JPS6160603A - Visible ray-curable composition for dental purpose - Google Patents

Abstract

PURPOSE:The title composition that contains a combination of an organic peroxide and a pyrylium salt as a photopolymerization initiator, thus being suitable for use as a tooth crown or denture bed material, because it can be cured sufficiently even in deep places in a short time with visible rays. CONSTITUTION:The objective composition for dental purposes contains (A) ethylenically unsaturated compounds such as triethylene glcyol dimethacrylate, (B) 0.001-10 wt% of an organic peroxide based on component A, and (C) 0.0001-1wt% of a compound of the formula [R1-R2 are H, halogen, alkyl, haloalkyl, ethylenyl, styryl which may have alkylamino, phenyl which may be substituted with alkyl or the like, nitro, primary amino, hydroxyl; X is O, S; Y is aninic functional group] as a photosensitizer. Thus, the composition can be cured with visible rays in a short time into more than 5mm depth and shows high safety, good clinical operability and economy.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a dental composition that can be polymerized and hardened by irradiation with visible light. In the present invention, the dental composition is:
It includes dental crown materials, denture base materials, dental adhesive restorative materials, dental impression materials, etc. that contain ethylenically unsaturated compounds.

[Conventional technology]

Conventionally, the polymerization and curing methods for these dental compositions include curing using a redox polymerization initiator such as benzoyl peroxide and tertiary amine, and curing using a photosensitizer such as benzoin alkyl ether and ultraviolet rays. A method of curing by irradiation has been used.

[Problem that the invention seeks to solve]

Room-temperature curing products using redox polymerization initiators are powder-curable.
Because it is a liquid type or paste-paste type kneading method, air bubbles easily enter the cured resin.
It also had the disadvantage that it cured quickly and the operation time was short. On the other hand, in the case of ultraviolet curing type, the penetration of ultraviolet rays into materials is weak, the curing depth of the composite resin is limited to within 2 volumes, and ultraviolet rays with short wavelengths of 32 oi or less are harmful to the human body. There are problems such as the need for protection with filters, etc., and the mercury lamp used in the irradiation device deteriorates and has a short lifespan.

[Means to solve the problem]

The inventors of the present invention have conducted extensive research in order to obtain a dental composition that does not have the above-mentioned drawbacks, and as a result, they have discovered a dental composition that is completely light and heavy.

That is, the present invention comprises 1 m or 2 m or more of an ethylenically unsaturated compound, 1 ai or 2 ai or more of an organic peroxide, and a biryllium salt or thiopyrylium salt represented by the following general formula (1) as a photosensitizer. or 2g1 or more.

As the ethylenically unsaturated compound used in the present invention, all ethylenically unsaturated compounds conventionally used in dental compositions can be used, but examples thereof include methacrylic acid derivatives such as methyl methacrylate, 2- Hydroxyethyl methacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1.2-bis(3-
methacryloxy-2-hydroxypropoxy)ethane,
2,2-bis(4-(3-methacryloxy-2-hydroquinepropoxy)phenyl)propane, bisphenol A dimethacrylate.

The organic peroxide used in the present invention, such as 2-hydroxy-1,3-dimethacryloxybrotrimethylhexamethylene dicarbamate, has an oxygen-dispersion bond t-1 in the molecule.
Examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, and tert-butyl hydroperoxide. , cumene hydro, peroxide,
Diisopropylbenzene hydroperoxide, para-menthane hydroperoxide, ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tertiary butyl peroxide) Hexane, acetyl peroxide, octanoyl peroxide, lauroyl peroxide, 3,5.5-)limethylhexanoyl peroxide, benzoyl peroxide, diinoprobil baroxydicarbonate, di-2-ethylhexyl peroxide dicarbonate, di(
3-Methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyin butyrate, tert-butyl peroxyoctanoate, tert-butyl peroxybenzoate, di-tert-butyl peroxyin 7 tallate, 2, 5-dimethyl-2
,5-di(benzoylperoxy)hexane, 3,3'
, 4. 4'-tetra-(tert-butylperoxycarbonyl)benzopheno/%313'4.4'
-tetra-(tertiaryamylperoxycarbonyl)benzophenonep 3.3', 4.4'-tetra(tertiaryhexyloxycarbonyl)benzophenone9.3.3',4.4-tetra(tertiaryamylperoxycarbonyl) oxycarbonyl)benzo72/n, 3.
3', 4. 4'-tetra(cumylperoxycarbonyl)benzophenone, 3°3', 4r 4'-
Tetra (para-ingrovir cumyl baroxycarbonyl) benzophenone, etc.

In the pyrylium salt or thiopyrylium salt represented by the general formula (1) used in the present invention, the anionic functional group represented by Y includes verchlorate, fluoroborate, fluorophosphonate, fluorophosphonate, chloroaluminate, sulfur acetate, and methane. Sulfate thiocyanate, sulfate, nitrate, acetate, etc.

As a specific example of the compound represented by the general formula (1), for example, 4-(4-butoxyphenyl)-2゜6-bis(4-
methoxyphenyl) biryllium fluoroborate, 4-
(4-Butoxyphenyl)-2+ 6-cyphenyl deopyrilicum fluoroborate, 4-(4-butoxyphenyl)-2,6-bis(4-methoxyphenyl)thiopyrylium fluoroborate, 2,6-bis( 4-methoxyphenyl)-4-phenylthiovirylium fluoroborate, 4-(4-butoxyphenyl)-2゜6-cyphenylpyrylium fluoroantimonate, 2-methyl-4,6-bis(4-methoxyphenyl) ) Thiopyrylium fluoroborate, 2゜4.6-tri(4-methoxyphenyl)thiopyrylium barchlorate, 4-(3
, 4-jethoxyphenyl)-2,6-bis(4-methoxy722/I/)thiopyrylium fluoroborate,
4-(4-dimethylaminophenyl)-2,6-cyphenylthiovirylium perchlorate, 2-nitro-4,
6-bis(4-dimethylaminostyryl)bilylium fluoroborate, 2-methoxy-4-naphthyl-6-styrylthiopyrylium fluoroborate, 2-amino-
4,6-bis(4-butoxyphenyl)thiopyrylium verchlorate, 2-(4-nitrophenyl)-4,6
-Bis(4-)゛tylphenyl)thiopyrylium fluoroborate, 2-hydroxy-4,6-bis(4-dimethylaminostyryl)virilikumperchlorate, 2-
(3,4-dichlorophenyl")-4-(4-methoxyphenyl)-6-phenylpyrylium fluoroborate and the like.

The dental composition of the present invention comprises one or more of the ethylenically unsaturated compounds described above, 181 or 2i or more of an organic peroxide, and one or more pyrylium salts or thiopyrylium salts as a photosensitizer. It contains two or more types as active ingredients, and its composition includes Bi-IJ, which is a photosensitizer.
The degree a of the 17um salt or the thiopyridium salt is 0.0001 to 1% by weight, more preferably 0.001 to 0.5% by weight, based on the ethylenically unsaturated compound. If the concentration of the photosensitizer is less than 0.0001% by weight, the dye composition will not be cured by visible light, and if it exceeds 1% by weight, the thickness of the monolayer (hardening depth) will decrease, and sanitary issues may arise. I also don't like it.

The concentration i of the organic peroxide is 0.001 to 10% by weight relative to the ethylenically unsaturated compound, more preferably 0.001 to 10% by weight.
01 to 5% by weight. If this concentration is less than O1001 wt.s., the composition will not be cured, and if it exceeds 10 wt.%, the physical properties of the cured product will deteriorate, which is not preferable.

The dental composition of the present invention may be used by appropriately adding a filler as necessary. The filler may be, for example, apatite, soda glass, quartz, silica gel, zirconium glass, etc., or may be spherical, finely powdered, platelets, fibers, whiskers, or have an irregular shape. Good too. Further may be necessary.

The dental composition of the present invention uses an optimal combination of an organic peroxide and the photosensitizer as a photopolymerization initiator.The visible light irradiator used in the present invention emits light having a wavelength within the above-mentioned range. If so, all can be used. Such light sources include xenon lamps, halogen lamps, fluorescent lamps, tungsten lamps, metal halide lamps, and visible laser lamps.

The dental composition of the present invention is mixed in advance into a liquid by a supplier, filled into a light-shielded container, and supplied to a doctor. After applying, filling or molding the dental composition of the present invention, a doctor can polymerize and harden it using visible light emitted from an irradiator.

〔Effect of the invention〕

It is hardened and has a hardening depth of 5 m or more for use in dentistry. [Examples] The present invention will be explained in more detail below with reference to Examples and Comparative Examples. These examples are provided for illustrative purposes and are not intended to limit the invention in any way.

Examples 1 to 10 Compositions were prepared by uniformly dissolving an organic peroxide and a photosensitizer in an ethylenically unsaturated compound at the composition ratio shown in Table 1. This composition was polymerized and cured by irradiating visible light from a distance of 10 in the inner diameter, 10 in the depth and 3 in the upper part of the cylinder. Further, the curing depth at this time was measured using a micrometer after taking out the polymerized cured product from the cylinder and removing unreacted materials, and the results are shown in Table 1.

As is clear from the results in Table 1, the dental composition of the present invention can be irradiated with visible light for a short period of about 20 to 40 seconds, and can be cured to a sufficient hardening depth (5- or more). It can be seen that it is excellent as a crown material, denture base material, dental adhesive restorative material, and dental impression material, and has good clinical operability.

Comparative Examples 1 to 4 Tests similar to those in Examples were conducted using triethylene glycol dimethacrylate as the ethylenically unsaturated compound and adding an organic peroxide and a photosensitizer having the composition shown in Table 2.

Claims (4)

[Claims] (1) One or more ethylenically unsaturated compounds, one or more organic peroxides, and a pyrylium salt or thiopyrylium salt represented by the following general formula [I] as a photosensitizer. A visible light-curable dental composition comprising one or more of the above. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] In the formula, R_1, R_2, and R_3 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an ethylene group, a styryl group, an alkoxy group, a phenyl group, Naphthyl group, alkylphenyl group, alkoxyphenyl group, hydroxyphenyl group, halophenyl group, nitrophenyl group,
It represents an aminophenyl group, an alkylaminophenyl group, an alkylaminostyryl group, a nitro group, an amino group or a hydroxyl group, X represents an oxygen atom or a sulfur atom, and Y represents an anionic functional group. (2) The composition according to claim 1, wherein the concentration of the photosensitizer is 0.0001 to 1% by weight based on the ethylenically unsaturated compound. (3) The composition according to claim 1 or 2, wherein the concentration of the organic peroxide is 0.001 to 10% by weight based on the ethylenically unsaturated compound. (4) The ethylenically unsaturated compound is triethylene glycol dimethacrylate, hexamethylene glycol dimethacrylate, 2,2-bis[4-(3-methacryloxy-2-hydroxypropoxy)phenyl]propane,
Di-2-methacryloxyethyl-2,2,4-trimethylhexamethylene dicarbamate and 1,2-bis(
The composition according to claim 1, 2, or 3, wherein the composition is one or more selected from 3-methacryloxy-2-hydroxypropoxy)ethane.