EP3174694A1 - Efficient production of composite semifinished products and components in a wet pressing method using hydroxy functionalized (meth)acrylates which are duroplastically crosslinked using isocyanates or uretdiones - Google Patents

Abstract

The invention relates to a method for producing composite semi-finished products and components. In order to produce the semifinished products or components, (meth)acrylate monomers, (meth)acrylate polymers, multi-functionalized (meth)acrylates, hydroxy functionalized (meth)acrylate monomers, and/or hydroxy functionalized (meth)acrylate polymers are mixed with di- or poly isocyanates or uretdione materials. The liquid mixture is applied onto fiber materials, such as carbon fibers, glass fibers, or polymer fibers for example, using known methods and polymerized using a first temperature increase, a redox accelerator, or a photo-initiation. After the polymerization process, for example at room temperature or a temperature of up to 120 °C, thermoplastics are produced which can then still be deformed. The hydroxy functionalized (meth)acrylate components can then be crosslinked with the isocyanates or uretdiones which are already present in the system in a press at a second temperature which is at least 20 °C higher than the polymerization temperature. At the same time, the final component is shaped in said press. In this manner, dimensionally stable duroplastics or crosslinked composite components can be produced.

Description

 Efficient production of composite semi-finished products and components in a wet-pressing process using hydroxy-functionalized (meth) acrylates prepared by means of isocyanates or

 Uretdions be thermosetting crosslinked.

Field of the invention

The invention relates to a process for the production of composite semi-finished products and components. For the production of the semifinished products or components, one mixes (meth) acrylate monomers,

(Meth) acrylate polymers, polyfunctionalized (meth) acrylates, hydroxy-functionalized

 (Meth) acrylate monomers and / or hydroxy-functionalized (meth) acrylate polymers with di- or polyisocyanates or with uretdione materials. This liquid mixture is applied by known methods to fibrous material such as e.g. Carbon fibers, glass fibers or polymer fibers applied and by means of a first increase in temperature, a redox accelerator or by means

Photoinitiation started a polymerization.

 After polymerization, e.g. at room temperature or up to 120 ° C, arise thermoplastics or weakly crosslinked systems that can be formed during polymerization or subsequently. The hydroxy-functionalized (meth) acrylate components may then be reacted with the isocyanates or uretdiones already present in the system at a second temperature at least 20 ° C above the polymerization temperature e.g. be networked under molding in a press. At the same time, the shaping of the final component takes place in this press. In this way, dimensionally stable thermosets or networked composite components can be produced. Fiber-reinforced materials in the form of composite materials are already used in many industrial applications, e.g. using wet-lay-up technology, because of its special mechanical properties and low weight used in many applications. In the industrial processing of such systems in particular short cycle times and high storage stability - even at room temperature - needed. Short cycle times are particularly important in terms of short press times of presses and / or other tools, since the investments are particularly high for these devices.

There are various methods for producing composite materials. The methods are not suitable for mass production yet. An already relatively efficient process for the production of composite components is the wet pressing process. Here, fibers with matrix are pressed in a press into a component in final geometry. The impregnation of the fibers is often done directly in the press. This is disadvantageous because it increases the time of use of the press. Initial attempts to carry out the impregnation outside the press have hitherto been cumbersome because matrix material drips from the impregnated preform, the preform is sticky and not dimensionally stable. The impregnated preform can therefore not or only with difficulty be inserted automatically in the press. Partly, the impregnated preforms are therefore frozen and transported frozen in the press. This is costly and cumbersome. State of the art

In addition to polyesters, vinyl esters and epoxy systems, there are a number of specialized resins in the field of crosslinking matrix systems. These include polyurethane resins, which, because of their toughness, damage tolerance and strength, are used in particular for the production of composite profiles via pultrusion processes. A disadvantage is often called the toxicity of the isocyanates used. However, the toxicity of epoxy systems and the hardener components used there is to be regarded as critical. This is especially true for known sensitizations and allergies.

The wet pressing process based on epoxy resins can be found in WO 2014/078219 or WO

2014/078218 be read. Here, the impregnation of the fiber materials with the resin and the curing of the resin with simultaneous shaping in the same tool. Such a procedure has the very big disadvantage of a very long tool document time. Another disadvantage is that the resulting high waste, must be discarded or disposed of to matrix-crosslinked fiber material.

Prepregs and composites based thereon based on epoxy systems are described, for example, in WO 98/5021 1, EP 309 221, EP 297 674, WO 89/04335 and US 4,377,657. In WO 2006/043019 a process for the production of prepregs based on

Epoxy resin polyurethane powders described. Furthermore, prepregs based on powdered thermoplastics are known as matrix. WO 99/64216 describes prepregs and composites as well as a method for their production in which emulsions with polymer particles of such small size are used that a single-fiber covering is made possible. The polymers of the particles have a viscosity of at least 5000 centipoise and are either thermoplastics or crosslinking polyurethane polymers.

EP 0590702 describes powder impregnations for the production of prepregs in which the powder consists of a mixture of a thermoplastic and a reactive monomer or prepolymer. WO 2005/091715 likewise describes the use of thermoplastics for the production of prepregs.

Prepregs with a matrix based on 2-component polyurethanes (2-K-PUR) are also known. The category of 2-component PU essentially comprises the classic reactive polyurethane resin systems. In principle, it is a system of two separate components. While the governing component of one component is always one

Polyisocyanate, such as polymeric methylene diphenyl diisocyanates (MDI), these are in the second component polyols or in recent developments and amino or amine-polyol mixtures. Both parts are mixed together just before processing. Then the Chemical curing by polyaddition to form a network of polyurethane or polyurea. 2-component systems have a limited processing time (pot life) after mixing of both components, since the onset of reaction leads to a gradual increase in viscosity and finally to gelation of the system. Numerous influencing factors determine the effective time of its processability: reactivity of the reactants, catalysis, concentration, solubility, moisture content, NCO / OH ratio and

Ambient temperature are the most important [see: Lackharze, Stoye / Friday, Hauser-Verlag 1996, pages 210/212]. The disadvantage of prepregs based on such 2-component PUR systems is that only a short time is available for processing the prepreg into a composite. Therefore, such prepregs are not stable for several hours, let alone days storage.

Apart from the different binder base, moisture-curing paints correspond largely to analogous 2K systems both in their composition and in their properties. In principle, the same solvents, pigments, fillers and auxiliaries are used. Unlike 2K paints, these systems tolerate before they are applied

Stability reasons no moisture.

DE 102009001793.3 and DE 102009001806.9 disclose a process for the preparation of storage-stable prepregs, essentially composed of A) at least one fibrous carrier and B) at least one reactive powdery polyurethane composition

Matrix material described.

 The systems can also have poly (meth) acrylates as cobinders or polyol components. In DE 102010029355.5, such compositions are characterized by a

Direct melt impregnation method spent in the fiber material. In DE 102010030234.1 by pretreatment with solvents. Disadvantage of these systems is the high melt viscosity or the use of solvents, which must be removed in the meantime, or may also bring disadvantages in terms of toxicology.

task

The object of the present invention in the light of the prior art was to provide a new technology for the production of composite semi-finished products or components, which compared to the prior art shorter cycle times or shorter press and / or Werkzeugbelegzeiten allow in the production.

In particular, intermediates of the process should be storage stable for several days or weeks prior to final cure.

Furthermore, a simple transport of the intermediate stages, hereinafter also referred to as a preform, without gluing or loss of shape, eg with a robot arm, be possible. Furthermore, the present invention has the object, in the production of

Composites produce less waste and the resulting waste of a

To make further use accessible. In particular, it was an object of the present invention to provide an accelerated process for the production of composite semifinished products or components which makes it possible to impregnate the fiber material outside the shaping press without special measures being taken when transferring it to the press or a tool. such as a strong cooling would have to be made possible.

Further, not explicitly mentioned tasks may result from the description, the examples and the claims.

solution

The tasks are solved by means of a novel process for the production of composite semi-finished products and their further processing into molded parts. This novel method has the following method steps:

I. Preparation of a liquid, reactive composition,

 II. Direct impregnation of a fibrous carrier with the composition of I.

 III. Polymerization of monomer components in the liquid composition at a temperature T-i, and optional preliminary shaping,

IV. Final shaping of the later molded part in a press and / or in another tool and

V. simultaneous curing of the isocyanate component in the composition in this press at a temperature T ₂ , which is at least 20 ° C higher than the temperature Ti in step III.

Between process steps III. and IV. The semi-finished product can optionally be stored for a longer period of time. Furthermore, the semifinished product can be tempered between these two process steps at a temperature, for example, between 30 and 100.degree. C., preferably between 40 and 70.degree.

The liquid, reactive composition consists essentially of the following

components:

 A) A (meth) acrylate-based reactive resin component containing at least one

(Meth) acrylate monomer and at least one poly (meth) acrylate, wherein at least one component of the resin component has hydroxy groups.

B) at least one blocked di- or polyisocyanate and / or at least one uretdione as isocyanate component. With the formulation described can be in step III. dry, storage-stable and optionally dimensionally stable impregnated prepregs or preforms - hereinafter referred to as

Intermediate product - manufacture outside the press.

With the in step III. The liquid mixture used is impregnated well outside the press, e.g. in a lower mold, and not in the actual pressing tool, which is used in the process steps IV and V. In this case, this sub-form simultaneously one of several sub-forms of the press train, which are driven with the intermediate product in each case in the press represent. Alternatively, a diaphragm forming technique may be used here.

The mixture is polymerized with or without temperature supply outside the press. The result is a thermoplastic semi-finished, which is dry and not sticky. This thermoplastic semifinished product shows when removed from the lower mold good dimensional stability can be automatically removed from the lower mold and placed in the hot press. It is also possible to insert several layers of these thermoplastic semi-finished products in the press. Furthermore, other layers, e.g. made of metal, wood, plastics or other material to be inserted into the press. For example, so-called inserts can be used to realize cable ducts or bolting points in the later molded part. At this point in the process, trimming or trimming of the semifinished product is also possible.

In the press under temperature, the hydroxy-functionalized (poly) (meth) acrylates are crosslinked with the isocyanates, which are formed at temperature T ₂ from the uretdiones already present in the system or blocked isocyanates, so that a dimensionally stable thermoset component is formed.

The amount ratio of the resin component A) to the isocyanate component B) is preferably between 90:10 and 40:60. Most preferably, the resin component and the isocyanate component are present in such a proportion to each other

 Hydroxy group of the resin component A) 0.3 to 1, 0, preferably 0.4 to 0.8, particularly preferably 0.45 to 0.65 uretdione groups this corresponds to 0.6 to 2.0, preferably 0.8 to 1, 8 and particularly preferably 0.9 to 1.3 externally blocked isocyanate groups of the isocyanate component are omitted. It should be noted at this point that the resin component in addition to the

According to the invention contained (meth) acrylate monomers and poly (meth) acrylates may also contain other ingredients that contribute to the OH number. These include in particular the optionally contained, described below polyols.

In this case, the resin component A) is at least composed of 30% by weight to 100% by weight of monomers and 0% by weight to 70% by weight of prepolymers. The term monomers includes

(Meth) acrylates and monomers which can be copolymerized with (meth) acrylates and which are in this Balance is not crosslinking agents, ie di-, tri- or oligo- (meth) acrylates, or is urethane (math) acrylates.

The resin component is in particular at least composed of 0 to 10% by weight, preferably 0 to 3% by weight, of crosslinking agent, which is preferably a di-, tri- or oligo-

(Meth) acrylate, 20 to 100% by weight, preferably 30 to 90% by weight, particularly preferably 35 to 80% by weight and particularly preferably 40 to 60% by weight of monomers, 0 to 20% by weight, preferably 1 to 10% by weight of urethane ( meth) acrylates, 0 to 70% by weight, preferably 5 to 40% by weight and particularly preferably 10 to 30% by weight of one or more prepolymers and 0 to 10% by weight, preferably 0.5 to 8% by weight and more preferably 1, 5 to 5% by weight of one or more initiators. In a particular embodiment, the resin may further contain 0 to 50% by weight, preferably 5% to 30% by weight and more preferably to 25% by weight of one or more polyols. The exact selection of these polyols will be described below. The advantage of this system according to the invention lies in the production of a deformable thermoplastic semifinished product / prepreg, which is thermoset crosslinked in a further step during the production of the composite components. The starting formulation is liquid and thus suitable for the impregnation of fiber material without the addition of solvents. The semi-finished products are stable in storage at room temperature. The resulting moldings have a, compared to other polyurethane systems, increased heat resistance. Compared to common epoxy systems, they are characterized by greater flexibility. In addition, such matrices can be designed to be light-stable and thus used for the production of visible carbon parts without further painting.

 Furthermore, the molded parts according to the invention have the great advantage over the prior art that they can be produced with less waste, or the resulting waste can be reused and mostly does not have to be disposed of. In the current single-stage processes according to the prior art, the cutting of the component or the deburring takes place after the production of the component. The separated material consisting of the crosslinked matrix and the fibers used in these cases can not continue to be used to add value and is e.g. supplied to the thermal disposal. In the present

Case may be the blank of the thermoplastic semi-finished. The blend can be reused in other processes, such as SMC, where short cut fibers are used.

Another advantage of the present invention is that the method without the

Use of clamping frame can be performed. As a result, significantly less material overhangs, which are later separated as waste, fall in this process.

Surprisingly, it was found that sufficiently impregnated, reactive and storage-stable

Composite semifinished products can be prepared by making them with the above combination of a (meth) acrylate reaction resin and an isocyanate component.

This gives composite semi-finished products with at least the same but also improved processing properties compared with the prior art, which are more efficient for the production Composite can be used for a wide variety of applications in the construction, automotive, aerospace, power engineering (wind turbine) and marine and shipbuilding industries. The reactive compositions which can be used according to the invention are environmentally friendly, cost-effective, have good mechanical properties, are easy to process and, after hardening, are distinguished by a good weather resistance and by a balance between hardness and flexibility.

Further advantages of the present invention are that during shaping e.g. can use cheap sub-forms or diaphragms instead of only expensive to produce pressing tools.

 In addition, a particularly good impregnation of the carrier material by using a low-viscosity composition is possible.

 Furthermore, a partial reaction takes place, in the form of polymerization outside the press. This automation of the process are much easier to implement.

Furthermore, the intermediate from process step III. not sticky, dry, especially stable in form and storage. Thus, an automated transfer of this intermediate product in the press is easy to carry out. Thus, and by the other advantages of the present invention, in particular the cycle time in the press is significantly shortened. This is especially possible because both the impregnation and parts of the reaction take place outside the press.

In addition, the intermediate can be stacked from step III, sawn, post-processed and preformed before step IV.

In addition, in this process step, waste from the inventive

Molded part are incorporated. However, such an approach is less preferred than using the blend in other SMC processes with short fiber material.

It has been found, particularly surprisingly, that a production of these composite semi-finished products that is significantly faster than the prior art is possible by the method according to the invention. The shaping in process step IV. Can take place on an already solid and easy to transport intermediate. Only when the shaping has taken place, then in step V. then the final curing to the finished composite semi-finished product. This method has the additional advantage that it can be automated very well continuously. So it is possible in particular the first curing of the

Process step III. on the one hand and the shaping and final hardening in the

 On the other hand, to carry out process steps IV. And V. in separate devices. As a result, the cycle times compared to the prior art, with only one curing step, in addition significantly shorten. Furthermore, the method is thus feasible in a continuously operated production line.

The term composite semi-finished products is used in the context of this invention synonymous with the terms prepreg, preform or organic sheet. A prepreg is usually a precursor for thermoset composite components. An organic sheet is usually a precursor for thermoplastic composites.

The carrier material

The fibrous carrier in the present invention is made of fibrous material (also commonly called reinforcing fibers). In general, any material making up the fibers is suitable, but fibrous 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, e.g. Fabric combinations of aramid and glass fibers, or carbon and glass fibers may be used. Likewise, hybrid composite components with prepregs of different fibrous carriers can be produced.

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

M-glass, C-glass, ECR-glass, D-glass, AR-glass or hollow glass fibers). Carbon fibers are generally used in high performance composites, where lower density relative to glass fiber and high strength are also important factors.

Carbon fibers (also carbon fibers) are industrially produced fibers from carbonaceous raw materials which 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. As natural fibers here are all

Refers to textile fibers and fibrous materials derived from vegetable and animal material (e.g., wood, cellulose, cotton, hemp, jute, linen, sisal, bamboo fibers). Aramid fibers have a negative, similar to carbon fibers

 Thermal expansion coefficients, so become shorter when heated. Their specific strength and elastic modulus are significantly lower than those 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 is the

Compressive strength of aramid fiber composite materials significantly lower. Known brand name for aramid fibers are Nomex ^® and Kevlar ^® from DuPont, or Teijinconex ^®, Twaron ^® and Technora ^® from Teijin. Particularly suitable and preferred are carriers of glass fibers, carbon fibers, aramid fibers or ceramic fibers. The fibrous 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 fibrous carrier. An overview of

Reinforcing fibers contains "Composites Technologies", Paolo Ermanni (Version 4), Script for the Lecture ETH Zurich, August 2007, Chapter 7. The support material is usually preformed before process step II by placing it in the lower mold, the press or the tool.

isocyanate

As the isocyanate component, blocked diisocyanates or polyisocyanates internally blocked as second embodiments are used as the first embodiment with blocking agents. The internally blocked isocyanates are so-called uretdiones.

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. A list of possible di- and polyisocyanates and reagents for their external blocking can be found in the German patent application DE 102010030234.1.

The external blocking agents for the di- or polyisocyanates are preferably ethyl acetoacetate, diisopropylamine, methyl ethyl ketoxime, diethyl malonate, ε-caprolactam, 1, 2,4-triazole, phenol or substituted phenols and / or 3,5-dimethylpyrazole.

The polyisocyanates used according to the invention are externally blocked in a first embodiment. In question come to external blocking agents, such as in DE

102010030234.1 are found. In the used in this embodiment di- or

Polyisocyanates, are preferably hexamethylene diisocyanate (HDI),

Diisocyanatodicyclohexylmethane (H ₁₂ MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate (TMDI) and / or norbornane diisocyanate (NBDI), wherein the isocyanurates can also be used. preferred

Blocking agents are 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. The particularly preferred hardener components are isophorone diisocyanate (IPDI) adducts containing isocyanurate moieties and ε-caprolactam blocked isocyanate structures. In addition, the isocyanate component may be 0.01 to 5.0% by weight, preferably 0.1 to 5.0% by weight.

Catalysts included. Organometallic compounds such as dibutyltin dilaurate, zinc octoate or bismuth neodecanoate, and / or tertiary amines, particularly preferably 1,4-diazabicyclo [2.2.2.] Octane, are preferably used as catalysts. Tertiary amines are used in particular in concentrations between 0.001 and 1% by weight. These reactive polyurethane compositions used according to the invention can be cured, for example, under normal conditions, for example with DBTL catalysis, from 160 ° C., usually from about 180 ° C. In a second, preferred embodiment, the isocyanate components are present with an internal block. 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.

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 processes for the dimerization of isocyanates to uretdiones is provided by J. Prakt. Chem. 336 (1994) 185-200. In general, the reaction of isocyanates to uretdiones in the presence of soluble dimerization catalysts such. B.

 Dialkylaminopyridinen, trialkylphosphines, phosphorous 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 can be freed from the catalyst in the course of the monomer separation. The addition of catalyst poisons can be dispensed with in this case. Basically, for the production of uretdione-containing

Polyisocyanates suitable for a wide range of isocyanates. The above di- and polyisocyanates can be used.

Preferred for both the embodiment of the externally blocked isocyanates and for the embodiment of the uretdiones 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) used. Very particular preference is given to using IPDI, HDI, TMDI and H ₁₂ MDI, it also being possible to use the isocyanurates. Most preferably, IPDI and HDI are used for the matrix material. The reaction of these polyisocyanates containing uretdione groups with uretdione group-containing curing agents a) involves the reaction of the free NCO groups with hydroxyl-containing monomers or polymers. Preferred uretdione hardeners a) have a free NCO content of less than 5% by weight and a content of uretdione groups of 3 to 60% by weight, preferably 10 to 40% by weight (calculated as C ₂ N ₂ O ₂ , molecular weight 84). Preference is given to polyesters and monomeric dialcohols. In addition to the uretdione groups, the hardeners may also have isocyanurate, biuret, allophanate, urethane and / or urea structures.

The isocyanate component is preferably below 40 ° C in solid form and above 125 ° C in liquid form. Optionally, the isocyanate component further from the Polyurethane chemistry known adjuvants and additives. With respect to the uretdione-containing embodiment, the isocyanate component has a free NCO content of less than 5% by weight and a uretdione content of from 3 to 60% by weight. In addition, the isocyanate composition of this embodiment may contain 0.01 to 5% by weight, preferably 0.3 to 2% by weight of at least one catalyst selected from quaternary ammonium salts, preferably tetralkylammonium salts, and / or quaternary

Phosphonium salts with halogens, hydroxides, alcoholates or organic or

inorganic acid anions as counterion, and optionally 0.1 to 5% by weight, preferably 0.3 to 2% by weight of at least one co-catalyst selected from either at least one epoxy and / or at least one metal acetylacetonate and / or quaternary ammonium acetylacetonate and / or quaternary Containing phosphonium acetylacetonate. All quantities for the (co) catalysts are based on the total formulation of the matrix material.

Examples of metal acetylacetonates are zinc acetylacetonate, lithium acetylacetonate and

Tin acetylacetonate, alone or in mixtures. Zinc acetylacetonate is preferably used. Examples of quaternary ammonium acetylacetonates or quaternary

 Phosphonium acetylacetonates can be found in DE 102010030234.1. Particular preference is given to using tetraethylammonium acetylacetonate and tetrabutylammonium acetylacetonate.

Of course, mixtures of such catalysts can be used.

Examples of the catalysts can be found in DE 102010030234.1. These catalysts may be added alone or in mixtures. Preference is given to using tetraethylammonium benzoate and tetrabutylammonium hydroxide. As epoxide-containing co-catalysts, e.g. Glycidyl ethers and glycidyl esters, aliphatic epoxides, diglycidyl ethers based on bisphenol A and glycidyl methacrylates in question. 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), glycidyl ester of versatic acid

(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 types of polypoets with free epoxy groups. It can also be used mixtures. Preference is given to using ARALDIT PT 910 and 912.

Depending on the composition of the reactive or highly reactive isocyanate component used and optionally added catalysts, both the rate of

Crosslinking reaction in the production of composite components and the properties of the matrix can be varied within wide ranges. resin components

According to the invention, reaction resins based on methacrylate are used as the resin components. The notation (meth) acrylates encompasses both methacrylates and acrylates, as well as mixtures of methacrylates and acrylates. Both the monomers and the prepolymers can contain up to 25% by weight of a monomer which is copolymerizable or copolymerized with (meth) acrylates, based on the respective component. Examples of such monomer are in particular styrene or 1-alkenes. In addition, other components may optionally be included. As auxiliaries and additives in addition regulators, plasticizers, stabilizers and / or inhibitors can be used. In addition, dyes, fillers, wetting, dispersing, separating and leveling agents, adhesion promoters, UV stabilizers, defoamers and rheology additives can be added. Crucial to the present invention is that at least a portion of the monomers and / or prepolymers of the resin component have hydroxyl groups as functional groups. Such hydroxy groups react with the free isocyanate groups or uretdione groups from the isocyanate component with addition. With this reaction, the composite semifinished product is finally cured in process step V. The resin component in this case has an OH number of 10 to 600, preferably from 20 to 400 mg, more preferably from 40 to 200 mg KOH / gram. In this case, the broader limits relate in particular, but not restrictively, to the embodiment explained in more detail below, in which the resin component contains, in addition to the monomers and the optional prepolymers, further polyols. In the embodiment where a pure (meth) acrylate resin without polyols is used, the OH number is preferably between 10 and 200 mg KOH / g.

In particular, the amount of the functional groups is chosen so that each

Hydroxy group of the resin components 0.6 to 2.0 isocyanate equivalents or 0.3 to 1, 0, preferably 0.4 to 0.8 and particularly preferably 0.45 to 0.65 uretdione groups of the isocyanate component omitted. This corresponds to 0.6 to 2.0, preferably 0.8 to 1, 6 and more preferably 0.9 to 1, 3 externally blocked isocyanate groups of the isocyanate component.

The monomer contained in the reaction resin is preferably

Compounds selected from the group of (meth) acrylates such as

Alkyl (meth) acrylates which have been obtained by esterification with straight-chain, branched or cycloaliphatic alcohols having 1 to 40 carbon atoms, for example methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate or 2 -Ethylhexyl (meth) acrylate.

Also suitable as constituents of monomer mixtures are additional monomers having a further functional group, such as α, β-unsaturated mono- or dicarboxylic acids, for example acrylic acid, methacrylic acid or itaconic acid; Esters of acrylic acid or methacrylic acid with dihydric alcohols, for example hydroxyethyl (meth) acrylate or

 Hydroxypropyl (meth) acrylate; Acrylamide or methacrylamide; or dimethylaminoethyl (meth) acrylate. Further suitable constituents of monomer mixtures are, for example, glycidyl (meth) acrylate or silyl-functional (meth) acrylates.

An optional constituent of the reaction resin according to the invention are the crosslinkers. These are, in particular, polyfunctional methacrylates, such as allyl (meth) acrylate. Particularly preferred are di- or tri- (meth) acrylates such as, for example, 1,4-butanediol di (meth) acrylate,

Tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate or

Trimethylolpropane tri (meth) acrylate.

 A slight crosslinking in process step III. disturbs the shaping in

Process step IV. Not or hardly. For this, these crosslinkers, contained in small amounts, contribute to the intermediate from step III. in addition to stabilize. However, the crosslinker content may not exceed 10% by weight, preferably at most 5% by weight of

Component A).

Specifically, the composition of the monomers according to proportion and composition will be suitably chosen with regard to the desired technical function and the substrate to be wetted.

In addition to the monomers listed, the resin component also contains polymers which are referred to as prepolymers for better distinctness within the scope of this protective right. At least 80% by weight of the polymer portion is poly (meth) acrylates. In addition, up to 20% by weight of other prepolymers, in particular polyesters or polyethers may be included. However, the prepolymers preferably consist exclusively of poly (meth) acrylates.

These prepolymers are used to improve the polymerization properties, the

mechanical properties, adhesion to the substrate, the viscosity adjustment during processing in steps II. And III., As well as the optical requirements of the resins used. The poly (meth) acrylates may have the hydroxy functionalities exclusively or in addition to the monomers. However, it is also possible that the prepolymers have no functional groups or at least no hydroxyl groups, and that the functional groups are exhibited exclusively by the monomers of component A). Furthermore, the prepolymers may have additional functional groups for adhesion promotion.

Said poly (meth) acrylates are generally composed of the same monomers as already listed with respect to the monomers in the resin system. They can be obtained by solution, emulsion, suspension, bulk or precipitation polymerization and are added to the system as a pure substance. As a regulator in the polymerization to the prepolymer as well as an additional ingredient in

Component A), all compounds known from radical polymerization can be used. Preference is given to using mercaptans such as n-dodecylmercaptan. Likewise, conventional UV stabilizers can be used. The UV stabilizers are preferably selected from the group of the benzophenone derivatives, benzotriazole derivatives, thioxanthonate derivatives, piperidinolcarboxylic ester derivatives or cinnamic acid ester derivatives.

Substituted phenols, hydroquinone derivatives, phosphines and phosphites are preferably used from the group of stabilizers or inhibitors.

The rheology additives used are preferably polyhydroxycarboxamides, urea derivatives, salts of unsaturated carboxylic esters, alkylammonium salts of acidic phosphoric acid derivatives, ketoximes, amine salts of p-toluenesulfonic acid, amine salts of sulfonic acid derivatives and aqueous or organic solutions or mixtures of the compounds. It has been found that rheology additives based on pyrogenic or precipitated, optionally also silanized, silicas having a BET surface area of 10 to 700 nm ² / g are particularly suitable.

Defoamers are preferably selected from the group of alcohols, hydrocarbons, paraffin-based mineral oils, glycol derivatives, derivatives of glycolic acid esters, acetic acid esters and polysiloxanes used.

Optional PH-functional cobinders

Optionally, in addition to the methacrylate-based reaction resins, the resin composition may contain polyols as OH-functional co-binders which also undergo a crosslinking reaction with the isocyanate components. By adding these polyols, which are not reactive in process step III, the rheology and thus the processing of the semi-finished products from process step III, as well as the end products can be adjusted more accurately. Thus, for example, the polyols in the semifinished product from process step III act as a plasticizer or more precisely as a reactive diluent. The polyols may be added in such a way that up to 80%, preferably up to 50% of the OH

Functionalities of the reaction resin to be replaced by these. With respect to the amount, the polyols may constitute up to 50% by weight, preferably at most 30% by weight and more preferably at most 25% by weight of the resin composition.

Suitable OH-functional cobinders are in principle all polyols customarily used in PU chemistry, as long as their OH functionality is at least two, preferably between three and six, where diols (difunctional polyols) are only in mixtures with polyols which contain more than two OH Have functionalities used. The functionality of a polyol compound is understood to mean the number of OH groups of the molecule capable of reacting. For the purpose of use, it is necessary to use polyol compounds having an OH functionality of at least 3 in order to react with the isocyanate groups of the Uretdione build a three-dimensional dense polymer network. Of course, it is also possible to use mixtures of different polyols.

A simple suitable polyol is, for example, glycerol. Other low molecular weight polyols, for example, by the company Perstorp ^® under the product names polyol ^®, polyol ^® R or Capa ^{®, manufactured} by Dow Chemicals under the product name Voranol ^® RA, Voranol ^® RN, Voranol ^® RH or Voranol ^® CP, by the company BASF under the name Lupranol ^® and sold by DuPont under the name Terathane ^® . Specific products, indicating the hydroxyl numbers and the molecular weights, for example, in the German patent application with the

Priority record 102014208415.6 be read.

As an alternative to the mentioned low molecular weight polyols, it is also possible to use oligomeric polyols. These are, for example, known linear or branched hydroxyl-containing polyesters, polycarbonates, polycaprolactones, polyethers, polythioethers, polyesteramides, polyurethanes or polyacetals, preferably polyester or

Polyether. These oligomers preferably have a number average molecular weight of 134 to 4000. Particularly preferred are linear hydroxyl-containing polyester - polyester polyols - or mixtures of such polyesters. They are e.g. by reacting diols with lower amounts of dicarboxylic acids, corresponding dicarboxylic anhydrides, corresponding dicarboxylic acid esters of lower alcohols, lactones or

 Hydroxycarboxylic acids produced. Examples of suitable building blocks of such polyesters can also be found in the German patent application with priority record 102014208415.6.

Particular preference is given to using polyesters as oligomeric polyols whose OH number is between 25 and 800, preferably between 40 and 400, whose acid number is at most 2 mg KOH / g and whose molar mass is between 200 and 4000 g / mol, preferably between 300 and 800 g / mol. The OH number is determined analogously to DIN 53 240-2; the acid number in accordance with DIN EN ISO 21 14. The molar mass calculated from hydroxyl and carboxyl end groups.

Equally preferably, polyethers are used as oligomeric polyols. These wise

in particular an OH number between 25 and 1200, preferably between 250 and 1000 and a molar mass M _w between 100 and 2000 g / mol, preferably between 150 and 800 g / mol. An example of a particularly suitable polyether is Lupranol® ^® 3504/1 BASF Polyurethanes GmbH. The molecular weight M _n is measured here by means of gel permeation chromatography against a PMMA standard.

As a very particularly preferred example, polycaprolactones are used as oligomeric polyols whose OH number is between 540 and 25, the acid number of which is between 0.5 and 1 mg KOH / g is and whose molar mass is between 240 and 10,000 g / mol. Suitable polycaprolactones are Capa 3022, Capa 3031, Capa 3041, Capa 3050, Capa 3091, Capa 3201, Capa 3301 Capa 4101, Capa 4801 Capa 6100, Capa 6200, Capa 6250, all from Perstorp, Sweden.

Of course, mixtures of polycaprolactones, polyesters, polyethers and polyols can be used.

The polymerization in process step III

The polymerization in process step III. occurs at a temperature T-i at which the

Polymerization of (meth) acrylates is carried out, the isocyanate but not react with the hydroxy groups. This requires a corresponding initiator. These initiators are preferably thermally activatable initiators, photoinitiators or radical-forming redox systems; the initiators are preferably peroxides or redox systems.

Examples of photoinitiators are hydroxyketones and / or bisacylphosphines. Suitable thermally activatable initiators are above all peroxides, azo initiators or redox systems. In particular, peroxides are suitable. The choice of initiator results for the skilled person from its half-life and the process step III. used temperature T- | , In a particular variant, the thermally activatable initiators are combined with an accelerator. Such systems are not only faster but also activatable at lower temperatures. Suitable initiators and in particular combinations of initiators and

Accelerators can be read, for example, in EP 2 454 331. The combination of the initiators with the accelerators is referred to there as the redox starter system.

The sum of the initiators in component A), wherein the sum of component A) comprises the sum of the two individual components mixed to component A), lies in one

Concentration between 0 and 10% by weight, preferably between 0.2 and 8.0% by weight, more preferably between 0.5 and 6.0% by weight and especially preferably between 1, 5 and 5.0% by weight. This concentration is based on the pure initiator. It is quite possible or even common for the initiator to be added in a solvent or phlegmatizer. These amounts of substance added in small amounts are taken into account neither in the material balance of the resin nor in the material balance of the composition.

Solvents usually evaporate during further processing.

Phlegmatizers such as linseed oil or waxes are only very negligible

 Concentration before and have a maximum softening effect in the final product.

Process step III, the curing of the resin component is preferably carried out directly after

Process step II. The curing takes place in process step by a thermally initiated polymerization of the monomers in the resin component A). It is important to ensure that the

Temperature Ti below the required for step V final curing temperature T ₂ lies. The temperature Ti is preferably in process step III. between 20 and 120 ° C, more preferably below 100 ° C. Ti is the temperature of the lower mold or the tool, in the process step III. is started or cured. At the same time, the temperature may increase to a certain extent due to the exothermic nature of the polymerization. Preferably, the formulation should be adjusted so that the temperature throughout the polymerization throughout at least 20 ° C below the temperature T ₂ remains.

The polymer compositions used according to the invention provide a very good flow with low viscosity and thus a good impregnation and in the cured state excellent chemical resistance. When using aliphatic crosslinkers such as IPDI or H ₁₂ MDI, and by the inventive use of the functionalized

Poly (meth) acrylates is additionally achieved a good weather resistance.

The intermediates produced according to the invention from process step III. are also very stable on storage at room temperature conditions, usually several weeks and even months. They can thus be further processed at any time into composite semi-finished products or components. This is the essential difference from the prior art systems which are reactive and not shelf-stable, as they start immediately after application e.g. to react to polyurethanes and thus to crosslink.

Thereafter, the storable composite semi-finished products can be added at a later date

Composite components are further processed. By using the composite semifinished products according to the invention, a very good impregnation of the fibrous support takes place due to the fact that the liquid resin components containing the isocyanate component wet the fiber of the support very well, whereby the thermal stress of the polymer composition can lead to an incipient second crosslinking reaction a previous one

Homogenization of the polymer composition is avoided, further fall the

Process steps of grinding and sieving into individual particle size fractions away, so that a higher yield of impregnated fibrous support can be achieved.

A further great advantage of the composite semifinished products produced according to the invention is that the high temperatures required, at least for a short time, in the melt impregnation method or in the sintering of pulverulent reactive polyurethane compositions are not absolutely necessary in this method according to the invention.

Particular aspects of the method according to the invention

Process step II, the impregnation, is carried out by soaking the fibers, fabrics or scrims with the reactive composition prepared in process step I. Preferably, the impregnation is carried out at a temperature of at most 60 ° C, more preferably at

Room temperature. In method step III, a first shaping can already take place in parallel. Thus, it is possible that, for example, in the case of very detailed and at the same time curved shapes of the end product, the semi-finished product is already roughly adapted to the complicated shape of this tool before being inserted into the press or another tool in process step IV, and thus a better product quality, eg in terms of a high dimensional accuracy, is achieved. For simpler forms of the final product, however, it is preferred that the shaping takes place exclusively in process step IV. Furthermore, it is possible, in particular when the semifinished products are temporarily stored from method step III, that preheating and preforming of the semifinished product take place in an intermediate step between method steps III and IV. The

Temperature in this intermediate step should naturally be below the curing temperature of the process step V.

For accelerated automation of the method, it is also possible to use several shells, which are driven one after the other in the same tool, or the same press. Thus, parallel to method step IV, other lower shells can already be occupied simultaneously and optionally a preheating and / or preforming in this

Lower shell done. In a particular embodiment of the invention, in addition, the impregnation of process step II and the polymerization of process step III, as well as an optional preliminary shaping can already take place in such a lower shell. Alternatively, a diaphragm can be used.

The composite semifinished products / prepregs produced according to the invention have both after process step III. as well as after process step V. a very high storage stability

Room temperature. This is at least a few days at room temperature, depending on the incorporated reactive polyurethane composition. As a rule, the composite semi-finished products are stable for several weeks at 40 ° C and below, as well as at room temperature for several years. 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 fibrous carrier.

Before process step IV, the intermediates from process step III. be combined and cut to different shapes as needed. In particular, the

Consolidation of several composite semi-finished products into a single composite and before the final cross-linking of the matrix material to the matrix cut, sewn or otherwise fixed. Material which is obtained as a waste during cutting can, as described above, be used for further processes.

In method step V, the final curing of the composite semi-finished products to form parts, which are thermoset crosslinked. This is done by thermal curing of the hydroxy groups the resin component 1 with the isocyanate component. In the context of this invention, this process of producing the composite semi-finished products from the precursors of process step III. depending on the curing time preferably at temperatures between 100 and 200 ° C, preferably above 160 ° C when using reactive matrix materials (variant I), or provided with appropriate catalysts highly reactive matrix materials (variant II) at temperatures above 100 ° C. In particular, the curing is carried out at a temperature between 100 and 200 ° C, more preferably at a temperature between 120 and 200 ° C and particularly preferably between 140 and 200 ° C. The time for curing the invention

The polyurethane composition used is within 1 to 60 minutes, preferably between 1 and 5 minutes, depending on the component complexity.

The reactive polyurethane compositions used according to the invention have a very good flow and thus a good impregnation ability and in the cured state an excellent chemical resistance. In addition, when using aliphatic crosslinkers (for example IPDI or H12MDI), a good weathering resistance is achieved.

Furthermore, the method according to the present invention has the additional advantages that during the process steps IV. And V. only a very small shrinkage and a slight shrinkage occur and the end product has a comparison with the prior art comparable systems a particularly good surface quality.

However, it is also possible to use special catalysts for accelerating the reaction of the second curing in process step V. Quaternary ammonium salts, preferably carboxylates or hydroxides, particularly preferably in combination with epoxides or

Metallacetylacetonate, preferably in combination with quaternary ammonium halides. These catalyst systems can ensure that the cure temperature for the second cure goes down to 100 ° C, or lower cure times are required at higher temperatures.

Further components of composite semi-finished products

In addition to the resin component, the carrier material and the isocyanate component, the composite semifinished products may have further additives. So, for example

Sunscreens such as e.g. 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%. Fillers and pigments such. B. titanium dioxide can in an amount up to 30% by weight of

Total composition can be added.

In addition, additives such as leveling agents, for example polysilicones or adhesion promoters, for example based on acrylate, can be added for the preparation of the reactive polyurethane compositions according to the invention. The invention also provides the use of prepregs or composite semi-finished products, in particular with fibrous carriers made of glass, carbon or aramid fibers. The invention also relates, in particular, to the use of the composite semifinished products produced according to the invention for the production of composites in boatbuilding and shipbuilding, in the aerospace industry

 Space technology, in the automotive industry, for two-wheelers, preferably motorcycles and bicycles, in the fields of automotive, construction, medical technology, sports, electrical and electronics industry, power generation plants, e.g. for rotor blades in wind turbines. In addition to the method according to the invention and the use of the immediate

 Process product are also special semi-finished part of the present invention. These semi-finished products are characterized in particular by a fibrous carrier and a

Matrix material, wherein the matrix material of a cured resin component and an unreacted isocyanate component in a ratio between 90 to 10 and 40 to 60 is composed. In particular, this resin component consists of at least 30% by weight of a cured reaction resin based on (meth) acrylate, and has an overall OH number between 10 and 600 mg KOH / g. These OH numbers describe in particular

Composition containing additional polyol components. In embodiments in which a pure (meth) acrylate resin is used without additional polyols, the OH number is generally between 10 and 200 mg KOH / g.

 An example of such a semi-finished product may be independent of the polyol

Embodiment, for example, be taken from the process step III of the method according to the invention.

Examples

The following glass fiber scrims or fabrics were used in the examples:

Glass filament fabric 296 g / m ² - Atlas, Finish FK 144 (Interglas 92626) Preparation of uretdione-containing hardener H:

 1 19.1 g of IPDI uretdione (Evonik Industries) were dissolved in 100 ml of methyl methacrylate and admixed with 27.5 g of propanediol and 3.5 g of trimethylolpropane. After addition of 0.01 g of dibutyltin dilaurate was heated with stirring to 80 ° C for 4 h. Thereafter, no free NCO groups could be detected titrimetrically. The hardener H has an effective NCO latent content of 12.8% by weight, based on solids.

 For examples 1 and 2, two of these hardeners a) and b) were prepared by identical procedures.

Reactive polyurethane composition Reactive polyurethane compositions having the following formulas have been reported

Preparation of the prepregs and the composite used.

example 1

Table 1

To make the component, 10 layers of fiberglass fabric were stacked in a 25x25 cm metal tool and purged with nitrogen.

 The starting materials from the table were mixed in a premixer and then dissolved. This mixture can be used at RT for about 15 min before it gels.

 The matrix was then placed on the fiber. During the closing process, the matrix dispersed in the tool and wetted the reinforcing fibers. After 20 min, the reaction is complete at RT and the preform (here equivalent to semi-finished) was removed from the tool. The preform of Example 1 showed after the reaction a weight loss based on matrix of about 2% by weight.

The preform was then pressed in a further tool for 1 h at 180 ° C and 50 bar and thereby fully crosslinked the matrix material. The hard, rigid, chemical-resistant and impact-resistant composite components (plate goods) had a glass transition temperature T _g of 1 18 ° C.

Example 2

In Example 2, the procedure was analogous to Example 1. Only a resin component which additionally contained non- (meth) acrylic polyols was used. The composition is shown in Table 2.

The procedure of Example 2 was carried out according to Example 1. In this case, a weight loss of the preform after the reaction of 1% by weight instead of 2% by weight was measured in Example 1. The hard, stiff, chemical-resistant and impact-resistant composite components (plate goods) had a glass transition temperature T _g of 80 ° C and were slightly more flexible overall than the plates of Example 1.

Table 2

 Hardener H (60% in MMA) containing uretdione groups

(NCO effective: 7.9%) Hardener component b) 54% by weight

 OH-functional monomer of

 3-hydroxypropylm ethacrylate (H PM A) resin component 6% by weight

Methyl methacrylate (MMA) monomer of the resin component 22% by weight

Polyol R3215 polyol in resin component 16% by weight

Dibenzoyl peroxide initiator 1% by weight

N, N-bis- (2-hydroxyethyl) -p-toluidine accelerator 1% by weight

Claims

claims:

Process for the production of composite semi-finished products and their further processing into molded parts, comprising the following process steps

 I. Preparation of a liquid, reactive composition,

 II. Direct impregnation of a fibrous carrier with the composition of I.

III. Polymerization of monomer components in the liquid composition at a temperature T-i,

 IV. Forming the later molded part in a press and / or another tool and

V. simultaneous curing of the isocyanate component in the composition in this press at a temperature T ₂ ,

 wherein the composition consists essentially of the following components:

A) a (meth) acrylate-based reactive resin component containing at least one (meth) acrylate monomer and at least one poly (meth) acrylate, at least one constituent of the resin component having hydroxyl groups,

 B) at least one blocked di- or polyisocyanate and / or at least one

 Uretdione as isocyanate component,

and wherein the temperature T _{2 is} at least 20 ° C higher than the temperature T- | ,

A method according to claim 1, characterized in that the quantity ratio of the resin component to the isocyanate component is between 90:10 and 40:60.

Method according to one of claims 1 or 2, characterized in that the temperature Ti in step III. between 20 and 120 ° C, preferably between 40 and 100 ° C, and that the temperature T ₂ in step V. between 140 and 200 ° C.

A method according to any one of claims 1 to 3, characterized in that the resin component A) is at least composed of

 From 20% to 100% by weight of monomers,

 0 wt% to 70 wt% prepolymers.

A method according to claim 4, characterized in that the resin component A) is at least composed of

 0% to 10% by weight crosslinker,

 From 30% to 90% by weight monomers,

 0% to 20% by weight of urethane (meth) acrylates,

 0% to 40% by weight of prepolymers,

 0 wt% to 10 wt% of one or more initiators and

5% to 50% by weight of one or more polyols.

6. The method according to any one of claims 1 to 5, characterized in that it is the initiator to hydroxy ketones and / or bisacylphosphines as a photoinitiator and / or a peroxide as a thermally activatable initiator and / or a

 Redox accelerator is, and that the sum of the initiators in a concentration between 0.2 and 6.0% by weight is included in the composition.

7. The method according to any one of claims 1 to 6, characterized in that the fibrous carrier consists largely of glass, carbon, plastics such as polyamide (aramid) or polyester, natural fibers, or mineral fiber materials such as basalt fibers or ceramic fibers, and that the fibrous carrier as textile

 Non-woven fabric, knitted fabric, knitted or knitted fabrics, non-meshed packages such as fabrics, scrims or netting, long-fiber or short-fiber materials.

8. The method according to at least one of claims 1 to 7, characterized in that di- or polyisocyanates of component B), selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), diisocyanatodicyclohexylmethane (H ₁₂ MDI), 2-methylpentane diisocyanate (MPDI) , 2,2,4-Trimethylhexamethylendiisocyanat / 2,4,4-trimethylhexamethylene diisocyanate (TMDI) and / or norbornane diisocyanate (NBDI), wherein the isocyanurates are used, are used as the isocyanate component, and that these di- or polyisocyanates with an external blocking agent , 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, are blocked. 9. The method according to any one of claims 1 to 8, characterized in that the isocyanate component additionally contains 0.01 to 5.0% by weight of catalysts, preferably dibutyltin dilaurate, zinc octoate, bismuth neodecanoate, and / or tertiary amines, preferably 1, 4-Diazabicylco [2.2.2.] Octane, in amounts of 0.001 to 1.0% by weight. 10. The method according to any one of claims 1 to 7, characterized in that as isocyanate component uretdiones prepared from 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) and / or norbornane diisocyanate (NBDI).

1 1. A method according to claim 10, characterized in that the isocyanate component is below 40 ° C as a pure substance in solid form and above 125 ° C in liquid form, a free NCO content of less than 5% by weight and a uretdione content of 3 to 60% by weight, and that the isocyanate component additionally contains 0.01 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. 12. The method according to any one of claims 10 or 1 1, characterized in that the isocyanate component additionally 0.1 to 5% by weight of at least one co-catalyst selected from either

 at least one epoxide and / or at least one metal acetylacetonate and / or quaternary ammonium acetylacetonate and / or quaternary phosphonium acetylacetonate, and optionally known from polyurethane chemistry auxiliaries and additives.

13. The method according to any one of claims 1 to 12, characterized in that the resin component and the isocyanate component in such a ratio to each other, that for each hydroxyl group of the resin component 0.3 to 1, preferably 0.4 to 0.8 , Particularly preferably 0.45 to 0.65 uretdione eliminated.

14. The method according to claim 5, characterized in that the resin component 10th

Wt% to 30 wt% of the additional polyol, and that the polyol is a low molecular weight polyol having 3 to 6 OH functionalities, a polyester having a molecular weight M _{n of} between 200 and 4000 g / mol, an OH number between 25 and 800 mg

KOH / g and an acid number less than 2 mg KOH / g, a polyether having an OH number between 25 and 1200 mg KOH / g and a molar mass M _n between 100 and 2000 g / mol or is a mixture of at least two of these polyols ,

Process according to Claim 14, characterized in that the polyester is a polycaprolactone having an OH number between 25 and 540, an acid number between 0.5 and 1 mg KOH / g and a molar mass between 240 and 2500 g / mol is.

Use of moldings produced by the method according to any one of claims 1 to 15 in marine and shipbuilding, in aerospace, in the automotive industry, for motorcycles preferred motorcycles and bicycles, in the automotive, construction, medical, sports, electrical and electronics industry,

 Energy generation systems, such as for rotor blades in wind turbines. 17. Semi-finished product comprising a fibrous carrier and a matrix material, wherein the

Matrix material of a cured resin component and an unreacted isocyanate component in a ratio of between 90:10 and 40:60 is composed, characterized in that the resin component consists of at least 30 wt% of a cured (meth) acrylate-based reaction resin, and that the resin component has an OH number between 10 and 600 mg KOH / g.