1. A dental photocurable composition, wherein,

which comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator and (D) a photopolymerization accelerator,

and (C) a photoacid generator comprising (C-1) an iodonium salt compound formed with an anion having a logS of-4 or less.

2. The dental photocurable composition according to claim 1, wherein,

the composition contains 0.5 parts by mass or more of an iodonium salt compound of (C-1) and an anion having a logS of-4 or less per 100 parts by mass of the polymerizable monomer (A).

3. The dental photocurable composition according to claim 1 or 2, wherein,

the iodonium salt compound (C-1) containing an anion having a logS of-4 or less comprises an aryl iodonium salt composed of an anion having an organic group and at least one atom selected from the group consisting of P, B, Al, S and Ga and an aryl iodonium cation.

4. The dental photocurable composition according to claim 1 or 2, wherein,

the iodonium salt compound (C-1) containing an anion having a logS of-4 or less comprises an aryl iodonium salt composed of an anion having an organic group in which at least 1 or more H is substituted with F and at least one atom selected from among P, B, Al, S and Ga, and an aryl iodonium cation.

5. The dental photocurable composition according to any one of claims 1 to 4, wherein,

the photopolymerization accelerator (D) contains an aliphatic tertiary amine compound.

6. The dental photocurable composition according to any one of claims 1 to 4, wherein,

the photopolymerization accelerator (D) contains (D-1) an aliphatic tertiary amine compound having no primary hydroxyl group of 2 or more.

7. The dental photocurable composition according to any one of claims 1 to 6, wherein,

which is a dental photocurable composition in a single dosage form,

the photosensitive resin composition contains 0.005-1.0 parts by mass of a photosensitizer (B), 0.5-10.0 parts by mass of a photoacid generator (C), and 0.01-20 parts by mass of a photopolymerization accelerator (D) per 100 parts by mass of a polymerizable monomer (A).

8. The dental photocurable composition according to any one of claims 1 to 6, wherein,

which is a two-part type dental photocurable composition,

consists of a first paste and a second paste,

the specific gravity of the first paste and the second paste is 1: 0.8 to 1.2 parts by weight,

the photosensitive paste comprises 0.01-2.0 parts by mass of a photosensitizer (B), 1.0-20 parts by mass of a photoacid generator (C), and 0.02-40 parts by mass of a photopolymerization accelerator (D), based on 200 parts by mass of the polymerizable monomer (A) contained in the first paste and the second paste.

Background

The photocurable composition for dental use is used for the treatment of oral cavity in the dental field, and is applied to dental adhesive materials, dental composite resins, dental abutment building materials, dental resin cement, dental coating materials, dental pit and fissure sealant materials, dental cosmetic materials, dental loose tooth fixing adhesive materials, dental glass cement, dental cutting materials, dental 3D printing materials, and the like.

Japanese patent No. 4093974 proposes a photopolymerization initiator containing a photoacid generator (a triazine compound or a specific aryliodonium salt), a sensitizer, and an electron donor compound as a photopolymerization initiator.

Japanese patent No. 4596786 proposes a photopolymerization initiator containing a photoacid generator (a triazine compound or a specific aryliodonium salt), a sensitizer, and an electron donor compound as a photopolymerization initiator.

Disclosure of Invention

However, the dental photocurable compositions using the conventional photopolymerization initiators described in japanese patent nos. 4093974 and 4596786 cannot obtain sufficient physical properties after storage at low temperatures.

The purpose of the present invention is to provide a dental photocurable composition that can exhibit excellent mechanical and physical properties even after returning from low temperatures to room temperature.

The dental photocurable composition of the present invention comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, wherein the photoacid generator comprises (C-1) an iodonium salt compound formed with an anion having a logS of-4 or less.

The dental photocurable composition of the present invention also exhibits excellent mechanical physical properties after returning from low temperature to room temperature.

Detailed Description

In the present invention, the iodonium salt-based compound formed from (C-1) and an anion having a log S of-4 or less can be contained in an amount of 0.5 parts by mass or more per 100 parts by mass of the polymerizable monomer (A).

In the present invention, the iodonium salt compound formed by (C-1) and an anion having a logS of-4 or less may include an aryliodonium salt having an anion containing an organic group and one or more atoms selected from P, B, Al, S and Ga.

In the present invention, the iodonium salt compound formed between (C-1) and an anion having a logS of-4 or less may include an aryliodonium salt having an anion containing an organic group in which at least 1 or more H is substituted with F and one or more atoms selected from P, B, Al, S and Ga.

In the present invention, the photopolymerization accelerator (D) may contain an aliphatic tertiary amine compound.

In the present invention, (D-1) an aliphatic tertiary amine compound having no 2 or more primary hydroxyl groups can be contained as the photopolymerization accelerator (D).

The present invention provides a dental photocurable composition which can be a one-pack type, comprising, per 100 parts by mass of (A) a polymerizable monomer, (B) 0.005 to 0.5 parts by mass of a photosensitizer, (C) 0.5 to 10.0 parts by mass of a photoacid generator, and (D) 0.01 to 20 parts by mass of a photopolymerization accelerator.

In the present invention, the photocurable composition may be a two-pack type, and comprises a first paste and a second paste, wherein the specific gravity of the first paste and the second paste is 1: 0.8 to 1.2 parts by mass of (B) a photosensitizer, 1.0 to 20 parts by mass of (C) a photoacid generator, and 0.02 to 40 parts by mass of (D) a photopolymerization accelerator, with respect to 200 parts by mass of the total of (A) polymerizable monomers contained in the first and second pastes.

The components of the dental photocurable composition of the present invention will be described in detail below. The dental photocurable composition of the present invention is used as 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 sealant, a dental cosmetic material, a dental loose tooth fixing adhesive material, a dental hard resin, a dental cutting material, or a dental 3D printing material.

In the dental clinic, in order to restore the aesthetic and functional defects of teeth caused by caries, breakage, or the like, a treatment is performed in which a prosthetic device made of ceramic or a dental hard resin is directly restored with a dental composite resin or indirectly restored with a dental resin cement. Furthermore, dental coating materials for protecting hypersensitive or formed living pulp teeth from external irritation or secondary caries, and dental pit crack sealer for preventing caries by filling up complicated pits such as deciduous teeth, are used for dental adhesive materials for bonding dental composite resins to various dental materials and natural teeth, dental loose tooth fixing adhesive materials for fixing loose teeth, and dental pit crack sealer for filling up complicated pits such as deciduous teethA dental cosmetic material for temporarily restoring aesthetic quality due to tooth discoloration, and a dental abutment building material for forming an abutment when a crown portion collapses due to dental caries. In recent years, composite materials such as dental cutting materials for producing prosthetic devices by CAD/CAM machining and dental 3D printing materials for producing prosthetic devices by 3D printing have been newly developed, and various dental materials are used for treatment. The above-mentioned materials are mixed with a resin matrix composed of a plurality of polymerizable monomers, various fillers such as an inorganic filler and an organic-inorganic composite filler, and a polymerization initiator according to the use thereof, and are prepared into a uniform paste. Some of the materials are used by filling a dental filling composite resin in the form of an uncured paste into a tooth, imparting an anatomical shape of a natural tooth with a dental instrument such as a device, and irradiating the tooth with light such as a dental light irradiator to cure the dental filling composite resin. For the irradiation light from the light irradiator, a light intensity of 100 to 2000mW/cm in a wavelength range of about 360 to 500nm is generally used²Left and right output light sources. On the other hand, the dental resin cement is used for bonding a prosthetic device to a socket or an abutment, and is cured by light irradiation after the prosthetic device is mounted on the socket or the abutment.

As a photopolymerization initiator used for such dental materials, a photosensitizer and a system in which an appropriate photopolymerization accelerator is combined with the photosensitizer are widely used. As the photosensitizer, an acylphosphine oxide compound, an α -diketone compound, and particularly an α -diketone compound are known to have polymerization initiating ability in a visible light wavelength region having little influence on the human body. In addition, as a polymerization accelerator combined with a photosensitizer, a tertiary amine compound is known, and the combination of an α -diketone compound and a tertiary amine compound has high polymerization activity against light and is therefore used in the field of dental materials. The dental photocurable composition containing the photopolymerization initiator exhibits excellent mechanical properties such as hardness, flexural strength, and compressive strength required for various materials.

However, when the combination of the α -diketone compound and the tertiary amine compound is used as a photopolymerization initiator, there arises a problem of lack of stability to ambient light. That is, when an operator performs irradiation with white light (ambient light) such as a dental lamp or an indoor lamp like a fluorescent lamp in the oral cavity and uses only the combination of the α -diketone compound and the tertiary amine compound as a photopolymerization initiator, the operator has a problem that curing is gradually performed during operations such as filling, build-up welding, and mounting, since the operator exhibits high sensitivity to not only the irradiation light but also the ambient light, and the operation becomes difficult.

In order to solve the above problems, a photopolymerization initiator including an aryl iodonium salt as a photoacid generator, a sensitizer, and an electron donor compound has been proposed, but there is a problem in solubility in the dental photocurable composition, and since precipitation occurs when the composition is stored at low temperature, sufficient physical properties may not be exhibited when the dental photocurable composition is used after being transported to a cold region.

The present inventors have found that the photocurable dental composition of the present invention exhibits excellent physical properties without causing precipitation during storage at low temperatures when using a photoacid generator having high lipid solubility, and have completed the present invention. More specifically, it was found that the lipid solubility of the anion of the aryliodonium salt has a large influence on the solubility of the polymerizable monomer. The present inventors have found that a photocurable composition for dental use, which contains an aryliodonium salt formed with an anion having a Log Solubility of a specific value, is stable in properties even under storage conditions of refrigeration and freezing, and that Log S is a measure of water Solubility which is a property contrary to fat Solubility and is obtained by calculation, and have completed the present invention.

[ (A) polymerizable monomer ]

The polymerizable monomer (a) of the present invention can be used without limitation as long as it is a known one. In the polymerizable monomer or the compound having a polymerizable group described in the present invention, the polymerizable group is preferably a group exhibiting radical polymerizability, and specifically, from the viewpoint of easy radical polymerization, the polymerizable group is preferably a (meth) acrylic group and/or a (meth) acrylamide group. In the present specification, "(meth) acrylic group" means an acrylic group and/or a methacrylic group, "(meth) acryloyl group" means an acryloyl group and/or a methacryloyl group, "(meth) acrylate" means an acrylate and/or a methacrylate, and "(meth) acrylamide" means acrylamide and/or methacrylamide. It is also possible to use a polymerizable monomer having a substituent at the α -position of the acrylic group and/or the acrylamide group. There are compounds having one radical polymerizable group, compounds having two radical polymerizable groups, compounds having three or more radical polymerizable groups, compounds having an acidic group, compounds having an alkoxysilyl group, a sulfur atom, and the like.

Specific examples of the polymerizable monomer having one radical polymerizable group and no acidic group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) 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- (dihydroxyethyl) (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2, 3-dibromopropyl (meth) acrylate, 3- (meth) acryloyloxypropyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane, (meth) acrylamide, and the like.

Specific examples of the polymerizable monomer having two radically polymerizable groups and no acidic group include 2, 2-Bis ((meth) acryloyloxyphenyl) propane, 2-Bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl ] propane (commonly known as "Bis-GMA"), 2-Bis (4- (meth) acryloyloxyphenyl) propane, 2-Bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-Bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2-Bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2-Bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2, 2-bis (4- (meth) acryloyloxydipropylphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxydiethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropylphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2-bis (4- (meth) acryloyloxypropylphenyl) propane, 2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane, a salt thereof, a hydrate thereof, a crystalline solid thereof, and a crystalline solid thereof, 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, butanediol 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, ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, ethylene glycol (2-acrylate, propylene glycol (2-acrylate, ethylene glycol (meth) acrylate, ethylene glycol (2-acrylate, ethylene glycol (2-acrylate, propylene glycol (2-acrylate, and propylene glycol (2-acrylate, ethylene glycol (2-acrylate, and propylene glycol (2-acrylate, and propylene glycol (2-acrylate, and propylene glycol (2-acrylate), and propylene glycol (2-2, 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 the polymerizable monomer having three or more radically polymerizable groups and no acidic group include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N- (2, 2, 4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1, 3-diol ] tetramethylacrylate, 1, 7-diacryloyloxy-2, 2, 6, 6-tetraacryloxymethyl-4-oxyheptane, and the like.

The polymerizable monomer having an acidic group can be used without limitation as long as it has one or more polymerizable groups and at least one acidic group such as a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonate group, a sulfonate group, and a carboxylic acid group.

Specific examples of the polymerizable monomer having a phosphoric acid group include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxydecyl undecyl dihydrogen phosphate, 12- (meth) acryloyloxydodecyl dihydrogen phosphate, 16- (meth) acryloyloxycetanyl dihydrogen phosphate, and mixtures thereof, 20- (meth) acryloyloxyeicosyl dihydrogen phosphate, bis [2- (meth) acryloyloxyethyl ] hydrogen phosphate, 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-bis (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl ] hydrogen phosphate; acid chlorides, alkali metal salts, ammonium salts of these compounds; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds.

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

Specific examples of the polymerizable monomer having a thiophosphoric acid group include 2- (meth) acryloyloxyethyl dihydrogen thiophosphate, 3- (meth) acryloyloxypropyl dihydrogen thiophosphate, 4- (meth) acryloyloxybutyl dihydrogen thiophosphate, 5- (meth) acryloyloxypentyl dihydrogen thiophosphate, 6- (meth) acryloyloxyhexyl dihydrogen thiophosphate, 7- (meth) acryloyloxyheptyl dihydrogen thiophosphate, 8- (meth) acryloyloxyoctyl dihydrogen thiophosphate, 9- (meth) acryloyloxynonyl dihydrogen thiophosphate, 10- (meth) acryloyloxydecyl dihydrogen thiophosphate, 11- (meth) acryloyloxydecyl hydrogen thiophosphate, 12- (meth) acryloyloxydodecyl hydrogen thiophosphate, 2- (meth) acryloyloxy hydrogen sulfide, 3- (meth) acryloyloxybutyl hydrogen thiophosphate, 5- (meth) acryloyloxy butyl hydrogen sulfide, 5- (meth) acryloyloxy-butyl) thiophosphate, 2- (meth) acryloyloxy-butyl hydrogen sulfide, 2- (meth) alkyl hydrogen sulfide, 2- (meth) acryloyloxy-butyl) thio-phosphate, 2-phosphate, and (meth) acryloyloxy-butyl-hydrogen sulfide, 16- (meth) acryloyloxycetaxalkyl thiophosphate dihydrogen ester, 20- (meth) acryloyloxyeicosyl thiophosphate dihydrogen ester; acid chlorides, alkali metal salts, ammonium salts of these compounds; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds. The polymerizable monomer having a thiophosphoric group may be classified as a polymerizable monomer having a sulfur atom.

Specific examples of the polymerizable monomer having a phosphonic acid group include 2- (meth) acryloyloxyethylphenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonoacetate, 10- (meth) acryloyloxydecyl-3-phosphonoacetate; acid chlorides, alkali metal salts, ammonium salts of these compounds; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds.

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

Polymerizable monomers having a carboxylic acid group are classified into (meth) acrylic compounds having one carboxylic acid group in the molecule and (meth) acrylic compounds having a plurality of carboxylic acid groups in the molecule. Specific examples of the (meth) acrylic compound having one carboxyl group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, O- (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, N- (meth) acryloylaspartic acid, N- (meth) acryloyltyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloylp-aminobenzoic acid, N- (meth) acryloylbenzoic acid, N- (meth) acryloylL-4-aminosalicylic acid, N- (meth) acryloylaspartic acid, N- (meth) acryloylL-4-aminosalicylic acid, N- (meth) acryloylaspartic acid, N-4-aminosalicylic acid, N- (meth) acryloylbenzoic acid, N- (meth) acryloylaspartic acid, N-p-4-aminobenzoic acid, N-4-acryloylbenzoic acid, N-4-aminobenzoic acid, N-4-aminobenzoic acid, N-4-acryloylbenzoic acid, or N-4-aminobenzoic acid, N-acryloylbenzoic acid, N-4-amino-4-amino-benzoic acid, or N-4-amino-4-amino-benzoic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydrogen malate; acid halides of these compounds; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds. Specific examples of the (meth) acrylic compound having a plurality of 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, and, 4- (meth) acryloyloxydecyl trimellitate, 2- (meth) acryloyloxyethyl-3 '- (meth) acryloyloxy-2' - (3, 4-dicarboxybenzoyloxy) propyl succinate; acid anhydrides and acid halides of these compounds; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds.

Specific examples of the polymerizable monomer having an alkoxysilyl group include a (meth) acrylic compound having one alkoxysilyl group in the molecule and a (meth) acrylic compound having a plurality of alkoxysilyl groups in the molecule. Examples thereof include 2- (meth) acryloyloxyethyltrimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 4- (meth) acryloyloxybutyltrimethoxysilane, 5- (meth) acryloyloxypentyltrimethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 7- (meth) acryloyloxyheptyltrimethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 9- (meth) acryloyloxynonyltrimethoxysilane, 10- (meth) acryloyloxydecyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane.

As long as the polymerizable monomer having a sulfur atom is a polymerizable monomer having one or more sulfur atoms and a polymerizable group, a known compound can be used without any limitation. Specifically, the compound has a partial structure such as-SH, -S-, > C ═ S, > C-S-C <, > P ═ S, or the like, or the above structure is produced by tautomerism. Specific examples thereof include 10-methacryloyloxydecyl-6, 8-dithiooctanoate, 6-methacryloyloxyhexyl-2-thiouracil-5-carboxylate, 2- (11-methacryloyloxyundecylthio) -5-mercapto-1, 3, 4-thiadiazole, and 10- (meth) acryloyloxydecyl thiophosphate.

There is no limitation to use an oligomer or prepolymer having at least one polymerizable group in the molecule other than the polymerizable monomers. Further, there is no problem even if a substituent such as a fluorine group is present in the same molecule. The polymerizable monomers described above can be used not only alone but also in combination of a plurality of types.

The dental photocurable composition of the present invention can contain a known polymerizable monomer having an acid group as the polymerizable monomer (a) to impart adhesiveness to dentin and a prosthetic device. Preferably 10-methacryloyloxydecyl dihydrogen phosphate or 6-methacryloyloxyhexyl phosphoryl acetate. From the viewpoint of imparting adhesiveness, the amount of the acidic group-containing polymerizable monomer is 1 part by mass or more, and more preferably 10 parts by mass or more, relative to 100 parts by mass of the total amount of the polymerizable monomers contained in the dental photocurable composition.

The dental photocurable composition of the present invention can contain a silane coupling agent as the polymerizable monomer (a) in order to impart adhesiveness to the glass ceramic. Any known silane coupling agent can be used without limitation, but 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, and 11-methacryloxyundecyltrimethoxysilane are preferable. From the viewpoint of imparting adhesiveness, the amount of the polymerizable monomer is 1 part by mass or more, and more preferably 10 parts by mass or more and less than 20 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomers in the composition. Since the silane coupling agent as a polymerizable monomer is intended to impart adhesiveness to a resin material or the like containing a glass ceramic or a filler made of a glass ceramic, it is necessary to mix the silane coupling agent separately from a surface treatment agent for the filler.

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 adhesion to a noble metal. From the viewpoint of imparting adhesiveness, the amount of the polymerizable monomer having a sulfur atom to be blended is 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more and less than 10 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomers contained in the dental photocurable composition.

< photopolymerization initiator >

The photopolymerization initiator used in the dental photocurable composition of the present invention includes (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, and these are not particularly limited, and commonly used known compounds can be used without any limitation.

[ (B) photosensitizer ]

Specific examples of the photosensitizer (B) that can be used in the present invention include benzyl, camphorquinone carboxylic acid, camphorquinone sulfonic acid, α -naphthyl, naphthone, p '-dimethoxybenzyl, p' -dichlorobenzylacetyl, pentanedione, 1, 2-phenanthrenequinone, 1, 4-phenanthrenequinone, α -diketones such as 3, 4-phenanthrenequinone, 9, 10-phenanthrenequinone, and naphthoquinone, benzoin alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2, 4-diethylthioxanthone and 2, 4-diisopropylthioxanthone; benzophenones such as benzophenone, p-chlorobenzophenone, and 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-methylpropan-1-yl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) - (1-methylpropan-1-yl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) -tert-butylphosphine oxide, bis (2, 6-dimethoxybenzoyl) cyclohexylphosphine oxide, bis (2, 6-dimethoxybenzoyl) octylphosphine oxide, bis (2-methoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2-methoxybenzoyl) phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) octylphosphine oxide, bis (2-dimethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2-dimethoxybenzoyl) phosphine oxide, bis (2-methylpropan-1-yl) phosphine oxide, bis (2-methyl-ethyl) phosphine oxide, bis (2, 2-methyl-ethyl) phosphine oxide, 2-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-phenyl-methyl-ethyl-phenyl-methyl-ethyl-methyl-ethyl-methyl-phenyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl, Bis (2-methoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2, 6-diethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2, 6-diethoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2, 6-dibutoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2, 4-dimethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2, 4, 6-trimethylbenzoyl diphenylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) (2, 4-dipentyloxyphenyl) phosphine 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-dimethoxybenzoylbenzyloctylphosphine oxide, bis (2, 4, 6-trimethylbenzoyl) isobutylphosphine oxide and 2, 6-dimethoxybenzoyl-2, acylphosphine oxides such as 4, 6-trimethylbenzoyl-n-butylphosphine oxide, acylgermanium compounds such as bisbenzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis (4-methoxybenzoyl) dimethylgermanium and bis (4-methoxybenzoyl) diethylgermanium, α -aminophenylethanones such as 2-benzyl-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholinylphenyl) -acetone-1, benzyldimethylketal, benzyldiethylketal, ketals such as benzyl (2-methoxyethylketal), bis (cyclopentadienyl) -bis [2, 6-difluoro-3- (1-pyrrolyl) phenyl ] -titanium, and mixtures thereof, Metallocenes such as bis (cyclopentadienyl) -bis (pentafluorophenyl) -titanium, bis (cyclopentadienyl) -bis (2, 3, 5, 6-tetrafluoro-4-disiloxyphenyl) -titanium and the like.

(B) The photosensitizer can be appropriately selected depending on the wavelength, intensity, light irradiation time, and kind or blending amount of other components to be combined of the light used for polymerization. In addition, the photosensitizer can be used alone or in combination of two or more. Among these, α -diketone compounds having the maximum absorption wavelength in the visible light region are preferably used, more preferably camphorquinone compounds such as camphorquinone, camphorquinone carboxylic acid, and camphorquinone sulfonic acid, and particularly, camphorquinone is preferred from the viewpoint of easy availability.

In general, the amount of the photosensitizer (B) is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 1.0 part by mass, and still more preferably 0.05 to 1.0 part by mass, based on 100 parts by mass of the total amount of the polymerizable monomer (a) contained in the dental photocurable composition. When the amount of the photosensitizer added is less than 0.005 part by mass, polymerization activity against irradiated light is poor, and curing is insufficient. When the amount is more than 1.0 part by mass, sufficient curability is exhibited, but the stability to ambient light is shortened and the yellow tone is increased.

[ (C) photoacid generators ]

The dental photocurable composition of the present invention can contain (C-1) an iodonium salt compound formed with an anion having a logS of-4 or less as the photoacid generator (C). In the dental photocurable composition of the present invention, an iodonium salt compound of (C-1) and an anion having a logS of-4 or less and other known photoacid generators can be used without limitation. Specific examples thereof include triazine compounds, iodonium salt compounds, sulfonium salt compounds, sulfonate compounds, and the like. Among them, triazine compounds and iodonium salt compounds are preferable because of high polymerizability when used in combination with a sensitizer. More preferably an iodonium salt compound. Iodonium salt compounds are susceptible to sensitization by photosensitizers that absorb in the visible region.

Specific examples of the triazine compound 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- (p-trichloromethyl) -s-triazine, and the like, 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- (. alpha.,. beta. -trichloroethyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-styryl-4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (p-methoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (o-methoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (p-butoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3, 4, 5-trimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-biphenyl) -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 them, 2, 4, 6-tris (trichloromethyl) -s-triazine is preferable.

Any known iodonium salt compound can be used as long as it is known. Specifically, the structural formula of the iodonium salt compound can be represented by the following formula (1).

[(R1)₂I]⁺[A]^-Formula (1)

(in the formula [ (R1)₂I]⁺Is a cationic moiety, [ A ]]^-Is an anionic moiety, R1 represented by formula (1) represents an organic group bonded to I, and R1 are the same or different. For example, R1 represents 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, and these groups may be substituted with at least one member selected from the group consisting of an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyleneoxy group, an amino group, a cyano group, a nitro group and the like, and a halogen. )

Examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl groups and condensed polycyclic aryl groups such as naphthyl, anthryl, phenanthryl, pyrenyl, chrysenyl (chrysenyl), naphthacenyl, benzanthryl, anthraquinonyl, fluorenyl, naphthoquinone, and anthraquinone.

Examples of the heterocyclic group having 4 to 30 carbon atoms include cyclic substances containing 1 to 3 heteroatoms such as oxygen, nitrogen and sulfur, and these heteroatoms may be the same or different, and specific examples thereof include monocyclic heterocyclic groups such as thienyl, furyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidinyl and pyrazinyl, and condensed heterocyclic groups such as indolyl, benzofuryl, isobenzofuryl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, Xanthenyl (Xanthenyl), Thianthrenyl, phenoxazinyl, phenoxathinyl, chromanyl, isobenzodihydropyranyl, dibenzothienyl, xanthonyl (thioxanthyl), thioxanthyl (thioxanthyl) and dibenzofuranyl.

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

Specific examples of the alkenyl group having 2 to 30 carbon atoms include a straight-chain or branched alkenyl group such as a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and a 1-methyl-1-propenyl group.

Specific examples of the alkynyl group having 2 to 30 carbon atoms include straight-chain or branched alkynyl groups such as an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-methyl-1-propynyl group, and a 1-methyl-2-propynyl group.

The above-mentioned 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 may or may not have at least one substituent, and specific examples of the substituent include straight-chain alkyl group having 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, octadecyl group and the like; branched alkyl groups having 1 to 18 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like; cycloalkyl groups having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; a hydroxyl group; a linear or branched alkoxy group having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, or a dodecyloxy group; a linear or branched alkylcarbonyl group having 2 to 18 carbon atoms such as an acetyl group, a propionyl group, a butyryl group, a 2-methylpropionyl group, a heptanoyl group, a 2-methylbutyryl group, a 3-methylbutyryl group, and an octanoyl group; arylcarbonyl groups having 7 to 11 carbon atoms such as benzoyl and naphthoyl; a linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, or the like; aryloxycarbonyl groups having 7 to 11 carbon atoms such as a phenoxycarbonyl group and a naphthoxycarbonyl group; arylthiocarbonyl groups having 7 to 11 carbon atoms such as phenylthiocarbonyl group and naphthyloxysulfuryl group; a linear or branched acyloxy group having 2 to 19 carbon atoms such as an acetoxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isobutylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, an octadecylcarbonyloxy group; arylthio groups having 6 to 20 carbon atoms such as 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, 4- (methylthiobenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio and the like; straight-chain or branched alkylthio groups having 1 to 18 carbon atoms such as a methylthio group, an ethylthio group, a propylthio group, a tert-butylthio group, a neopentylthio group, a dodecylthio group and the like; aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, xylyl, naphthyl, and the like; a heterocyclic group having 4 to 20 carbon atoms such as thienyl, furyl, pyranyl, xanthenyl, chromanyl, isochromanyl, xanthenone, thioxanthone, dibenzofuranyl, etc.; aryloxy groups having 6 to 10 carbon atoms such as phenoxy groups and naphthoxy groups; linear or branched alkylsulfinyl groups having 1 to 18 carbon atoms such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, and octylsulfinyl; arylsulfinyl groups having 6 to 10 carbon atoms such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl; a linear or branched alkylsulfonyl group having 1 to 18 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, or an octylsulfonyl group; arylsulfonyl groups having 6 to 10 carbon atoms such as phenylsulfonyl group, tolylsulfonyl group (tosyl group), and naphthylsulfonyl group; an alkyleneoxy group; a cyano group; a nitro group; halogen such as fluorine, chlorine, bromine, and iodine.

Among the iodonium salt compounds, aryliodonium salts are preferable because of their high stability. In addition, in order to improve the fat solubility, it is preferable that the aryl group has a substituent. Specifically, linear alkyl groups such as methyl, propyl, octyl, decyl, undecyl, dodecyl, and tridecyl groups; a branched alkyl group such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, a functional group in which one or more of these groups are substituted with F, a perfluoroalkyl group, a halogen, or the like as a substituent.

The structure of the anion portion of the iodonium salt compound is not particularly limited, and examples thereof include structures having atoms such as halogen, P, S, B, Al, and Ga. From the viewpoint of safety, anions having As or Sb can be used, but are not preferable in dental applications. The anion preferably has an organic group such as an alkyl group and/or an alkoxy group and/or an aryl group, and most preferably has an organic group such as an alkyl group and/or an alkoxy group and/or an aryl group in which at least one or more H is substituted with F. Since the iodonium salt compound having such an anion has high solubility in the photocurable composition, it is expected that the production time can be shortened by preventing precipitation during low-temperature storage or long-term storage, or dissolving the iodonium salt compound in the composition in a short time. Further, iodonium salt compounds composed of anions having organic groups such as alkyl groups and/or alkoxy groups and/or aryl groups in which one or more H groups are substituted with F can be expected to have higher solubility. When the photoacid generator precipitates, the light color stability may be lowered or the bending strength may be lowered, which is not preferable. As the anion having an 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, an anion having an arbitrary atom can be used, but from the viewpoint of general versatility and safety, an anion having P, S, B, Al, or Ga is preferable.

Examples of the anion having no alkyl group and/or alkoxy group and/or aryl group include halogen such as chloride and bromide, high-halogen acid such as perchloric acid, aromatic sulfonic acid such as p-toluenesulfonate, camphorsulfonic acid, nitrate, acetate, chloroacetate, carboxylate, phenoxide, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, and the like. Among them, p-toluenesulfonate, camphorsulfonic acid and carboxylate are preferably used.

Due to [ A ] of the iodonium salt-based compound of the formula (1)]^-The anionic moiety has improved solubility in the photopolymerizable composition, and therefore, an anion having an organic group such as an alkyl group and/or an alkoxy group and/or an aryl group in which at least one or more H is substituted with F is preferable. Specifically, the iodonium salt compound of the formula (1) [ A ]]^-The preferred number of carbon atoms of the alkyl group of the anionic moiety is 1 to 8, preferably 1 to 4. Specific examples thereof include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The number ratio (F/H) of hydrogen atoms to fluorine atoms in the alkyl group is preferably 4 or more, and the number ratio (F/H) of hydrogen atoms to fluorine atoms in the alkyl group is preferably 9 or more. It is further preferred that all hydrogen atoms of the hydrocarbon are substituted by fluorine. An iodonium salt composed of anions having alkyl groups with different ratios of hydrogen atoms to fluorine atoms may be blended in the photocurable composition.

Specific examples of the alkyl group include CF₃、CF₃CF₂、(CF₃)₂CF、CF₃CF₂CF₂、CF₃CF₂CF₂CF₂、(CF₃)₂CFCF₂、CF₃CF₂(CF₃)CF、(CF₃)₃C, and the like linear or branched perfluoroalkyl group.

[ A ] of an iodonium salt compound of the formula (1)]^-The preferred number of carbon atoms of the alkoxy group of the anionic moiety is 1 to 8, preferably 1 to 4. Specific examples thereof include a linear alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and an octyloxy group, and a branched alkoxy group such as an isopropoxy group, an isobutoxy group, a sec-butoxy group and a tert-butoxy group. The number ratio (F/H) of hydrogen atoms to fluorine atoms in the alkyl group is 4 or moreThe number ratio (F/H) of hydrogen atoms to fluorine atoms in the alkyl group is preferably 9 or more. It is further preferred that all hydrogen atoms of the hydrocarbon are substituted by fluorine. An iodonium salt composed of anions having alkoxy groups with different ratios of hydrogen atoms to fluorine atoms may be blended in the photocurable composition.

Specific examples of the alkoxy group include CF₃O、CF₃CF₂O、CF₃CF₂CF₂O、(CF₃)₂CFO、CF₃CF₂CF₂CF₂O、(CF₃)₂CFCF₂O、CF₃CF₂(CF₃)CFO、CF₃CF₂CF₂CF₂CF₂O、CF₃CF₂CF₂CF₂CF₂CF₂CF₂CF₂CF₂O, etc., linear or branched perfluoroalkoxy.

In [ A ] of the iodonium salt-based compound of the formula (1)]^-The anionic moiety has a phenyl group in which at least one or more hydrogen atoms are substituted with a fluorine atom, and/or an alkyl group and/or an alkoxy group substituted with a fluorine atom. The alkyl group and/or alkoxy group substituted with a fluorine atom is preferably the above-mentioned group. Specific examples of particularly preferable phenyl groups include pentafluorophenyl (C)₆F₅) Trifluorophenyl (C)₆H₂F₃) Tetrafluorophenyl (C)₆HF₄) Trifluoromethyl phenyl (CF)₃C₆H₄) Bis (trifluoromethyl) phenyl ((CF)₃)₂C₆H₃) Pentafluoroethylphenyl (CF)₃CF₂C₆H₄) Bis (pentafluoroethyl) phenyl ((CF)₃CF₂)₂C₆H₃) Trifluoromethyl fluorophenyl (CF)₃C₆H₃F) Bis-trifluoromethylfluorophenyl ((CF)₃)₂C₆H₂F) Pentafluoroethyl fluorophenyl (CF)₃CF₂C₆H₃F) Bis-pentafluoroethyl-fluorophenyl ((CF)₃CF₂)₂C₆H₂F) And the like perfluorophenyl groups. In a photocurable compositionAn iodonium salt composed of anions having phenyl groups with different ratios of hydrogen atoms to fluorine atoms may be added.

[ A ] as an iodonium salt-based compound of the formula (1)]^-Specific examples of the anionic moiety include anions having P, and [ (CF)₃CF₂)₃PF₃]^-、[(CF₃CF₂CF₂)₃PF₃]^-、[((CF₃)₂CF)₂PF₄]^-、[((CF₃)₂CF)₃PF₃]^-、[((CF₃)₂CF)₄PF₂]^-、[((CF₃)₂CFCF₂)₂PF₄]^-、[((CF₃)₂CFCF₂)₃PF₃]^-And the like. Examples of the anion having S include [ (CF)₃SO₂)₃C]^-、[(CF₃CF₂SO₂)₃C]^-、[(CF₃CF₂CF₂SO₂)₃C]^-、[(CF₃CF₂CF₂CF₂SO₂)₃C]^-、[CF₃CF₂CF₂CF₂SO₃]^-、[CF₃CF₂CF₂SO₃]^-、[(CF₃CF₂SO₂)₃C]^-、[(SO₂CF₃)₃N]^-、[(SO₂CF₂CF₃)₂N]^-、[((CF₃)C₆H₄)SO₃]^-、[SO₃((CF₂CF₂CF₂CF₂)SO₃]^2-And the like. Examples of the anion having B include [ B (C)₆F₅)₄]^-、[(C₆H₅)B(C₆F₅)₃]^-、[(C₆H₅)B((CF₃)₂C₆H₃))₃]^-And the like. As anions with GaMention may be made of [ ((CF)₃)₄Ga)^-、[Ga(C₆F₅)₄]^-And the like. Examples of the anion having Al include [ ((CF)₃)₃CO)₄Al]^-、[((CF₃CF₂)₃CO)₄Al]^-And the like.

The dental photocurable composition of the present invention comprises (C-1) an iodonium salt compound formed with an anion having a logS of-4 or less as the photoacid generator (C).

logS is an indicator of the solubility of a compound in water and is used to predict the water solubility of a compound. In the present invention, the calculation is performed using the chemical drawing Professional software (ChemDraw Professional ver 18.1). The larger the logS value, the higher the water solubility, and the smaller the logS value, the lower the water solubility. As indices for expressing properties according to the structure of such compounds, distribution coefficients of LogP, CLogP, AlogP, LogD, and the like, HSP (hansen solubility parameter), tPSA (topological geometric polar surface area), and the like are known. These indices were compared with the results of experiments to confirm the correlation between the above-mentioned indices relating to solubility and the results of experiments, and among them, studies based on log s have resulted in the finding that the use of an iodonium salt compound improves the storage stability of the dental photocurable composition during storage at low temperatures. It is considered that when a photoacid generator having high solubility is added to a dental photocurable composition, the composition does not precipitate even when stored at low temperatures and exhibits sufficient physical properties when returned to room temperature. Further, it was confirmed that the storage stability was also excellent when the film was stored under high temperature conditions. Such iodonium salts have a high correlation with ClogP in the above-mentioned index, and generally, ClogP tends to be lower as the logS value is larger. When ClogP is used as a reference, an iodonium salt formed with an anion showing 1 or more ClogP is preferred. In the present invention, since it is possible to judge that the present invention is applicable to a large number of compounds when logS is used as an index, the present invention has been developed by conducting research using logS.

Examples of the anion having a logS of-4 or less include [ (CF)₃CF₂)₃PF₃]^-、[(CF₃CF₂CF₂)₃PF₃]^-、[((CF₃)₂CF)₂PF₄]^-、[((CF₃)₂CF)₃PF₃]^-、[((CF₃)₂CF)₄PF₂]^-、[((CF₃)₂CFCF₂)₂PF₄]^-、[((CF₃)₂CFCF₂)₃PF₃]^-、[(CF₃CF₂SO₂)₃C]^-、[(CF₃CF₂CF₂SO₂)₃C]^-、[(CF₃CF₂CF₂CF₂SO₂)₃C]^-、[B(C₆F₅)₄]^-、[(C₆H₅)B(C₆F₅)₃]^-、[(C₆H₅)B((CF₃)₂C₆H₃))₃]^-、[((CF₃)₄Ga]^-、[Ga(C₆F₅)₄]^-、[((CF₃)₃CO)₄Al]^-、[((CF₃CF₂)₃CO)₄Al]^-And the like.

On the other hand, if an anion having a log S of more than-4, i.e., an anion having a low fat solubility, is exemplified, chloride, bromide, nitrate, perchlorate, tetrafluoroborate, hexafluoroantimonate, hexafluorophosphate, p-toluenesulfonate, trifluoromethanesulfonate, etc. may be mentioned. Such anions have a high logS value and high water solubility, while they have a low ClogP value and low lipid solubility. For example, the anion shown above has a ClogP of 1 or less.

The anion log S in the iodonium salt compound (C-1) is-4 or less, preferably-5 or less. When an iodonium salt having a logS of more than-4 is added in an amount of 0.5 parts by mass or more per 100 parts by mass of the total amount of the polymerizable monomer (A) in the dental photocurable composition, the iodonium salt may precipitate during storage under low temperature conditions, and particularly, an anion having low solubility may not be uniformly dissolved in the dental photocurable composition. In the case where the photoacid generator is not uniformly dissolved in the dental photocurable composition or in the case where the photoacid generator precipitates, sufficient mechanical properties may not be exhibited, the light color stability is lowered, and the precipitated photoacid generator is observed as a black spot to affect the aesthetic property in some cases.

The iodonium salt compound of (C-1) and an anion having a logS of-4 or less is preferably contained in an amount of 0.5 parts by mass or more, more preferably 1.0 part by mass or more, based on 100 parts by mass of the total amount of the polymerizable monomer (A). If the amount is less than 0.5 parts by mass, the bending strength may be insufficient, and if the amount is 0.5 to less than 1.0 parts by mass, the bending strength tends to be lower than when 1.0 part by mass or more is contained. On the other hand, the iodonium salt compound formed by (C-1) and an anion having a logS of-4 or less is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the total amount of the polymerizable monomer (A). When the amount is more than 10 parts by mass, the stability to ambient light may be lowered, and the stability to light color may be lowered. In addition, in the case of 5 to 10 parts by mass, it cannot be expected that the bending strength is remarkably improved by increasing the amount of the iodonium salt compound formed by (C-1) and an anion having a log S of-4 or less, and therefore, the amount is most preferably 1.0 to 5.0 parts by mass based on 100 parts by mass of the total amount of the polymerizable monomer (A). The iodonium salt-based compound (C-1) can be used singly or in combination of 2 or more.

The photoacid generator (C) is not limited to the iodonium salt compound (C-1), and any photoacid generator other than the iodonium salt compound (C-1) may be used in combination. In this case, the amount of the photoacid generator (C) containing the iodonium salt compound (C-1) is preferably 0.5 to 10.0 parts by mass relative to 100 parts by mass of the total amount of the polymerizable monomer (a) in the dental photocurable composition of the present invention. More preferably 1.0 to 5.0 parts by mass. When the amount is less than 0.5 parts by mass, the polymerization accelerating ability may be poor and the curing may be insufficient. When the amount is more than 10 parts by mass, the curing property is sufficient, but the ambient light stability is shortened, and the discoloration such as browning of the cured product is increased.

The dental photocurable composition of the present invention may contain only the iodonium salt compound of (C-1) as the photoacid generator (C). The dental photocurable composition of the present invention may contain only an aryliodonium salt, which is a salt of an anion having an organic group and at least one atom selected from P, B, Al, S, and Ga and an aryliodonium cation. The dental photocurable composition of the present invention may contain, as the photoacid generator (C), only a salt of an anion having an organic group in which at least one or more H is substituted with F and any one or more atoms of P, B, Al, S, and Ga, and an aryl iodonium cation.

[ (D) photopolymerization Accelerator ]

The photopolymerization accelerator (D) used in the dental photocurable composition of the present invention is not particularly limited as long as it is a photopolymerization accelerator having a polymerization accelerating ability, and a known photopolymerization accelerator generally used in the dental field can be used without any limitation. As the photopolymerization accelerator, a primary to tertiary amine compound such as an aromatic amine compound or an aliphatic amine compound, an organic metal compound, a phosphine compound, or the like can be used. Among them, aliphatic tertiary amine compounds and organometallic compounds are preferable because of their excellent color stability.

The aromatic amine compound is ammonia (NH)₃) And (3) a compound in which 1 or more of H in (1) is substituted with an aromatic ring. Can react NH with₃The compound in which 1H is substituted with an aromatic ring is classified into an aromatic primary amine compound, NH₃The compound in which 1H is substituted with an aromatic ring and 1H which is different from the above is substituted with an aromatic ring or an alkyl group is classified as an aromatic secondary amine compound, and NH₃The compounds in which 1H of (a) is substituted with an aromatic ring and different 2H are substituted with an aromatic ring or an alkyl group are classified as aromatic tertiary amine compounds.

Specific examples of the aromatic primary amine compound include aniline, specific examples of the aromatic secondary amine compound include N-protected amino acids (esters) such as N-phenylbenzylamine, N-benzyl-p-anisidine, N-benzyl-o-phenetole, N-phenylglycine ethyl ester, and N-phenylglycine, and specific examples of the aromatic tertiary amine compound include N, N-dimethylaniline, N-diethylaniline, N-di-N-butylaniline, N-dimethyl-p-toluidine, N-dimethyl-m-toluidine, N-diethyl-p-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-methylaniline, p-ethylaniline, p-methylaniline, p-N-methylaniline, p-N-p-N-methylaniline, p-methylaniline, p-N-methylaniline, p-N-methylaniline, p-methylaniline, p-methylaniline, p-m-p-m-p-m-p-m-p, Ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-butoxyethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, amino p-dimethylaminobenzoate, methyl N, N-dimethyl anthranilate, N-dihydroxyethylaniline, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N-dimethyl-3, 5-dimethylaniline, 4-dimethylaminopyridine, N-dimethyl-alpha-naphthylamine, N-dimethyl-beta-naphthylamine, and the like.

Specifically, the organometallic compound includes organometallic compounds containing 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 organometallic compounds containing tin (Sn), vanadium (V), and copper (Cu). Specific examples of the organic metal compound containing tin (Sn) include dibutyltin diacetate, dibutyltin dimaleate, dioctyltin dilaurate, dibutyltin dilaurate, dioctyltin di-tert-carbonate, dioctyltin S, S' -diisooctylmercaptoacetate, tetramethyl-1, 3-diacetoxyditaxodistannoxane and the like, specific examples of the organic metal compound containing vanadium (V) include vanadium acetylacetonate, vanadium tetraoxide, vanadyl acetylacetonate, vanadyl stearate, vanadyl oxalate, vanadium sulfate, bis (1-phenyl-1, 3-butanedione) oxovanadium, bis (maltitol) vanadyl, vanadium pentoxide, sodium metavanadate and the like, and specific examples of the organic metal compound containing copper (Cu) include copper acetylacetonate, copper naphthenate, copper, Copper octoate, copper stearate, copper acetate.

The phosphine compound is a compound in which an organic group is trisubstituted at a P atom, and the aromatic phosphine compound is a phenyl-substituted compound having or not having 1 or more substituents at the P atom. Specific examples of the phosphine compound include trimethylphosphine, tributylphosphine, trihexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tris (2-thienyl) phosphine, diphenylpropylphosphine, di-t-butyl (3-methyl-2-butenyl) phosphine, methyldiphenylphosphine, triphenylphosphine, 2- (diphenylphosphino) styrene, 3- (diphenylphosphino) styrene, 4- (diphenylphosphino) styrene, allyldiphenylphosphine, 2- (diphenylphosphino) 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, trihexylphosphine, tri (2-octylphosphine), tricyclohexylphosphine, tris (2-thienyl) phosphine, diphenylphosphine, 3- (diphenylphosphino) styrene, 4- (diphenylphosphino) benzaldehyde, 2- (diphenylphosphino) benzoic acid, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (2-methyl-phenyl) phosphine, tris (2-phenyl) benzoate, tris (phenyl) phosphine, tris (phenyl) benzoate, tris (phenyl) phosphine, tris (phenyl) benzoate, tris (phenyl) phosphonium, tris (phenyl) phosphonium, tris (2-phenyl) phosphonium, tris (2-phenyl) phosphonium, tris (tris) phosphonium), tris (2-phenyl) phosphonium), tris (tris) phosphonium), or (tris) phosphonium), tris (tris) phosphonium), tris (, Tris (4-methoxyphenyl) phosphine, 2- (diphenylphosphino) biphenyl, tris (4-fluorophenyl) phosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine, tris (p-tolyl) phosphine, 2- (dimethylamino) phenyldiphenylphosphine, 3- (dimethylamino) phenyldiphenylphosphine, 4- (dimethylamino) phenyldiphenylphosphine, 2' -bis (diphenylphosphino) biphenyl, bis [2- (diphenylphosphino) phenyl ] ether, and the like. Among them, triphenylphosphine, 4- (phenylphosphino) benzoic acid, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, and tri (p-tolyl) phosphine are preferable.

The aliphatic amine compound means ammonia (NH)₃) And (3) a compound in which 1 or more of H in (b) is substituted with an alkyl group. For alkyl, the reaction product of CH₃-or-CH₂Classification as primary alkyl, of-CH₂Alkyl in which 1H of-has a substituent is classified as secondary alkyl, and-CH₂The alkyl group in which 2H's in-are substituted is classified as a tertiary alkyl group. For aliphatic amines, NH is₃Aliphatic amines in which 1H is substituted with an alkyl group are classified as primary aliphatic amines, NH₃Aliphatic amines in which 2H's are substituted with alkyl groups are classified as secondary aliphatic amine compounds, NH₃Aliphatic amines in which 3H's are substituted with alkyl groups are classified as aliphatic tertiary amine compounds.

Specific examples of the aliphatic primary amine compound include amino acids or amino acid esters such as benzhydrylamine, triphenylmethylamine, and glycine, specific examples of the aliphatic secondary amine compound include dibenzylamine, N-benzyl-1-phenylethylamine, bis (1-phenylethyl) amine, bis (4-cyanobenzyl) amine, N-benzyl protected amino acid, and N-benzyl protected amino acid ester, and specific examples of the aliphatic tertiary amine compound include tributylamine, tripropylamine, triethylamine, N-dimethylhexylamine, N-dimethyldodecylamine, N-dimethylstearylamine, N- [3- (dimethylamino) propyl ] acrylamide, N-dimethylformamide dimethyl acetal, N-dimethylacetamide dimethyl acetal, and the like, 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-butyldiethanolamine, N-lauryldiethanolamine, N-stearyldiethanolamine, triethanolamine, tribenzylamine, dibenzylglycine ethyl ester, N '- (2-hydroxyethyl) -N, N, N' -trimethylethylenediamine, 2- (dimethylamino) -2-methyl-1-propanol, N, N-dimethylformamide di-tert-butyl acetal, N, N-dimethyl-2, 3-dihydroxypropylamine, N-diethylethanolamine, 1-methyl-3-pyrrolidinol, 1- (2-hydroxyethyl) pyrrolidine, 1-isopropyl-3-pyrrolidinol, 1-piperidineethanol, 2- [2- (dimethylamino) ethoxy ] ethanol, N-dimethylglycine, N-dimethylglycine methyl ester, N-diethylglycine methyl ester, N-dimethylglycine ethyl ester, N-diethylglycine sodium salt, 2- (dimethylamino) ethyl acetate, N-methyliminodiacetic acid, N-dimethylaminoethylacrylate, N-diethylaminoethylmethacrylate, N-diethylcarbamoylethanolamine, N-diethylcarbamoylethanolamine, 1-methyl-3-pyrrolidinol, 1- (2-hydroxyethyl) pyrrolidine, 1-isopropyl-3-pyrrolidinol, 1-piperidineethanol, 2- [2- (dimethylamino) ethoxy ] ethanol, N-dimethylcarbamoylglycine methyl-ethyl-glycolate, N-dimethylaminoethyl-methylglycine, N-dimethylaminoethyl-acrylate, N-dimethylaminoethyl methacrylate, N-diethylaminoethylcarbamoylglycine, N-methyl-ethyl-1-piperidinol, N-dimethylaminoethyl-1-4-methyl-3-pyrrolidinol, N-dimethylaminoethyl-methyl-ethyl-methyl-3-methyl-glycine, N-methyl-glycine methyl-glycine, N-methyl-glycine methyl-ethyl acrylate, N-ethyl acrylate, N-ethyl acrylate, N-ethyl acrylate, N-ethyl acrylate, N-ethyl acrylate, N-ethyl, N-ethyl acrylate, N-ethyl, N-N, N-N, n, N-dibutylaminoethyl methacrylate, N-dibenzylaminoethyl methacrylate, 3-dimethylaminopropionitrile, tris (2-cyanoethyl) amine, N-dimethylallylamine, N-diethylallylamine, triallylamine, and the like.

(D) The photopolymerization accelerator particularly preferably uses an aliphatic tertiary amine compound. Since the aromatic amine compound has poor light color stability, if it is used for prosthetic devices, prosthetic materials, and adhesives in a site such as anterior teeth where light is likely to be irradiated, the color tone may change with time, which is not preferable. Further, by using an ultraviolet absorber in combination, suppression of temporal discoloration due to light can be expected. However, since the ultraviolet absorber is used as a general additive, it cannot be expected to improve mechanical physical properties by blending, and further, the yellow tone of the dental photocurable composition before curing may be increased, so that it is not preferable to blend a large amount of the ultraviolet absorber. For these reasons, it is preferable to use an aliphatic tertiary amine compound. In addition, depending on the composition of the dental photocurable composition, when the composition contains an aliphatic primary amine compound and an aliphatic secondary amine compound, high storage stability and high mechanical strength can be expected, and therefore, known substances can be used without any limitation.

Among the aliphatic tertiary amine compounds, amine compounds having not less than 2 primary hydroxyl groups in the molecule are preferable, and amine compounds having not more than 2 primary hydroxyl groups in the molecule are more preferable. Specific examples of the amine compound having 2 or more primary hydroxyl groups in the molecule include triethanolamine, methyldiethanolamine, and the like. When a cured product of a dental photocurable composition is stored for a long period of time, the amine compound having a primary hydroxyl group may be discolored. The discoloration tends to increase as the number of primary hydroxyl groups in the molecule increases, and is particularly significant when the number of primary hydroxyl groups in the molecule is 2 or more. Discoloration can be confirmed in a short period of time when the cured product is stored for a long period of time by storing the cured product in high-temperature water. When the discoloration is small under high-temperature water conditions, that is, when the thermal color stability is high, the discoloration is small when a cured product of the dental photocurable composition is used for a long period of time.

The (D) photopolymerization accelerator is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental photopolymerizable composition. When the amount is less than 0.01 part by mass, the mechanical strength may be insufficient. When the amount is more than 20 parts by mass, the curing property is sufficient, but the stability to ambient light is shortened, or discoloration such as browning of the cured product is increased, which is not preferable.

If necessary, the polymerization initiator (B) is a photosensitizer, (C) is a photoacid generator, and (D) is a photopolymerization accelerator, and the secondary treatment such as pulverization, carrier adsorption, and encapsulation in a microcapsule is not problematic. Further, these various photopolymerization initiators can be used alone or in combination of 2 or more, regardless of the polymerization method or polymerization method.

The dental photocurable composition of the present invention may contain only an aliphatic tertiary amine compound as the photopolymerization accelerator (D). The dental photocurable composition of the present invention may contain, as the photopolymerization accelerator (D), only (D-1) an aliphatic tertiary amine compound having no primary hydroxyl group of 2 or more. The dental photocurable composition of the present invention may contain, as the photopolymerization accelerator (D), only an aliphatic tertiary amine compound having no primary hydroxyl group in the molecule.

[ (E) Filler ]

The dental photopolymerizable composition of the invention can contain (E) a filler as another component. The filler (E) used in the present invention can be any conventionally used known filler without any limitation.

The type of the filler (E) is not limited as long as it is a known filler, and a filler may be blended according to the use thereof, and preferably a filler such as an inorganic filler, an organic filler, or an organic-inorganic composite filler is blended. These fillers can be used not only alone, but also in combination of a plurality of types regardless of the kind of the filler.

The chemical composition of the inorganic filler is not particularly limited, and specific examples thereof include silica, alumina, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramics, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, aluminum fluorosilicate glass, calcium aluminum fluorosilicate glass, strontium aluminum fluorosilicate glass, barium aluminum fluorosilicate glass, strontium calcium aluminum fluorosilicate glass, and strontium calcium aluminum fluorosilicate glass. In particular, barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, and fluoroaluminosilicate glass used for dental glass ionomer cement, resin-reinforced glass ionomer cement, resin cement, and the like can also be preferably used. The fluoroaluminosilicate glass described herein has a basic skeleton of silica and alumina, and contains an alkali metal for introducing non-crosslinkable oxygen. Further, the metal material has an alkaline earth metal as a modifying/coordinating ion including strontium and fluorine. In addition, in order to further impart X-ray opacity, it is a composition in which a lanthanoid element is incorporated into a skeleton. The lanthanide element also incorporates as a modification/coordination ion into the composition depending on the composition domain.

Specific examples of the organic filler include polymers such as polymethyl methacrylate, polyethyl methacrylate, a methyl methacrylate-ethyl methacrylate copolymer, an ethyl methacrylate-butyl methacrylate copolymer, a methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone, polyether sulfone, and polycarbonate.

Examples of the organic-inorganic composite filler include a composite filler in which the surface of a filler is polymerized and coated with a polymerizable monomer, a composite filler in which a filler and a polymerizable monomer are mixed and polymerized and then pulverized into an appropriate particle size, and a composite filler in which a filler is dispersed in a polymerizable monomer in advance and then emulsion polymerized or suspension polymerized, but are not limited to these composite fillers.

The filler (E) can be treated with a surface treatment material represented by a silane coupling agent for the purpose of improving affinity with a polymerizable monomer, dispersibility in a polymerizable monomer, mechanical strength of a cured product, and water resistance. The surface treatment material and the surface treatment method are not particularly limited, and a known method can be used without limitation. As the silane coupling agent used for the surface treatment of the filler, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane, hexamethyldisilazane or the like is preferable. In addition to the silane coupling agent, the surface treatment of the filler can be performed by a method using a titanate-based coupling agent or an aluminate-based coupling agent. The amount of the surface treatment material to be treated in the filler is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the filler before treatment.

The shape of the filler is not particularly limited, and fillers having any shape such as an amorphous shape, a spherical shape, a needle shape, a plate shape, a crushed shape, and a flake shape can be used. The average particle size of the filler is preferably in the range of 0.2 to 50 μm, more preferably 0.2 to 30 μm, still more preferably 0.2 to 20 μm, and yet more preferably 0.2 to 10 μm.

When the filler (E) is blended in the dental photocurable composition, it is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer (a), and in consideration of the formability and the like, it is preferably less than 500 parts by mass. When the amount of the filler is less than 10 parts by mass, the mechanical strength is improved when the filler is blended, and the effect of expression of thixotropic properties is insufficient, and when the amount is more than 1000 parts by mass, the paste property of the composition becomes hard and the handling may be difficult, and 1000 parts by mass or more may be included depending on the type of the filler and the surface treatment condition of the filler. For example, this case refers to a case where the specific gravity of the filler is high, a case where the amount of the surface treatment agent in the filler is large, or a case where a surface treatment agent having good affinity with the polymerizable monomer is used. The composition of the present invention exhibits effects regardless of the compounding amount of the filler.

The dental photocurable composition of the present invention may contain a chemical polymerization initiator. Examples of the organic peroxide as the chemical polymerization initiator include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, peroxydicarbonates, and hydroperoxides. Specific examples of diacyl peroxides include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3, 5, 5-trimethylhexanoyl peroxide, 2, 4-dichlorobenzoyl peroxide, and lauroyl peroxide. Specific examples of the peroxyesters include α -cumyl peroxyneodecanoate, t-butyl peroxypivalate, 2, 4-trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxy isophthalate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3, 3, 5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxymaleate, and the like. Specific examples of the dialkyl peroxides include di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 1, 3-bis (tert-butylperoxyisopropyl) benzene, and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) -3-hexyne. Specific examples of the peroxyketals include 1, 1-bis (t-butylperoxy) cyclohexane, 2-bis (t-butylperoxy) butane, n-butyl-4, 4- (t-butylperoxy) valerate, 1-bis (t-amylperoxy) cyclohexane, and the like. Specific examples of the ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide. Specific examples of the peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate. Specific examples of the hydroperoxides include 2, 5-dimethylhexane-2, 5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, and 1, 1, 3, 3-tetramethylbutyl hydroperoxide.

The organic peroxide may be used alone or in combination with 2 or more kinds thereof. Among these organic peroxides, benzoyl peroxide and cumene hydroperoxide are preferable from the viewpoint of curability. From the viewpoint of improving curability, the amount of the organic peroxide as the chemical polymerization initiator is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer (a). On the other hand, if the amount of the organic peroxide is less than 0.1 part by mass, the mechanical strength may be insufficient.

In order to improve curability, a chemical polymerization accelerator may be added to the dental photocurable composition of the present invention. Examples of the chemical polymerization accelerator include a4 th-cycle transition metal compound, a thiourea derivative, an aliphatic amine, an aromatic amine, sulfinic acid and a salt thereof, a borate compound, a sulfur-containing reductive inorganic compound, a nitrogen-containing reductive inorganic compound, a barbituric acid derivative, a triazine compound, a halogen compound, and the like. The amount of the chemical polymerization accelerator is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomers.

The 4 th period transition metal compound as the chemical polymerization accelerator means a metal compound of groups 3 to 12 of the 4 th period of the periodic table, and specifically, any metal compound of scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn) can be used without limitation. The above-mentioned transition metal elements may have a plurality of valences, and may be added to the dental photocurable composition of the present invention as long as the valences are stable. For example, Sc (3-valent), Ti (4-valent), V (3-, 4-or 5-valent), Cr (2-, 3-or 6-valent), Mn (2-to 7-valent), Fe (2-or 3-valent), Co (2-or 3-valent), Ni (2-valent), Cu (1-or 2-valent), and Zn (2-valent). Specific examples of the transition metal compound include scandium iodide (3 valent), titanium chloride (4 valent), titanium tetraisopropoxide (4 valent), etc., as the titanium compound, vanadium acetylacetonate (3 valent), vanadium tetraoxide (4 valent), vanadyl acetylacetonate (4 valent), vanadyl stearate (4 valent), vanadyl oxalate (4 valent), vanadium sulfate (4 valent), bis (1-phenyl-1, 3-butanedione) oxovanadium (4 valent), bis (maltol) oxovanadium (4 valent), vanadyl pentavanadate (5 valent), sodium metavanadate (5 valent), etc., as the manganese compound, manganese acetate (2 valent), manganese naphthenate (2 valent), etc., as the iron compound, iron acetate (2 valent), iron chloride (2 valent), iron oxide (3 valent), iron chloride (3 valent), etc., examples of the cobalt compound include cobalt acetate (2-valent) and cobalt naphthenate (2-valent), examples of the nickel compound include nickel chloride (2-valent) and the like, examples of the copper compound include copper chloride (1-valent), copper bromide (1-valent), copper chloride (2-valent) and copper acetate (2-valent) and examples of the zinc compound include zinc chloride (2-valent) and zinc acetate (2-valent).

Among them, a vanadium compound having a valence of 3 or 4, a copper compound having a valence of 2 are preferable, among them, a vanadium compound having a valence of 3 or 4 having a higher polymerization-promoting ability is more preferable, and a vanadium compound having a valence of 4 is most preferable. These transition metal compounds of the 4 th cycle may be used in combination in plural numbers as required. The amount of the transition metal compound to be blended 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 when the amount is less than 0.0001 part by mass, the polymerization acceleration effect may be insufficient, and when the amount is more than 1 part by mass, discoloration or gelation of the dental photocurable composition may occur, resulting in a decrease in storage stability.

The thiourea derivative as the chemical polymerization accelerator can be used without limitation as long as it is a known thiourea derivative. Specific examples thereof include dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl) thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N '- (2-hydroxyethyl) thiourea, N-benzylthiourea, 1, 3-dicyclohexylthiourea, N' -diphenylthiourea, 1, 3-di (p-tolyl) thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea and dicyclohexylthiourea. Among them, (2-pyridyl) thiourea, N-acetylthiourea and N-benzoylthiourea are preferable. These thiourea derivatives may be used in combination in plural numbers as required. The amount of the thiourea derivative blended 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 when less than 0.1 part by mass, the polymerization accelerating ability may be insufficient, and when more than 5 parts by mass, the storage stability may be lowered.

Examples of sulfinic acids and salts thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, 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, potassium 2, 4, 6-triethylbenzenesulfinate, lithium 2, 4, 6-triethylbenzenesulfinate, calcium 2, 4, 6-triethylbenzenesulfinate, 2, 4, 6-triisopropylbenzenesulfinic acid, Sodium 2, 4, 6-triisopropylsulfinate, potassium 2, 4, 6-triisopropylsulfinate, lithium 2, 4, 6-triisopropylsulfinate, calcium 2, 4, 6-triisopropylsulfinate, and the like, and sodium benzenesulfonate, sodium p-toluenesulfinate, and sodium 2, 4, 6-triisopropylsulfinate are particularly preferable.

Specific examples of the borate compound having 1 aryl group in the molecule include trialkylphenylboron, 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-butoxyphenyl) boron, trialkyl (m-butoxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (alkyl is at least one member selected from the group consisting of n-butyl, n-octyl and n-dodecyl groups), sodium salts thereof, Lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, picolinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, and the like. Specific examples of the borate compound having 2 aryl groups in 1 molecule include sodium salts of dialkyldiphenylboron, dialkylbis (p-chlorophenyl) boron, dialkylbis (p-fluorophenyl) boron, dialkylbis (3, 5-bistrifluoromethyl) phenylboron, dialkylbis [3, 5-bis (1, 1, 1, 3, 3, 3-hexafluoro-2-methoxy-2-propyl) phenyl ] boron, dialkylbis (p-nitrophenyl) boron, dialkylbis (m-nitrophenyl) boron, dialkylbis (p-butylphenyl) boron, dialkylbis (m-butylphenyl) boron, dialkylbis (p-butoxyphenyl) boron, dialkylbis (m-butoxyphenyl) boron, dialkylbis (p-octyloxyphenyl) boron and dialkylbis (m-octyloxyphenyl) boron (alkyl group is at least one selected from the group consisting of n-butyl, n-octyl and n-dodecyl), sodium salts of these, sodium salts, and sodium salts of these, Lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, picolinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, and the like. Specific examples of the borate compound having 3 aryl groups in 1 molecule include sodium salts of monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (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-butoxyphenyl) boron, monoalkyltri (m-butoxyphenyl) boron, monoalkyltri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (alkyl is 1 selected from n-butyl, n-octyl or n-dodecyl, etc.), sodium salts of monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (p-nitrophenyl) boron, monoalkyltri (m-octyloxyphenyl) boron, monoalkyltri (n-dodecyl, etc.), Lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, picolinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, and the like. Specific examples of the borate compound include borate compounds having 4 aryl groups in 1 molecule, and examples thereof include tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3, 5-bistrifluoromethyl) 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-butoxyphenyl) boron, tetrakis (m-butoxyphenyl) boron, tetrakis (p-octyloxyphenyl) boron, tetrakis (m-octyloxyphenyl) boron, (p-fluorophenyl) triphenylboron, (3, 5-bistrifluoromethyl) phenyltriphenylboron, (p-nitrophenyl) triphenylboron, (m-butoxyphenyl) triphenylboron, Sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, picolinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of (p-butoxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron and (p-octyloxyphenyl) triphenylboron.

Among these aryl borate compounds, from the viewpoint of storage stability, it is more preferable to use a borate compound having 3 or 4 aryl groups in 1 molecule. These aryl borate compounds may be used in 1 kind or in combination of 2 or more kinds.

Examples of the sulfur-containing reducing inorganic compound include sulfite, bisulfite, pyrosulfite, thiosulfate, thiosulfonate (thionate), and dithionite, and specific examples thereof include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decylthiol, and thiobenzoic acid.

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

Examples of the barbituric acid derivatives include barbituric acid, 1, 3-dimethylbarbituric acid, 1, 3-diphenylbarbituric acid, 1, 5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1, 3, 5-trimethylbarbituric acid, 1, 3-dimethyl-5-ethylbarbituric acid, 1, 3-dimethyl-n-butylbarbituric 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, Salts of 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-benzyl-5-phenylbarbituric acid and thiobarbituric acid (preferably alkali metal or alkaline earth metal based salts thereof ) Specific examples of the barbituric acid salts include sodium 5-butylbarbiturate, 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, and dilauryldimethylammonium bromide.

The dental photocurable composition of the present invention can contain no chemical polymerization initiator or chemical polymerization accelerator. The dental photocurable composition of the present invention can contain no polymerization initiator system for a polymerization system other than a photopolymerization system.

< other ingredients >

The dental photocurable composition of the present invention may contain components other than the components (a) to (D) as long as the effects of the present invention are not inhibited. For example, a polymerization inhibitor such as a benzophenone-based or benzotriazole-based ultraviolet absorber, hydroquinone monomethyl ether, or 2, 5-di-t-butyl-4-methylphenol; thiol compounds such as α -alkylstyrene compounds, n-butylmercaptan, and n-octylmercaptan; chain transfer agents such as terpenoid compounds such as limonene, myrcene, alpha-terpinene, beta-terpinene, gamma-terpinene, beta-pinene, and alpha-pinene; metal-capturing materials such as aminocarboxylic acid-based chelating agents and phosphonic acid-based chelating agents; a discoloration inhibitor, an antibacterial agent, a coloring pigment, water, a solvent which can be mixed with water at an arbitrary ratio, and other conventionally known additives.

The method for producing the dental photocurable composition of the present invention is not particularly limited. As a general method for producing a dental photocurable composition, for example, when the dental photocurable composition contains (E), a method can be mentioned in which a base body obtained by mixing (a) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator is prepared in advance, the base body and (E) a filler are kneaded, and bubbles are removed under vacuum to prepare a uniform paste. In the present invention, the above-described production method can also be used for production without any problem.

The dental photocurable composition of the present invention is used for dental adhesives, dental composite resins, dental abutment building materials, dental resin cement, dental coating materials, dental pit and fissure sealants, dental cosmetic materials, dental loose tooth fixing adhesives, dental hard resins, dental cutting materials, dental 3D printing materials, and the like.

< one-part type dental photocurable composition >

When the present invention is used in a one-part dental photocurable composition, the composition is preferably used as a dental material, particularly as 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 sealant, a dental cosmetic material, a dental loose tooth fixing adhesive material, a dental hard resin, a dental cutting material, or a dental 3D printing material, and particularly preferably used as 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 sealant, a dental cosmetic material, a dental loose tooth fixing adhesive material, or a dental hard resin. In the case of a dental photocurable composition in a single dosage form, it is expected that the technical error is small and the risk of mixing air bubbles is small.

< two-part dental photocurable composition >

When the present invention is applied to a two-part dental photocurable composition, the composition is preferably used as a dental material, in particular, as 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 sealant, a dental cosmetic material, a dental loose tooth fixing adhesive material, a dental hard resin, a dental cutting material, or a dental 3D printing material, and is particularly preferably used as a dental adhesive material, a dental composite resin, a dental abutment building material, or a dental resin cement. The two-pack type dental material is used by kneading immediately before using a two-pack divided into a first paste and a second paste. Kneading the first paste and the second paste in a ratio of 0.9-1.1: 1.0 or 0.8 to 1.2: a mass ratio of 1.0, preferably an equal volume ratio. The kneading method can be carried out by a known method such as manual kneading using a dedicated oscillation device, a doctor blade or the like, automatic kneading by a static mixer or the like. Since the components can be divided into two components and a compound which cannot be mixed in the same paste can be mixed separately, the storage stability is excellent.

The dental photocurable composition of the present invention comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, and the photoacid generator (C) may comprise only an iodonium salt compound formed from (C-1) and an anion having a logS of-4 or less. In addition, the components other than (a) to (D) may include only 1 or more of the above components.

[ examples ]

The following specifically describes examples of the present invention, but the present invention is not limited to these examples.

The materials used in the examples and comparative examples and their abbreviations are as follows.

[ (A) polymerizable monomer ]

Bis-GMA: 2, 2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxy) phenyl ] propane.

2.6E: 2, 2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane having an average molar number of addition of ethoxy groups of 2.6.

UDMA: n, N- (2, 2, 4-trimethylhexamethylene) bis [2- (aminocarboxy) ethanol ] methacrylate.

TEGDMA: triethylene glycol dimethacrylate.

NPG: neopentyl glycol dimethacrylate.

HEMA: 2-hydroxyethyl methacrylate.

MDP: 10-methacryloyloxydecyl dihydrogen phosphate.

MHPA: 6-methacryloyloxyhexylphosphonoacetate.

[ (B) photosensitizer ]

CQ: camphorquinone.

BAPO: phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide.

[ (D) photopolymerization Accelerator ]

< aliphatic tertiary amine >

< aliphatic tertiary amine compound having no primary hydroxyl group >)

TBA: tribenzylamine.

DBGE: n, N-dibenzylglycine ethyl ester.

DEAEMA: n, N-diethylaminoethyl methacrylate.

DMAEMA: n, N-dimethylaminoethyl methacrylate.

< aliphatic tertiary amine compound having 1 primary hydroxyl group >)

DBAE: n, N-dibenzylaminoethanol.

< aliphatic tertiary amine compound having 2 primary hydroxyl groups >

MDEOA: methyldiethanolamine.

< aliphatic tertiary amine compound having 3 primary hydroxyl groups >)

TEA: triethanolamine.

< aromatic tertiary amine Compound >

DMBE: ethyl N, N-dimethylaminobenzoate.

< organometallic Compound >

DBTL: dibutyltin dilaurate.

[ (E) Filler ]

The following shows a method for producing each filler for use in the production of the photocurable composition.

(Filler 1)

100.0g of a zirconium silicate filler (average particle diameter: 1.2 μm: 90 wt% of zirconia, 10 wt% of silica) was added with a silane coupling treatment solution obtained by stirring 50.0g of water, 35.0g of ethanol, and 7.0g of 8-methacryloyloxyoctyltrimethoxysilane as a silane coupling agent at room temperature for 2 hours, and the mixture was stirred and mixed for 30 minutes. Subsequently, heat treatment was performed at 140 ℃ for 15 hours to obtain filler 1.

(Filler 2)

100.0g of a zirconium silicate filler (average particle diameter: 0.8 μm, zirconium oxide: 85 wt%, silicon dioxide: 15 wt%) was added with a silane coupling treatment solution obtained by stirring 50.0g of water, 35.0g of ethanol, and 7.0g of 3-methacryloxypropyltrimethoxysilane as a silane coupling agent at room temperature for 2 hours, and stirred and mixed for 30 minutes. Subsequently, heat treatment was performed at 140 ℃ for 15 hours to obtain filler 2.

[ chemical polymerization initiator ]

CHP: cumene hydroperoxide.

BPO: benzoyl peroxide.

TPE: 1, 1, 3, 3-tetramethylbutylperoxy-2-ethylhexanoate.

[ chemical polymerization Accelerator ]

PTU: (2-pyridyl) thiourea.

DEPT: n, N-dihydroxyethyl-p-toluidine.

DMPT: n, N-dimethyl-p-toluidine.

COA: copper acetylacetonate.

VOA: vanadyl acetylacetonate.

[ ultraviolet absorbers ]

BT: 2- (2-hydroxy-5-methylphenyl) benzotriazole.

[ polymerization inhibitor ]

BHT: 2, 6-di-tert-butyl-4-methylphenol.

MeHQ: p-methoxyphenol.

[ fluorescent Agents ]

FA: 2, 5-Dihydroxyterephthalic acid diethyl ester.

[ (C) photoacid generators ]

The log S of the hydride of the iodonium salt anion was calculated using the chemical mapping Professional software (ChemDraw Professional ver 18.1).

An iodonium salt compound of < (C-1) and an anion having a logS of-4 or less

C1: bis [4- (tert-butyl) phenyl ] iodonium tetrakis (pentafluorophenyl) gallate (LogS: -15.1).

C2: di-p-tolyliodonium phenyltris (pentafluorophenyl) borate (LogS: -11.3).

C3: bis (4-tert-butylphenyl) iodonium tetrakis (nonafluoro-tert-butoxy) aluminate (LogS: -14.7).

C4: p-cumenyl (p-tolyl) iodonium tris (pentafluoroethanesulfonyl) methide (Logs: -5.3).

C5: diphenyliodonium tris (nonafluorobutanesulfonyl) methide (Logs: -9.4).

C6: bis (4-tert-butylphenyl) iodonium tris (pentafluoropropyl) trifluorophosphate (ClogP: -5.2).

C7: p-cumenyl (p-tolyl) iodonium tris (pentafluoroethyl) trifluorophosphate (ClogP: -7.2).

C8: p-cumenyl (p-tolyl) iodonium bis (trifluoromethyl) tetrafluorophosphate (ClogP: -4.7).

C9: p-cumenyl (p-tolyl) iodonium (trifluoromethyl) pentafluorophosphate (ClogP: -4.1).

< photoacid generator comprising anion having logS greater than-4 >

C11: bis (4-tert-butylphenyl) iodonium p-toluenesulfonate (LogS: -2.1).

C12: diphenyliodonium trifluoromethanesulfonate (Logs: -0.7).

C13: chlorodiphenyliodonium salt (Logs: 0.2).

C14: bis (4-tert-butylphenyl) iodonium hexafluorophosphate.

< method for producing single-dose dental photocurable composition >

All the components shown in Table 1 except the filler (E) were charged into a wide-mouth plastic container and mixed for 48 hours at 100rpm using a mixing rotor VMRC-5 to obtain a base. Then, the base and the filler (E) were put into a kneader, and after uniformly stirring, the mixture was defoamed in a vacuum to prepare a dental photocurable composition. In table 1, the abbreviations of the respective components are followed by parentheses which are added to the parts by mass of the respective components.

TABLE 1

< method for producing two-part dental photocurable composition >

All the components shown in Table 2 except for the filler (E) were charged into a wide-mouth plastic container and mixed for 48 hours at 100rpm using a mixing rotor VMRC-5 to obtain a base. Then, the base and the filler (E) were put into a kneader, and after uniform stirring, the mixture was deaerated in vacuo to obtain pastes 1 and 2, and then the pastes 1 and 2 were filled in a double syringe (5mL) manufactured by mixing and packaging company (ミックスパック), to prepare a dental photocurable composition. For the two-part type dental photocurable composition, a paste obtained by mixing the pastes 1 and 2 with a mixing tip (mixing tip) manufactured by mixing packaging company was used. The mixing head manufactured by the mixed packaging company is a static mixer, and when the mixer is used, the paste 1 and the paste 2 can be mixed in a ratio of 0.9-1.1: kneading at a volume ratio of 1.0, and kneading paste 1 and paste 2 in a mass ratio of 0.8 to 1.2: 1.0 was used. In table 2, the abbreviations of the respective components are followed by parentheses which are added to the parts by mass of the respective components.

TABLE 2

< accelerated test conditions >

The one-pack type dental photocurable composition and the two-pack type dental photocurable composition filled in each container were left to stand in a storage set at 40 ℃ (Daohand science corporation (ヤマト science corporation)) and a storage set at-5 ℃ (KGT-4010HC, Nippon Flitz corporation (Nippon フリーザー corporation)) for 6 months.

< evaluation 1: confirmation of appearance

After the one-pack dental photocurable composition and the two-pack dental photocurable composition stored at-5 ℃ were taken out from the storage, they were left to stand at room temperature of 15 to 25 ℃ for 1 week, and 1g of the paste was discharged from the container, and when no precipitate was visually observed, they were judged as a: the method is good; a case where 1 or more and 5 or less precipitates were confirmed was judged as B: within the allowable range; the cases where 5 or more were confirmed were judged as C: the appearance is problematic.

< evaluation 2: confirmation of storage stability by bending Strength >

After filling the dental photocurable composition into a stainless steel mold, a cover glass was placed on both sides of the mold, and the mold was pressed against a glass plate, followed by curing by irradiating 5 portions with light for 10 seconds using a photopolymerization irradiator (pen light: pine air). After curing, the cured product was taken out of the mold, and the back surface was irradiated with light again in the same manner to prepare a test sample (25X 2 mm: rectangular parallelepiped). The test specimen was immersed in water at 37 ℃ for 24 hours, and then subjected to a bending test. The two-part photocurable composition was subjected to a bending test within 1 hour after the irradiation with light. The bending test was carried out using an Instron universal tester (manufactured by Instron corporation, インストロン) under conditions of an inter-fulcrum distance of 20mm and a crosshead speed of 1 mm/min. The storage stability was evaluated using the results of the bending test (formula 2). If the change is more than-5% compared with before storage, the storage stability is high. If the change is between-5% and-15%, the storage stability is slightly poor. If it is a value lower than-15%, the storage stability is judged to be significantly poor.

(bending strength after storage (MPa) -bending strength before storage (MPa))/(bending strength before storage (MPa)) × 100 [% ] (formula 2)

Further, the flexural strength before the acceleration test was separately evaluated. The bending strength of the one-pack photocurable composition and the two-pack photocurable composition containing 100 parts by mass or more of the filler (E) per 100 parts by mass of the polymerizable monomer is judged to be good at more than 100MPa, applicable at 80 to 100MPa, and insufficient at less than 80 MPa. The bending strength of the one-pack photocurable composition and the two-pack photocurable composition containing less than 100 parts by mass of the filler (E) per 100 parts by mass of the polymerizable monomer is judged to be good at more than 90MPa, applicable at 60 to 90MPa, and insufficient at less than 60 MPa. The bending strength varies depending on the amount of the filler to be blended, and therefore different standards are set.

< evaluation 3: stability to ambient light

The height of a dental lamp (Luna-Vue S, manufactured by Setan corporation, モリタ) was adjusted using a photometer so that light with an illuminance of 8000. + -.1000 lx was irradiated to the sample setting part. After a glass slide (26X 16mm, thickness 2mm) was placed on a glass mixing plate laid with matt black paper, a sample of about 30mg was taken thereon. After the sample is exposed to light for 60. + -.5 seconds in the sample-setting part, the sample is taken out from the sample-setting part and immediately the other slide glass is pressed against the sample to form a thin layer. If the sample state at this time is not maintained in a physically uniform state, it is determined that curing is started, and the time until curing is evaluated in units of 5 seconds. The longer this time, the more excellent the ambient light stability. Regarding the stability of the ambient light, 90 seconds or more is judged to be good, 60 seconds or more to less than 90 seconds is judged to be applicable, and less than 60 seconds is judged to be insufficient. The ambient light stability indicates a time period during which the dental photocurable composition is discharged from the container and can be sufficiently changed in shape without being cured by ambient light such as a fluorescent lamp until the container is adapted. Since the space in the oral cavity is narrow, the operation is inconvenient, and the shape of natural teeth of each person is complicated, the longer the stability of ambient light is, the more preferable the adaptation to various cases is.

< evaluation 4: light color stability

After each of the dental photocurable compositions prepared was filled in a stainless steel mold (15. phi. times.1 mm: disk shape), a cover glass was placed from the top and pressure-bonded with a glass plate. The test specimen was cured by irradiation with light from a cover glass using a photopolymerization irradiator (Griplight II: air blown) for 1 minute, and after the cured product was taken out from the mold, the cover glass was removed and the color tone of the test specimen was measured. The test sample was placed on the background of a standard white plate (D65/10 ° X: 81.07, Y: 86.15, Z: 93.38) and color measurement was carried out using a spectrocolorimeter (manufactured by byk chemical corporation, ビックケミー) under predetermined conditions (light source: C, viewing angle: 2 °, measurement area: 11 mm). Subsequently, after the test sample was exposed to light for 24 hours by a hernia light exposure tester (Suntest CPS +), the color tone of the test sample was measured again, and the difference in color change was represented by Δ E calculated by the following formula.

ΔE＝{(ΔL*)²+(Δa*)²+(Δb*)²}^1/2

ΔL*＝L1*-L2*

Δa*＝a1*-a2*

Δb*＝b1*-b2*

Wherein L1 is the brightness index before light exposure, L2 is the brightness index after light exposure, a1 and b1 are the color quality index before light exposure, and a2 and b2 are the color quality index after light exposure. When Δ E is less than 5, it is determined that Δ E is preferably 5 to 10, and when Δ E is more than 10, it is determined that Δ E is preferable. When the light color stability is good, the color change is small during use and the aesthetic quality can be maintained high.

< evaluation 5: thermal color stability

After each of the dental photocurable compositions prepared was filled in a stainless steel mold (15. phi. times.1 mm: disk shape), a cover glass was placed from the top and pressure-bonded with a glass plate. The test sample was cured by irradiation with light from a cover glass using a photopolymerization irradiator (Griplight II: air blown) for 1 minute, and after the cured product was taken out from the mold, the cover glass was removed and the color tone of the test sample was measured. The test sample was placed on the background of a standard white plate (D65/10 ° X: 81.07, Y: 86.15, Z: 93.38) and color measurement was carried out using a spectrocolorimeter (manufactured by byk chemical corporation, ビックケミー) under predetermined conditions (light source: C, viewing angle: 2 °, measurement area: 11 mm). Then, the test sample was immersed in a container containing 10mL of water in a thermostat set at 70 ℃, and after standing for one week, the color tone of the test sample was measured again, and the difference in the discoloration was represented by Δ E calculated by the following formula.

ΔE＝{(ΔL*)²+(Δa*)²+(Δb*)²}^1/2

ΔL*＝L1*-L2*

Δa*＝a1*-a2*

Δb*＝b1*-b2*

Wherein L1 is the brightness index before dipping/standing, L2 is the brightness index after dipping/standing, a1 and b1 are the color quality indexes before dipping/standing, and a2 and b2 are the color quality indexes after dipping/standing. A, judging that the case that the Delta E is less than 5 is best; judging that the condition that the delta E is 5-10 is good; a case where Δ E is larger than 10 is determined to be applicable. When the thermal stability is good, the dental material is less discolored when used in the oral cavity for a long time, and can maintain a high aesthetic state for a long time.

The results of each test shown in tables 3 and 4 are described.

TABLE 3

TABLE 4

It was confirmed that the compositions described in the examples exhibited a flexural strength of 80MPa or more in the production stage and did not significantly decrease even when stored for a long period of time under low temperature conditions.

In examples A8, A9, A15, A16, A23, B8, B9, B15, B16 and B17, the amount of the photoacid generator added was slightly small, and the flexural strength was slightly low. On the other hand, it was confirmed that, when the amount of the photoacid generator blended was slightly large as in examples a12, a13, a14, and B14, the flexural strength tended to decrease during a storage test at a high temperature of 40 ℃, and the ambient light stability was shortened, and the light color stability was lowered. When the photoacid generator contains C8 and C9 of an iodonium salt compound which is a salt of an anion having a log s of-4 to-5 and an iodonium cation, storage stability at low temperature is not problematic even when the amount of the compound is small as in examples A8, a9, B8 and B9, storage stability of examples a10, a11, B10 and B11 in which the amount of the compound is increased and examples a12, a13, B12 and B13 in which the amount of the compound is further increased tend to be slightly lowered, and some precipitates are observed during storage at low temperature and light color stability tends to be slightly poor, but the amount of the precipitates varies within a range that can be used without problems. Further, it was confirmed that even the iodonium salt compound which is a salt containing an anion having a log S of more than-4 and an iodonium cation does not significantly affect the storage stability when the amount is a trace amount of about 0.1 part by mass relative to 100 parts by mass of the polymerizable monomer as in examples A16 and A17.

It was confirmed that examples a22 and B22 tended to decrease in bending strength due to a slightly smaller amount of the photosensitizer added, and examples a21, a47 and B21 tended to decrease in stability to ambient light and decrease in light color stability although they had high bending strength due to a slightly larger amount of the photosensitizer added. In addition, examples A36 and B36 in which the photosensitizer comprises BAPO, which is an acylphosphine oxide, tend to have a lower flexural strength than compositions in which the photosensitizer comprises an α -diketone compound.

It was confirmed that examples a18, a48, and B18 tended to have low flexural strength due to a slightly small amount of photopolymerization accelerator, and examples a19, a20, and B20 tended to have low ambient light stability and low light color stability although the flexural strength was high due to a slightly large amount of photopolymerization accelerator.

Examples a26, a27, B26, B27 contained Dibenzylaminoethanol (DBAE) having 1 primary hydroxyl group as a photopolymerization promoter, examples a28, B28 contained methyldiethanolamine having 2 primary hydroxyl groups as a photopolymerization promoter, and examples a29, B29 contained triethanolamine having 3 primary hydroxyl groups as a photopolymerization promoter. Comparing them, it was confirmed that the thermal color stability tended to decrease as the number of primary hydroxyl groups increased, and particularly, the thermal color stability was greatly decreased by having 2 or more primary hydroxyl groups.

Examples a30, a31, a32, B30, B31, B32 contained DMBE as an aromatic amine as a photopolymerization accelerator. It was confirmed that when the aromatic amine was contained, the light color stability was lowered. On the other hand, in the case of the composition containing the aromatic amine and the ultraviolet absorber as in examples a33, a34, B33, and B34, the decrease in light color stability can be prevented. However, since the ultraviolet absorber increases the yellow color of the cured product and does not contribute to improvement of physical properties by itself, the mechanical strength may be lowered by blending a large amount of the ultraviolet absorber, and therefore, it is more preferable to blend the ultraviolet absorber not.

Examples B41, B42, B44, and B45 contained an aromatic amine as a chemical polymerization accelerator, and similarly to the case of containing an aromatic amine as a photopolymerization accelerator, the light color stability tended to decrease. In addition, examples B42, B44, and B45, which contain an aromatic amine having 2 primary hydroxyl groups in the molecule, such as DEPT, also tend to have reduced thermal color stability.

Comparative examples CA1, CB1 did not cure or the flexural strength was significantly reduced because they did not contain a photosensitizer. Comparative examples CA2 and CB3 did not contain a photoacid generator, and therefore the flexural strength was significantly reduced. Comparative examples CA3 and CB2 did not contain a photopolymerization catalyst, and therefore the flexural strength was significantly reduced. Comparative examples CA4 to CA13 and CB4 to CB13 contain iodonium salt compounds which are salts of anions having a logS of more than-4 and iodonium cations. Although comparative examples CA4, CA5, CB5 and CB6 in which the amount of the photoacid generator added was small were not confirmed to have decreased storage stability, the bending strength was not sufficient. When the amount of the photoacid generator added was increased as in comparative examples CA6 to CA9 and comparative examples CB6 to CB9, the flexural strength was improved, but precipitates were observed during storage at low temperature, and the flexural strength tended to decrease. Further, it was confirmed that the light color stability was lowered. Further, it was confirmed that comparative examples CA10 to CA13 and comparative examples CB10 to CB13, in which the amount of the photoacid generator added was increased, further improved the flexural strength, but the storage stability was lowered and the light color stability was lowered in the low-temperature storage and the high-temperature storage. Solubility of the photoacid generator affects storage stability and color stability.

The dental photocurable composition of the present invention evaluated by examples can be used without any problem in any of the known dental photocurable compositions. The dental photocurable composition 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 sealant, a dental cosmetic material, a dental loose tooth fixing adhesive, a dental glass cement, a dental hard resin, a dental cutting material, a dental 3D printing material, or the like.

In the present specification, when a constituent element of the invention is described as either a singular or a plural, or when it is not described as being limited to a singular or a plural, the constituent element may be either a singular or a plural, unless otherwise clear from the context.

Although the present invention has been described with reference to the detailed embodiments, it will be understood by those skilled in the art that various changes and modifications can be made based on the matters disclosed in the present specification. Therefore, it is intended that the scope of the embodiments of the present invention include any changes or modifications.

According to the present invention, a dental photocurable composition that exhibits excellent mechanical physical properties even after returning from low temperatures to room temperature can be provided.