Method of preparing materials for copies,available especially for dental use

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to vinyl-based impression materials based on polyurethane resins, particularly suitable for dentistry.

By imprinting materials are meant substances which undergo curing from a plastic to a hard or elastic state. The impression materials are used in dentistry to obtain an identical impression of the mucosa and teeth. Preferably, materials for this purpose are used which cure to a rubber-elastic state.

The rubber-elastic compositions can be produced in various ways. In addition to the polymerization of unsaturated hydrocarbons with one or more double bonds, for example, curing of thioplasts, which is possible by reaction of aqueous solutions of alkali polysulfides with alkali dihalides, results in products having rubbery elastic properties. Other rubber-like products are produced by polycondensation of silicones. Another group of rubber-elastic products is obtained by polyaddition reaction of a polyester or polyether with a diisocyanate.

Thiocols have an unpleasant odor by crosslinking and after crosslinking. Polyurethanes are not physiologically safe since they contain free isocyanate groups. In addition, all of these materials exhibit a relatively high polymerization shrinkage; attempts have been made to replace this precipitation using a high proportion of fillers.

In addition, the rubber-elastic rubber-like compositions are prepared on an ethyleneimine base. These products, while having a relatively slight precipitation during polymerization, have the following drawbacks: When stored in water, there is a stronger volume change due to swelling. In addition, the products are not physiologically harmless as they crosslink through aziridine groups. In addition, some aziridines are known carcinogenic agents.

All dental materials used in dentistry are both limited in time and in terms of their curing time. After formulation of the reactive mixture, the processing time is generally about 3 minutes; the subsequent curing time is generally about 5 minutes.

Surprisingly, it has now been found that vinyl-containing polyurethane resins can be cold cured over time to practice in elastic rubber compositions and that these compositions do not have the above drawbacks when used as an impression material.

Thus, the present invention relates to the use of reaction products

(a) diisocyanates,

b) dihydroxy compounds having a molecular weight of 300 to 10,000, preferably 1000 to 8,000; and

c) unsaturated monohydroxy compounds, preferably hydroxyl group-containing acrylic and / or methacrylic acid derivatives, which are converted into a crosslinked state as an impression material, especially in dentistry, when the fingerprint is scanned.

and)

The diisocyanates which can be used according to the invention are:

ethylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate,

2,4-tolunylene diisocyanate a

2,6-tolunylene diisocyanate and mixtures thereof, isophorone diisocyanate, forondiisocyanate,

1.5-naphthalenediisocyanate,

1,3-cyclopentyl diisocyanate, m-phenylene diisocyanate and p-phenylene diisocyanate,

2,4.6-toluylene triisocyanate, 4,4 ', 4'-triphenylmethane diisocyanate,

1,3-xylylene diisocyanate a

1,4-xylylene diisocyanate,

3,3-dimethyl-4,4'-diphenylmethane diisocianate,

4,4'-diphenylmethane diisocyanate, 3,3'-dimethylbiphenylene diisocyanate,

4,4-bisphenylenediisocyanate, durenediisocyanate, 1-phenoxy-2,4'-phenylenediisocyanate, 1-tert-butyl-2,4-phenylenediisocyanate, methyl bis-4,4'-cyclohexyldiisocyanate, 1-chloro-2,4-phenylenediisocyanate, and

4_;4'-diphenyl ether diisocyanate,

In addition, it is possible to use high molecular weight and possibly also multi-functional polyisocyanates which are prepared from low molecular weight matrix by polymerization to uretdions or to isocyanurate derivatives. Examples include uretdione from 2 moles of 2,4-toluylene diisocyanate and polymerization products containing an isocyanurate ring of 2, - (-) - diisocyanate and 2,6-toluylene diisocyanate or hexamethylene diisocyanate; a system containing an average of 2 isocyanurate rings per molecule and made up of 5 moles of toluylene diisocyanate or a corresponding derivative of an average of 2 moles of toluylene diisocyanate and 3 moles of hexamethylenediisocyanate,

In addition, diisocyanates or polyisocyanates can be prepared by partial hydrolysis via carbamic acid and amine with higher urea or biuret-coupled systems, such as a biuret-bound compound, which are formally formed from 3 moles of hexamethylene diisocyanate with 1 mole of water and 1 mole of carbon dioxide ,

Also suitable isocyanate-containing substances are obtained in the reaction of diols or polyols with difunctional or polyfunctional isocyanates when the molar ratio of hydroxy compound to isocyanate is chosen such that free NCO groups are always retained in the statically formed reaction products and the molecular weight is not more than 2000 a 3000,

Particularly preferred isocyanate-containing compounds which may be used in the preparation of the resins of the invention are hexamethylene diisocyanate, toluylene diisocyanate, isophorone diisocyanate and 4,4'-diphenylmethylene diisocyanate,

(b)

The other isocyanate-reactive compounds of the invention are compounds having two isocyanate-reactive hydrogen atoms, having a molecular weight of from 300 to 10,000, preferably from 1000 to 8000,

These compounds in addition to those having amino, thiol or carboxyl groups are in particular polyhydroxyl compounds, in particular compounds having two to eight hydroxyl groups and a molecular weight in particular of 300 to 10,000, preferably 1000 to 8000, for example generally two hydroxyl groups containing polyesters , polyethers, polythioethers, polyacetals, polycarbonates and polyesteramides, which are known for the preparation of homogeneous and cellular polyurethanes,

Suitable hydroxyl groups containing polyesters are, for example, reaction products of polyvalent, preferably divalent, and optionally additionally trivalent alcohols with polyvalent, preferably dibasic carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters and lower polycarboxylic acid esters may also be used. alcohols or mixtures for the preparation of polyesters, The polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and may be optionally substituted, for example, by halogen atoms and / or may be unsaturated,

Examples include:

succinic, adipic, cork, azelaic, sebacic, phthalic, isophthalic, trimellitic, phthalic anhydride, terephthalic, hexahydrophthalic, tefrachlorophthalic, endomethylenetetrahydrophthalic, glutaric, maleic acid, maleic anhydride, fumaric acid, dimeric and trimeric acid oleic acid, optionally in admixture with monomeric fatty acids, terephthalic acid dimethyl ester and terephthalic acid bis-glycol ester.

Examples of polyhydric alcohols are:

ethylene glycol, propylene glycol (1,2) and propylene glycol (1,3 j, butylene glycol (1,4) and butylene glycol (2,3), hexanediol- (1,6 j, octanediol- (1,8), neopentyl glycol) , cyclohexanedimethanol- (1,4-bis-hydroxymethylcyclohexane J),

2-methyl-3,3-propanoiol, glycerine, trimethylolpropane, hexanetriol- (1,2,6], butantriol- (1,2,4), trimeithyloleyane, pentaerythritol, quinite, mannitol and sorbitol, methylglycoside, diethylene glycol, triethylene glycol , tetraeithylene glycol, polyeifhylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols.

The polyesters may have partially terminal carboxyl groups. Also useful are polyesters from lactones, such as ε-caprolactone, or from hydroxycarboxylic acids, such as ε-hydroxycaproic acid.

Also suitable according to the invention are, as a rule, two hydroxyl groups having polyethers of a known type and are prepared, for example, by polymerization of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, e.g. epoxides, optionally in admixture or sequentially to starting components with reactive hydrogen atoms such as water, alcohols, ammonia or amines, such as ethylene glycol, propylene glycol- (1,3) or propylene glycol- (1,2), 4,4'-dihydroxydiphenylpropane, aniline, ethanolamine. Particularly preferred are polyethers having predominantly (up to 90% by weight, based on all hydroxyl groups in the polyether) primary hydroxyl groups. Also polyethers modified with vinyl polymers are formed, for example, by polymerizing styrene and acrylonitrile in the presence of polyethers, as described in U.S. Pat. 3 383351, 3 304273

523093, 3 110695 and in German Patent No. 1 152536 are suitable as well. polybutadienes having hydroxyl groups are suitable.

Polythioethers which are mentioned in particular are the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or aminoalcohols. Depending on the CO components, the products are mixed polythioethers, polythioether esters or polyether thiesteresteramides.

Suitable polyacetals are, for example, glycols such as diethylene glycol, trithylene glycol, 4,4'-dioxethoxydiphenylmethyl methane, hexanediol and compounds which can be prepared from formaldehyde. Polyacetals useful in the present invention can also be prepared by polymerizing cyclic acetals.

Suitable polycarbonates having hydroxyl groups are compounds known per se, which can be prepared, for example, by reaction of diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol , triethylene glycol or tetraethylene glycol with diaryl carbonates, such as diphenyl carbonate, or with phosgene.

Polyesteramides and polyamides include, for example, polyhydric saturated and unsaturated carboxylic acids or their anhydrides, and polyamides saturated and unsaturated amino alcohols, diamines, polyamines and mixtures thereof obtained from polyesteramides and polyamides, predominantly linear condensates.

Also useful are the aforementioned polyhydroxyl compounds with urethane or urea groups, as well as optionally modified natural polyols such as castor oil, carbohydrates or starches. Addition products of alkylene oxides and phenol-formaldehyde resins or urea-formaldehyde resins or urea-formaldehyde resins are also useful in the present invention. _

Of course, mixtures of the above compounds with generally two isocyanate-reactive hydrogen atoms and a molecular weight of 300 to 10,000, for example mixtures of polyethers and polyesters, can be used.

C)

Polymerizable isocyanate-reactive hydrogen compounds are used as the third component of the compositions of the present invention. Preferably, hydroxyalkylation products of acrylic acid and / or methacrylic acid such as hydroxypropyl acrylic ester, hydroxyethyl methacrylic acid ester and hydroxypropyl methacrylic acid ester are used.

The three components from which the polyurethane compositions with vinyl groups according to the invention are prepared, namely diisocyanates, dihydroxy compounds. and hydroxyalkyl esters of acrylic and / or methacrylic acid are reacted in the following stoichiometric ratio: 2 moles of diisocyanate and 2 moles of hydroxyalkyl acrylate and / or methacrylic acid are used per mole of dihydroxy compound. However, variations are possible from this rule: in particular, it is possible first to lengthen numerous molecules of the dihydroxy compound by first reacting with the diisocyanates before reacting the ends with the hydroxyalkyl ester of acrylic and / or methacrylic acid.

Suitably, the vinyl-containing polyurethane compositions according to the invention are prepared in the presence of known catalysts. Suitable catalysts are:

Tertiary amines such as triethylamine, tributylamine, Nmethylmorpholine, N-ethylmorpholine, N-cocomorpholine, N, N, N ', N'-tetramethylethylenediamine,

1,4-dibzabicyclo (2.2.2) octane,

N-methyl-N'-dimethylaminoethylpiperazine, N, N-dimethylbenzylamine, bis- (N, -methylaminoethyl) adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, N, N-dimethylcyclohexylamyl, N, N, N, N'-tetraπ 1 & lt; 1 & gt; -butanediamine, N, N-dimethyl-p-phenylethtiamm, 1,2-dimethylimidazole, 2-methylimidazole.

Suitable catalysts are also known Manni bases from secondary amines, such as dimethylamine, and aldehydes, preferably formaldehyde, or ketones, such as acetone, methlethylketone, cyclohexanone and phenols, such as phenol, monylphenol, bisphenol.

The tertiary amines with active hydrogen atoms to the isocyanate groups as catalysts are, for example, triethanolamine, triisopropanolamine, N-meteyldietethanolaline, N-ethyldiethanolamine, N, N-chloro (N, N-methyl), as well as their reaction products. with alkylene oxides such as propylene oxide and / or ethylene oxide.

Further suitable catalysts are silaamines with carbon and silicon compounds, as described, for example, in German Pat. No. 1,292,290, which corresponds to U.S. Pat. No. 3,620,984, such as 2,2,2-Crimethyl-2-silamarphaline, 1,3-diethylamino-methyl-ethyldisilcoxane.

Possible catalysts are also nitrogenous bases such as tetraalkyl monohydroxide, alkali hydroxides such as sodium hydroxide, alkaline phenols such as sodium phenolate, or alkali alcoholates such as sodium methylate. Hexahydrotriazines can also be used as catalysts.

Organometallic compounds, in particular organic tin compounds, can also be used as catalysts.

Possible organic tin compounds are, in particular, stannous salts of carboxylic acids, such as stannous acetate, stannous octoate, stannous etihihexoate and stannous laurate, and tin (IV) compounds such as stannous dibutoxyd, stannic dibutyl tin, stannic dibutyl dilate, tin dioctyldiacetate. Of course, all of the above catalysts can be used in mixtures.

Other suitable catalysts and a description of how catalysts operate are disclosed in Kunststoff-Handbuch (Handbook on Plastics), Volume VII, Vieweg and Hochtlen, Carl-Hanser-Verlag, Munich 1966, for example, pages 96-102.

The catalysts are generally used in an amount of about 0.001 to 10% by weight, based on the total amount.

In the process for the preparation of the compositions according to the invention, the dihydroxy compounds can be admixed with the acrylic and / or methacrylic acid diacrylate ester and reacted with the subsequently introduced diisocyanate. Generally, however, a reaction method in which an equal amount of an unsaturated hydroxyalkyl ester and a diisocyanate is first reacted, followed by reacting the precondensate with the dihydroxy compound, is generally recommended. In principle, however, the method of preparation is governed by the properties it has. have an unsaturated urethane mass.

In order to prevent premature gelling of the composition and to guarantee its shelf life, it is expedient to add one or more polymerization inhibitors during the preparation. Suitable auxiliaries of this kind, which are added in an amount of 0.001 to 0.1% by weight, based on the mixture as a whole, are, for example, phenols and phenol derivatives, preferably spherically hindered phenols, which have phenol hydroxyl in both respects. C 1 -C 6 alkyl; amines, preferably secondary arylamines and derivatives thereof, quinones, copper (I) salts of organic acids or copper (I) halide and phosphite addition products, but also phosphites themselves.

Examples include:

4,4'-bis- (2,6-t-butylphenol),

1,3,5-methyl-14,1-2,4,6-methyl-8- (3,5-tetra-tert-butyl-4-hydroxybenzyl) benzene,

4,4^<6-Butadiene-bis- (6-tert-butyl-4-m-creso), 3,5-di-tert-diethyl ester, butyl-4-hydroxybenzylphosphonic acid,

N, N'-bis- (naphthyl) -phenylenediamine,

N, N'-bis- (1-methylhexyl) -p-phenylenediamine, phenyl-4-naphthylamine,

4,4'-bis- (α, α-dimethylbenzyl) diphenylamine,

1.3.5- tris- (3,5-di-tert-butyl-4-

(1) -hexahydro-syn-triazine, hydroquinone, p-benzoquinone,

2.5-di-t-butyquinone, toluhydroquinone, p-tert, butylpyrocatechin-3-methylpyrocatechin, e-ethylporocatechin, chloranil, naphthoquinone, copper naphthenate, copper octoate, copper chloride / triphenyl phosphite, copper chloride / trimethyl phosphite, chloride // rischlorethylphosphite, cuprous chloride / triyroyylphosphite, yara-nitrosodimethylaniline, triethylphosphite.

Other suitable stabilizers are described in "Methoden der organischen Chemie" (Houben-Weylj, 4, edition, Vol. XIV / 1, pp. 433-452, 756, edited by Georg Thiama, Stuttgart, 1961).

Also a very suitable stabilizer is phenothiazine.

The compositions prepared according to the invention from the above-mentioned components and in the manner described above can be used as imprinting materials in dentistry. The compositions are particularly well suited for this purpose since no shrinkage or exceptionally slight shrinkage is observed at all when they are cured into rubbery materials.

The compositions of the present invention are cured using known curing catalysts, which are used, for example, to cure so-called unsaturated polyester resins. Suitable polymorphic initiators are peroxides, optionally in the presence of accelerators such as aromatic amines or cobalt compounds, while curing. at higher temperatures it may be carried out by peroxides alone or by free-radical initiators such as dinitrile and azoisobutyric acids, accelerators, preferably aromatic amines, must be added at room temperature to cure. Typical curing of vinyl-containing polyurethane compositions according to the invention may be carried out e.g. by weight of benzoylyeroxide and 1% by weight of N, N-dimethylaniline,

It is also possible to cure by energy-rich radiation, such as electron or gamma radiation, or in cases where the composition contains a photoinitiator additive, ultraviolet rays. Suitable tors are, for example, benzophenone and its derivatives, benzoin and its derivatives such as benzoinether, anthraquinones and aromatic disulfides,

The viscosity behavior must be such that the masses can be used properly. Such desirable viscosity behavior can be achieved to a large extent by stoichiometry and the choice of reactants in the synthesis of unsaturated urethane resins. , It is also possible to influence the desired processing consistency with the consent of diluents and fillers in the desired way, Diluents include, for example, inert organic solvents such as hydrocarbons, toluene, xylene, ethers such as diethyl ether, ethylene glycols, but also liquid polyethers, alcohols such as ethanol, butanol, octanol, glycols or glycerin, particularly preferred. diluents are so-called plasticizers used, for example, in processing. It is also possible to use, for example, phthalic acid esters or adipic acid esters as well as phosphoric acid esters. Also suitable are phenyl alkane sulfonates,

In special cases, diluents can be used in polymerized vinyl monomers. Examples include acrylic acid esters, methacrylic acid esters, styrene, vinyl acetate. Preferred acrylic esters are isooctyl acrylic acid, acrylic acid dodecyl ester, hexanediol-1,6-diacrylate, trimethylolyroyanetriacrylate, ethylene glycol diol xrylate, as well as the corresponding methacrylic acid esters,

Other formulation excipients include: animal and vegetable fats such as cottonseed oil, peanut oil, corn germ oil, olive oil, castor oil and sesame oil, waxes, paraffin, polyethylene glycols, silicones, etc.

The fillers may be reinforcing and / or non-reinforcing fillers. By reinforcing fillers are meant. fillers having a surface area of ​​at least 50 m²/G. Examples which may be mentioned are: fumed silica, silica dioxide aerogels, calcium silicate, diatomaceous earth, titanium dioxide. Non-reinforcing fillers include: silica flour, sea sand, zirconium silicate, aluminum silicate, aluminum hydroxide, aluminum oxide, zinc oxide, gypsum, limestone, dolomite, calcined gypsum, chalk, but also organic fillers such as starches and powders plastics such as powdered polyethylene, powdered polyvinyl chloride, powdered polyamide.

Mixtures of fillers may also be used. The filler is preferably used in an amount of 1 to 90% by weight, in particular 5 to 80% by weight, based on the total weight of the respective base material.

Non-reinforcing fillers are preferably used in an amount of more than 10% by weight, based on the weight of the composition. whole.

The reinforcing fillers are preferably used in an amount of 1 to 10% by weight, based on the impression material. However, larger amounts of reinforcing fillers may also be used, as long as this does not suffer from uniformity of the mass.

The impression materials of the invention may also contain flavorants such as peppermint oil or eucalyptus oil and sweeteners such as saccharin. They can also be colored with both soluble organic dyes and organic or inorganic pigments.

In contrast to all prior art products used as impression materials, the impression materials prepared according to the invention are characterized by a particular curing behavior. Unlike, for example, polymers and thiocols whose viscosity slowly increases immediately after the curing components have been added, the mass prepared according to the process of the invention, used under dental treatment conditions, changes only insignificantly, while for example polyethers and thlocols reach their final Shore hardness after 30 minutes, the final Shore hardness of the compositions according to the invention is reached immediately at the end of curing, i.e. in a substantially shorter time, after about 4-5 minutes. It is further recalled that, in contrast to thiocols and polyethers, a high degree of Shore hardness is already achieved with very low proportions of fillers. The special properties of the impression materials according to the invention can be adjusted by selecting suitable starting materials so that the mechanical and processing properties can be adjusted according to the end use of the impression materials.

Compared to the rubber-elastic impression materials used hitherto, for example on a thiocol base, the compositions according to the invention have the great advantage that they do not smell. Furthermore, the very good adhesion or tackiness of the compositions according to the invention is emphasized, in particular with regard to metals and plastics, which are the materials used for the production of impression spoons.

Packaging of impression materials according to the invention is possible both in batches and in larger quantities. The addition of a peroxide hardener is possible both in liquid and in solid or paste form, and in the case of paste hardeners all the above-mentioned peroxide-stable additives and fillers can be used. Preferably, the curing paste has a similar consistency to the impression paste, and preferably the hardener is dispensed in the form of the same extruded length as the master paste.

The novel vinyl groups containing the vinyl groups prepared by the process according to the invention are preferably used in dentistry. It goes without saying that their use is not limited to dentistry. They can be used in all cases where an exact contour imprint is required. The molds obtained in this way can be conventionally filled with gypsum or other pouring compositions to obtain a positive copy of the originally imprinted article.

The following examples illustrate the preparation and use of the vinyl group-containing polyurethanes of the invention.

Example 1

In a 2-liter round-bottomed flask with dropping funnel, stirrer and air supply, 581 grams of hexamethylene diisocyanate are introduced and slowly mixed with a mixture of 504 g of hydroxypropyl methacrylate, 1.12 g of phenothiazine at 60 ° C. and 5.3 g stannous octoate solution (Desmorapld SN, Bayer AG). After the exothermic reaction subsided, this condensation product was stirred into 4559 g of a linear polyester of adipic acid and diethylene glycol (molecular weight 2100, hydroxyl number 40 + 5) at 60 ° C and air, after a reaction time of 10 hours at 60 ° C. has an analytically detectable content of isocyanate groups of 0.14% and a viscous resin is obtained after cooling the reaction product.

Example 1

With the same stoichiometric composition as in the example. 1, hydroxypropyl methacrylate, a polyester prepared from adipic acid and diethylene glycol, phenothiazine and stannous octoate are mixed and reacted at 60 DEG C. with hexamethylene diisocyanate under air. After a reaction time of 15 hours at room temperature, a dense viscous resin is formed in which 0.34% of the free isocyanate groups can be detected analytically.

Example 3

Similar to Example 1, 432 g of hydroxypropyl nitroacrylate are reacted,

1.7 g of phenothiazine, 5 g of stannous octoate solution, 485 g of hexamethylene diisocyanate and 5880 g of a linear polyester of adipic acid, butanediol and ethylene glycol (molecular weight 4000, hydroxyl number 28.6). After a reaction time of 10 hours, a dense viscous resin is formed containing 0.05% free isocyanate groups.

Example 4

116 g of hydroxyethyl acrylate, 0.06 g of p-methoxyphenol, 1.0 g of triethylamine, 168 g of hexamethylene diisocyanate and 1000 g of linear polypropylene oxide (molecular weight 2000 + 100, hydroxyl number 56 + 3) were reacted as described in Example 2. A thin liquid resin with a viscosity of 2400 mPa.s is formed.

Example 5

In the manner described in Example 1, 852 g of toluylene-2,4-diisocyanate, 720 g of hydroxypropyl nitroacrylate, 0.3 g of p-methoxyphenol, 4 g of stannous octoate solution and 3256 g of adipic acid polyester and diethylene glycol (mol. Weight 2100) are reacted. , hydroxyl number 40 + 5). After a reaction time of 12 hours at 60 DEG C., a dense viscous resin is obtained in which no free isocyanate groups can be detected analytically.

Example 6

220 g of isophorone diisocyanate, 144 g, were reacted as described in Example 1. hydroxypropyl methacrylate, 0.33 g phenothiazine and 1302 g polyester from adipic acid and diethylene glycol (molecular weight 2100, hydroxyl number 40 + 5). After 24 hours at 60 ° C a dense viscous resin is obtained with a free isocyanate group content of 0.51%.

Example 7 parts by weight of the resin described in Example 1 are mixed in a kneader with 20 parts by weight of talc, 4 parts by weight of calcium silicate, 15.9 parts by weight of linear polyester of molecular weight 2000 and 0.1 parts by weight of p-dimethyltoluidine for one hour.

parts by weight of the paste described above are intimately mixed with 0.2 parts by weight of a paste composed of 50% by weight of dibenzoyl peroxide and 50% by weight of dibutyl phthalate for 30 seconds. Curing is complete after about 4 minutes. The following values ​​are obtained when measuring linear shrinkage:

minutes —0.013% minutes -0.007 o / o hour + -0.020> / o hours + -0.033% hours + -0.018%

EXAMPLE 8 parts by weight of the resin described in Example 2 are mixed for one hour in a kneader with 37.8 parts by weight of talc, 8.1 parts by weight of dioctyl phthalate and 0.1 parts by weight of p-dimethylxylidine.

parts by weight of the paste described above are mixed with 2 parts by weight of paste composed of 4 parts by weight of 50% dibenzoyl peroxide in dibutyl phthalate, 61 parts by weight of talc and 35 parts by weight of dibutyl phthalate. The following Shore hardnesses were measured:

<td>4 minutes 30. seconds</td><td> 58</td>

<td>6 minutes</td><td> 60</td>

<td>8 minutes</td><td> 60</td>

<td>10 minutes</td><td> 61</td>

<td>The value is measured linearly</td><td>precipitation after 2</td>

hours 30 minutes 0.0294%.

Example 9 parts by weight of the resin described in Example 3 are mixed in a kneader with 12 parts by weight of phenylsulfonic acid phenyl ester (Mesamoll).^R from Bayer AG), with 12 parts by weight of a 400 MW linear polyester, 22 parts by weight of talc and 5 parts by weight of polypropylene powder and 0.1 parts by weight of dimethylaniline for two hours.

parts by weight of the paste described above are mixed with 4 parts by weight of paste consisting of 4 parts by weight of 50% dichlorobenzoyl peroxide in dibutyl phthalate, 60 parts by weight of Annaline (gypsum) and 36 parts by weight of alkylsulfonic acid phenyl ester (Mesamoll)^R of Bayer AG). The following linear shrinkage values ​​were obtained:

minutes minutes 1 hour hour hours —0.037% —0.060% —0.075% —0.117% —0.126% —0.212%

Example 10

33.3 parts by weight of the resin prepared as described in Example 3, 7.4 parts by weight of the resin prepared as described in Example 1, and 9.3 parts by weight of alkyl sulfonic acid phenyl ester (Mesamoll.RTM. From Bayer AG).

18.5 parts by weight of a linear molecular weight polyester of 2000, 18.5 parts by weight of talc, 12.9 parts by weight of powder polyethylene and 0.1 part by weight of p-dimethyltoluidine are mixed for 4 hours in a kneader.

parts by weight of the paste described above are mixed with 2 parts by weight of the peroxide paste described in Example 8. For linear shrinkage, the following values ​​are obtained:

minutes —0.013% minutes hour hours hours —0.007% ± 0.000% ± 0.009% —0.004%

Value for permanent deformation

1.11% and for elastic deformation of hoonot 5.68 θ / o.