CA1256237A

CA1256237A - Substance for the preparation of plastic and/or hard substances for dental-technical, (dental)medical and related purposes, process for its production and the use thereof

Info

Publication number: CA1256237A
Application number: CA000465578A
Authority: CA
Inventors: Frauke H.F. Von Nostitz
Original assignee: NOSTITZ F VON
Current assignee: NOSTITZ F VON
Priority date: 1983-10-19
Filing date: 1984-10-16
Publication date: 1989-06-20
Also published as: ATE56134T1; IE58156B1; ZA848074B; FI78612B; KR850002949A; GR80669B; EP0138232A2; FI78612C; DE3337986A1; IE842692L; FI844124L; DK498784D0; PT79382B; NO165222B; ES8603751A1; DK498784A; NO844162L; JPS60115505A; DE3483128D1; PT79382A

Abstract

Abstract:

A substance is described for the preparation of plas-tic or hard substances for dental technical and (dental) medical and related uses, which includes, apart from a thermoplastic and the conventional additives, 0.05 to 10 % by weight of jojoba oil. Further a process is disclosed for the production of the inventive sub-stances as well as the use thereof.

Description

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Substance for the Preparation of plastie and/or hard substanees for dental-teehnical,(dental)medical and related purposes, Process for its production and the Use thereof . _ _ The invention eoneerns a susbtanee for the preparation of plastie and/or hard substances for dental-technieal, (dental) medical and related purposes, a process for its production, and the use thereof.
The use of aery~c or methacry~c ~ide~ for (dental) medieal and technieal purposes, espeeially when taking jaw impressions as well as for the inner lining of plastic dentures ete., is known. It is also known that 10 additives sueh as plasties of another type, eellulose derivates,(natural) resins(e.g. eopal, sandarae), para-ffin, wax,oil, dyes and fillers should be added for this purpose to the aeryl- or methaeryl aeid esters. DE-OS
27 18 017 describes the addition of metal soap and/or 15 metal silicate to sueh plastic or hard substances for dental technical and (dental)medieal reasons.

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The acryl- or methacryl acid ester is generally used in such a way that a powder, bead or splinter gran-ulate of a polymer or mix polymer of these compounds is dissolved in a liquid monomer and this solution is hardened optionally with addition of promoters.But when using such mixtures there are certain drawbacks.

While the dissolution of the powder in the liquid is relatively time-consuming,in the case of cold poly-merization in the powder-liquid system,parts of the polymer remain undissolved, which causes a loss of stability and homogeneity of the material. It is desirable to create a substance which ensures easier processing, optionally on the basis of improved vis-cosity and plasticity of the material.

The cold polymers containina monomer methylmethacryl-ate are also regarded as irritating to mucous membranes.
In this respect too it is desirable to create an im-proved dental substance which would avoid or reducethis disadvantage. In addition burns can result in the mouth from the rapid polymerization of cold polymers.
When producing linings from momomeric methy~thacryl-ate,the products do not always have perfectly smooth surfaces,and are therefore partially absorbent of the saliva,making the microflora in the mouth more easily attacked.

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'~L256237 The invention is therefore based on the object of creating a substance of the type above which, owing to its improved viscosity, ensures easier and faster processing, has better mechanical strength and develops a healing effect at pressure p~ints and inflammations in the oral region as well as in linked dentures, forms smooth surfaces, is devoid of smell and taste as well as being compatible with the mucous membranes, while maintaining optimal fittins~ over more lengthy periods of time. This substance should be easily adjustable if necessary to the required c:onsistency, e.y. hard or elastic or remaining soft, respectively.

Various aspects of this invention are as follows:
A substance useful as a dental-technical, dental-medical and medical molding and lining material comprising, a substrate selected from the group consisting of monomeric and/or polymeric or copolymeric acrylic or methacrylic ester, a hardening substance for said substrate, and jojoba oil, the jojoba oil being present in an amount of 0.05 to 10% by weight of total material of said substance.

A substance useful as a dental-technical, dental-medical and medical molding and lining material comprising a two-component system, said two-component system comprising, (a) a powder system comprising a polymeric acrylic or methacrylic ester, a metal soap and a hardening substance for said ester, and ~J`:~
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(b) a liquid system comprising a monomeric acrylic or methacrylic ester and from 0.05 to 10% by weight of jojoba oil.

A process for the preparation of dental-technical, dental-medical and medical molding and lining materials, comprising the mixing of a two-component system, consisting of 0 (a) a powder system which comprises a pol~meric acrylic or methacrylic ester, a metal soap and a hardening substance for the acrylic or methacrylic ester, and (b) a liquid system consisting of a monomeric acrylic or methacrylic ester and 0.05 to 10% by weight of jojoba oil.

By way of added explanation, the object above is solved inventively by the availability of a substance of the type above, which is characterized in that it comprises, apart from the thermoplastic and conventional additives, from 0.05 to 10% by weight of jojoba oil.

This oil as used in the invention is the oil of the jojoba plant, which belongs to the buxaceae family, after extraction and purification. Hereinafter the term jojoba oil, as used in the invention, also covers jojoba wax.

It is preferable to use the jojoba oil together with the other components for the manufacture of plastic or hard substances according to the invention in a concentration of 0.1 to 5% by weight.

: - . - . . . . . - , , ~2~;6237 By adding jojoba oil to the substance for the prod-uction of plastic or hard substances as in the invent-ion, it is possible to improve the workability,tough-ness,hardness and strength as well as the surface prop-erties and the durability in the mouth(no aging mani-festations),as well as the brittleness,odor formation, and unattractive color formation, while the inventive substance dev~ops a healing effect at the pressure points and inflammations in the oral region as well as with linked dentures, and to obtain non-porous,non-brittle and non-shrinking substances which are also especially compatible with the mucous membranes and which are suitable for the most varied (dental) medical and dental-technical and other purposes to an outstand-ing degree. Using the inventive substances it is inparticular possible to attain elastic,hard or perman-ently soft molding materials or inner linings as des-ired, in which the hardness or the elasticity can be regulated fully as required. In particular the inventive substance is characterized by the fact that an option-ally plastic or hard dental-technical or dental-medical substance can be produced which maintains its optimal fitting and viscosity or plasticity in the mouth over long periods, develops a healing effect at the pressure points and inflammations in the oral area as well as with linked dentures, and possesses a good mucous membrane compatibility.

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- 5 - ~2~;623~7 As the solvent or dispersion agent for the homo-,co-, or mix-polymer share, the methyl ester of acrylic and/
or of methacrylic acid can be used as well as the hot polymerization of acrylates without the methyl ester additive. This embodiment of the invention is considered especially when hot polymerization is effected or the polymerization in the mouth of the patient himself is omitted. An especially preferred substance accord-ing to the invention has however no substantial share or(especially advantageous) no share of monomeric acrylic acid- or methacry~c acid methyl esters, but instead of them high boiling point ester derivates of the named acids are used. Here special consideration is given to a content of at least one monomeric acrylic and/or meth-acrylic acid ester having from 6 to 10 carbon atoms.
Examples are provided by 2,3-epoxypropyl-, n- or t-- butyl,n- or cyclohexyl-methacrylic acid ester or mixt-ures of these monomers. Equally good use can be made of the analogous esters of the acrylic acid, while it may be especially expedient to use mixtures of the named monomeric acrylic acid esters and methacrylic acid est-ers. Although the use of ester derivates with a total of from 6 to 10 carbon atoms is preferred, at least partially ester derivates of acrylic- or methacrylic acid may be used, whose total carbon number is below the range shown as preferred above from 6 to 10 carbon atoms, for example methacrylic acid-dodecyl ester, methacrylic acid-triethyleneglycol-mono-ethyl ester, methacrylic acid-ethylhexyl ester etc.A specially advantageous monomer is lastly a reaction product of glycidylmethacrylate and bisphenol A.

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The polymers may be basically polyacrylates and-methacryl-ates or mix and/or copolymers. In addition certain shares of plastics of another type may be present, such as polyvinylchloride, polyvinylacetate, or polyvinylalcohol.
Preferred is a mixture of polymethacrylates with average molecular weight. Among them especially favorable are those which have good solubility properties in the monomeric shares used and in the solvent shares partly contained therein. Such polymethylmethacrylate mixtures of average molecular weight,which for example are soluble in esters,ketons,chlorinated aliphatic hydrocarbons,cyc-lic ethers etc, and have thermoplastic properties, can be obtained from the trade.
-15 Preferably the thermoplastic is thus,before polymerization,a mixture of monomers and polymers or of mix polymers of -acrylic and methacrylic acid esters. This mixture is preferably present as a paste or as a solution.

20 The polymer share in the monomeric solution,which option-ally contains additives,can vary within wide limits Normal-ly polymer shares between 10 and 70% by weight based on the total composition are present.A specially preferred range of the share of weight of the polymer amounts to 25 from 10 to 40% based on the total substance, since it easily provides especially fluid-to-pasty and doughy substances which can be cast, injected, distributed with the spatula or squeezed as fluid,doughy ~r pasty substances from pressure vessels and thus distributed.

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~ 256~'~17 To these solutions or syrup, -the pastes or doughy sub-stances of polymers or mix polymers in the monomer mixt-ure metal soaps and/or silicates, a catalyst and option-ally an accelerator are added for hardening.

Stearates, laurates, oxystearates,palmitates,montanates, oleates or ricinoleates of metals such as for example aluminium, magnesium,or calcium have been found suitable as the metal soaps.Preferred are the alkaline earth soaps, which should be present in finely divided form.Special preference is given to the use of magnesium stearate and calcium stearate. The added amounts of metal soap(s) and their mixtures add up advantageously to from 0.1 to 10%
by weight, based on the total substance.

As the silicates whose addition has been found favorable it is primarily alkali silicates which are considered, ~ especially the trade-obtained soluble waterglass compounds of which both sodium- and calcium silicate or mixed alkali silicates can be used. Especially suitable is alkali alumi num silicate. The amount added of such a silicate is pre-fereably 1.5~ to 5% based on the total amount of the sub-stance. In these waterglass preparations, the so-called oil number should not be more than 26, while an oil number 25 - of about 22 has performed especially well.

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- 8 - ~25~ 7 In the event oE special stress on the plastic or hard substance for dental-technical or (dental) medical and related uses, it may be expedient to provide a share o~
a cross-linking agent in the inventive substance.Among the known substances effective for the cross-linking of methacrylate or of acrylate, special suitability attaches to olefinic dimethylacrylates such as ethylene dimethyi-acrylate, propylene dimethy~acrylate, polyethyleneglycol dimethyacrylate.It is expedient that the optionally used polyethyleneglycol dimethyacrylate cross-linking agent should have a relatively low molecular weight.
The cross-linking agent which is especially suitable for the prevention of the later emergence of stress cracks can for example be added in amounts of from 0.1 to 10%
by weight, based on the total substance.

The cross-linking agent can however also be used in larger amounts and can partly replace the monomeric (meth)acrylate. According to one embodiment of this in-vention,which can be seen as being preferred for certainapplications, the monomeric share is ~otally replaced by a monomeric cross-linking agent.In the latter case, the polymer share would be exclusively dissolved in the monomeric cross-linking agent.

- 9 - 3L;256237 n one preferred embodiment the inventive substance for the manufacture of plastic or hard substances for dental-technical and (dental) medical purposes consists of a two-component system, with special preference for a powder system and a liquid system, in which the powder system includes the polymer plastic and optionally the metal soap, filler and peroxide(catalyst), while the liquid system includes the monomeric acrylate, the soften-er, the accelerator as well as the jo~oba oil.

Moreover to increase the lasting ability of the subs-tance according to the invention,a small amount of sta-bilizers or inhibitors is added thereto, which prevent any unintended further polymerization of the solution when it is stored.For this purpose e.g. the phenol compounds such as aminophenole,dibutylmethyl-phenol, or butylhydroxyanisol or even hydroquinone,pyrogallol, or pyrocatechol may be considered. These inhibitors can be added in amounts of from about 2 to 100 ppm of the substance.

Methacrylates usually have a typical bitter aftertaste, which temporarily, for example when fitting the ~unctional) impression tray with the molding mater-ial or the lining of a denture, may be found disturbing.

To overcome this problem, the addition of sweeteners freeof carbohydrates, such as cyclamates, or of anti-cariogen-ic sugar additives on a carbohydrate base, for example xylite, may be performed; the mixture of sodium cyclamate with 10~ saccharine well knowninthe trade has been found specially useful. Moreover the solution can contain the usual colorants.

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-. ' -, ~ , . -: , ' 1 o ~2~i~237 The catalyst used to harden the plastic substance can be added basically in powder form. But it is used with advantage in the form of a solution in a solvent which is preferably easy to dissolve since in this way it is 5 distributed easily and evenly in the acrylate solution.
In the manner known per se, for the catalysts or init-iators one can use peroxides, such as hydrogen peroxide, tert.butylhydroperoxide,cumylhydroperoxide, as well as dialkyl- and diarylperoxides, ketone peroxides, diacyl-peroxides such as di-benzoyl peroxide, or peroxic acids, as well as azo compounds, such as azo-di-isobutyric acid nitrile and azodicarbonamide, which are used optionally in solvents such as dibutyl-phthalate,methanol,acetic ester, acetone or methylethylketone.
In the case of catalyst systems which are self-hardening, i.e. without the additional use of heat the hardening is effected,an accelerator or activator,which effects the decomposition of the initiator and thus the start of the polymerization of the monomer into polymer, should be include~ in the actual accelerator or initiator.For such acceleration, tertiary amines,alkyl-,alkylaryl- and oxyal-kylamines have proved satisfactory, as well as reducing agents such as sulphinic acids or dithionite, which can be added in amounts of from 1 to 3% by weight. But in-stead of the above listed catalyst systems, naturally all the other systems usable for the polymerization of acrylates or methacrylates may be employed. For example as the accelerator,consideration may be given to para-toluolamine in amounts of between 0.5 and 2% by weight.The accelerator ispreferably contained in the syrup or paste or in the liquid itself, according to the invention.

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But the hardening can be performed in the absence of accelerators, for example ~y the influence of ultra-violet rays.In the case of hot polymerization the harden-ing is achieved without accelerator by the supply of heat.

The inventive substances are preferably made in such a way that directly before the use of the substance in a two-componen~ system which cons~ists of a powder system comprising the polymer, and optionally fillers and metal soaps, and a liquid system consisting of the monomeric acrylate, which optionally comprises softener,accelerat-or and the inventive jojoba oil, the mixing is performed.

In the practical use of the inventive substance, for exam-ple for lining a prosthesis, the substance is applied on the previously roughened surface of the prosthesis which has expediently been solvated with a solvent, and is inserted in the mouth of the patient,~here within a few minutes the substance fullypolymerizes under pressure and optionally with the exclusion of air. When carrying out repairs to dental prostheses for exampl~ it is ad-vantageous to cover the applied inventive substance with glass- or ~ellophan~ paper, since the hardening should take place expediently with the exclusion of air.

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Using the inventive substances in dantal-medical or dental-technical work has the great advantage that now only the finished polyacrylate solution has to be made to solidify in the minimal tima by adding a catalyst solution, preferably in the form of a two-component system comprising a powder system and a liquid system, without any shrinkage or aging of the material taking place with the passage of time, while the optimal fitting and moulding can be attained by the moulding or lo lining material. As seems desirable, elastic, permanently soft or hard dental substances can be obtained and the polymerization can take place entirely in the mouth of the patient, without burns, erosions or irritation of the mucous membranes occurring, even in the case of cold polymerization.

The inventive substances are primarily suitable for dental purposes, such as the individual production of an adapted function impression tray with the corresponding moulding for the manufacture of a dental prosthesis, as the moulding and lining material for the production of a tooth guard, especially for sportsmen, and generally as impression substances, for linings and repairs of dental prostheses. But they can also be used in other ways, for ~5 example as finger nail replacements or for otoplasty, the repair of hearing aidsl as well as for the lining of leg and arm prostheses and the like, as skin replacements, for the production of soft and bone portions in medicine as well as for cosmetic corrections in medicine.

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, - .'' ' - ~ ' - 13 - ~ ~5~X3 7 A special advantage of the inventive substances consists of the fact that owing to their easy manipulation, they can also be used in self-medication,e.g. for those who use partial or total prostheses,for cosmetic corrections in self-medication,such as for example correction of the laughing wrinkles for users of prostheses.

The following examples are to explain in more detail the inventive substance as well as the process for its production and its use, without limiting the scope of the invention. The named components in the examples may be present in the form of sepa.rate preliminary doses, optionally as a kit.

Example 1 In a mixing vessel, 25% parts by weight of a copolymer con-sisting of 96 parts by weight methyl methacrylate and

4 parts by weight of ethylacrylate are mixed in 75 parts by weight of acrylic acid cyclohexylester, to which 1%
p-toluolamine and 2g 1,4-butane-dioldimethacrylate are added. Instead of the cycloalkylester one can also use 65 parts by weight of a mixture of methycrylate acid-tertiary-butyl ester and methacrylateacid methyl ester in a ratio of 1:1 or of 1:2. To the syrup thus obtained 2% of a normal trade alkalialuminiumsilicate and 2.5%
of magnesium stearate as well as 1% of jojoba ~il are added.

When using,a solution of 5 parts by weight benzoyl peroxide d~s~ol~ed ~n25 parts by weight of dibutylphthal-ate is added to this mixture dropwise. After a short time the substance begins to become viscous, so that it can now be applied to the prepared prosthesis and in-serted in the patient's mouth.In a few minutes it hardens,forming a hard inner lining.

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_xample 2:

50 parts of a copolymer, comprising 96 parts by weight of methyl methacrylate and 4 parts by weight of ethyl acrylate, are dissolved in a mixture of 50 parts methacrylacid-tertiary-butyl ester,methacryl acid-methylester and methacryl acid-n-hexylester, which are mixed in a ratio of 1:1:1.To this quantity 3~ of magnesium stearate and 1~ of a commercial alkali aluminium silicate, 1% p-toluolamine and 1~
jojoba oil are added. As in example 1 to process this substance a benzoylperoxide solut:ion is added drop-wise and in a short time a viscous substance is ob-tained which is easy to spread on the prosthesis and quickly provides an elastic lining which has an ex-cellent fit, is stable and shows almost no shrinkage.

Example 3:

A dental guard for sportsmen was prepared as follows, wherein the starting point was a function impression tray such as is described in DE-OS 27 18 017. This impression tray of a thermoplastic material is adjusted to the individual dental and jaw situation by light pressure after immersion in hot water at 70 C in order to soften it.

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~Z~ 3~7 selow a mold/lining material consisting of 40% by weight polyacrylate, about 55% by weight metacryl acid hexyl ester, 1~ by weight calciumstearate and 1~ jojoba oil, with the usual hardeners and acceler-ators,is poured into the function impression tray,and the latter is again adapted to the dental and jaw conditions in the mouth. The above-named mold/
lining material was produced from atwo-components sys-tem which was mixed directly before use. After about 10 minutes the elastic mold/lining material has poly-merized and forms a soft buffer zone between the relatively hard material of the tray and the teeth.
To the extent that the impression tray used is pro-vided with recesses in the occlusal overlay area,a part of the mold/lining material penetrates beyond that area through said recesses when pressed by the impression tray filled with the mold/lining material, is polymerized there and forms a soft buffer zone between the lower and upper rows of teeth~Since the process can be carried out simply, such a dental guard as that described above can be produced by the sports-man himself.

In the same way the above material may also serve,as a molding material which is poured into a prepared impression tray already adapted to the jaw situation of the patient, to obtain a more exact,non-shrinking impression which is true to the model. It is especially advantageous according to the invention that when using an impression tray of acrylate plastic with the mold material also based on acrylate, the use of an adhesive is not required, as is necessary with the commercial molding materials.Thereby in a simple way an improved function impression tray or situation im-pression for making a denture or partial denture can bemade,while producing better-fitting and better-placed prostheses.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A substance useful as a dental-technical, dental-medical and medical molding and lining material comprising, a substrate selected from the group consisting of monomeric and/or polymeric or copolymeric acrylic or methacrylic ester, a hardening substance for said substrate, and jojoba oil, the jojoba oil being present in an amount of 0.05 to 10% by weight of total material of said substance.

2. A substance according to claim 1 wherein said substrate is present in an amount of at least about 60%
by weight of total material of said substrate.

3. A substance according to claim 1 or claim 2 including an accelerator for the hardening of said ester.

4. A substance according to claim 1 or 2 including a metal soap.

5. A substance according to claim 1 or 2 including a silicate.

6. A substance according to claim 1 or 2 including from 0.1 to 10% by weight of a metal soap.

7. A substance according to claim 1 or 2 including calcium stearate.

8. A substance according to claim 1 or 2 including magnesium stearate.

9. A substance according to claim 1 or 2 including from 1.5 to 5% by weight of alkaline aluminum silicate.

10. A substance according to claim 1 or 2 including a cross-linking agent.

11. A substance according to claim 1 or 2 including an olefinic dimethacrylate as a cross-linking agent.

12. A-substance according to claim 1 or 2 including a (poly)-ethyleneglycol dimethacrylate as a cross-linking agent.

13. A substance according to claim 1 or 2 wherein the amount of said jojoba oil is from 0.1 to 5% by weight.

14. A substance according to claim 1 or 2 wherein said substrate comprises monomer and/or polymer methylmethacrylate.

15. A substance according to claim 1 or 2 wherein said ester has 6 to 10 carbon atoms.

16. A substance according to claim 1 or 2 wherein said ester is a hexyl ester.

17. A substance according to claim 1 or 2 which is in the form of a two-component system, the two component system comprising:
(a) a powder system which comprises a polymeric acrylic or methacrylic ester and a hardening substance therefor, and (b) a liquid system comprising a monomeric acrylic or methacrylic ester, jojoba oil and an accelerator.

18. A substance useful as a dental-technical, dental-medical and medical molding and lining material comprising a two-component system, said two-component system comprising, (a) a powder system comprising a polymeric acrylic or methacrylic ester, a metal soap and a hardening substance for said ester, and (b) a liquid system comprising a monomeric acrylic or methacrylic ester and from 0.05 to 10% by weight of jojoba oil.

19. A process for the preparation of dental-technical, dental-medical and medical molding and lining materials, comprising the mixing of a two-component system, consisting of (a) a powder system which comprises a polymeric acrylic or methacrylic ester, a metal soap and a hardening substance for the acrylic or methacrylic ester, and (b) a liquid system consisting of a monomeric acrylic or methacrylic ester and 0.05 to 10%
by weight of jojoba oil.