WO2012038200A1 - Prepregs on the basis of a storage-stable reactive or highly reactive polyurethane composition - Google Patents

Abstract

The invention relates to prepregs, which are chromatically adjusted with pigment or dye preparations, on the basis of a storage-stable reactive or highly reactive polyurethane composition.

Description

 Prepregs based on storage-stable reactive or highly reactive

polyurethane composition

The invention relates to prepregs colored with pigment or dyestuff formulations on the basis of storage-stable reactive or highly reactive polyurethane compositions.

Prepregs based on storage-stable reactive or highly reactive

Polyurethane compositions are known from DE 102009001793, DE 102009001806,

DE 10201029355 known.

The object of the present invention was to enable the production of color-adjusted prepregs based on storage-stable reactive or highly reactive polyurethane composition.

The object of the present invention is accomplished with pigment or dye preparations suitable for powder coating applications which are used in prepreg preparation in the matrix material composition on the basis of storage-stable reactive or highly reactive

Polyurethane compositions are already included.

The invention relates to colored prepregs,

essentially made up of

 A) at least one fiber-shaped carrier

and

 B) at least one reactive or highly reactive polyurethane composition as

 Matrix material,

 the polyurethane compositions essentially comprising mixtures of a polymer having isocyanate-reactive functional groups b) as binder and internally blocked and / or blocked blocking agents with di- or polyisocyanate as hardener a),

 wherein the matrix material in addition

 1. Pigments with particle diameter of <150 nm

 and or

 2. Dyes

 contains.

The preparation of the prepregs can be done in principle by any method. Suitably, a powdery polyurethane composition B) containing the dyes or pigments is by powder impregnation, preferably by a

Scattering applied to the carrier. Also possible are vortex sintering, pultrusion, or spraying. The powder (total or fraction) is preferably spread over the fiber-shaped carrier, for. B. on webs of glass, carbon, or aramid fiber fabric / fabric, applied and then fixed. In order to avoid powder losses, the fiber-shaped carrier, which is acted upon with powder, is preferably heated directly after the scattering process in a heating section (eg with IR emitters) so that the particles are sintered, whereby temperatures of 80 to 100 ° C. are not exceeded should prevent the reaction of the highly reactive matrix material. These prepregs can be combined and cut to different shapes as needed.

The prepregs can also be produced by the direct melt impregnation method. The principle of the direct melt impregnation method of the prepregs is that first of all a reactive or highly reactive polyurethane composition B) containing the dyes or pigments of their individual components in the

Melt is produced. This melt of the dyes or pigments containing reactive polyurethane composition B) is then applied directly to the fiber-shaped carrier A), that is, there is an impregnation of the fiber-shaped carrier A) with the melt from B). Thereafter, the cooled storable prepregs can be further processed into composites at a later date. By direct melt impregnation method according to the invention there is a very good impregnation of the fiber-shaped carrier, due to the fact that the case of liquid low viscous reactive

Polyurethane compositions very well wet the fiber of the wearer.

The prepregs can also be produced by means of a solvent. The principle of the process for the production of prepregs is then that first a solution or a dispersion which contains the dyes or pigments, reactive or highly reactive polyurethane composition B) is prepared from their individual components, in a suitable common solvent. This solution or dispersion of the reactive polyurethane composition B) is then applied directly to the fiber-shaped carrier A), wherein the fiber-shaped carrier is impregnated / impregnated with this solution. Subsequently, the solvent is removed. The solvent is preferably completely removed at low temperature, preferably <100 ° C., by, for example, thermal treatment or vacuum application. After that they can be freed again from the solvent storable prepregs are later processed into composites. By the inventive method is a very good impregnation of the fiber-shaped carrier, due to the fact that the solutions of the reactive

Polyurethane compositions very well wet the fiber of the wearer.

As suitable solvents for the process according to the invention, it is possible to use all aprotic liquids which are not reactive towards the reactive ones

Polyurethane compositions are, have a sufficient solubility against the individual components of the reactive polyurethane composition used and in the process step of the solvent removal to the slightest trace (<0.5% by weight) of the reactive

Polyurethane composition impregnated prepreg can be withdrawn, with a recycling of the separated solvent is advantageous.

Examples include: ketones (acetone, methyl ethyl ketone,

Methyl isobutyl ketone, cyclohexanone), ether (tetrahydrofuran), esters (n-propyl acetate, n-butyl acetate, isobutyl acetate, 1,2-propylene carbonate, propylene glycol methyl ether acetate).

After cooling to room temperature, the prepregs according to the invention have a very high storage stability at room temperature as soon as the matrix material has a Tg of at least 40 ° C. This is depending on the contained reactive

Polyurethane composition at least a few days at room temperature, but usually the prepregs are storage stable for several weeks at 40 ° C and below. The prepregs produced in this way are not sticky and therefore very easy to handle and continue to process. The inventively used reactive or highly reactive

Accordingly, polyurethane compositions have very good adhesion and distribution on the fiber-shaped carrier.

During the further processing of prepregs to composites z. B. by pressing at elevated temperatures, there is a very good impregnation of the fiber-shaped carrier, due to the fact that the liquid low viscous reactive or highly reactive polyurethane compositions before the crosslinking reaction wet the fiber of the carrier very well before by the crosslinking reaction of the reactive or highly reactive Polyurethane composition at elevated temperatures, a gelling occurs or cures the complete polyurethane matrix.

The prepregs produced in this way can be combined and cut to different shapes as needed. To consolidate the prepregs into a single composite and to crosslink the matrix material to the matrix, the prepregs are cut, optionally sewn or otherwise fixed and pressed in a suitable mold under pressure and, if appropriate, by applying a vacuum. In the context of this invention, this process of producing the composites from the prepregs takes place depending on the curing time at temperatures above about 160 ° C when using reactive matrix materials (variant I), or in with

corresponding catalysts provided highly reactive matrix materials (variant II) at temperatures above 100 ° C.

Depending on the composition of the used reactive or highly reactive

Polyurethane composition and optionally added catalysts, both the speed of the crosslinking reaction in the production of the composite components and the properties of the matrix can be varied within wide ranges.

In the context of the invention, the reactive or highly reactive polyurethane composition used for producing the prepregs is defined as matrix material, and in the description of the prepregs, the still reactive or highly reactive polyurethane composition applied to the fiber by the process according to the invention.

The matrix is defined as the composite crosslinked matrix materials from the reactive or highly reactive polyurethane compositions.

carrier

 The fiber-shaped carrier in the present invention consists of fiber-shaped material (also often called reinforcing fibers). In general, any material that makes up the fibers is suitable, but is preferably fiber material made of glass, carbon, plastics, such. As polyamide (aramid) or polyester, natural fibers or mineral fiber materials such as basalt fibers or ceramic fibers (oxide fibers based on aluminum oxides and / or silicon oxides) used. Also mixtures of fiber types, such as. B. fabric combinations of aramid and glass fibers, or

Carbon and glass fibers can be used. Likewise, hybrid composite components with prepregs of different fiber-shaped carriers can be produced.

Glass fibers are the most commonly used fiber types mainly because of their relatively low price. In principle, here are all types of glass-based

Reinforcing fibers suitable (E-glass, S-glass, R-glass, M-glass, C-glass, ECR-glass, D-glass, AR-glass, or hollow glass fibers). Carbon fibers generally come in High-performance composites are used, where the lower density in relation to the glass fiber and at the same time high strength is an important factor. Carbon fibers (also carbon fibers) are industrially produced carbon-containing fibers

Starting materials that are converted by pyrolysis into graphitic carbon. A distinction is made between isotropic and anisotropic types: isotropic fibers have only low strength and less technical importance, anisotropic fibers show high strength and stiffness with low elongation at break. Natural fibers are here all textile fibers and fiber materials, which are derived from vegetable and animal material (eg., Wood, cellulose, cotton, hemp, jute, linen, sisal, bamboo fibers). Similar to carbon fibers, aramid fibers have a negative coefficient of thermal expansion and thus become shorter when heated. Their specific strength and elastic modulus are significantly lower than that of carbon fibers. In conjunction with the positive expansion coefficient of the matrix resin can be manufactured dimensionally stable components. Compared to carbon fiber reinforced plastics, the compressive strength of aramid fiber composites is significantly lower. Known brand names for aramid fibers are Nomex® and Kevlar® from DuPont, or Teijinconex®, Twaron® and Technora® from Teijin. Particularly suitable and preferred are carriers made of glass fibers, carbon fibers, aramid fibers or ceramic fibers. The fiber-shaped material is a textile fabric. Suitable fabrics are nonwoven fabrics, as well as so-called knits, such as knitted fabrics and knits, but also non-meshed containers such as fabrics, scrims or braids.

In addition, a distinction long fiber and short fiber materials as a carrier. Also suitable according to the invention are rovings and yarns. All materials mentioned are suitable in the context of the invention as a fiber-shaped carrier. An overview of

Reinforcing fibers contains "Composites Technologies, Paolo Ermanni (Version 4), Script for the Lecture ETH Zurich, August 2007, Chapter 7".

matrix material

In principle, all, even other storage-stable storage-stable reactive or highly reactive polyurethane compositions are suitable as matrix materials. According to the invention, suitable polyurethane compositions consist of mixtures of a functional group-reactive with respect to NCO groups-containing polymers b) (binder), also referred to as a resin, and temporarily deactivated, ie internally blocked and / or blocked with blocking agents, di- or polyisocyanates, too as hardener a) (component a)). Suitable functional groups of the polymers b) (binders) are hydroxyl groups, amino groups and thiol groups which react with the free isocyanate groups with addition and thus crosslink and harden the polyurethane composition. The

Binder components must have a solid resin character (glass transition temperature greater than room temperature). Suitable binders are polyesters, polyethers, polyacrylates, polycarbonates and polyurethanes having an OH number of 20 to 500 mg KOH / gram and an average molecular weight of 250 to 6000 g / mol. Particularly preferred

hydroxyl-containing polyesters or polyacrylates having an OH number of 20 to 150 mg KOH / gram and an average molecular weight of 500 to 6000 g / mol.

Of course, mixtures of such polymers can be used. The amount of polymers b) containing the functional groups is selected such that each functional group of component b) contains 0.6 to 2 NCO equivalents or 0.3 to 1 uretdione group of component a).

As hardener component a) blocked or internally blocked (uretdione) di- and polyisocyanates are used with blocking agents.

 The diisocyanates and polyisocyanates used according to the invention can consist of any desired aromatic, aliphatic, cycloaliphatic and / or (cyclo) aliphatic di- and / or polyisocyanates.

As aromatic di- or polyisocyanates, in principle, all known aromatic compounds are suitable. Particularly suitable are 1, 3 and 1, 4-phenylene diisocyanate, 1, 5-naphthylene diisocyanate, tolidine diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate ( 2,4'-MDI), 4,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates (MDI) and oligomers

Diphenylmethane diisocyanates (polymer-MDI), xylylene diisocyanate,

Tetramethylxylylene diisocyanate and triisocyanatotoluene.

Suitable aliphatic di- or polyisocyanates advantageously have 3 to 16

Carbon atoms, preferably 4 to 12 carbon atoms, in the linear or branched alkylene radical and suitable cycloaliphatic or (cyclo) aliphatic diisocyanates advantageously 4 to 18 carbon atoms, preferably 6 to 15 carbon atoms, in the cycloalkylene radical. Under (cyclo) aliphatic diisocyanates, the skilled worker understands at the same time cyclic and aliphatic bound NCO groups, as z. B. isophorone diisocyanate is the case. In contrast, is meant by cycloaliphatic diisocyanates those which have only directly attached to the cycloaliphatic ring NCO groups, for. B. H ₁₂ MDI. Examples are cyclohexane diisocyanate, Methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, propane diisocyanate, butane diisocyanate,

Pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate,

Nonane diisocyanate, nonane triisocyanate, such as 4-isocyanatomethyl-1, 8-octane diisocyanate (TIN), decane and triisocyanate, undecanediol and triisocyanate, dodecanedi and triisocyanates.

Preference is given to isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI),

Diisocyanatodicyclohexylmethane (H ₁₂ MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI). Very particular preference is given to using IPDI, HDI, TMDI and / or H ₁₂ MDI, the isocyanurates also being usable. Also suitable are 4-methyl-cyclohexane-1, 3-diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 3 (4) - isocyanatomethyl-1-methylcyclohexyl isocyanate, 2-Isocyanatopropylcyclohexyl isocyanate, 2,4'-methylenebis (cyclohexyl ) diisocyanate, 1, 4-diisocyanato-4-methyl-pentane.

Of course, mixtures of di- and polyisocyanates can be used.

Furthermore, preference is given to using oligoisocyanates or polyisocyanates which are prepared from the abovementioned diisocyanates or polyisocyanates or mixtures thereof by linking by means of urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine , Oxadiazinetrione or iminooxadiazinedione structures.

Particularly suitable are isocyanurates, especially from IPDI and / or HDI.

The polyisocyanates used in the invention are blocked. In question come to external blocking agents such. Ethyl acetoacetate, diisopropylamine,

Methyl ethyl ketoxime, diethyl malonate, ε-caprolactam, 1, 2,4-triazole, phenol or substituted phenols and 3,5-dimethylpyrazole.

 The preferred hardener components are IPDI adducts containing isocyanurate moieties and ε-caprolactam blocked isocyanate structures.

An internal blocking is possible and this is preferably used. The internal blocking takes place via a dimer formation via uretdione structures which, at elevated temperature, split back into the originally present isocyanate structures and thus initiate crosslinking with the binder.

Optionally, the reactive polyurethane compositions may contain additional catalysts. These are organometallic catalysts, such as. B.

Dibutyltin dilaurate (DBTL), tin octoate, bismuth neodecanoate, or tertiary amines such as z. B. 1, 4-diazabicyclo [2.2.2.] Octane, in amounts of 0.001 - 1 wt .-%. These reactive polyurethane compositions used in this invention are used under normal conditions, for. B. with DBTL catalysis, from 160 ° C, usually cured from about 180 ° C and designated as variant I.

For the preparation of the reactive polyurethane compositions customary in powder coating technology additives such as leveling agents, for. As polysilicone or acrylates, light stabilizers z. As sterically hindered amines, or other auxiliaries, such as. As described in EP 669 353, be added in a total amount of 0.05 to 5 wt .-%.

In the context of this invention, reactive (variant I) means that the reactive polyurethane compositions used according to the invention, as described above, cure at temperatures of from 160 ° C., depending on the nature of the carrier.

The reactive polyurethane compositions used in the invention are used under normal conditions, for. B. with DBTL catalysis, from 160 ° C, usually from about 180 ° C cured. The time for curing the inventively used

Polyurethane composition is usually within 5 to 60 minutes.

A matrix material B) is preferably used in the present invention, from a polyurethane compositions B) containing reactive uretdione groups, essentially containing a) at least one curing agent containing uretdione groups, based on

 Polyadditionsverbindungen of aliphatic, (cyclo) aliphatic or

 cycloaliphatic uretdione-containing polyisocyanates and

hydroxyl-containing compounds, wherein the hardener is below 40 ° C. in solid form and above 125 ° C. in liquid form and has a free NCO content of less than 5% by weight and a uretdione content of 3 to 25% by weight, b) at least one hydroxyl-containing polymer which is in liquid form below 40 ° C. in solid form and above 125 ° C. and has an OH number between 20 and 200 mg KOH / gram, c) if appropriate at least one catalyst, d) optionally auxiliaries and additives known from polyurethane chemistry, so that the two components a) and b) are present in the ratio that 0.3 to 1 uretdione group of component a) is required for each hydroxyl group of component b), preferably 0.45 to 0.55. The latter corresponds to an NCO / OH ratio of 0.9 to 1, 1 to 1.

Uretdione group-containing polyisocyanates are well known and are described, for example, in US 4,476,054, US 4,912,210, US 4,929,724 and EP 417,603. A Comprehensive Review of Industrially Relevant Techniques for Dimerization of

Isocyanates to uretdiones provides the J. Prakt. Chem. 336 (1994) 185-200. In general, the reaction of isocyanates to uretdiones takes place in the presence of more soluble

Dimerization catalysts such. For example, dialkylaminopyridines, trialkylphosphines,

Phosphoric acid triamides or imidazoles. The reaction - optionally carried out in solvents, but preferably in the absence of solvents - is stopped when a desired conversion is achieved by addition of catalyst poisons. Excess monomeric isocyanate is subsequently separated by short path evaporation. If the catalyst is volatile enough, the reaction mixture in the course of the monomer separation from

Catalyst can be freed. The addition of catalyst poisons can be dispensed with in this case. In principle, a wide range of isocyanates is suitable for the preparation of polyisocyanates containing uretdione groups. The above di- and polyisocyanates can be used. Preferably, however, di- and

Polyisocyanates of any aliphatic, cycloaliphatic and / or

(cyclo) aliphatic di- and / or polyisocyanates. According to the invention

Isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI),

Diisocyanatodicyclohexylmethane (H ₁₂ MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI). Very particular preference is given to using IPDI, HDI, TMDI and / or H ₁₂ MDI, the isocyanurates also being usable.

Most preferably, IPDI and / or HDI are used for the matrix material. The reaction of these polyisocyanates containing uretdione groups with uretdione-containing curing agents a) involves the reaction of the free NCO groups with

hydroxyl-containing monomers or polymers, such as. As polyesters, polythioethers, polyethers, polycaprolactams, polyepoxides, polyester amides, polyurethanes or low molecular weight di-, tri- and / or tetra alcohols as chain extenders and optionally monoamines and / or monoalcohols as chain terminators and has been frequently described (EP 669 353, EP 669 354 DE 30 30 572, EP 639 598 or EP 803 524). Preferred uretdione hardeners a) have a free NCO content of less than 5% by weight and a content of uretdione groups of 3 to 25% by weight, preferably 6 to 18% by weight (calculated as C2N2O2, molecular weight 84) , Preference is given to polyesters and monomeric dialcohols. Besides the uretdione groups, the hardeners can also

Isocyanurate, biuret, allophanate, urethane and / or urea structures.

In the case of the hydroxyl-containing polymers b), preference is given to using polyesters, polyethers, polyacrylates, polyurethanes and / or polycarbonates having an OH number of 20-200 in mg KOH / gram. Particular preference is given to using polyesters having an OH number of 30-150, an average molecular weight of 500-6000 g / mol, which are below 40 ° C. in solid form and above 125 ° C. in liquid form. Such

Binders have been described, for example, in EP 669 354 and EP 254 152.

Of course, mixtures of such polymers can be used. The amount of the hydroxyl-containing polymers b) is chosen so that each

Hydroxyl group of component b) 0.3 to 1 uretdione group of component a), preferably 0.45 to 0.55, is omitted. Optionally, in the reactive

Polyurethane compositions B) additional catalysts c) may be included. These are organometallic catalysts, such as. As dibutyltin dilaurate, zinc octoate, bismuth neodecanoate, or tertiary amines, such as. B. 1, 4-diazabicyclo [2.2.2.] Octane, in amounts of 0.001 - 1 wt .-%. These reactive used in the invention

Polyurethane compositions are used under normal conditions, e.g. B. with DBTL catalysis, from 160 ° C, usually cured from about 180 ° C and referred to as variant I.

For the preparation of the reactive and highly reactive

Polyurethane compositions may be those customary in powder coating technology

Additives such as leveling agents, eg. As polysilicone or acrylates, light stabilizers z. B.

sterically hindered amines, or other adjuvants, such as. As described in EP 669 353, be added in a total amount of 0.05 to 5 wt .-%.

The reactive polyurethane compositions used in the invention are used under normal conditions, for. B. with DBTL catalysis, from 160 ° C, usually from about 180 ° C cured. The reactive polyurethane compositions used according to the invention provide a very good flow and thus a good impregnating ability and in the

cured state excellent chemical resistance. When using aliphatic crosslinkers (eg IPDI or H ₁₂ MDI) is also a good

Weather resistance reached. Particularly preferred in the invention, a matrix material is used

out

 B) at least one highly reactive uretdione groups

 A polyurethane composition substantially containing

 a) at least one hardener containing uretdione groups

 and

 b) optionally at least one polymer reactive with NCO groups

 functional groups;

 c) 0.1 to 5 wt .-% of at least one catalyst selected from quaternary

 Ammonium salts and / or quaternary phosphonium salts with halogens, hydroxides, alcoholates or organic or inorganic acid anions as counterion;

 and

 d) 0.1 to 5 wt .-% of at least one co-catalyst selected from

 d1) at least one epoxide

 and or

 d2) at least one metal acetylacetonate and / or quaternary

 Ammonium acetylacetonate and / or quaternary phosphonium acetylacetonate; e) optionally known from polyurethane chemistry auxiliaries and additives.

In particular, a matrix material B) is used

B) containing at least one highly reactive powdered Uretdiongruppen

 A polyurethane composition as matrix material, essentially containing a) at least one uretdione group-containing hardener, based on

 Polyadditionsverbindungen of aliphatic, (cyclo) aliphatic or

 cycloaliphatic uretdione groups contained polyisocyanates and

 hydroxyl-containing compounds, wherein the hardener is below 40 ° C. in solid form and above 125 ° C. in liquid form and has a free NCO content of less than 5% by weight and a uretdione content of 3 to 25% by weight, b) at least one hydroxyl-containing polymer which is in liquid form below 40 ° C in solid form and above 125 ° C and has an OH number between 20 and 200 mg KOH / gram;

 c) 0.1 to 5 wt .-% of at least one catalyst selected from quaternary

Ammonium salts and / or quaternary phosphonium salts with halogens, hydroxides, alcoholates or organic or inorganic acid anions as counterion; d) 0.1 to 5 wt .-% of at least one co-catalyst selected from

 d1) at least one epoxide

 and or

 d2) at least one metal acetylacetonate and / or quaternary

 Ammonium acetylacetonate and / or quaternary phosphonium acetylacetonate; e) optionally known auxiliaries and additives from polyurethane chemistry, so that the two components a) and b) are present in the ratio that 0.3 to 1 uretdione group of component a) is required for each hydroxyl group of component b), preferably 0, 6 to 0.9. The latter corresponds to an NCO / OH ratio of 0.6 to 2 to 1 or 1, 2 to 1, 8 to 1. These inventively used highly reactive

 Polyurethane compositions are cured at temperatures of 100 to 160 ° C and referred to as variant II.

According to the invention, suitable highly reactive uretdione-containing polyurethane compositions comprise mixtures of temporarily deactivated, ie uretdione-containing (internally blocked) di- or polyisocyanates, also referred to as hardeners a), and the catalysts c) and d) present in the invention and optionally additionally

functional groups - reactive with NCO groups - having polymer (binder), also referred to as resin b). The catalysts ensure curing of the

Uretdione group-containing polyurethane compositions at low temperature. The uretdione-containing polyurethane compositions are thus highly reactive.

As component a) and b) are used as described above.

As catalysts under c) quaternary ammonium salts are preferred

Tetralkylammonium salts and / or quaternary phosphonium salts with halogens,

Hydroxides, alcoholates or organic or inorganic acid anions as counterion used. Examples are:

 Tetramethylammonium formate, tetramethylammonium acetate,

 Tetramethylammonium propionate, tetramethylammonium butyrate, tetramethylammonium benzoate, tetraethylammonium formate, tetraethylammonium acetate,

 Tetraethylammonium propionate, tetraethylammonium butyrate, tetraethylammonium benzoate, tetrapropylammonium formate, tetrapropylammonium acetate,

Tetrapropylammonium propionate, tetrapropylammonium butyrate,

Tetrapropylammonium benzoate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate and Tetrabutylammonium benzoate and tetrabutylphosphonium acetate, tetrabutylphosphonium formate and ethyltriphenylphosphonium acetate,

Tetrabutylphosphonium benzotriazolate, tetraphenylphosphonium phenolate and trihexyltetradecylphosphonium decanoate, methyltributylammonium hydroxide, methyltriethylammonium hydroxide, tetramethylammonium hydroxide,

Tetraethylammonium hydroxide, tetrapropylammonium hydroxide,

Tetrabutylammonium hydroxide, tetrapentylammonium hydroxide,

Tetrahexylammonium hydroxide, tetraoctylammonium hydroxide,

Tetradecylammonium hydroxide, tetradecyltrihexylammonium hydroxide,

Tetraoctadecylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, tri-methylphenylammonium hydroxide, triethylmethylammonium hydroxide, tri-methylvinylammonium hydroxide,

Methyltributylammonium methoxide, methyltriethylammonium methoxide, tetramethylammonium methoxide, tetraethylammonium methoxide,

Tetrapropylammonium methoxide, tetrabutylammonium methoxide,

Tetrapentylammonium methoxide, tetrahexylammonium methoxide,

Tetraoctylammonium methoxide, tetradecylammonium methoxide,

Tetradecyltrihexylammonium methoxide, tetraoctadecylammonium methoxide, benzyltrimethylammonium methoxide, benzyltriethylammonium methoxide, trimethylphenylammonium methoxide, triethylmethylammonium methoxide, trimethylvinylammonium methoxide, methyltributylammoniumethanolate, methyltriethylammoniumethanolate, tetramethylammoniumethanolate,

Tetraethylammoniumethanolate, tetrapropylammoniumethanolate,

Tetrabutylammonium ethanolate, tetrapentylammonium ethanolate,

Tetrahexylammonium ethoxide, tetraoctylammonium methoxide,

Tetradecylammoniumethanolate, tetradecyltrihexylammoniumethanolate, tetraoctadecylammoniumethanolate, benzyltrimethylammoniumethanolate, benzyltriethylammoniumethanolate, tri-methylphenylammoniumethanolate, triethylmethylammoniumethanolate, tri-methylvinylammoniumethanolate, methyltributylammoniumbenzylate, methyltriethylammoniumbenzylate,

Tetramethylammonium benzylate, tetraethylammoniumbenzylate,

Tetrapropylammonium benzylate, tetrabutylammonium benzylate,

Tetrapentylammonium benzylate, tetrahexylammoniumbenzylate,

Tetraoctylammonium benzylate, tetradecylammoniumbenzylate,

Tetradecyltrihexylammoniumbenzylate, tetraoctadecylammoniumbenzylate, benzyltrimethylammoniumbenzylate, benzyltriethylammoniumbenzylate, trimethylphenylammoniumbenzylate, triethylmethylammoniumbenzylate, tri methylvinylammoniumbenzylat, tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium, benzyltrimethylammonium, tetrabutylphosphonium hydroxide, Tetrabutylphosphoniumfluorid, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide,

Benzyltrimethylammonium chloride, benzyltriethylammonium chloride,

Benzyltripropylammonium chloride, benzyltributylammonium chloride,

Methyltributylammonium chloride, methyltripropylammonium chloride,

Methyltriethylammonium chloride, methyltriphenylammonium chloride,

Phenyltrimethylammonium chloride, benzyltrimethylammonium bromide,

Benzyltriethylammonium bromide, benzyltripropylammonium bromide,

Benzyltributylammonium bromide, methyltributylammonium bromide,

Methyltripropylammonium bromide, methyltriethylammonium bromide,

Methyltriphenylammonium bromide, phenyltrimethylammonium bromide,

Benzyltrimethylammonium iodide, benzyltriethylammonium iodide,

 Benzyltripropylammonium iodide, benzyltributylammonium iodide, methyltributylammonium iodide, methyltripropylammonium iodide, methyltriethylammonium iodide,

Methyltriphenylammonium iodide and phenyltrimethylammonium iodide,

Methyltributylammonium hydroxide, methyltriethylammonium hydroxide,

Tetramethylammonium hydroxide, tetraethylammonium hydroxide,

Tetrapropylammonium hydroxide, tetrabutylammonium hydroxide,

Tetrapentylammonium hydroxide, tetrahexylammonium hydroxide,

Tetraoctylammonium hydroxide, tetradecylammonium hydroxide,

Tetradecyltrihexylammonium hydroxide, tetraoctadecylammonium hydroxide,

Benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide,

Trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide,

Trimethylvinylammonium hydroxide, tetramethylammonium fluoride,

 Tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride and benzyltrimethylammonium fluoride. These catalysts may be added alone or in mixtures. Preference is given to tetraethylammonium benzoate and / or

Tetrabutylammonium hydroxide used.

The proportion of catalysts c) may be 0.1 to 5 wt .-%, preferably from 0.3 to 2 wt .-%, based on the total formulation of the matrix material.

A variant of the invention includes the attachment of such catalysts c) to the functional groups of the polymers b) with a. In addition, these catalysts may be surrounded with an inert shell and encapsulated with it.

As co-catalysts d1) epoxides are used. In question come here z. B.

Glycidyl ethers and glycidyl esters, aliphatic epoxides, diglycidyl ethers based on bisphenol A and glycidyl methacrylates. Examples of such epoxides are triglycidyl isocyanurate (TGIC, trade name ARALDIT 810, Huntsman), mixtures of terephthalic acid diglycidyl ester and trimellitic triglycidyl ester (trade name ARALDIT PT 910 and 912, Huntsman),

Versatic acid glycidyl ester (trade name KARDURA E10, Shell), 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate (ECC), diglycidyl ether based on bisphenol A (trade name EPIKOTE 828, Shell) ethylhexyl glycidyl ether, butyl glycidyl ether, pentaerythritol tetraglycidyl ether, (trade name POLYPOX R 16, UPPC AG) as well as other polypoctypes with free epoxy groups. It can also be used mixtures. Preference is given to using ARALDIT PT 910 and 912 used.

Suitable cocatalysts d2) are metal acetylacetonates. Examples of these are zinc acetylacetonate, lithium acetylacetonate and tin acetylacetonate, alone or in

Mixtures. Zinc acetylacetonate is preferably used.

Also suitable as cocatalysts d2) are quaternary ammonium acetylacetonates or quaternary phosphonium acetylacetonates.

 Examples of such catalysts are tetramethylammonium acetylacetonate,

Tetraethylammonium acetylacetonate, tetrapropylammonium acetylacetonate,

Tetrabutylammonium acetylacetonate, benzyltrimethylammonium acetylacetonate,

Benzyltriethylammonium acetylacetonate, tetramethylphosphonium acetylacetonate,

Tetraethylphosphonium acetylacetonate, tetrapropylphosphonium acetylacetonate,

Tetrabutylphosphonium acetylacetonate, Benzyltrimethylphosphoniumacetylacetonat, Benzyltriethylphosphoniumacetylacetonat. Particularly preferred

Tetraethylammoniumacetylacetonat and / or tetrabutylammonium acetylacetonate used. Of course, mixtures of such catalysts can be used.

The proportion of cocatalysts d1) and / or d2) can be from 0.1 to 5% by weight, preferably from 0.3 to 2% by weight, based on the total formulation of the matrix material.

With the help of the inventively used highly reactive and thus at low temperature curing polyurethane compositions B) can at 100 to 160 ° C. Curing temperature not only saves energy and curing time, but it can also use many temperature-sensitive carrier.

Highly reactive (variant II) in the context of this invention means that the uretdione group-containing polyurethane compositions used according to the invention cure at temperatures of 100 to 160 ° C, depending on the nature of the carrier. This curing temperature is preferably from 120 to 150.degree. C., more preferably from 130 to 140.degree. The time for curing the polyurethane composition used according to the invention is within 5 to 60 minutes.

Contain the highly reactive uretdione used in the invention

Polyurethane compositions B) offer a very good flow and thus a good impregnation and in the cured state an excellent

Chemical resistance. When using aliphatic crosslinkers (eg IPDI or H ₁₂ MDI), a good weathering resistance is additionally achieved.

As pigments, in principle, all known pigments are suitable.

Pigments from known classes of natural and synthetic inorganic pigments are used. As natural pigments come earth colors such. As green soil, yellow ocher or umber in question, as well as mineral colors such. B.

Iron oxides, malachite or cinnabar. In addition, inorganic synthetic pigments such. As carbon black, chromium pigments, cobalt pigments, iron pigments, ultramarine blue, or white pigments such. As titanium dioxide suitable. Also suitable are natural organic pigments and synthetic organic pigments such as azo pigments (brilliant yellow, permanent red), polycyclic pigments (phthalocyanine blue, heliogen green) or diketopyrrolopyrrole pigments. Also suitable are metallic effect pigments or pearlescent pigments.

Examples of such pigments are: Berlin Blue (Pigment Blue 27 Cl 77510), Brilliant Yellow (Pigment Yellow 74 Cl 1 1741), Cadmium Yellow (Pigment Yellow 35 Cl 77205), Cadmium Red (Pigment Red 108 Cl 77202), Chrome Oxide Green (Pigment Green 17 Cl 77288), Cobalt Blue (Pigment Blue 28 Cl 77346), cobalt blue turquoise bright (Pigment Blue 36 Cl 77343), cobalt violet light (Pigment Violet 49 Cl 77362), iron oxide black (Pigment Black 1 1 Cl 77499), Irgazin Red (Pigment Red 254 Cl 561 10), Manganese Violet (Pigment Violet 16 Cl 77742), Phthalocyanine Blue (org.) (Pigment Blue 15 Cl 74160), titanium white (Pigment White Cl 77891), Ultramarine Blue (Pigment Blue 29 Cl 77007), Ultramarine Red A (Pigment Red 259 Cl 77007), Umber (Pigment Brown 7 Cl 77491). Suitable dyes are all known dyes, in particular

Reactive dyes, disperse dyes, pigment dyes, acid dyes,

Developmental dyes, cationic or basic dyes, coupling dyes, mordant dyes, vat dyes, metal complex dyes, substantive dyes.

Important and applicable for the purposes of the invention classes of dyes are anthraquinone dyes, azo dyes, Dioxazinfarbstoffe, Indigo dyes, nitro dyes, nitrosofar, phthalocyanine, sulfur dyes, triphenylmethane.

Specially suitable for powder coating applications dyes and pigments are z. B. in the writings of the Fa. Clariant "Colorants for Powder Coatings" (2005) and BASF. "Colorants and additives from BASF for powder coatings" (2008) listed.

Overall, pigment preparations are preferred since dyes are at least one

have limited light stability or weathering stability, which limit the direct outdoor use of the composite components produced from the correspondingly colored prepregs according to the invention.

The dyes are contained in an amount of 15 to wt .-% in the matrix material B).

Pigments are contained in an amount of 0.5 to 20 wt .-% in the matrix material B).

The preparation of the Matixmaterials can be carried out as follows: The

Homogenization of all components for the preparation of the polyurethane composition B) can be carried out in suitable aggregates, such. As heated stirred tanks, kneaders, or extruders, carried out, with upper temperature limits of 120 to 130 ° C should not be exceeded. The mixture of the individual components preferably takes place in an extruder at temperatures which, although above the melting ranges of the individual

Components are below but below the temperature at which the crosslinking reaction starts. The use directly from the melt or after cooling and production of a powder is then possible. The preparation of the polyurethane composition B) can also be carried out in a solvent by mixing in the abovementioned aggregates.

Subsequently, we processed the matrix material B) depending on the method with the carrier A) to the prepregs. The prepregs according to the invention and the composite components have a fiber volume fraction of greater than 50%, preferably greater than 50-70%, particularly preferably from 50 to 65%.

The reactive or highly reactive used according to the invention as a matrix material

Polyurethane compositions essentially consist of a mixture of a reactive resin and a hardener. This mixture has a Tg of at least 40 ° C after a melt homogenization and usually reacts only above 160 ° C, in the reactive polyurethane compositions, or above 100 ° C in the highly reactive polyurethane compositions to form a crosslinked polyurethane and thus forms the matrix of Composites. This means that the prepregs according to the invention, after their preparation, are composed of the carrier and the applied reactive polyurethane composition as matrix material, which is present in uncrosslinked, but reactive form.

The prepregs are thus stable in storage, usually several days and even weeks and can thus be further processed into composites at any time. This is the essential difference to the two-component systems already described above, which are reactive and not storage-stable, since they immediately begin to react and crosslink after application to polyurethanes.

The preparation of the prepregs according to the invention can be carried out by means of the known systems and apparatuses according to Reaction Injection Molding (RIM), Reinforced Reaction Injection Molding (RRIM), Pultrusinsverfahren, by applying the solution in a roll mill or by means of a hot doctor blade, or other methods.

The invention also relates to the use of prepregs, in particular with fiber-shaped carriers made of glass, carbon or aramid fibers.

The invention also provides the use of the prepregs according to the invention, for the production of composites in boat and shipbuilding, in aerospace engineering, in the automotive industry, for two räd he, preferably motorcycles and bicycles, in the areas

Automotive, Construction, Medical, Sports, Electrical and Electronics,

Power generation plants, eg. B. for rotor blades in wind turbines.

The invention also relates to the prepregs of the invention

manufactured composite components. Examples

Reactive polyurethane composition

 A reactive polyurethane composition having the following formulation was used to make the prepregs and composites.

The comminuted feedstocks from the table are intimately mixed in a premixer and then homogenized in the extruder to a maximum of 130 ° C. This reactive

Polyurethane composition can then be used after milling to prepare the prepregs after the powder impregnation process. For the direct melt impregnation method, the homogenized melt mixture produced in the extruder can be used directly. For the solvent-based process, no upstream melt homogenization is required. DSC measurements

 The DSC investigations (glass transition temperature determinations and

Reaction enthalpy measurements) are carried out with a Mettler Toledo DSC 821 e according to DIN 53765.

The glass transition temperature of the extrudate was determined to be 62 ° C., the reaction enthalpy for the crosslinking reaction in the fresh state was 65.5 J / g

 After crosslinking the matrix of the prepreg, the glass transition temperature rose to 80 ° C and a heat flux for crosslinking was no longer detectable. For the results see Figure 1.

Used fiberglass scrims and fiberglass fabrics:

The following fiberglass scrims and fiberglass scrims were used in the Examples, hereafter referred to as Type I and Type II.

Type I is a canvas E-glass fabric 281 L, article No. 3103 of the company "Schlösser &Cramer" The fabric has a basis weight of 280 g / m ² .

The type II GBX 600 item number 1023 is a sewn biaxial E-glass scrim (-45 / + 45) from the company "Schlösser &Cramer", which refers to two layers of fiber bundles that lie one above the other and This structure is held together by other fibers which, however, are not made of glass The surface of the glass fibers is equipped with a standard sizing which is modified with aminosilane The scrim has a basis weight of 600 g / m ² .

Production of prepregs

 The preparation of the prepregs by means of direct melt impregnation method according to DE 102010029355.

Storage stability of the prepregs

 The storage stability of the prepregs was determined on the basis of the glass transition temperatures and the reaction enthalpies of the crosslinking reaction by means of DSC investigations.

The cross-linking ability of the PU prepregs is not affected by storage at room temperature for a period of 5 weeks. Time (days Tg [° C]

 Storage time)

 2 62

 14 64

 28 62

 35 63 curing

 enthalpy

 Time (days [y / g]

 Storage time)

 2 65

 14 67

 28 67

 35 66

Composite device manufacturing

 The composite components are produced by means of a pressing technique known to the person skilled in the art on a composite press. The direct-melt impregnation method

produced, homogeneous prepregs were pressed on a table press to composite materials. This table press is the Polystat 200 T of the company

Schwabenthan, with which the prepregs are pressed at temperatures between 120 and 200 ° C to the corresponding composite plates. The pressure is varied between normal pressure and 450 bar. Dynamic crimping, d. H. Depending on the component size, thickness and polyurethane composition and thus the viscosity adjustment at the processing temperature, changing pressurizations may prove advantageous for the wetting of the fibers.

In one example, the temperature of the press is increased from 90 ° C during the Aufschmelzphase to 1 10 ° C, the pressure is increased after a melting phase of 3 minutes to 440 bar and then dynamically (7 times with each 1 minute duration) between 150 and 440 bar varies, the temperature is continuously increased to 140 ° C. Subsequently, the temperature is raised to 180 ° C and at the same time the pressure at 350 bar until the removal of the composite component from the press after 30 minutes height, is held. The hard, stiff, chemical-resistant and impact-resistant composite components (Sheet goods) with a fiber volume fraction of> 50% are in terms of

Curing degree (determined by DSC) examined. The determination of

Glass transition temperature of the cured matrix shows the progress of crosslinking at different curing temperatures. In the used

 Polyurethane composition is complete after about 25 minutes, the crosslinking, in which case no reaction enthalpy for the crosslinking reaction is more detectable.

Claims

claims 1. Prepregs, essentially composed of  A) at least one fiber-shaped carrier  and  B) at least one reactive or highly reactive polyurethane composition as matrix material,  the polyurethane compositions essentially comprising mixtures of a polymer having isocyanate-reactive functional groups b) as binder and internally blocked and / or blocked blocking agents with di- or polyisocyanate as hardener a),  wherein the matrix material in addition  1. Pigments with particle diameter of <150 nm  and or  2. Dyes  contains. 2. Prepregs according to claim 1,  wherein the matrix material B) has a Tg of at least 40 ° C. 3. prepregs according to at least one of the preceding claims,  characterized,  the prepregs have a fiber volume fraction of greater than 50%, preferably greater than 50 to 70%, particularly preferably from 50 to 65%. 4. prepregs according to at least one of the preceding claims,  characterized,  that as pigments of the natural and / or synthetic inorganic pigments are included. 5. prepregs according to at least one of the preceding claims,  characterized,  that dyes selected from reactive dyes, disperse dyes,  Pigmentary dyes, acid dyes, developing dyes, cationic or basic dyes, coupling dyes, mordant dyes, vat dyes, Metal complex dyes, substantive dyes, are included. 6. prepregs according to at least one of the preceding claims,  characterized,  that polymers b) with hydroxyl groups, amino groups and thiol groups, in particular polyesters, polyethers, polyacrylates, polycarbonates and polyurethanes having an OH number of 20 to 500 mg KOH / gram and an average molecular weight of 250 to 6000 g / mol, are used. 7. prepregs according to at least one of the preceding claims,  characterized,  that di- or polyisocyanates selected from isophorone diisocyanate (IPDI), Hexamethylene diisocyanate (HDI), diisocyanatodicyclohexylmethane (H12MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate (TMDI) and / or norbornane diisocyanate (NBDI), more preferably IPDI, HDI, TMDI and / or H ₁₂ MDI, where also the isocyanurates are used, can be used as starting compounds for the component a). 8. prepregs according to at least one of the preceding claims,  characterized,  external blocking agents selected from ethyl acetoacetate,  Diisopropylamine, methyl ethyl ketoxime, diethyl malonate, ε-caprolactam, 1, 2,4-triazole, phenol or substituted phenols and / or 3,5-dimethylpyrazole, to  Blocking of a) are used. 9. Prepregs according to at least one of the preceding claims,  characterized,  in that IPDI adducts, the isocyanurate groups and ε-caprolactam blocked isocyanate structures are used as component a). 10. Prepregs according to at least one of the preceding claims,  characterized,  the reactive polyurethane compositions B) contain additional catalysts, preferably dibutyltin dilaurate, zinc octoate, bismuth neodecanoate, and / or tertiary amines, preferably 1,4-diazabicyclo [2.2.2] octane, in amounts of 0.001-1% by weight. 1 1. Prepregs according to at least one of the preceding claims, containing substantially at least one polyurethane matrix composition B) containing at least one reactive uretdione group-containing polyurethane composition  a) at least one hardening agent containing uretdione groups, based on  Polyadditionsverbindungen from aliphatic, (cyclo) aliphatic or cycloaliphatic uretdione groups containing polyisocyanates and  hydroxyl-containing compounds, wherein the hardener is present below 40 ° C. in solid form and above 125 ° C. in liquid form, has a free NCO content of less than 5% by weight and a uretdione content of 3 to 25% by weight,  b) at least one hydroxyl-containing polymer which is in liquid form below 40 ° C. in solid form and above 125 ° C. and has an OH number between 20 and 200 mg KOH / gram,  c) optionally at least one catalyst,  d) optionally auxiliaries and additives known from polyurethane chemistry, so that the two components a) and b) are present in the ratio that 0.3 to 1 uretdione group of component a) is required for each hydroxyl group of component b), preferably 0, 45 to 0.55. Prepregs according to at least one of claims 1 to 9, containing at least one highly reactive powdery uretdione-containing polyurethane composition B) as matrix material, substantially containing a) at least one hardener containing uretdione groups  and b) optionally at least one polymer reactive with NCO groups  functional groups; c) 0.1 to 5 wt .-% of at least one catalyst selected from quaternary  Ammonium salts and / or quaternary phosphonium salts with halogens, hydroxides, alcoholates or organic or inorganic acid anions as counterion; and d) 0.1 to 5 wt .-% of at least one co-catalyst selected from  d1) at least one epoxide  and or  d2) at least one metal acetylacetonate and / or quaternary Ammonium acetylacetonate and / or quaternary phosphonium acetylacetonate; e) optionally known from polyurethane chemistry auxiliaries and additives. 13. Prepregs according to at least one of the preceding claims 1 to 9 or 12 containing at least one highly reactive powdery Uretdiongruppen  Polyurethane composition B) as matrix material, essentially containing a) at least one uretdione group-containing hardener, based on  Polyaddition compounds of aliphatic, (cyclo) aliphatic or cycloaliphatic uretdione groups containing polyisocyanates and hydroxyl-containing compounds, wherein the curing agent is below 40 ° C in solid form and above 125 ° C in liquid form and a free NCO content of less than 5 wt. % and a uretdione content of 3 - 25 wt .-%,  b) at least one hydroxyl-containing polymer which is in liquid form below 40 ° C in solid form and above 125 ° C and has an OH number between 20 and 200 mg KOH / gram;  c) from 0.1 to 5% by weight of at least one catalyst selected from quaternary ammonium salts and / or quaternary phosphonium salts with halogens, hydroxides, alcoholates or organic or inorganic acid anions as counterion;  and  d) 0.1 to 5 wt .-% of at least one co-catalyst selected from  d1) at least one epoxide  and or  d2) at least one metal acetylacetonate and / or quaternary ammonium acetylacetonate and / or quaternary  Phosphoniumacetylacetonat;  e) optionally known auxiliaries and additives from polyurethane chemistry, so that the two components a) and b) are present in the ratio that 0.3 to 1 uretdione group of component a) is required for each hydroxyl group of component b), preferably 0, 6 to 0.9. 14. Use of the prepregs according to at least one of the preceding claims 1 to 13, in particular with fiber-shaped carriers made of glass, carbon or aramid fibers. 15. Use of the prepregs according to at least one of claims 1 to 13,  for the production of composites in boat and shipbuilding, in the air and Spacecraft, in the automotive industry, for bicycles preferred motorcycles and bicycles, in the fields of automotive, construction, medical, sports, electrical and bicycle Electronics industry, power generation plants, such as rotor blades for wind turbines. 16. Composite components produced from prepregs according to at least one of claims 1 to 13.