JPH0212202B2 - - Google Patents

Description

[Detailed description of the invention]

That is, the present invention relates to a veneer crown or a jacket crown in which an opaque layer, a dentin layer, and an enamel layer are sequentially built up on a metal casting crown or a resin crown, and the dentin layer has a general formula. (However, R is a saturated aliphatic hydrocarbon residue, R' is an unsaturated aliphatic hydrocarbon residue, and n is a positive number from 1 to 3.) Unsaturated carbonate and carboxylic acid unsaturated ester ( This is a veneer or jacket crown characterized by using a powdered copolymer of the present invention (excluding unsaturated esters of tartaric acid and unsaturated esters of epoxysuccinic acid). Traditionally, veneers and jacket crowns are widely used in the dental industry. The veneer crown is generally a metal cast crown with resin built up on the surface. For example, first, an opaque layer with good adhesiveness is formed in contact with a metal cast crown, then a dentin layer is formed on top of the opaque layer to reproduce the color tone of natural teeth, and finally, a transparent color is reproduced, It is used in a form with an enamel layer formed to protect the dentin layer. The jacket crown is used in the form of a metal cast crown or a resin crown with the opaque layer, dentin layer, and enamel layer successively built up. Generally, each layer is formed by separately preparing a powdered resin component and a liquid or paste monomer component, and thoroughly kneading the two components by a dentist or technician. Therefore, the powdered resin component can be said to be an extremely important factor, since it not only affects the workability of dentists and technicians, but also greatly affects the long-term use of dentures. Therefore, there is a need for materials for veneers or jacket crowns to have sufficient abrasion resistance to be usable, to have excellent physical properties such as impact resistance and bending strength, and to be easy to work with. Ta. The inventors of the present invention have conducted extensive research in order to meet these demands. As a result, they discovered a specific copolymer that has a number of excellent properties when used in the dentin layer of a vest or jacket crown, and completed the present invention. That is, the present invention relates to a veneer crown or a jacket crown in which an opaque layer, a dentin layer, and an enamel layer are sequentially built up on a metal casting crown or a resin crown, and the dentin layer has a general formula. (However, R is a saturated aliphatic hydrocarbon residue, R' is an unsaturated aliphatic hydrocarbon residue, and n is a positive number from 1 to 3.) Unsaturated carbonate and carboxylic acid unsaturated ester ( This is a veneer or jacket crown characterized by using a powdered copolymer of the present invention (excluding unsaturated esters of tartaric acid and unsaturated esters of epoxysuccinic acid). One component of the dentin layer of the veneer or jacket crown used in the present invention is of the general formula

It is an unsaturated carbonate represented by the formula: (where R is a saturated aliphatic hydrocarbon residue, R' is an unsaturated aliphatic hydrocarbon residue, and n is a positive number from 1 to 3). The above unsaturated carbonates are known.
For example, the unsaturated carbonate polymer is used as a synthetic resin lens in glasses, optical equipment, and the like. Therefore, in the present invention, these known materials can be used as they are. Of course, in the present invention, the method for producing the unsaturated carbonate is not limited, and any method may be used. As an example of a typical method, the following method is preferably employed. For example, a method for producing an unsaturated carbonate is a method in which an unsaturated carbonate is produced by reacting a chloroformic acid ester obtained by a reaction between an alcohol and phosgene with an unsaturated alcohol: a method of producing an unsaturated carbonate by reacting an alkali metal carbonate, alcohol, and carbon dioxide gas,
A method for producing an unsaturated carbonate by reacting the reaction product with an unsaturated organic halide; a method for producing an unsaturated carbonate by reacting an alkali metal carbonate, alcohol, an unsaturated organic halide, and carbon dioxide, etc. There is. The object of the present invention is, as mentioned above, to improve veneers or jacket crowns, particularly the dentin layer. Therefore, the carbonate must be an unsaturated carbonate that can be polymerized. In this sense, R' in the above general formula is most preferably an unsaturated aliphatic hydrocarbon residue having 2 to 4 carbon atoms. In general, carbonates in which R' is a vinyl group, that is, an unsaturated aliphatic hydrocarbon residue having 2 carbon atoms, have limited industrial production methods and are highly polymerizable, so carbonates with 3 to 4 carbon atoms are generally not suitable for industrial production. Unsaturated aliphatic hydrocarbon residues are most widely used. In addition, unsaturated carbonates in which R' is an unsaturated hydrocarbon residue having 5 or more carbon atoms tend to have poor polymerizability and may be difficult to manufacture. It is often inferior to saturated carbonate. Similarly, R in the general formula has 2 to 5 carbon atoms, preferably 2 to 5 carbon atoms.
A saturated aliphatic hydrocarbon residue of 4 is preferably used. Further, in the general formula, n is a positive number from 1 to 3, depending on the raw material for producing the unsaturated carbonate. Examples of typical unsaturated carbonates include monoethylene glycol bis (allyl carbonate), diethylene glycol bis (vinyl carbonate), diethylene glycol bis (allyl carbonate), triethylene glycol bis (allyl carbonate), diethylene glycol bis (methallyl carbonate), Unsaturated carbonates such as dipropylene glycol bis(allyl carbonate), dibutylene glycol bis(allyl carbonate), dipentanediol bis(allyl carbonate), and diethylene glycol bis(butenyl carbonate) are preferably used. Another component forming the dentin layer of the veneer or jacket crown used in the present invention is a carboxylic acid unsaturated ester. The carboxylic acid unsaturated ester may be used without particular limitation as long as it can be copolymerized with the unsaturated carbonate, but a copolymer of tartaric acid unsaturated ester or epoxysuccinic acid unsaturated ester and the unsaturated carbonate may be used. Since its use as a crown material has already been proposed by the applicant, it is excluded from the carboxylic acid unsaturated esters of the present invention. Examples of carboxylic acid unsaturated esters preferably used in the present invention include maleic acid,
These are unsaturated esters of vinyl, allyl, butenyl, etc. of carboxylic acids such as fumaric acid, phthalic acid, and isophthalic acid. The unsaturated ester most preferably has two or more unsaturated bonds in order to crosslink with the unsaturated carbonate and exhibit excellent physical properties. More specific examples of those that are generally most preferably used industrially include allyl cinnamate, diallyl oxalate, diallyl itaconate, diallyl adipate, diallyl pimelate, diallyl dicricolate, diallyl glutarate, and malic acid. These include diallyl, triallyl citrate, diallyl maleate, methylallyl maleate, diallyl fumarate, diallyl phthalate, diallyl isophthalate, dibutenyl butarate, diallyl diethylene glycol diphthalate, and the like. The dentin layer used in the present invention is a copolymer of the unsaturated carbonate and the unsaturated carboxylic acid ester, and the mixing ratio of the copolymer components can range from 1 to 99% for one component, but generally is preferably selected so that the unsaturated carbonate content is 50% or more. The method for carrying out the above copolymerization is not particularly limited and any known polymerization or copolymerization method can be employed, but generally copolymerization is carried out in the presence of a radical initiator such as benzoyl peroxide, lauroyl peroxide, isopropyl peroxydicarbonate, etc. It is preferable to do so. The copolymer used in the dentin layer of the veneer or jacket crown of the present invention is used as a dental crown material by kneading it with a liquid or paste monomer. Further, the copolymer is in the form of a powder.
The degree of powderiness is not particularly limited, but in general, those in the range of 1 to 350μ are most widely used, and if necessary, pulverization is also suitable. Further, the liquid or paste monomer for kneading the resin for the inner layer of the present invention is not particularly limited, and known monomers can be used. Examples of those that can be generally used suitably include methyl methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 2,2 bis[4
(2-Methacryloxyethoxy)phenyl]propane, bisphenol A dimethacrylate, and the like are preferably used. It is also a preferred embodiment to add a small amount of peroxide such as benzoyl peroxide. As is clear from the examples described below, the dentin layer forming the veneer crown or jacket crown of the present invention has extremely good hardness, abrasion resistance, and water resistance, as well as extremely good compressive strength and impact resistance. It is something. EXAMPLES In order to explain the present invention more specifically, Examples and Comparative Examples will be described below, but the present invention is not limited to these Examples. The abbreviations and test methods used in the examples are as shown below. BAC; diethylene glycol bis(allyl carbonate) DAP; diallyl phthalate BMEPP; 2,2-bis(4-methacryloxyphenyl) propane DEDMA; diethylene glycol dimethacrylate BPO; benzoyl peroxide PBAC; polydiethylene glycol bis(allyl carbonate) PMMA; polymethyl Methacrylate DAIP; diallyl isophthalate MADA; diallyl maleate FADA; diallyl fumarate 1) Hardness test Brinell hardness was measured using a micro Brinell hardness meter at a load of 25 kg and a loading time of 30 seconds. The size of the test piece used was 20 mm x 20 mm x 3 mm (thickness). 2) Water absorption test After the sample was made to have a constant weight, it was immersed in distilled water at 37°C for 7 days, and the weight increase due to water absorption was divided by the surface area to determine the amount of water absorbed. The size of the test piece is 10mm x 10mm x
A 3 mm (thickness) one was used. 3) Abrasion test A toothbrush type abrasion tester was used to conduct a test piece that had absorbed water. The wear conditions were 23°C, a load of 300g, and a wear distance of 4500m, and the wear amount was expressed as the wear depth divided by the specific gravity. White Lion toothpaste was used as the anti-friction material, and Spring Trion (made of nylon) was used as the toothbrush.
The size of the test piece used was 10 mm x 10 mm x 3 mm (thickness). 4) Compression test Dry test piece 3mm x 3mm x using a universal testing machine
Compressive strength was measured for 3 mm pieces. 5) Bending test Dry test piece 10mm x 30mm x using a universal testing machine
The bending strength was measured for a 3 mm (thickness) piece. 6) Impact test A falling ball impact test was conducted using a steel ball weighing 10 g, and the test piece was 20 mm x 20 mm x 3 mm (thickness).
The height at which 50% destruction occurs was determined. 7) Condensation test A 1:1 powder-liquid kneaded product was thoroughly drained of liquid components on tissue paper, then polymerized at 130°C for 15 minutes and the surface condition was observed. Example 1 A test piece was prepared with the following composition to make it similar to the composition of the dentin layer, which is the inner layer of a veneer. That is, the general formula shown in Table-1

A resin powder consisting of a copolymer of unsaturated carbonate and DAP represented by the formula and BMEPP (trade name D-2,
6E (Shin Nakamura Chemical) 60 parts by weight and DEDMA (trade name NK
−2G, Shin Nakamura Chemical) 40 parts by weight (BPO1
% by weight) at a weight ratio of 1:1, and poured the kneaded mixture into a glass mold of 20 mm x 50 mm x 3 mm (thickness) at 130°C for 15 minutes at an air pressure of 5Kg/cm ²
A test piece was prepared by polymerization under heating. Cut out test pieces for each test from this test piece,
The physical properties were measured and the results shown in Table 1 were obtained. Furthermore, No. 6 and No. 7 in Table 1 are PBAC and No. 7 for comparison.
These are the results of a similar implementation using PMMA.
The types of resins in Table 1 are indicated by the number (value of n) in the general formula of the unsaturated carbonate and the number of carbon atoms in R and R'. In addition, in Nos. 1 to 5, even when the kneaded product was condensed and polymerized, the surface of the polymerized product was completely polymerized, but in No. 6, the surface of the polymer was covered with white powder.

[Table] Example 2 Using BAC instead of the resin in Table 1 of Example 1
The same procedure as in Example 1 was carried out except that a copolymer with DAIP, MADA, or FADA was used. The results were as shown in Table-2. However, in the column of resin type in Table 2, the copolymer components and their composition ratios are shown. Further, in the same manner as in Example 1, in all cases where this powder-liquid kneaded product was condensed and polymerized, there was no powder blowing on the surface and it was completely aggregated.

【table】

Claims (1)

[Scope of Claims] 1. A veneer crown or a jacket crown in which an opaque layer, a dentin layer, and an enamel layer are sequentially built up on a metal cast crown or a resin crown, where the dentin layer has a general formula. (However, R is a saturated aliphatic hydrocarbon residue, R' is an unsaturated aliphatic hydrocarbon residue, and n is a positive number from 1 to 3.) Unsaturated carbonate and carboxylic acid unsaturated ester ( 1. A front crown or jacket crown characterized by using a powdered copolymer with a powdery copolymer (excluding unsaturated esters of tartaric acid and unsaturated esters of epoxysuccinic acid). 2. The veneer crown or jacket crown according to claim 1, wherein the unsaturated carbonate is diethylene glycol bis(allyl carbonate) or triethylene glycol (allyl carbonate).