DE3631282A1 - Process for the production of reinforced plastic mouldings using fibre materials which have been pretreated with thermocurable resin, and the use of the thermocurable resins as sizes and/or binders for fibre materials - Google Patents

Abstract

The invention relates to an improved process for the production of mouldings from fibre-reinforced plastic, in which the fibre materials are subjected to pretreatment with a thermocurable resin which contains A) at least one amino-containing polymerisation, polyaddition and/or polycondensation product having a mean molecular weight Mn of from 500 to 10,000 and containing on average at least two hydroxyl, primary and/or secondary amino groups per molecule, and B) at least one crosslinking agent from the group consisting of polyureas, polyurea-polyurethanes, urea condensation products, amino resins and/or phenolic resins, and to the use of the thermocurable resins as sizes and/or binders for fibre materials, preferably made from glass, carbon, aromatic polyamides (nylons) and aromatic polyesters.

Description

Process for the production of molded articles from with fiber materials reinforced plastics are known. As fiber materials can organic or inorganic fibers of any length or rovings be used. However, fabrics such as z. B. Mats, fleeces, fabrics or felt. The fiber materials are usually in an amount of 5 to 75 wt .-%, based on the finished Molding weight used.

As plastics use z. B. thermoplastically processable Polymerization, polycondensation or polyaddition products, wherein Examples include: polypropylene, polyester such. B. polyethylene or polybutylene terephthalate, polyamide or thermoplastic polyurethanes. However, reaction plastics, such as. B. Epoxy resins, unsaturated polyester resins, through activated alkaline Lactam polymerization produced polyamides and by the polyisocyanate polyaddition process manufactured polyurethane, polyurea or Polyurethane polyurea elastomers.

It is known that glass mat-reinforced thermoplastics can be produced by making glass fiber mats continuously with a thermoplastic melt impregnated and then pressed into finished parts (Kunststoffe 72 (1982), Pages 341-347).

According to CH-A-3 50 799 (US 29 03 338) reinforced plastic molded parts can also be produced by injection molding. After this The plastic is viscous with such a process low flow rate injected into the mold that do not move the fiber mats in the flow direction of the plastic, the plastic does not change its temperature during the filling process and presses the fiber mats against one or both of the mold walls, but without to penetrate the fabrics or fiber mats. After completely filling the In a second reaction phase, the mold is still liquid Plastic is pressed under pressure into the fabric or fiber mats and by changing the mold temperature z. B. by heating thermosetting unsaturated polyester resins or by cooling Thermoplastics, solidified.  

The production of hollow bodies or those derived therefrom is also known open molded parts in rotary casting according to the activated process anionic polymerization of lactams (DE-A-15 95 638 (GB-11 33 840)). For the production of reinforced hollow bodies, according to the DE-A-20 64 598 (US-37 80 157) the activated anionic lactam polymerization with the help of rotary casting in the presence of reinforcing materials, preferably glass fibers with a length of 0.2 to 24 mm in a biaxially rotating molding tool.

Polyurethane or polyurethane-polyurea elastomers can also be reinforced with glass fibers for the production of moldings. Procedure for Manufacture of such moldings are described, for example, by H. Boden et. al in Kunststoffe 68 (1978), pages 510-515 or J. Hutchinson et al or S. H. Metzger et al in the Journal of Cellular Plastics Sept./Oct. 1981, pages 263 to 273. As a fiber-containing reinforcing agent for Manufacture of compact or cellular polyurethane, polyurea or Polyurethane-polyurea moldings in closed molds one shot systems according to the reaction injection molding technique are according to DE-A-34 13 938 one or more polyurethane thermosets with a compressive strength from 1.1 to 0.1 N / mm² at 30% compression, which, based on the total weight, 50 to 95 wt .-% of a flat Contain fiber structure.

To achieve at least sufficient adhesion between the plastic matrix and reinforcing agents, the fiber materials depending on the type of used plastic with suitable sizes. Flat reinforcing fiber materials are expediently additional provided with a binder to ensure an optimal bond of the fibers to ensure among themselves. For strengthening the fibers with each other can also mechanical methods such. B. needling, find application.

For the production of molded articles from fiber-reinforced polyamide alkaline polymerization of lactams, e.g. B. according to DE-A-35 21 230 the reinforcing, arbitrated or non-arbitrated Fiber materials pretreated with an organic polyisocyanate subject. Using polyurethane or epoxy resins as Binders and amino-functional organosilanes can be used as sizes also according to the teaching of US-A-43 58 502 semi-finished products with a good Surface. For mechanically consolidated glass fiber mats Difficulties with impregnation with the plastic matrix often occur that lead to surface defects on the finished part. Will the Molded body made of reinforced polyamide after the active alkaline Lactam polymerization using the commonly used reaction injection molding technique  (RIM) manufactured, so the fabrics swim at fill the mold away, unless it mechanically solidified will. This deficiency can be overcome, provided that after the Teaching of DE-A-35 21 230 or US-A-43 58 502 solidified fabrics used. A disadvantage of this method, however, is that the obtained semi-finished products difficult or not at all to finished parts Allow to be pressed, since the solidified fibrous fabrics do not assume the required contour or are so rigid that the fiber filaments penetrate the plastic matrix and thereby finished parts with extreme poor surface and inadequate mechanical properties be formed.

The object of the present invention is an additive to develop the above or all of the disadvantages partially eliminated and as a sizing agent and binder alike is effective.

Surprisingly, this task could be accomplished by pretreating the as Reinforcing agents used fiber materials with a thermosetting Resin which contains at least one polymerization polyaddition containing amino groups and / or polycondensation product and at least one contains specially selected crosslinking agent.

The invention thus relates to a method for producing Shaped bodies made of fiber-reinforced plastic, which is characterized is that the fiber materials are pretreated with a subject to thermosetting resin that contains

• A) at least one polymerization, polyaddition containing amino groups and / or polycondensation product with a medium Molecular weight _n  from 500 to 10,000, which on average per molecule at least two hydroxyl, primary and / or secondary amino groups owns and
• B) at least one crosslinking agent from the group of the polyureas, Polyurea polyurethanes, urea condensation products, Amino and / or phenoplasts.

Another object of the invention is the use of thermosetting Resins that contain

• A) at least one polymerization, polyaddition containing amino groups and / or polycondensation product with an average molecular weight   _n  from 500 to 10,000, which on average per molecule at least two hydroxyl groups, primary and / or secondary amino groups owns and
• B) at least one crosslinking agent from the group of the polyureas, Polyurea polyurethanes, urea condensation products, Amino and / or phenoplasts

as sizes and / or binders for fiber materials.

The thermosetting resins which can be used according to the invention are partial known and are used in their protonated form as water-dispersible cationic resins for electrocoating or as thermosetting coating agents for solventborne paints or for the Powder coating.

However, it was surprising and unpredictable that the thermosetting Resins as sizes or binders, preferably as sizes and Binders are equally suitable for the production of moldings made of fiber-reinforced plastics and in particular for the production of Semi-finished products made of flat fiber structures and thermoplastic materials or preferably reaction plastics. In particular, couldn't those pretreated with thermosetting resins are expected flat fiber structures in connection with the activated Alkaline lactam polymerization according to the RIM process for production of fiber-reinforced polyamide moldings can be processed. Since the activated alkaline lactom polymerization as is known in the presence of strongly basic catalysts, such as. B. sodium lactamate, at temperatures from 120 to 180 ° C, extreme demands are placed on the chemical and thermal stability of the thermosetting resin, especially if the flat fiber structures are additionally contoured.

The structural components contained in the heat-resistant resins are in individual to say the following:

The build-up component (A) can be an amino group-containing polymerization, Polycondensation and / or preferably a polyaddition product an average molecular weight _n  from 500 to 10,000, preferably from 600 to 3000 and selected from the various connection classes. It is only important that they average at least two per molecule Have hydroxyl groups and / or primary and / or secondary amino groups. Examples of suitable materials are polyesters containing amino groups, Polyethers, polyurethanes, polyacrylate resins, epoxy resins and their reaction products with alcohols and / or amines.  

Reaction products are preferably used as structural component (A) from one or more aromatic and / or aliphatic epoxy resins and one or more primary, secondary or tertiary mono- and / or Polyamines and reaction products from the above-mentioned starting materials and one or more polyalcohols with at least two hydroxyl groups.

Suitable epoxy resins are, for example, polyglycidyl ethers as made from Polyphenols and / or polyhydric alcohols and epichlorohydrin getting produced. Examples of suitable polyphenols are 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1,1-ethane u. a. and for polyhydric alcohols are ethanediol, 1,2- or 1,3-propanediol and 1,4-butanediol.

If elasticization is desired, long-chain polyvalent ones can also be used Alcohols are used. The polyhydric alcohols become larger as equivalent amounts based on the epoxy groups present used, products with terminal hydroxyl groups are formed. Puts if, on the other hand, smaller than equivalent quantities are used, products are created with terminal epoxy groups that continue e.g. B. with one or more primary, secondary or tertiary mono- and / or polyamines implemented can be. The implementation of the epoxides with the polyhydric alcohols is conveniently in the presence of a catalyst such as. B. Dimethylbenzylamine and at higher temperatures, e.g. B. at about 50 to 150 ° C. carried out.

The epoxy resins can be used directly or after reaction with less than equivalent amounts of polyhydric alcohols, based on epoxy groups, be reacted with primary or secondary amines. Instead of the amines can also alkanolamines such. B. ethanolamine, methylethanolamine and / or diethanolamine can be used. For production of Polyaddition products (A) in addition to or instead of hydroxyl groups keep primary and / or secondary amino groups bound, the optionally modified with polyhydric alcohols with epoxy resins primary diamines or polyamines with at least one primary or secondary amino group and optionally further primary, secondary and / or brought to reaction tertiary amino groups. Come as diamines especially those with 2 to 6 carbon atoms in the alkylene radical in Consider how. B. ethylenediamine, 1,2- or 1,3-diamino-propane, 1,4-di-amino-butane, 1,5-diaminopentane and / or 1,6-diaminohexane and N-mono- and N, N- or N, N'-dialkyl-substituted di- and / or higher polyamines with 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms in the alkyl radical such as. B. N, N-dimethyl-propylenediamine, N, N-dimethyl-ethylenediamine and N-ethyl-butyl-diamine.  

Another possibility as a construction component with suitable products To produce primary amino groups is the sales of epoxy resins secondary amines that contain blocked primary amino groups. Examples for such amines are the diketimine of diethylene triamine, the ketimine of Aminoethylethanolamine and the ketimine of N-methyl-ethylenediamine. The Ketimines can be easily separated from the free amines and one Ketone, e.g. B. methyl isobutyl ketone, with removal of water. When reacting with epoxy resins, only the secondary amino group reacts, then the ketimine can be split by adding water, the free primary amino group regresses.

Products that use a contain sufficient amount of amino groups to with after protonation Acids to become water soluble or water dispersible.

Crosslinking agents (B) are polyureas, polyurea-polyurethanes, Urea condensation products, aminoplasts, phenoplasts or mixtures of at least two of the crosslinking agents mentioned Use.

Suitable polyureas are produced by reacting at least an organic polyisocyanate with at least one secondary monoamine. If the reaction is carried out using one or more polyalcohols Carried out at least two hydroxyl groups, is obtained according to the invention usable polyurea polyurethanes.

Any aliphatic, cycloaliphatic, alicyclic and / or aromatic polyvalent Isocyanates are used. Examples of suitable polyisocyanates are Diisocyanates such as hexamethylene, 2-methylpentamethylene, 2-ethylbutylene, Isophorone, cyclohexane-1,4-, 2,4- and 2,6-tolylene diisocyanate and the corresponding mixtures of isomers, 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate and mixtures of diphenylmethane diisocyanates and Polyphenyl polymethylene polyisocyanates. Modified ones are also suitable Polyisocyanates, for example carbodiimide, urethane, biuret and / or Polyisocyanate mixtures containing isocyanurate groups from the aforementioned polyisocyanates. The polyisocyanates can be used individually or in Form of mixtures are used. Preferably used 1,6-hexamethylene diisocyanate, biuret groups and / or isocyanate groups containing hexamethylene diisocyanate mixtures, isophorone diisocyanate and Mixtures of 2,4- and 2,6-tolylene diisocyanates, especially in Weight ratio 80:20.  

Secondary monoamines are primarily secondary aliphatic, cycloaliphatic or araliphatic amines with a boiling point below 200 ° C, preferably those with a boiling point between 100 and 200 ° C. Examples of suitable secondary aliphatic amines are Dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, Dihexylamine and isomers thereof, such as e.g. B. diisopropylamine, too asymmetrical, such as N-ethyl-1-propanamine. Examples of suitable ones Cycloaliphatic or araliphatic amines are dicyclohexylamine and N-methylaniline.

Additional polyols are used to produce the polyurea polyurethanes or mixtures used. Suitable polyols have at least two, preferably 2 to 4 hydroxyl groups. These can be low molecular weight defined connections such as B. alkanediols with 2 to 12, preferably 2 up to 6 carbon atoms in the alkylene radical, for example ethane, 1,2 or 1,3-propane, 2,2-dimethyl-propane, 1,4-butane, 1,5-pentane, 1,6-hexane-diol, Diethylene glycol, dipropylene glycol, glycerin and trimethylolpropane or also higher molecular weight, advantageously di and / or trifunctional Polyester and / or polyether polyols with molecular weights up to 10,000, preferably from 500 to 3000.

The amounts of the sub-components for the production of the polyureas or Polyurea polyurethanes are chosen so that the ratio of NCO groups to amino groups or to the sum of amino and hydroxyl groups 1: 1 to 2: 1, preferably 1: 1 to 1.5: 1.

The reaction takes place in the case of polyisocyanate polyaddition reactions usual reaction conditions, for example at temperatures up to 100 ° C, preferably from 18 to 60 ° C. Are the substitutes and that Reaction product liquid at the reaction temperature, so can without solvent be worked, but in general you will in the reaction an inert solvent such as. B. an ether, ester, ketone or Carry out hydrocarbon.

For the production of the thermosetting resins, the structural component (A) in an amount of 30 to 95 parts by weight, preferably 60 to 85 parts by weight and the polyureas and / or polyurea polyurethanes (B) in an amount of 5 to 70 parts by weight, preferably 40 to 15 parts by weight used. For components with low viscosity, these can be in Substance can be mixed, possibly up to temperatures is heated to a maximum of 130 ° C. Components of higher viscosity are before Mixture dissolved in organic solvents. Common can  Solvents such as B. alcohols, ketones, esters, ethers, hydrocarbons etc. can be used.

Suitable urea condensation products as crosslinking agents (B) produced by polycondensation of at least one primary di and / or polyamine with urea, at least one secondary monoamine and optionally one or more polyalcohols at elevated temperature, optionally in the presence of catalysts and separation of the emerging ammonia.

Among those to be used for the preparation of the urea condensation products Starting materials must be carried out in detail as follows:

The primary di- and / or polyamines are in principle all aliphatic, cycloaliphatic and aromatic polyamines at least contain two primary amino groups, except non-cyclic aliphatic amines with less than 4 carbon atoms between the primary amino groups and cycloaliphatic or aromatic amines, the primary amino groups by less than 3 carbon atoms from each other are separated, since these amines and ureas are cyclic Form ureas. The primary di- and / or polyamines can in addition to the primary amino groups still further functional groups, such as. B. secondary or tertiary amino groups, hydroxyl groups or ether groups, contain. Examples of suitable amines are 1,4-diaminobutane, 1,6-diaminohexane, Heptamethylene diamine, octamethylene diamine, nonamethylene diamine, Decamethylenediamine, dodecamethylenediamine or branched aliphatic primary diamines such as B. the isomer mixture of 9- and 10-aminostearylamine or from 9- and 10-aminomethylstearylamine, 4,9-dioxadodecanediamine-1,12, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodiphenylmethane, toluenediamine, tris- (amino-ethyl) -amine and tris (aminopropoxy-ethyl) amine.

In addition to such polyamines with a low, defined molecular weight are also oligomeric polyamines with molecular weights up to 3000 can be used. Examples of such polyamines are polyether polyamines by reductive cyanoethylation of polyols, such as polytetrahydrofuran or polyoxyalkylene polyols, such as. B. polyoxyethylene, Polyoxypropylene or polyoxypropylene polyoxyethylene polyols can be produced are. Such products contain terminal primary amino groups in Form of aminoalkoxy groups.

The amines described above can be used alone or in a mixture can be used together.  

The urea is advantageously used in a commercially available form.

In principle, any secondary amines can be used as secondary amines will. Preferred are those which have a boiling point of less than Have 250 ° C, particularly preferably those with a boiling point of 100 up to 200 ° C. Examples of particularly preferred amines are di-n-propylamine, Di-iso-propylamine, di-n-butylamine, di-iso-butylamine and di-n-hexylamine.

Optionally, a polyalcohol with at least 2 hydroxyl groups can also be used. The concomitant use of such polyalcohols can be found in In many cases, the products are more compatible with the Guide component (A). Polyalcohol with more than two hydroxyl groups can to increase the functionality of the urea condensation products be used. Examples of usable polyalcohols are ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, trimethylolpropane, trishydroxyethyl isocyanurate and pentaerythritol.

To produce the urea condensation products, the primary di- and / or polyamines, urea, secondary monoamines and optionally polyalcohols are reacted with one another at elevated temperature, e.g. B. by heating them together gradually up to 140 to 230 ° C, preferably up to 150 to 210 ° C. It is generally not necessary to use a catalyst, but catalysts such as basic catalysts, e.g. B. sodium methylate or acidic catalysts, such as p-toluenesulfonic acid or β- naphthalenesulfonic acid, heavy metal salts, preferably CU-I salts, such as copper-I-chloride or copper-I-bromide in amounts of up to 3% by weight, based on the Total amount of starting materials are used.

It is not necessary to use all starting materials at the same time, it can e.g. B. also first the urea and the primary diamine and / or polyamine 110 to 150 ° C are reacted and then the secondary amine either all at once or progressing sales are gradually added accordingly, expediently one Temperature of 140 to 230 ° C is maintained. The gradual encore lends itself in cases where a secondary amine with relative low boiling point is used and the process is not under pressure is carried out. After the addition has ended, 1 is generally left react up to 20 hours.

If polyalcohols are used, these can be used together with the amines be added to the urea, but it is also possible to only add the  primary di- and / or polyamides, urea and secondary monoamines for Bring reaction and then react with the polyalcohol.

The proportions in which the individual components are used are not critical. One is generally within a Equivalent ratio of NH₂ groups of the primary di- and / or polyamines to NH₂ groups of urea to NH groups of the secondary monoamine to OH groups of the polyalcohol from 1: 1.2 to 2.4: 0.2 to 20: 0 to 0.9 work out or about 2 equivalents of the total per mole of urea Use diamine and / or polyamine, secondary monoamine and polyalcohol. Around An excess of polyalcohol may also accelerate the reaction are used, which is removed again at the end of the reaction.

The preparation of the urea condensation products can be inert Solvents such as higher boiling hydrocarbons or ethers be performed. Examples of suitable solvents are toluene and xylene and hydrocarbon fractions with a boiling range of 120 to 200 ° C or as ether 5,8-dioxadodecane. The reaction can also be without Solvents are carried out.

For the production of the thermosetting resins, the structural component (A) in an amount of 40 to 90 parts by weight, preferably 60 to 90 parts by weight, and the urea condensation products (B) in an amount of 60 up to 10 parts by weight, preferably 40 to 10 parts by weight, where the build-up components in the presence or absence of solvents can be mixed.

Amino and / or phenolic resins are also suitable as crosslinking agents (B) Consider. Low methylolated are preferably used highly etherified aminoplast resins or a methylolated as phenolic resins Phenol etherified with allyl alcohol on the phenolic OH group, or a methylolated mono- or polyphenol, the methylol groups of which are at least partially etherified.

Suitable aminoplast groups are the reaction products of urea and Melamines with aldehydes that are further etherified with an alcohol can. Examples of suitable aminoplast resin components are urea, Ethylene urea, 2-oxo-4-hydroxy-hexahydropyrimidine, thiourea, Melamine, benzoguanamine and acetoguanamine; Examples of usable Aldehydes are formaldehyde, acetaldehyde, isobutyraldehyde and propionaldehyde, preferably formaldehyde and isobutyraldehyde. The aminoplast resins can be used in the alkylene form; preferably these However, resins used in the ether form, the etherifying agent being a  is monohydric alcohol having 1 to about 8 carbon atoms. examples for suitable aminoplast resins are methylol urea, dimethoxymethylol urea, butylated polymeric urea-formaldehyde resins, hexamethoxymethylmelamine, methylated polymeric melamine-formaldehyde resins and butylated polymeric melamine formaldehyde resins. Are well suited for Example of low methylolated, highly etherified product types. Aminoplast resins and methods for their preparation are in "Encyclopedia of Polymer Science and Technology ", Volume 2 (1965), pages 1 to 91, Interscience Publishers.

The usual reaction products of phenols are included as phenolic resins To name aldehydes which have reactive methylol groups or their Aza analogues from aldehydes and amines, e.g. B. secondary amines (cf. e.g. DE-OS 23 20 536, DE-PS 23 20 301, DE-PS 23 57 075 and DE-PS 25 54 080). These resins may depend on the one at the first condensation applied phenol / aldehyde molar ratio a monomeric or polymeric Show nature. Specific examples of those used to manufacture the phenolic resins phenols used are phenol, o-, m- or p-cresol, 2,4-xylenol, 3,4-xylenol, 2,5-xylenol, cardanol and p-tert-butylphenol. For aldehydes which can be used for this reaction are formaldehyde, acetaldehyde, Propionaldehyde and isobutyraldehyde, preferably formaldehyde and isobutyraldehyde. Particularly useful phenolic resins are polymethylolphenols, in which the phenol group has an alkyl radical (e.g. one Methyl or ethyl group) is etherified. Are to be used preferably Products that have allyl ether groups. Phenolic resins and their Manufacturing methods are described in "Encyclopedia of Polymer Science and Technology ", volume 10 (1969), pages 1 to 68, Interscience Publishers, described. Bisphenols such as bisphenol A and novolaks or such Products whose methylol groups are at least partially alcoholic have been etherified are preferred.

The proportion of the aminoplast or phenoplast resin used in the thermosetting resin is about 20 to 50% by weight, preferably 25 to 40 wt .-%, based on the total weight of the structural component (A) and Aminoplast or phenoplast resins (B). To make the thermosetting Resins are the starting materials (A) and (B) at room temperature or mixed slightly elevated temperature. Should it be from manufacturing or application-related reasons may be necessary, e.g. B. to methylol groups To remove amino or phenolic resins, the resin combination at higher To keep temperatures, for example, about 70 to 120 ° C, so must incipient condensation, d. H. a loss of NH₂ functions will.  

The thermosetting resins from the polymer groups containing amino groups, Polyaddition and / or polycondensation products (A) and the Crosslinking agents (B) can be applied in a conventional manner to the Fiber materials are applied. Conveniently, the However, thermosetting resins as stable aqueous dispersions with a Solids content from 0.1 to 50% by weight, preferably from 1 to 40% by weight, and in particular from 2 to 35% by weight, based on the total weight of the Dispersion applied. Under a stable dispersion is a Understanding dispersion in which the dispersed phase does not settle or, if a certain sedimentation occurs, this easily again is redispersible. The average particle size of the resin phase is in generally less than 10 µm, preferably less than 5 µm. The expression However, dispersion also includes homogeneous aqueous solutions that are optically clear appear.

For the dispersion in water, the thermosetting resins are at least partially neutralized to form cationic groups, e.g. B. salts of primary, secondary or tertiary amines. For this an acid, such as. B. Formic acid, acetic acid, lactic acid or phosphoric acid stirred in and with Diluted water to the processing concentration. The degree of Neutralization depends on the type of thermosetting resin and it is generally sufficient that only so much acid is added that the Resin is dispersible in water and the dispersion is the desired one Has flow properties to form a film on the fiber material.

The stable aqueous dispersions obtained with a solids content from 0.1 to 50% by weight, based on the weight of the dispersion a thermosetting resin consisting of

• A) at least one polymerization, polyaddition containing amino groups and / or polycondensation product with an average molecular weight _n  from 500 to 10,000, which on average per molecule at least two hydroxyl, primary and / or secondary amino groups owns and
• B) at least one crosslinking agent from the group of the polyureas, Polyurea polyurethanes, urea condensation products, Amino and / or phenolic resins

find use as sizes and / or binders for fiber materials, especially for fiber materials made of glass, carbon, aromatic polyamides or aromatic polyesters.  

As fiber materials for the production of moldings from fiber-reinforced Plastics are organic and preferably inorganic fibers used. Individual fibers of any length, e.g. B. from 0.1 to 0.8 cm, preferably from 0.2 to 0.6 cm and diameters from 1 to 50 µm, preferably 7 to 20 microns or rovings with z. B. 40 to 9600 tex, preferably 1200 to 4800 tex are used, which may also be used can be provided with usual sizes, although the Sizing content expediently does not exceed 0.5% by weight. As fiber materials however, fibrous sheets are preferably used, such as B. mats, fleece, fabric or felt. The fibers can for example from cellulose, aromatic polyesters, polyurethanes or Polyamides exist. Asbestos as organic fiber materials, Rock wool, carbon and preferably glass. In particular Glass fiber mats with basis weights of 150 to are used 1200 g / m², preferably from 200 to 900 g / m², individually or in several Layers needled or preferably solidified by needles, e.g. B. by Sewing with, for example, polyester threads can be used.

The fiber materials are usually used in an amount of 5 to 75 wt .-%, preferably from 20 to 60 wt .-%, based on the weight of the finished molding, used.

The thermosetting resin is used to pretreat the fiber materials in such an amount that the content on the fiber material is 0.01 up to 8% by weight, preferably 0.4 to 2.5% by weight and in particular 0.8 to 2.2 wt .-%, based on the weight of the fiber material. The optimal amount can be for a certain fiber material and Determine certain thermosetting resin easily through a preliminary test.

The thermosetting resin, optionally dissolved, can be in a suitable volatile, inert solvent, by known methods such as. B. by Sayings and preferably potions are applied to the fiber material. In the preferred embodiment, the thermosetting resin is passed through at least partial neutralization with acids dispersed in water Fiber material, in particular the glass mat consolidated by needles the aqueous dispersion and soaked at 20 to 90 ° C, preferably 30 to 70 ° C dried, with a physical hardening of the glass mat entry. Then the treated glass mat is in one Molding tool, which in its spatial form the molded body to be produced corresponds at 100 to 190 ° C, preferably 120 to 180 ° C in 0.5 to 30 min, preferably 1 to 30 min deformed and cured at the same time. The dimensionally stable preform obtained can be temporarily stored at room temperature or directly for the production of molded articles from fiber-reinforced Reaction plastics are used.  

According to another process variant, the aqueous dispersion of thermosetting resin in roving production at a temperature up to 90 ° C as a size applied to the glass fiber. From such rovings manufactured glass mats do not require any further impregnation with the thermosetting resin dispersion, but can be directly described Be deformed and hardened. However, if you use the pre-traded rovings directly as reinforcing agents, e.g. B. for production unidirectional molded body, flat reinforced semi-finished products made of glass mat reinforced Thermoplastics or reinforced thermoplastics, is one Curing is not absolutely necessary before the molded article is manufactured.

Can be used to produce the shaped bodies by the process according to the invention basically all thermoplastics are used as matrix material, however, easy flowing thermoplastics are preferred. As thermoplastic Processable plastics are mentioned as examples of polypropylenes, Polyamides, polyalkylene terephthalates, preferably polyethylene and / or polybutylene terephthalates, polyurethanes, polyoximethylenes e.g. B. Polyoxymethylene homo- and / or copolymers, polycarbonates or Mixtures of at least two of the thermoplastically processable plastics. The introduction of the pretreated fiber materials, preferably the fibrous fabrics and especially the glass fiber mats in the Thermoplastics are carried out in a manner known per se, for example by Mixing with short glass fibers in the extruder and subsequent extrusion or for fabrics, preferably by soaking with the thermoplastic melt. Suitable methods are described for example in Kunststoffe 72 (1982), pages 341 ff, Kunststoffe 66 (1976), pages 793 ff and K. Plastic and Kauschuk Zeitung 1981, page 219.

However, they have proven particularly useful as plastics and therefore Reaction plastics, z. B. unsaturated polyester resins, epoxy resins, vinyl ester resins, bismaleimides and cyanate resins, or preferably those from the group of the polyurethane, Polyurea, polyurethane-polyurea elastomers or in particular Polyamides, the elastomers being produced according to the Polyisocyanate polyaddition process and the polyamides by activated alkaline lactam polymerization. The moldings from the fibrous Sheets and the reactants polyurethane, polyurea, Polyurethane-polyurea elastomers or polyamides expediently with the help of reaction injection molding technology (RIM; reaction-injection-molding). This process engineering is also known from numerous literature and patent publications. For example, we would like to refer to DE-B-26 22 951 (US 42 18 543), EP-A-69 286, DE-A-34 13 938 and EP-A-1 34 992.  

The fiber-reinforced polyamide molded articles are produced as has already been explained, expediently by activated alkaline Polymerization of lactams. This procedure is described, for example, in Kunststoff-Handbuch, Volume VI, Polyamide, Carl Hanser Verlag 1966, pages 46 to 49 described in detail. There are two components from, the one component containing a catalyst lactam melt and the other component is an activator-containing lactam melt. The two components are mixed into a pretreated one Forming tool containing fiber materials transported and there polymerized.

The preferred lactam is ε- capralactam, and pyrrolidone, capryllactam, laurolactam, enanthlactam and the corresponding C-substituted lactams can also be used. The lactams can also be modified, for example with polyetherols, prepolymeric isocyanates or with bisacyl lactams according to DE-A-24 12 106.

Suitable catalysts are e.g. B. alkali and alkaline earth metal compounds of lactams, such as sodium ε- caprolactamate, or of short-chain aliphatic carboxylic acids, such as sodium or potassium formate, or of alcohols with 1 to 6 carbon atoms, such as sodium methylate or potassium tert-butoxide. In addition, alkali metal or alkaline earth metal hydrides, hydroxides or carbonates can also be used, as well as Grignard compounds such as caprolactam magnesium bromide. The catalysts are usually used in amounts of 0.1 to 10 mol%, based on total lactam.

Possible activators are: N-acyl lactams, such as N-acetyl prolactam, Bisacyl lactams, substituted triazines, carbodiimides, ketenes, cyanamides, Mono- and polyisocyanates, as well as masked isocyanate compounds. they are preferably used in amounts of 0.1 to 10 mol%.

The impact strength of the molding compositions can be increased by conventional additives such as Polyoxyalkylene glycols with molecular weights from 2000 to 100,000 increased be, further by adding reactive or non-reactive Rubbers such as B. graft polymers.

The lactam can be polymerized in the presence of customary stabilizers be performed. A combination of CuI is particularly advantageous and KI in a molar ratio of 1: 3, which in amounts of 50 to 100 ppm copper, based on total lactam, the activator-containing component is added. Other suitable examples are cryptophenols, amines and Triphenylphosphine.  

Other additives are inorganic fillers in amounts from 10 to 60 wt .-% (based on the molded part), which is not the polymerization disturb, e.g. B. metal powder, quartz powder, metal oxides, graphite, carbon black, Silica gel, pigments, wollastonite and chalk. Light stabilizers, optically brightening substances, flame retardants, Crystallization accelerators, such as. B. talc or polyamide-2.2, Lubricants such as molybdenum sulfide and shrinkage reducing substances be added.

The addition of defoamers in quantities of 0.05 to 5% by weight, preferably 0.1 to 1% by weight, which includes the inclusion prevent air bubbles in the molded part. Preferred defoamers are 5 to 20% by weight solutions of diene polymers, in particular polybutadiene, in organic, especially aromatic solvents. Such Defoamers are marketed by Mallinckrodt ®BYK A 500 and A 501 offered.

It is also expedient to add internal release agents in amounts of 0.05 to 2% by weight, for example of stearates of calcium, sodium or Potassium, stearyl stearate or octadecyl alcohol.

This preferred manufacturing method corresponds to one modified reaction injection molding technology (RIM) for polyisocyanate polyaddition reactions e.g. B. from Piechota and Röhr in "integral foams", Carl Hanser Verlag 1975, pages 34 to 37, and the aforementioned Patent publications is described.

The two components are separated into one in feed tanks Temperature above the melting point of the lactam, preferably to 80 up to 140 ° C, tempered. With hydraulically driven, heated plunger pumps the components become one through heated pipes also promoted heated mixing head. When pressing into it Forming tool, the broaching piston of the mixing head is withdrawn and the Both precisely dosed components enter the open mixing chamber are mixed there intimately and into the flanged mold pressed in. This generally happens under a pressure greater than 1 bar, preferably from 1.1 to 300 bar and in particular at 2 to 80 bar. Basically, it is also possible to work without pressure if you by using special equipment ensures that the melt flows into the mold quickly enough. Within 2 to 50 seconds preferably from 3 to 20 sec, the lactam melt is completely of that Mixing head converted into shape. Nitrogen purging of the mold is not required.  

The molding tool is expediently at a temperature of 100 to 180 ° C, preferably to 125 to 160 ° C and in particular to 130 to 150 ° C preheated. Because the fibrous sheet is already in the mold beforehand had been inserted, this also has the mold temperature accepted. The lactam melt quickly heats up in the mold their temperature and polymerizes within a period of less than 3 min. In general, the finished molded part can already after Be removed from the mold for 1 to 2 minutes. At a Polymerization temperature between 120 and 180 ° C creates a high molecular weight Polyamide with a K value (according to Fikentscher, cellulose chemistry 13, (1932), p. 58) of more than 100, preferably from 110 to 160, the content of monomers and oligomers below 3%, preferably below 2%. The K value can be increased by adding known regulators, e.g. B. long-chain aliphatic monoamines, such as stearylamine, or crosslinkers, such as e.g. B. methylene biscaprolactam or isocyanurated hexamethylene diisocyanate, to be controlled.

According to the process described, large-area molded parts, For example, produce plates between 0.5 and 20 mm thick. These can be semi-finished by pressing at temperatures above the Melting point of the polyamide to be processed into finished parts. If you have appropriately designed shapes and contoured mats used, but you can also produce finished parts directly.

The fiber-reinforced fibers produced by the process according to the invention Moldings are characterized by good mechanical properties and a flawless surface. They are particularly suitable as molded parts for the automotive and aircraft industries, for example for body parts, such as fenders and doors, as well as for technical housings and Manufacture of sandwich parts.

The percentages given in the examples relate to the weight.

example 1 Production of the polyaddition product containing amino groups (A1):

To 400 parts by weight at 80 ° C heated hexamethylene diamine was Stir an 80% by weight solution of 400 parts by weight of a commercially available Epoxy resin based on 2,2-bis (4-hydroxiphenyl) propane with a Epoxy equivalent weight of 500 in toluene added. After it has subsided the exothermic reaction was allowed to react at 100 ° C for 30 min react completely. The excess hexamethylene diamine and toluene were added distilled off under a pressure of 15 mbar, the reaction mixture  reached a temperature of 180 ° C. Then in one Thin film evaporator at 180 ° C and 2.5 mbar traces of free diamine separated. The polyaddition product obtained had an amine number of 169 mg KOH / g and a softening point of 95 ° C.

Representation of the amino group-containing polycondensation product (A2):

200 parts by weight of the polyaddition product (A1), 30 parts by weight dimerized Fatty acid (®Priol 1010 from Unilever AG) and 20 parts by weight of xylene were gradually heated to 190 ° C and water then condensed at this temperature for one hour. After this The reaction mixture was first cooled to 130 ° C. with 9 parts by weight Butylglycol and then diluted with 70 parts by weight of isobutanol. The The polycondensation product obtained had a solids content of 70% by weight.

Production of the polyurea or polyurea polyurethane (B):

1 equivalent of the respective polyisocyanate was introduced, with one diluted isocyanatinized solvent so that the end product is a Had concentration of 50 wt .-% and with stirring and exclusion of moisture the secondary amine, optionally together with the polyol, added over 30 minutes at 80 ° C. Then the approach stirring continued at 80 ° C until an NCO value of <1 was reached.

table

in the table mean:

HDI: 1,6-hexamethylene diisocyanate IHDI: partially isocyanurated HDI with an NCO content of 22% by weight DBA: dibutylamine TMP: trimethylol propane  

Preparation of the aqueous thermosetting resin dispersion:

100 parts by weight of the polycondensation product (A2) were mixed with 60 parts by weight Polyurea (B1) or alternatively polyurea-polyurethane (B2) mixed. After adding 2.2 parts by weight of acetic acid, the resin water-dilutable. After distilling off the organic solvent a 35% by weight aqueous dispersion was set.

Example 2 Production of the urea condensation product (B3)

58 parts by weight of hexamethylenediamine, 60.1 parts by weight of 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane and 90 parts by weight of urea were within heated from 2 hours to 160 ° C. This split from about 120 ° C Ammonia. The reaction mixture first became liquid and then solidified to a white crystal mass. The temperature was raised until at 180 ° C a clear melt emerged. At this temperature, within 8 hours 193.5 parts by weight of dibutylamine were added. After the addition is complete was held at 180 to 190 ° C until the reflux stopped came, which took about 4 hours. After cooling, it froze Urea condensation product to a colorless, glassy mass with a softening point of around 100 ° C.

Preparation of the aqueous thermosetting resin dispersion

100 parts by weight of the polycondensation product (A2) from Example 1 and 42.8 parts by weight of the urea condensation product described above (B3) were mixed intimately. After adding 2.4 parts by weight of acetic acid the resin became water-dilutable. After distilling off the organic Solvent was a by adding deionized water 35% by weight aqueous dispersion.

Example 3 Production of the polyaddition product (A3)

In a suitable reactor, 970 parts by weight of a commercially available Bisphenol A polyglycidyl ether with an epoxy equivalent weight of 435 and 265 parts by weight of a commercially available polycaprolactone diol (PCP 0200 from Union Carbide Corp.). This approach was set to 100 ° C heated under nitrogen and there were 0.46 parts by weight of benzyldimethylamine admitted. The reaction mixture was further heated to 130 ° C and for  held at this temperature for about 1.5 hours. The approach was then based on Cooled 110 ° C and there were 110 parts by weight of methyl isobutyl ketone in the Reaction vessel introduced. Then 39.8 parts by weight of a 73 wt .-% was non-liquid solution of methylisobutyldiketimine of diethylenetriamine in methyl isobutyl ketone and then 100 parts by weight of methyl isobutyl ketone admitted. It was cooled until the mixture reached a temperature of 70 ° C had achieved. Then 53.1 parts by weight of diethylamine were added and the Batch again heated to 120 ° C and 3 hours at this temperature held.

Production of the heat-resistant resin dispersion

100 parts by weight of the polyaddition product (A3) were 43.4 parts by weight of the polyurea polyurethane (B2) mixed according to Example 1. After addition 2.13 parts by weight of acetic acid made the resin water-dilutable. After this The toluene was distilled off by adding distilled water set a 35 wt .-% aqueous dispersion.

Example 4 a) Production of the glass mat preform:

A glass mat solidified by sewing with polyester threads with a The basis weight of 600 g / m² was placed in a 4% by weight bath aqueous thermosetting resin dispersion, prepared according to Example 1, submerged. The glass mat was then allowed to dry at room temperature. The glass mat solidified through physical networking. The glass mat was cut in a cutting machine and in one Forming tool made of steel, which has the spatial shape of an underbody protective covering (Cw sheet) had at a temperature of 150 ° C in 20 minutes hardened. The resin content of the glass mat was approximately 2% by weight. The contoured glass mat was demolded and stored at room temperature, keeping the outline.

b) Production of a fiber-reinforced, contoured shaped body by activated alkaline lactam polymerization according to the RIM method

Component recipe:

39.375 parts by weight of caprolactam, 9.0 parts by weight of a 17.5% by weight solution of sodium lactamate in caprolactam, 1.25 parts by weight Talkum I.T. extra and 0.375 parts by weight calcium stearate.

Component II recipe:

38.15 parts by weight of caprolactam, 9.0 parts by weight of a solution of 83.5% by weight of caprolactam and 16.5% by weight of hexamethylene diisocyanate, 1.5 parts by weight of a 50% by weight solution of isocyanurated hexamethylene diisocyanate in caprolactam, 0.1 part by weight of CuJ / triphenylphosphine / Mn (II) CO₃ and 1.25 parts by weight Talkum I.T. extra

Component I was preheated to 100 ° C, component II to 128 ° C. Components I and II were in a self-cleaning mixing head Broaching pistons manufactured by Elastogran Maschinenbau, Straßlach, mixed in a weight ratio of 1: 1. The steel mold had it Contours of an underbody protection plate for a car. In the mold 2 contoured preforms were made from glass mats, as below 4a). The molding tool including the one included Preforms were preheated to a temperature of 150 ° C. Within The lactam mixture was mixed out of the mixing head under 7 seconds Pressure of 20 bar injected into the mold. After 2 minutes it was the finished fiber-reinforced molded article is removed from the mold. The molded body had one Total weight of 980 g, a glass content of 43.8 wt .-%, a thickness of 2 mm and a flexural modulus of elasticity, measured according to DIN 53 457 in the dry Condition at + 23 ° C, from 7870 N / mm₂.

The molded body showed a flawless, good surface quality. No polymerisation disturbances were found.

Example 5

The procedure was analogous to that of Example 4a), but the in Example 2 described thermosetting resin dispersion. The one to soak the dispersion related to the glass mat had a concentration of 4% by weight.

The molded body was produced analogously to the information in Example 4b). The The molded body obtained had a tensile strength in accordance with DIN 53 455 in the dry Condition of 185 N / mm² and good surface quality. Polymerization disorders were not observed.

Example 6

The procedure was analogous to that of Example 4a, but the in Example 3 described a thermosetting resin dispersion. The one to soak the dispersion concentration used was 4% by weight.  

The finished part produced in the same way as in Example 4b had one Flexural strength according to DIN 53 452 in the dry state of 190 N / mm² and a good surface quality. Polymerization disorders were not observed.

Example 7

A size-free roving with 1440 tex made of 80 tex threads and 20 µm thick Filaments, consisting of EG glass, were made with the thermosetting Resin dispersion of Example 1 coated at 70 to 80 ° C. For this Roving was made by needling a glass mat with a basis weight of 600 g / m² manufactured using the following two process variants were processed

a) without further curing and b) curing of the resin at 180 ° C in 20 minutes.

The glass mats (a) and (b) treated in this way were treated with a Soaked polypropylene melt and then the semi-finished product Heated to 210 ° C and in a mold heated to 80 ° C Precast parts pressed. The finished parts according to both process variants had an excellent surface.

Example 8 Production of the polyaddition product (A4)

1614.6 parts by weight of a diglycidyl ether from epichlorohydrin and Bisphenol A with an epoxy value of 0.5 and 403.0 parts by weight of one same resin with an epoxy value of 0.2 were in 864.5 parts by weight of toluene dissolved at 70 ° C.

2678.0 parts by weight of this solution were added within 2.5 hours 869.2 parts by weight of hexamethylenediamine were metered in at 70.degree. The excess Amine was partially removed at 150 ° C under reduced pressure and that Concentrate in a thin film evaporator at 190 ° C and a pressure of 0.3 mbar freed from excess amine.

The product had a softening point of 70 ° C and a total nitrogen content from 4.7% by weight, of which 1.9% by weight to primary, 2.6% by weight secondary and 0.2% by weight tertiary amino groups.  

Production of the amino group-containing polycondensation product (A5)

400 parts by weight of the polyaddition product (A4) described above were with 55.0 parts by weight of dimer fatty acid (e.g. ®Pripol 1015), 20 parts by weight Stearic acid, 7 parts by weight triphenylphosphine, 80.0 parts by weight isodecanol and 25 parts by weight of toluene and heated to 100 ° C; subsequently 2.15 parts by weight of amidosulfonic acid became warm in 5 parts by weight of water dissolved, added and heated to 160 ° C in 1.5 hours, toluene, the added water and parts of the water of reaction, as well as ammonia from 140 ° C have been removed. The batch was kept at 170 ° C. until a viscosity of 1650 mPa · s at 150 ° C (measured with the Epprecht viscometer) was. The acid number was 6.3. The mixture was diluted with a Mixture of 123 parts by weight of ethylene glycol and 100 parts by weight of ethanol.

Preparation of the aqueous thermosetting resin disposition

466 parts by weight of the amino group-containing polycondensation product (A5) were with 128 parts by weight of a melamine-formaldehyde resin (B4) (Melamine: formaldehyde: methoxy groups equal approximately 1: 4: 3; Solids content: approx. 70% by weight; ®Cymel 325 from Cyanamid) and 46.0 parts by weight of a melamine-formaldehyde resin (B5) (hexamethylolmelamine completely etherified with methanol and ethanol, solids content approx. 95 wt% z. B. ®Cymel 1116) and 20 parts by weight of isodecanol and 9.4 parts by weight Mixed acetic acid. Thereafter, with the addition of demineralized Water the organic solvents under reduced pressure (water jet vacuum) separated and the aqueous thermosetting resin disposition a solids content of 35% by weight.

Example 9 Production of the polycondensation product (A6) containing amino groups

800 parts by weight of the polyaddition product (A4), produced in accordance with Example 8, 280 parts by weight of dimer fatty acid (for example ®Pripol 1014 from the company Unilever AG), 35.0 parts by weight of stearic acid, 18.0 parts by weight of triphenylphosphine, 24 parts by weight of ethylenediamine dissolved in 188.0 parts by weight of phenylglycol, 54 parts by weight of benzyl alcohol and 85.0 parts by weight of toluene were mixed and the mixture at 170 ° C while removing water condensed until an acid number of 3 to 4 mg KOH / g was reached. The Condensate was mixed with 9.6 parts by weight of 1-methoxypropanol-2, 75 parts by weight Butylglycol, 110 parts by weight of ethanol and 135 parts by weight of water and Diluted 11.3 parts by weight of acetic acid and then filtered the solution. The The polycondensate solution had a solids content of 64% by weight and a Amine number of 69 mg KOH / g.  

Production of the phenolic resin (B6)

1075.0 parts by weight of phenol, 1886.0 parts by weight of aqueous formaldehyde solution (40 wt .-%) and 148.5 parts by weight of zinc acetate (Zn (CH₃COO) ₂ × 2 H₂O) were slowly heated to 90 ° C and 3.5 hours at this temperature held.

The mixture was then cooled, 200 parts by weight of methanol were added and 30 ° C within one hour 146.5 parts by weight of 40 wt .-% o-phosphoric acid added dropwise and filtered from the crystalline precipitate formed.

The clear resin solution was at 35 ° C under reduced pressure in a Equipment equipped with effective coolers by circling Concentrated 1260 parts by weight of distillate (mainly water), finally 740 parts by weight of isodecyl carbamate were added and at 40 ° C another 560 parts by weight of distillate are removed.

The resulting resin solution was filtered through a pressure filter and washed with 4 parts by weight of di-n-butylamine were added. The condensation product indicated average molecular weight of 272.

At 70 ° C and 120 ° C and a pressure of 1.0 mbar, the product was in one refurbished two-stage thin-film evaporator. You got 1910 parts by weight of a light-colored resin with a solids content of 92% by weight, an average molecular weight of 478 and a viscosity of 480 mPas / 100 ° C (measured with the ICI plate / cone viscometer). The Residual phenol content was 0.12% by weight; the zinc content was 44 ppm.

Preparation of the aqueous thermosetting resin dispersion:

For the production of 3000 parts by weight of a 10% by weight aqueous thermosetting resin dispersion were 328.0 parts by weight of the amino group-containing Polycondensation product (A6) and 115 parts by weight of Phenolic resin (B6), which is obtained by post-condensation at 95 to 100 ° C a viscosity of 600 m · Pas / 100 ° C, corresponding to an average Molecular weight of 585, and then to a solids content of 80% by weight was set in ethanol, mixed well, with 5.0 parts by weight Protonated acetic acid and slowly with deionized water diluted with simultaneous separation of the ethanol under reduced Pressure (water jet vacuum). The dispersion obtained had a pH from 7.15.  

Example 10

The procedure was analogous to that of Example 4a), but the in Aqueous thermosetting resin dispersion described in Example 8. The for Dispersion used had a solids content of 4% by weight.

The finished part produced in the same way as in Example 4b) had one Flexural strength according to DIN 53 452 in the dry state of 190 N / mm² and a good surface quality. Polymerization problems on the molded part were not observed.

Example 11

The procedure was analogous to that of Example 4a, but the in Example 9 described an aqueous thermosetting resin dispersion. The for Dispersion used had a solids content of 4% by weight.

The finished part produced in the same way as in Example 4b had one Flexural strength according to DIN 53 452 in the dry state of 186 N / mm² and a good surface quality. Polymerization problems on the molded part were not observed.

Claims (24)

1. Process for the production of molded articles from fiber-reinforced Plastic,characterized, that one of the fiber materials Pretreat with a thermosetting resin that contains

• A) at least one polymer group containing amino groups, Polyaddition and / or polycondensation product with one average molecular weight _n  from 500 to 10,000, which in the Means per molecule at least two hydroxyl, primary and / or has secondary amino groups and
• B) at least one crosslinking agent from the group of polyureas, polyurea-polyurethanes, urea condensation products, amino and / or phenolic resins.

2. The method according to claim 1, characterized in that the thermosetting resin as component (A) at least one reaction product from one or more aromatic and / or aliphatic epoxy resins and one or more primary, secondary or tertiary Contains mono- and / or polyamines. 3. The method according to claim 1, characterized in that the thermosetting resin as component (A) at least one reaction product one or more aromatic and / or aliphatic epoxy resins, one or more primary, secondary or tertiary Mono- and / or polyamines and one or more polyalcohols contains at least two hydroxyl groups. 4. The method according to claim 1, characterized in that the thermosetting resin as component (B) at least one polyurea contains, prepared by reacting at least one organic Polyisocyanate with at least one secondary monoamine. 5. The method according to claim 1, characterized in that the thermosetting resin as component (B) at least one polyurea polyurethane contains, produced by reacting at least one organic polyisocyanate with one or more polyalcohols at least two hydroxyl groups and at least one secondary Monoamine.   6. The method according to claim 1, characterized in that the thermosetting resin as component (B) at least one urea condensation product contains, made by polycondensation of at least one primary diamine and / or polyamine with urea, at least one secondary monoamine and optionally one or several polyalcohols at elevated temperature, optionally in Presence of catalysts and separation of the ammonia formed. 7. The method according to claim 1, characterized in that the thermosetting resin as component (B) a low methylolated, contains highly etherified aminoplast resin. 8. The method according to claim 1, characterized in that the Thermosetting resin as the phenolic resin of component (B) contains methylolated phenol attached to the phenolic OH group with allyl alcohol is etherified or a methylolated mono- or polyphenol, whose methylol groups are at least partially etherified. 9. The method according to claim 1, characterized in that the thermosetting resin as a stable aqueous dispersion with a solids content from 0.1 to 50% by weight, based on the total weight of the Dispersion, is present. 10. The method according to claim 1, characterized in that the content of thermosetting resin based on the fiber material 0.01 to 8 wt .-% on the weight of the fiber material. 11. The method according to claim 1, characterized in that the plastic is thermoplastically processable. 12. The method according to claim 1, characterized in that as a plastic thermoplastically processable polypropylene, polyamide, polyalkylene terephthalate, preferably polyethylene and / or polybutylene terephthalate, Polyurethane, polyoxymethylene and / or polycarbonate is used. 13. The method according to claim 1, characterized in that one with the thermosetting resin pretreated fiber materials with a melt impregnated from thermoplastic. 14. The method according to claim 1, characterized in that as Plastic a reaction plastic from the group of polyamide, Polyurethane, polyurea or polyurethane-polyurea elastomers used.   15. The method according to claims 1 and 14, characterized in that the polyamide is made by activated alkaline lactam polymerization. 16. The method according to claims 1 and 14, characterized in that the polyurethane, polyurea or polyurethane-polyurea elastomers are produced by the polyisocyanate polyaddition process. 17. The method according to claim 1, characterized in that the shaped body be produced by the RIM process. 18. The method according to claim 1, characterized in that as Fiber materials organic or inorganic fibers or flat Fiber structures made from such fibers are used. 19. The method according to claim 1, characterized in that the Fiber material made of glass, carbon, aromatic polyamides or aromatic polyesters. 20. Use of thermosetting resins that contain

• A) at least one polymer group containing amino groups, Polyaddition and / or polycondensation product with one average molecular weight _n  from 500 to 10,000, which in the Means per molecule at least two hydroxyl, primary and / or has secondary amino groups and
• B) at least one crosslinking agent from the group of polyureas, polyurea-polyurethanes, urea condensation products, amino and / or phenoplasts

as layers and / or binders for fiber materials. 21. Use of stable aqueous dispersions with a solids content from 0.1 to 50 wt .-%, based on the dispersion weight, the contain a thermosetting resin consisting of

• A) at least one polymer group containing amino groups, Polyaddition and / or polycondensation product with one average molecular weight _n  from 500 to 10,000, which in the Means at least two hydroxyl, primary and / or per molecule has secondary amino groups and  
• B) at least one crosslinking agent from the group of polyureas, polyurea-polyurethanes, urea condensation products, amino and / or phenoplasts

as layers and / or binders for fiber materials. 22. Use of thermosetting resins according to claim 20 as layers and / or binders for fiber materials made of glass, carbon, aromatic polyamides or aromatic polyesters.