Extrusion mas,for stomatology purposes

Inventor: _

Patent holder: Bayer Aktiengesellschaft, Leverkusen (Federal Republic of Germany)

Impression material, especially for dental purposes i

The subject of the invention is an impression material, especially for dental purposes, in which polyurethane resins containing vinyl groups are used.

Impression materials are understood to mean the masses that change from a plastic state into a hardened or elastic state by a hardening process. Impression materials are used in dentistry to recreate the shape corresponding to the mucosa and teeth. For this purpose, masses that are hardenable to a gum-type elastic consistency are preferably used. .

The production of flexible rubber products can be carried out in various ways. In addition to the polymerization of unsaturated hydrocarbons with one or more double bonds, for example curing to obtain products with elastic properties. thioplasts, which can take place by reaction of aqueous solutions of alkali metal polysulfides with aliphatic dihalides. Rubber-like products are also obtained by polycondensation of silicones. Rubber-type elastic products can also be produced by polyaddition of polyester or polyether with a diisocyanate.

Thiocols before and after cross-linking have an unpleasant odor. Polyurethanes are not physiologically indifferent as they contain free isocyanate groups. Moreover, all of these masses exhibit relatively high polymerization shrinkage which attempts are made to compensate for by incorporating a high proportion of fillers.

Rubber-elastic masses similar to rubber on ethylene bases are also produced₅ ny. These products show a relatively low polymerization shrinkage, but have the following disadvantages: when water is added to the water, there are strong changes in volume due to the swelling processes, moreover, these products are not inert to₁₀ physiological because they become cross-linked through the aziridine end groups, and some aziridines are known to be carcinogens. All impression materials used in dentistry have both time constraints₁₅ in terms of their processing time and hardening period. After the preparation of the reactive mixture, usually a work-up period of about 3 minutes is available. The next hardening period usually takes about 5 minutes.

Unexpectedly, it has been found that polyurethane resins containing vinyl groups can be hardened during these practical periods into elastic rubber-like masses, these masses used as matte₂₅ Impression materials do not show the above-mentioned disadvantages.

The subject of the invention is therefore the impression material, especially for storhatological purposes, which becomes netted in the process of forming.₃₀ oil, containing the products of seolation. a) diisocyanate 110 798

110 798 .

ionates b) dihydroxy compounds with a molecular weight of 300 to 10,000, preferably 1,000 to

..- 8000 and c) monohydroxy vinyl compounds, preferably acrylic and / or methacrylic acid derivatives containing hydroxyl groups. As substances of group a), it is possible to use diisocyanates, such as ethylene diisocyanate, hexamethylene diisocyanate, cyclohexane 1,4-diisocyanate, 2,4- and 2,6-toluene diisocyanate and mixtures thereof, isophorone diisocyanate, phorono diisocyanate, -1,5-naphthalene diisocyanate. , 1,3-cyclopentylene diisocyanate, m- and p-phenylenedisocyanate, toluene triisocyanate, 4,4 ', 4-triphenylmethanedriisocyanate, 1,3- and 1,4-xylylene diisocyanate, *' 3,3'-dimethyl-4,4'- diphenyl- _;melariidiisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylene diisocyanate, 4,4'-diphenylene diisocyanate, durene diisocyanate, J-phenoxy-2,4'-phenylenedisocyanate, 1st order. butyl-2,4-phenylenediisocyanate, methyl-β-bis-4,4'-cyclohexyldiisocyanate, 1-chloro-2,4-phenylenediisocyanate and 4,4'-di-phenylenediisocyanate.

It is also possible to use higher molecular weight and optionally also higher functional polyisocyanates which are prepared from lower basic substances by polymerization into uretdiones or isocyanurate derivatives. Examples are uretdione with 2 moles of 2,4-toluene diisocyanate and 2 moles of toluene diisocyanate containing isocyanurate-containing polymerization products from 2,4- and 2,6-toluene diisocyanate or hexamethylene diisocyanate, a system with an average of 2 isocyanurate rings per molecule and formed from 5 moles of toluene diisocyanate. or a suitable derivative of an average of 2 moles of toluene diisocyanate and 3 moles of hexamethylene diisocyanate.

It is also possible to prepare from di- or polyisocyanates by partial hydrolysis via the carbamic acid step and the high-amine ⁴other urea or burette coupled systems, such as e.g. a biuret coupled compound which is formally formed from 3 moles of hexamethylene diisocyanate with the addition of 1 mole of water and the removal of 1 mole of carbon dioxide. ⁴

Preferred isocyanate-containing substances are also obtained during the reaction of di- or polyols with di- or poly-functional isocyanates, if the mole ratio of the hydroxyl compound to the isocyanate is taX, ⁵¹that in the statistically formed reaction products, free NCO functions remain constantly, and the molar weight does not exceed 2000-3000.

Particularly preferred compounds containing- _5im and isocyanate groups suitable for use in the resins according to the invention are hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate and 4,4'-diphenylmethane diisocyanate. _{e (}

Components b) used in the compositions according to the invention are compounds having two hydrogen atoms capable of reacting with isocyanates and having a molecular weight of 300 to 10,000, in particular

1000—8000. '

As such compounds, in addition to compounds containing amino groups, thiol groups or carboxyl groups, it is preferable to use polyhydroxy compounds, especially compounds containing 2 to 8 ₅ hydroxyl groups, in particular compounds with a molecular weight of 300-10,000, preferably 1,000-8,000, for example polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyesteramides generally containing two hydroxyl groups, such as are known for the preparation of homogeneous and cellular polyurethanes. '

Polyesters containing hydroxyl groups are, for example, the products of multivalent, preferably divalent reactions ₅ and optionally trivalent alcohols with multivalent, preferably divalent carboxylic acids. Instead of free acids. polycarboxylic acid compounds can also be used for the preparation of polyesters, suitable without_Q polycarboxylic acid hydrides or polycarboxylic acid esters with lower alcohols, or mixtures of these compounds. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and can be optionally substituted,⁷ for example, atoms, halogen and / or may be unsaturated.

Examples of such compounds are succinic acid, adipic acid, cork acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic acid anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride. acid anhydride, endomethylene tetra phthalic acid, glutaric acid anhydride, maleic acid, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally ₍ in admixture with monomeric fatty acids, terephthalic acid dimethyl ester and terephthalic acid bis glycol ester.

Polyvalent alcohols used are e.g. ethylene glycol, propylene glycol-1,2 and -1,3, butylene glycol-1,4 and -2,3, hexanol-1,6, octafTcliol-1,8, neopentyl glycol, cyclohexanedimethanol (1,4-bis- hydroxymethylcyclohexane), 2-methyl-1,3-propandiol, glycerin, trimethylolpropane, hexantriol-1,2,6, butantriol-1,2,4, trimethylethane, pentahyrrite, quinite, mannitol and sorbitol, methylglycoside and also diethylene glycol , triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols *, dibutylene glycol and polybutylene glycols. The polyesters may contain some carboxyl end groups. Polyesters of fatons, for example ε-caprolactone, or of hydroxycarboxylic acids, for example, ε-hydroxycaproic acid, can also be used.

The polyethers generally used according to the invention which generally contain two hydroxyl groups are of a known type. They are obtained, for example, by the polymerization of epoxides, such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or *

epichlorohydrin with each other, for example in the presence of BF₃or by attaching these epoxides, optionally in admixture or sequentially, to starting components with reactive hydrogen atoms such as water, alcohols, ammonia or amines, for example ethylene glycol, 1,3-propylene glycol, or -1,2, 4,4'-dihydroxy-diphenylpropane, aniline, ethanolamine.

Preference is given to those polyethers which for the most part (up to -90% by weight based on all OH groups present in the polyether) contain primary OH groups. Preference * is also given to polyethers modified with vinyl polymers, e.g. by the polymerization of styrene and acrylonitrile in the presence of polyethers (U.S. Patents No. 3,383,351, 3,304,273, 3,523,093, 3,110,695 and German Patent No. 1,152,536). ) as well as polybutadienes containing OH groups.

* Polythioethers are, in particular, the condensation products of thiodiglycol molecules with one another and / or with other glycols, dicarboxylic acids, formaldehyde, amino carboxylic acids or amino alcohols. Depending on the ingredients, mixed polythioethers, polythioether esters or polythioether esters are obtained as products.

Polyacetals are, for example, compounds obtained from glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxyethoxydiphenyl dimethylmethane, hexadiol and formaldehyde. It is also possible to obtain polyacetals which can be used according to the invention by polymerization of cyclic acetals.

As hydroxyl-containing polycarbonates, known substances are used which can be prepared, for example, by reacting diols such as 1,3-propanediol, 1,4-butanediol and / or 1,6-hexanediol, dimethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates such as diphenyl carbonate, or with phosgene.

The polyesters and polyamides include, for example, compounds obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines; polyamines and mixtures thereof, with linear condensation products being preferred. '

It is also possible . use polyhydroxy compounds containing urethane or urea groups and optionally modified natural polyols such as castor oil, carbohydrates or starch. It is also possible to introduce linkage products of alkylene oxides to phenol-formaldehyde resins or to urea-formaldehyde resins.

It is of course also possible to use mixtures of the abovementioned compounds having generally two hydrogen atoms capable of reacting with isocyanates and having a molecular weight of 300 to 10,000, for example mixtures of polyethers and polyesters.

As components c) of the materials according to the invention, polymerizable vinyl compounds with an isocyanate-reactable hydrogen are used. Preference is given to introducing oxyalkylation products of acrylic and / or methacrylic acid, such as acrylic acid hydroxyethyl ester, acrylic acid hydroxypropyl ester, methacrylic acid hydroxyethyl ester and methacrylic acid hydroxypropyl ester.

The three components from which the polyurethane masses containing vinyl groups, namely diisocyanates, dihydroxy compounds and hydroxyalkyl esters of acrylic acid and / or methacrylic acid are compiled according to the invention, are preferably introduced in the following proportions: per 1 mole of the dihydroxy compound, 2 moles of diisocyanate and 2 moles of hydroxyalkyl ester of acrylic acid and / or methacrylic acid. However, deviations from this rule are possible, in particular, a larger number of the dihydroxy compound molecules can first be extended by reaction with / with diisocyanates before the molecule ends are loaded with acrylic and / or methacrylic acid hydroxyalkyl esters. '

The polyurethane compositions used according to the invention which contain vinyl groups are preferably prepared in the presence of known catalysts. Such catalysts are tertiary amines such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N-cocomorpholine, Ν, Ν, '-tetramethylethylenediamine,

1.4- diaza-bicyclo- (2,2,2) -octane, N-methyl-N'-dimethylamino-ethyl-piperazine, N, N-dimethylbenzylamine, di- (N, N-dimethylaminoethyl) adipate, Ν, Ν- dimethyltyenzylamine, pentomethyldimethylenetriamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N-dimethyl-P-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole. Also used as catalysts are the known Mannich bases from secondary amines such as dimethylamine and aldehydes, preferably formaldehyde, or ketones such as acetone, methyl ethyl ketone, cyclohexanone, and phenols such as phenol, nonylphenol, bisphenol.

The tertiary amines with isocyanate-active hydrogen atoms as catalysts are, for example, triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldimethanolamine, N, N-dimethylethanolamine, and reaction products thereof. with alkilerite oxides such as propylene oxide and / or ethylene oxide.

In addition, silaamines having carbon-silicon bonds are used as catalysts, such as those described in German Patent No. 1,229,290 (equivalent to U.S. Patent No. 3,620,984), for example

2.2.4-trimethyl-2-silamorpholine, 1,3-diethylaminomethyl-tetramethyl-disiloxane.

Nitrogen-containing bases such as tetraalkylammonium hydroxides are also used as catalysts, furthermore alkali metal hydroxides such as sodium hydroxide, alkali metal phenates such as sodium phenate, or alcohols.

alkali metal halides such as sodium methoxide. Hexahydrotriazines can also be used as catalysts.

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

Tin salts in carboxylic acids, such as cinna acetate, stannous heptane carboxylate, stannous ethyl pentane carboxylate and stannous laurate, as well as tin compounds, for example dibutyltin oxide, dibutyltin dichloride, dibutyltinyltin, dibutyltinnicin, dibutyltartin, are preferably used as organic tin compounds. dioctyltins. It is of course also possible to use all the abovementioned catalysts in the form of mixtures.

Further examples of suitable catalysts - and details on how they work are described in Kunststoff-Handbuch, Vol. VII, Vieweg ₂and Hóchtlen, Carl Hanser, Munich, 1966, pp. 96-102.

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

In the preparation of the compounds used according to the invention, the dihydroxy compound is mixed with_vol hydroxyalkyl ester of acrylic and / or methacrylic acid and reacted with the subsequently supplied diisocyanate. On₃in general, however, it is preferable to react by reacting equimolar amounts of the unsaturated hydroxyalkyl ester and the diisocyanate and then reacting the precondensate with the dihydroxy compound. In general, however, the procedure depends on the properties that the unsaturated urethane mass should exhibit.

In order to prevent premature gelling of these masses and to guarantee storage properties, one or more _s polymerization inhibitors. Suitable auxiliaries of this type in an amount of 0.001-0.1% by weight, based on the total mixture, are, for example, phenols and phenol derivatives, preferably spherically hindered phenols, which in both positions are ortho to the phenolic groups hydroxyl groups contain alkyl substituents, o

1-6 carbon atoms, amines, especially secondary amines _&secondary and their derivatives, quinones, cuprous salts of organic acids or products of attaching cuprous halides to phosphites, and also phosphites as such.

Examples of such compounds are mentioned ₅4,4'-bis- (2,6-di-tertiary butylphenol), 1,3,5-trimethyl-2,4,6-tris- (3,5-di-tertiary butyl-) 4-hydroxy-benzyl) -benzene, 4,4'-butylidene-bis- (6-tertiary butyl-m-cresol), 3,5-di-tertiary acid diethyl ester. butyl-4-hydroxybenzylphosphonic, l) T, N'-bis- (p-naphthyl) -p-phenylenediamine, N, N'-bis-U-methylhephenyl J-p-phenylenediamine, phenylenediamine, 4,4 ' -bis- (α, α-dimethylbenzyl) -diphenylamine, 1,3,5-tris (3,5-two-tertiary butyl-4-hydroxy-hydrocinnamoyl) -hexane-s-₆.

-triazine, hydroquinone, p-benzoquinone, 2,5-two-tertiary. butylquinone, toluhydroquinone, p-tertiary. butylpyrocatechin, 3-methylpyrocatechin, 4-ethylpyrocatechin, chloranil, naphthoquinone, naphthenate₅ copper, copper heptanecarboxylate, cuprous chloride (triphenyl phosphite, cupric chloride) trimethyl phosphite, cuprous chloride (tris-chloroethyl phosphite, cuprous chloride) tripropyl phosphite, p-nitrosodimethylaniline, phosphorus₀ triethyl forin.

Further suitable stabilizers are described in "Methoden der organischen Chemie" (Houben-Weyl), 4th Edition, Vol. XIV / 1, pp. 433-452, 756, Georg JThieme, Stuttgart, 1961.

Phenothiazine is also a very good stabilizer.

The masses prepared from the above-described ingredients in the above-described manner may be used as impression material in dentistry. During their hardening into rubber-like shapes, no or only a very small degree of polymerization shrinkage is observed.

The hardening of these compositions is carried out with the aid of conventional curing catalysts, for example as used for the curing of so-called unsaturated polyester resins. Suitable polymerization starters are peroxides optionally in the presence of accelerators such as¹ aromatic amines or cobalt compounds. The elevated temperature curing can be performed with peroxides alone or with radical starters such as azoisobutyric acid dinitrile, while curing at room temperature requires the addition of accelerators, preferably aromatic amines. The usual curing for polyurethane compositions containing vinyl groups according to the invention can be carried out on⁵ Example with addition of 1% by weight of benzoyl peroxide and 1% by weight of N, N-dimethylaniline.

Curing can also be carried out with energy-rich radiation, such as electron rays or gamma rays, or with ultraviolet light if photoinitiators are added to the resin. A suitable photoinitiator is, for example, benzophenone and its derivatives, benzoin and its derivatives such as benzoin ether, anthraquinone and aromatic disulfides. , -_v

When introducing the polyurethane masses according to the invention into dental practice, it is assumed that a certain viscosity will be maintained, which must be selected so that it is possible to use it in practice. The maintenance of the desired viscosity can be achieved to a large extent by means of the stoichiometry of the reaction components in the synthesis of unsaturated urethane resins.

The desired consistency can also be influenced by selecting the diluents and fillers in the desired manner. Diluents are, for example, inert organic solvents, such as hydrocarbons, toluene, xylene, and furthermore, ethers, such as diethyl ether, ethylene glycols.

as well as liquid polyethers, alcohols such as ethanol, butanol, octanol, glycol and glycerin. Particularly 'preferred diluents are' so-called plasticizers, such as are used, for example, in the treatment of polyvinyl chloride. For example, esters of phthalic acid or esters of adipic acid and esters of phosphoric acid can also be used. The phenyl esters of the alkanesulfonates are also preferred.

In some cases, it may be desirable to use polymerizable vinyl monomers as diluents. For example, esters of acrylic acid, esters of methacrylic acid, styrene, vinyl acetate can be added.

Preference is given to using acrylic acid esters such as acrylic acid isooctyl ester, acrylic acid dodecyl ester, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, ethylene glycol diacrylate and the corresponding methacrylic acid esters.

Other excipients mentioned are animal and vegetable fats, such as cotton seed oil, peanut oil, corn germ oil, olive oil, castor oil and sesame oil, furthermore waxes, paraffin, polyethylene glycols, silicones, etc.

In the case of fillers, reinforcing and / or non-reinforcing fillers can be used. Reinforcing fillers are understood to mean fillers having at least 50 m²/ g area. Examples are progenically produced silicon dioxide, silicon dioxide aerogels, calcium silicate, diatomaceous earth, titanium dioxide.

As non-reinforcing fillers, quartz flour, sea sand, zirconium silicate, aluminum silicate, aluminum hydroxide, aluminum oxide, zinc oxide, gypsum, limestone, dolomite, gypsum, chalk, as well as fillers of organic origin such as starch and powdered materials are mentioned. plastics such as polyethylene powder, polyvinyl chloride powder, polyamide powder.

Mixtures of different fillers can also be included. The fillers are 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 base materials. The non-reinforcing fillers are preferably used in an amount greater than 10% by weight of the total weight. _

The reinforcing fillers are preferably used in an amount of 1 to 10% by weight of the impression material. However, larger amounts of reinforcing fillers can also be used as long as the uniformity of the masses is not adversely affected.

The impression compositions according to the invention may also contain flavor enhancing additives, for example peppermint or eucalyptus oil, and sweeteners, for example saccharin. They can also be colored with organic dyes, as well as with organic or inorganic pigments.

. In contrast to all other products hitherto used in impression materials, the material according to the invention is distinguished by a particular hardening behavior. Contrary to e.g. of polyethers and thiokols, the viscosity of which increases slowly immediately after the addition of the hardener components, the material according to the invention changes only slightly during the treatment period required in dentistry, moreover, when, for example, polyethers and thiokols only reach their final hardness after about 30 minutes, the material according to according to the invention, it obtains its final hardness just after the hardening has finished, ie in a much shorter time, after approximately 4-5 minutes. *

It should also be emphasized that high desirable. the degree of hardness, in contrast to the thiokol P polyethers, is achieved even with a very low proportion of fillers in the compositions according to the invention. The specific properties of the impression materials according to the invention vary greatly depending on the selection of the appropriate starting materials, so that the mechanical and processing properties can be adapted to any application of the impression material.

In contrast to the previously used, flexible as rubber^with impression materials, e.g. based on thiokols, the material according to the invention has the considerable advantage that it is odorless. It should also be emphasized that the products according to the invention have a very good adhesion or adhesive capacity, in particular to metals and plastics, i.e. materials from which impression trays are made.

The finished impression material can be packaged both in pre-proportioned form and in larger quantities. The peroxide curing agent can be added in liquid, solid or pasty form, and in the case of pasty hardeners any of the abovementioned excipients and peroxide-stable fillers can be included. The hardener paste preferably has a similar consistency to the impression paste, and preferably the hardener is dosed in parallel with the base paste. - '

The new polyurethane resins containing vinyl groups are advantageously used in the field of dentistry. It is obvious, however, that their application is not limited to this field. They can be used wherever you need to accurately reproduce contours. The thus obtained forms can be filled in the usual way with plaster or. other casting materials in order to obtain a positive copy of the original object.^!

The following examples explain the production and use of the new vinyl group-containing polyurethane resins in more detail.

Example I. A 2-liter round bottom flask equipped with a dropping funnel, stirrer, and air injection device are charged _;581 g of hexamethylene diisocyanate and, while passing air at 60 ° C, slowly mixed with a mixture of 504 g of hydroxypropyl methacrylate, 1.12 g of phenothiazine and 5.3 g of hep110 798 solution,

tin tancarboxylate (Desmorapid SN, Bayer AG). After completion of the exothermic reaction, this condensation product is introduced with stirring at 60 ° C while air is passed through 4559 g of a linear polyester made of adipic acid and dimethylene glycol (molecular weight == 2100, hydroxyl number = 40 ± 5). After 10 hours at 60 ° C, the content of the analytically determined NCO 'groups was 0.14%. After . after cooling the reaction product, a sticky resin is obtained. *

Example II. Using the stoichiometric composition as in Example 1, hydroxypropyl methacrylate, polyester of adipic acid and diethylene glycol, phenothiazine and tin heptane carboxylate are mixed and reacted with hexamethylene diisocyanate at 60 ° C while air is passed through. After 15 hours a liquid is obtained in at room temperature, a resin in which 0.34% of free groups can still be detected by analysis

NCO. '

Example III. Analogously to Example 1, 432 g of hydroxypropyl methacrylate, 1.7 g of phenothiazine, 5 g of tin heptane carboxylate solution, 485 g of hexamethylene diisocyanate and 5880 g of linear polyester made of adipic acid, butandiol and ethylene glycol (molecular weight = 4000, 'hydroxyl number = 5, 28.6). After a reaction time of 10 hours, a viscous resin is obtained with a free content. isocyanate groups of 0.05%. ,

Example IV. Analogously to Example 2, 116 g of acrylic acid hydroxyethyl ester, 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) are reacted. = 56 ± 3). The result is a fluid resin with a viscosity of 2400 cps._x

EXAMPLE 5 By analogy with Example 1, 852 g of toluene-2,4-diisocyanate, 720 g of hydroxypropyl methacrylate, 0.3 g of p-methoxyphenol, 4 g of tin heptanecarboxylate solution and 3256 g of polyester of adipic acid and diethylene glycol (molecular weight) are reacted. = 2100, hydroxyl number = 40 ± 5). After 12 hours at 60 ° C, a viscous resin is obtained, in which the presence of free NCO groups can no longer be detected analytically.

Example VI. According to Example 1, 220 g of isophorone diisocyanate, 44 g of hydroxypropyl methacrylate, 0,3 0.33 g of phenothiazine and 1302 g of adipic acid-dimethylene glycol polyester (molecular weight == 2100, hydroxyl number = 40 ± 5) are reacted. After 24 hours at 60 ° C, a viscous resin with a free NCO content of 0.51% is obtained.

Example VII. 60 parts by weight of the resin described in Example 1 are mixed in a crusher with 20 parts by weight of talcum powder, 4 parts by weight of calcium silicate, 15.9 parts by weight of a linear molecular weight polyester.¹² 2,000 and 0.1 parts by weight of p-dimethyltoluidine in 1 hour. .

parts by weight of the above paste are vigorously mixed for 30 seconds with 0.2 parts by weight of a paste consisting of 50% by weight of dibenzoyl peroxide and 50% by weight of dibutyl phthalate. Curing is complete after approximately 4 minutes.

As a result of linear shrinkage measurement, the following results are obtained:

15'= -0,013%.

• 30 '= - 0.007%' lh = + 0.020%

6h = + 0.033%

24h = + 0.018% <

Example VIII. 54 parts by weight of the resin described in Example 2 are mixed in a crusher with 37.8 parts by weight of talcum, 8.1 parts by weight of dioctyl phthalate and 0.1 parts by weight of p-dimethyloxylidine for 1 hour.

parts by weight of the above-described paste are mixed with 2 parts by weight of a paste consisting 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 hardness limits were obtained:

4'30 : 58 6' : 60

8' : 60

10' : 61 '

The linear shrinkage at 2 hours 30 minutes is 0.0294%.

Example IX. 44 parts by weight of the resin described in Example 3 are mixed in a crusher with 12 parts by weight of alkylsulfonic acid phenyl ester (Mesamoll^R from Bayer AG), 12 parts by weight of a linear polyester with a molecular weight of 400, 22 parts by weight of talc, 5 parts by weight of polypropylene powder and 0.1 parts by weight of dimethylaniline for 2 hours.

parts by weight of the above-described paste are mixed with 4 parts by weight of a paste consisting of 4 parts by weight of 50% dichlorobenzoyl peroxide in dibutyl phthalate, 60 parts by weight of annaline (calcined gypsum) and 36 parts by weight of alkylsulfonic acid phenyl ester (Mesamoll) ^R by Bayer AG).

The following values ​​of linear shrinkage were found: 15 '= - 0.037%

30 '= - 0.060% lh = - 0.075%

3h = - 0.117%

6h = - 0.126%

24h = - 0.212%

Example 10 33.3 parts by weight of the resin prepared according to Example 3 and 7.4 parts by weight of the resin prepared according to Example 1, 9.3 parts by weight of alkylsulfonic acid phenyl ester (Mesamoll ^R from Bayer AG), 18.5 parts by weight of a linear 2000 molecular weight polyester, 18.5 parts by weight of talc, 12.9 parts by weight of polyethylene powder 110 798 and 0.1 part by weight of p-dimethyl toluidine are mixed in a crusher for 4 hours. .

parts by weight of the above-described paste are mixed with 2 'parts by weight of the peroxide paste described in Example 8. The following linear shrinkage values ​​were found^:

15' : - 0,013%

30 ': - 0.007% lh: ± O *⁰/·

4h: + 0.009%

24h: - 0.004%

The virility of the persistent deformation is

1.11%, and the value of elastic deformation is 5.68%.