JP6925601B2 - Dental visible light polymerizable composition - Google Patents

Description

The present invention relates to a dental visible light polymerizable composition. More specifically, the present invention relates to a visible light polymerizable composition having a small mechanical strength at the time of curing and a shrinkage stress at the time of curing. The dental visible light polymerizable composition according to the present invention is preferably suitable as a dental filling restoration material, a dental cement, a dental adhesive, a dental abutment construction material, etc., particularly as a dental filling restoration material. It is used for.

Polymer materials using photopolymerization are widely used as paints, printing, adhesives, semiconductors, dental materials and the like. The useful points as compared with the polymer material using heat are that local polymerization is possible and that the time from the start to the completion of polymerization is relatively short. On the other hand, since the polymerization rate is very high, a large amount of stress is applied to peripheral members such as a mold, which causes problems such as peeling and deformation.

In order to solve this problem, methods such as reduction of the concentration of polymerizable groups and reduction of the polymerization rate by adding a chain transfer agent have been considered. Although it is possible to reduce the polymerization shrinkage stress by these methods, the strength of the polymer material is also reduced. For this reason, a new problem has arisen when applied to a material requiring high mechanical strength, particularly a dental material.

In the treatment of dental caries and associated defects, restorations are generally performed using dental adhesives and dental filling restoration materials. Restorative treatment is performed by the following procedure. That is, first, the carious portion is scraped to form a cavity, then a dental adhesive is applied to the cavity, dried, and irradiated with visible light to cure. Subsequently, the dental filling restoration material is filled on the cured adhesive layer, and the filler is cured by photopolymerization by irradiating with visible light.

In the above-mentioned treatment, there is a problem that a large contraction stress associated with hardening due to polymerization of the dental filling restoration material causes exfoliation from the dentin and, in the worst case, falls off from the tooth cavity. Therefore, a dental filling restoration material having a low shrinkage stress has been required.

In recent years, various studies have been conducted to develop dental filling restoration materials having low shrinkage stress. For example, it has been proposed to reduce the concentration of polymerizable groups in a dental filler by blending a bulky dendritic compound (for example, Patent Document 1). However, in this method, in order to obtain a sufficient effect, it is necessary to add a large amount of the dendritic compound, and by adding a large amount of the dendritic compound, the crosslink density of the dental filling restoration material is increased. There was a problem that it was small and its mechanical strength was insufficient.

In addition to this, a method of blending a polymerizable monomer with ring opening during polymerization has been proposed (for example, Patent Document 2). However, the structure of such a polymerizable monomer is limited, and it is difficult to design a dental filler in consideration of various physical characteristics. In particular, many polymerizable monomers have a low-strength skeleton, and it is very difficult to achieve both high strength and low shrinkage stress.

Further, a method of blending a chain transfer agent in order to adjust the rate of polymerization has been proposed (for example, Patent Document 3). However, when such a chain transfer agent is blended, there is a problem that the final degree of polymerization is lowered and the mechanical strength of the cured product is lowered.

Further, a composition containing an α-diketone compound as a compound having a quinone structure is known (for example, Patent Document 4), and the α-diketone compound is blended for the purpose of use as a photosensitizer. In addition to α-diketone compounds, single molecule cleavage type photopolymerization initiators such as acylphosphine oxide are also generally known. However, in the embodiment in which a compound having a quinone structure other than the α-diketone compound is used in combination with the polymerization initiator composed of a combination of the α-diketone compound and the amine compound, or in addition to the single molecule cleavage type photopolymerization initiator, the α-diketone compound is further added. No description or suggestion has been made regarding the mode in which a compound having a quinone structure other than the above is used in combination.

Japanese Unexamined Patent Publication No. 2006-298919 Japanese Unexamined Patent Publication No. 5-255442 Japanese Unexamined Patent Publication No. 2009-227591 Japanese Unexamined Patent Publication No. 2014-231493

An object of the present invention is to provide a dental visible light polymerizable composition having sufficient mechanical strength and low shrinkage stress during curing.

The present inventors have conducted diligent studies in order to solve the above problems. As a result, it has a polymerization initiator or a single molecule cleavage type photopolymerization initiator composed of a combination of a (meth) acrylic group-containing polymerizable monomer and an α-diketone compound and an amine compound, and a quinone structure other than the α-diketone compound. We have found that the visible photopolymerizable composition containing a compound has sufficient strength and low shrinkage stress during curing, and has completed the present invention.

That is, the present invention comprises (a) a bifunctional aromatic (meth) acrylic group-containing polymerizable monomer and / or a bifunctional aliphatic (meth) acrylic group-containing polymerizable monomer (meth) acrylic. It comprises a group-containing polymerizable monomer, a first polymerization initiator composed of a combination of (b) (b1) α-diketone compound and (b2) amine compound, or (b3) a single molecule cleavage type photopolymerization initiator. A polymerization initiator selected from any of the second polymerization initiators, (c) a compound having a quinone structure other than the α-diketone compound , including a 1,4-naphthoquinone compound or a 9,10-anthraquinone compound. (1) The above (b1) and (c) with respect to (a) 100 parts by mass of the above (a) when the visible photopolymerizable composition contains the first polymerization initiator. ) Is 0.2 to 2.0 parts by mass, and (2) the (a) 100 parts by mass of the above (a) when the visible photopolymerizable composition contains the second polymerization initiator. A dental visible photopolymerizable composition, wherein the total amount of b3) and (c) is 0.2 to 2.0 parts by mass.

According to the present invention, there is provided a visible light polymerizable composition having sufficient mechanical strength and low shrinkage stress during curing.

The visible light polymerizable composition according to the present invention can be usefully used as various curable materials used in dental materials by utilizing the property that the shrinkage stress due to the polymerization is extremely small. Specific examples thereof include dental filling restoration materials, dental cements, dental adhesives, dental abutment construction materials, etc., and in particular, when the tooth cavity is filled and cured, it is cured. It is most useful as a dental filling restoration material because it is difficult for a gap to be formed between the body and the inner wall of the tooth cavity and the occurrence of secondary caries can be greatly reduced.

The visible photopolymerizable composition according to the present invention is a composition that can be polymerized by irradiating with visible light (about 400 nm to 700 nm), and (a) (meth) acrylic group-containing polymerizable monomer. A polymerization initiator selected from either (b) a polymerization initiator composed of a combination of (b1) an α-diketone compound and (b2) an amine compound, or (b3) a single molecule cleavage type photopolymerization initiator, and (b3). c ) It comprises a 1,4-naphthoquinone compound or a 9,10-anthraquinone compound, which is a compound having a quinone structure other than the α-diketone compound.

Hereinafter, each component of the visible light polymerizable composition of the present invention will be described.
(A) (Meta) Acryloyl Group-Containing Polymerizable Monomer The (meth) acrylic group-containing polymerizable monomer can be appropriately selected from known compounds and used. Among them, a polyfunctional polymerizable monomer having a plurality of (meth) acrylic groups is preferably used from the viewpoint of improving the curing rate, the mechanical properties of the cured product, the water resistance, the coloring resistance, and the like. Typical examples of the polyfunctional (meth) acrylic group-containing polymerizable monomer are the bifunctional polymerizable monomer, the trifunctional polymerizable monomer, and the tetrafunctional polymerization shown in (1) to (3) below. Sexual monomers can be mentioned.

(1) Bifunctional Polymerizable Monomer Examples of the bifunctional polymerizable monomer include an aromatic compound-based polymerizable monomer and an aliphatic compound-based polymerizable monomer.

Examples of the aromatic compound-based polymerizable monomer include 2,2'-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane and 2,2'-bis [4. -(Meta) acryloyloxyphenyl] propane, 2,2'-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 2,2'-bis [4- (meth) acryloyloxydiethoxyphenyl] propane, 2,2'-bis [4- (meth) acryloyloxytetraethoxyphenyl] propane, 2,2'-bis [4- (meth) acryloyloxypentaethoxyphenyl] propane, 2,2'-bis [4-( Meta) acryloyloxydipropoxyphenyl] propane, 2,2'-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane, 2- [4- (meth) acryloyloxydiethoxyphenyl] -2- [4- (Meta) cryloyloxytriethoxyphenyl] propane, 2- [4- (meth) acryloyloxydipropoxyphenyl] -2- [4- (meth) cryloyloxytriethoxyphenyl] propane, 2,2-bis [ Examples thereof include 4- (meth) chryloyloxypropoxyphenyl] propane; and diadect obtained from the addition of an OH group-containing vinyl monomer and an aliphatic diisocyanate compound.

Examples of the OH group-containing vinyl monomer include methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 3-chloro-2-hydroxypropyl methacrylate, and acrylates corresponding to these methacrylates. Examples of the diisocyanate include diisocyanate methylbenzene and 4,4'-diphenylmethane diisocyanate.

Examples of the aliphatic compound-based polymerizable monomer include 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene. Glycoldimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates, 1,8-octane. Methacrylates such as diol dimethacrylate, 1,10-decanediol dimethacrylate, ethylene glycol diglycidyl ether dimethacrylate, acrylates corresponding to these methacrylates; And so on.

Examples of the OH group-containing vinyl monomer include those similar to those exemplified above, and examples of the aliphatic diisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, and isophorone diisocyanate. , Methylene bis (4-cyclohexamethylene diisocyanate) and the like.

(2) Trifunctional polymerizable monomer Examples of the trifunctional polymerizable monomer include methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, and trimethylolmethane trimethacrylate; Examples thereof include acrylates corresponding to these methacrylates.

(3) Tetrafunctional Polymerizable Monomer Examples of the tetrafunctional polymerizable monomer include pentaerythritol tetramethritol, pentaerythritol tetraacrylate; and diadect obtained from an adduct of a diisocyanate compound and glycidol dimethacrylate. Can be mentioned.

Examples of the diisocyanate compound include diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 4,4-diphenylmethane diisocyanate, and trilene-2,4. − Diisocyanate and the like can be mentioned. Further, if necessary, a monofunctional (meth) acrylate-based polymerizable monomer may be used.

Examples of the monofunctional (meth) acrylate-based polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. Examples thereof include glycidyl (meth) acrylate.

When a large amount of hydrophobic polymerizable monomer is contained as the polymerizable monomer, an amphipathic polymerizable monomer may be used in combination.

Examples of the amphoteric (meth) acrylate-based polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethylene glycol di (meth) acrylate (polyethylene glycol polymerization degree 9 to 9 to). 50), 1,2,3,4-butanetetraol-1,4-di (meth) acrylate and the like can be mentioned. These polyfunctional (meth) acrylate-based polymerizable monomers may be used alone or in combination of two or more.

(B) Polymerization Initiator The visible light polymerization composition of the present invention comprises a combination of an α-diketone compound and an amine compound as a polymerization initiator in order to polymerize a (meth) acrylic group-containing polymerizable monomer. A polymerization initiator selected from either a polymerization initiator or a single molecule cleavage type photopolymerization initiator is blended. Above all, a polymerization initiator composed of a combination of an α-diketone compound and an amine compound is preferably used from the viewpoint of efficiently absorbing visible light and initiating polymerization. In addition, both a polymerization initiator composed of a combination of an α-diketone compound and an amine compound and a single molecule cleavage type photopolymerization initiator may be used in combination.

Hereinafter, the polymerization initiator that can be used in the present invention will be described.
(B1) α-diketone compound The α-diketone compound that can be used in the visible light polymerization composition of the present invention is a compound that is excited by light irradiation and initiates polymerization together with the (b2) amine compound. Species or two or more species can be used.

Typical examples include camphorquinone, camphorquinone carboxylic acid, camphorquinone sulfonic acid, benzyl, diacetyl, acetylbenzoyl, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrene quinone, acenaphthenquinone and the like. Can be mentioned. Above all, camphorquinone is preferably used from the viewpoint of efficiently absorbing visible light. Further, two or more kinds of α-diketone compounds can be used in combination. These α-diketone compounds may be used alone or in combination of two or more.

(B1) If the blending amount of the α-diketone compound is too large, curing proceeds under ambient light, and sufficient operation time cannot be obtained, and if it is too small, sufficient curability cannot be obtained. The blending amount of the (b1) α-diketone compound, which is unlikely to cause these problems, is in the range of 0.1 to 2.0 parts by mass per 100 parts by mass of the (a) (meth) acrylic group-containing polymerizable monomer. It is preferably used in the range of 0.2 to 0.5 parts by mass.

(B2) Amine Compound The amine compound that can be used in the visible light polymerization composition of the present invention is a compound that initiates polymerization together with the (b1) α-diketone compound that has been excited by light irradiation, and these are one kind. Alternatively, two or more types can be used.

As the amine compound, known ones can be used without limitation, and may be any of primary amine, secondary amine and tertiary amine, and may be either aliphatic amine or aromatic amine. .. When used for dentistry, there are few problems such as odor, so a secondary or tertiary amine compound is generally used, and a tertiary amine compound is particularly preferable. These can be used alone or in combination of two or more.

Typical examples are aliphatic primary amine compounds such as 2-ethylhexylamine, n-butylamine, n-hexylamine, n-octylamine; diethylamine, dibutylamine, diallylamine, diisopropylamine, di-2-ethylhexylamine, Aliphatic secondary amine compounds such as di-n-octylamine; triethylamine, tributylamine, triallylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N-methyldiethanolamine, N-ethyldiethanolamine , N-propyldiethanolamine, N-ethyldialylamine, N-ethyldibenzylamine, dimethylethanolamine, diethylethanolamine, dipropylethanolamine, triethanolamine, tri (isopropanol) amine, tri (2-hydroxybutyl) amine, Tertiary amine compounds such as tribenzylamine; secondary aromatic amine compounds such as N-methylaniline, N-methyl-p-toluidine; N, N-dimethylaniline, N, N-diethylaniline, N, N -Di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo- N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylamino Amyl benzoate, N, N-dimethylanthranic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostylben, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 2,2 '-(N-Butylimi C) It is a tertiary aromatic amine compound such as diethanol, and more preferably N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine. , N-Ethyldiallylamine, N-ethyldibenzylamine, dimethylethanolamine, diethylethanolamine, triethanolamine, triethylamine, tributylamine. These amine compounds may be used alone or in combination of two or more.

(B2) If the blending amount of the amine compound is too large, problems of odor and coloring occur, and if it is too small, sufficient curability cannot be obtained. The blending amount of the (b2) amine compound that does not cause these problems is preferably in the range of 0.01 to 10 parts by mass per 100 parts by mass of the (a) (meth) acrylic group-containing polymerizable monomer. In particular, it is more preferable to use it in the range of 0.02 to 5 parts by mass.

(B3) Single-Molecular Cleavage Photopolymerization Initiator The single-molecule-cleaving photopolymerization initiator that can be used in the visible photopolymerization composition of the present invention is a compound that independently cleaves and initiates polymerization by light irradiation. These can be used alone or in combination of two or more. It is a single molecule cleavage type polymerization initiator, and an acylphosphine oxide-based polymerization initiator is preferable.

Representative examples include monoacylphosphine oxide, bisacylphosphine oxide, acetophenone derivative, benzyldimethylketal derivative, α-hydroxyketone derivative, α-aminoketone derivative, acylphosphine oxide derivative, and acylgerman derivative. These single molecule cleavage type photopolymerization initiators may be used alone or in combination of two or more.

(C) Compound having a quinone structure other than the α-diketone compound The greatest feature of the present invention is the (a) (meth) acrylic group-containing polymerizable monomer, (b1) α-diketone compound and (b2) amine. In a system containing a polymerization initiator selected from either a polymerization initiator composed of a combination with a compound or (b3) a single molecule cleavage type photopolymerization initiator, quinones other than the (c) α-diketone compound are further added. The point is that a compound having a structure is blended. By coexisting each component, the effect of achieving both high curability and low polymerization shrinkage stress is produced. The reason for this effect is presumed as follows. That is, a compound having a quinone structure other than the α-diketone compound acts as a chain transfer agent by accepting hydrogen atoms and radical species of the (meth) acrylic group-containing polymerizable monomer during polymerization, and also absorbs visible light. It has a function as a radical generator that takes in energy from the activated α-diketone compound or a single molecule cleavage type polymerization initiator and generates radical species. Therefore, it is considered that both high curability and low polymerization shrinkage stress can be achieved at the same time.

In the present invention, the compounds having a quinone structure other than α- diketone compound, in a multi-cyclic compound of monocyclic or aromatic aromatic excluding α- diketone compound means a compound having two ketone structure .. In the present invention, a 1,4-naphthoquinone compound or a 9,10-anthraquinone compound is used as such a compound. These can be used alone or in combination of two or more.

Specifically, the 1,4-naphthoquinone compound and the 9,10-anthraquinone compound exemplified below are exemplified as preferable compounds. Typical examples are 1,4-naphthoquinone, 5-methyl-1,4-naphthoquinone, 6-methyl-1,4-naphthoquinone, 6,7-dimethyl-1,4-naphthoquinone, 5-butyl-1,4. -Naphthoquinone, 6-butyl-1,4-naphthoquinone, 6,7-dibutyl-1,4-naphthoquinone, 5-pentyl-1,4-naphthoquinone, 6-pentyl-1,4-naphthoquinone, 5-chloro-1 , 4-Naphthoquinone, 6-chloro-1,4-naphthoquinone, 6,7-dichloro-1,4-naphthoquinone, 5-hydroxy-1,4-naphthoquinone, 6-hydroxy-1,4-naphthoquinone, 5,8 -Dihydroxy-1,4-naphthoquinone, 5,6,8-trihydroxy-1,4-naphthoquinone, 5-methoxy-1,4-naphthoquinone, 6-methoxy-1,4-naphthoquinone, 5,8-dimethoxy- 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, 2-ethyl-1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, 2-methoxy-1,4-naphthoquinone, 2-chloro- 1,4-Naphthoquinone, 2-amino-1,4-naphthoquinone, 2,5-dimethyl-1,4-naphthoquinone, 2,6-dimethyl-1,4-naphthoquinone, 2,6,7-trimethyl-1, 4-Naphthoquinone, 2-methyl-5-butyl-1,4-naphthoquinone, 2-methyl-6-butyl-1,4-naphthoquinone, 2-methyl-6,7-dibutyl-1,4-naphthoquinone, 2- Methyl-5-pentyl-1,4-naphthoquinone, 2-methyl-6-pentyl-1,4-naphthoquinone, 2-methyl-5-chloro-1,4-naphthoquinone, 2-methyl-6-chloro-1, 4-Naphthoquinone, 2-methyl-6,7-dichloro-1,4-naphthoquinone, 2-methyl-5-hydroxy-1,4-naphthoquinone, 2-methyl-6-hydroxy-1,4-naphthoquinone, 2- Methyl-5,8-dihydroxy-1,4-naphthoquinone, 2-methyl-5,6,8-trihydroxy-1,4-naphthoquinone, 2-methyl-5-methoxy-1,4-naphthoquinone, 2-methyl -6-methoxy-1,4-naphthoquinone, 2-methyl-5,8-dimethoxy-1,4-naphthoquinone, 2-hydroxy-5-methyl-1,4-naphthoquinone, 2-ethyl-5-methyl-1 , 4-Naphthoquinone, 2-ethyl-6-methyl-1,4-naphthoquinone, 2-ethyl-6,7-dimethyl-1,4-naphthoquinone, 2-Ethyl-5-butyl-1,4-naphthoquinone, 2-ethyl-6-butyl-1,4-naphthoquinone, 2-ethyl-6,7-dibutyl-1,4-naphthoquinone, 2-ethyl-5- Pentyl-1,4-naphthoquinone, 2-ethyl-6-pentyl-1,4-naphthoquinone, 2-ethyl-5-chloro-1,4-naphthoquinone, 2-ethyl-6-chloro-1,4-naphthoquinone, 2-Ethyl-6,7-dichloro-1,4-naphthoquinone, 2-ethyl-5-hydroxy-1,4-naphthoquinone, 2-ethyl-6-hydroxy-1,4-naphthoquinone, 2-ethyl-5, 8-Dihydroxy-1,4-naphthoquinone, 2-ethyl-5,6,8-trihydroxy-1,4-naphthoquinone, 2-ethyl-5-methoxy-1,4-naphthoquinone, 2-ethyl-6-methoxy -1,4-naphthoquinone, 2-ethyl-5,8-dimethoxy-1,4-naphthoquinone, 2-hydroxy-6-methyl-1,4-naphthoquinone, 2-hydroxy-6,7-dimethyl-1,4 -Naftquinone, 2-hydroxy-5-butyl-1,4-naphthoquinone, 2-hydroxy-6-butyl-1,4-naphthoquinone, 2-hydroxy-6,7-dibutyl-1,4-naphthoquinone, 2-hydroxy -5-Pentyl-1,4-naphthoquinone, 2-hydroxy-6-pentyl-1,4-naphthoquinone, 2-hydroxy-5-chloro-1,4-naphthoquinone, 2-hydroxy-6-chloro-1,4 -Naftquinone, 2-hydroxy-6,7-dichloro-1,4-naphthoquinone, 2,5-dihydroxy-1,4-naphthoquinone, 2,6-dihydroxy-1,4-naphthoquinone, 2,5,8-tri Hydroxy-1,4-naphthoquinone, 2,5,6,8-tetrahydroxy-1,4-naphthoquinone, 2-hydroxy-5-methoxy-1,4-naphthoquinone, 2-hydroxy-6-methoxy-1,4 -Naftquinone, 2-hydroxy-5,8-dimethoxy-1,4-naphthoquinone, 2-methoxy-5-methyl-1,4-naphthoquinone, 2-methoxy-6-methyl-1,4-naphthoquinone, 2-methoxy -6,7-Dimethyl-1,4-naphthoquinone, 2-methoxy-5-butyl-1,4-naphthoquinone, 2-methoxy-6-butyl-1,4-naphthoquinone, 2-methoxy-6,7-dibutyl -1,4-naphthoquinone, 2-methoxy-5-pentyl-1,4-naphthoquinone, 2-methoxy-6-pe Ntyl-1,4-naphthoquinone, 2-methoxy-5-chloro-1,4-naphthoquinone, 2-methoxy-6-chloro-1,4-naphthoquinone, 2-methoxy-6,7-dichloro-1,4- Naphthoquinone, 2-methoxy-5-hydroxy-1,4-naphthoquinone, 2-methoxy-6-hydroxy-1,4-naphthoquinone, 2-methoxy-5,8-dihydroxy-1,4-naphthoquinone, 2-methoxy- 5,6,8-Trihydroxy-1,4-naphthoquinone, 2,5-dimethoxy-1,4-naphthoquinone, 2,6-dimethoxy-1,4-naphthoquinone, 2,5,8-trimethoxy-1,4 -Naphthoquinone, 2-chloro-5-methyl-1,4-naphthoquinone, 2-chloro-6-methyl-1,4-naphthoquinone, 2-chloro-6,7-dimethyl-1,4-naphthoquinone, 2-chloro -5-butyl-1,4-naphthoquinone, 2-chloro-6-butyl-1,4-naphthoquinone, 2-chloro-6,7-dibutyl-1,4-naphthoquinone, 2-chloro-5-pentyl-1 , 4-Naphthoquinone, 2-chloro-6-pentyl-1,4-naphthoquinone, 2,5-dichloro-1,4-naphthoquinone, 2,6-dichloro-1,4-naphthoquinone, 2,6,7-trichloro -1,4-naphthoquinone, 2-chloro-5-hydroxy-1,4-naphthoquinone, 2-chloro-6-hydroxy-1,4-naphthoquinone, 2-chloro-5,8-dihydroxy-1,4-naphthoquinone , 2-Chloro-5,6,8-trihydroxy-1,4-naphthoquinone, 2-chloro-5-methoxy-1,4-naphthoquinone, 2-chloro-6-methoxy-1,4-naphthoquinone, 2- Chloro-5,8-dimethoxy-1,4-naphthoquinone, 2-amino-5-methyl-1,4-naphthoquinone, 2-amino-6-methyl-1,4-naphthoquinone, 2-amino-6,7- Dimethyl-1,4-naphthoquinone, 2-amino-5-butyl-1,4-naphthoquinone, 2-amino-6-butyl-1,4-naphthoquinone, 2-amino-6,7-dibutyl-1,4- Naphthoquinone, 2-amino-5-pentyl-1,4-naphthoquinone, 2-amino-6-pentyl-1,4-naphthoquinone, 2-amino-5-chloro-1,4-naphthoquinone, 2-amino-6- Chloro-1,4-naphthoquinone, 2-amino-6,7-dichloro-1,4-naphthoquinone, 2-amino-5-hydroxy-1,4-naphthoquinone, 2-a Mino-6-hydroxy-1,4-naphthoquinone, 2-amino-5,8-dihydroxy-1,4-naphthoquinone, 2-amino-5,6,8-trihydroxy-1,4-naphthoquinone, 2-amino -5-methoxy-1,4-naphthoquinone, 2-amino-6-methoxy-1,4-naphthoquinone, 2-amino-5,8-dimethoxy-1,4-naphthoquinone, 2,3-dimethyl-1,4 -Naphthoquinone, 2,3-diethyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-1,4-naphthoquinone, 2-methyl-3-methoxy-1,4-naphthoquinone, 2,3-dihydroxy-1 , 4-Naphthoquinone, 2,3-dimethoxy-1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, 2-amino-3-chloro-1,4-naphthoquinone, 2,3,6-trimethyl -1,4-naphthoquinone, 2,3,6,7-tetramethyl-1,4-naphthoquinone, 2,3-dimethyl-5-butyl-1,4-naphthoquinone, 2,3-dimethyl-6-butyl- 1,4-Naphthoquinone, 2,3-dimethyl-6,7-dibutyl-1,4-naphthoquinone, 2,3-dimethyl-5-pentyl-1,4-naphthoquinone, 2,3-dimethyl-6-pentyl- 1,4-Naphthoquinone, 2,3-dimethyl-5-chloro-1,4-naphthoquinone, 2,3-dimethyl-6-chloro-1,4-naphthoquinone, 2,3-dimethyl-6,7-dichloro- 1,4-Naphthoquinone, 2,3-dimethyl-5-hydroxy-1,4-naphthoquinone, 2,3-dimethyl-6-hydroxy-1,4-naphthoquinone, 2,3-dimethyl-5,8-dihydroxy- 1,4-Naphthoquinone, 2,3-dimethyl-5,6,8-trihydroxy-1,4-naphthoquinone, 2,3-dimethyl-5-methoxy-1,4-naphthoquinone, 2,3-dimethyl-6 −methoxy-1,4-naphthoquinone, 2,3-dimethyl-5,8-dimethoxy-1,4-naphthoquinone, 2,6-dimethyl-3-hydroxy-1,4-naphthoquinone, 2,6,7-trimethyl -3-hydroxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-butyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-6-butyl-1,4-naphthoquinone, 2-methyl -3-hydroxy-6,7-dibutyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-pentyl-1,4-naphthoquinone, 2-methyl-3-hydroquinone C-6-Pentyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-5-chloro-1,4-naphthoquinone, 2-methyl-3-hydroxy-6-chloro-1,4-naphthoquinone, 2- Methyl-3-hydroxy-6,7-dichloro-1,4-naphthoquinone, 2-methyl-3,5-dihydroxy-1,4-naphthoquinone, 2-methyl-3,6-dihydroxy-1,4-naphthoquinone, 2-Methyl-3,5,8-trihydroxy-1,4-naphthoquinone, 2-methyl-3,5,6,8-tetrahydroxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-5- Methyl-1,4-naphthoquinone, 2-methyl-3-hydroxy-6-methoxy-1,4-naphthoquinone, 2-methyl-3-hydroxy-5,8-dimethoxy-1,4-naphthoquinone, 2,3- Dichloro-6-methyl-1,4-naphthoquinone, 2,3-dichloro-6,7-dimethyl-1,4-naphthoquinone, 2,3-dichloro-5-butyl-1,4-naphthoquinone, 2,3- Dichloro-6-butyl-1,4-naphthoquinone, 2,3-dichloro-6,7-dibutyl-1,4-naphthoquinone, 2,3-dichloro-5-pentyl-1,4-naphthoquinone, 2,3- Dichloro-6-pentyl-1,4-naphthoquinone, 2,3,5-trichloro-1,4-naphthoquinone, 2,3,6-trichloro-1,4-naphthoquinone, 2,3,6,7-tetrachloro -1,4-naphthoquinone, 2,3-dichloro-5-hydroxy-1,4-naphthoquinone, 2,3-dichloro-6-hydroxy-1,4-naphthoquinone, 2,3-dichloro-5,8-dihydroxy -1,4-naphthoquinone, 2,3-dichloro-5,6,8-trihydroxy-1,4-naphthoquinone, 2,3-dichloro-5-methoxy-1,4-naphthoquinone, 2,3-dichloro- 6-methoxy-1,4-naphthoquinone, 2,3-dichloro-5,8-dimethoxy-1,4-naphthoquinone, 2-amino-3-chloro-6-methyl-1,4-naphthoquinone, 2-amino- 3-Chloro-6,7-dimethyl-1,4-naphthoquinone, 2-amino-3-chloro-5-butyl-1,4-naphthoquinone, 2-amino-3-chloro-6-butyl-1,4- Naftquinone, 2-amino-3-chloro-6,7-dibutyl-1,4-naphthoquinone, 2-amino-3-chloro-5-pentyl-1,4-naphthoquinone, 2-amino-3-chloro-6- pen Chill-1,4-naphthoquinone, 2-amino-3-chloro-5-chloro-1,4-naphthoquinone, 2-amino-3,6-dichloro-1,4-
Naphthoquinone, 2-amino-3,6,7-trichloro-1,4-naphthoquinone, 2-amino-3-chloro-5-hydroxy-1,4-naphthoquinone, 2-amino-3-chloro-6-hydroxy- 1,4-Naphthoquinone, 2-amino-3-chloro-5,8-dihydroxy-1,4-naphthoquinone, 2-amino-3-chloro-5,6,8-trihydroxy-1,4-naphthoquinone, 2, −Amino-3-chloro-5-methoxy-1,4-naphthoquinone, 2-amino-3-chloro-6-methoxy-1,4-naphthoquinone, 2-amino-3-chloro-5,8-dimethoxy-1 , 4-Naphthoquinone and other naphthoquinone compounds, 9,10-anthraquinone, 1,4-dihydro-9,10-anthraquinone, 2-methyl-1,4-dihydro-9,10-anthraquinone, 2-chloro-1,4 −Dihydro-9,10-anthraquinone, 6-methyl-1,4-dihydro-9,10-anthraquinone, 2,6-dimethyl-1,4-dihydro-9,10-anthraquinone, 2-chloro-6-methyl -1,4-dihydro-9,10-anthraquinone, 2,6-dichloro-1,4-dihydro-9,10-anthraquinone, 1,2,3,4-tetrahydro-9,10-anthraquinone, 2-methyl -1,2,3,4-tetrahydro-9,10-anthraquinone, 2-chloro-1,2,3,4-tetrahydro-9,10-anthraquinone, 6-methyl-1,2,3,4-tetrahydro -9,10-anthraquinone, 2,6-dimethyl-1,2,3,4-tetrahydro-9,10-anthraquinone, 2-chloro-6-methyl-1,2,3,4-tetrahydro-9,10 -Antraquinone, 2,6-dichloro-1,2,3,4-tetrahydro-9,10-anthraquinone, 9,10-anthraquinone, 2-methyl-9,10-anthraquinone, 2-chloro-9,10-anthraquinone , 6-Methyl-9,10-anthraquinone, 2,6-dimethyl-9,10-anthraquinone, 2-chloro-6-methyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, 1, , 4-Dihydro-9,10-anthraquinone, 1,2,3,4-tetrahydro-9,10-anthraquinone, 2-methyl-1,4-dihydro-9,10-anthraquinone, 2-methyl-1,2 , 3,4-Tetrahydro-9,10-anthraquinone, 2-chloro-1,4-dihydro-9, Examples thereof include anthraquinone compounds such as 10-anthraquinone and 2-chloro-1,2,3,4-tetrahydro-9,10-anthraquinone. The compounds having a quinone structure other than these α-diketone compounds may be used alone or in combination of two or more.

(C) If the compounding amount of the compound having a quinone structure other than the α-diketone compound is too large, a coloring problem occurs, and if it is too small, a sufficient effect of reducing the polymerization shrinkage stress tends not to be obtained. Further, it is sufficient that the total amount of the compounding amount of the (b1) α-diketone compound or (b3) single molecule cleavage type photopolymerization initiator and the compound having a quinone structure other than (c) α-diketone compound is too small. Hard to obtain curability. Therefore, the blending amount of the compound having a quinone structure other than the (c) α-diketone compound is 0.2 to 2.0 parts by mass per 100 parts by mass of the (a) (meth) acrylic group-containing polymerizable monomer. Is preferable.

When the polymerization initiator is a combination of (b1) α-diketone and (b2) amine compound, the total amount of (b1) α-diketone compound and compound having a quinone structure other than (c) α-diketone compound is (a). ) (Meta) The amount is preferably 0.2 parts by mass or more with respect to 100 parts by mass of the acrylic group-containing polymerizable monomer, and more preferably 0.2 to 2.0 parts by mass. .. Further, the compounding ratio of the (b1) α-diketone compound and the compound having a quinone structure other than the (c) α-diketone compound, that is, the (b1) α-diketone compound: the quinone structure other than the (c) α-diketone compound. The compound having is preferably used in the range of 80:20 to 20:80, and more preferably used in the range of 60:40 to 40:60.

When the polymerization initiator is (b3) a single molecule cleavage type photopolymerization initiator, the total amount of (b3) the single molecule cleavage type photopolymerization initiator and (c) a compound having a quinone structure other than the α-diketone compound is (b3). a) The amount is preferably 0.2 parts by mass or more, and more preferably 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the (meth) acrylic group-containing polymerizable monomer. preferable. Further, the compounding ratio of (b3) the single molecule cleaving type photopolymerization initiator and (c) the compound having a quinone structure other than the α-diketone compound, that is, (b3) the single molecule cleaving type photopolymerization initiator: (c). Compounds having a quinone structure other than the α-diketone compound are preferably used in the range of 80:20 to 20:80, and more preferably in the range of 60:40 to 40:60.

When both a polymerization initiator composed of a combination of (b1) α-diketone and (b2) an amine compound and (b3) a single molecule cleavage type photopolymerization initiator are used in combination as the polymerization initiator, (b1) The total amount of the α-diketone, the (b3) single molecule cleavage type photopolymerization initiator and the compound having a quinone structure other than the (c) α-diketone compound is 100 mass of the (a) (meth) acrylic group-containing polymerizable monomer. It is preferably 0.2 parts by mass or more, and more preferably 0.2 to 2.0 parts by mass. Further, the total amount of (b1) α-diketone and (b3) single molecule cleavage type photopolymerization initiator and the compounding ratio of the compound having a quinone structure other than (c) α-diketone compound, that is, ((b1)). α-diketone + (b3) single molecule cleaving type photopolymerization initiator): (c) Compounds having a quinone structure other than the α-diketone compound are preferably used in the range of 80:20 to 20:80, 60. It is more preferable to use it in the range of: 40 to 40:60.

The visible light polymerizable composition of the present invention is a compound having a quinone structure other than the above-mentioned (a) (meth) acrylic group-containing polymerizable monomer, (b) polymerization initiator, and (c) α-diketone compound. In addition, (d) filler can be optionally contained.

The filler (d) is not particularly limited and may be appropriately selected from known compounds and used, and examples thereof include an inorganic filler, an organic-inorganic filler, and an organic filler.

Examples of the inorganic filler include silica, zirconia, titania, silica-zirconia, silica-titania, barium glass, strontium glass, lanthanum glass, fluoroaluminosilicate glass, and itterbium fluoride.

The average particle size of these inorganic fillers is not particularly limited and may be 0.01 μm to 1000 μm, which is the size generally used as a dental material, but 0.01 μm to 5 μm is preferable. Further, the refractive index of the filler is not particularly limited, and may be 1.4 to 1.7 which is possessed by a general dental filler.

The shape of these inorganic fillers is not particularly limited and may be amorphous, spherical or substantially spherical, but a spherical inorganic filler is particularly preferable from the viewpoint of polishability.

The organic-inorganic composite filler is a granular material obtained by adding a polymerizable monomer to the above-mentioned inorganic filler in advance, forming a paste, polymerizing the mixture, and pulverizing the mixture, or agglomerated particles of the inorganic filler. Is impregnated with the polymerizable monomer and then polymerized to be used. Further, as the organic filler, granules obtained by polymerizing the above-mentioned polymerizable monomer are used.

The average particle size of these organic-inorganic composite fillers and organic fillers is not particularly limited and may be 0.1 μm to 1000 μm, which is a size generally used as a dental material, but 0.1 μm to 0.1 μm. 500 μm is preferable. Further, the refractive index of the filler is not particularly limited, and may be 1.4 to 1.7 which is possessed by a general dental filler. The filler may be used alone, or may be used in combination with a plurality of fillers having different particle size ranges, average particle diameters, refractive indexes, and materials.

The shape of the organic-inorganic composite filler and the organic filler is not particularly limited and may be amorphous, spherical or substantially spherical. Among them, the spherical inorganic filler is used from the viewpoint of polishability. preferable.

By hydrophobicizing the filler with a surface treatment agent typified by a silane coupling agent, the compatibility with the polymerizable monomer can be improved, and the mechanical strength and water resistance can be improved.

The method for hydrophobization is not particularly limited, and examples thereof include known methods. That is, as the silane coupling agent, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane. , Vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ -Glysidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, hexamethyldi Hydrophobization using silazane or the like can be mentioned.

The blending amount of the filler is not particularly limited, but is preferably 50 parts by mass to 1500 parts by mass, and more preferably 70 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the above-mentioned polymerizable monomer.

The visible light polymerizable composition of the present invention may further contain other additives. The other additives are not particularly limited as long as they do not interfere with the effects of the present invention, and can be selected according to the intended purpose, and various components contained in known dental curable compositions can be applied. .. For example, a polymerization inhibitor can be added to improve storage stability, and if necessary, an organic thickener such as a polymer compound such as polyvinylpyrrolidone, carboxymethyl cellulose, or polyvinyl alcohol can be added. be. Further, various additives such as an ultraviolet absorber, a dye, an antistatic agent, a pigment, a fluorescent pigment, and a fragrance can be blended as needed.

The visible light polymerizable composition according to the present invention can be usefully used as various curable materials used in dental materials by utilizing the property that the shrinkage stress due to the polymerization is extremely small. Specific examples thereof include dental filling restoration materials, dental cements, dental adhesives, dental abutment construction materials, etc., and in particular, when the tooth cavities are filled and cured, they are cured. It is most useful as a dental filling restoration material because it is difficult for a gap to be formed between the body and the inner wall of the tooth cavity and the occurrence of secondary caries can be greatly reduced. It is most effective when used for filling and repairing tooth cavities and secondary cavities.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The compounds and abbreviations (in parentheses) used in the following Examples and Comparative Examples are shown below.

(A) (Meta) acrylic group-containing polymerizable monomer ・ 2,2′-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane (Bis-GMA)
-Triethylene glycol dimethacrylate (3G).

(B) Polymerization initiator (b1) α-diketone compound ・ Camphorquinone (CQ)
(B2) Amine compound-p-dimethylaminobenzoic acid ethyl ester (DMBE)
(B3) Single molecule cleavage type photopolymerization initiator ・ Monoacylphosphine oxide (MAPO)
-Bisacylphosphine oxide (BAPO).

(C) A compound having a quinone structure other than the α-diketone compound ・ 1,4-naphthoquinone (NQ)
・ 9,10-Anthraquinone (AQ)
-5-Methyl-1,4-naphthoquinone (MNQ).

(D) Filler-Spherical silica-zirconia, γ-methacryloyloxypropyltrimethoxysilane surface-treated product; average particle size; 0.5 μm (E-1)
-Spherical silica-titania, γ-methacryloyloxypropyltrimethoxysilane surface-treated product; average particle size; 0.08 μm (E-2).

(E) Other additives-Dibutylhydroxytoluene (BHT)
・ Hydroquinone methyl ether (HQME)
-Α-Methylstyrene dimer (MSD).

(1) Measurement of Vickers hardness A mold made of polyacetal having holes with a diameter of 7 mm and a height of 1 mm is filled with a visible light-polymerizable composition and pressure-welded with a polypropylene film. Light irradiation was performed for 20 seconds at a wavelength (wavelength: 400-520 nm) manufactured by Tokuyama Corporation.
Using a micro hardness tester (PMT-X7 type: Matsuzawa Seiki), the obtained cured product was pressed with a Vickers indenter, and the diagonal length of the dent formed in the test piece was determined with a load of 100 gf and a load holding time of 30 seconds. It was measured.
The Vickers hardness was calculated by the following formula.
HV = F / S = 2Fsinθ / 2d ² = 1.8544F / d ²
(Here, HV: Vickers hardness, F: load (Kgf), S: surface area of the depression (mm ² ), d: diagonal length of the depression (mm), θ: facing angle of the diamond indenter).

The test was conducted on 5 points, and the average was calculated. Furthermore, it was evaluated whether the value had sufficient hardness. The evaluation criteria are as follows.
◎ ・ ・ Vickers hardness is 40 or more 〇 ・ ・ Vickers hardness is 30 or more △ ・ ・ Vickers hardness is 15 or more × ・ ・ Vickers hardness is less than 15.

(2) Measurement of polymerization shrinkage stress One-up bond F Plus (registered trademark: Tokuyama Dental Co., Ltd.) is applied as a dental adhesive to the bottom of a simulated tooth cavity with a diameter of 6 mm and a depth of 2 mm, and a dental light irradiator (registered trademark: Tokuyama Dental Co., Ltd.) Light irradiation was performed for 10 seconds using (manufactured by Tokuyama Dental Co., Ltd.). Then, the visible light-polymerizable composition was embedded so as to fill the simulated tooth cavity, and the light was irradiated with a dental light irradiator Tokuso Power Light (manufactured by Tokuyama Corporation, wavelength: 400-520 nm) for 20 seconds. The stress at this time was measured with a universal tensile tester Autograph (AG-5000D: Shimadzu Corporation).

(3) Evaluation of tooth cavity compatibility A columnar cavity with a depth of 2 mm and a diameter of 4 mm was formed on the anterior teeth of the bovine mandible removed within 24 hours after slaughter using a dental diamond bar. Then, Bond Force (registered trademark: Tokuyama Dental Co., Ltd.) was applied as a dental adhesive to the entire inside of this tooth cavity, and after applying compressed air to remove the solvent, the dental light irradiator Tokuyama Power Light (Tokuyama) Light irradiation was performed for 10 seconds using a company manufactured by the company, wavelength: 400-520 nm). Subsequently, the visible light-polymerizable composition was filled so as to fill the tooth cavity, and light was irradiated with a dental light irradiator Toxo Power Light for 20 seconds. The test piece thus obtained was immersed in water at 37 ° C. overnight, and then cut vertically with respect to the bottom of the fossa using a diamond cutter to prepare a test piece. The exposed cut surface is polished with water-resistant abrasive paper (# 3000, # 1500) and diamond slurry (6 μm, 3 μm, 1 μm, 0.25 μm), and the polished surface is polished using a laser microscope (VK9700: KEYENCE). The cavities were observed and the cavities were evaluated for compatibility. The evaluation criteria are as follows.
◎ ・ ・ The conforming part is 100% of the whole 〇 ・ ・ The conforming part is 90% or more of the whole △ ・ ・ The conforming part is 80% or more of the whole × ・ ・The number of conforming parts is less than 80 in total.

[Example 1]
(A) As the (meth) acrylic group-containing polymerizable monomer, a Bis-GMA / 3G (60 wt% / 40 wt%) mixture is used, and as the (b1) α-diketone compound with respect to 100 parts by weight of the mixture. CQ (0.2 parts by weight), (b2) DMBE (0.3 parts by weight) as an amine compound, (c) NQ (2.0 parts by weight), BHT (2.0 parts by weight) as a compound having a quinone structure other than the α-diketone compound. 0.1 part by weight) was mixed. After stirring until each component was completely dissolved, it was mixed with E-1 (164 parts by mass) and E-2 (71 parts by mass) and kneaded to prepare a visible light polymerizable composition. The composition is shown in Table 1. The visible light-polymerizable composition thus prepared was measured by each of the above-mentioned methods. The results are shown in Table 2.

[Examples 2 to 16, Comparative Examples 1 to 4],
The amount of the polymerization initiator, the compound having a quinone structure other than the (d) α-diketone compound, or the MSD is changed to the amount shown in Table 1, and the dental filler is prepared in the same manner as in Example 1. Was prepared.
The composition is shown in Table 1. The visible light-polymerizable composition thus prepared was measured by each of the above-mentioned methods. The results are shown in Table 2.

Each of the Examples and Comparative Examples shown in Table 1 contains the following components in addition to the compounding components listed in Table 1.
(A) (Meta) acrylic group-containing polymerizable monomer: Bis-GMA (60 parts by mass), 3G (40 parts by mass), (d) Filler: E-1 (164 parts by mass), E-2 ( 71 parts by mass), other additives: BHT (0.1 parts by weight).

As shown in Table 1, each of the dental fillers of Examples 1 to 11 containing a compound having a quinone structure other than the α-diketone compound does not contain a compound having a quinone structure other than the α-diketone compound (comparison). Compared with Example 1), it showed higher Vickers hardness and lower polymerization shrinkage stress. From the comparison of Examples 1 to 7, the compounding ratio of the α-diketone compound and the compound having a quinone structure other than the α-diketone compound is preferably 20:80 to 80:20, more preferably 40:60 to 60:40. , 50:50 can be confirmed to be the best. The effect of accelerating the curing of compounds having a quinone structure other than the α-diketone compound and the α-diketone compound and the effect of suppressing the polymerization shrinkage stress of compounds having a quinone structure other than the α-diketone compound are best balanced. It is considered that this is because it is a compounding ratio. From the comparison of Examples 1 and 8 to 12, a higher effect appears when the total amount of the compound having a quinone structure other than the α-diketone compound and the α-diketone compound is 0.2 parts by mass or more. .. It is considered that this is because sufficient curability cannot be ensured if the total amount of the compound having a quinone structure other than the α-diketone compound and the α-diketone compound is small. From the comparison of Examples 1, 13 and 14, it was confirmed that when the compound having a quinone structure other than the α-diketone compound is a naphthoquinone compound, the effect of reducing the polymerization shrinkage stress is particularly high. It is considered that the naphthoquinone compound has a small molecular size and can promote an efficient chain transfer reaction. From the comparison of Examples 11, 15 and 16, it was confirmed that when the polymerization initiator was camphorquinone, the curability and the effect of reducing the polymerization shrinkage stress were higher.

In Comparative Examples 2 to 4, α-methylstyrene dimer (MSD) was blended as a chain transfer agent in place of a compound having a quinone structure other than the α-diketone compound. Although α-methylstyrene dimer has the effect of suppressing polymerization shrinkage stress, it is difficult to achieve both high curability and low polymerization shrinkage stress by adjusting the compounding ratio with the α-diketone compound. Can be confirmed. This is because the polymerization shrinkage stress increases as the compounding ratio of the α-diketone compound increases, and the Vickers hardness decreases as the compounding ratio of the α-diketone compound decreases.

Claims (4)

(A) Bifunctional aromatic (meth) acrylic group-containing polymerizable monomer and / or bifunctional aliphatic (meth) acrylic group-containing polymerizable monomer (meth) acrylic group-containing polymerizable single amount A first polymerization initiator composed of a combination of the body, (b) (b1) α-diketone compound and (b2) amine compound, or a second polymerization initiator composed of (b3) a single molecule cleavage type photopolymerization initiator. Dental visible photopolymerization comprising a polymerization initiator selected from any of the above, (c) a compound having a quinone structure other than the α-diketone compound , a 1,4-naphthoquinone compound or a 9,10-anthraquinone compound. It is a sex composition
(1) When the visible light polymerizable composition contains the first polymerization initiator, the total amount of (b1) and (c) to be blended with respect to 100 parts by mass of (a) is 0.2 to 2.0. It is a mass part
(2) When the visible light polymerizable composition contains the second polymerization initiator, the total amount of the above (b3) and (c) to be blended with respect to 100 parts by mass of the (a) is 0.2 to 2.0. It is a mass part,
A dental visible light polymerizable composition characterized by this. The dental visible photopolymerizable composition according to claim 1, wherein the single molecule cleavage type photopolymerization initiator (b3) is an acylphosphine oxide-based polymerization initiator. (1) When the visible light polymerizable composition contains the first polymerization initiator, the blending ratio of the (c) to the total mass of the (b1) and the (c) is 40% by mass to 80% by mass. is the percentage,
(2) When the visible light polymerizable composition contains the second polymerization initiator, the mass-based compounding ratio (b3): (c) of the above (b3) and the above (c) is 80:20 to 20. : 80. The dental visible light polymerizable composition according to claim 1 or 2. A dental filling restoration material comprising the dental visible light polymerizable composition according to any one of claims 1 to 3.