JP2023133025A - Dental photocurable composition excellent in color tone stability - Google Patents

Abstract

To provide a dental photocurable composition which can achieve both sufficient mechanical strength and color tone stability after curing.SOLUTION: There is provided a dental photocurable composition which comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photo acid generator, (D) a polymerization accelerator and (D1) a hindered amine compound as the polymerization accelerator (D).SELECTED DRAWING: None

Description

The present invention relates to dental photocurable compositions.

Dental photocurable compositions are used in the dental field, including dental adhesives, dental composite resins, dental abutment construction materials, dental resin cements, dental coating materials, and dental pits and fissures. It is applied to sealing materials, dental manicure materials, dental movable teeth fixing adhesives, dental glass ionomer cements, dental hard resins, dental cutting materials, dental 3D printer materials, etc.

Patent Documents 1 and 2 propose a photopolymerization initiator containing a photoacid generator (a triazine compound or a specific aryliodonium salt), a sensitizer, and an electron donor compound. There is. Patent Document 3 proposes a cationically polymerizable composition containing a hindered amine compound and an iodonium salt compound.

Patent No. 4093974 Patent No. 4596786 Japanese Patent Application Publication No. 2006-249040

However, these compositions have problems in achieving both sufficient mechanical strength and color stability after curing.

An object of the present invention is to provide a dental photocurable composition that can have both sufficient mechanical strength and color stability after curing.

The present invention includes (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a polymerization accelerator, and (D) as a polymerization accelerator (D1). A dental photocurable composition containing a hindered amine compound is provided.

The dental photocurable composition of the present invention can have both sufficient mechanical strength and color stability after curing.

In the present invention, a dental photocurable composition in which the hindered amine compound (D1) is an aliphatic tertiary amine compound can be provided.

In the present invention, (C) an aryliodonium salt is included as a photoacid generator, and the aryliodonium salt contains an anion having an organic group and one or more atoms of P, B, Al, S, and Ga, and an aryl iodonium salt. It can be a dental photocurable composition that is a salt with an iodonium cation.

In the present invention, (C) an aryliodonium salt is included as a photoacid generator, and the aryliodonium salt includes at least one organic group in which H is substituted with F and any one of P, B, Al, S, and Ga. The dental photocurable composition can be a salt of an anion having one or more atoms and an aryliodonium cation.

In the present invention, a dental photocurable composition in which the polymerizable monomer (A) is a radically polymerizable monomer can be provided.

In the present invention, (A) contains 0.02 to 1 part by mass of (B) a photosensitizer to 100 parts by mass of polymerizable monomer, and (C) contains 0.1 to 5 parts by mass of photoacid generator. A dental photocurable composition containing 0.2 to 5 parts by mass of (D1) hindered amine compound can be prepared.

Hereinafter, the dental photocurable composition of the present invention will be explained in detail.
The dental photocurable composition of the present invention is a dental adhesive material, a dental composite resin, a dental abutment building material, a dental resin cement, a dental coating material, a dental pit and fissure sealing material, a dental It is applied as a nail polish material, dental movable teeth fixing adhesive, dental glass ionomer cement, dental hard resin, dental cutting material, dental 3D printer material, etc.

In clinical dentistry, in order to aesthetically and functionally restore tooth defects caused by caries, fracture, etc., we use the direct restoration method using dental adhesives and composite resins, as well as ceramics and dental hard resins. An indirect method of repairing the prosthetic device with dental resin cement is being performed. In addition, we offer dental composite resins, various dental materials, and dental adhesives for attaching natural teeth, dental adhesives for fixing loose teeth, and external stimulation for hypersensitivity and vital teeth after formation. Dental coating materials to protect against secondary caries, dental pit and fissure sealants to prevent caries by filling deep fissures in molar teeth, and temporarily improve aesthetics by masking tooth discoloration. A dental manicure material is used to recover the tooth, and a dental abutment construction material is used to form an abutment tooth when the crown of the tooth collapses due to caries. In recent years, new composite materials have been developed, such as materials for dental cutting to make prosthetic devices using CAD/CAM processing, and materials for dental 3D printers to make prosthetic devices using 3D printers, and various dental materials are being used for treatment. used. The above materials are prepared into a uniform paste by mixing a resin matrix made of several types of polymerizable monomers, various fillers such as inorganic fillers and organic-inorganic composite fillers, and a polymerization initiator depending on the application. be done. To give an example of some materials, composite resin for dental fillings is used as an unhardened paste to fill the tooth, and after giving it the anatomical form of a natural tooth using dental instruments such as instruments, it is It is used by curing it by irradiating it with light using a commercially available light irradiator. For the irradiation light from the light irradiator, a light source with an output of about 100 to 2000 mW/cm ² of light intensity in the wavelength range of about 360 to 500 nm is generally used. On the other hand, dental resin cement is used when bonding a prosthetic device to a cavity or an abutment tooth, and is cured by irradiating it with light after the prosthesis device is attached to the cavity or an abutment tooth.

As photopolymerization initiators used in dental materials, photosensitizers and systems in which a photosensitizer is combined with a suitable photopolymerization accelerator are widely used. Acylphosphine oxide compounds and α-diketone compounds are known as photosensitizers, and α-diketone compounds in particular have the ability to initiate polymerization in the wavelength range of visible light, which has little effect on the human body. Furthermore, photoacid generators and tertiary amine compounds are well known as compounds that can be combined with photosensitizers. A combination of an α-diketone compound, a photoacid generator, and a tertiary amine compound has high polymerization activity against irradiated light, and is therefore used in the field of dental materials. A dental photocurable composition containing the photopolymerization initiator exhibits excellent mechanical properties such as hardness, bending strength, and compressive strength required for various materials.

Compounds such as dimethylamino methacrylate and diethylamino methacrylate are used as typical aliphatic tertiary amine compounds used in such photopolymerization initiators, but these compounds have an odor peculiar to amines. I didn't like it in that respect. Furthermore, aliphatic tertiary amine compounds having a primary hydroxyl group such as methyldiethanolamine and triethanolamine are known. However, when an amine compound having a primary hydroxyl group is blended into a composition in combination with a photoacid generator, there is a problem in that the cured product discolors when used for a long period of time.

The inventors have discovered that the above problem can be solved by incorporating a hindered amine compound, which is usually used as a light stabilizer, into a dental photocurable composition as a photopolymerization accelerator, and have completed the present invention.

[(A) Polymerizable monomer]
As the polymerizable monomer (A) contained in the dental photocurable composition of the present invention, any known polymerizable monomer can be used without any restriction. In the polymerizable monomer or compound having a polymerizable group according to the present invention, the polymerizable group preferably exhibits radical polymerizability. Specifically, from the viewpoint of easy radical polymerization, the polymerizable group is ( A meth)acrylic group and/or a (meth)acrylamide group are preferred. In this specification, "(meth)acrylic" means acrylic and/or methacrylic, "(meth)acryloyl" means acryloyl and/or methacryloyl, and "(meth)acrylate" means acrylate and/or methacrylic. "(meth)acrylamide" means acrylamide and/or methacrylamide. Polymerizable monomers having a substituent at the α-position of the acrylic group and/or acrylamide group can also be preferably used. There are those that have one radically polymerizable group, those that have two radically polymerizable groups, those that have three or more radically polymerizable groups, those that have an acidic group, those that have an alkoxysilyl group, and those that have a sulfur atom.

Specific examples of polymerizable monomers having one radically polymerizable group and no acidic group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. ) acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, propylene glycol mono(meth)acrylate, glycerol mono( meth)acrylate, erythritol mono(meth)acrylate, N-methylol(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N,N-(dihydroxyethyl)(meth)acrylamide, methyl(meth)acrylate, ethyl(meth)acrylamide ) acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, Examples include 3-(meth)acryloyloxypropyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, and (meth)acrylamide.

Specific examples of polymerizable monomers having two radically polymerizable groups and no acidic group include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3 -(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)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-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl) -2-(4-(meth)acryloyloxydiethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyditriethoxyphenyl)propane, 2- (4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2 -bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitate, glycerol di(meth)acrylate, 1-(acryloyloxy)-3-( methacryloyloxy)-2-propanol, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl Glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate , 1,10-decanediol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA"), 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, and the like.

Specific examples of polymerizable monomers having three or more radically polymerizable groups and no acidic groups include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, and trimethylolmethane tri( meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(amino Examples include carboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like.

The polymerizable monomer having an acidic group has one or more polymerizable groups and at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, or a carboxylic acid group. Any polymerizable monomer can be used without restriction. By including a polymerizable monomer having an acidic group, it is possible to impart adhesiveness to teeth and prosthetic devices.

Specific examples of polymerizable monomers having a phosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, and 4-(meth)acryloyloxybutyl. Dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyl Oxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-( meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate, bis[2-(meth)acryloyloxyethyl]hydro Genphosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[ 9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyl Oxyethylphenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl] hydrogen phosphate; acid chlorination of these and (meth)acrylamide compounds in which the ester bonds of these compounds are replaced with amide bonds.

Specific examples of polymerizable monomers having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl pyrophosphate], bis[4-(meth)acryloyloxybutyl] pyrophosphate, and bis[6-(meth)acryloyloxybutyl pyrophosphate]. (meth)acryloyloxyhexyl], bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate; acid chlorides, alkali metal salts, ammonium salts thereof; and Examples include (meth)acrylamide compounds in which the ester bonds of these compounds are replaced with amide bonds.

Specific examples of polymerizable monomers having a thiophosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, and 4-(meth)acryloyl. Oxybutyldihydrogenthiophosphate, 5-(meth)acryloyloxypentyldihydrogenthiophosphate, 6-(meth)acryloyloxyhexyldihydrogenthiophosphate, 7-(meth)acryloyloxyheptyldihydrogenthiophosphate, 8-(meth)acryloyloxyoctyldihydrogenthiophosphate, 9-(meth)acryloyloxynonyldihydrogenthiophosphate, 10-(meth)acryloyloxydecyldihydrogenthiophosphate, 11-(meth)acryloyloxyun Decyl dihydrogenthiophosphate, 12-(meth)acryloyloxidedecyldihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyldihydrogenthiophosphate, 20-(meth)acryloyloxyicosyldihydrogenthiophosphate ; their acid chlorides, alkali metal salts, and ammonium salts; and (meth)acrylamide compounds in which the ester bonds of these compounds are replaced with amide bonds. Note that the polymerizable monomer having a thiophosphoric acid group is also classified as a polymerizable monomer having a sulfur atom.

Specific examples of polymerizable monomers having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyl Oxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxy Examples include decyl-3-phosphonoacetate; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

Specific examples of the polymerizable monomer having a sulfonic acid group include 2-(meth)acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate, and the like.

Polymerizable monomers having a carboxylic acid group are classified into (meth)acrylic compounds having one carboxyl group in the molecule and (meth)acrylic compounds having multiple carboxyl groups in the molecule. Specific examples of (meth)acrylic compounds having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloyl aspartic acid, O-(meth)acryloyl Tyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4 - aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen malate; acid halides of these; and these Examples include (meth)acrylamide compounds in which the ester bond of the compound is replaced with an amide bond. Specific examples of (meth)acrylic compounds having multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1- Dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid , 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate ; these acid anhydrides, acid halides; and (meth)acrylamide compounds in which the ester bonds of these compounds are replaced with amide bonds.

Preferred examples include 10-methacryloyloxydecyl dihydrogen phosphate and 6-methacryloxyhexylphosphonoacetate. The amount of the polymerizable monomer having an acidic group is 1 part by mass or more, based on the total amount of 100 parts by mass of the polymerizable monomer contained in the dental photocurable composition, from the viewpoint of imparting adhesive properties. Preferably, the blending amount is 10 parts by mass or more and 50 parts by mass or less. If it is less than 1 part by mass, adhesion to tooth, metals, and metal oxides may not be sufficiently developed, and if it is more than 50 parts by mass, storage stability may be deteriorated.

Specific examples of polymerizable monomers having an alkoxysilyl group include (meth)acrylic compounds and (meth)acrylamide compounds having one alkoxysilyl group in the molecule, and (meth)acrylamide compounds having multiple alkoxysilyl groups in the molecule. Examples include (meth)acrylic compounds and (meth)acrylamide compounds. 2-(meth)acryloxyethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 4- (meth)acryloxybutyltrimethoxysilane, 5-(meth)acryloxypentyltrimethoxysilane, 6-(meth)acryloxyhexyltrimethoxysilane, 7-(meth)acryloxyheptyltrimethoxysilane, 8-(meth)acryloxyheptyltrimethoxysilane, ) acryloxyoctyltrimethoxysilane, 9-(meth)acryloxynonyltrimethoxysilane, 10-(meth)acryloxydecyltrimethoxysilane, and 11-(meth)acryloxyundecyltrimethoxysilane. Furthermore, 3,3-dimethoxy-8,37-dioxo-2,9,36-trioxa-7,38-diaza-3-silatetracontan-40-yl (meth)acrylate has a urethane group or an ether group. , 2-((3,3-dimethoxy-8-oxo-2,9,18-trioxa-7-aza-3-silanonadecane-19-oyl)amino)-2-methylpropane-1,3-diyldi(meth) ) acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,18-trioxa-7,20-diaza-3-siladocosan-22-yl (meth)acrylate, 3,3-dimethoxy-8,22 -Dioxo-2,9,12,15,18,21-hexaoxa-7,23-diaza-3-silapentacan-25-yl (meth)acrylate, 3,3-dimethoxy-8,22-dioxo-2,9 , 12,15,18,21,26-heptaoxa-7,23-diaza-3-silaoctacosan-28-yl (meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15 , 18-pentaoxa-7,20-diaza-3-siladocosan-22-yl (meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18,23-hexaoxa-7 , 20-diaza-3-silapentacosan-25-yl (meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,12,15,18-pentaoxa-7-aza-3-silanonadecane) -19-oil)amino)-2-methylpropane-1,3-diyldi(meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosane-23 -yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21,24-tetraoxa-18-aza-4-silahexacosan-26-yl (meth)acrylate, 4,4-diethoxy-13 -Oxo-3,12,17-trioxa-14-aza-4-silanonadecane-19-yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silaicosan -20-yl(meth)acrylate, 2-methyl-2-((11-(triethoxysilyl)undecyloxy)carbonylamino)propane-1,3-diyldi(meth)acrylate.

The dental photocurable composition of the present invention can contain a polymerizable monomer having a sulfur atom as the polymerizable monomer (A) in order to impart adhesiveness to noble metals. As the polymerizable monomer having a sulfur atom, any known compound can be used without any restriction as long as it is a polymerizable monomer having one or more sulfur atoms and a polymerizable group. Specifically, it refers to a compound having a partial structure such as -SH, -SS-, >C=S, >CSC<, >P=S or resulting from tautomerism. Specific examples include 10-methacryloxydecyl-6,8-dithiooctanate, 6-methacryloxyhexyl-6,8-dithiooctanate, 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate, 2-( Examples include 11-methacryloyloxyundecylthio)-5-mercapto-1,3,4-thiadiazole and 10-(meth)acryloyloxydecyldihydrogenthiophosphate.

In addition to these polymerizable monomers, oligomers or prepolymers having at least one polymerizable group in the molecule may be used without any limitation. Furthermore, there is no problem even if a substituent such as a fluoro group is present in the same molecule. The polymerizable monomers described above can be used not only alone but also in combination.

The dental photocurable composition of the present invention may contain a silane coupling agent as (A) a polymerizable monomer in order to impart adhesiveness to glass ceramics. Any known silane coupling agent can be used without limitation, but 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 11-methacryloxyundecyltrimethoxysilane and the like are preferred. From the viewpoint of imparting adhesive properties, the blending amount is 1 part by mass or more, more preferably 5 parts by mass or more and less than 20 parts by mass, based on 100 parts by mass of the total amount of polymerizable monomers in the composition. Since the silane coupling agent as a polymerizable monomer is intended to impart adhesion to glass ceramics and resin materials containing fillers made of glass ceramics, it is blended separately from the filler surface treatment agent.

The dental photocurable composition of the present invention can contain a polymerizable monomer having a sulfur atom as the polymerizable monomer (A) in order to impart adhesiveness to noble metals. The amount of the polymerizable monomer having a sulfur atom is 0.01 part by mass or more based on the total amount of 100 parts by mass of the polymerizable monomer contained in the dental photocurable composition from the viewpoint of imparting adhesive properties. More preferably, the amount is 0.1 parts by mass or more and less than 20 parts by mass.

Although the polymerizable monomer contained in the dental photocurable composition of the present invention may contain a polymerizable monomer having a cationically polymerizable functional group, it may cause a decrease in storage stability. Therefore, when a polymerizable monomer having a cationic polymerizable functional group is contained, it is preferable to limit the content to an extent that does not affect storage stability.

Examples of polymerizable monomers having a cationic polymerizable functional group include vinyl ether compounds, epoxy compounds, oxetane compounds, cyclic ether compounds, and cyclic carbonate compounds.

The dental photocurable composition of the present invention may not contain a polymerizable monomer having a cationically polymerizable functional group. The dental photocurable composition of the present invention can contain only a polymerizable monomer having a radically polymerizable functional group in the molecule. Preferred radically polymerizable functional groups are (meth)acrylic groups and/or (meth)acrylamide groups, and only polymerizable monomers having (meth)acrylic groups and/or (meth)acrylamide groups can be included.

<Photopolymerization initiator>
The dental photocurable composition of the present invention contains a photopolymerization initiator. A photopolymerization initiator is a polymerization initiator that can initiate polymerization by irradiating it with light. The photopolymerization initiator contained in the dental photocurable composition of the present invention includes (B) a photosensitizer, (C) a photoacid generator, and (D) a polymerization accelerator. As these compounds, commonly used and known compounds can be used without any restriction.

[(B) Photosensitizer]
Specific examples of the photosensitizer (B) that can be used in the present invention include benzyl, camphorquinone, camphorquinone carboxylic acid, camphorquinone sulfonic acid, α-naphthyl, acetonaphcene, p,p'-dimethoxybenzyl , p,p'-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, α-diketones such as naphthoquinone, benzoin , benzoin alkyl ethers such as benzoin methyl ether and benzoin ethyl ether, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2 , thioxanthone such as 4-diisopropylthioxanthone, benzophenone such as benzophenone, p-chlorobenzophenone, p-methoxybenzophenone, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2 ,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylprop-1-yl)phosphine oxide, bis (2,6-dimethoxybenzoyl)-(1-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, Bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylprop-1-yl)phosphine oxide , bis(2,6-diethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, -dibutoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenyl Phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis (2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoyl Acylphosphine oxides such as benzyl octylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide and 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide, bis Acylgermanium compounds such as benzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis(4-methoxybenzoyl)dimethylgermanium, and bis(4-methoxybenzoyl)diethylgermanium, 2-benzyl-dimethylamino-1-( α-Aminoacetophenones such as 4-morpholinophenyl)-butanone-1, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-propanone-1, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl (2- methoxyethyl ketal), bis(cyclopentadienyl)-bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]-titanium, bis(cyclopentadienyl)-bis(pentanefluorophenyl) )-titanium, bis(cyclopentadienyl)-bis(2,3,5,6-tetrafluoro-4-disiloxyphenyl)-titanium, and other titanocenes.

(B) The photosensitizer can be appropriately selected depending on the wavelength, intensity, and light irradiation time of the light used for polymerization, as well as the types and amounts of other components to be combined. Further, the photosensitizers can be used alone or in combination of two or more types. Among these, α-diketone compounds having a maximum absorption wavelength in the visible light region are preferably used, and camphorquinone compounds such as camphorquinone, camphorquinone carboxylic acid, and camphorquinone sulfonic acid are more preferable. Camphorquinone is particularly preferred because it is easily available.

Usually, the blending amount of (B) photosensitizer is 0.02 to 1.0 parts by mass based on 100 parts by mass of the total amount of (A) polymerizable monomers contained in the dental photocurable composition. It is preferably 0.05 to 0.5 parts by mass, and more preferably 0.05 to 0.5 parts by mass. (B) If the amount of the photosensitizer is less than 0.02 parts by mass, the polymerization activity against irradiation light may be poor and curing may be insufficient. When more than 1.0 parts by mass is added, sufficient curability is exhibited, but the environmental light stability is shortened and the yellowish tinge increases.
The dental photocurable composition of the present invention may contain only an α-diketone compound as the photosensitizer (B).

[(C) Photoacid generator]
As the photoacid generator (C) used in the dental photocurable composition of the present invention, any known compound can be used without limitation. Specific examples include triazine compounds, iodonium salt compounds, sulfonium salt compounds, and sulfonic acid ester compounds. Among these, triazine compounds and iodonium salt compounds are preferred because they have high polymerizability when used in combination with a sensitizer. More preferably, iodonium salt compounds are used. Iodonium salt compounds are susceptible to sensitization by photosensitizers that absorb in the visible light region.

Specific examples of triazine compounds include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis (trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p -methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)- 4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s -triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2- [2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)- s-triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4, 6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(1- naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis (2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis( trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N -diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine. Among these, 2,4,6-tris(trichloromethyl)-s-triazine is preferred.

Any known iodonium salt compound can be used. To give a specific example, the structural formula of the iodonium salt compound can be represented by the following formula (1).

[Formula (1)]
[(R1)₂I]⁺ [A]^-

([(R1) in the formula₂I]⁺is a cationic part, [A]^-is an anion moiety, R1 shown in formula (1) represents an organic group bonded to I, and R1 may be the same or different. R1 is, for example, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms. These are alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, It may be substituted with at least one member selected from the group consisting of arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogen. )

In the above, the aryl group having 6 to 30 carbon atoms includes monocyclic aryl groups such as phenyl group, and condensed groups such as naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, and anthraquinone. Examples include polycyclic aryl groups.

Examples of the heterocyclic group having 4 to 30 carbon atoms include cyclic ones containing 1 to 3 heteroatoms such as oxygen, nitrogen, and sulfur, and these may be the same or different. is a monocyclic heterocyclic group such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl , carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthanyl, thioxanthonyl, dibenzofuranyl, and other fused polycyclic heterocyclic groups.

Specific examples of alkyl groups having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl, and octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, and tert-pentyl. , branched alkyl groups such as isohexyl, and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

Specific examples of alkenyl groups having 2 to 30 carbon atoms include linear chains such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 1-methyl-1-propenyl. Or branched ones can be mentioned.

Further, specific examples of alkynyl groups having 2 to 30 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl, 1-methyl- Examples include straight chain or branched ones such as 2-propynyl.

The above aryl group having 6 to 30 carbon atoms, heterocyclic group having 4 to 30 carbon atoms, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, or alkynyl group having 2 to 30 carbon atoms has at least one Specific examples of substituents include linear alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, and octadecyl; isopropyl, isobutyl, sec-butyl, tert- Branched alkyl groups with 1 to 18 carbon atoms such as butyl; cycloalkyl groups with 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; hydroxy groups; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy , tert-butoxy, dodecyloxy, etc. Straight chain or branched alkoxy group having 1 to 18 carbon atoms; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl, etc. carbon Straight-chain or branched alkylcarbonyl group having 2 to 18 carbon atoms; arylcarbonyl group having 7 to 11 carbon atoms such as benzoyl and naphthoyl; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec- Straight chain or branched alkoxycarbonyl groups having 2 to 19 carbon atoms such as butoxycarbonyl and tert-butoxycarbonyl; Aryloxycarbonyl groups having 7 to 11 carbon atoms such as phenoxycarbonyl and naphthoxycarbonyl; phenylthiocarbonyl, naphthoxythiocarbonyl, etc. Arylthiocarbonyl group having 7 to 11 carbon atoms; linear or straight chain having 2 to 19 carbon atoms such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octadecylcarbonyloxy, etc. Branched acyloxy group; phenylthio, biphenylthio, methylphenylthio, chlorophenylthio, bromophenylthio, fluorophenylthio, hydroxyphenylthio, methoxyphenylthio, naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4- [4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl-chlorophenylthio, 4-benzoyl-methylthiophenylthio, Arylthio groups with 6 to 20 carbon atoms such as 4-(methylthiobenzoyl)phenylthio and 4-(ptert-butylbenzoyl)phenylthio; arylthio groups with 1 to 18 carbon atoms such as methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, and dodecylthio; Straight chain or branched alkylthio group; Aryl group with 6 to 10 carbon atoms such as phenyl, tolyl, dimethylphenyl, naphthyl; 4 to 10 carbon atoms such as thienyl, furanyl, pyranyl, xanthenyl, chromanyl, isochromanyl, xanthonyl, thioxanthonyl, dibenzofuranyl, etc. 20 heterocyclic groups; Aryloxy groups having 6 to 10 carbon atoms such as phenoxy and naphthyloxy; Straight chain or branched alkyl groups having 1 to 18 carbon atoms such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, etc. Sulfinyl group; Arylsulfinyl group having 6 to 10 carbon atoms such as phenylsulfinyl, tolylsulfinyl, naphthylsulfinyl; Straight chain or branched having 1 to 18 carbon atoms such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, octylsulfonyl, etc. Alkylsulfonyl group; Arylsulfonyl group having 6 to 10 carbon atoms such as phenylsulfonyl, tolylsulfonyl (tosyl group), naphthylsulfonyl; Alkyleneoxy group; Cyano group; Nitro group; Halogen such as fluorine, chlorine, bromine, iodine, etc. can be mentioned.

Among iodonium salt compounds, aryliodonium salts are preferred because they have high stability. Moreover, in order to improve fat solubility, it is preferable that the aryl group has a substituent. Specifically, straight chain alkyl groups such as methyl, propyl, octyl, decyl, undecyl, dodecyl, and tridecyl, and branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl. Alternatively, a functional group in which one or more H of these hydrocarbon groups is replaced with F, a perfluoroalkyl group, a halogen, etc. are suitable as the substituent.

The structure of the anion moiety of the iodonium salt compound is not particularly limited, but examples thereof include those containing atoms such as halogen, P, S, B, Al, and Ga. Although anions containing As or Sb can be used from the viewpoint of safety, they are not preferred for dental applications. Further, the anion preferably has an organic group such as an alkyl group and/or an alkoxy group and/or an aryl group, and furthermore, an alkyl group and/or an alkoxy group in which at least one H is substituted with F. It is most preferable to have an organic group such as and/or an aryl group. Iodonium salt compounds having such anions have high solubility in dental photocurable compositions, so they can be used to prevent precipitation during low-temperature storage or long-term storage, and because they dissolve in the composition in a short time. It is expected that manufacturing time will be shortened. Further, an iodonium salt compound consisting of an anion having an organic group such as an alkyl group and/or an alkoxy group and/or an aryl group in which one or more H is substituted with F can be expected to have even higher solubility. If the photoacid generator precipitates, it is not preferable because it may cause a decrease in photocolor stability or a decrease in bending strength. For such anions having at least one organic group such as an alkyl group and/or an alkoxy group and/or an aryl group in which at least one H may be substituted with F, anions having any atoms can be used. However, from the viewpoint of versatility and safety, those containing P, S, B, Al, and Ga are preferable.

Examples of anions not having an alkyl group and/or an alkoxy group and/or an aryl group include halogens such as chloride and bromide, perhalogen acids such as perchloric acid, aromatic sulfonic acids such as p-toluenesulfonate, and camphorsulfone. Examples include acids, nitrates, acetates, chloroacetates, carboxylates, phenolates, tetrafluoroborates, hexafluorophosphates, hexafluoroantimonates, hexafluoroarsenates, and the like. Among these, p-toluenesulfonate, camphorsulfonic acid, and carboxylate are preferably used.

Since the anion moiety of [A] ^- in the iodonium salt compound of formula (1) improves solubility in the dental photocurable composition, an alkyl group in which at least one H is substituted with F; An anion having an organic group such as/or an alkoxy group and/or an aryl group is preferable. Specifically, the alkyl group of the anion moiety of [A] ^- in the iodonium salt compound of formula (1) preferably has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl, branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl, and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples include alkyl groups. The ratio of the number of hydrogen atoms to fluorine atoms in the alkyl group (F/H) is 4 or more, preferably the ratio of the number of hydrogen atoms to fluorine atoms in the alkyl group (F/H) is 9 or more. More preferably, all hydrogen atoms in the hydrocarbon are substituted with fluorine. Iodonium salts consisting of anions having alkyl groups with different ratios of hydrogen atoms and fluorine atoms may be blended into the dental photocurable composition.

Further, specific examples of alkyl groups include CF ₃ , CF ₃ CF ₂ , (CF ₃ ) ₂ CF, CF ₃ CF 2 CF ₂ , CF ₃ CF ₂ CF _{2 CF 2} , (CF ₃ ) ₂ CFCF ₂ , Straight chain or branched perfluoroalkyl groups such as CF ₃ CF ₂ (CF ₃ )CF and (CF ₃ ) ₃ C are mentioned.

The alkoxy group of the anion moiety of [A] ^- in the iodonium salt compound of formula (1) preferably has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include straight chain alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentoxy and octoxy, and branched alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy and tert-butoxy. The ratio of the number of hydrogen atoms to fluorine atoms in the alkyl group (F/H) is 4 or more, preferably the ratio of the number of hydrogen atoms to fluorine atoms in the alkyl group (F/H) is 9 or more. More preferably, all hydrogen atoms in the hydrocarbon are substituted with fluorine. Iodonium salts consisting of anions having alkoxy groups with different ratios of hydrogen atoms and fluorine atoms may be blended into the dental photocurable composition.

Further, specific examples of alkoxy groups include CF ₃ O, CF ₃ CF ₂ O, CF ₃ CF ₂ CF ₂ O, (CF ₃ ) ₂ CFO, CF ₃ CF 2 CF _{2 CF 2 O} , (CF ₃ ). _{2 Straight chain such as CFCF2O , CF3CF2 ( CF3 ) CFO , CF3CF2CF2CF2CF2O , CF3CF2CF2CF2CF2CF2CF2CF2CF2O _ _ _} or a branched perfluoroalkoxy group.

In the phenyl group of the anion moiety of [A] ^- of the iodonium salt compound of formula (1), at least one hydrogen atom is a fluorine atom, and/or an alkyl group and/or an alkoxy group in which at least one hydrogen atom is substituted with a fluorine atom. It has a phenyl group substituted with The alkyl group and/or alkoxy group substituted with a fluorine atom are preferably those described above. Specific examples of particularly preferable phenyl groups include pentafluorophenyl group (C ₆ F ₅ ), trifluorophenyl group (C ₆ H ₂ F ₃ ), tetrafluorophenyl group (C ₆ HF ₄ ), and trifluoromethylphenyl group ( CF ₃ C ₆ H ₄ ), bis(trifluoromethyl) phenyl group ((CF ₃ ) ₂ C ₆ H ₃ ), pentafluoroethylphenyl group (CF ₃ CF ₂ C ₆ H ₄ ), bis(pentafluoroethyl) Phenyl group ((CF ₃ CF ₂ ) ₂ C ₆ H ₃ ), trifluoromethylfluorophenyl group (CF ₃ C ₆ H ₃ F), bistrifluoromethylfluorophenyl group ((CF ₃ ) ₂ C ₆ H ₂ F) , a perfluorophenyl group such as a pentafluoroethylfluorophenyl group (CF ₃ CF ₂ C ₆ H ₃ F), and a bispentafluoroethyl fluorophenyl group ((CF ₃ CF ₂ ) ₂ C ₆ H ₂ F). Iodonium salts consisting of anions having phenyl groups having different ratios of hydrogen atoms and fluorine atoms may be blended into the dental photocurable composition.

As specific examples of the anion moiety of [A] ⁻ in the iodonium salt compound of formula (1), the anion having P is [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₄ PF ₂ ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , and the like. Anions having S include [(CF ₃ SO ₂ ) ₃ C] ⁻ , [(CF ₃ CF ₂ SO ₂ ) ₃ C] ⁻ , [(CF ₃ CF ₂ CF ₂ SO ₂ ) ₃ C] ⁻ , [( CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₃ C] ^- , [CF ₃ CF ₂ CF ₂ CF ₂ SO ₃ ] ^- , [CF ₃ CF ₂ CF ₂ SO ₃ ] ^- , [(CF ₃ CF ₂ SO ₂ ) ₃ C] ^- , [(SO ₂ CF ₃ ) ₃ N] ^- , [(SO ₂ CF ₂ CF ₃ ] ₂ N] ^- , [((CF ₃ ) C ₆ H ₄ ) SO ₃ ] ^- , [SO ₃ ((CF ₂ CF ₂ CF ₂ CF ₂ )SO ₃ ] ^2- and the like. Examples of anions having B include [B(C ₆ F ₅ ) ₄ ] ⁻ , [(C ₆ H ₅ )B((CF ₃ ) ₂ C ₆ H ₃ ) ₃ ] ⁻ , [(C ₆ H ₅ )B(C ₆ F ₅ ) ₃ ] ⁻ , etc. As an anion having Ga, [((C ₆ F ₅ ) ₃ ( C ₆ H ₅ )Ga)] ⁻ , [((C ₆ F ₅ ) ₃ (C ₄ F ₉ )Ga)] ⁻ , [((C ₆ H ₂ F ₃ ) ₄ Ga)] ⁻ , [((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga)] ^- , [[((CF ₃ ) ₄ Ga)] ^- , [Ga(C ₆ F ₅ ) ₄ ] ^-, etc. As an anion containing Al, [( (CF ₃ ) ₃ CO) ₄ Al] ^- , [((CF ₃ CF ₂ ) ₃ CO) ₄ Al] ^-, and the like.

The dental photocurable composition of the present invention preferably contains 0.1 to 5 parts by mass of (C) a photoacid generator based on the total amount of (A) 100 parts by mass of polymerizable monomers, and further Preferably it is 0.2 to 5 parts by mass. If the amount of the photoacid generator is less than 0.1 parts by mass, the ability to promote polymerization may be poor and curing may be insufficient. When more than 5 parts by mass is blended, although sufficient curability is exhibited, environmental light stability may be lowered, resulting in shorter operating time, and discoloration may increase, such as the cured product becoming brownish.

The photoacid generator that can be used in the dental photocurable composition of the present invention is not limited to the photoacid generators shown in the specific examples, and two or more types can be used in combination.

The dental photocurable composition of the present invention comprises (C) an anion having an organic group and one or more atoms of P, B, Al, S, and Ga as a photoacid generator, and an aryliodonium cation. It may contain only an aryliodonium salt which is a salt of. The dental photocurable composition of the present invention includes (C) as a photoacid generator, at least one organic group in which H is substituted with F, and any one or more of P, B, Al, S, and Ga. It may contain only a salt of an anion having an atom of and an aryliodonium cation.

[(D) Polymerization accelerator]
The polymerization accelerator (D) used in the dental photocurable composition of the present invention is not particularly limited as long as it has the ability to promote polymerization, and any known polymerization accelerator commonly used in the dental field may be used without any restrictions. be able to. (D) Polymerization accelerators include aromatic amine compounds, primary to tertiary amine compounds such as aliphatic amine compounds, phosphine compounds, organometallic compounds, fourth period transition metal compounds, thiourea derivatives, sulfinic acids, and their like. Salts, borate compounds, reducing inorganic compounds containing sulfur, reducing inorganic compounds containing nitrogen, barbituric acid derivatives, triazine compounds, halogen compounds, etc. can be used.

An aromatic amine compound refers to a compound in which one or more H atoms of ammonia (NH ₃ ) are substituted on an aromatic ring. A compound in which one H of _NH3 is substituted with an aromatic ring is an aromatic primary amine compound, and a compound in which one H of _NH3 is substituted with an aromatic ring and a different H is substituted with an aromatic ring or an alkyl group. Aromatic secondary amine compounds are those in which one H of _NH3 is substituted with an aromatic ring, and those in which two different H's are substituted with aromatic rings or alkyl groups are called aromatic tertiary amine compounds. Can be classified.

Specific examples of aromatic primary amine compounds include aniline, and specific examples of aromatic secondary amine compounds include N-phenylbenzylamine, N-benzyl-p-anisidine, and N-benzyl-o-phenetidine. , N-phenylglycine ethyl, and N-phenylglycine. Specific examples of aromatic tertiary amine compounds include N,N-dimethylaniline, N,N-diethylaniline, and , N-di-n-butylaniline, N,N-dibenzylaniline, p-N,N-dimethyl-toluidine, m-N,N-dimethyl-toluidine, p-N,N-diethyl-toluidine, p- Bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid 2-butoxyethyl, p-dimethylaminobenzoic acid 2-ethylhexyl, p-dimethylaminobenzoic acid aminoester, N,N-dimethylanthrani Rick acid methyl ester, N,N-dihydroxyethylaniline, N,N-diisopropanolaniline, p-N,N-dihydroxyethyl-toluidine, p-N,N-dihydroxypropyl-toluidine, p-dimethylaminophenyl alcohol, Examples include p-dimethylaminostyrene, N,N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine, and N,N-dimethyl-β-naphthylamine. Among these, p-dimethylaminobenzoic acid ethyl ester is preferred.

A phosphine compound refers to a compound in which the P atom is substituted with three organic groups, and an aromatic phosphine compound refers to a compound in which the P atom is substituted with a phenyl group which may have one or more substituents. Specific examples of phosphine compounds include trimethylphosphine, tributylphosphine, trihexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tri(2-thienyl)phosphine, diphenylpropylphosphine, di-tert-butyl(3-methyl -2-Butenyl)phosphine, methyldiphenylphosphine, triphenylphosphine, 2-(diphenylphosphino)styrene, 3-(diphenylphosphino)styrene, 4-(diphenylphosphino)styrene, allyldiphenylphosphine, 2-(diphenyl) phosphino)benzaldehyde, 3-(diphenylphosphino)benzaldehyde, 4-(diphenylphosphino)benzaldehyde, 2-(phenylphosphino)benzoic acid, 3-(phenylphosphino)benzoic acid, 4-(phenylphosphino) Benzoic acid, tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, 2-(diphenylphosphino)biphenyl, tris(4-fluorophenyl)phosphine, tri( o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, 2-(dimethylamino)phenyldiphenylphosphine, 3-(dimethylamino)phenyldiphenylphosphine, 4-(dimethylamino)phenyldiphenyl Examples include phosphine, 2,2'-bis(diphenylphosphino)biphenyl, and bis[2-(diphenylphosphino)phenyl]ether. Among these, triphenylphosphine, 4-(phenylphosphino)benzoic acid, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, and tri(p-tolyl)phosphine are preferred.

The aliphatic amine compound refers to a compound in which one or more H of ammonia (NH ₃ ) is substituted with an alkyl group. For an alkyl group, CH ₃ - or -CH ₂ - is a primary alkyl group, one H of -CH ₂ - has a substituent as a secondary alkyl group, and two H of -CH ₂ - have a substituent. Those having this are classified as tertiary alkyl groups. Aliphatic amines are aliphatic primary amine compounds in which one H of _NH3 is substituted with an alkyl group, and aliphatic secondary amine compounds in which two H of _NH3 are substituted with alkyl groups. Amine compounds in which three H's of _NH3 are substituted with alkyl groups are classified as aliphatic tertiary amine compounds.

Specific examples of aliphatic primary amine compounds include benzhydrylamine, triphenylmethylamine, amino acids and amino acid esters such as glycine, and specific examples of aliphatic secondary amine compounds include dibenzylamine, Examples include N-benzyl-1-phenylethylamine, bis(1-phenylethyl)amine, bis(4-cyanobenzyl)amine, N-benzyl-protected amino acids or N-benzyl-protected amino acid esters, and aliphatic tertiary amines. Specific examples of the compounds include tributylamine, tripropylamine, triethylamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethylstearylamine, N-[3-(dimethylamino)propyl ] Acrylamide, N,N-dimethylformamide dimethyl acetal, N,N-dimethylacetamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dimethylformamide dipropyl acetal, N,N-dimethylformamide di-tert- Butyl acetal, 1-(2-hydroxyethyl)ethyleneimine, N,N-dimethylethanolamine, N,N-dimethylisopropanolamine, N,N-diisopropylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N- Ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, N-stearyldiethanolamine, triethanolamine, triisopropanolamine, tribenzylamine, dibenzylglycine ethyl ester, N'-(2-hydroxyethyl)-N,N, N'-trimethylethylenediamine, 2-(dimethylamino)-2-methyl-1-propanol, N,N-dimethyl-2,3-dihydroxypropylamine, N,N-diethylethanolamine, 1-methyl-3-pyrrolidinol , 1-(2-hydroxyethyl)pyrrolidine, 1-isopropyl-3-pyrrolidinol, 1-piperidineethanol, 2-[2-(dimethylamino)ethoxy]ethanol, N,N-dimethylglycine, N,N-dimethylglycine Methyl, N,N-diethylglycine methyl, N,N-dimethylglycineethyl, N,N-diethylglycine sodium, 2-(dimethylamino)ethyl acetate, N-methyliminodiacetic acid, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diisopropylaminoethyl methacrylate, N,N-dibutylaminoethyl methacrylate, N,N-dibenzylaminoethyl methacrylate, 3-dimethylaminopropionitrile, tris(2-cyanoethyl) Examples include amine, N,N-dimethylallylamine, N,N-diethylallylamine, and triallylamine.

Specific examples of the above organometallic compounds include scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu). ), tin (Sn), zinc (Zn), and zirconium (Zr), and preferably contains tin (Sn), vanadium (V), and copper (Cu). Specific examples of organometallic compounds containing tin (Sn) include dibutyl-tin-diacetate, dibutyl-tin-dimaleate, dioctyl-tin-dimalate, dioctyl-tin-dilaurate, dibutyl-tin-dilaurate, and dioctyl-tin-diversatate. , dioctyl-tin-S,S'-bis-isooctylmercaptoacetate, tetramethyl-1,3-diacetoxydistanoxane, etc. Specific examples of organometallic compounds containing vanadium (V) include vanadium acetylacetonate. , divanadium tetroxide, vanadyl acetylacetonate, vanadium stearate, vanadyl oxalate, vanadyl sulfate, oxobis(1-phenyl-1,3-butanedionate) vanadium, bis(maltorate)oxovanadium, vanadium pentoxide, Examples include sodium metavanadate, and specific examples of organometallic compounds containing copper (Cu) include copper acetylacetone, copper naphthenate, copper octylate, copper stearate, and copper acetate.

Among these, trivalent or tetravalent vanadium compounds and divalent copper compounds are preferred, and trivalent or tetravalent vanadium compounds having higher polymerization promoting ability are more preferred, and tetravalent vanadium compounds are most preferred. A plurality of types of these fourth period transition metal compounds may be used in combination, if necessary. The blending amount of the transition metal compound is preferably 0.0001 to 1 part by mass based on 100 parts by mass of the total amount of the polymerizable monomer (A), and if it is less than 0.0001 part by mass, the polymerization promotion effect may be insufficient. If it exceeds 1 part by mass, it may cause discoloration or gelation of the dental photocurable composition, resulting in a decrease in storage stability.

As the thiourea derivative, any known thiourea derivative can be used without limitation. Specific examples include dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl)thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea. Urea, N-benzylthiourea, 1,3-dicyclohexylthiourea, N,N'-diphenylthiourea, 1,3-di(p-tolyl)thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea , N-benzoylthiourea, diphenylthiourea, dicyclohexylthiourea and the like. Among these, (2-pyridyl)thiourea, N-acetylthiourea, and N-benzoylthiourea are preferred. A plurality of these thiourea derivatives may be used in combination, if necessary. The blending amount of the thiourea derivative is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the total amount of the polymerizable monomer (A), and if it is less than 0.1 part by mass, the polymerization promoting ability may be insufficient. However, if it exceeds 5 parts by mass, storage stability may decrease.

Examples of sulfinic acids and their salts include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, and sodium benzenesulfinate. , potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate , lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, 2, Potassium 4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, 2,4, Examples include sodium 6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, etc. Among them, sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferred.

Specific examples of borate compounds having one aryl group in one molecule include trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluorophenyl) boron, trialkyl ( 3,5-bistrifluoromethyl)phenylboron, trialkyl[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, trialkyl(p -nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl (p-butyloxyphenyl) boron, trialkyl ( m-butyloxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron, and trialkyl (m-octyloxyphenyl) boron (alkyl groups consist of n-butyl, n-octyl, n-dodecyl, etc.) at least one selected from the group) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, Examples include methylquinolinium salt, ethylquinolinium salt, and butylquinolinium salt. Specific examples of borate compounds having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron, and dialkyldi(3,5-bistrifluoromethyl). Phenylboron, dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, dialkyldi(p-nitrophenyl)boron, dialkyldi(m- Nitrophenyl)boron, dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron, dialkyldi(p-butyloxyphenyl)boron, dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p-octyloxyphenyl) ) Sodium salt, lithium salt of boron and dialkyldi(m-octyloxyphenyl)boron (the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, n-dodecyl group, etc.) , potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts and butylquinolinium salts Examples include. Specific examples of borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron, monoalkyltri(p-fluorophenyl)boron, and monoalkyltri(p-chlorophenyl)boron. 3,5-bistrifluoromethyl)phenylboron, monoalkyltri[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, monoalkyltri (p-nitrophenyl)boron, monoalkyltri(m-nitrophenyl)boron, monoalkyltri(p-butylphenyl)boron, monoalkyltri(m-butylphenyl)boron, monoalkyltri(p-butyloxyphenyl) ) boron, monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(p-octyloxyphenyl)boron and monoalkyltri(m-octyloxyphenyl)boron (alkyl group is n-butyl group, n-octyl group) or n-dodecyl group), sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt , butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, and the like. Specific examples of borate compounds having four aryl groups in one molecule include tetraphenylboron, tetrakis(p-chlorophenyl)boron, tetrakis(p-fluorophenyl)boron, and tetrakis(3,5-bistrifluoride). fluoromethyl)phenylboron, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, tetrakis(p-nitrophenyl)boron, tetrakis (m-nitrophenyl)boron, tetrakis(p-butylphenyl)boron, tetrakis(m-butylphenyl)boron, tetrakis(p-butyloxyphenyl)boron, tetrakis(m-butyloxyphenyl)boron, tetrakis(p- octyloxyphenyl)boron, tetrakis(m-octyloxyphenyl)boron, (p-fluorophenyl)triphenylboron, (3,5-bistrifluoromethyl)phenyltriphenylboron, (p-nitrophenyl)triphenylboron, (m-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron and (p-octyloxyphenyl)triphenylboron sodium salt, lithium salt, Potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc. can be mentioned.

Among these arylborate compounds, from the viewpoint of storage stability, it is more preferable to use a borate compound having three or four aryl groups in one molecule. Further, these arylborate compounds can be used alone or in combination of two or more.

Examples of reducing inorganic compounds containing sulfur include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, dithionites, and specific examples include sodium sulfite and potassium sulfite. , calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, thiobenzoic acid, and the like.

Examples of the reducing inorganic compound containing nitrogen include nitrites, and specific examples include sodium nitrite, potassium nitrite, calcium nitrite, and ammonium nitrite.

Examples of barbituric acid derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid. acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbituric acid Toolic acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid , 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5- Methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1 - Salts of benzyl-5-phenylbarbituric acid and thiobarbituric acids (alkali metal or alkaline earth metals are preferred); specific examples of these salts of barbituric acids include 5-butylbarbituric acid; Examples include sodium, sodium 1,3,5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate.

Specific examples of the halogen compound include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide, and the like.

The dental photocurable composition of the present invention contains (D1) a hindered amine compound as (D) a polymerization accelerator.

Dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate have been used in conventional dental photocurable compositions, but there is room for improvement due to the strong odor characteristic of amines. Therefore, aliphatic tertiary amine compounds having a hydroxyl group, such as methyldiethanolamine and triethanolamine, which have relatively low odor, are sometimes preferably used. However, among aliphatic tertiary amine compounds having (B) a photosensitizer and (C) a photoacid generator and a primary hydroxyl group, N derived from the amine is used as a starting point to move to the α-position carbon and/or the β-position carbon. A cured product of a dental photocurable composition containing a photopolymerization initiator combined with an amine compound having a primary hydroxyl group has a tendency to noticeably discolor over time. This discoloration over time can be estimated through accelerated testing. For example, a test in which the product is immersed in water at a high temperature of 50 to 70°C is used as an accelerated test to predict discoloration after long-term use, and is used as an index to predict discoloration after long-term use. For this reason, a photopolymerization initiator containing (B) a photosensitizer, (C) a photoacid generator, and the aliphatic tertiary amine compound having a primary hydroxyl group has a dental photocurable property. After the composition is cured, discoloration occurs over time, which is unfavorable from an aesthetic point of view. As a result of the inventors' studies, they found that hindered amine compounds are suitable as polymerization accelerators. Generally, hindered amine compounds are used as additives for the purpose of photostability and storage stability. In the present invention, it has been discovered that a hindered amine compound can be used as a polymerization accelerator, and the color difference between the cured product of the dental photocurable composition immediately after curing and after a long period of time is small, and the degree of discoloration is reduced. Furthermore, since it tends to exhibit the effect of a photostabilizer, which is known as the effect of hindered amine compounds, high color stability can be expected both with respect to discoloration over time and discoloration upon exposure to light.

（式中、Ｒ_１はＨまたは有機基、Ｘは有機基である。） (D1) When defining the hindered amine compound by structure, formula (2) is exemplified.
[Formula (2)]

(In the formula, R ₁ is H or an organic group, and X is an organic group.)

(D1) Examples of hindered amine compounds include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, bis(1,2,2 , 6,6-pentamethyl-4-piperidyl), 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1 , 2,3,4-tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, N,N'-bis(2,2,6,6-tetramethylpiperidine- 4-yl)hexane-1,6-diamine, butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate bis(1,2,2,6,6-pentamethyl-4-piperidyl), N1,N3-bis(2,2,6,6-tetramethylpiperidin-4-yl)isophthalamide, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carborate, methacryl Acid 2,2,6,6-tetramethyl-4-piperidyl, 2,2,6,6-tetramethyl-4-piperidylpropyltriethoxysilane, dimethylsuccinate-4-hydroxy-2,2,6, Examples include 6-tetramethylpiperidinoethanol copolymer. In addition, 1,2,2,6,6-pentamethyl-4-piperidinol or 2,2,6,6-tetramethyl-4-piperidinol as described in JP 2001-71640 or JP 2019-127450 Compounds that can be synthesized by reacting 2-isocyanatoethyl methacrylate or 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 1,2,2,6,6-pentamethyl-4-piperidinol or 2- , a compound obtained by adding ethylene oxide to 2,6,6-tetramethyl-4-piperidinol and esterifying it with acrylic acid or methacrylic acid, and 1,2,2,6,6-pentamethyl-4-piperidinol. Or by reacting a compound obtained by adding ethylene oxide to 2,2,6,6-tetramethyl-4-piperidinol and 2-isocyanatoethyl methacrylate or 2-(2-methacryloyloxyethyloxy)ethyl isocyanate. Compounds that can be synthesized can also be preferably used. Since such a compound has a radically polymerizable group, even if it is blended in excess, it will be eluted from the cured product of the dental photocurable composition to copolymerize with the (A) polymerizable monomer. This is preferable because it can be expected to be less difficult. Among the hindered amine compounds, aliphatic tertiary amine compounds are preferably used, and among them, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, and the above-mentioned 1,2,2,6 ,6-pentamethyl-4-piperidinol or ethylene oxide adduct of 1,2,2,6,6-pentamethyl-4-piperidinol and 2-isocyanatoethyl methacrylate or 2-(2-methacryloyloxyethyloxy)ethyl isocyanate. Compounds produced by the reaction of isocyanate groups with polymerizable groups such as nerto, and compounds obtained by esterifying the ethylene oxide adduct of 1,2,2,6,6-pentamethyl-4-piperidinol with acrylic acid, methacrylic acid, etc. can be preferably used.

The dental photocurable composition of the present invention does not contain (D) an amine compound having two or more primary hydroxyl groups at the α-position carbon and/or β-position carbon as a photopolymerization accelerator, starting from amine-derived N. It is preferable. The α-position carbon and β-position carbon herein refer to the first carbon adjacent to the amine-derived N as the α-position carbon, and the second carbon next to it as the β-position carbon. If the primary hydroxy group starts from N and bonds to a carbon other than the α-position carbon and/or the β-position carbon, it will not cause discoloration. In the present invention, amine-derived N refers to a case where what is bonded to N is hydrogen or a hydrocarbon group. For example, it is distinguished from N derived from an amide bond, urethane bond, urea bond, azo group, or nitro group.

The dental photocurable composition of the present invention can be substantially free of aromatic amine compounds. "Substantially not included" refers to the case where it is contained in an amount of less than 0.1 part by mass, preferably less than 0.01 part by mass, per 100 parts by mass of the polymerizable monomer. However, this does not apply if it is contained as an impurity in the raw material and does not affect the physical properties. Further, the dental photocurable composition of the present invention may not contain an aromatic amine compound as (D) a photopolymerization accelerator. Moreover, when an aromatic amine compound is included, it is preferable that an ultraviolet absorber is included. (D1) A hindered amine compound is usually used as a light stabilizer. In particular, it is known that the photostabilizing effect is remarkable when used in combination with an ultraviolet absorber. The same applies to the dental photocurable composition of the present invention, and even if it contains a compound that causes significant discoloration when exposed to light, such as an aromatic amine compound, the discoloration can be achieved by blending the hindered amine compound (D1). It can be expected that discoloration can be greatly reduced by incorporating a UV absorber.

These polymerization initiators (B) photosensitizer, (C) photoacid generator, and (D) photopolymerization accelerator are processed as necessary by pulverization, adsorption to a carrier, or encapsulation in microcapsules. There is no problem even if the following processing is performed. Furthermore, these various types of photopolymerization initiators can be used alone or in combination of two or more types, regardless of the polymerization mode or polymerization method.

(D) The photopolymerization accelerator is preferably 0.2 to 10 parts by mass based on 100 parts by mass of the total amount of the (A) polymerizable monomer contained in the dental photocurable composition. If the amount is less than 0.2 parts by mass, mechanical strength may be insufficient. If more than 10 parts by mass is added, although sufficient curability is achieved, environmental light stability may be shortened and discoloration of the cured product may increase, such as browning or yellowing, which is not preferable.

The amount of the hindered amine compound (D1) is preferably 0.2 to 5 parts by mass based on 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental photocurable composition. If the amount is less than 0.2 parts by mass, mechanical strength may be insufficient. If more than 5 parts by mass is added, although sufficient curability is achieved, environmental light stability may be shortened and discoloration of the cured product may increase, such as browning or yellowing, which is not preferable.

[(E) Filler]
As the filler (E) used in the present invention, commonly used and known fillers can be used without any limitations.

(E) There are no restrictions on the type of filler as long as it is a known filler, and fillers can be blended according to the purpose, such as inorganic fillers, organic fillers, organic-inorganic composite fillers, or sustained release ions. It is preferable to mix a filler such as a synthetic glass. The dental photocurable composition of the present invention may use the exemplified fillers alone or in combination of two or more.

The chemical composition of the inorganic filler is not particularly limited, but specific examples include silicon dioxide, alumina, titania, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, Borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium Examples include fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, and the like. In particular, barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, fluoroaluminosilicate glass, etc. used in dental glass ionomer cement, resin-reinforced glass ionomer cement, resin cement, etc. can also be suitably used. The fluoroaluminosilicate glass mentioned here has a basic skeleton of silicon oxide and aluminum oxide, and contains an alkali metal for non-crosslinking oxygen introduction. Furthermore, it has alkaline earth metals including strontium and fluorine as modification/coordination ions. It is also a composition in which a lanthanide series element is incorporated into the skeleton to provide additional X-ray opacity. These lanthanoid series elements are also incorporated into the composition as modification/coordination ions depending on the composition range.

Hydrophobized inorganic fine particles may be included as an inorganic filler. The primary particles of the hydrophobic inorganic fine particles preferably have an average particle diameter of 0.1 to 50 nm, and are preferably treated with a silane coupling agent and/or modified silicone oil to make them hydrophobic. By blending, in addition to improving bending strength, it can be expected to suppress sedimentation of the inorganic filler and impart rheological properties.

Specific examples of organic fillers include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, Examples include polymers such as polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, and polycarbonate.

Examples of organic-inorganic composite fillers include fillers whose surfaces are polymerized and coated with polymerizable monomers, fillers and polymerizable monomers mixed and polymerized, and then pulverized to an appropriate particle size. Alternatively, fillers are dispersed in polymerizable monomers in advance and subjected to emulsion polymerization or suspension polymerization, fillers are dispersed in polymerizable monomers and solvent in advance and polymerized after spray drying, or fillers are pre-filled. Examples include, but are not limited to, those in which the agent is dispersed in a solvent, spray-dried, impregnated with a polymerizable monomer, and then polymerized.

The sustained ion release glass is characterized by sustained release of at least one of fluorine ions, strontium ions, borate ions, and aluminum ions. It is preferable that a plurality of these ions be sustainedly released at the same time.

The sustained ion release glass used in the present invention may contain any ion without any restriction as long as it contains one or more glass skeleton-forming elements that form a glass skeleton and one or more glass modification elements that modify the glass skeleton. Time-release glasses can also be used. These sustained ion release glasses can be used not only alone but also in combination. Furthermore, in the present invention, glass amphoteric elements that have the role of either a glass skeleton-forming element or a glass-modifying element depending on the glass composition are included in the category of glass skeleton-forming elements. Specific examples of the glass skeleton-forming elements contained in the sustained ion release glass include silica, aluminum, boron, phosphorus, etc., and these can be used not only alone but in combination. Specific examples of glass modifying elements include halogen elements such as fluorine, bromine, and iodine, alkali metal elements such as sodium and lithium, and alkaline earth metal elements such as calcium and strontium. can be used not only singly but also in combination. Among these, it is preferable to include silica, aluminum, and boron as glass skeleton forming elements, and fluorine, sodium, and strontium as glass modifying elements. Specifically, silica glass containing strontium and sodium, fluoroaluminosilicate glass, Examples include fluoroborosilicate glass and fluoroaluminoborosilicate glass. Furthermore, from the viewpoint of sustained release of fluorine ions, strontium ions, borate ions, and aluminum ions, fluoroaluminoborosilicate glass containing strontium is more preferable. Specific examples of the glass composition range include: SiO ₂ : 15-35% by mass, Al ₂ O ₃ : 15-30% by mass, B ₂ O ₃ : 5-20% by mass, SrO: 20-45% by mass, F: 5 to 15% by mass, Na ₂ O: 0 to 10% by mass. This glass composition can be confirmed by using instrumental analysis such as elemental analysis, Raman spectroscopy, and fluorescent X-ray analysis, but no matter which analysis method is used, if the measured value matches these composition ranges, there is no difference. No problem.

There are no particular limitations on the method for producing these sustained ion release glasses, and they can be produced by a melting method, a sol-gel method, or the like. Among these, the method of manufacturing by a melting method using a melting furnace is preferable from the viewpoint of ease of glass composition design including selection of raw materials. Although the sustained ion release glass used in the present invention has an amorphous structure, there is no problem with glass containing a part of crystalline structure, and furthermore, there is no problem with glass having amorphous structure and glass with crystalline structure. There is no problem even if it is a mixture of. Whether or not the glass structure is amorphous can be determined using an analytical instrument such as X-ray diffraction analysis or a transmission electron microscope. Among these, the sustained ion release glass used in the present invention preferably has an amorphous structure, which is a homogeneous structure, since various ions are sustainedly released depending on the equilibrium relationship with the ion concentration in the external environment.

Furthermore, in order to improve the sustained release of ions from the sustained ion release glass, it is a preferred embodiment to functionalize the glass surface by surface treatment to improve the sustained release of ions. Specific examples of surface treatment materials used for surface treatment include surfactants, fatty acids, organic acids, inorganic acids, monomers, polymers, various coupling agents, silane compounds, metal alkoxide compounds, and partial condensates thereof. Among these surface treatment materials, it is preferable to perform composite surface treatment using an acidic polymer and a silane compound.

This composite surface treatment is a method in which the ion sustained release glass surface is coated with a silane compound and then the surface is treated with an acidic polymer, and will be specifically explained below. A silane compound represented by formula (3) is mixed into an aqueous dispersion containing ion sustained release glass that has been finely pulverized to a desired average particle size (D50) by pulverization, etc., and this is hydrated in the system. It is decomposed or partially hydrolyzed to form a silanol compound, which is then condensed to form polysiloxane, which is then coated on the surface of a sustained ion release glass to obtain a polysiloxane-coated sustained ion release glass.

[Formula (3)]

(In the formula, Z is RO ^- , X is halogen, Y is OH ^- , R is an organic group having 8 or less carbon atoms, n, m, and L are integers from 0 to 4, and n+m+L=4)

Specific examples of the silane compound represented by formula (3) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraallyloxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, and trimethoxysilane. Examples include chlorosilane, triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane, diethoxydichlorosilane, tetraphenoxysilane, tetrachlorosilane, silicon hydroxide (silicon oxide hydrate), and more preferably tetramethoxysilane and It is tetraethoxysilane.

Further, a low condensate of a silane compound represented by formula (3) is more preferable. For example, it is a low condensation silane compound obtained by partially hydrolyzing and condensing tetramethoxysilane and tetraethoxysilane. These compounds can be used alone or in combination. Furthermore, an organosilane compound can also be added as a part of the silane compound represented by formula (3) during the polysiloxane treatment.

An ion sustained release glass can be obtained by subjecting the polysiloxane-coated sustained ion release glass obtained in the previous step to an acidic polymer treatment in which it is reacted with an acidic polymer. For the acidic polymer treatment, equipment commonly used in the industry can be used as long as it is a dry flow type stirrer, such as a Henshil mixer, a super mixer, a high speed mixer, and the like. The reaction of the acidic polymer to the ion sustained release glass on which the polysiloxane film is formed can be carried out by contacting the glass with an acidic polymer solution by impregnation, spraying, or the like. For example, it is sufficient to dry-fluidize polysiloxane-coated sustained ion release glass, disperse an acidic polymer solution from above in the fluidized state, and stir thoroughly. At this time, the method of dispersing the acidic polymer solution is not particularly limited, but a dropping or spraying method that allows uniform dispersion is more preferable. Further, the reaction is preferably carried out at around room temperature; as the temperature rises, the reaction between the acid-reactive element and the acidic polymer becomes faster and the formation of the cement phase becomes non-uniform.

It is preferable to perform post-reaction heat treatment to remove moisture within the cement reaction phase. If water remains in the cement reaction phase, it will be disadvantageous in terms of strength, but since the filler of the present invention is covered and strengthened by a coupling agent condensate film, a decrease in mechanical strength is suppressed. The heat treatment method after the acidic polymer treatment is not particularly limited, and any known general method can be used. Preferably, the equipment used for the heat treatment is a box-shaped hot air dryer or the like, or a rotary heat treatment device capable of uniform heating. The heat treatment temperature ranges from room temperature to 200°C, more preferably from 40 to 150°C. If the temperature is lower than this range, removal of the aqueous medium will be insufficient, and if it is higher than this range, the organic layer of the acidic polymer may decompose or discolor. Since the heat treatment time depends on the capacity of the dryer, etc., there is no problem as long as the time allows sufficient removal of the aqueous medium. After the heat treatment, the heat-treated product can be easily crushed by applying shearing force or impact force, and the crushing method can be carried out using the equipment used in the above reaction.

There is no problem with the solvent used to prepare the acidic polymer solution used in the reaction as long as the acidic polymer is dissolved therein, and examples thereof include water, ethanol, ethanol, acetone, and the like. Among these, water is particularly preferred because it allows the acidic groups of the acidic polymer to dissociate and react uniformly with the surface of the core basic filler.

The weight average molecular weight of the polymer dissolved in the acidic polymer solution is in the range of 2,000 to 50,000, preferably in the range of 5,000 to 40,000. When treated with an acidic polymer having a weight average molecular weight of less than 2,000, no acidic polymer reaction phase is formed in the polysiloxane-coated sustained ion release glass, and as a result, sustained ion release properties tend to decrease. On the other hand, when treated with an acidic polymer having a weight average molecular weight exceeding 50,000, the viscosity of the acidic polymer solution increases, making it difficult to uniformly treat the polysiloxane-coated ion sustained release glass. The acidic polymer concentration in 100 parts by weight of the acidic polymer solution is preferably in the range of 3 to 25 parts by weight, more preferably in the range of 8 to 20 parts by weight. When the acidic polymer concentration is less than 3 parts by mass, the acidic polymer reaction phase described above becomes brittle, and the effect of improving sustained ion release cannot be obtained. In addition, if the acidic polymer concentration exceeds 25 parts by mass, it will be difficult to uniformly diffuse through the polysiloxane layer (porous), making it impossible to obtain a homogeneous acidic polymer reaction phase, and the ion sustained release glass coated with polysiloxane Since a reaction occurs immediately upon contact with the material, problems such as the formation of strongly reacted aggregates occur. Further, the amount of the acidic polymer solution added to the polysiloxane-coated ion sustained release glass is preferably in the range of 6 to 40 parts by weight, more preferably 10 to 30 parts by weight. Based on this addition amount, the optimum amount of acidic polymer for the polysiloxane-coated sustained release glass is 1 to 7 parts by weight, and the optimum amount of water is 10 to 25 parts by weight.

Acidic polymers that can be used to form an acidic polymer reaction phase on the surface of polysiloxane-coated ion sustained release glass by the above method include phosphoric acid residues, pyrophosphoric acid residues, thiophosphoric acid residues as acidic groups. Any copolymer or homopolymer of a polymerizable monomer having an acidic group such as , carboxylic acid residue, or sulfonic acid group can be used without any problem. Specific examples of these polymerizable monomers include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, and citraconic acid. Acid, 4-(meth)acryloyloxyethoxycarbonylphthalic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic anhydride, 5-(meth)acryloylaminopentylcarboxylic acid, 11-(meth)acryloyloxy-1,1 -Undecanedicarboxylic acid, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, 1,3-dihydrogen phosphate (meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl phosphate, 2-(meth)acryloyloxyethyl-2'-bromoethyl phosphate, (meth)acryloyloxyethylphenyl Phosphonate, di(2-(meth)acryloyloxyethyl) pyrophosphate, 2-(meth)acryloyloxyethyl dihydrogendithiophosphate, 10-(meth)acryloyloxydecyl dihydrogenthiophosphate, and the like. Among the polymers (co)polymerized using these polymerizable monomers, α-β has a relatively slow acid-base reaction with the acid-reactive elements contained in the polysiloxane-coated ion sustained release glass. It is preferable to use a homopolymer or copolymer of unsaturated carboxylic acid, and specific examples thereof include acrylic acid polymer, acrylic acid-maleic acid copolymer, acrylic acid-itaconic acid copolymer, and the like.

The filler (E) mentioned above is used in the silane coupling material for the purpose of improving the affinity with the polymerizable monomer, the dispersibility in the polymerizable monomer, and the mechanical strength and water resistance of the cured product. It can be treated with typical surface treatment materials. Such surface treatment materials and surface treatment methods are not particularly limited, and include a method of spraying the surface treatment material while stirring a powdered filler, and a method of dispersing and mixing the filler and surface treatment material in a solvent. Any known method can be employed without limitation, such as a method of supplying a silane coupling material in the form of vapor or gas to the surface of the filler. Silane coupling materials used for surface treatment of fillers include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, and vinyltris(2-methoxysilane). ethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxy Preferred examples include octyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, and hexamethyldisilazane. Further, in addition to the silane coupling material, the surface treatment of the filler can be performed by a method using a titanate coupling material or an aluminate coupling material. The amount of the filler treated with the surface treatment material is preferably 0.01 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the filler before treatment.

(E) The shape of the filler is not particularly limited, and any shape of filler such as spherical, acicular, plate-like, crushed, and scale-like can be used. Further, the average particle diameter of the filler is preferably in the range of 0.01 μm to 50 μm, more preferably 0.01 μm to 30 μm, even more preferably 0.05 μm to 20 μm, and even more preferably 0.05 μm to 10 μm.

When the dental photocurable composition of the present invention contains (E) a filler, it is preferably 500 parts by mass or less per 100 parts by mass of (A) polymerizable monomer. When a filler is included, it can be expected that the strength of the physical properties will be improved, and when the filler exceeds 500 parts by mass, the operability of the dental photocurable composition may be reduced.

<Other ingredients>
Further, the dental photocurable composition of the present invention may contain components other than the above-mentioned components (A) to (E) as long as they do not impede the effects of the present invention. For example, excipients such as fumed silica, benzophenone-based and benzotriazole-based ultraviolet absorbers, hydroquinone, hydroquinone monomethyl ether, polymerization inhibitors such as 2,5-ditertiarybutyl-4-methylphenol, α- Alkylstyrene compounds, mercaptan compounds such as n-butylmercaptan, n-octylmercaptan, terpenoid compounds such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, α-pinene, etc. Chain transfer agents, metal supplements such as aminocarboxylic acid chelating agents, phosphonic acid chelating agents, discoloration inhibitors, antibacterial materials, coloring pigments, water and solvents that can be mixed with water in any ratio, and other Components such as conventionally known additives can be optionally added as necessary.

The method for producing the dental photocurable composition of the present invention is not particularly limited. As a general method for producing dental photocurable compositions, (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a polymerization accelerator are mixed in advance. After producing a matrix, this matrix and the filler (E) are kneaded, and air bubbles are removed under reduced pressure to prepare a uniform paste. Also in the present invention, it can be manufactured by the above manufacturing method without any problems.

The dental photocurable composition of the present invention is a dental adhesive, a dental composite resin, a dental abutment building material, a dental resin cement, a dental coating material, a dental pit and fissure sealing material, a dental It is preferably used for manicure materials, dental wobble teeth fixing adhesives, dental hard resins, dental cutting materials, and dental 3D printer materials, particularly preferably dental adhesives, dental composite resins, and dental materials. It is preferable to use it for an abutment building material, a dental resin cement, a dental coating material, a dental pit and fissure sealing material, a dental manicure material, and a dental moving tooth fixing material.

The dental photocurable composition of the present invention may contain only (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator. . Further, as components other than (A) to (D), only one or more of the above-mentioned components may be included.

Examples of the present invention will be specifically described below, but the present invention is not limited to these Examples.

The materials used in Examples and Comparative Examples and their abbreviations are shown below.
[(A) Polymerizable monomer]
・BisGMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane ・2.6E: 2,2-bis(4) with an average number of added moles of ethoxy group of 2.6 -(meth)acryloyloxypolyethoxyphenyl)propane/UDMA: N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)ethanol]methacrylate/NPG: Neopentyl glycol dimethacrylate/TEGDMA : Triethylene glycol dimethacrylate, MDP: 10-methacryloyloxydecyl dihydrogen phosphate, MHPA: 6-methacryloxyhexylphosphonoacetate, MET: 4-methacryloxyethyl trimellitic acid

[(B) Photosensitizer]
・CQ: Camphorquinone ・BAPO: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

・Ｃ２：ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムトリス（ペンタフルオロプロピル）トリフルオロホスフェート

・Ｃ３：ｐ－クメニル（ｐ－トリル）ヨードニウムトリス（ペンタフルオロエチル）トリフルオロホスフェート

・Ｃ４：ｐ－クメニル（ｐ－トリル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート

・Ｃ５：ビス［４－（ｔｅｒｔ－ブチル）フェニル］ヨードニウムテトラ（ノナフルオロ－ｔｅｒｔ－ブトキシ）アルミン酸塩

・Ｃ６：ｐ－クメニル（ｐ－トリル）ヨードニウムテトラ(ペンタフルオロフェニル)ガレート

＜有機基及びＰ、Ｂ、Ａｌ、Ｓ、Ｇａのいずれか１つ以上の原子を有するアニオンと、アリールヨードニウムカチオンとの塩＞
・Ｃ１１：ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウム－ｐ－トルエンスルホナート

＜有機基及びＰ、Ｂ、Ａｌ、Ｓ、Ｇａのいずれか１つ以上の原子を有するアニオンと、アリールヨードニウムカチオンとの塩ではない光酸発生剤＞
・Ｃ２１：ジフェニルヨードニウムクロリド

・Ｃ２２：２，４，６，－トリス（トリクロロメチル）－１，３，５－トリアジン

・Ｃ２３：ジフェニルヨードニウム－２－カルボキシラート一水和物

[(C) Photoacid generator]
<Salt of an aryliodonium cation and an anion having at least one organic group in which H is substituted with F and one or more atoms of P, B, Al, S, and Ga>
・C1: Bis(4-tert-butylphenyl)iodonium nonafluorobutane sulfonate

・C2: Bis(4-tert-butylphenyl)iodonium tris(pentafluoropropyl)trifluorophosphate

・C3: p-cumenyl (p-tolyl) iodonium tris (pentafluoroethyl) trifluorophosphate

・C4: p-cumenyl (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate

・C5: bis[4-(tert-butyl)phenyl]iodonium tetra(nonafluoro-tert-butoxy) aluminate

・C6: p-cumenyl (p-tolyl) iodonium tetra(pentafluorophenyl) gallate

<Salt of an anion having an organic group and one or more atoms of P, B, Al, S, and Ga and an aryliodonium cation>
・C11: Bis(4-tert-butylphenyl)iodonium-p-toluenesulfonate

<Photoacid generator that is not a salt of an organic group and an anion having one or more atoms of P, B, Al, S, and Ga and an aryliodonium cation>
・C21: diphenyliodonium chloride

・C22: 2,4,6,-tris(trichloromethyl)-1,3,5-triazine

・C23: diphenyliodonium-2-carboxylate monohydrate

［脂肪族第２級アミン化合物］
・Ｄ１－４：メタクリル酸２，２，６，６－テトラメチル－４－ピペリジル

＜他の第３級アミン化合物＞
＜＜脂肪族第３級アミン化合物＞＞
・ＴＢＡ：トリベンジルアミン
＜＜２つ以上の１級のヒドロキシル基を有する脂肪族第３級アミン化合物＞＞
・ＭＤＥＯＡ：メチルジエタノールアミン
・ＴＥＡ：トリエタノールアミン
＜＜芳香族第３級アミン化合物＞＞
・ＤＭＢＥ：Ｎ，Ｎ‐ジメチルアミノ安息香酸エチル
・ＤＨＰＴ：Ｎ，Ｎ－ジ（２－ヒドロキシプロピル）－ｐ－トルイジン [(D) Polymerization accelerator]
[(D1) Hindered amine compound]
[Tertiary aliphatic amine compound]
・D1-1: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate ・D1-2: Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate
・D1-3: 2-(2-((((1,2,2,6,6-pentamethylpiperidin-4-yl)oxy)carbonyl)amino)ethoxy)ethyl methacrylate

[Aliphatic secondary amine compound]
・D1-4: 2,2,6,6-tetramethyl-4-piperidyl methacrylate

<Other tertiary amine compounds>
<<Aliphatic tertiary amine compound>>
・TBA: Tribenzylamine <<Aliphatic tertiary amine compound having two or more primary hydroxyl groups>>
・MDEOA: Methyldiethanolamine ・TEA: Triethanolamine <<Aromatic tertiary amine compound>>
・DMBE: Ethyl N,N-dimethylaminobenzoate ・DHPT: N,N-di(2-hydroxypropyl)-p-toluidine

[(E) Filler]
The manufacturing method of each filler used in the preparation of the dental photocurable composition is shown below.

(Filler E1)
To 100.0 g of fluoroaluminosilicate glass (average particle size 1.1 μm), 50.0 g of water, 35.0 g of ethanol, and 3.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were added at room temperature for 2 hours. The silane coupling treatment solution obtained by stirring was added, and the mixture was stirred and mixed for 30 minutes. Thereafter, heat treatment was performed at 100° C. for 15 hours to obtain filler E1.

(Filler E2)
For 100.0 g of zirconium silicate filler (average particle size 0.8 μm: zirconia 85 wt%, silica 15 wt%), 50.0 g of water, 35.0 g of ethanol, and 3-methacryloyloxypropyltrimethoxysilane 5 as a silane coupling material. 0g was stirred at room temperature for 2 hours, the resulting silane coupling treatment solution was added, and the mixture was stirred and mixed for 30 minutes. Thereafter, heat treatment was performed at 100° C. for 15 hours to obtain filler E2.

(Filler E3)
After mixing various raw materials such as silicon dioxide, aluminum oxide, boron oxide, sodium fluoride, and strontium carbonate, the mixture is melted at 1400°C to make glass A (glass composition: SiO ₂ : 22.5% by mass, Al ₂ O ₃ : 20.0% by mass, B ₂ O ₃ : 12.3% by mass, SrO: 35.7% by mass, Na ₂ O: 2.5% by mass, F: 7.0% by mass). Next, the obtained glass A was ground for 100 hours using a vibration mill, and then further ground for 3 hours using a wet bead mill. To 100 g of the obtained pulverized material, 4.5 g of a low condensate of a silane compound "MKC silicate MS56S" (SiO ₂ content 56.0% by mass, degree of polymerization 2 to 100, manufactured by Mitsubishi Chemical Corporation) was added, The mixture was stirred and mixed for about 90 minutes. After mixing for a predetermined time, the resulting treated slurry was aged in a hot air dryer at 50° C. for 40 hours, heated to 150° C., moored for 6 hours, and then cooled to obtain a heat-treated product. The obtained heat-treated product was placed in a Henschel mixer and crushed at 1800 rpm for 5 minutes. After crushing, a polysiloxane-treated product with good fluidity was obtained.
(Acidic polymer treatment)
100 g of the polysiloxane-treated product was placed in a Henschel mixer, and while stirring, 16.0 g of a polyacrylic acid aqueous solution (polymer concentration 13% by mass, weight average molecular weight 20,000, manufactured by Nacalai) was sprayed onto the mixture. After spraying, the powder taken out from the mixer was heated at 100° C. for 3 hours in a hot air dryer to obtain a polysiloxane-polyacrylic acid treated product.
(silane treatment)
Polysiloxane-polyacrylic acid treated product: For 100 g, add 100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 8-methacryloyloxypropyltrimethoxysilane as a silane coupling material at room temperature for 2 hours. The silane coupling treatment solution obtained by stirring was added, and the mixture was stirred and mixed for 30 minutes. Thereafter, heat treatment was performed at 100° C. for 15 hours to obtain filler E3.

(Filler E4)
To 100 g of the above polysiloxane treated product, 100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 8-methacryloyloxyoctyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours. The obtained silane coupling treatment liquid was added and mixed with stirring for 30 minutes. Thereafter, heat treatment was performed at 100° C. for 15 hours to obtain filler E4.

(Filler E5)
Aerosil R-711 (manufactured by Evonik)
(Filler E6)
Titanium oxide R-820 (manufactured by Ishihara Sangyo Co., Ltd.)

[Ultraviolet absorber]
・BT: 2-(2-hydroxy-5-methylphenyl)benzotriazole [polymerization inhibitor]
・MeHQ: p-methoxyphenol [fluorescent agent]
・FA: Diethyl 2.5-dihydroxyterephthalate

<Method for producing dental photocurable composition>
Everything except the filler (E) shown in Table 1 was placed in a wide-mouth plastic container, and mixed using a mix rotor VMRC-5 at 100 rpm for 48 hours to obtain a matrix. After that, the matrix and the filler (E) were put into an autorotation-revolution kneader, stirred uniformly, and defoamed under vacuum to obtain a paste, which was then filled into a 2 mL PP syringe and filled with dental light. A curable composition was prepared. In Table 1, the part by mass of each component is written in parentheses after the abbreviation of each component.

(1) Bending strength After filling the prepared dental photocurable composition into a stainless steel mold, placing cover glasses on both sides and pressing with a glass mixing plate, use a photopolymerization irradiator (Pembrite, manufactured by Shofu). ) was used to irradiate light at 5 locations for 10 seconds each to cure. After curing, the cured product was taken out from the mold, and the back surface was also irradiated with light in the same manner, and it was used as a test specimen (25×2×2 mm: rectangular parallelepiped shape). The test specimen was immersed in water at 37° C. for 24 hours, and then subjected to a bending test. The bending test was conducted using an Instron universal testing machine (manufactured by Instron) at a distance between fulcrums of 20 mm and a crosshead speed of 1 mm/min. The bending strength of the dental photocurable composition was judged to be good if it was 100 MPa or more, applicable if it was 90 to less than 100 MPa, somewhat low if it was 80 to less than 90 MPa, and insufficient if it was less than 80 MPa.

(2) Thermochromic stability After filling a stainless steel mold (15φ×1 mm: disk shape) with the prepared dental photocurable composition, a cover glass was placed from above and pressure bonded using a glass plate. The cover glass was irradiated with light for 1 minute using a photopolymerization irradiator (Grip Light II: manufactured by Shofu) to cure it. After taking out the cured product from the mold, the cover glass was removed and the color tone of this specimen was I measured the color. For color measurement, place the specimen on the background of a standard white plate (D65/10° The measurement was carried out under certain conditions (light source: C, viewing angle: 2°, measurement area: 11 mm). After that, the test specimen was immersed in a container containing 10 mL of water in a constant temperature chamber set at 70°C, and after being allowed to stand for one week, the color tone of the test specimen was measured again, and the difference in color change was calculated using the following formula. It is expressed as ΔE calculated from

ΔE={(ΔL*) ² + (Δa*) ² + (Δb*) ² } ^1/2
ΔL*=L1*−L2*
Δa*＝a1*−a2*
Δb*=b1*−b2*

Here, L1* is the lightness index before immersion and standing, L2* is the lightness index after immersion and standing, a1*, b1* is the color quality index before immersion and standing, a2*, b2* is immersion - Color quality index after standing still. A case where ΔE was less than 10 was judged as A, as it was good, and a case where ΔE was 10 or more was judged as B, as it was unsatisfactory. Thermochromic stability is measured in order to predict the color change when the cured product is used for a long time.The smaller the ΔE, the smaller the color change when the cured product is used for a long time, which makes it suitable for dental materials that require aesthetics. Preferably used.

(3) Light color stability After filling a stainless steel mold (15φ×1 mm: disk shape) with the prepared dental photocurable composition, a cover glass was placed from above and pressed against the mold using a glass plate. The cover glass was irradiated with light for 1 minute using a photopolymerization irradiator (Grip Light II: manufactured by Shofu) to cure it. After taking out the cured product from the mold, the cover glass was removed and the color tone of this specimen was I measured the color. For color measurement, place the specimen on the background of a standard white plate (D65/10° The measurement was carried out under certain conditions (light source: C, viewing angle: 2°, measurement area: 11 mm). After that, the test piece was exposed to light for 24 hours using a xenon lamp light exposure tester (Suntest CPS+), and the color tone of the test piece was measured again, and the difference in color change was expressed as ΔE calculated from the following formula. .

ΔE={(ΔL*) ² + (Δa*) ² + (Δb*) ² } ^1/2
ΔL*=L1*−L2*
Δa*＝a1*−a2*
Δb*=b1*−b2*

Here, L1* is the lightness index before light exposure, L2* is the lightness index after light exposure, a1*, b1* is the color index before light exposure, a2*, b2* is the color index after light exposure It is. A: Good if ΔE is less than 5; B: Applicable when ΔE is between 5 and less than 8; C: Applicable when ΔE is between 8 and less than 10; C: Applicable when ΔE is 10 or more. It was judged as insufficient. Photocolor stability is measured in order to predict the color change when the cured product is used for a long period of time in a place where it is exposed to light, and the smaller the ΔE, the smaller the color change even if the cured product is exposed to light for a long time. .

The results in Table 2 will be described.

It was confirmed that the compositions described in Examples had sufficient bending strength and color stability.

(D1) Examples containing aliphatic tertiary amine compounds D1-1, D1-2, and D1-3 as the hindered amine compound tended to exhibit excellent bending strength when preferred blending amounts were included. On the other hand, it was confirmed that among the hindered amine compounds (D1), Examples 19 and 20 containing D1-4, which is an aliphatic secondary amine compound, tended to have slightly inferior bending strength.

Example 2 with a small amount of camphorquinone, a photosensitizer, Example 4 with a small amount of a photoacid generator, and Example 7 with a small amount of a photopolymerization accelerator tend to have low bending strength. there were.
Similarly, in Example 6 with a slightly smaller amount of photosensitizer, Example 3 with a slightly smaller amount of photoacid generator, and Example 5 with a slightly smaller amount of (D1) hindered amine compound, the bending strength was It tended to be slightly lower. On the other hand, Example 4, which contained a large amount of photosensitizer, and Example 2, which contained large amounts of photoacid generator and photopolymerization accelerator, tended to have somewhat poor light color stability.

Although Example 31 containing BAPO as a photosensitizer had good bending strength, the photocolor stability tended to decrease. In addition, when measuring the environmental light stability separately, the time was shorter than when only camphorquinone was included. Since longer environmental photostability is preferred, the photosensitizer is preferably only α-diketones including camphorquinone.

Does not contain a salt of an aryliodonium cation and an anion having at least one organic group in which H is substituted with F and one or more atoms of P, B, Al, S, or Ga as a photoacid generator. Among Examples, Example 8 contains a C11 photoacid generator which is a salt of an organic group and an anion having one or more atoms of P, B, Al, S, and Ga, and an aryliodonium cation. The light color stability was slightly lowered, and Examples 9 to 11 containing other photoacid generators tended to have even lower light color stability.

Among Examples 5, 7, 19, 20, 23 to 28 containing an aromatic tertiary amine compound, Examples 5, 7, 23, 24, and 25, which did not contain an ultraviolet absorber, tended to have poor light color stability. It was there.

Example 28, which did not contain a filler, showed a lower bending strength than the example which contained a filler, and Example 29, which contained a large amount of filler, had a hard property and tended to have poor operability. .

Comparative Examples 1, 2, and 3, which did not contain a photosensitizer, photoacid generator, or photopolymerization accelerator, tended not to cure or to have low bending strength. Comparative Examples 4 and 5 containing amine compounds having a primary hydroxyl group at the α- or β-position carbon of amine-derived N tended to have low thermal color stability and were poor in color tone stability.

According to the present invention, it is possible to provide a dental photocurable composition that can achieve both sufficient mechanical strength and color stability after curing.

Claims (6)

(A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a polymerization accelerator,
(D) A dental photocurable composition containing (D1) a hindered amine compound as a polymerization accelerator. The dental photocurable composition according to claim 1, wherein the hindered amine compound (D1) is an aliphatic tertiary amine compound. (C) containing an aryliodonium salt as a photoacid generator;
The dental photocuring method according to claim 1 or 2, wherein the aryliodonium salt is a salt of an aryliodonium cation and an anion having an organic group and one or more atoms of P, B, Al, S, and Ga. sexual composition. (C) containing an aryliodonium salt as a photoacid generator;
The aryliodonium salt is a salt of an aryliodonium cation and an anion having at least one organic group in which H is substituted with F and one or more atoms of P, B, Al, S, or Ga. Item 2. The dental photocurable composition according to item 1 or 2. The dental photocurable composition according to any one of claims 1 to 4, wherein the polymerizable monomer (A) is a radically polymerizable monomer. (A) For 100 parts by mass of polymerizable monomer,
(B) Contains 0.02 to 1 part by mass of a photosensitizer,
(C) Contains 0.1 to 5 parts by mass of a photoacid generator,
(D1) containing 0.2 to 5 parts by mass of a hindered amine compound;
The dental photocurable composition according to any one of claims 1 to 5.