CA1109597A - Dental compositions - Google Patents
Dental compositionsInfo
- Publication number
- CA1109597A CA1109597A CA301,369A CA301369A CA1109597A CA 1109597 A CA1109597 A CA 1109597A CA 301369 A CA301369 A CA 301369A CA 1109597 A CA1109597 A CA 1109597A
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- CA
- Canada
- Prior art keywords
- polymerizable
- dental composition
- dental
- ester
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
ABSTRACT OF THE DISCLOSURE
An improved dental composition having increased compressive strength and abrasion resistance and shortened hardening time, including a radical-inducing compound and a polymerizable acrylic or methacrylic acid ester or diester compound with at least 20 percent by weight of the polymer-izable compound being the diacrylic or dimethacrylic acid ester of bishydroxymethyltricyclo [5.2.1.02,6]-decane. Other monofunctional or difunctional acrylic or methacrylic acid esters as well as fillers, pigments and stabilizers can be included.
An improved dental composition having increased compressive strength and abrasion resistance and shortened hardening time, including a radical-inducing compound and a polymerizable acrylic or methacrylic acid ester or diester compound with at least 20 percent by weight of the polymer-izable compound being the diacrylic or dimethacrylic acid ester of bishydroxymethyltricyclo [5.2.1.02,6]-decane. Other monofunctional or difunctional acrylic or methacrylic acid esters as well as fillers, pigments and stabilizers can be included.
Description
S~
This invention relates to dental compositions.
It is well known that dental compositions which contain polymerizable monomers which are to be used ~or the ~illing o~ teeth ~nd for dentures can be hardened by a polymeri-zation reaction induced by radicals~ Esters of acrylic acid and methacrylic acid are monomers which are suitable for these purposes. If bifunctional acrylic acid esters are employed in such polymerization reactions, three-dimensional, cross-linked thermosetting masses of great hardness and abrasion resistance are obtained. U.S. Patent 3,066,112 describes the use of one dimethacrylic acid ester, derived from bisphenol A
and obtainable by its reaction with glycidylmethacrylate, to be used specifically for the preparation of tooth fillings~
Similar products, which however are free of any hydroxyl groups, are described by British Patent 1,267~564 and U.S. Patent 3,~23,740 which are identical with German Patent 1,921,~69.
The polymers obtained by means of these substances have the advantage that they will remain dimensionally stable even in the presence of wàter due to the absence of the hydroxyl groups which is in contrast to the masses described by U.S. Patent 3,066~112 which, being produced by the addition of the bisphenol A to the epoxy group of the glycidylmethacrylate, contain two hydroxyl ~roups per molecule of the dimethacrylic acid compound.
These known bifunctional methacrylic acid esters are utilized in combination with radical-forming polymerization catalysts or initiators, especially in dentistry as masses or compositions for the filling of teeth and represent a definite improvement when compared with the previously used Bi . . - . - . . . . . 1 :, ' ' . ,. ~ ,1, . , . . .
5~7 methylmethacrylates. They will polymerize quickly and thoroughly without any residual monomers and have a lesser con~raction at polymerization which is a main advantage. The hardened materlal possesses a high compressive strength as reported in the papers writ~en by Henry L. Lee et al in J. Dent. Res. 48, pages 526 to 535 (1969) and by H. Durner in "Zahnaerztliche Welt/Reform", 81, page 764 ~1972).
However, these masses obtained by the use of known bifunctional methacrylic esters, in spite of the relatively great strength of the fillings and dentures, still do not meet all dental re~uirements. Tooth fillings a~d dentures are 5ubjected in the course of their use to an enormous chewing pressure and to wear by abrasion. It is for this reason that many dentists, in spite of the availability of these prepara-tions, are still using amalgam for the filling of teeth although this latter material is deficient in esthetic respect and there are some objections to its use in view of its mercury content.
Attempts have been made by the admixture of fillers~ especially powdered silica or fine amorphous silicic acid, to improve still further the strength and abrasion characteristics of the polymerized masses. Such attempts, also including the use of tri- and tetra-functional methacrylic acid esters, were proposed by the published German application~ 24 05 578, 24 32 013 and 24 38 411. However, the resulting products were not satisfactory.
~ he compressive strength values attained at the present time are in the general range of 2,200 to 2,~0 kg/cm~O Such products are acceptable in many instances but there is still a desire for tooth fillings and dentures of even greater strength and resistance to abrasion which are based on easily obtainable raw materials which can then be rapidly polymerized by the use of standard polymerization catalysts and initiators and which will fully harden within a short period of time, even without any increase in temperature.
In one embodiment, the present invention provides a dental composition, especially for tooth fillings and dentures, including at least two components, one component comprising a polymerizable diacrylic acid ester selected from the group consisting of the diacrylic acid or dimethacrylic acid ester of bishydroxymethyltricyclo [5.2.1. o2 ~6] -decane and mixtures thereof, the other component comprising a radical-forming sub-stance. The term "radical-forming substance" will be under-stood to include a compound which will form radicals under irradiation by light.
In another embodiment, the present invention provides a method for forming dental fillings and prosthetic dental appli-ances in which a polymerizable diacrylic or di~ethacrylic acid ester is polymerized to form a hardened product, the improvement ~herein at least 20 percent by weight of said polymerizable ester is the ester of bishydroxymethyltricyclo [5.2.1. o2 ~ 6]_ decane.
In still another embodiment, the present invention provides an improved dental composition having shortened harden-ing time and after hardening, increased compressive stren~th and abrasion resistance comprising a polymerizable acrylic or metha-crylic acid ester or diester and a radical-forming compound, at least 20 percent of the polymerizable ester being the diacrylic acid or dimethacrylic acid ester of bishydroxymethyltricyclo [5,2.1.02'6]-decane.
_ 4 _ -It has been found unexpectedly and surprisingly that diacrylic or dimethacrylic acid esters of blshydroxymethyl-tricyclo [5.2.1.O2'6]-decane are particularly suitable poly-merizable components for dental materials and will lead t~
dimensionally stable and hard polymerization products. The diacrylic or dimethacrylic acid ester compounds can be produc-ed easily by esterifying dihydroxymethyltricyclodecane with aerylic or methaerylic acid or a derivative thereof by means of standard processes.
Dihydroxymethyltricyclo [5.2.1.02'6]-decane is com-mercially available and can be expressed by the following structural formula : I~ ~f H20H
H~H2 - ~ 4 (I) As a result o~ the standard processes used for the preparation of this tricyclodecane derivative, the hydroxy-methyl radicals can be in the 3- and 4-position as well as in the 9- and 8-position of the tricyclodecane molecule. The commercially available product, described for example in the published German patent application 1 618 384, normally will contain these isomeric compounds. The published German applica-tion 1 694 868 describes the use of such compound for the manu-~aeturing of polyadducts based in triglycidylisocyanurate.
B~ - 5 -.
The bifunc~ional bisacrylic acid esters or bismeth-acrylic acid esters of the dihydroxymethyltricyclodecane are compounds expressed by the general formula
This invention relates to dental compositions.
It is well known that dental compositions which contain polymerizable monomers which are to be used ~or the ~illing o~ teeth ~nd for dentures can be hardened by a polymeri-zation reaction induced by radicals~ Esters of acrylic acid and methacrylic acid are monomers which are suitable for these purposes. If bifunctional acrylic acid esters are employed in such polymerization reactions, three-dimensional, cross-linked thermosetting masses of great hardness and abrasion resistance are obtained. U.S. Patent 3,066,112 describes the use of one dimethacrylic acid ester, derived from bisphenol A
and obtainable by its reaction with glycidylmethacrylate, to be used specifically for the preparation of tooth fillings~
Similar products, which however are free of any hydroxyl groups, are described by British Patent 1,267~564 and U.S. Patent 3,~23,740 which are identical with German Patent 1,921,~69.
The polymers obtained by means of these substances have the advantage that they will remain dimensionally stable even in the presence of wàter due to the absence of the hydroxyl groups which is in contrast to the masses described by U.S. Patent 3,066~112 which, being produced by the addition of the bisphenol A to the epoxy group of the glycidylmethacrylate, contain two hydroxyl ~roups per molecule of the dimethacrylic acid compound.
These known bifunctional methacrylic acid esters are utilized in combination with radical-forming polymerization catalysts or initiators, especially in dentistry as masses or compositions for the filling of teeth and represent a definite improvement when compared with the previously used Bi . . - . - . . . . . 1 :, ' ' . ,. ~ ,1, . , . . .
5~7 methylmethacrylates. They will polymerize quickly and thoroughly without any residual monomers and have a lesser con~raction at polymerization which is a main advantage. The hardened materlal possesses a high compressive strength as reported in the papers writ~en by Henry L. Lee et al in J. Dent. Res. 48, pages 526 to 535 (1969) and by H. Durner in "Zahnaerztliche Welt/Reform", 81, page 764 ~1972).
However, these masses obtained by the use of known bifunctional methacrylic esters, in spite of the relatively great strength of the fillings and dentures, still do not meet all dental re~uirements. Tooth fillings a~d dentures are 5ubjected in the course of their use to an enormous chewing pressure and to wear by abrasion. It is for this reason that many dentists, in spite of the availability of these prepara-tions, are still using amalgam for the filling of teeth although this latter material is deficient in esthetic respect and there are some objections to its use in view of its mercury content.
Attempts have been made by the admixture of fillers~ especially powdered silica or fine amorphous silicic acid, to improve still further the strength and abrasion characteristics of the polymerized masses. Such attempts, also including the use of tri- and tetra-functional methacrylic acid esters, were proposed by the published German application~ 24 05 578, 24 32 013 and 24 38 411. However, the resulting products were not satisfactory.
~ he compressive strength values attained at the present time are in the general range of 2,200 to 2,~0 kg/cm~O Such products are acceptable in many instances but there is still a desire for tooth fillings and dentures of even greater strength and resistance to abrasion which are based on easily obtainable raw materials which can then be rapidly polymerized by the use of standard polymerization catalysts and initiators and which will fully harden within a short period of time, even without any increase in temperature.
In one embodiment, the present invention provides a dental composition, especially for tooth fillings and dentures, including at least two components, one component comprising a polymerizable diacrylic acid ester selected from the group consisting of the diacrylic acid or dimethacrylic acid ester of bishydroxymethyltricyclo [5.2.1. o2 ~6] -decane and mixtures thereof, the other component comprising a radical-forming sub-stance. The term "radical-forming substance" will be under-stood to include a compound which will form radicals under irradiation by light.
In another embodiment, the present invention provides a method for forming dental fillings and prosthetic dental appli-ances in which a polymerizable diacrylic or di~ethacrylic acid ester is polymerized to form a hardened product, the improvement ~herein at least 20 percent by weight of said polymerizable ester is the ester of bishydroxymethyltricyclo [5.2.1. o2 ~ 6]_ decane.
In still another embodiment, the present invention provides an improved dental composition having shortened harden-ing time and after hardening, increased compressive stren~th and abrasion resistance comprising a polymerizable acrylic or metha-crylic acid ester or diester and a radical-forming compound, at least 20 percent of the polymerizable ester being the diacrylic acid or dimethacrylic acid ester of bishydroxymethyltricyclo [5,2.1.02'6]-decane.
_ 4 _ -It has been found unexpectedly and surprisingly that diacrylic or dimethacrylic acid esters of blshydroxymethyl-tricyclo [5.2.1.O2'6]-decane are particularly suitable poly-merizable components for dental materials and will lead t~
dimensionally stable and hard polymerization products. The diacrylic or dimethacrylic acid ester compounds can be produc-ed easily by esterifying dihydroxymethyltricyclodecane with aerylic or methaerylic acid or a derivative thereof by means of standard processes.
Dihydroxymethyltricyclo [5.2.1.02'6]-decane is com-mercially available and can be expressed by the following structural formula : I~ ~f H20H
H~H2 - ~ 4 (I) As a result o~ the standard processes used for the preparation of this tricyclodecane derivative, the hydroxy-methyl radicals can be in the 3- and 4-position as well as in the 9- and 8-position of the tricyclodecane molecule. The commercially available product, described for example in the published German patent application 1 618 384, normally will contain these isomeric compounds. The published German applica-tion 1 694 868 describes the use of such compound for the manu-~aeturing of polyadducts based in triglycidylisocyanurate.
B~ - 5 -.
The bifunc~ional bisacrylic acid esters or bismeth-acrylic acid esters of the dihydroxymethyltricyclodecane are compounds expressed by the general formula
(2) ~2~ ~ / \ / (2) (II) where R represents the methylene acrylate radical of the formula -CH -OC0-C - CH (III) and where R' can be either H or CH30 In the general formula (II), the symbol CH~2~ is meant to indicate that two H~atoms are present at this C-atom of the isomeric compound if the radical R is not present there.
These esters can be easily prepared in accordance with conventional methods by esterifying the dihydroxymethyl-tricyclodecane with the free acrylic acids in the presence of suitable catalysts, or by trans-esterification and the use of acrylic acid esters of lower alcohols, for example methacrylic aeid methylester. By the admixture of polymerization inhibitors, such as p-methoxyphenol, during esterification or trans-ester_ ification, undesirable polymerization at higher temp~ratures ean thus be preven-ted in known manner.
,., The bifunctional ac~ylic esters of formula (II) are colorless, very fluid oils which due to their viscosity (which is relatively light in comparison with the bifunctional methacrylic acid esters used heretofore in dentistry), can be processed very readily. The compositions prepar~d in accordance with the present invention can contain known radical-pxoducing substances used for such polymerization purposes and in the same amounts as generally used for such purposes.
Suitable polymerization catalysts are, among other substances, peroxide ox azo-compounds, especially lauroyl peroxide, chlorobenzoyl peroxide and the like. For ields of application requiring rapid polymerization at room temperature, especially in the case of materials used for the ~illing of teeth, the known oxidation-reduction systems are preferably used, which systems usually consist of one peroxide and one reducing agent. The reducing agent can be, for example, amines, sulphinic acids, substituted sulphones, so-called CH-active compounds such as barbituric acids or ~-diketones. Non~dis-coloring redox systems are preferably used. I~ amine-containing xedox-systems are employed, amines should be selected which are relatively stable with respec~ to discoloring, especially N,N-bishydroxyalkyl-3,5-xylidines or N,N-bis-hydroxyalkyl-3,5-di~t-butylanilines.
If compounds are present which will initiate polymeri-zation when subjected to visible or ultra~violet light, it becomes possible to attain a rapid polymexization by irradiation, a particularly advantageous feature for many purposes.
Compositions containing suitable W initiators are very stahle in the dark and the substances proposed by the invention will therefore permit the manufacture of single-unit preparations which are ready for use. For this purpose, a conventional initiator for ultra-violet polymerization, for example, benzoin, benzoin ether, ~-substituted benzoins or benzoin ethers~ benzil, benzilketals, halogeneous aromatic compounds such as halogen-methylated benzophenones and the like is dissolved in the bifunctional esters. The admixture of small quantities of organic phosphites will lead to an even gxeater acceleration of rapidly progressing polymerization by ultra-violet light.
Single-unit preparations containing polymerization initiators which react to visible light can be hardened with particular ease. Initiators of this type are, for example, combinations of quinones and aliphatic amines, or combination of benzilketals, benzophenones or quinones with amines.
Preparations containing such initiator systems are suficiently stable in the dark and allow sufficient time for processing under daylight or other light of usual intensity. ~Iowever, polymerization will be rapid if the substance is subjected to an intensive visible irradiation furnished by a special light source.
~ he bifunctional esters of the present invention are designed for materials to be used in the dental field which includes tooth fillers as well as preparations for building up portions of a tooth, coating and sea1ing masses, .
: . :
priming materials for cavities, materials for jackets, bridges and facings, masses for the manu~acture of artificial teeth, materials for prosthetic devices as well as orthodontic devices.
In practice, these materials can be utilized in all cases where synthetic or polymerizable materials are normally used in the dental field.
The substances can be used either as two-component systems, for example, as preparations consisting of one unit containing the monomer and one filling-material unit which contains the polymerization catalyst, or in the form of two liquid components or two paste components, with the two components o redox-systems distributed among the two units.
It is also possible to prepare the substances proposed by the invention in a pre-apportioned form, that is, in plastic containers where the components are originally kept separately and where a mechanical mixing process will occur when the two components are combined with each other. Another advantageous use is possible in the polymerization of tooth-filling and sealing masses initiated by ultra-violet or visible light, where the masses are furnished, preferably in the form of single units ready for use.
The bifunctional methacrylic acid esters which are used in accordance with the present invention result in an increase in the strength of the materials in comparison with materials used heretofore. It is possible, for example, to raise the compressive strength of tooth fillings, accomplished with standard paste-paste preparations, from approxima~ely 2,500 kg/cm2 to approximately 4,000 l~g/cm2 simply by replacing the known bifunctional methacrylic esters with the esters proposed by the present invention. Furthermore, the hardening will then also be greatly accelerated. If standard redox-systems are being used, the time elapsing from the start of the gelling up to the final hardening will be reduced to one-half or even one-fourth of the conventional time without any change in the processing time (that is, the time up to the start of the polymerization). This feature is particularly important in case of preparations which are applied inside the mouth, especially when tooth fillings are being inserted.
The bifunctional esters used in accordance with the present invention can be mixed with conventional monofunctional acrylic esters and methacrylic esters. They can also be util-ized in conjunction with known bifunctional methacrylic esters.
For example, an admixture of bifunctional esters disclosed by British Patent 1,267,564, U. S. Patent 3,923,740 or German Patent 1,921,869, which are free of hydroxyl groups, can be used to define a specific refractive index, or the co-use oE
esters which were disclosed by U. S~ Patent 3,066,122 and - which do contain hydroxyl groups, can serve to define a low but specifica]ly desired water absorption by the polymeriza-tion products which in many cases is expedient in order to avoid marginal leaking of tooth fillings. The combinations of the substances proposed by the invention with these known monomeric d:iacrylates or alkanedioldiacrylates result sur prisingly in polymerization products possessing a strength which is only slightly lower and in some instances even greater ~3 - 10 -.
j . , . , . , . ,, . . , . ,, ,, . ~ . . . ...
5~
than the strength of the substances of the invention employed without any admixture. Such mixtures should contain at least 20 percent of the particular tricyclodecane monomers proposed by the invention, based on the total polymerizable monomeric content of the composition. I~nown bifunctional monomers which are particularly suitable for this novel combination with the monomeric compounds of the invention are the diacrylate or di-methacrylate of hexanediol, 2,2-bis-[p-(~-hydroYyethoxy)-phenyl]-propane or of 2,2-bis-[p-(~-hydroxypropoxy)-phenyl]-10 propane. On the basis of such combinations, it becomes possibleto create particularly high-grade dental preparations, especial-ly compositions for the filling and sealing of teeth, either on a paste/paste basis or in the form of single-unit systems. In the case of the first-mentioned method, one paste can contain a tricyclodecane monomer substance proposed by the invention, and the other a known monomeric substance, if the redox catalyst system is used, one paste will contain the peroxide and the other paste the activator. The single-unit systems comprise mixtures of the diacrylates proposed by the invention and known monomers such as hexanedioldimethacrylate. After the mixture of o~ the two pastes tor after irradiation of the compositions which contain polymerization activators responsive to light), hardening will occur, resulting in polymerization products with superior strength characteristics.
The use of conventional fillers is possible and eff~ctive. Especially suitable are quartz and quartz glass, as well as other glasses, for example, glasses having alumino-silicate bases, and glasses which will provide the dental mat-erials with some opacity to X-rays, such as barium and lanthanum glasses. These inorganic fillers are silanized in a ~nown manner.
The same applies to fibers, for example, quartz or glass fibers, which can be admixed to improve the mechanical c~aracteristics B
$~7 of the materials. Insoluble inorganic salts or minerals, for example, calcium fluoride, can also be used as fillers. The exclusive or additional use of micro-fine fillers, especially amorphous SiO2 or A1203, with particle sizes ranging from 10 to 10 6 mm, can also lead to advantageous results, especially for the stabilization of viscosity.
The admixture of organic polymers generally used for dental medicine and technology, especially in connection with the manufacture of dentures, is also feasible. Particularly applicable are the polymethacrylic esters, usually available in pearl-form and tinted to match the color of the teeth. Obvious-ly, conventional pigments, soluble dyes and so-called brighten-ers, used to produce a white fluorescence, etc. can also be admi~ed with the materials proposed by the in~ention.
In order to prevent premature polymerlzation, it will be expedient to admix antioxidants, especially of the phenolic type, for example, p-methoxyphenol, hydroquinone or 2,6-di-t-butyl-p-cresol, into the composition of the present invention.
The compositions can also contain UB-absorbing s~abilizers to prevent discoloration caused by light, for example, derivatives of benzotriazoles, benzophenones or benzoic acid phenyl esters.
The latt~r admixtures are especially useful for preparations which are not polymerized by ultra-violet light.
The various additional ingredients such as W-initia-tors, fillers, pigments, antioxidants and the like described a above are utilized in the composition of the present invention in amounts corresponding to those generally utilized for such materials in compositions according to the present state of -the art.
~ .
; . . - . I
Th~ invention is additionally illustrated in connec-tion with the following Examples which are to be considered as illustrative of the present invention. It should be understood, however, that the invention is not limited to the specific details of the Examples. In these Examples, ~he bis-hydroxy-methyltricyclo-[5.2.1.02'6]-decane is referred to as T-diol, and its diacrylic acid and dimethacrylic acid esters as T-diacrylate or T-dimethacrylate, respectively.
E_AMPLE 1 ~Preparation of the bifunctional methacrylester of the T-diol) 98 grams of T-diol, 129 grams of methacrylic acid and 200 ml of cyclo~exane are heated in the presence of 7 grams of p-toluenesulphonic acid and 0.3 grams of picric acid for 24 hours while the water is distilled off. The reaction product is then rinsed repeatedly with a 2N-caustic soda solution and water and decolorized by treating it with A12O3.
10 mgrams of p-methoxyphenol are admixed as a stabilizer to prevent premature polymerization, and the cyclohexane, used as solvent, is removed by evacuation.
The reaction yields 124 grams of dimethacrylate ester in the form of an almost colorless, very fluid oil having the following properties:
Viscosity at 25~C 1.~ P
1.~008 Double bond equivalent 170; 169 .
~ ~$~
(Prepara~ion of the bifunctional acr~vlic ester of the T-diol) 196 grams of T-diol, 216 grams of acrylic acid and 400 ml of hexane are heated in the presence of 14 grams of p-toluenesulphonic acid and 0.7 gram of picric acid for six hours while t}le water is distilled off. After processing as described in Example 1, there is obtained 171 grams of a colorless oil with the following properties:
Viscosity at 25C 1.2 P
nD0 1.5040 Double bond equivalent 155; 158 EXAMPLE_3 (Preparation of an acrylic-methacrylic mixed ester of the T-diol) 59 grams of T-diol, 22 grams of acryllc acid, 52 grams of methacrylic acid, 100 ml of cyclohexane, 4 grams of p-toluenesulphonic acid and 0.16 grams of picric acid are together heated and the reaction mixture is processed as described in Example 1. There is obtained 71 grams o~ a colorless oil with the following properties:
Viscosity at 25C 1.2 P
nDO 1.5020 Double bond equivalent 168, 172 Approximately 40% of the ester groups of the resulting product are acrylic acid radicals.
~B 1~
5~
(Comparative Test, polymerization by heat) For this comparative test, the known product used is a dimethacrylate derived from bisphenol-A, produced in accordance with the example 10 of German Patent 1,921,869.
In order to determine the compressive stren~th of the ultimate polymerization products, the known dimethacrylate as well as the T-dimethacrylate of the invention (formed in a manner as in Example 1) are each mixed with 0.6% of lauroyl peroxide, the two solutions are filled into ten cylindrical forms, each form possessing a diameter of 4 mm and a height of 8 mm, and heated, at a temperature of 130C for 30 minutes.
The following average values for compressive strength are found when the test specimens are measured:
Product according to the present invention1 720 kg/cm2 Product according to example 2 10 of German Patent 1,921,869 1 150 kg/cm (Comparative Test, oxidation-reduction polymerization) Two solutions are prepared containing the same amount of T-dimethacrylate. Dissolved in one solution is 0.8% of N,N-bis-hydroxyethyl-3,5-di t-butylaniline and dissolved in the other solution is 1.0% of p-chlorobenzoyl peroxide~
After mixing of equal parts of the resulting solutions, forms are filled in the same manner as described in Example 4. ~
hard, transparent polymerization product is obtained after a few minutes.
- ~5 -In the same manner, there are prepared similar solu-tions from the dimethacrylate of 2,2-bis-[p-(~-hydroxypropoxy)-phenyl]-propane, the synthesis o~ which is described in German Patent 1,921,869. These solutions are processed to form speci-men or like dimensions.
The specimens are stored for 24 hours at 36C.The following data are then found for the average compressive strength:
Product acco.rding to the 2 present invention 1 640 kg/cm Product of the present 2 state of the art 1 160 kg/cm (Paste/paste preparation for tooth fillings) Two pastes(denominated "A" and "B") are prepared by kneading together the following: .
Paste A) 2.4 grams of N,N-bishydroxyethyl-3~5-di-t-butylaniline, dissolved in 300 grams of T-methacrylate 1.8 grams of amorphous, silanized SiO2 with an average primary particle size of 12 nm and 990 grams of silanized quartz powder ( ~60~um) tinted to match the tooth color Paste B~ 300 grams of T-dimethacrylate 1.8 grams of the SiO2 as used in Paste A
990 grams of silanized quartz powder (C 60/um tinted to match the tooth color and containing 6.0 grams of p-chlorobenzoyl peroxide.
..~ 7 ~ hen equal parts of the two pastes A and B are mixed together, a relatively smooth, easily applied mass is obtained which can be inserted in the usual manner into pre-finished cavities and which will harden there within approximately three minutes. The filling can then be finished and polished.
(Comparative Test) The process described in E~ample 6 is repeated and ~ive cylindrical forms are prepared for each paste with the dimensions as listed in Example 4.
For comparison purposes, two pastes are prepared with the same composition as in Example 6 except that the di-methacrylate disclosed in German Patent 1,921,869 and listed in Exampl~ 5 above, is substituted for the T-dimethacrylate.
Cylindrical forms are prepared in the identical-manner for each c~omposition. After 24-hour storage at 36C, the following average values for compressive strength are found:
Pastes based on T-dimethacrylate 4,050 kg/cm2 Pastes according to the present 2 state of the art 2,630 kg/cm (Paste/paste preparation for tooth fillings) Two pastes (denominated "A" and "B`' are prepared by kneading together the following:
......
- ~ :
- Paste A) 1.8 grams of ~ bis-hydroxyethyl-3,5-di-t-butylaniline, dissolved in 300 grams of T-diacrylate 1.8 grams of amorphous, silanized SiO2 at an average primary particle size of 12 nm and 990 grams of silanized quartz powder (<60 ~lm~, tinted to match the tooth color, and Paste B) 300 grams of T-diacrylate 1.8 grams of SiO2 as used in Paste A
990 grams of silanized quartz powder (~O~um), tinted to match the tooth color and containing 6.0 grams of p-chlorobenzoyl peroxide.
When equal parts of the two pastes are mixed together, the processing span (counting from the beginning of the inter-mixing) is approximately 1 minute and 50 seconds at 24~C. The hardening process is then checked by means of a rheometer and it is thus determined that the mass has substantially solidi-fied and hardened after an additional 25 seconds~
The comparative paste/paste mixtu.re prepared in Example 7 in accordance with the present state of art requires, at the identical processi~g span and temperature, approximately 90 seconds for the subsequent hardening which shows that the compositions prepared in accordance with the present invention harden more rapidly, allowing an earlier finishing operation, thus advantageously reducin~ the waiting time for the dentlst and patient for the completion of a filling.
E~ 18 -.
(Combination of T-diacrylate of the present invention ~ith a dimethacrylate prepared in accordance with the present state of the art) Two pastes (denominated "A" and "B") are prepared~
Paste A corresponds to Paste ~ of Example 8. Paste B (the peroxide-containing paste) corresponds to Paste B of Example 8 except that the dimethacrylate of 2,2-bis-[p-(~-hydro~ypropoxy-) phenyl]-propane disclosed ~y German Patent 1,921,S69 is utilized in place of the T-diacrylate.
The pastes are mixed in a ratio (by weight) of 1 : 1 and the compressive strength is determined by means of test specimen as described in Example 4. The average value so measured is 3,640 kg/cm2 which is definitely higher than for standard preparations for the filling of teeth even though only one of the components was prepared on the basis of a substance proposed by the present invention.
~Preparation for tooth fillings in a pre-apportioned form) Mixing containers àS proposed by the published German application 23 24 296 are used. 96 mgrams of T-diacrylate, containing 0.3~ of N,N-bis-hydroxyethyl-3,5-di-t-butylaniline are fused as individual units into foil cushions which consist of aluminum lined wi'h polypropylene. The cushions are fastened under a clasp which embraces the main pocket. The main pocket is filled in each case with 330 mgrams of silanized quartz powder (~60 ~m), tinted to match the tooth color and containing 0.2% of p-chlorobenzoyl peroxide.
: . ' ' ; .: '' . , Pressure is then exerted upon the clasp by a suitable device, causing the foil cushion to burst and its contents to enter the main pocket. The container is then placed into a mechanical shaker, mixed and the resulting mi~ture is inserted directly into a properly prepared tooth cavity. The processing span is approximately 2 minutes at 23C, and the hardening ls substantially completed after another 1 minute.
(Comparative abrasion tests) Paste/paste preparations based on T-dimethacrylate as defined in Example ~ and based on the diester disclosed by German Patent 1,921,869 as defined in Example 7, in each case mixed in a 1 : 1 ratio, are prepared.
In order to test the abradability of these compositions, round test specimen of 20 mm diameter and 1.5 mm thickness are produced in properly formed metallic molds. Their weight is then determined. The specimen are then contacted for 24 hours by a suspension of calcium carbonate in water (weight ratio of 1 : 1.5) and by motor-driven standardi~ed circular brushes of 10 mm diameter rotating at 60 rpm. The bearing weight of the brushes is 500 grams. After drying, the loss of weight of the specimen is determined with the following results:
Abrasion Loss Preparation based on T-dimethacrylate 0.3 mgram Preparation according to the state 2O7 mgram of the art -- ~0 --~ ~r~5~7 ~ he already low abrasion of the preparation according to the state of art is reduced still further by use of a sub-stance propos~d by the invention, approximately by a power of ten, thus again proving the superiority of the novel preparation of the present invention for the filling of teeth.
. . .
(Tooth-filling material which is polymerizable by ultra-violet light) A composition for tooth filling which can be hardened by ultra-violet light and which is ready for use is prepared by first mixing 100 grams of T-dimethacrylate with 0.5 gram of ~-(2-cyanethyl)-benzoinmethylether and kneading the resulting mixture with 5 grams of the SiO2 powder defined in Example 8 and 345 grams of silanized quartz powder (particle size ~!60 ~n), tinted to match the color of the tooth.
When irradiated by a commercially available UV
polymerization unit with a 70 mW output, a mass with a thickness of 2 mm hardens after six seconds.
. .
(Tooth-filling material which is polymerizable by visible light) By kneading together of 20 grams of T-acrylate, 88 grams of silanized quartz powder (~60 ~ ), tinted to match the tooth colox, 1 gram of SiO2 as defined in Example 8, 0.8 gram of methacrylic acid-(N,N-dimethylamino)-ethylester and 4 mgrams of phenanthrenequinone, there is obtained a preparat~on for the filling of teeth which is ready for use an~ which will remain in ~.
_. :
5~ ~
easily workable condition in diffused daylight or under a standard 65-watt bulb for more than five minutes. Hardening is accomplished by irradia~ion with a halogen-projector lamp (12 V, 75 watt) and cold-light mirror. Light with wavelengths ~400 nm is screened off by a filter. After an irradiation time of 20 seconds, the mass with a thickness of 2.5 mm is hardened.
(Sealing composition for dental-enamel fissures) Two solutions are prepared based on T-dimethacrylate, with one solution containing 0.45% of N,N-bishydroxyethyl-p-toluidine and the other 0.4~ of chlorobenzoyl peroxide. Equal portions of these solutions are then mixed together.
The sealing composition so produced is applied to the enamel of the tooth after it has been slightly etched in the usual manner with a 30~ solution of phosphoric acid.
Hardening begins after approximately one minute and is substan-tially complete after approximately two minutes, resulting in a seal that is smooth and resistant to abrasion.
(Coating preparations for too h fillings which can be hardened by ultra-violet light including the combination of known diacrylates with substances proposed by the invention) The various diacrylates listed in the Table below are admixed in the parts by weight indicated therein. 0.3%
hy wei~ht of benzildimethylketal and 0.5% by weight of didecyl-phenylphosphite are dissolved in each mixture and 35~ by weight o~ silanized, pyro-SiO2 is added and uniformly distributed.
The coating compositions so obtained can be spread easily.
The compressive strength of coatings based on these compositions is measured by the use of specimen having the di-mentions 2 x 2 x 4 mm. Hardening is accomplished by irradia-tion with a commercially available W-polymerization unit with an output of 70 mW. The values obtained are shown in the Table below.
Compressive 10 Composition strength2 (in parts by weight) (kg/cm ) . . . ~
T-diacrylate T-dimeth- hexane- hexane-acrylate diol- diol-dimeth- diacrylate acrylate _ _ __ 100 o o o 3,940 0 100 0 0 3,900 -0 50 0 5,750 0 50 50 0 6,030 o 66.7 33.3 o 5,300 0 0 50 5,~00 _ ._ _ . _ . . .
Surprisingly, combinations of the diester compounds proposed by the present invention with the hexanedioldi(meth)-acrylate in weight ratios ranging from 1 : 1 to 2 1 show substantially greater compressive strength values than when -only the substances proposed -by the invention are used. The use of a coating composition based on the pure hexanedioldi-(meth)acrylate wlthout the admixture of T-diacrylate and/or - 23 ~
- .
~$~
T-dimethacrylate is not Ieasible in practice due to the enor-mous brittleness of the hardened mass~ The combination with the the T-diester compound in the manner proposed by the present invention reduces this brittleness and, at the same time, im-proves the compressive strength of the hardened composition.
(Manufacture of a jacket crown) A paste is made of T-acrylate-methacrylate (mixed esters prepared in accordance with Example 3) and solid poly-methylmethacrylate in pearl form, commercially available invarious tooth color schemes in a ratio of 2 : 3. The several color shades o~ the pearl polymerization product were previous-ly mixed in each case with 0.4% of lauroyl peroxide.
Onto an isolated tooth base, serving as a model/
there are deposited layers of the necessary color shades to match the color of the natural teeth. Each layer is briefly heated to approximately 140C by a flow of hot air. After the completion of the crown, polymerization is carried out for 10 minutes at 150aC. The crown so obtained is very highly resis-tant to abrasion and appears very close to the natural teeth.
EX~MPLE-17 (~acing of a bridge consisting of noble metals) T-methacrylate and polymethylmethacrylate-pearl poly-merization product, tinted to match the color of the teeth and previously impregnated with 0.4% of lauroyl peroxide are used.
as in Example 16, by making the two components into a paste, at a ratio of 2 : 3.
Onto the frame of the bridge (which is provided in the usual manner with retaining means) the individual color shades are applied in layers at the front side, with each layer hardened as described in Example 16.
The facings are distinguished by their excellent stability and especially by a high resistance to abrasion throughout their use inside the mouth. In addition, their appearance is faultless.
The principles, preferred embodiments and modes of operation of the present invention have been described in the foregoing specification. The invention which is intended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.
. . .
These esters can be easily prepared in accordance with conventional methods by esterifying the dihydroxymethyl-tricyclodecane with the free acrylic acids in the presence of suitable catalysts, or by trans-esterification and the use of acrylic acid esters of lower alcohols, for example methacrylic aeid methylester. By the admixture of polymerization inhibitors, such as p-methoxyphenol, during esterification or trans-ester_ ification, undesirable polymerization at higher temp~ratures ean thus be preven-ted in known manner.
,., The bifunctional ac~ylic esters of formula (II) are colorless, very fluid oils which due to their viscosity (which is relatively light in comparison with the bifunctional methacrylic acid esters used heretofore in dentistry), can be processed very readily. The compositions prepar~d in accordance with the present invention can contain known radical-pxoducing substances used for such polymerization purposes and in the same amounts as generally used for such purposes.
Suitable polymerization catalysts are, among other substances, peroxide ox azo-compounds, especially lauroyl peroxide, chlorobenzoyl peroxide and the like. For ields of application requiring rapid polymerization at room temperature, especially in the case of materials used for the ~illing of teeth, the known oxidation-reduction systems are preferably used, which systems usually consist of one peroxide and one reducing agent. The reducing agent can be, for example, amines, sulphinic acids, substituted sulphones, so-called CH-active compounds such as barbituric acids or ~-diketones. Non~dis-coloring redox systems are preferably used. I~ amine-containing xedox-systems are employed, amines should be selected which are relatively stable with respec~ to discoloring, especially N,N-bishydroxyalkyl-3,5-xylidines or N,N-bis-hydroxyalkyl-3,5-di~t-butylanilines.
If compounds are present which will initiate polymeri-zation when subjected to visible or ultra~violet light, it becomes possible to attain a rapid polymexization by irradiation, a particularly advantageous feature for many purposes.
Compositions containing suitable W initiators are very stahle in the dark and the substances proposed by the invention will therefore permit the manufacture of single-unit preparations which are ready for use. For this purpose, a conventional initiator for ultra-violet polymerization, for example, benzoin, benzoin ether, ~-substituted benzoins or benzoin ethers~ benzil, benzilketals, halogeneous aromatic compounds such as halogen-methylated benzophenones and the like is dissolved in the bifunctional esters. The admixture of small quantities of organic phosphites will lead to an even gxeater acceleration of rapidly progressing polymerization by ultra-violet light.
Single-unit preparations containing polymerization initiators which react to visible light can be hardened with particular ease. Initiators of this type are, for example, combinations of quinones and aliphatic amines, or combination of benzilketals, benzophenones or quinones with amines.
Preparations containing such initiator systems are suficiently stable in the dark and allow sufficient time for processing under daylight or other light of usual intensity. ~Iowever, polymerization will be rapid if the substance is subjected to an intensive visible irradiation furnished by a special light source.
~ he bifunctional esters of the present invention are designed for materials to be used in the dental field which includes tooth fillers as well as preparations for building up portions of a tooth, coating and sea1ing masses, .
: . :
priming materials for cavities, materials for jackets, bridges and facings, masses for the manu~acture of artificial teeth, materials for prosthetic devices as well as orthodontic devices.
In practice, these materials can be utilized in all cases where synthetic or polymerizable materials are normally used in the dental field.
The substances can be used either as two-component systems, for example, as preparations consisting of one unit containing the monomer and one filling-material unit which contains the polymerization catalyst, or in the form of two liquid components or two paste components, with the two components o redox-systems distributed among the two units.
It is also possible to prepare the substances proposed by the invention in a pre-apportioned form, that is, in plastic containers where the components are originally kept separately and where a mechanical mixing process will occur when the two components are combined with each other. Another advantageous use is possible in the polymerization of tooth-filling and sealing masses initiated by ultra-violet or visible light, where the masses are furnished, preferably in the form of single units ready for use.
The bifunctional methacrylic acid esters which are used in accordance with the present invention result in an increase in the strength of the materials in comparison with materials used heretofore. It is possible, for example, to raise the compressive strength of tooth fillings, accomplished with standard paste-paste preparations, from approxima~ely 2,500 kg/cm2 to approximately 4,000 l~g/cm2 simply by replacing the known bifunctional methacrylic esters with the esters proposed by the present invention. Furthermore, the hardening will then also be greatly accelerated. If standard redox-systems are being used, the time elapsing from the start of the gelling up to the final hardening will be reduced to one-half or even one-fourth of the conventional time without any change in the processing time (that is, the time up to the start of the polymerization). This feature is particularly important in case of preparations which are applied inside the mouth, especially when tooth fillings are being inserted.
The bifunctional esters used in accordance with the present invention can be mixed with conventional monofunctional acrylic esters and methacrylic esters. They can also be util-ized in conjunction with known bifunctional methacrylic esters.
For example, an admixture of bifunctional esters disclosed by British Patent 1,267,564, U. S. Patent 3,923,740 or German Patent 1,921,869, which are free of hydroxyl groups, can be used to define a specific refractive index, or the co-use oE
esters which were disclosed by U. S~ Patent 3,066,122 and - which do contain hydroxyl groups, can serve to define a low but specifica]ly desired water absorption by the polymeriza-tion products which in many cases is expedient in order to avoid marginal leaking of tooth fillings. The combinations of the substances proposed by the invention with these known monomeric d:iacrylates or alkanedioldiacrylates result sur prisingly in polymerization products possessing a strength which is only slightly lower and in some instances even greater ~3 - 10 -.
j . , . , . , . ,, . . , . ,, ,, . ~ . . . ...
5~
than the strength of the substances of the invention employed without any admixture. Such mixtures should contain at least 20 percent of the particular tricyclodecane monomers proposed by the invention, based on the total polymerizable monomeric content of the composition. I~nown bifunctional monomers which are particularly suitable for this novel combination with the monomeric compounds of the invention are the diacrylate or di-methacrylate of hexanediol, 2,2-bis-[p-(~-hydroYyethoxy)-phenyl]-propane or of 2,2-bis-[p-(~-hydroxypropoxy)-phenyl]-10 propane. On the basis of such combinations, it becomes possibleto create particularly high-grade dental preparations, especial-ly compositions for the filling and sealing of teeth, either on a paste/paste basis or in the form of single-unit systems. In the case of the first-mentioned method, one paste can contain a tricyclodecane monomer substance proposed by the invention, and the other a known monomeric substance, if the redox catalyst system is used, one paste will contain the peroxide and the other paste the activator. The single-unit systems comprise mixtures of the diacrylates proposed by the invention and known monomers such as hexanedioldimethacrylate. After the mixture of o~ the two pastes tor after irradiation of the compositions which contain polymerization activators responsive to light), hardening will occur, resulting in polymerization products with superior strength characteristics.
The use of conventional fillers is possible and eff~ctive. Especially suitable are quartz and quartz glass, as well as other glasses, for example, glasses having alumino-silicate bases, and glasses which will provide the dental mat-erials with some opacity to X-rays, such as barium and lanthanum glasses. These inorganic fillers are silanized in a ~nown manner.
The same applies to fibers, for example, quartz or glass fibers, which can be admixed to improve the mechanical c~aracteristics B
$~7 of the materials. Insoluble inorganic salts or minerals, for example, calcium fluoride, can also be used as fillers. The exclusive or additional use of micro-fine fillers, especially amorphous SiO2 or A1203, with particle sizes ranging from 10 to 10 6 mm, can also lead to advantageous results, especially for the stabilization of viscosity.
The admixture of organic polymers generally used for dental medicine and technology, especially in connection with the manufacture of dentures, is also feasible. Particularly applicable are the polymethacrylic esters, usually available in pearl-form and tinted to match the color of the teeth. Obvious-ly, conventional pigments, soluble dyes and so-called brighten-ers, used to produce a white fluorescence, etc. can also be admi~ed with the materials proposed by the in~ention.
In order to prevent premature polymerlzation, it will be expedient to admix antioxidants, especially of the phenolic type, for example, p-methoxyphenol, hydroquinone or 2,6-di-t-butyl-p-cresol, into the composition of the present invention.
The compositions can also contain UB-absorbing s~abilizers to prevent discoloration caused by light, for example, derivatives of benzotriazoles, benzophenones or benzoic acid phenyl esters.
The latt~r admixtures are especially useful for preparations which are not polymerized by ultra-violet light.
The various additional ingredients such as W-initia-tors, fillers, pigments, antioxidants and the like described a above are utilized in the composition of the present invention in amounts corresponding to those generally utilized for such materials in compositions according to the present state of -the art.
~ .
; . . - . I
Th~ invention is additionally illustrated in connec-tion with the following Examples which are to be considered as illustrative of the present invention. It should be understood, however, that the invention is not limited to the specific details of the Examples. In these Examples, ~he bis-hydroxy-methyltricyclo-[5.2.1.02'6]-decane is referred to as T-diol, and its diacrylic acid and dimethacrylic acid esters as T-diacrylate or T-dimethacrylate, respectively.
E_AMPLE 1 ~Preparation of the bifunctional methacrylester of the T-diol) 98 grams of T-diol, 129 grams of methacrylic acid and 200 ml of cyclo~exane are heated in the presence of 7 grams of p-toluenesulphonic acid and 0.3 grams of picric acid for 24 hours while the water is distilled off. The reaction product is then rinsed repeatedly with a 2N-caustic soda solution and water and decolorized by treating it with A12O3.
10 mgrams of p-methoxyphenol are admixed as a stabilizer to prevent premature polymerization, and the cyclohexane, used as solvent, is removed by evacuation.
The reaction yields 124 grams of dimethacrylate ester in the form of an almost colorless, very fluid oil having the following properties:
Viscosity at 25~C 1.~ P
1.~008 Double bond equivalent 170; 169 .
~ ~$~
(Prepara~ion of the bifunctional acr~vlic ester of the T-diol) 196 grams of T-diol, 216 grams of acrylic acid and 400 ml of hexane are heated in the presence of 14 grams of p-toluenesulphonic acid and 0.7 gram of picric acid for six hours while t}le water is distilled off. After processing as described in Example 1, there is obtained 171 grams of a colorless oil with the following properties:
Viscosity at 25C 1.2 P
nD0 1.5040 Double bond equivalent 155; 158 EXAMPLE_3 (Preparation of an acrylic-methacrylic mixed ester of the T-diol) 59 grams of T-diol, 22 grams of acryllc acid, 52 grams of methacrylic acid, 100 ml of cyclohexane, 4 grams of p-toluenesulphonic acid and 0.16 grams of picric acid are together heated and the reaction mixture is processed as described in Example 1. There is obtained 71 grams o~ a colorless oil with the following properties:
Viscosity at 25C 1.2 P
nDO 1.5020 Double bond equivalent 168, 172 Approximately 40% of the ester groups of the resulting product are acrylic acid radicals.
~B 1~
5~
(Comparative Test, polymerization by heat) For this comparative test, the known product used is a dimethacrylate derived from bisphenol-A, produced in accordance with the example 10 of German Patent 1,921,869.
In order to determine the compressive stren~th of the ultimate polymerization products, the known dimethacrylate as well as the T-dimethacrylate of the invention (formed in a manner as in Example 1) are each mixed with 0.6% of lauroyl peroxide, the two solutions are filled into ten cylindrical forms, each form possessing a diameter of 4 mm and a height of 8 mm, and heated, at a temperature of 130C for 30 minutes.
The following average values for compressive strength are found when the test specimens are measured:
Product according to the present invention1 720 kg/cm2 Product according to example 2 10 of German Patent 1,921,869 1 150 kg/cm (Comparative Test, oxidation-reduction polymerization) Two solutions are prepared containing the same amount of T-dimethacrylate. Dissolved in one solution is 0.8% of N,N-bis-hydroxyethyl-3,5-di t-butylaniline and dissolved in the other solution is 1.0% of p-chlorobenzoyl peroxide~
After mixing of equal parts of the resulting solutions, forms are filled in the same manner as described in Example 4. ~
hard, transparent polymerization product is obtained after a few minutes.
- ~5 -In the same manner, there are prepared similar solu-tions from the dimethacrylate of 2,2-bis-[p-(~-hydroxypropoxy)-phenyl]-propane, the synthesis o~ which is described in German Patent 1,921,869. These solutions are processed to form speci-men or like dimensions.
The specimens are stored for 24 hours at 36C.The following data are then found for the average compressive strength:
Product acco.rding to the 2 present invention 1 640 kg/cm Product of the present 2 state of the art 1 160 kg/cm (Paste/paste preparation for tooth fillings) Two pastes(denominated "A" and "B") are prepared by kneading together the following: .
Paste A) 2.4 grams of N,N-bishydroxyethyl-3~5-di-t-butylaniline, dissolved in 300 grams of T-methacrylate 1.8 grams of amorphous, silanized SiO2 with an average primary particle size of 12 nm and 990 grams of silanized quartz powder ( ~60~um) tinted to match the tooth color Paste B~ 300 grams of T-dimethacrylate 1.8 grams of the SiO2 as used in Paste A
990 grams of silanized quartz powder (C 60/um tinted to match the tooth color and containing 6.0 grams of p-chlorobenzoyl peroxide.
..~ 7 ~ hen equal parts of the two pastes A and B are mixed together, a relatively smooth, easily applied mass is obtained which can be inserted in the usual manner into pre-finished cavities and which will harden there within approximately three minutes. The filling can then be finished and polished.
(Comparative Test) The process described in E~ample 6 is repeated and ~ive cylindrical forms are prepared for each paste with the dimensions as listed in Example 4.
For comparison purposes, two pastes are prepared with the same composition as in Example 6 except that the di-methacrylate disclosed in German Patent 1,921,869 and listed in Exampl~ 5 above, is substituted for the T-dimethacrylate.
Cylindrical forms are prepared in the identical-manner for each c~omposition. After 24-hour storage at 36C, the following average values for compressive strength are found:
Pastes based on T-dimethacrylate 4,050 kg/cm2 Pastes according to the present 2 state of the art 2,630 kg/cm (Paste/paste preparation for tooth fillings) Two pastes (denominated "A" and "B`' are prepared by kneading together the following:
......
- ~ :
- Paste A) 1.8 grams of ~ bis-hydroxyethyl-3,5-di-t-butylaniline, dissolved in 300 grams of T-diacrylate 1.8 grams of amorphous, silanized SiO2 at an average primary particle size of 12 nm and 990 grams of silanized quartz powder (<60 ~lm~, tinted to match the tooth color, and Paste B) 300 grams of T-diacrylate 1.8 grams of SiO2 as used in Paste A
990 grams of silanized quartz powder (~O~um), tinted to match the tooth color and containing 6.0 grams of p-chlorobenzoyl peroxide.
When equal parts of the two pastes are mixed together, the processing span (counting from the beginning of the inter-mixing) is approximately 1 minute and 50 seconds at 24~C. The hardening process is then checked by means of a rheometer and it is thus determined that the mass has substantially solidi-fied and hardened after an additional 25 seconds~
The comparative paste/paste mixtu.re prepared in Example 7 in accordance with the present state of art requires, at the identical processi~g span and temperature, approximately 90 seconds for the subsequent hardening which shows that the compositions prepared in accordance with the present invention harden more rapidly, allowing an earlier finishing operation, thus advantageously reducin~ the waiting time for the dentlst and patient for the completion of a filling.
E~ 18 -.
(Combination of T-diacrylate of the present invention ~ith a dimethacrylate prepared in accordance with the present state of the art) Two pastes (denominated "A" and "B") are prepared~
Paste A corresponds to Paste ~ of Example 8. Paste B (the peroxide-containing paste) corresponds to Paste B of Example 8 except that the dimethacrylate of 2,2-bis-[p-(~-hydro~ypropoxy-) phenyl]-propane disclosed ~y German Patent 1,921,S69 is utilized in place of the T-diacrylate.
The pastes are mixed in a ratio (by weight) of 1 : 1 and the compressive strength is determined by means of test specimen as described in Example 4. The average value so measured is 3,640 kg/cm2 which is definitely higher than for standard preparations for the filling of teeth even though only one of the components was prepared on the basis of a substance proposed by the present invention.
~Preparation for tooth fillings in a pre-apportioned form) Mixing containers àS proposed by the published German application 23 24 296 are used. 96 mgrams of T-diacrylate, containing 0.3~ of N,N-bis-hydroxyethyl-3,5-di-t-butylaniline are fused as individual units into foil cushions which consist of aluminum lined wi'h polypropylene. The cushions are fastened under a clasp which embraces the main pocket. The main pocket is filled in each case with 330 mgrams of silanized quartz powder (~60 ~m), tinted to match the tooth color and containing 0.2% of p-chlorobenzoyl peroxide.
: . ' ' ; .: '' . , Pressure is then exerted upon the clasp by a suitable device, causing the foil cushion to burst and its contents to enter the main pocket. The container is then placed into a mechanical shaker, mixed and the resulting mi~ture is inserted directly into a properly prepared tooth cavity. The processing span is approximately 2 minutes at 23C, and the hardening ls substantially completed after another 1 minute.
(Comparative abrasion tests) Paste/paste preparations based on T-dimethacrylate as defined in Example ~ and based on the diester disclosed by German Patent 1,921,869 as defined in Example 7, in each case mixed in a 1 : 1 ratio, are prepared.
In order to test the abradability of these compositions, round test specimen of 20 mm diameter and 1.5 mm thickness are produced in properly formed metallic molds. Their weight is then determined. The specimen are then contacted for 24 hours by a suspension of calcium carbonate in water (weight ratio of 1 : 1.5) and by motor-driven standardi~ed circular brushes of 10 mm diameter rotating at 60 rpm. The bearing weight of the brushes is 500 grams. After drying, the loss of weight of the specimen is determined with the following results:
Abrasion Loss Preparation based on T-dimethacrylate 0.3 mgram Preparation according to the state 2O7 mgram of the art -- ~0 --~ ~r~5~7 ~ he already low abrasion of the preparation according to the state of art is reduced still further by use of a sub-stance propos~d by the invention, approximately by a power of ten, thus again proving the superiority of the novel preparation of the present invention for the filling of teeth.
. . .
(Tooth-filling material which is polymerizable by ultra-violet light) A composition for tooth filling which can be hardened by ultra-violet light and which is ready for use is prepared by first mixing 100 grams of T-dimethacrylate with 0.5 gram of ~-(2-cyanethyl)-benzoinmethylether and kneading the resulting mixture with 5 grams of the SiO2 powder defined in Example 8 and 345 grams of silanized quartz powder (particle size ~!60 ~n), tinted to match the color of the tooth.
When irradiated by a commercially available UV
polymerization unit with a 70 mW output, a mass with a thickness of 2 mm hardens after six seconds.
. .
(Tooth-filling material which is polymerizable by visible light) By kneading together of 20 grams of T-acrylate, 88 grams of silanized quartz powder (~60 ~ ), tinted to match the tooth colox, 1 gram of SiO2 as defined in Example 8, 0.8 gram of methacrylic acid-(N,N-dimethylamino)-ethylester and 4 mgrams of phenanthrenequinone, there is obtained a preparat~on for the filling of teeth which is ready for use an~ which will remain in ~.
_. :
5~ ~
easily workable condition in diffused daylight or under a standard 65-watt bulb for more than five minutes. Hardening is accomplished by irradia~ion with a halogen-projector lamp (12 V, 75 watt) and cold-light mirror. Light with wavelengths ~400 nm is screened off by a filter. After an irradiation time of 20 seconds, the mass with a thickness of 2.5 mm is hardened.
(Sealing composition for dental-enamel fissures) Two solutions are prepared based on T-dimethacrylate, with one solution containing 0.45% of N,N-bishydroxyethyl-p-toluidine and the other 0.4~ of chlorobenzoyl peroxide. Equal portions of these solutions are then mixed together.
The sealing composition so produced is applied to the enamel of the tooth after it has been slightly etched in the usual manner with a 30~ solution of phosphoric acid.
Hardening begins after approximately one minute and is substan-tially complete after approximately two minutes, resulting in a seal that is smooth and resistant to abrasion.
(Coating preparations for too h fillings which can be hardened by ultra-violet light including the combination of known diacrylates with substances proposed by the invention) The various diacrylates listed in the Table below are admixed in the parts by weight indicated therein. 0.3%
hy wei~ht of benzildimethylketal and 0.5% by weight of didecyl-phenylphosphite are dissolved in each mixture and 35~ by weight o~ silanized, pyro-SiO2 is added and uniformly distributed.
The coating compositions so obtained can be spread easily.
The compressive strength of coatings based on these compositions is measured by the use of specimen having the di-mentions 2 x 2 x 4 mm. Hardening is accomplished by irradia-tion with a commercially available W-polymerization unit with an output of 70 mW. The values obtained are shown in the Table below.
Compressive 10 Composition strength2 (in parts by weight) (kg/cm ) . . . ~
T-diacrylate T-dimeth- hexane- hexane-acrylate diol- diol-dimeth- diacrylate acrylate _ _ __ 100 o o o 3,940 0 100 0 0 3,900 -0 50 0 5,750 0 50 50 0 6,030 o 66.7 33.3 o 5,300 0 0 50 5,~00 _ ._ _ . _ . . .
Surprisingly, combinations of the diester compounds proposed by the present invention with the hexanedioldi(meth)-acrylate in weight ratios ranging from 1 : 1 to 2 1 show substantially greater compressive strength values than when -only the substances proposed -by the invention are used. The use of a coating composition based on the pure hexanedioldi-(meth)acrylate wlthout the admixture of T-diacrylate and/or - 23 ~
- .
~$~
T-dimethacrylate is not Ieasible in practice due to the enor-mous brittleness of the hardened mass~ The combination with the the T-diester compound in the manner proposed by the present invention reduces this brittleness and, at the same time, im-proves the compressive strength of the hardened composition.
(Manufacture of a jacket crown) A paste is made of T-acrylate-methacrylate (mixed esters prepared in accordance with Example 3) and solid poly-methylmethacrylate in pearl form, commercially available invarious tooth color schemes in a ratio of 2 : 3. The several color shades o~ the pearl polymerization product were previous-ly mixed in each case with 0.4% of lauroyl peroxide.
Onto an isolated tooth base, serving as a model/
there are deposited layers of the necessary color shades to match the color of the natural teeth. Each layer is briefly heated to approximately 140C by a flow of hot air. After the completion of the crown, polymerization is carried out for 10 minutes at 150aC. The crown so obtained is very highly resis-tant to abrasion and appears very close to the natural teeth.
EX~MPLE-17 (~acing of a bridge consisting of noble metals) T-methacrylate and polymethylmethacrylate-pearl poly-merization product, tinted to match the color of the teeth and previously impregnated with 0.4% of lauroyl peroxide are used.
as in Example 16, by making the two components into a paste, at a ratio of 2 : 3.
Onto the frame of the bridge (which is provided in the usual manner with retaining means) the individual color shades are applied in layers at the front side, with each layer hardened as described in Example 16.
The facings are distinguished by their excellent stability and especially by a high resistance to abrasion throughout their use inside the mouth. In addition, their appearance is faultless.
The principles, preferred embodiments and modes of operation of the present invention have been described in the foregoing specification. The invention which is intended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.
. . .
Claims (12)
1. A dental composition, especially for tooth fillings and dentures, including at least two components, one component comprising a polymerizable diacrylic acid ester selected from the group consisting of the diacrylic acid or dimethacrylic acid ester of bishydroxymethyltricyclo [5.2.1.02,6]-decane and mixtures thereof, the other component comprising a radical-forming substance.
2. The dental composition of Claim 1, wherein said composition further includes at least one of fillers, stabilizers and pigments.
3. The dental composition of Claim 1, wherein said composition further includes other polymerizable monofunctional or difunctional acrylic or methacrylic acid esters.
4. The dental composition of Claim 3, wherein said other polymerizable diacrylic acid esters include the acrylic acid or methacrylic acid esters of at least one compound selected from hexanediol; 2,2 bis-[p-(hydroxyethoxy-)phenyl]-propane;
and 2,2 bis [p-(?-hydroxypropoxy-)phenyl]-propane.
and 2,2 bis [p-(?-hydroxypropoxy-)phenyl]-propane.
5. The dental composition of Claim 3, wherein at least 20% of said polymerizable diacrylic acid esters are esters of said bishydroxymethyltricyclo[5.2.1.02,6]-decane.
6. The dental composition of Claim 1, wherein said radical-forming substance is an oxidation-reduction system.
7. The dental composition of Claim 1, wherein said composition includes an initiator for photo-polymerization.
8. The dental composition of Claim 1, wherein said components are each liquid or in a liquid form in combination with another liquid component.
9. The dental composition of Claim 1, wherein at least one of said components is in a paste form in combination with a filler.
10. The dental composition of Claim 1, wherein both of said components are in paste form.
11. In a method for forming dental fillings and pros-thetic dental appliances in which a polymerizable diacrylic or dimethacrylic acid ester is polymerized to form a hardened product, the improvement wherein at least 20 percent of said polymerizable ester is the ester of bishydroxymethyltricyclo [5.2.1.02'6] -decane.
12. An improved dental composition having shortened hardening time and after hardening increased compressive strength and abrasion resistance comprising a polymerizable acrylic or methacrylic acid ester or diester and a radical-forming compound, at least 20 percent of the polymerizable ester being the diacrylic acid or dimethacrylic acid ester of bishydroxymethyltricyclo [5.2.1.02,6]-decane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH004823/77 | 1977-04-19 | ||
| CH482377A CH629664A5 (en) | 1977-04-19 | 1977-04-19 | Polymerisable composition for dental purposes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1109597A true CA1109597A (en) | 1981-09-22 |
Family
ID=4283163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA301,369A Expired CA1109597A (en) | 1977-04-19 | 1978-04-18 | Dental compositions |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS53130896A (en) |
| AT (1) | AT355728B (en) |
| BE (1) | BE866091A (en) |
| CA (1) | CA1109597A (en) |
| CH (1) | CH629664A5 (en) |
| DD (1) | DD135995A5 (en) |
| DE (1) | DE2816823C2 (en) |
| FR (1) | FR2387646A1 (en) |
| GB (1) | GB1576080A (en) |
| NL (1) | NL182049C (en) |
| SE (1) | SE436684B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4674980A (en) * | 1982-05-03 | 1987-06-23 | Den-Mat, Inc. | Dental composite and porcelain repair |
| USRE35264E (en) * | 1981-05-04 | 1996-06-04 | Dentsply Research & Development Corp. | Dental adhesive system |
| US11944692B2 (en) | 2018-06-19 | 2024-04-02 | Voco Gmbh | Thermoactive dental composite composition |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2931925A1 (en) * | 1979-08-07 | 1981-02-26 | Bayer Ag | (METH) ACRYLIC ACID ESTERS OF TRICYCLIC DECANDIOLES CONTAINING ETHER GROUPS |
| US4375966A (en) * | 1981-08-24 | 1983-03-08 | Sybron Corporation | System for making direct oral impression tray |
| DE3522006A1 (en) * | 1985-06-20 | 1987-01-02 | Bayer Ag | (METH) ACRYLIC ACID DERIVATIVES OF TRICYCLODECANES AND THEIR USE |
| DE3522005A1 (en) * | 1985-06-20 | 1987-01-02 | Bayer Ag | (METH) ACRYLIC ACID ESTERS AND THEIR USE |
| DE3607331A1 (en) * | 1986-03-06 | 1987-09-10 | Espe Pharm Praep | (METH) ACRYLIC ACID ESTERS AND THEIR USE FOR THE PRODUCTION OF DENTAL MATERIALS |
| DE3609038A1 (en) * | 1986-03-18 | 1987-09-24 | Espe Stiftung | ROENTGENOPAKE POLYMERIZABLE DENTAL MATERIALS |
| WO1988005651A1 (en) * | 1987-02-04 | 1988-08-11 | Dental Composite Ltd. | Radiopaque glass ionomer cement liner for dental cavities |
| DE3708618A1 (en) * | 1987-03-17 | 1988-09-29 | Kulzer & Co Gmbh | PLASTIC SPARE PARTS |
| DE3837569A1 (en) * | 1988-11-04 | 1990-05-10 | Espe Stiftung | DENTAL MATERIALS CURABLE WITH VISIBLE LIGHT |
| JPH0733404B2 (en) * | 1989-10-11 | 1995-04-12 | 三洋化成工業株式会社 | Molding composition and method for producing molded article |
| DE4032505A1 (en) * | 1990-10-12 | 1991-08-14 | Thera Ges Fuer Patente | Use of dental filling compsn. with high filler content - to fix inlay, onlay or facing by high frequency vibration |
| DE19502751A1 (en) * | 1995-01-23 | 1996-08-08 | Ivoclar Ag | Mfg. plastic models for producing dental prostheses |
| DE19961342B4 (en) | 1999-12-17 | 2004-02-19 | 3M Espe Ag | Radically curable urethane prepolymers and their use |
| DE10058830B4 (en) | 2000-11-27 | 2005-01-27 | 3M Espe Ag | Use of branched polyacids in dental compositions and dental compositions containing branched polyacids |
| DE10107985C1 (en) | 2001-02-19 | 2002-04-18 | 3M Espe Ag | Polymerizable formulation used for coating and/or bonding substrates or as dental formulation, contains organosilicon compound with aliphatic and cycloaliphatic epoxide groups, filler and initiator, inhibitor and/or accelerator |
| DE10124028B4 (en) | 2001-05-16 | 2010-02-18 | 3M Espe Ag | Self-adhesive dental materials |
| US8084514B2 (en) * | 2005-05-13 | 2011-12-27 | E. I. Du Pont De Nemours And Company | Materials leading to improved dental composites and dental composites made therefrom |
| DE102007034457A1 (en) * | 2007-07-20 | 2009-01-22 | Heraeus Kulzer Gmbh | Dental composites with low shrinkage stress and high flexural strength |
| WO2011034780A1 (en) | 2009-09-15 | 2011-03-24 | 3M Innovative Properties Company | Dental implant abutments and methods of use |
| DE102009043355A1 (en) | 2009-09-29 | 2011-04-07 | Christa Hillebrand | Correction procedure for fingernails or toenails |
| DE102010035856A1 (en) | 2010-08-30 | 2012-03-01 | Heraeus Kulzer Gmbh | Dental material comprises molecularly dispersed octenidine dihydrochloride, which is dissolved in solubilizing hydroxy functionalized dental monomers |
| DE102010046697A1 (en) | 2010-09-28 | 2012-03-29 | Kettenbach Gmbh & Co. Kg | Polymerizable dental material with reactive paste former, cured dental material and their use |
| US8915736B2 (en) | 2010-09-30 | 2014-12-23 | Voco Gmbh | Composition comprising a monomer with a polyalicyclic structure element for filling and/or sealing a root canal |
| EP2436365B1 (en) | 2010-09-30 | 2017-03-08 | VOCO GmbH | Composite material comprising a monomer with a polyalicyclic structure element |
| US8669302B2 (en) | 2010-09-30 | 2014-03-11 | Voco Gmbh | Composite material comprising a monomer with a polyalicyclic structure element as a sealing material |
| DE102012001978A1 (en) * | 2012-02-02 | 2013-08-08 | Voco Gmbh | Dental composite materials containing tricyclic plasticizers |
| WO2014033280A2 (en) | 2012-08-31 | 2014-03-06 | Kettenbach Gmbh & Co. Kg | Radically polymerisable dental material, cured product and usage |
| DE102013008176A1 (en) | 2012-10-05 | 2014-04-10 | Voco Gmbh | Kit and method for the indirect chairside production of composite inlays |
| EP3338756B1 (en) | 2016-12-21 | 2020-02-26 | VOCO GmbH | Storage-stable resin-modified glass ionomer cement |
| DE102021113969A1 (en) | 2021-05-31 | 2022-12-01 | Mühlbauer Technology Gmbh | Monomer mixture for the production of a dental material |
| DE102022116577A1 (en) | 2022-07-04 | 2024-01-04 | Mühlbauer Technology Gmbh | Monomer mixture for producing a dental material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH557674A (en) * | 1968-05-15 | 1975-01-15 | Espe Pharm Praep | MATERIAL FOR THE PRODUCTION OF FILLINGS AND DENTAL REPLACEMENT PARTS. |
-
1977
- 1977-04-19 CH CH482377A patent/CH629664A5/en not_active IP Right Cessation
-
1978
- 1978-04-18 CA CA301,369A patent/CA1109597A/en not_active Expired
- 1978-04-18 FR FR7811389A patent/FR2387646A1/en active Granted
- 1978-04-18 DD DD78204856A patent/DD135995A5/en unknown
- 1978-04-18 DE DE2816823A patent/DE2816823C2/en not_active Expired
- 1978-04-18 JP JP4620278A patent/JPS53130896A/en active Granted
- 1978-04-18 NL NLAANVRAGE7804096,A patent/NL182049C/en not_active IP Right Cessation
- 1978-04-18 BE BE186873A patent/BE866091A/en not_active IP Right Cessation
- 1978-04-18 SE SE7804386A patent/SE436684B/en not_active IP Right Cessation
- 1978-04-18 GB GB15266/78A patent/GB1576080A/en not_active Expired
- 1978-04-18 AT AT273278A patent/AT355728B/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE35264E (en) * | 1981-05-04 | 1996-06-04 | Dentsply Research & Development Corp. | Dental adhesive system |
| US4674980A (en) * | 1982-05-03 | 1987-06-23 | Den-Mat, Inc. | Dental composite and porcelain repair |
| US11944692B2 (en) | 2018-06-19 | 2024-04-02 | Voco Gmbh | Thermoactive dental composite composition |
Also Published As
| Publication number | Publication date |
|---|---|
| NL182049B (en) | 1987-08-03 |
| SE436684B (en) | 1985-01-21 |
| DE2816823C2 (en) | 1982-04-29 |
| FR2387646A1 (en) | 1978-11-17 |
| DD135995A5 (en) | 1979-06-13 |
| DE2816823A1 (en) | 1978-10-26 |
| FR2387646B1 (en) | 1984-08-10 |
| GB1576080A (en) | 1980-10-01 |
| CH629664A5 (en) | 1982-05-14 |
| BE866091A (en) | 1978-08-14 |
| JPS631281B2 (en) | 1988-01-12 |
| SE7804386L (en) | 1978-10-20 |
| NL7804096A (en) | 1978-10-23 |
| NL182049C (en) | 1988-01-04 |
| JPS53130896A (en) | 1978-11-15 |
| ATA273278A (en) | 1979-08-15 |
| AT355728B (en) | 1980-03-25 |
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