirements of the automotive industry for a reference material for the Automotive interior meets, ie that even with stretching and padding of the composite layer material, the textile structure of the textile support layer is not visible on the surface and the visible surface by UV irradiation in the

Essentially not discolored.

For the cover layer fiction, according to polyurethane compositions on a high-solids basis, that is, with a solvent content <20 mass percent used. To the

In order to further improve the environmental compatibility of the composite layer material and to reduce the toxicity, it has proved to be advantageous if, for the polyurethane cover layer, a high-solids polyurethane system with a solvent content of less than

10 percent by mass is used.

Preferably, the glass transition temperature of the polyurethane topcoat (cured film) is less than -40 ° C, more preferably less than -50 ° C.

For the polyurethane topcoat isocyanates based on aromatic, z. B.

Methylene diisocyanate, toluene diisocyanate or Naphthyldiisocyanat be used. In order to further improve the aging resistance of the composite sheet material, it is advantageous for the polyisocyanates to be aliphatic polyisocyanates.

The polyfunctional isocyanates and / or polyfunctional isocyanate prepolymers of the solvent-free or low-solvent high-solids polyurethane system of the polyurethane topcoat preferably have a degree of functionalization of 2 or higher and a content of free isocyanate groups of between 4 and 20 percent by mass, in particular between 5 and 13 percent by mass. This degree of functionalization requires that isocyanate prepolymers be used, i. H. prepolymerized

Extend compounds of monomeric aliphatic isocyanates with one or more chains, such as di- and / or higher functional polyols (eg., Polypropylene glycols, polytetramethylene glycols, polyethylene glycols or also

side chain branched polyols such as 2-hydroxymethyl-2-ethyl-1,3-propanediol = 1,1,1-trimethylolpropane, etc.). As monomeric diisocyanates for the construction of the prepolymers are especially 1,6-hexane diisocyanate (HDI), isophorone diisocyanate (IPDI) or dicyclohexylmethane-4,4'-diisocyanate (H12MDI) in question. But also prepolymers, for example based on 1,4-cyclohexane diisocyanate or

Bis (isocyanatomethyl) cyclohexane are suitable.

As corresponding polyols to the isocyanate compounds polyfunctional hydroxyl-containing compounds based on polytetra-, polypenta and / or polyhexamethylene glycol are used. These are preferably those based on polytetramethylene glycol. Preferably, the molecular weight of the polyol is more than 250 g / mol. Such polyols having molecular weights between 250 and 6000 g / mol are z. B. from Invista available.

In addition to the aforementioned polyols, which must necessarily be present in the high-solid polyurethane system, other commonly used for the construction of

Polyurethanes used polyols and / or CH-acidic compounds are used. These are, in particular, aliphatic polyols which are bifunctional or higher-functional and in particular may be particularly reactive at the functionalized ends. The

Reactivity enhancement is achieved by partial or complete epoxidation of primary hydroxyl end groups. Reactive towards isocyanates are also at the reactive centers less sterically hindered polyols such as copolymers of adipic acid and 1,6-hexanediol containing terminal hydroxyhexyl groups with primary hydroxyl groups. An example of sterically hindered polyols are

Polypropylene polyether polyols containing terminally branched hydroxypropyl groups and thus secondary hydroxyl groups.

The optionally further polyols present in the high-solid polyurethane composition may be commercially available polyester polyols, polyether polyols, polythioether polyols,

Polycarbonate polyols and hydroxyl-containing aliphatic polyacetals and

hydroxyl-containing aliphatic polycarbonates having molecular weights of 20 to 12,000 g / mol, preferably from 250 to 2000 g / mol. To the high-solid polyurethane system, other compounds can be added to modify the properties of the reacted system, which with

Isocyanates can react by reactive hydrogen atoms by substituting part of the polyols. Such compounds contain two or more reactive groups which are present as OH groups, SH groups, NH groups, NH ₂ groups or CH-acidic groups, for example in β-diketo compounds. The proportion of polyols with secondary hydroxy functionality should be excluded or set as low as possible. Preferably, the primary and secondary hydroxyl functionalities of the polyol should be in a ratio greater than 10: 1, more preferably greater than 50: 1.

The high-solid polyurethane system of the polyurethane topcoat necessarily contains a metallic catalyst. This is according to an advantageous embodiment of the invention, a catalyst, which only at a temperature of more than 100 ° C, the

Polyurethane formation reaction delayed catalyzed. Preferably, this will be done

Metal catalysts based on zinc, zirconium, lead, tin, nickel and / or bismuth used. Such delayed-acting metal catalysts, which can be additionally delayed with the aid of additional complexing compounds such as acetylacetone or 2-ethylhexanoic acid, are known from the prior art, wherein z. Reference may be made, for example, to US Pat. No. 6,140,381 and DE 10 2006 056 956 A1.

The composite layer material according to the invention has at least one outwardly facing lacquer layer, based on polyurethane and / or acrylate polymers, applied to the polyurethane cover layer. This serves to improve the serviceability, in particular with regard to the abrasion properties, the scratch resistance, the

Cleaning properties, resistance to detergents and solvents, the degree of gloss, the color and / or the aging properties. The lacquer layer can to further

Improvement of the aging behavior of the composite layer material to be dyed or pigmented. One or more paint layers can be provided. The lacquer layers can be based on solvent-based or aqueous polyurethane and / or acrylate systems, which are prepared by conventional printing processes, for. B. in direct or indirect screen gravure or reverse roller coating can be applied. Preferably, at least one of the paint layers is crosslinked. Suitable crosslinked lacquer layers are, in particular, systems which crosslink via electromagnetic radiation (UV light crosslinking, electron beam crosslinking) or systems crosslinking thermally or via chemical reactions, such as isocyanate- or carbodiimide-crosslinking polyurethane systems. The crosslinking of the paint layers offers the advantage that a better resistance to cleaning media and / or an improved

Cleaning behavior after soiling of the surface can be achieved.

To further reduce the volatile hydrocarbons (VOC) in the production and in the end product, it is also advantageous if the laminating layer and / or the polyurethane intermediate layer are based on essentially solvent-free starting substances.

The polyurethane intermediate layer or the polyurethane intermediate layers based on an unblocked high-solid polyurethane system is or are preferably prepared using unblocked isocyanate prepolymers, polyols, optionally polyamines and a catalyst (for example described in EP 1 059 379 B1 or in DE 10 2006 056 956 AI), wherein the catalyst in the production and storage of the reactive masses allows a long processing time (pot life) and when annealed in a furnace rapid curing to a polymer film. Preferably, these systems contain no solvents.

The isocyanate prepolymers used in the intermediate layer are usually composed of polyols and isocyanates based on, for example,

Hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (HMDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-

Trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexanoethylene diisocyanate (TMDI), Norbornane diisocyanate (NBDI), methylene diphenyl diisocyanate (MDI),

Diisocyanatomethylbenzen, especially the 2,4- and 2,6-isomers and technical mixtures of both isomers (TDI), tetramethylxylylene diisocyanate (TMXDI) and naphthylene diisocyanate (NDI) or derivatives of these isocyanates such. B.

Isocyanurates, uretdiones, allophanates and / or biurets, particular preference being given to aromatic isocyanate prepolymers based on MDI, TDI, TMXDI or NDI.

Polyurethanes on this aromatic basis are compared to aliphatic ones

Polyurethanes cheaper. However, if the structures according to the invention are exposed to particular light, UV and / or heat loads, the aliphatic polyurethane starting materials are to be preferred.

The polyurethane intermediate layer can be compact. In order to avoid the visibility of the textile structure on the surface of a composite material when using very extensible textiles such as a PET-based Fang-Krepp knitted fabric with a basis weight of 120 g / m ² and a more pleasant

To create impression haptics, the polyurethane intermediate layer is preferably foamed. This can be achieved by a by the addition of an agent which foams under heat, so that in the cured state, a film with

small-cell, uniformly distributed foam bubbles is formed. Furthermore, the starting materials for forming the polyurethane film will be chosen so that the

Glass transition temperature of this film (measured in a DSC measurement at a heating rate of 10 ° C / min) is less than -40 ° C and preferably less than -50 ° C.

In the textile backing layer may be z. B. to needle or water jet nonwovens, knitted fabrics, knitted fabrics, woven fabric, spacer knitted fabrics, vertical pile threads containing nonwovens (eg., Multiknit or Optiknit) act. The basis weights are usually 50 to 500 g / m ² . The following materials may be used as the basis of the threads: mixtures of cotton and polyester (usually based on polyethylene terephthalate), lyocell, polyamides, polyethylene terephthalate, polyacrylates, aramides. According to an advantageous development of the invention, the textile carrier layer contains flame-retardant textiles in order to achieve a high flame resistance. As such flame-retardant textiles can then either be used, which are equipped with flame retardants, or there are used those which are usually already less flammable, these are, for example, textiles based on not equipped with flame retardants polyethylene terephthalate. In the case of the latter, their textile threads already contain flame-retardant units in the polymer chains or are textiles based on flame-retardant aromatic polyamides (eg.

Kevlar ^®, Nomex ^®) or other flame retardant polymers (for example, Lenzing FR ^®, Basofil ^®, Twaron ^®, KERMEL ^®, BelcoTex ^®, ^® pyrone, Trevira CS ^®, polysulfonamide (Tanlon ^®), polyphenylene sulfide). It is also possible to use textiles based on glass fibers,

Mineral fibers, metal threads or polymer threads containing metallic components.

The textile carrier layer is bonded to the subsequent layer with a laminating compound which forms the laminating layer. The laminating mass penetrates as far as possible into the textile carrier layer and forms the connection to the subsequent layer / layer. For the laminating layer applied to the textile carrier layer, a solvent-containing laminating adhesive which cures by evaporation of the solvent is often used as laminating compound. However, preference is given to using solvent-free and co-solvent-free aqueous dispersion laminating compounds, in particular those based on polyurethanes. Alternatively, so-called thermoplastic hotmelt adhesives can be used. These can be, for example, thermoplastic powders applied by means of scattering processes, such as polyesters or polyamides, or thermoplastic films applied via a slot die or pressure roll. Also used are methods such as spraying from nozzles or methods using a rotating discharge nozzle. Reactive thermoplastic laminating adhesives can also be used which crosslink after application and solidification under the influence of ambient moisture. It is also possible to use thermoplastic open adhesive tape or textiles containing applied thermoplastic elements, for example in the form of a dot doping as a laminating layer. Another possibility of lamination is the use of high-solid polyurethane compounds as they are for the intermediate layer can be used, which can be used in particular for the lamination of nonwovens.

For an improved bondability of the composite layer material and for better processing in subsequent work steps can also the bottom of the

Composite sheet material, i. the textile carrier on the side facing away from the laminating layer with at least one paint, adhesive or primer layer and / or with other layers (for example, polyurethane foams for better padding or thin films of, for example, thermoplastic polyurethane for processing in behind spraying or Hinterschäumverfahren provided) become.

For aesthetic reasons, the surface visible to the customer may be the

Composite sheet material, d. H. the polyurethane topcoat with the possibly existing paint layers, with a pressure (eg images, patterns) are provided. In addition, the surface may be provided with a structure and / or transparent lacquer layers and / or transparent foil layers.

Auxiliaries and additives such as lubricants, rheology aids, thickeners, flame retardants, stabilizers against oxidative, thermal, hydrolytic, radiation-induced or microbial degradation or aging, release agents, pigments, reinforcing substances, fillers or blowing agents can be used in all layers of the composite layer material according to the invention. Such auxiliaries and additives are described, for example, in H. Zweifel, Plastics Additives Handbook, 5th Edition. Carl Hanser Verlag, Munich.

For a particularly good flexibility and processability of the composite layer material, the individual layers preferably have the following layer thicknesses:

Laminating layer: 1 to 400 μιη, preferably 10 to 200 μιη

Polyurethane interlayer: 50 to 1000 μιη, preferably 150 to 750 μιη

Polyurethane top layer: 20 to 1000 μιη, preferably 40 to 400 μιη

Lacquer layer: 1 to 100 μιη, preferably 3 to 20 μιη. The usual basis weights for the individual layers are:

textile carrier layer: 50 to 500 g / m ²

Polyurethane interlayer (s): 100 to 800 g / m ² (dry)

Polyurethane topcoat: 40 to 800 g / m ² (dry)

Lacquer layer: 1 to 100 g / m ² (dry)

The composite layer material according to the invention can be carried out from the textile by layer-wise application (for example doctoring with a knife or by printing) and subsequent thermal curing

Composite layer material is subsequently shaped as a rule. However, the preparation preferably takes place by means of a reverse coating process (see also Ullmann's Encyclopedia of Industrial Chemistry, 6th ed., Wiley-VCH, Weinheim 2002, Chapter "Leather Imitations" by C. Zürbig and H.-H. Kruse) Method on a support (for example based on paper or a polymer such as polyolefins or silicones), which has the negative surface structure of the later reference material, first applied the solvent-free or low-solvent high-solid polyurethane system for the cover layer using a knife blade and subsequently in an oven Thereafter, the polyurethane high-solid mass of the intermediate layer is again applied with a knife blade, which in turn is cured in the oven. into which a textile carrier egg Subsequently, the applied layer is again dried in the oven, whereby the textile carrier permanently bonds to the rest of the construction, and finally the structured carrier is separated from the manufactured one

Composite material. The composite material is subsequently provided with one or more layers of paint by means of customary printing processes for adjusting the properties such as feel, visual appearance, degree of gloss, abrasion and creaking resistance and soiling and cleaning behavior. The entire composite can then be used in the usual way

Lamination process such as a Flammenkaschierung be further processed. The composite layer material according to the invention can be used both in the fashion technical field (shoes, bags, clothing, etc.) and in other areas where coated textiles are used. By avoiding toxic substances, there are no concerns about direct contact with human skin. The high flexibility and abrasion resistance makes that

Composite layer material particularly suitable for shoe materials.

Preferably, the composite layer material according to the invention is used as a decorative interior material z. In transportation, shipbuilding, furniture, etc., especially as surface-structured cover materials. The advantageous ones

Properties of the composite sheet material are used when they are used in areas which come into contact with the clothed or unclothed human skin and at the same time are exposed to dynamic loads:

These can include bellows, steering wheel covers, door balustrades, arm rests,

Backrests, headrests and in particular all types of seats in or outside the automobile.

Another possible application of the composite sheet material relates to sports equipment where high flexibility and high abrasion resistance are required, such as footballs.

The invention will now be explained in more detail by way of examples. The sole FIGURE 1 shows schematically a composite layer material according to the invention with a textile carrier layer 5, a laminating layer 4 applied thereon with a layer thickness of 1 to 400 μm, a polyurethane intermediate layer 3 based on an unblocked high-solid polyurethane system with a layer thickness of 50 to 1000 μm one

Polyurethane top layer 2 with a layer thickness of 20 to 1000 μιη and an outer lacquer layer 1 with a layer thickness of 1 to 100 μιη. The polyurethane cover layer 2 is based on a solvent-free or low-solvent high-solid polyurethane system which a) polyfunctional isocyanates and / or polyfunctional

Isocyanate prepolymers and b) at least one polyfunctional hydroxyl group-containing Compound based on polytetra-, polypenta and / or polyhexamethylene glycol and c) has at least one metallic catalyst.

Comparative and exemplary embodiments with the layer structure according to the figure have been used to produce composite layer materials which are only known in the chemical field

Composition of polyurethane topcoat 2 different. The other layers were identical for all materials shown in the following Table 1 and composed as follows: PERMUTHANE SU-9517 based paint layer 1 (Stahl, Germany), PERMUTEX WF-73-549 (Stahl , The Netherlands) and BAYHYDROL UH XP 2648 (Bayer Material Science, Germany)

Polyurethane interlayer 3: 500 g of poly (oxypropylene) triol (Mw = 6000 g / mol), 610 g of poly (oxypropylene) diol (Mw = 4000 g / mol), 400 g of MDI

(Methylene diphenyl diisocyanate oligomer) (Mw = 1200 g / mol), 10 g of nickel acetylacetonate 10 g in poly (oxypropylene) glycol (composition corresponds to Example 1 of EP 1 059 379 B1) Lamination 4: MDI-polyester-TPU dissolved in MEK (wt. ratio 3: 7) textile carrier layer 5: knitted fabric based on cotton / polyethylene terephthalate fibers (35/65% by weight) with a surface weight of 140 g / m ² (Reichenbach,

Germany)

The polyurethane topcoats 2 were composed and prepared as follows: Comparative Example 1

1000 g Impranil ELH A (polyurethane, solvent-based:

Toluene / methoxypropanol / isopropanol, Bayer Material Science, Germany) were applied to a grained carrier with a knife blade in a thickness of 180 μιη and then dried for 2 min at 80 ° C and 2 min at 120 ° C. Comparative Example 2:

1000 g Larithane HS 969 (butanone oxime-blocked high-solid prepolymer with diamine crosslinker, Novotex, Italy) were homogeneously mixed with 71 g of 4,4-diamino-3,3-dimethyldicyclohexylmethane (BASF, Germany) by means of a paddle stirrer and in a thickness of 200 μιη applied to a grained support with a knife blade and then cured at 160 ° C for 4 min.

Comparative Example 3

1000 g of aliphatic, polyester-polycarbonate-based anionic, aqueous

Polyurethane dispersion were applied with a knife blade in a thickness of 180 μιη on a grained carrier and then dried for 2 min at 80 ° C and 2 min at 100 ° C.

Comparative Example 4

1000 g of polycarbonate diol with a molecular weight of 2000 g / mol and

1,256 g of IPDI-polytetramethylene glycol prepolymer (with 8% by mass of free NCO groups, use in excess: index 1.22) as a high-solid polyurethane system and 7 g of dioctyltin bis (-isooctylmercaptoacetate) became homogeneous with a paddle stirrer mixed and applied at a thickness of 200 μιη to a grained carrier with a knife blade and then cured at 160 ° C for 4 min.

Example 1:

1000 g of polytetramethylene glycol, Mw = 2000 g / mol, 639 g of IPDI-polytetramethylene glycol prepolymer (with 8% by mass of free NCO groups, use in excess: Index 1.22) and 3.5 g of dioctyltin-bis (- isooctylmercaptoacetate) are mixed homogeneously with a paddle stirrer and applied at a thickness of 200 μm to a grained support with a knife blade and subsequently cured at 160 ° C. for 4 minutes.

Example 2:

1000 g of polytetramethylene glycol, Mw = 1000 g / mol,

1279 g of IPDI-polytetramethylene glycol prepolymer (with 8% by mass of free NCO groups, use in excess: Index 1.22) and 7 g of dioctyltin bis (isooctylmercaptoacetate) are homogeneously mixed with a paddle stirrer and are in the strength of 200 μιη on applied a grained support with a knife blade and then cured at 160 ° C for 4 min.

Example 3:

1000 g of polytetramethylene glycol, Mw = 650 g / mol, 1975 g of IPDI-polytetramethylene glycol prepolymer (with 8% by mass of free NCO groups, use in excess: Index 1.22) and 10.5 g of dioctyltin-bis (- isooctylmercaptoacetate) are mixed homogeneously with a paddle stirrer and applied at a thickness of 200 μm to a grained support with a knife blade and subsequently cured at 160 ° C. for 4 minutes.

The composite sheet materials thus produced were examined for their cold flexibility, abrasion resistance, and volatile toxic substance content. The following test methods were used for this purpose: Flexibility or cold flexibility according to the Ballyfex test (DIN 53351 (2003)) at +20 and -10 ° C. with determination of the cycles without visible surface damage, i. at the maximum the grade 1 or 2 (grading according to DIN 16922) is reached. - Abrasion resistance in the saddle abrasion test (GMW 14125-Coding G): Determination of the strokes without damaging the surface. The saddle abrasion test simulates, in a very good way, the abrasion stress experienced by an automobile seat during its lifetime. Resists a reference material of a load of at least 4000 strokes, it is assumed that a sufficient abrasion resistance over the automotive life.

- Determination of volatile toxic substances: Evidence of individual substance analysis in the test according to VDA 278 (VOC and Fog value). No substances considered to be toxic or as a CMR substance shall be detectable in an amount greater than or equal to 1 ppm (CMR = carcinogenic, mutagenic or reprotoxic substance, divided into categories of 1 to 3 depending on proven harmfulness).

The results are shown in Table 1. Table 1

From Table 1, it can be seen that although the composite layer materials according to the comparative examples often still a relatively high abrasion resistance can be achieved, the flexibility and especially the low flexibility of the comparative examples in any case that is sufficient. For example, automakers are demanding at least 30,000 - 50,000 cycles without damage at -10 ° C in the Ballyflex test. Only the inventive examples 1 to 3 show a particularly high low-temperature flexibility with very high abrasion resistance, at the same time no volatile toxic substances could be detected.

Claims

claims

1. Composite layer material, comprising at least the following layers:

a textile carrier layer (5),

a laminating layer (4) connected to the textile carrier layer (5),

a polyurethane intermediate layer (3) based on an unblocked high-solid polyurethane system,

a polyurethane cover layer (2),

- And at least one outwardly facing on the polyurethane cover layer (2) applied paint layer (1) based on polyurethane and / or acrylate polymers, characterized in that the polyurethane cover layer (2) on a

solvent-free or low-solvent high-solid polyurethane system based, the a) polyfunctional isocyanates and / or polyfunctional isocyanate prepolymers and b) at least one polyfunctional hydroxyl-containing compound based on polytetra-, polypenta and / or polyhexamethylene glycol and

c) has at least one metallic catalyst.

2. Composite layer material according to claim 1, characterized in that for the

Polyurethane top layer (2) a high-solid polyurethane system with a

Solvent content of less than 10 percent by mass is used.

3. Composite layer material according to claim 1 or 2, characterized in that the polyfunctional isocyanates and / or polyfunctional isocyanate prepolymers of the solvent-free or low-solvent high-solid polyurethane system of

Polyurethane top layer (2) have a degree of functionalization of 2 or higher and a content of free isocyanate groups between 4 and 20 mass percent.

4. Composite layer material according to at least one of the preceding claims,

characterized in that the at least one polyfunctional

hydroxyl-containing compound based on polytetramethylene glycol.

5. Composite layer material according to at least one of the preceding claims, characterized in that the at least one metallic catalyst catalyses the polyurethane formation reaction delayed only at a temperature of more than 100 ° C.

6. Composite layer material according to at least one of the preceding claims,

characterized in that at least one of the paint layers (1) is crosslinked.

7. Composite layer material according to at least one of the preceding claims,

characterized in that the laminating layer (4) and / or the

Polyurethane interlayer (3) to be substantially solvent-free

Base substances are based.

8. Composite layer material according to at least one of the preceding claims,

characterized in that the polyurethane intermediate layer (3) is foamed.

9. Composite layer material according to at least one of the preceding claims,

characterized in that isocyanate prepolymers are used for the polyurethane intermediate layer (3).

10. Composite layer material according to at least one of the preceding claims,

characterized in that the textile carrier layer (5) contains flame-resistant textiles.

11. Composite layer material according to at least one of the preceding claims,

characterized in that the individual layers have the following layer thicknesses:

Laminating layer (4): 1 to 400 μιη

Polyurethane interlayer (3): 50 to 1000 μιη

Polyurethane top layer (2): 20 to 1000 μιη

Lacquer layer (1): 1 to 100 μιη

12. A method for producing the composite sheet material according to claim 1 by a reverse coating method.

13. Use of the composite layer material according to claim 1 as a decorative

Interior materials, in particular as surface-structured cover materials.