JPH0378843B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a dental composition that can be polymerized and cured by irradiation with visible light. In the present invention, the dental composition refers to a dental crown material, a denture base material, a dental adhesive restorative material containing an ethylenically unsaturated compound,
Includes dental impression materials, etc. [Prior Art] Conventionally, methods for polymerizing and curing these dental compositions include curing using redox polymerization initiators such as benzoyl peroxide and tertiary amines, and photointensifiers such as benzoin alkyl ether. A method of curing the sensitizer by irradiating it with ultraviolet light has been used. [Problems to be solved by the invention] Room-temperature curing types using redox-based polymerization initiators use a one-component powder type or paste-paste type kneading system, so air bubbles are likely to enter the cured resin. It also had shortcomings such as fast curing and short operating time. On the other hand, in the case of ultraviolet curing type, UV rays have weak material permeability, the curing depth of composite resin is limited to 2 mm or less, and ultraviolet rays with short wavelengths of 320 nm or less are harmful to the human body, so filters are required. There are other problems, such as the need to protect the irradiation device with a mercury lamp, and the mercury lamp used in the irradiation device deteriorates and has a short lifespan. [Means for solving the problem] As a result of repeated research in order to obtain a dental composition free from the above-mentioned drawbacks, the present inventors have discovered a combination of organic peroxide and pyrylium salts as a photopolymerization initiator. We have discovered an excellent dental composition that polymerizes and cures with visible light. That is, the present invention comprises one or more ethylenically unsaturated compounds, one or more organic peroxides, and a pyrylium salt or thiopyrylium represented by the following general formula [] as a photosensitizer. The present invention provides a visible light curable dental composition comprising one or more salts. [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 ethylenyl group, a styryl group, an alkoxy group, a phenyl group, a naphthyl group, an alkylphenyl group, or an alkoxyphenyl group. group, hydroxyphenyl group, halophenyl group, nitrophenyl group, aminophenyl group,
It represents 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. ] 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-hydroxypropoxy)phenyl]
Propane, bisphenol A dimethacrylate,
2-hydroxy-1,3-dimethacryloxypropane, hexamethylene glycol dimethacrylate, di-2-methacryloxyethyl-2,2,4
- Trimethylhexamethylene dicarbamate, etc. In addition, acrylic acid derivatives, styrene and its derivatives, etc. can also be used in the present invention. The organic peroxide used in the present invention includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule, examples of which include methyl ethyl ketone peroxide, cyclohexanone peroxide, and acetylacetone peroxide. , 1,1-bis(tertiary butyl peroxy)cyclohexane, tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, ditertiary butyl peroxide, tertiary butyl Cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, acetyl peroxide, octanoyl peroxide, lauroyl peroxide, 3,5,5-
Trimethylhexanoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyisobutyrate , tertiary butyl peroxyoctanoate, tertiary butyl peroxybenzoate, ditertiary diperoxy isophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, 3,3',4 , 4'-tetra-(tertiarybutylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(tertiaryamylperoxycarbonyl)benzophenone,
3,3',4,4'-tetra(tertiaryhexylperoxycarbonyl)benzophenone, 3,
3',4,4'-tetra(tertiary octylperoxycarbonyl)benzophenone, 3,3',
4,4'-tetra(cumylperoxycarbonyl)
Examples include benzophenone, 3,3',4,4'-tetra(para-isopropylcumylperoxycarbonyl)benzophenone, and the like. In the pyrylium salt or thiopyrylium salt represented by the general formula [] used in the present invention, Y
Examples of anionic functional groups represented by include perchlorate, fluoroborate, fluorophosphonate, fluoroantimonate, chloroaluminate, sulfur acetate, methosulfate, thiocyanate, sulfate, nitrate, acetate, and the like. Specific examples of the compound represented by the general formula [] include 4-(4-butoxyphenyl)-2,6
-Bis(4-methoxyphenyl)pyrylium fluoroborate, 4-(4-butoxyphenyl)-
2,6-diphenylthiopyrylium fluoroborate, 4-(4-butoxyphenyl)-2,6-bis(4-methoxyphenyl)thiopyrylium fluoroborate, 2,6-bis(4-methoxyphenyl) -4-phenylthiopyrylium fluoroborate, 4-(4-butoxyphenyl)-2,6-
diphenylpyrylium fluoroantimonate,
2-Methyl-4,6-bis(4-methoxyphenyl)thiopyrylium fluoroborate, 2,4,
6-tri(4-methoxyphenyl)thiopyrylium perchlorate, 4-(3,4-diethoxyphenyl)-2,6-bis(4-methoxyphenyl)
Thiopyrylium fluoroborate, 4-(4-dimethylaminophenyl)-2,6-diphenylthiopyrylium perchlorate, 2-nitro-4,
6-bis(4-dimethylaminostyryl)pyrylium fluoroborate, 2-methoxy-4-naphthyl-6-styrylthiopyrylium fluoroborate, 2-amino-4,6-bis(4-butoxyphenyl)thiopyrylium park Loreto, 2-
(4-nitrophenyl)-4,6-bis(4-butylphenyl)thiopyrylium fluoroborate,
2-Hydroxy-4,6-bis(4-dimethylaminostyryl)pyrylium perchlorate, 2-
(3,4-dichlorophenyl)-4-(4-methoxyphenyl)-6-phenylpyrylium fluoroborate and the like. The dental composition of the present invention comprises one or more ethylenically unsaturated compounds, one or more organic peroxides, and one pyrylium salt or thiopyrylium salt as a photosensitizer. species or two
It contains as an active ingredient more than a species,
The composition is such that the concentration of pyrylium salt or thiopyrylium salt as a photosensitizer is 0.0001 to 1% by weight, more preferably 0.001 to 0.5% by weight, based on the ethylenically unsaturated compound. The concentration of photosensitizer
If it is less than 0.0001% by weight, the composition will not be cured by visible light, and if it exceeds 1% by weight, the thickness of the cured layer (cured depth) will decrease, and it is also unfavorable from a sanitary standpoint. The concentration of the organic peroxide is 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, based on the ethylenically unsaturated compound. If this concentration is less than 0.001% by weight, the composition will not be cured, and if it exceeds 10% by weight, 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. Examples of fillers include apatite, soda glass, quartz, silica gel,
These include borosilicate glass, synthetic sapphire (alumina) and radiopaque filler materials such as barium oxide and zirconium glasses, which may be spherical, finely divided, platelets, fibers, whiskers, or have irregular shapes. You may do so. Furthermore, if necessary, appropriate amounts of polymerization inhibitors, antioxidants, stabilizers, pigments, thickeners, etc. may be added in addition to the above-mentioned components. The dental composition of the present invention is easily cured by irradiation with visible light in the wavelength range of 400 nm to 700 nm by using an optimal combination of an organic peroxide and the photosensitizer as a photopolymerization initiator. Any visible light irradiator used in the present invention can be used as long as it emits light having a wavelength within the above-mentioned range, and examples of such light sources include xenon lamps,
There are halogen lights, fluorescent lights, tungsten lights, metal halide lights, and visible laser lights. The dental composition of the present invention is mixed in advance into a single liquid by a supplier, filled into a light-shielded container, and supplied to a doctor. The doctor applies the dental composition of the present invention,
After being filled or molded, it can be polymerized and cured by visible light emitted from an irradiator. [Effects of the Invention] Since the dental composition of the present invention uses a specific photopolymerization initiator, it is easily cured in a short time by visible light, and has a cure depth of 5 mm or more, which is excellent for dental use. In addition to safety,
It is also excellent in terms of clinical operability and economy. [Examples] The present invention will be explained in more detail below using 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 ratios shown in Table 1. This composition was filled in a polyethylene cylinder with an inner diameter of 10 mm and a depth of 10 mm, and polymerized and cured by irradiating visible light from a distance of 3 mm from the top of the cylinder using a dental halogen lamp (150 watts, maximum emission wavelength 490 nm). 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 substances, 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 cured to a sufficient hardening depth (5 mm or more) by irradiation with visible light for a short period of about 20 to 40 seconds. It can be seen that it is excellent as a 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. The results are shown in Table 2, and it was found that if the amount of organic peroxide or photosensitizer used in the present invention is below a predetermined concentration, the composition will not harden and there will be no effect. Even if the amount exceeds a predetermined concentration, sufficient hardening depth cannot be obtained. Even if a conventional ultraviolet ray photosensitizer is used, it will not cure under visible light.

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[Table] Other abbreviations are the same as in Table-1.

Claims (1)

[Scope of Claims] 1. One or more ethylenically unsaturated compounds, one or more organic peroxides, and a pyrylium salt or pyrylium salt represented by the following general formula [] as a photosensitizer. A visible light-curable dental composition comprising one or more thiopyrylium salts. [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 ethylenyl group, a styryl group, an alkoxy group, a phenyl group, a naphthyl group, an alkylphenyl group, or an alkoxyphenyl group. group, hydroxyphenyl group, halophenyl group, nitrophenyl group, aminophenyl group,
It represents 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(3-methacryloxy-2-hydroxypropoxy)ethane The composition according to claim 1, 2, or 3, which is one or more selected from the following.