JPS6089406A - Restorative dental material of resin type - Google Patents

Abstract

PURPOSE:A restorative dental material of resin type having improved compression strength, operation efficiency, long-term shelf stability, wherein a specific polyfunctional monomer is combined with a copolymerizable unsaturated monomer, and a polymerization catalyst is stored in a container different from that of an activator and the polyfunctional monomer. CONSTITUTION:A restorative dental material consisting of (A) a polyfunctional monomer containing 3-4 acrylic acid groups or methacrylic acid groups, preferably a compound shown by the formula I or formula II (R is H, or CH3), (B) an unsaturated monomer copolymerizable with the polyfunctional monomer, preferably bisphenol A diglycidyl methacrylate, etc., (C) a polymerization catalyst for the monomer, (D) an activator for the monomer, and (E) a filler, wherein the component B is divided into two, one of them is blended with the components C and E, and the other is blended with the components A, D, and E, each of them is premixed, they are stored in different containers, having improved compression strength, operation efficiency during kneading, and stability of product.

Description

[Detailed description of the invention] The present invention relates to a novel dental resin restorative material.

Specifically, a polyfunctional monomer having 3 or 4 acrylic acid groups or methacrylic acid groups, an unsaturated monomer copolymerizable with the polyfunctional monomer, a polymerization catalyst for the monomer, In the dental resin restorative material comprising the monomer activator and filler, the unsaturated monomer that can be copolymerized with the polyfunctional monomer is divided into two parts, and one of the unsaturated monomers is In the polymerization of monomers, the unsaturated monomer is premixed with a catalyst and filler and held in a container, while the other unsaturated monomer is held in a container premixed with a monomer activator and filler, and the acrylic acid is A dental resin restorative material characterized in that the entire amount of a polyfunctional monomer having three or four groups or methacrylic acid groups is premixed in a container containing a monomer activator and a filler. be.

Conventionally, various dental resin-based restorative materials are known and commercially available. A typical example is to hold the unsaturated monomer and filler in two separate containers, and hold the monomer catalyst and monomer activator in each container. The monomer catalyst and activator are mixed together for the first time by taking out equal amounts of material from both containers and kneading them, thereby curing the monomers. The dental resin thread restorative material is not only required to have good storage stability and high compressive strength, but also to have good operational aspects such as ease of kneading and uniformity. It is common to use a combination of monomer types, filler types, etc. depending on the requirements.

However, none of the conventional products satisfies all of the above requirements, leaving room for improvement.

With the above background in mind, the present inventors have developed a dental resin thread restorative material that has better compressive strength, better product stability, that is, long-term storage stability, and moreover, has better operability. As a result, a polyfunctional monomer having 3 or 41β1 acrylic acid groups or methacrylic acid groups is used in combination with other copolymerizable monomers, and the polyfunctional monomer is specified for a specific container. By premixing with the compound, 1. The above assignment! Confirmed that a tooth repair material could be obtained that solved the problem.
This led us to propose the present invention.

That is, the present invention relates to a polyfunctional monomer having three or four acrylic acid groups or methacrylic acid groups.

An unsaturated monomer copolymerizable with the polyfunctional monomer.

In the dental resin thread restoration material comprising a polymerization catalyst for the monomer, an activator for the monomer, and a filler, the unsaturated monomer that can be copolymerized with the polyfunctional monomer is divided into two parts, and One unsaturated monomer is held in a container premixed with a polymerization catalyst and a filler, and the other unsaturated monomer is premixed with a polymerization catalyst and a filler upon activation of the monomer. The polyfunctional monomer, which is held in a container and has three or four acrylic acid groups or methacrylic acid groups, is premixed in a container containing a monomer activator and a filler. This is a dental resin thread restorative material characterized by:

One of the monomers serving as the resin raw material used in the present invention is a polyfunctional monomer having three or four acrylic acid groups or methacrylic acid groups. These polyfunctional monomers can be used without particular limitation as long as they have three or four acrylic acid groups or methacrylic acid groups bonded together, but those of the following formula are generally preferably used.

or (However, in the above α) and 0 formulas, B represents a hydrogen atom or a methyl group) For example, tetramethylolmethane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethanetetraacrylate, tetra Methylolmethanetetramethacrylate and the like may be used alone or in combination.

Further, one of the simple substances serving as the resin raw material used in the present invention is an unsaturated monomer that can be copolymerized with the polyfunctional monomer. The above-mentioned monomers may be those already known as resin raw materials in the dental field without particular limitation. Typical examples that are particularly preferably used include, for example, hisphenol A diglycidyl methacrylate (hereinafter referred to as BiB-GMA).
), triethylene glycol dimethacrylate (hereinafter abbreviated as 3GDM), 2-bismethacryloxyethoxydiphenylpropane.

These include bisphenol A dimethacrylate and neopentyl glycol dimethacrylate.

Further, as the monomer polymerization catalyst used in the present invention, polymerization catalysts known in the dental field can be used. Typical examples of catalysts commonly used are peroxides such as benzoyl peroxide, 4-chlorobenzoyl peroxide, and lauroyl peroxide. The amount of the catalyst used is generally 0.01 to 5 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of the resin composition.
．． It may be used in a proportion of 1 to 2 parts by weight.

Furthermore, as the monomer activator used in the present invention, those activators known in the dental field can be used. Typical examples of those generally suitably used include H,N-dimethyl-P
-) Louisin, N.

N-bis-(2-hydroxyethyl)-4-methylacholine, N, 1! -bis-(2-hydroxyethyl)-3
, 4-dimethylaniline and other amines. The amount of the activator used is generally 0.00 parts by weight per 100 parts by weight of the resin composition.
It may be used in a proportion of 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight.

Also, the filler used in the present invention is not particularly limited, and any filler that can be used as a filler for dental resin thread restoration materials may be used. Generally quartz powder.

Glass powder, aluminum oxide powder, silica powder, aluminum nitride powder, boron nitride powder, etc. can be used.

In addition, the present inventors previously proposed Japanese Patent Application Laid-Open No. 58-1104.
The inorganic oxide powder shown in No. 14 is also suitable. These powders may be used as they are, but they may be coated with the polyfunctional monomer, unsaturated monomer, or a mixture of these monomers, or coated with γ-methacryloxypropyltrimethoxysilane or vinyltrimethoxysilane. It is also suitable to use it after treatment with a coupling agent such as ethoxysilane. The amount of these fillers used is generally 60 to 90% by weight, preferably 70 to 90% by weight of the weight of the resin thread.

In the dental resin thread restorative material of the present invention, the unsaturated monomer that copolymerizes with the polyfunctional monomer is divided into two parts, and one of the unsaturated monomers is a monomer polymerization catalyst and The unsaturated monomer is premixed with a filler and held in a container, and the other unsaturated monomer is premixed with a monomer activator and a filler and held in a separate container.

The mixing ratio of each component to be premixed in both containers may be appropriately determined based on the operability when taking out the contents from each container and kneading the two for use. For example, the components divided into a catalyst-containing container and an activator-containing container are an unsaturated monomer copolymerizable with the polyfunctional monomer and a filler.

Generally, the unsaturated monomer is present at 10% of the total composition weight in each container.
The filler is preferably in the range of 15-30% by weight and 60-40% by weight of the total composition in each container.
It may be selected to be 90% by weight, preferably in the range of 70 to 90% by weight.

In addition to the unsaturated monomer and filler, a monomer polymerization catalyst and an activator are held in separate containers in the two containers. The reason for this is that if the catalyst and activator are mixed in the same container, polymerization of the monomers will occur and the resin thread repair material of the present invention cannot be stored for a long period of time.

In addition to the unsaturated monomers mentioned above, polyfunctional monomers having three or four acrylic acid groups or methacrylic acid groups may be used as the monomers used in the resin thread repair material in the present invention. Required. The reason for using the polyfunctional monomer is to ensure that the resin thread repair material of the present invention exhibits sufficient compressive strength when cured, and also to improve operability when kneading the resin thread repair material of the present invention. It's to make things better. The above-mentioned polyfunctional monomer is a known compound as described above, and exhibits excellent performance when used as a monomer for a dental resin thread restoration material. However, according to long-term research conducted by the present inventors, it has been found that when the polyfunctional monomer is premixed with a monomeric catalyst, the catalyst is decomposed and deactivated during storage for several months. The reason for this is not clear, but the industrially produced polyfunctional monomer may contain impurities that cause catalyst deactivation that cannot be separated by industrial purification, or the polyfunctional monomer itself is unstable. Therefore, it is thought that during long-term storage, polymerization gradually occurs due to the action of the catalyst, leading to deactivation of the catalyst. Therefore, the polyfunctional monomer cannot be divided into two containers and used by premixing with other unsaturated monomers and fillers. This phenomenon is extremely important when commercializing dental resin thread restoration materials, and when combining the components of the present invention, it is absolutely necessary to premix the monomeric catalyst and the polyfunctional monomer. I can't do that. Therefore, in the present invention, it is necessary to premix the polyfunctional monomer with the monomer activator and filler and hold it therein.

The amount of the polyfunctional monomer of the present invention to be used depends on the type of monomer used, the physical properties required for the dental resin thread restoration material, etc.
4, - Although it cannot be generally limited, it is generally preferable to select it so that it is in the range of 10 to 50% by weight, preferably 20 to 40% by weight, based on the total of the polyfunctional monomer and the unsaturated monomer. .

In the dental resin thread restoration material of the present invention, additives such as polymerization inhibitors and pigments are preferably added to each container in a spoon-like manner, as is known in the dental field.

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.

Example 1 An inorganic oxide was obtained according to the example of JP-A No. 1111458-110414. That is, water 5.4.9 and tetraethyl silicate (Si (002H5) 4. Nippon Colcoat Chemical Co., Ltd., trade name: Ethyl silicate 2 B) 20
8I was dissolved in 1.21 g of methanol, and this solution was hydrolyzed with stirring at room temperature for about 2 hours, and then 540 g of tetrabutyl titanate (T1 (0-n04Hg) 41 manufactured by Nippon Soda) was mixed with 0.0 g of Improper Tool. A mixed solution of a hydrolyzate of tetraethyl silicate and tetrabutyl titanate was prepared by adding the mixture to a solution dissolved in 500 mg of tetraethyl silicate with stirring. Next, a glass reaction vessel with an internal volume of 10 J and equipped with a stirrer was filled with 15 A' of methanol, and 500 g of ammonia aqueous solution (concentration 25% by weight) was added thereto to prepare an ammoniacal methanol solution. A mixed solution of tetraethyl silicate hydrolyzate and tetrabutyl titanate was added over about 2 hours while maintaining the temperature of the reaction vessel at 20°C. A few minutes after the addition of tuna began, the reaction solution became milky white. After the addition was completed, stirring was continued for 1 hour, and the solvent was removed from the milky white reaction liquid using an evaporator, and the mixture was further dried under reduced pressure at 80°C to obtain a milky white powder (hereinafter referred to as silica/titania filler). Ta.

As a result of scanning electron micrographs, the shape of the powder was spherical, the particle size was in the range of 0.10 NO, 20 μm, and the standard deviation value of the particle size was 1.20. Also B
The specific surface area determined by the ET method was 120 trt/y.

A part of the silica/titania filler obtained as described above was subjected to B i S -G M A /3 G D M
The silica/titania filler content was added to the monomers in a mixing ratio of 6/4 at a rate of 78% by weight, and polymerized in the presence of a catalyst (benzoyl peroxide). A polymer-coated filler was thus obtained, and the polymer-coated filler was ground to 10-100 microns.

Next, each component was premixed in separate containers (A, B) so as to have the following composition ratio.

(I) A'8 vessel composition and composition ratio (c) Catalyst benzoyl peroxide 0.46% by weight ■ B vessel composition and composition ratio Note 1) The polyfunctional monomer is manufactured by Shin Nakamura Chemical Co., Ltd. (product name NK Esthe 7LL) /A-TMM-3L) was blown.

0H20000E
H: OH2 (4swt%) OH20H OH20000H=OH2 Station (cJ OH%CoH0000H2-0-OH20H(5
wt %) - 0H200001 (=OH2) Calculate equal numbers from the above human container and B container and dry the room for 30 seconds (2
As a result of measuring the physical properties of the product kneaded and hardened at 5°C, the compressive strength was 3,880%. When this product was finished with Soflex (manufactured by 3M), a smooth surface was easily obtained without excessively scraping the resin surface, and the transparency was good.

Further, the above kA container and B container were stored in constant temperature baths maintained at 23°C and 37°C, respectively, and a stability test was conducted for the period shown in Table 1. The results were as shown in Table 1.

A queen test was conducted for comparison. That is, the monomer composition of both the human container and B container in Example 1 was B15.
- Leaf A: A stability test was carried out in the same manner as in Example 1, except that the proportions were equal to 9.7% claw amount, 3GDM: 6.4% electric charge, and polyfunctional monomer: 6.9% fi amount. The results were as shown in the column "Comparison M" in Table 1.

Table 1 Example Z Implementation except that tetramethylolmethanetetraacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., trade name NK Ester A-TMM-T) was used instead of the polyfunctional monomer used in Example 1. A stability test was conducted as in Example 1. As a result, the decomposition rate of benzoyl peroxide was 0.5% or less even after 40 days in a constant temperature bath at 37°C.

For comparison, a test similar to that of the comparative product in Table 1 of Example 1 was conducted, and the results showed that 50% of the benzoyl peroxide had decomposed after 40 days in a constant temperature bath at 37°C.

patent applicant Tokuyama Soda Co., Ltd.

Claims (1)

[Claims] A polyfunctional monomer having 3 or 4 acrylic acid groups or methacrylic acid groups, an unsaturated monomer copolymerizable with the polyfunctional monomer, a polymerization catalyst for the monomer, and the monomer. In a dental resin restorative material consisting of an activator and a filler, the unsaturated monomer copolymerized with the polyfunctional monomer is divided into two parts, and one of the unsaturated monomers is the monomer. The unsaturated monomer is premixed with a polymerization catalyst and a filler and held in a container, and the other unsaturated monomer is held in a container premixed with a monomer activator and a filler and has an acrylic acid group or a methacrylic acid group. 3 or 4
1. A dental resin-based restorative material, characterized in that the entire amount of the polyfunctional monomers contained therein is premixed in a container containing a monomer activator and a filler.