DE2240517A1 - EQUALIZABLE HEAT-RESISTANT COMPRESSION COMPOUNDS AND THEIR USE FOR THE PRODUCTION OF MOLDED BODIES WITH A SMOOTH SURFACE - Google Patents

Description

"Evenly colorable, thermosetting molding compounds and their Use for the production of moldings with a smooth surface "

Priority; September 7, 1971, V.St.A., No. I78 385

The invention relates to uniformly colorable, heat-curable molding compounds based on unsaturated polyesters, the
are particularly suitable for the production of moldings with a smooth surface, which are also dimensionally stable.

Those used in the manufacture of thermoset reinforced plastic articles Polyester molding compounds used generally consist of a mixture of an unsaturated polyester and an ethylenically unsaturated monomer such as styrene, vinyl toluene or methacrylic acid methyl ester, as a resin component in connection with reinforcing agents, such as fillers »or fibers,

The unsaturated monomer serves as a carrier material for the polyester and contributes unsaturated bonds, which with those of the polyester to form a cross-linked,

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three-dimensional, infusible copolymer react. In practice, of course, it is usually a free radical supplying compound incorporated into the mixture, which decomposes on heating and thereby the interpolymerization initiated. Depending on the end use purpose, the resin composition can

O ther additives,
optionally / such as polymerization accelerator or

or

- contain retarders, mold release agents, UV stabilizers / fire retardants. Of course, in the Formulation dyes incorporated if colored reinforced moldings are required.

Polyester resin-based molding compounds are usually used as a premix in compression molding, compression molding and injection molding processes as well as in the hand lay-up process, i.e. in the preform and mat press process.

Although the long-known reinforced polyesters by these pressing techniques are generally satisfactory can be processed, they still have considerable shortcomings. For example, molded bodies can be molded from these masses Cooling shrink and throw; they also show often wavy, rough surfaces and hollows.

The aforementioned deficiencies of the conventional polyester molding compounds are by and large more thermosetting due to the development Molding compounds based on polyester have been eliminated, which also contain a thermoplastic polymer additive, e.g. polymethacrylic acid methyl ester, Polystyrene, styrene-acrylonitrile mixed poly-

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merisate, vinyl chloride-vinyl acetate copolymers and Polyvinyl acetate, to name just a few suitable thermoplastics. Molding compounds of this type are described, for example, in the USA patent 3,503,921, in Canadian Patent 820,399 and described in British Patent Specification 936,351. Moldings pressed from such modified polyester molding compounds show better and better surface properties Dimensional stability as such that have been produced with the previously known unmodified polyester molding compounds.

Unsaturated polyester molding compounds with thermoplastic additives are commonly known in the art as "low profile" polyesters because they result in molded articles, e.g. "Bendix Microcorder" measured, extremely low millionths of a centimeter values, which means low surface roughness or ripple. However, the thermoplastic polymers incorporated into such molding compounds are primarily Line viewed as fillers or additives as they are not a compatible, integral part of the resin when it cures of the molding compound, but by means of suitable extraction processes are detachable.

Although this / . "

"Little profiled" polyester molding compounds consistently produce moldings with good surface properties and shape
Stability results / strongly colored formulations, in particular those with strong or darker pigments or dyes, often molded articles which have a strongly speckled and / or speckled or marbled appearance. Such form

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bodies are of course for numerous commercial areas of application, e.g. in the automotive industry or as a housing for apparatus construction, unsuitable.

The object of the present invention was therefore to find unsaturated polyester molding compounds to make available that are suitable for the production of strongly colored moldings that are both uniform are colored and despite the existing reinforcement material a smooth surface and good dimensional stability exhibit. This object is achieved by the invention.

The invention thus relates to uniformly colored, thermosetting molding compounds, consisting of

(a) about 30 to 70 parts by weight of a polymerizable unsaturated Polyester,

(b) about 29 to about 69 parts by weight of an ethylenically unsaturated one Monomers and

(c) about 1 to 10 parts by weight of a styrene-diene block copolymer with a polystyrene content of 27 * 1 percent by weight and with an average molecular weight of 73,000 to 150,000, as well as, if applicable

(d) fillers, reinforcing fibers, stabilizers, inhibitors, accelerators, mold release agents, pigments, Dyes, chemical thickeners and / or other common additives and processing aids.

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Sufficient amounts of reinforcing agent are added to the molding compounds with mineral fillers, pigments or dyes and free radical generating compounds added to the crosslinking initiate between the polymerizable compounds. If necessary, others that are customary in the art can also be used Additives such as UV stabilizers, polymerization inhibitors,

or
retardants / mold release agents can be used.

The moldings produced from this thermosetting molding compound show good dimensional stability, have smooth surfaces and are evenly colored.

The styrene-diene block copolymers used in the inventive Molding compounds are used as "little profiled" additives, i.e. due to the smooth surfaces and good dimensional stability are generally known in the art as "thermoplastic elastomers" and are used as adhesives, Sealants and coatings used. They make a difference the structure is basically both homopolymers and random copolymers; she are rather block copolymers, each polymer chain consisting of three blocks in the arrangement X-Y-X. "X" represents one amorphous polymer chain with a transition temperature in the glass-like state above room temperature, i.e. it is a thermoplastic polymer. "Y" represents an amorphous polymer chain with a

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The transition temperature to the glassy state is well below room temperature, i.e. it is an elastomer. In particular

the block copolymers of the molding compositions according to the invention contain either polybutadiene chains, B, or polyisoprene chains, I, as the elastomeric middle block on the one hand and polystyrene chains, S, as thermoplastic blocks on the other. For the sake of simplicity, the styrene-butadiene-styrene block copolymers are referred to below as "SBS copolymers" and the styrene-isoprene-styrene block copolymers as "SIS copolymers ¹¹ " in the following.

In the particularly preferred styrene-oil according to the invention Copolymer is the molecular weight of the polystyrene block typically 10,000 to 20,000, that of the polybutadiene block at 50,000 to 75,000 and that of the polyisoprene block at 50,000 to 110,000. These copolymers are commercially available and are in ketones, esters and numerous hydrocarbons, especially aromatics such as benzene and toluene, soluble.

During the hardening of the "slightly profiled" polyester molding compounds probably also takes the styrene-diene copolymer by means of its reactive double bonds on the Cross-linking part and is within the hardened polyester base chemically bound, so that you get a really homogeneous, compatible resin system. That actually such a thing chemical reaction takes place, is evidenced by the fact that the hardened press races do not have paint stains or have speckles or marbling,

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even if very bright or bold colors are used. In contrast, the polyester molding compounds, coloring matter and the \ aforementioned saturated thermoplastic Polymerisatzusätze contain, after curing strong Farbsprenkelung and / or -fleckigkeit on. Such an uneven coloration results from the inhomogeneous nature of the overall resin system in these molding compounds, ie the cured polyester and the saturated polymer additive are present as two separate phases, and the dye probably only has an affinity for one of these resin phases.

That the styrene-diene block copolymer in the cured Polyester base mass is chemically bound, i.e. cross-linked, is further proven by the fact that it is an irreversible forms crosslinked structure when heated in the presence of a peroxide alone. This networked structure is in solvents, which easily dissolve an untreated copolymer, insoluble.

Because of the hardening in the polyester molding compounds according to the invention homogeneous resin system that forms, these molding compounds have in comparison to the well-known "little profiled" Polyester molding compounds, which contain saturated non-crosslinked thermoplastic additives, a better resistance to Chemicals and climatic influences. In addition, show the inventive Compared to the known molding compounds, molding compounds have a better resistance to surface blemishes.

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Apart from the improved coloring achieved, there is a Another advantage of using the styrene-diene block copolymers as "poorly profiled" thermoplastic polymer additives is that, compared to the amounts of the previously used saturated thermoplastic polymer additives, the In order to achieve an equally good result, it was necessary to use smaller amounts of the block copolymers to create the desired surface improvement in the moldings. For example is the incorporation of 1 to 10 parts by weight of the Blockmiachpolymerlsats, based on the total weight of the resin system, in generally sufficient to produce a to create improved surface properties and the desired dimensional stability. In general, however, 2 to 25 parts by weight of the saturated thermoplastic are required to achieve the to achieve the same improvement.

In the molding compounds according to the invention, the mixture fraction (a) Usable unsaturated polyesters are prepared by conventional methods, such as those by reacting one or more polyhydric alcohols and one or more polycarbonate or polybasic acids. In the In practice, the so-called unsaturated polyesters from polyhydric alcohols and polycarboxylic acids are used as the preferred "linear" or "mainly linear" polyesters are used, i.e. those which have no or only a few crosslinks between the Polyester molecules, as evidenced by the fact that such polyesters are soluble in solvents such as acetone. These polyesters are usually mainly used by

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Esterification of a dihydric alcohol with a dibasic acid, optionally in conjunction with small amounts of polyhydric Alcohols with more than two hydroxyl groups and / or polybasic acids with more than two carboxyl groups. Of course, some of the unsaturated acid can also be replaced by a saturated acid, e.g. by oxalic, malonic, sebacic, Phthalic or tetrahydrophthalic acid. Other modifications the esterification are obvious to the person skilled in the art, since these are customary and known process steps.

In making a typical linear polyester, the esterification is carried out essentially to completion, i.e. up to to an acid number below about 80, with an addition polymerization is avoided to a greater extent. However, the production of the polyester component is not contrary

was the subject of the present invention. ■. ·

Particularly preferred polyesters which can be used according to the invention are by converting 0.8 to 1.2 mol of ethylene glycol, diethylene glycol, Propylene glycol, dipropylene glycol and / or neopentyl glycol with 1.0 mole each of maleic and / or fumaric acid, ο-phthalic acid, isophthalic acid, Tetrahydrophthalic acid, adipic acid or their anhydrides are obtained. Modified diethylene, dipropylene, ethylene, propylene or neopentyl maleates or fumarates can be used, as can bisphenol-modified ones and halogenated or phosphorus-containing acids or glycols are used, the latter two components provide chemical-resistant and flame-retardant polyester. These compounds are currently used for reasons of economy and because of the desirable properties ^ which they

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in the end product, preferred.

The unsaturated monomer of the resin system in the invention thermosetting molding compound has at least one remainder

CHp = C- for crosslinking with the unsaturated polyester during of hardening on. Generally any monomer is

the way it is

/ has been used in lOiyestersystemen is suitable · Special monomers that are more desirable because of their availability, reactivity and others Properties currently preferred are styrene, vinyltoluene, chlorostyrene, tert-butylstyrene, diallyl phthalate, Vinyl acetate and methyl methacrylate.

Presently, about 0.2 to 1.6, preferably 0.3 to 1.5, monomer
^ e part polyester preferred to have the most effective crosslinking

and to ensure thermosetting.

Although the mixture of polyester, monomer and block copolymer together with pigment, various fillers or reinforcing agents through heat alone

can be hardened, hardening becomes preferable

promoted by adding a suitable curing initiator. Suitable curing initiators are benzoyl peroxide, tert-butyl peroctoate, tert-butyl peroxy (trimethyl) acetate, di-tert-butyl -peroctoate, tert-butyl perbenzoate, cyclohexanone peroxide, di- -tert-butyl-peroxide, tert-butyl-peracetate, tert-butyl-peroxy-isopropyl-carbonate, tert-butyl-azo-isobutyronitrile, di- tert-butyl diperphthalate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) -hexane, 1, i-di-tert-butyl-peroxy- ^ i ^ fS-trimethylcyclohexane, 2- (tert-butylazo) isobutyronitrile, lauryl peroxide, iso-

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propylbenzene hydroperoxide, tert-butylbenzene hydroperoxide, methyl ethyl ketone peroxide, i-Hydroxy-cyclohexyl-hydroperoxide-i or Mixtures of such initiators.

Advantageous "initiator concentrations are about 0.1 to 30 percent by weight, based on the total weight of the three-component resin system. The hardening of the molding compound under

is usually /

Heat and pressure / in closed forms,

preferably carried out in positive pressure forms. The curing speed the molding compound can also be modified by adding suitable inhibitors, 'such as hydroquinone,

tert-butyl catechol, benzaldehyde or tetrachloroquinone, or by suitable accelerators, such as certain amines, e.g. dimethylaniline, diethylaniline, di- -n-propylaniline, dimethyl-p-toluidine, p-diethylamino-azobenzene, Dimethyl-m-aminophenol, as well as metal salts such as cobalt or manganese naphthenate, to be influenced.

/ Molding compounds

The invention also relates to the use of the new / for the production / reinforced

/ Evenly colorable / Moldings with a smooth surface. . This embodiment is characterized in that the thermosetting molding compounds are mixed with a filler, an initiator, a mold release agent, a color component and optionally a former thickener, then a fiber reinforcement mat is impregnated with the resulting mixture and finally. the impregnated mat is heated under pressure in a mold for a sufficient time and the resin binder is hardened in the process.

You can also use the reinforcement fibers and / or the fiber reinforcement

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Premix the agent directly with the other components and then immediately follow the hardening stage.

/ like a TrKperfolle, Finally it is also possible to apply part of the molding compound with the remaining additives on a substrate surface first.

on it
to arrange /

put on it a fiber reinforcement mat or reinforcement fibers / and then a second carrier film coated with the molding compound with the first to form a sandwich structure join together and finally cure the latter as indicated above.

In the manufacture of the invention, reinforced thermosetting Press masseu ·. becomes the resin system, i.e. the mixture of unsaturated polyester, unsaturated monomers and the styrene

about -Diene block copolymer, with about 50 to / 600 parts by weight Reinforcing agents processed per 100 parts by weight of resin system. There are about 25 to 250 parts by weight of these reinforcing agents generally fillers, while 25 to about 350 parts by weight are fiber reinforcing agents.

Examples of suitable ones. Fillers are clay, ground limestone or whipped chalk, plaster of paris, talc, and calcium carbonate Cellulose in any form. Aluminum hydrate, sodium borate and antimony oxide can be used to increase the flame resistance will. Suitable reinforcing agents are glass staple fibers, glass mats, sisal, asbestos and other synthetic fibers, such as Nylon-ι polyester and acrylic fibers, as well as high temperature fibers, especially carbon and boron fibers

The molding compounds usually also contain plasticizers and mold release agents. The amount of these additives used in each case is equivalent to

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their - puncture in the molding compound.

Embodiment / According to a preferred / "' ~ for the production of a press

Compression molding compounds are usually 50 to 70 percent by weight unsaturated polyester with 50 to 50 percent by weight unsaturated monomers to an easily manageable one

while/

' Liquid mixed, /' the festive unsaturated monomers. is premixed with the normally solid styrene-diene block copolymer to form a syrup.

The molding compounds according to the invention are generally about 30 to 300 seconds at temperatures of about 121 to 163 ° C and Pressures from about 3.5 to 14 atmospheres depending on the shape of the desired Pressed molded body. Compression molding, compression molding or injection molding "processes" are just like any other, with thermosetting Resins in general, applied. Pressing process ^ suitable.

The . . . Examples illustrate the invention. Parts are by weight unless otherwise stated.

example 1

An unsaturated polyester for use in molding compounds according to the invention is made by esterifying 1.05 mol of propylene glycol, 0.5 mol of isophthalic acid and 0.5 mol of maleic anhydride to an acid number below 20 are prepared. (The acid number is the number of milligrams of alkali, calculated as potassium hydroxide, used to neutralize the free acid in a sample of, 1 g is required.)

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Example 2 (comparative example)

A reinforced molded body is made from a conventional unsaturated polyester that is not thermoplastic whatsoever Contains polymer incorporated as a "little profiled" additive. A premix is prepared using the polyester of Example 1, wherein

the components listed below 1 to 2 minutes /
/ "Tn mixed in a high shear mixer

will:

Parts

unsaturated polyester

Example 1 50

Styrene 50

tert-butyl benzoate (as initiator) 1 zinc stearate (as mold release agent) 3

240 parts of calcium carbonate as filler and 2.4 parts of a 50 percent brown pigment paste ("V-31160" from Ferro

/ Minutes added Chera. Corp.) are then added to the mixture "during 1 to 2 ~] '.

Thereafter, the resulting mixture is subjected to high shear for 4 to 5 minutes mixed.

The mixture obtained is _with glass fibers 6.35 mm long ("OCF 832" from Owens Corning) in a Pflei-

30, 5 x 30,5 x Ot32 _cm / those kneader mixed, then in a / plate shape

introduced and pressed for 2 minutes at 149 ⁰ C and 70 atm. . The molded body is then removed from the mold

and cooled to room temperature ·. j) _eT molded body has warped strongly and shows a relatively rough surface, ^ ⁶ but no color fleoke aafweiet »

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A numerical evaluation for the relative surface smoothness to obtain, the surface smoothness of the pressed plate with a "Bendix Microcorder" (from Bendix Corp., Industrial Metrology Division) according to the manufacturer's instructions No. J5O44O specified procedure. The microcorder values are determined by measuring in any four areas. Each value represents the mean of four 1 * 27 cm sections lengthways a 5 cm long track. The mean of the four tracks represents the required millionth! Centimeter value for the entire plate.

The average surface smoothness of the plate produced is Ο., ΟΟδ mm (317 microinches measured with the Bendix microcorder). Lower values are preferred because they mean smoother surfaces.

Example 3

According to Example 2, a polyester molding compound is produced, with a /
/ Premix of 46.8 parts of polyester, 48.8 parts of styrene and the same amounts of initiator and zinc stearate as in Example 2 4.7 parts of a styrene-butadiene block copolymer ("KRATON 1102" from Shell Chemical Company) are incorporated .
The mixture produced is pressed as in Example 2 and the press plate is removed from the mold and cooled to room temperature. The molded body obtained is dimensionally stable and has a smooth surface. The average surface smoothness of the

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Disk, i.e. the microcorder value is 0.003 mm (118 Microinches) and is therefore much better than the dee Comparative molding of Example 2. In the molding obtained

visible / there is no color speckles / and the color purity and intensity correspond to that of the comparative tablet.

Examples 4-9

Further polyester molding compounds are made according to Example 2 manufactured, - . by incorporating the thermoplastics listed in Table I below as "less profiled" additives willei. Each recipe uses 40.5 parts of the unsaturated Polyester of Example 1, 45.0 parts of styrene and 13.5 parts of the respective thermoplastic are used. The amounts of Initiator, calcium carbonate, zinc stearate and brown pigment paste ("V-31160" from Ferro Chem. Corp.) are the same as in example 2.

The moldings produced from the polyester batches show the following color properties. The results for that produced from the molding compound according to the invention Moldings of Example 3 are used for comparison purposes.

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- 17 - 2240517 powerful,
dark TABLE I frosted,
bright example thermoplastic polymer Il 3. SBS block mixed polymer Paint sprinkle - color
lung degree η 4th 1,2-polybutadiene (low
Molecular weight) no Il 5 1,2-polybutadiene (high
Molecular weight) strong ti 6th vinyl chloride vinyl acetate
Mixed polymer It It 7th Polymethacrylic acid methyl ester . Il 8th Polyvinyl fluoride Il 9 Polyvinylidene fluoride Il Il

As was to be expected, the above polyester approaches the thermoplastic polymer other than that of the invention 'Styrene-diene-Blociimisohpalymerisat contain, although, also moldings with a much smoother surface than those those made from similar polyester batches without additives. ■ have been. In contrast to the polyester molding compounds according to the invention deliver however. such polyester approaches

colored moldings that. numerous speckles of color

to show »/

and a marbled appearance / The color level of these moldings is overall matt and light ..

Example 10

An unsaturated polyester for use in molding compounds according to the invention is made by esterifying 1.05 mol of propylene glycol miij. 0.33 moles of isophthalic acid and 0.67 moles of fumaric acid up to an acid number below 30.

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Examples 11-1J According to Example 2, further reinforced products according to the invention are used Polyester molding compounds prepared, the st ^ rol-diene block copolymers shown in Table II below be incorporated. Moldings are then produced from the batches as described above.

The following results are obtained:

TABLE II

Polyester of Example 10, parts styrene, parts

SBS misoh polymer, parts

( ¹¹ KRATON 1102 "from Shell Chem. · Corp.) SBS copolymer, parts

("KRATON 1101" from Shell Chem. Corp.) SIS copolymer, parts

("KRATON 1107" from Shell Chem. Corp.) tert-butyl perbenzoate, parts Zinc stearate, parts calcium carbonate, parts black pigment paste, parts ("V-31770" from Ferro Chem. Corp.)

Appearance of the moldings? Staining

Color grade

Microinches
(in millimeters

8th example 13th 11 8th 12th 46.8 46, 7th 46.8 48.8 48, 48.8 ——— 4, ___

4.7

4.7

1" 0 1 "O 1 , 0 3, 0 3 , 0 3 , 0 240 125 125 7, 5 7th 7th , 5 no no no

strong strong strong dark dark dark

109 193 212

0.0028 0.005 0.0054)

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Examples 14-18

For comparison purposes, colored 3? Olyeste.rpreasinassen Manufactured without reinforcements, either polymethacrylic acid methyl ester (PMMA.) or a styrene-butadiene block copolymer ^ BS) contained in different amounts «The approaches used and the results obtained are given in Table III.

Polyester des
Example IQ TABLE III 15th 16 17th 18th Parts example Styrene H 47 47 51 51 Parts PMMA 55 45 45 45 45 Parts SBS 45 8th - 4th - Parts initiator - - 8th - 4th Parts Mold release agents - 1 Ί 1 1 Parts Calcium carbonate 1 0.5 0.5 0.5 0.5 Parts -0.5 100 100 100 100 100

pigment

Parts

(50 percent green pigment paste "V ~ 32640 ^H from Ferro Chem» Corp.)

Appearance of the moldings:
No speckles of color. strong none moderate none

Color grade

no . strong none massive

strong

strong- bright, strong- bright, strong matt tig matt tig

As can be seen from the results, the aforementioned approaches yield the saturated thermoplastic polymer PMMA Contain, moldings with clear speckles of color and a marbled appearance. In contrast, the moldings that made of polyester pressed cups with a content of the SBS block

as well

copolymers have been produced, / uniform and strong

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tig colored like those obtained from polyester batches without thermoplastic additives.

None of the incorporated additives can significantly influence the degree of hardening of the polyester, as can the slight reduction the Barcol hardness values for moldings with incorporated additives compared to the HKrt values for Shaped body without additives shows.

of the experiment using If, in a repetition / of the above approaches, oil fiber are incorporated, the polyester without thermoplastic polymer gives moldings, the surface of which is pronounced The other approaches provide moldings with much smoother surfaces.

Example 19

For comparative determination of the surface resistance

Staining /
against / in the case of a "poorly profiled" polyester molding compound according to the invention, a glass fiber-reinforced polyester molding compound is produced in vegetable Example 2, 1 part of tert-butyl peroctoate as initiator, 1 part of a mold release agent and 100 parts of calcium carbonate together with 4-1 parts of the polyester from example 10.49 parts of styrene and 10 parts of an SBS block copolymer can be used.

Similar approaches are made in which, instead of the SBS block copolymer, saturated thermoplastic polymers such as vinyl chloride-vinyl acetate copolymer, polystyrene or polymethacrylic cure methyl ester are used. ^ ⁶ * this

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sets will be 13 »5 parts of the thermoplastic in question Polymer used together with 40 parts of polyester and 4-6 parts of styrene.

Each approach is placed on 2 layers of a 57 g mat ("O.C.F. M8600") poured and covered with a 0.25 mm veil. Each of the impregnated mats is in a 30.5 x 30.5 χ 0.32 cm Plattenτ form pressed for 2 minutes at 149 ° C and 35 atm.

The relative stain resistance of the molded body surfaces is determined in accordance with ASTM D-2299-68. It the following results are obtained:

Testsub- stain resistance

punch saturated thermoplastic SBS block

Polymer additives polymer

Mustard G G

Ketchup B B

Margarine C A

wet tea bag C B

.Lemon C B

A = no staining

B = superficial staining, easily removable by washing,

C = considerable staining that cannot be easily removed and / or etching of the molded body surface causes the from the batches with an SBS-Blockmisehpolymerisat content Moldings produced have better stain resistance than those produced from batches with a content of saturated thermoplastic polymers have been obtained.

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Example 20

According to example 2, an approach

using a mixture of 29.9 parts of the polyester from Example 10 and 4-1.3 parts of one according to the method of U.S. Patent 3,536,782 manufactured as an unsaturated polyester component. The reaction of maleic anhydride, tetrahydrophthalic anhydride and a glycol mixture produced polyester contains 10 to 50 weight percent bromine, which is bound to the tetrahydrophthalic acid is. 10 parts of SBS block copolymer are used in this batch and 5 parts of antimony trioxide incorporated.

The moldings produced from this approach show uniformity colored surfaces. The moldings are also self-extinguishing (time: 1.4 seconds) with a UL-94 rating from SE - 0.

Examples 21 and 22

Incorporating unsaturated polymerizable monomer mixtures As described above, polyester molding compounds according to the invention of the following formulations are produced:

21 22

Polyester of Example 10 styrene

Methyl methacrylate vinyl acetate

SBS block copolymer tert-butyl perbenzoate

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203 203 Parts 110 110 Parts 71 Parts 71 Parts 16 16 Parts 4th 4th Parts

2 2 Parts 400 400 Parts 32 32 Parts

., 21 22

Mold release agent calcium carbonate

black pigment paste
($ 50 pesticide content)
("V-31770" from Ferro Chem. Corp.)

Each batch is poured onto 2 layers of a 57 g mat ("0.CePo M8600") as in Example 19. Each of the impregnated mats is ^{pressed for 120 seconds at 135 °} C. and 35 atm.

The resulting press plates are colored and homogeneously

or marbling /

show no color speckles / those from the vinyl acetate containing approach produced molded body has a somewhat less powerful Parbgrad than that of the approach with Methacrylic acid methyl ester.

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Claims (1)

Claims lJ Evenly colored, thermosetting molding compounds consisting the end (a) about 30 to 70 parts by weight of a polymerizable unsaturated Polyester, (b) about 29 to about 69 parts by weight of an ethylenically unsaturated one Monomers and (c) about 1 to 10 parts by weight of a styrene-diene block copolymer with a polystyrene content of 27 * 1 percent by weight and with an average molecular weight of 73,000 to 150,000, as well as, if applicable (d) fillers, reinforcing fibers, stabilizers, inhibitors, accelerators, mold release agents, pigments, Dyes, chemical thickeners and / or other common additives and processing aids. 2. molding compounds according to claim 1, characterized in that the mixture portion (c) is a styrene-butadiene block copolymer, in which the molecular weight of the polystyrene block is 10,000 to 20,000 and that of the polybutadiene block is 50,000 to 75,000. 3. molding compounds according to claim 1, characterized in that the Oemischteil (c) is a styrene-isoprene block copolymer in which the molecular weight of the polyisoprene block is 50,000 to 110,000. k. Molding compounds according to claim 1, characterized in that the 30981 1/0997 Mixture fraction (a) is an unsaturated polyester consisting of 0.8 up to 1.2 moles of a polyhydroxyl compound per 1 mole of a polycarboxylic acid or a polycarboxylic acid mixture has been prepared. 5. molding compounds according to claim 4, characterized in that the polyester of fumaric acid and / or isophthalic acid, and an alkyl glycol has been made. 6. molding compounds according to claim 4, characterized in that the polyester of maleic anhydride and / or isophthalic acid and an alkylene glycol. 7 · molding compounds according to claim 1 to 6, characterized in that the mixture fraction (b) is styrene. 8. molding compounds according to claim 1 to 6, characterized in that the mixture fraction (b) is methyl methacrylate. 9- Use of the molding compounds according to claims 1 to 8 for production evenly colored shaped body with a smooth surface. 10. Embodiment according to claim 9 »characterized in that a thermosetting molding compound according to claims 1 to 8 with a filler, an initiator, a mold release agent, a color component and optionally mixed with a chemical thickener, then with the resulting mixture a fiber reinforcement mat impregnated and finally heated the impregnated mat in a mold for a sufficient time under pressure and thereby 309811/0997 the resin binder hardens. 11. AusfUhrungsform according to claim 9 * characterized in that that a thermosetting molding compound according to claims 1 to 8 / Reinforcing fibers are premixed with a filler, an initiator, a mold release agent, / and optionally a chemical thickener and then the resulting premix is heated under pressure in a mold for a sufficient time and the resin binder cures in the process. 12. Aus guide horn according to claim 9 *, characterized in that a thermosetting molding compound according to claim 1 to 8 is premixed with a filler, an initiator, a mold release agent, a chemical thickener, a pigment and an accelerator, the resulting premix as a coating on a carrier film applies, then arranges reinforcing fibers on the resin coating, then joins a second carrier film coated with the molding compound with the first to form a sandwich structure, allows this to age and finally cures the aged sandwich structure in a mold under pressure. Ij5. Design according to claim 12 for the production of moldings with fire-retardant properties, characterized in that / it is used that a thermosetting molding compound / its mixture portion (a) is a polymerizable unsaturated polyester with a content of 10 to 50 percent by weight of chemically bound bromine, based on the polyester, is used as the coating. 309811/0997