DE1516455A1 - Abutment tooth and support gel consisting of non-volatile dimethacrylate as the only polymerizable component - Google Patents

Description

Abutment tooth and support gel made of non-volatile dimethacrylate as the only polymerizable component The invention relates to a novel, paste-like and polymerizable pasty plastic compound, which in particular for the formation or replication of teeth is used and in hardened Condition forms a hard, impact-resistant and abrasion-resistant dental product0 This Product is particularly suitable for the manufacture of artificial teeth or Plastic crowns; However, it can also be preformed in the same way Strips of filling compound can be used for fillings, inlets or the like. The plastic connection is pigmented in such a way that it corresponds to the scar of a natural tooth. The paste-like dental mass according to the invention is particularly notable before hardening due to their extremely low volatility and their extremely good shelf life at room temperature (at least 6 months and longer) and after hardening through their excellent abrasion resistance and impact resistance. All of these properties are in Compared to the previously customary methacrylate paste mixtures of an unexpectedly better quality.

The composition according to the invention consists essentially of one Mixture of a non-volatile liquid bifunctional bionic ester of acrylic and methacrylic acid Jilt certain dihydric aliphatic alcohols with> s to 8 carbon atoms as a liquid 3estestandii, while the one used to thicken the liquid Synthetic resin filler a finely divided methyl methacrylate polymer or a copolymer of methyl methacrylate, being the volatility of the liquid bifunctional Methacrylate; or acrylate monomers is less than that of dibutyl phthalate, what in turn requires a correspondingly longer shelf life, while the hardness of the cured liquid phase also differ in terms of their abrasion resistance characterized by unprecedented maximum values.

As both the solid and the liquid phase of the dough-like filling compound consist of an optically transparent acrylic resin, a misoh resin is obtained, in which extremely desirable transparency properties are given, whereby it It is now possible to change the color and the shades of the teeth by appropriate Adding suitable pigment substances precisely and reliably to the natural ones Align teeth.

The liquid, non-volatile dimethacrylate ester, which is the only one Component forms the liquid phase in which the synthetic resin filler and the pigment dispersed, has excellent wetting properties for those opacifying pigments, which are generally used in dentistry, for example 'titanium dioxide, Zinc oxide, copper oxide, iron oxide, cobalt oxide, barium sulfate, soot, burnt umber, Oadmium selenide, cadmium sulfide and mixtures of the substances listed above.

The invention is based on the finding that while some are not volatile monomers are very good for the production of artificial abutment teeth or the like. suitable, but they are too brittle to be used as a material for repair, restoration and to be used for patchwork. It would therefore be assumed that acrylate diesters are so brittle that they are completely useless for the manufacture of teeth. To this assumption would have to be exercised on the outer surface of the brittle diacrylate ester A sharp blow will result in it splintering completely. It has now been surprising found that the tooth structure does not splinter or be destroyed when used as a Abutment tooth is produced in such a way that one of the dough-like according to the invention composition existing surface overlay on a solid polymethyl methacrylate Core is molded.

The composite tooth structure consists of a polymethyl methacrylate core and an abrasion resistant plastic outer liner is known and the same is true also for processes for the production of such teeth. An example of the structure Such an abutment tooth is in the American PS 2 793 436 (Gotlib) or also described in American PS 2,477,268 (Saffir).

Processes for the production of such abutment teeth are in the American PS 2,528,219 (Beagin) disclosed.

The teeth according to the invention and the method for their production cannot be represented in drawings as these drawings differ from the above-mentioned known teeth or working methods would not distinguish. The advantages achieved with the invention are based in particular on the composition the special dental compound, which consists of two components, namely a first Group of non-volatile and somewhat brittle substances for the production of abutment teeth and a second group of substances from such compositions, which are all glycols with the exception of the butylene and propylene glycols of the first group.

So far it has always been the case that none of these polyglycols can be processed into non-porous (heavily foamed) structures without that these substances would become excessively brittle. For example, there is the only known practical use for the pure solid diester in that highly porous prosthetic structure by Wichterle et al., which was issued on March 28, 1961 U.S. Patent 2,976,576 is disclosed. Wichterle et al. had suggested at the time the product as a kind of sponge, filter or surgical implant for blood vessels etc. to use. In this context it is important to note that Wichterle i.a. polymerized a monomer alone and did not attempt the dough-like mixtures to recycle somehow.

As can be seen from the above, there is the liquid Component for the tooth made from a dimethacrylate ester with 4 - 8 carbon atoms in alcohol or polyethylene glycol, with a degree of polymerization of 2 to 6, or Polypropylene glycol with a degree of polymerisation from 2 to 6, while in the case of the restoration substance, hereinafter referred to simply as 11 Auflagegel11, the ester is an alcohol with 5 - 8 carbon atoms and the same ethylene u. Propylene glycol esters with a degree of polymerization of 2 to 6 can be used.

The difference between these two types is also established on the volatility properties.

With these certain non-volatile bifunctional monomers, which are not suitable for use as support gels, but without further ado Can be used for making composite acrylic teeth they are butylene glycol dimethacrylates and diacrylates, in which both linear and branched types of butylene glycol exist, and around the propylene glycol dimethacrylate and diacrylates, which have both a linear and a branched structure.

One of the common substances with non-volatile properties are considered a non-volatile material in dentistry is dibutyl phthalate, that compared to the non-volatile liquid component of the invention may be.

Another comparatively used component is methyl methacrylate monomer with a boiling point of 10,000.

The third component is ethylene glycol dimethacrylate, hereinafter referred to as "ADMA" for short.

This substance is the usual one available in the trade Crosslinking agent which occurs in the arrangement according to the invention @ @leht @@@ va @ a @@ is.

The following is a more detailed description of the properties of the non-volatility arise if ÄDMA is excluded and preferably triethylene glycol dimethacrylate is used.

The volatility of monomeric triethylene glycol dimethacrylate is preferred The volatility of dibutyl phthalate is used as a crosslinking agent very close.

Various vapor pressure and temperature values are given below, to illustrate the relative volatility of the non-volatile crosslinking agent which forms the entire monomer phase of the dental paste according to the invention, wherein a a corresponding comparison is made with methyl methacrylate and dibutyl phthalate.

Volatility in Hg 0 ° C 50 ° C 100 ° C 150 ° C methyl methacrylate 8.5 125 760 dibutyl phthalate 0.001 0.008 0.1 1.5 triethylene glycol dimethacrylate (SR 205 (TÄDMA) 0.001 0.01 0.01 1 tetraethylene glycol dimethacrylate 0.001 0.01 0.01 0.1 polyethylene glycol 200 dimethacrylate 0.01 0.01 0.01 2 1,3-butylene glycol dimethacrylate 0.01 0.1 1 15 ethylene glycol dimethacrylate (ÄDMA) 0.01 0.1 8 120 The volatility of ÄDMA at 1000C is such that within evaporate about 4% within 4 hours at 1000C and about 8% within 8 hours.

The solvency of ADMA at 1000C is much higher than that from TÄDMA at 1000C. The solubility of ethylene glycol dimethacrylate is similar so big that at room temperature one made of polymer and monomers existing mixture, as in the case of the preferably formed composition using of ethylene glycol dimethacrylate, forms a gel and as a result becomes too rigid> so that it can still be processed and deformed. As from the comparison above shows, only ÄDiA has a viability that occurs during a certain storage period exhibits excessive weight loss, while with all other dimethacrylates the volatility behavior is far better than that of the usual dibutyl phthalates is.

The crosslinking density of ÄDMB is so high that of ÄDMA paste manufactured cured products are overly brittle, while in comparison the products made from TÄDMA are not very brittle. In addition, all surrender Dimethacrylates, including the more volatile ADMA compounds, which are completely impermeable to water and also have the necessary resistance against saponification under the influence of the former which become effective in the mouth Own substances. It is believed that thanks to these properties, the one longer chain crosslinking structure and the ester content in the molecule are inherent, in the hardened tooth favorable plasticizing process occurs, by which the brittleness is reduced, which in terms of effectiveness as Crosslinking agent is extremely surprising.

These properties are those of glycol diacetate and diglycol diacetate to face. zinc explanation is given on the basis of glycol diacetate which is an excellent solvent that contains a lot more polymers dissolves than dibutyl phthalate and forms a stickier dough that is heavier mix. The glycol diacetate has a processing temperature of 1000C a very high evaporation rate. After about 4 hours are already 30% evaporated and in the course of a 9-hour processing time already 40% evaporated, while evaporating up to 60% within a period of 16 hours. So this plasticizer is incorporated into a denture and overnight heated to 1000 \ j1, most of this liquid emollient goes lost by heating. Furthermore, it can also be taken from the completed Pull out the dental prosthesis so that the flexibility thus achieved is not permanent Effect is and so a noticeable difference in comparison to the hardness and the toughness can be determined, as it is by the higher glycol dimethacrylates be awarded.

If diethylene glycol diacetate is used instead, this will result in the problem of volatility, but not the problem of stiffer and heavier ones Processable paste dissolved, as the diacetate is also a very strong solvent for methyl methacrylate polymers, i.e. it is stronger than dibutyl phthalate and processing in the manner of mixing and deformation are made as a result far more difficult. More serious, however, is the flat part, that liquid glycol diacetate or diglycol diacetate is soluble in water, for example 14.3 g of glycol diacetate Dissolve in 100 ccm of water at room temperature. The solubility of diglycol diacetate is therefore above 6-8%, so that it is extracted in the mouth.

Glycol diacetate is about 100 times less light at room temperature volatile as methyl methacrylate. When using the Doolittle test procedure of "Industrial Closely. Chem., Vol. 27, p. 1169 (1935) " Glycol diacetate a Evaporation rate number of 100% after 375 hours at room temperature (25 ° C) and evaporated under atmospheric pressure.

Under the same conditions, methacrylate evaporates 100% within of 2.1 hours and diglycol diacetate to 2% within 500 hours.

At the elevated temperatures of 10,000, at which the doughy dental substance is cured, the vapor pressure of the usual non-volatile plasticizer is definitely so high that it has to be taken into account during manufacture and processing a high-quality hardened dental substance is actually obtained.

This volatility effect is compounded by the increased solubility effect difficult, which has the consequence that more polymer over a longer period of time is dissolved in the monomer, which in turn increases the viscosity and the suitability the pasty mass is reduced for processing.

Vapor pressure in mm Hg at various temperatures in ° O Ester 0.1 mm 1 mm 5mm 10mm 760mm dibutyl phthalate 1130 1480 1800 1950 3400 C dibenzyl phthalate 185 250 - - 277 with decay tricresyl phosphate 155 200 234 250 TÄDMA (SR 205) 115 150 168 185 -Methyl glycol phthalate 129 163 202 218 -Polyglycol dimethacrylate 105 145 160 - - ++) ÄDMA CSR 206) - - 95 114 350 butylene glycol dimethacrylate 73 103 128 140 290 In the volatility table above: +) TÄDMA = triethylene glycol dimethacrylate ++) ÄDMA = ethylene glycol dimethacrylate The invention for Äuflagegels that can be used for tooth restoration are characterized in particular by their relative proportions high density and due to their absolutely pore-free nature, whereby it is is a result that, with regard to the teaching of Wichterle, among others, according to the U.S. Patent 2,976,576 is totally unexpected.

But those are particularly unexpected in the case of the rind noted excellent properties such as abrasion resistance, hardness, toughness without brittleness, aging resistance and impact resistance are concerned, in particular if one takes into account how brittle, heavily stressed in the mass polymerized solid dimethacrylate, for example ADMA, which is also per se in the invention was to be expected.

The dental gel polymer commonly used in dentistry consists of a dough-like mixture of methyl methacrylate polymer and methyl methacrylate monomer, the proportions of monomer between 20 and 40% and the proportions of polymers between 80 and 60%, as is also shown in US Pat. No. 2,234,993 (Vernon et al.) is revealed. This mixture is colored, pigmented and shaded. The paste is polymerized by being at elevated temperatures of until deformed about 105 ° C in the cuvette at pressures up to about 50 kg / cm2 (700 psi) is to part in for the desired tooth part, jaw part or gum tissue the appropriate form to be brought. It becomes about 5-15% I) ibutyl phthalate plasticizer used to improve the moisture resistance of the polymer, Das Polymer plasticized with dibutyl phthalate has improved deformation properties and properties Machining properties.

With regard to the polymerizability of methyl methacrylate monomer in the presence of a residual catalyst at room temperature, this dough-like mixture must according to Vernon among others at low temperatures, for example in a refrigerator, be kept in a hermetically sealed container to prevent that a slow hardening by evaporation of the monom @@@ due to the high vapor pressure takes place at room temperature, (see US Pat. No. 2,234,993, p 2, Column 1, Line 74 to Column 2, Line 2, Vernon.) Once in storage If hardening has occurred, the dough-like gel from Vernon can be used at all no longer edit and even if it is under the most favorable terms available is stored, its handling still remains difficult, i.e. it cannot be easily cut or deformed in the tooth shape, either when plasticized with dibutyl phthalate. Used excessively to soften Monomer added, so this also has a correspondingly excessive shrinkage Deformation result.

Attempts have already been made by third parties to improve this gel; in this context, for example, US Pat. No. 2,315,503 (Growell et al.) and U.S. Patent 2,874,832 (Gordon). From Orowell et al. became proposed to use a vinyl ester polymer for the solid phase, but due to the type and amount of reacting monomer, e.g. methyl methacrylate in proportions of 10-40 in terms of be-weight% on the total weight of the mixture, the vinyl gel showed the same defects in terms of high viscosity, poor shelf life and limited shelf life like that of Vernon proposed gel.

In the Journal of Polymer Science, 1951, Fox and Loshaek reported on their attempts to improve this gel.

Your proposal was to use ethylene glycol dimethacrylate, Propylene glycol dimethacrylate and hexamethyl englykoldi methacrylate to use them in a mixture with Crosslinking methyl methacrylate monomer with joint copolymerization however, crosslinking effects between 60 and 80 ° h in the presence of a free radical Polymerization catalyst (free radical polymerization catalyst) and at temperatures from around 800C, the niche polymerization process being considered industrial practically feasible wet manufacturing process can be considered. Fox among others consider increased proportions of methyl methacrylate monomer to be essential and the monofunctional monomer was proportionately increased in order to increase the polymerization efficiency to improve the crosslinking agent, thereby reducing the percentage of crosslinked Groups in the polymer compared to the available groups was improved, although the total number of links fell.

With regard to this pioneering work was made by Bach people on this Area hitherto always assumed that to the extent that the ethylene glycol dimethacrylate in the ethylene glycol dimethacrylate-methyl methacrylate fluid system of 10 20 increases, the peroxide cured products made at 800C becoming increasingly harder, more brittle and tense, this latter characteristic the increasing internal tension means that that is present in the form of a strip The molded product must not be ground or cut with a sharp tool can without it breaking or at least there being a risk of it breaks along the existing cleavage lines and internal stresses, so that Fragments of shiny plastic are obtained.

As a result, it was in favor of the quantitative use of crosslinking agents there is always a certain upper limit given by the type of ethylene glycol dimethacrylate, if they were exceeded, excessive internal stresses had to be expected would occur. In addition, this addition is strongly dependent on the Hartilrlg temperature, the cure rate, the cure effectiveness and the adjustment during the annealing treatment.

As the peroxide initiator is generally in the form of a standard amount is used and the temperature when performing the cuvette procedure Inside very tightly prescribed limits existed up to the present one. invention no alternative to the elimination of the internal tension Trouble. All that remained was to reduce the Degree of networking in this way to prevent the occurrence of such tension and it therefore had to a corresponding networking limit can be set at which it is still possible was to achieve the desired cure.

With increasing length of the chain between the alcohol groups in the crosslinking agent there is a low molecular weight crosslinking and a relatively higher effectiveness, so that by a sufficient conversion into crosslinked polymer the advantages achieved by the crosslinking are increased, at the same time a decrease in hardness occurs. For this reason and with In practice, ethylene glycolite has so far taken account of the costs involved Methacrylate started out, the upper limit always being kept below about 25 mol became less, even when this crosslinking agent was weight-related was effective than those crosslinking agents which have longer chains. Accordingly was not believed until the present invention was realized that it is possible to obtain deformable plastic products that can be used in grinding and Cutting would not splinter if one was the only component of the monomer phase Crosslinking agent would be used.

This deleterious feature of ethylene glycol dimethacrylate is also evident when using trimethylolpropane trimethacrylate, however the latter, in terms of the occurrence of tension, is even worse when it is polymerized with benzoyl peroxide in large quantities or with a small quantity Methyl methacrylate is copolymerized in larger amounts. It is not suitable readily for shaping either in the presence of other polymers or as unmodified product and in view of this deficiency the monomer appeared in the not usable as homopolymer on an industrial scale.

In all cases the use of homopolymers arise from the diacrylates brittle products, which owing to their inherent properties splinter and break too easily, so that they neither cover whole teeth nor as material for patching out teeth with water-impermeable properties.

When using these trimethylolpropane trimethacrylate products specially plasticized and properly polymerized by special processes, see above that corresponding complex mixtures arose, so it was true possible, to eliminate the splinter and breakage property, however, the results were hardly any Worth talking about and were not suitable for general use in dentistry. With this type of application, the requirements for resistance can be met mechanical extraction, aging resistance 'moisture resistanceX abrasion resistance and impact resistance as well as color fastness with plasticized mixtures of this type only so difficult to achieve that it cannot be assumed that in achieving it a suitable gel for this purpose successes can be achieved.

It was therefore completely unexpected and surprising that the invention Crosslinking agents, which form the entire monomer phase, with regard to their durability were far better than the usual crosslinked methyl methacrylate coating gels or cross-linked methyl methacrylate seams.

Ethylene glycol dimethaorylate is also included as a monomer in the paste system unsuitable in that the solvent power is also excessively high and consequently a stiff gel is obtained which hardens very strongly and cannot be processed quickly what is either due to the extraction of the catalyst from the polymer or on simple solvation of the polymer by the monomer traced back causing extremely high viscosity.

Trimethylolpropane trimethacrylate, on the other hand, forms what the dissolving power is concerned at the other extreme and is a very poor solvent in the paste system. If the dental polymer is preferably used in a certain amount When the composition is used, there is no solvation at room temperature and the mass remains sandy, i.e. it is ready to be deformed in the Cell completely unsuitable.

If the mass is deformed according to a special premixing process, so the tooth thus obtained is of such excessive brittleness that it is considered to be practical Uses is completely useless.

The polymer in the paste can be produced in such a way that there is no residual peroxide is present, i.e.Li. it is peroxid @ rel, which improves the paste will. For example, it is possible to keep the polymer for 16 hours to heat, so that in an analysis for the best determination of residual peroxide such is not determined. If this polymer is used with the preferred monomer concentration mixed, it cures neither in 30 minutes nor at a temperature of 10,000 in 60 minutes from so that from practical considerations evident is that (at an estimated minimum of 0> 01%) some residual peroxide is required. However, the analyzed amount of benzoyl peroxide becomes the remainder is present in the polymer, instead an appropriate amount of monomer is added and dissolved in this and then this substance is combined with the peroxide-free polymer mixed, this mixture becomes hard and non-deformable within a few days. As can be seen from the above examples, the monomer must have the property have to solvate the polymer without extracting the peroxide before not the hardening is to be carried out.

Example I Formation of a support gel 90g of a suspension polymerized Polymer of methyl methacrylate (clear grains with a diameter of 0.5 - 1.0 mm), with 10% dibutyl phthalate in the monomer and a remainder peroxide of about 0. 1% (specification conditions for teeth not more than o. 0Yo) in the form of benzoyl peroxide and its viscosity molecular weight was 500,000 pigmented with basic additions: - 24 -F-2100 (fluorescent Zinc oxide) 0.14 g Permalba (Ditanium Dioxide, Magnesium Sulphate) 0.025 g Cadmium Yellow F-5512 (Cadmium Sulphide) 0.0015 g Cadmium Red F-5893 (Cadmium Sulphide) 0.0010 g Ivory Black (Carbon black) 0.0005 g This pigmented tooth tip concentrate was composed treated with 3 pounds of stones in a ball mill for 10 minutes and then with 90 g of clear polymer mixed.

To 55 g of the pigmented polymer described above, 45 g SR-205 (triethylene glycol dimethacrylate) with a hydroquinone content of 200 particles per million admitted. This mixture was stirred thoroughly and then allowed to stand. After the lapse of 24 hours, the viscosity was such that the substance when used the procedural techniques customary in dentistry using the conventional ones Acrylic resins are more common than those used in the manufacture of crowns and bridges 1packbaren11 could be considered. After 7 days the viscosity was ideal. in the Allow the next 6 months to use the gel at room temperature in one A slight increase in viscosity was noted, but even after 6 Monoton had elapsed, the gel could still be produced without further ado use a tooth rest.

Example II The same methyl methacrylate polymer as in Example I was using 0.2% azoisobutyrylonitrile as a catalyst (molecular weight 600,000) produced and pigmented, with a slightly different pignient composition was used in accordance with the following information: methyl methacrylate polymer (15% butyl phthalyl butyl glycolate) (Monsanto B16) 90 g B-2215 (fluorescent zinc oxide) 0.10 g Ti02 (titanium dioxide) 0.02 g cadmium yellow F-6489 (cadmium sulfide) 0.0005 g Cadmium Orange F-5895 Cadmium Sulphide) 0.0008 g Iron Black (Iron Oxide) 0.0002 g This pigmented tooth tip paste was mixed with 3 pounds of stones in one for 10 minutes Ball mill treated.

To 70 g of the powder described above, 30 g of SR-210 (polyethylene glycol 200 dimethacrylate) added, which in turn monomethyl ether of hydroquinone in a proportion of 500 Particles per million had been added.

This mixture was stirred. After 8 hours became a part of the mixture is removed and placed between polyethylene foils in a slightly warmed up'orm (45 ° C) introduced. This structure was molded in such a way that it could be used as a cutting surface used for a front tooth. The gel thus obtained was in terms of its Rigidity similar to conventional luxury vinyl resin commonly used for crowns and bridges is used.

Example III To 60 g of the polymer described in Example II 40 g of 1.6 hexamethylene glycol dimethacrylate were added, the dimethylcyclohexylamine added at a rate of 500 parts per million. This mixture was stirred and then left to stand for 7 days. Then it turned out to be as a ready-to-use paste-like substance, which corresponds to the type of inlay Example VI was processed further.

Example IV Tooth Composition The granular polymer was through Suspension polymerization of methyl methaorylate with 10% dibutyl phthalate and0.5% Benzoyl peroxide prepared using the procedure described in Example I. The molecular weight was 425,000. This polymer was used to form the tooth body shade pigmented as follows: polymer 45.4 g brown concentrate + (burnt sienna) 0.366 g red concentrate + (cadmium selenide) 0.91 g yellow concentrate + (cadmium selenide) 1.530 g black concentrate + (carbon black) 3.660 g TiO2 (titanium dioxide) 1.3 g +) produced using 1 part pigment and 99 parts polymer by Treatment in the ball mill.

This pigmented polymer was in a pan mill for 5 minutes mixed.

To 60 g of the above-described polymer were 40 g of SR-205 (triethylene glycol dimethacrylate) added which has a hydroquinone content of 60 parts per million borates.

The mixture was stirred and allowed to stand for 2 days. Afterward it was processed into a tooth as described in Example VII.

Example V A polymer was made by suspension polymerization of methyl methacrylate with 7% dibutyl phthalate and 0.4% benzoyl peroxide accordingly Example I made.

The molecular weight was 550,000.

This polymer was used to achieve a tooth body shade pigmented as follows: polymer 45.4 g brown concentrate + (burnt sienna) 0.366 g red concentrate + (cadmium selenide) 0.91 g yellow concentrate + (cadmium selenide) 1.530 g black concentrate + (carbon black) 3.660 g TiO2 (titanium dioxide) 1.3 g +) made by using 1 part pigment and 99 parts polymer and treatment same in a ball mill.

The polymer pigmented in this way was pan milled for 5 minutes mixed.

To 60 g of the above-described polymer were 40 g of SR-205 (triethylene glycol dimethacrylate) at a hydroquinone content of 60 parts per million. The mixture was stirred and left to stand for 2 days. Then it was according to the Details from Example VII processed into a tooth.

Example VI Curing of the Auflagegelß as inlay It was after normal procedures for making an inlay followed. Under the use of Justi- "Namilont shade" 65 "+ became a paste-like intended for the tooth cap Mass produced. This body was left in the bottle at 1000C for 15 minutes hardened. Then the essay was removed and the body substance so far Sanded off until the desired tooth shape was obtained. The obtained according to Example I. Gel was applied to the surface of the body, and then the Attachment of the slightly warmed form pressed down. Thereupon the gel tooth tip became boi 10000 cured for 30 minutes.

Finally the bottle was chilled on the table for 30 minutes and then the inlay is broken out, finished, polished and finally in a central tooth used as a class 4 inlay. This inlay showed no signs of wear or abrasion for 1 year and it did there is also no noticeable change in color.

+) Justi'tNamilontt shade "65" is pigmented Acrylic polymer gray-white tint made from inorganic pigments according to the example V.

Example VII Curing the Tooth Composition Die according to Example Tooth body composition prepared 1V was used to form the surface shape Back teeth around a core of lightly cross-linked standard acrylic paste The two-layer body thus formed was then placed in a metal mold cured, the top of the mold was designed such that it was the desired External shape of the tooth corresponded. The wet was for 3 minutes at 980C with a Cured pressure of about 120 kg / cm2 (1700 psi). Then the top became the form removed and applied to the surface from the composition according to Example IV produced cutting body applied. Then a second one was placed on this surface The upper part of the shape is placed on the shape of the finished tooth corresponded and the mold was then heated for 3 minutes at a temperature of 980C in a press set.

The mold was then post-cured for a further 3 minutes at 1500C.

The tooth thus made turned out to be hard and strong and proved its resilience to all those stress tests that he was exposed to his properties for both practical and practical use to be determined for experimental use0 The material can be fixed with a Grind the disc very hard (it is similar to porcelain) and can be achieved until it is achieved polished to a high gloss surface. During the polymerization, the shrinkage is des triethylene glycol dimethacrylate S-205 theoretically 69% of the comparatively used Shrinkage of methyl methacrylate. Since the degree of polymerization is about 80%, the actual shrinkage comes closer to 55 * of methyl methacrylate.

There is a very good chance that at least one end group polymerized and consequently not extractable. So then comes the proportional one Distribution of 55 parts of polymer to 45 parts of monomer of triethylene glycol dimethacrylate (SR-205) the 2 parts by weight of polymer to 1 part by weight of methyl methacrylate monomer very close once you get the whole occurring during the polymerization Compare shrinkage.

This was theoretically achieved in clinical trials Result confirmed by the fact that there were no indentations or indentations, as found in a crown made of a high monomer content pasty material had been produced.

In all of the examples described above, the suspension polymer of methyl methacrylate by the usual process originally developed by Crawford which is disclosed in US Pat. No. 2,108,044 and US Pat. No. 2,191,520 Described is, where as preferably stabilizers for the suspension either Starch or methyl cellulose can be used.

The particle size distribution is preferably between Tyler sieve sizes No. 80 (clear mesh size 0.175 mm) and Tyler sieve size No. 200 (clear mesh size 0.074 mm) if the polymer product prepared according to the invention is used for the purposes of Dentistry is used. A typical size distribution of the polymer powder, which is particularly suitable for the application according to the invention in dentistry, is as follows: Table I Particle size of the polymer powder material Amount retained by Tyler sieve size no ... (%) 50 60 80 100 200 over 200 Dental prosthesis base 0 1-5 30-40 20-30 10-15 1 Tooth restoration 0 1-5 20-30 10-15 30-40 0.2-2 The powder particles used or intended for the purpose of tooth restoration are somewhat finer spherical granules than those used for the formation of Zakner replacement bases can be used. Otherwise are those used for tooth restoration Products similar to denture resins. Usually the powder granules have no uniform and uniform particle size, but most products each contain the most varied particle sizes within a certain range.

The illustrative examples of the Particle sizes apply to methacrylate copolymers, the methacrylate copolymers by polymerizing liquid material with a content of 60% methyl methacrylate and 40% ethyl acrylate or 30% methyl methacrylate, 30% butyl methacrylate and 40% ethyl acrylate having rubbery properties is obtained but are nevertheless characterized by their surface hardness, whereby those products which contain methyl methacrylate in a higher proportion are harder than those Products in which methyl methacrylate is present in a lower proportion.

So long at least 60 wt .-% of the liquid polymerizable monomer material formed from a methacrylate ester may other polymerizable monomers can be added in a limited amount to suit the properties of the polymer to change, whereby the achievable changes in specialist circles on the stand are already well known in the art. By adding up to 40% more aromatic Vinyl monomers, e.g.

B. styrene, vinyltulene will give the product a solubility in aromatic Solvents bestowed. Up to 40% acrylic acid ester of the lower monovalent ones Aliphatic alcohols with 6-8 carbon atoms can be used to make a elasticizing effect with improved adhesion to the solid manufactured To achieve polymer.

With the methacrylate ester, up to 105'o methacrylic acid, itaconic acid or acrylic acid can be mixed.

To achieve a particle size between 0.01 and 0.4 p, a smaller particle size distribution by way of b-Ka @ rter emulsion polymerization can be achieved.

Suitable catalysts for the polymerization are the free radical polymerization catalysts (free radical polymerization catalysts), such as the peroxides, e.g.

Benzoyl peroxide, phthaloyl peroxide, substituted benzoyl peroxides, z, B, Acetyl peroxide, caproyl peroxide, lauroyl peroxide, cinnamoyl peroxide, acetylbenzoyl peroxide, Methyl ethyl ketone peroxide, sodium peroxide, hydrogen peroxide, di-tert.

Butyl peroxide, tetralin peroxide, urea peroxide, etc., the hydroperoxides, e.g. cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, tert. Butyl hydroperoxide, methyl ethyl ketone hydroperoxide, 1-hydroxy-cyclohexyl hydroperoxide-1, etc. azo compounds such as 2,2'-azo-bisisobutyrylonitrile, 2,2'-azo-bis-isovaleronitrile, etc. the per compounds, e.g. ammonium persulfate, sodium perborate, sodium perchlorate, Potassium persulfate, etc.

The catalysts can either be used alone or in the form of a catalyst mixture can be used. As preferably the catalyst used is Benzoyl peroxide to be mentioned0 In general, any desired amounts of catalyst can be used can be used, but normally that catalyst concentration is included the satisfactory results can be obtained within a range of 0.1 and 2.0% by weight of the total polymerizable composition.

There is also the possibility of producing dental materials To use vermilion, mercury sulfide and oadmium red with zinc or titanium oxide, in order to achieve the desired pink shade, as it is for the denture bases plastics used is desired. By using cadmium yellow leaves get a deep yellow to orange. Pigments like carbon black and the Oxides of iron, zinc or titanium are harmless and can be used successfully to achieve various shades of gray and brown can be used. The burned and Raw umber and sienna earths and the ocher substances are particularly suitable to achieve a wide variety of brown tones. As further suitable pigments Ultramarine blue and Ohrom green and yellow are used to achieve special tints to call. The pigments used for the production of dental porcelain are suitable yourself without also for methaor, ylat crowns and inlays, while all pigments used for dental rubber for the mixture according to the invention can be used. Soluble dyes often have a tendency to remain in the mouth and consequently to assume a lighter shade, and for this reason they are generally not appropriate. With those currently commercially available The pigments are generally relatively stable throughout dental products. With the exception of the clear, transparent qualities, most resins have different qualities Degree of cloudiness. The oxides of zinc in particular serve as opacifiers or of titanium.

Of these, however, titanium dioxide is the more effective substance, so that only very small amounts of it have to be added, hardening of the crown, Bridge and Overlay Gel In the preferred method, the material is 30 minutes treated for a long time in a plaster or stone mold in a water bath at 1000C.

There is also the option of using a hot lamp press to apply the gel (hot lamp press) to heat and with the help of a corresponding Shaping the mold, then removing the mold and curing it with the heating lamp to be carried out completely. This type of hardening generally takes about 15 Minutes or less.

A disadvantage of the fact that the upper molding is not in place and Place being burdened is that in this ball it is impossible to get the shape can actually be reproduced in every detail. For numerous uses however, this is irrelevant. This means that the tooth can also be converted into a be brought into the appropriate shape that it cures with a hot tool is pressed.

As a preferred method for deforming the external tooth according to the invention the compression deformation occurs at a relatively low temperature, for example about 1020C in a metal mold or a cuvette, which is used The pressure values applied are between 140 and 700 kg / cm2 in order for the bottle to be a to achieve maximum impermeability and a high-gloss, porcelain-like surface. Dental products manufactured in this way are characterized by dimensional tolerances of 0.0127 mm the end.

As can be seen from the foregoing, come as appropriate liquid bifunctional methacrylate esters for composition of artificially manufactured molded teeth, in particular the following substances are in question : (A) Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethyl glycol dimethacrylate at polyethylene glycol dimethacrylate from polyethylene glycol 200 polyethylene glycol dimethacrylate from polyethylene glycol 400 polyethylene glycol dimethacrylate from polyethylene glycol 500 Neopentyl glycol dimethacrylate 2-methyl-2-butylpropane dimethacrylate tetramethylene glycol dimethacrylate Hexamethylene glycol dimethacrylate 1,3-butylene glycol dimethacrylate 1,3 propylene glycol dimethacrylate (B) Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate Polyethylene glycol 200 diacrylate polyethylene glycol 400 diacrylate polyethylene glycol 600 diacrylate Neopentyl glycol diacrylate, hexamethylenglycol diacrylate 1,3-Butylene glycol diacrylate 1,3-Propylene glycol diacrylate For curing medium Temperatures, for example at 60-100 ° C, can be benzoyl peroxide or lauroyl peroxide be used. Azobisisobutyrylonitrile is a typical example of an azo free radical catalyst (azo free radical catalyst), in which at lower temperatures, for example 6000, a product with a high degree of polymerisation and at higher temperatures, for example 75-100 ° C a product with a lower degree of polymerization obtained will.

In addition, accelerators, for example aromatic amines, Ascorbic acid, cobalt salts or REDOX activators with the free radical polymer cation catalyst (free radical polymerization catalyst), for example organic or inorganic peroxide can be used.

In particular, the tertiary Aainaktivatoren such as N, N-dimethylaniline, N, N-dimethyl-p-toluidine, dimethylcyclohexylamine, or trihexylamine with such Syrup substances brought to use. This kind of activators is used in an advantageous manner in the preparation according to the invention used by dentures.

The method of using these peroxides is not the same careful control of the polymerization, especially during the accelerated exothermic stage, as is the case when curing polyesters if a bubble free product with good clarity and the other desired properties should be preserved.

In the case of the bulking compound mixture according to the invention, the previously known occur Difficulty in removing dissolved gases, adjusting shrinkage in volume and appropriate control of the exothermic reaction, in particular after the material has reached gel consistency, does not appear. The invention Mixtures can be made using one or more catalysts as well polymerize using more than one temperature value. The inventive Mixture can be used in essentially the same way as methacrylates Use embedding purposes.

The great advantage is that according to the invention one with peroxide catalyzed bulk polymerization of methyl methacrylate performed so that after a 20-30% conversion into polymer has been reached, the rate of polymerization is strongly accelerated and that with this acceleration also a corresponding one Increase in the degree of polymerization is associated.

In those cases where the usual Procedure result in deformation difficulties, there is also the possibilityX to Manufacture of reinforced parts using glass-filled paste-like substances.

Preferably, chopped glass fibers are used together with additional fillers Use, the aser content being between 5 and 30%, depending on which Ratio the additional fillers should be present. The dental filling masses filled in this way can be preformed.

The molded part has smooth surfaces and only at the points of A few flow lines are noticeable in the glass orientation. Otherwise it can harden any temperature can be used.

The preformed filler compound present in strip form is in a Protected packaging form in which it is either detachable on a carrier pad hung up or else Detachably inserted between two protective layers is. The pre-formed filling compound strips can easily be made into small pieces cut. In this form, it is used in particular for patching up and making of restoration work being carried out at elevated temperatures up to around 1000C and can optionally also be polymerized at higher pressure.

Claims (13)

Claims 1. Artificial abutment tooth, characterized in that that it has an inner core made of solid polymethyl methacrylate, which can be easily networked and either wholly or partially from an external edition is enclosed, which consists of the free radical polymerized Mixture of a solid, finely divided methyl methacrylate polymer, copolymer or a mixture thereof and liquid polymerizable dimethacrylate ester consists, with the dimethacrylate ester being the only component of the polymerized forms liquid phase and contains an alcohol component from the group of the aliphatic polyhydric alcohols with 4 to 8 carbon atoms, polyethylene glycol with a degree of polymerization of 2 to 6 and polypropylene glycol with a degree of polymerization comes from 2 to 6. 2. Artificial abutment tooth according to Anspuruc @ 1, thereby gek @@ næ * ichnet that the outer layer is pigmented and titanium dioxide, zinc oxide, Copper oxide, iron oxide, cobalt oxide, barium sulfate, carbon black, burnt umber, Oadmium selenide, cadmium sulfide and mixtures thereof are used, with pigment and polymer in one first son centration evenly in the Outer layer are distributed so that an inner shading layer is formed. 3, artificial build-up tooth according to claim 2, characterized in that that the pigmented outer layer is more strongly pigmented in its inner layer, so that in this way the tooth body shading is achieved while in the upper layer is less pigmented, so that at the tip of the tooth a lighter shade is given. 4. Artificial external tooth according to claim 3, characterized in that that the outer tip of the tooth is not pigmented and that immediately next to this tip Adjacent areas have gradually darkening pigmentation. 5. Artificial build-up tooth according to claim 3, characterized in that that the support layer is the finely divided solid polymer of methyl methacrylate contains in the outer area to improve the uniformity of the dispersion of the polymer in the liquid with a non-volatile ester plasticizer softened lit. 6. Tooth according to claim 5, characterized in that as a plasticizer Dibutyl phthalate is used. 7. Tooth according to claim 5 characterized in that as a dimethacrylate ester Triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate or 1,2-butylene glycol dimethacrylate is used. 8o pack, characterized in that it consists of a carrier layer and consists of a pre-formed strip of a storable pigmented tooth filling compound, which can be easily removed from the support and which at room temperature can be stored for long periods of time without hardening or dries out, the filling compound having the following composition an inert stable solid opacifying pigment, a non-volatile liquid polymerizable dimethacrylate ester a polyhydric alcohol from the group of aliphatic glycols with 4 to 8th Carbon atoms, polyethylene glycol with a degree of polymerization of 2 to 6 and Polypropylene glycol with a degree of polymerization from 2 to 6, the liquid Ester is less volatile than dibutyl phthalate and is the only liquid Part of the dental filling compound represents, as a thickening substance a solid, finely divided methyl methacrylate polymer for the liquid component is used, the proportionate intimately in the liquid dimethacrylate ester until browning the gevan- ned tooth filling material consistency is dispersed, the methyl methacrylate polymer is obtained by peroxide polymerization and contains an amount of peroxide which is sufficient to polymerize the tooth filling substance if it is left on a Curing temperature of about 1000C is heated0 9. Pack according to claim 8, characterized characterized in that the tooth filling compound present in strip form is releasable between two protective lagren is inserted and titanium oxide, zinc oxide, copper oxide, Iron oxide, cobalt oxide, barium sulfate, cadmium selenide, cadulium sulfate and their mixtures be used. 10. Pack according to claim 8, characterized in that the tooth filling compound strip one part colored in a darker shade and another in one lighter shade has pigmented portion. 11. Pack according to claim 8, characterized in that as a liquid Dimethacrylate ester triethylene glycol dimethacrylate is used. 12. Inlay, characterized by an outer exposed part from the free radical polymerized mixture of a solid finely divided methyl methacrylate polymer, copolymers or mixtures thereof with liquid polymerizable dimethacrylate ester, the dimethacrylate ester represents the only component of the polymerized liquid phase and one Contains alcohol component which is a polyhydric aliphatic alcohol with 4 and 8 carbon atoms, polyethylene glycol with a degree of polymerisation between 2 and 6 or is Elypropylene Glycol with a degree of polymerization between 2 and 6. 13th edition, characterized by an exposed outer part consisting of the free radical polymerized mixture a solid, finely divided methyl methacrylate polymer, copolymer or their mixtures with liquid polymerizable dimethacrylate ester, wherein the dimethacrylate ester is the only component of the polymerized liquid phase and contains an alcohol component that is a polyhydric aliphatic alcohol with 4 to 8 carbon atoms, polyethylene glycol with a degree of polymerization of 2 to 6 or polypropylene glycol with a degree of polymerization of 2 to 6.