Dental light-curing composition with excellent color stability

Abstract

To provide a dental photocurable composition having sufficient mechanical strength while having excellent color tone stability after curing.SOLUTION: A dental photocurable composition comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, which is (D1) a tertiary amine compound represented by formula (1) (where each R1 is an ether bond, an ester bond, a urethane bond, an unsaturated double bond, an aromatic ring, an organic group optionally having a halogen, or H, which may be the same as or different from each other; R2 is an organic group optionally having a hydroxy group, or an aromatic ring optionally having a substituent; the compound represented by formula (1) does not have a primary hydroxy group at α-carbon and / or β-carbon of N).SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a photocurable composition for dental use. [Background technology]

[0002] In the dental field, photocurable dental compositions are used and are applied to dental adhesives, dental composite resins, dental core buildup materials, dental resin cements, dental coating materials, dental pit and fissure sealing materials, dental manicure materials, dental tooth stabilization adhesives, dental glass ionomer cements, dental hard resins, dental cutting materials, dental 3D printing materials, and more.

[0003] Patent documents 1 and 2 propose a photopolymerization initiator comprising a photoacid generator (triazine compound or specific aryliodonium salt), a sensitizer, and an electron donor compound, while patent document 3 proposes a resin composition containing N,N-di(2-hydroxypropyl)-p-toluidine, which is superior to conventional tertiary amines in that it exhibits lower coloration after curing. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 4093974 [Patent Document 2] Patent No. 4596786 [Patent Document 3] Japanese Patent Publication No. 1-031706 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, these compositions presented challenges in achieving both sufficient mechanical strength and color stability after curing.

[0006] An object of the present invention is to provide a dental photocurable composition capable of achieving both sufficient mechanical strength and color tone stability after curing.

Means for Solving the Problems

[0007] The present invention provides a dental photocurable composition containing (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a tertiary amine compound represented by formula (1) as a polymerization accelerator. [Formula (1)]

Chemical Formula

Effects of the Invention

[0008] The dental photocurable composition of the present invention can achieve both sufficient mechanical strength and color tone stability after curing.

Modes for Carrying Out the Invention

[0009] In the present invention, the tertiary amine compound represented by formula (1) (D1) can be a tertiary aliphatic amine compound represented by formula (1) (D11).

[0010] In the present invention, the photoacid generator (C) contains an aryliodonium salt, and the aryliodonium salt can be a salt of an aryl iodonium cation and an anion having an organic group and one or more atoms of any one of P, B, Al, S, and Ga.

[0011] In the present invention, (C) the photoacid generator comprises an aryliodonium salt, and the aryliodonium salt may be a salt of an aryliodonium cation with an anion having an organic group in which at least one H is substituted with F and one or more atoms from P, B, Al, S, and Ga.

[0012] The present invention may include a tertiary aromatic amine compound represented by formula (1) (D12) and a tertiary aliphatic amine compound.

[0013] In the present invention, (A) Per 100 parts by mass of polymerizable monomer, (B) Contains 0.02 to 1 part by mass of a photosensitizer, (C) Contains 0.02 to 10 parts by mass of a photoacid generator, (D11) May contain 0.2 to 10 parts by mass of a tertiary aliphatic amine compound represented by formula (1).

[0014] In the present invention, (A) Per 100 parts by mass of polymerizable monomer, (B) Contains 0.02 to 1 part by mass of a photosensitizer, (C) Contains 0.02 to 10 parts by mass of a photoacid generator, (D) Contains 0.2 to 10 parts by mass of polymerization accelerator, (D) The polymerization accelerator may contain 0.02 to 1 part by mass of a tertiary aromatic amine compound represented by formula (1) (D12).

[0015] The components of the dental photocurable composition of the present invention will be described in detail below. The photocurable dental composition of the present invention can be used as a dental adhesive, dental composite resin, dental core buildup material, dental resin cement, dental coating material, dental pit and fissure sealing material, dental manicure material, dental tooth fixing adhesive, dental glass ionomer cement, dental hard resin, dental cutting material, dental 3D printer material, etc.

[0016] In dental practice, to restore the aesthetic and functional properties of teeth lost due to caries or fracture, treatment is performed using direct methods, which involve restoration with dental adhesives and composite resins, and indirect methods, which involve restoring prosthetic devices made of ceramics or dental hard resins with dental resin cement. In addition, dental adhesives are used to attach dental composite resins, various dental materials, and natural teeth; dental adhesives are used to stabilize mobile teeth; dental coatings are used to protect hypersensitive teeth and vital teeth after preparation from external stimuli and secondary caries; dental pit and fissure sealing materials are used to prevent caries by filling deep fissures in molars; dental manicure materials are used to temporarily restore aesthetics by masking tooth discoloration; and dental core buildup materials are used to form abutment teeth when the crown has collapsed due to caries. In recent years, new composite materials have been developed, such as dental milling materials for creating prosthetic devices using CAD / CAM processing, and dental 3D printing materials for creating prosthetic devices using 3D printers. A wide variety of dental materials are now used in treatment. These materials are prepared by mixing a resin matrix consisting of several polymerizable monomers, various fillers such as inorganic fillers and organic-inorganic composite fillers, and polymerization initiators, according to their intended use, to create a uniform paste. For example, dental composite resins are filled into teeth in an uncured paste state, then shaped to resemble natural teeth using dental instruments, and finally cured by irradiation with light from a dental light curing unit. The light emitted from the light curing unit generally has a wavelength range of approximately 360-500 nm and a light intensity of 100-2000 mW / cm². 2 A light source with a certain level of output is used. On the other hand, dental resin cement is used to bond prosthetic devices to cavities or abutment teeth, and is hardened by light irradiation after the prosthetic device is attached to the cavity or abutment tooth.

[0017] For use as photopolymerization initiators in dental materials, systems combining photosensitizers or photopolymerization accelerators are widely used. Acylphosphine oxide compounds and α-diketone compounds are known as photosensitizers, and α-diketone compounds, in particular, exhibit polymerization initiation ability in the visible light wavelength range, which has minimal impact on the human body. Furthermore, photoacid generators and tertiary amine compounds are well-known compounds to be combined with photosensitizers. The combination of α-diketone compounds, photoacid generators, and tertiary amine compounds exhibits high polymerization activity in response to irradiated light and is therefore used in the field of dental materials. Dental photocurable compositions containing these photopolymerization initiators exhibit excellent mechanical properties such as hardness, flexural strength, and compressive strength required for various materials.

[0018] Typical tertiary amine compounds used as photopolymerization initiators include methyldiethanolamine, triethanolamine, and p-tolylethanolamine, all of which have a primary hydroxyl group. However, when amine compounds with a primary hydroxyl group are incorporated into a composition in combination with a photoacid generator, they have the problem of discoloration when the cured product is used for a long period of time. Although the detailed principle is unknown, discoloration tends to occur when acidic compounds such as polymerizable monomers with acidic groups are included, not just in photoacid generators. Therefore, it is presumed that the coexistence of the acid produced by the photoacid generator and the amine compound with a primary hydroxyl group is the cause of the discoloration.

[0019] We found that the above problems can be solved by incorporating a tertiary amine compound with a specific structure into a dental photocurable composition. More specifically, we found that the above problems can be improved by using a tertiary amine compound having two or more secondary and / or tertiary hydroxyl groups, and thus completed the present invention.

[0020] [(A) Polymerizable monomers] The polymerizable monomer (A) contained in the dental photocurable composition of the present invention can be used without limitation as long as it is known. In the polymerizable monomer or compound having a polymerizable group described in the present invention, the polymerizable group is preferably one that exhibits 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 this specification, "(meth)acrylic" means acrylic and / or methacrylic, "(meth)acryloyl" means acryloyl and / or methacryloyl, "(meth)acrylate" means acrylate and / or methacrylate, and "(meth)acrylamide" means acrylamide and / or methacrylamide. Polymerizable monomers having substituents at the α-position of the acrylic group and / or acrylamide group can also be preferably used. These include those having one radical polymerizable group, two radical polymerizable groups, three or more radical polymerizable groups, those having an acidic group, an alkoxysilyl group, a sulfur atom, etc.

[0021] Specific examples of polymerizable monomers 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 Examples include -hydroxyethyl (meth)acrylamide, N,N-(dihydroxyethyl)(meth)acrylamide, methyl (meth)acrylate, ethyl (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, etc.

[0022] Specific examples of polymerizable monomers having two radical polymerizable groups and no acidic groups include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, and 2,2-bis(4-(meth) Liloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxydiethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyditriethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxy Xyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitate, glycerol di(meth)acrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate Triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,Examples include 4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA") and 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane.

[0023] Specific examples of polymerizable monomers having three or more radical polymerizable groups and no acidic groups include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, and 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane.

[0024] Polymerizable monomers having acidic groups can be used without restriction, as long as they have one or more polymerizable groups and at least one acidic group such as a phosphate group, pyrophosphate group, thiophosphate group, phosphonic acid group, sulfonic acid group, or carboxylic acid group. Including polymerizable monomers having acidic groups can impart adhesion to tooth structure and prosthetic devices.

[0025] Specific examples of polymerizable monomers having a phosphate 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, and 8-(meth) Acryloyl oxyoctyl dihydrogen phosphate, 9-(meth)acryloyl oxynonyl dihydrogen phosphate, 10-(meth)acryloyl oxydecyl dihydrogen phosphate, 11-(meth)acryloyl oxyundecyl dihydrogen phosphate, 12-(meth)acryloyl oxide decyl dihydrogen phosphate, 16-(meth)acryloyl oxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyl oxyicosyl dihydrogen phosphate 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-di( Examples include 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, and ammonium salts of these compounds; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0026] Specific examples of polymerizable monomers 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)acryloyloxydecyl] pyrophosphate; their acid chlorides, alkali metal salts, ammonium salts; and (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond.

[0027] Specific examples of polymerizable monomers having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, 4-(meth)acryloyloxybutyl dihydrogenthiophosphate, 5-(meth)acryloyloxypentyl dihydrogenthiophosphate, 6-(meth)acryloyloxyhexyl dihydrogenthiophosphate, 7-(meth)acryloyloxyheptyl dihydrogenthiophosphate, 8-(meth)acryloyloxyoctyl dihydrogenthiophosphate, and 9-(meth)acryloyl Examples include hydroxynonyl dihydrogenthiophosphate, 10-(meth)acryloyloxydecyl dihydrogenthiophosphate, 11-(meth)acryloyloxyundecyl dihydrogenthiophosphate, 12-(meth)acryloyloxidedecyl dihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogenthiophosphate, 20-(meth)acryloyloxyicosyl dihydrogenthiophosphate; acid chlorides, alkali metal salts, and ammonium salts of these compounds; and (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond. Polymerizable monomers having a thiophosphate group are also classified as polymerizable monomers having a sulfur atom.

[0028] Specific examples of polymerizable monomers 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, and ammonium salts of these compounds; and (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond.

[0029] Specific examples of polymerizable monomers having a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid and 2-sulfoethyl (meth)acrylate.

[0030] Polymerizable monomers containing a carboxylic acid group are classified into (meth)acrylic compounds having one carboxyl group in the molecule and (meth)acrylic compounds having multiple carboxyl groups in the molecule. Specific examples of (meth)acrylic compounds having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid, and 3-(meth)acryloylo Examples include xybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen malate; halides of these acids; and (meth)acrylamide compounds obtained by replacing the ester bonds of these compounds with amide bonds.Specific examples of (meth)acrylic compounds having multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxidedodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, and 4-(meth) Examples include acryloyloxyethyl trimellitate, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate; their acid anhydrides and acid halides; and (meth)acrylamide compounds in which the ester bonds of these compounds are replaced with amide bonds.

[0031] Preferably, examples include 10-methacryloyloxydecyl dihydrogen phosphate or 6-methacryloxyhexyl phosphonoacetate. From the viewpoint of imparting adhesion, the amount of polymerizable monomer having an acidic group is 1 part by mass or more, more preferably 10 parts by mass or more and 50 parts by mass or less, relative to the total amount of polymerizable monomers in 100 parts by mass of the dental photocurable composition. If the amount is less than 1 part by mass, sufficient adhesion to tooth structure, metals, and metal oxides may not be achieved, and if it is 50 parts by mass or more, storage stability may decrease.

[0032] Specific examples of polymerizable monomers having alkoxysilyl groups include (meth)acrylic and (meth)acrylamide compounds having one alkoxysilyl group in the molecule, and (meth)acrylic and (meth)acrylamide compounds having multiple alkoxysilyl groups in the molecule. Examples include 2-(meth)acryloxyethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane, 5-(meth)acryloxypentyltrimethoxysilane, 6-(meth)acryloxyhexyltrimethoxysilane, 7-(meth)acryloxyheptyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 9-(meth)acryloxynonyltrimethoxysilane, 10-(meth)acryloxydecyltrimethoxysilane, and 11-(meth)acryloxyundecyltrimethoxysilane.Furthermore, as examples of those having urethane or ether groups, there are 3,3-dimethoxy-8,37-dioxo-2,9,36-trioxa-7,38-diaza-3-silatetracontane-40-yl(meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,18-trioxa-7-aza-3-cyranonadecane-19-oil)amino)-2-methylpropane-1,3-diyldi(meth)acrylate, and 3,3-dimethoxy-8,19-dioxo-2,9,18-trioxa-7,20-diaza-3-siladocosane-22-yl(meth)acrylate. Relate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21-hexaoxa-7,23-diaza-3-silapentacosan-25-yl(meth)acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21,26-heptaoxa-7,23-diaza-3-silaoctacosan-28-yl(meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18-pentaoxa-7,20-diaza-3-siladocosan-22-yl(meth)acrylate, 3,3-dimeth Toxy-8,19-dioxo-2,9,12,15,18,23-hexaoxa-7,20-diaza-3-silapentacosan-25-yl(meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,12,15,18-pentaoxa-7-aza-3-cyranonadecane-19-oil)amino)-2-methylpropane-1,3-diyldi(meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosane-23-yl(meth)acrylate, 4,4-diethoxy-17-o Examples include xo-3,16,21,24-tetraoxa-18-aza-4-silahexacosan-26-yl(meth)acrylate, 4,4-diethoxy-13-oxo-3,12,17-trioxa-14-aza-4-cyranonadecane-19-yl(meth)acrylate, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silaikosane-20-yl(meth)acrylate, and 2-methyl-2-((11-(triethoxysilyl)undecyloxy)carbonylamino)propane-1,3-diyldi(meth)acrylate.

[0033] The dental photocurable composition of the present invention may contain a polymerizable monomer having a sulfur atom as (A) polymerizable monomer to impart adhesion to noble metals. Any known polymerizable monomer having one or more sulfur atoms and a polymerizable group can be used without any limitations. Specifically, this refers to compounds having substructures such as -SH, -SS-, >C=S, >CSC<, >P=S, or compounds resulting from tautomerism. Specific examples include 10-methacryloxydecyl-6,8-dithiooctanate, 6-methacryloxyhexyl-6,8-dithiooctanate, 6-methacryloyloxyhexyl2-thiouracil-5-carboxylate, 2-(11-methacryloyloxyundecylthio)-5-mercapto-1,3,4-thiadiazole, and 10-(meth)acryloyloxydecyldihydrogenthiophosphate.

[0034] There are no restrictions on using oligomers or prepolymers having at least one polymerizable group in the molecule other than these polymerizable monomers. Furthermore, there is no problem with having substituents such as fluorogroups within the same molecule. The polymerizable monomers described above can be used individually or in combination.

[0035] The dental photocurable composition of the present invention may contain a silane coupling agent as a polymerizable monomer (A) to impart adhesion to glass ceramics. Any known silane coupling agent can be used without limitation, but 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, and 11-methacryloxyundecyltrimethoxysilane are preferred. From the viewpoint of imparting adhesion, the amount of the silane coupling agent is 1 part by mass or more, more preferably 5 parts by mass or more and less than 20 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers in the composition. The silane coupling agent as a polymerizable monomer is intended to impart adhesion to glass ceramics and resin materials containing glass ceramic fillers, and is therefore formulated separately from the filler surface treatment agent.

[0036] The dental photocurable composition of the present invention may contain a polymerizable monomer having a sulfur atom as (A) polymerizable monomer in order to impart adhesion to noble metals. From the viewpoint of imparting adhesion, the amount of polymerizable monomer having a sulfur atom is 0.01 parts by mass or more, more preferably 0.1 parts by mass or more and less than 20 parts by mass, relative to the total amount of polymerizable monomers contained in 100 parts by mass of the dental photocurable composition.

[0037] The photocurable dental composition of the present invention may contain polymerizable monomers having cationic polymerizable functional groups, but it is preferable to contain only polymerizable monomers having radical polymerizable functional groups.

[0038] <Photopolymerization initiator> The dental photocurable composition of the present invention contains a photopolymerization initiator. A photopolymerization initiator is a polymerization initiator that can initiate polymerization by irradiation with light. The photopolymerization initiator contained in the dental photocurable composition of the present invention includes (B) a photosensitizer, (C) a photoacid generator, and (D) a polymerization accelerator. These can be any commonly used and known compounds without any limitations.

[0039] [(B) Photosensitizer] Specific examples of photosensitizers (B) that can be used in the present invention include benzyl, camphorquinone, camphorquinone carboxylic acid, camphorquinone sulfonic acid, α-naphthyl, acetonafthene, p,p'-dimethoxybenzyl, p,p'-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, naphthoquinone and other α-diketones, benzoin, benzoin methyl ether, benzoin ethyl ether and other benzoin Alkyl ethers, thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, benzophenones such as benzophenone, p-chlorobenzophenone, p-methoxybenzophenone, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl) Phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropyl-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylpropyl-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl (2-methylpropyl-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylpropyl-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylpropyl-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylpropyl-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylpropyl-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylpropyl-1-yl)phosphine oxide, bis(2,4,6-Trimethylbenzoyl)phenylphosphine oxide, 2,4,6-Trimethylbenzoyldiphenylphosphine oxide, Bis(2,4,6-Trimethylbenzoyl)(2,4-Dipentoxyphenyl)phosphine oxide, Bis(2,6-Dimethoxybenzoyl)benzylphosphine oxide, Bis(2,6-Dimethoxybenzoyl)-2-phenylpropylphosphine oxide, Bis(2,6-Dimethoxybenzoyl)-2-phenylethylphosphine oxide, Bis(2,6-Dimethoxybenzoyl) Benzoyl)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-2,4,6-trimethylbenzoyl Acyl phosphine oxides such as n-butylphosphine oxide, acyl germanium compounds such as bisbenzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis(4-methoxybenzoyl)dimethylgermanium, and bis(4-methoxybenzoyl)diethylgermanium, 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-diethylamino-1-(4-morpholinophenyl) Examples include α-aminoacetophenones such as -propanone-1, ketals such as benzyldimethyl ketal, benzyl diethyl ketal, and benzyl(2-methoxyethyl ketal), and titanocenes such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]-titanium, bis(cyclopentadienyl)-bis(pentanefluorophenyl)-titanium, and bis(cyclopentadienyl)-bis(2,3,5,6-tetrafluoro-4-disiloxyphenyl)-titanium.

[0040] (B) The photosensitizer can be appropriately selected depending on the wavelength, intensity, and duration of light used for polymerization, as well as the type and amount of other components used in combination. The photosensitizer can be used alone or in combination of two or more types. Among these, α-diketone compounds having a maximum absorption wavelength in the visible light region are preferably used, and more preferably, camphorquinone compounds such as camphorquinone, camphorquinone carboxylic acid, and camphorquinone sulfonic acid are preferred, with camphorquinone being particularly preferred because it is readily available.

[0041] Typically, the amount of (B) photosensitizer is preferably 0.02 to 1.0 parts by mass, and more preferably 0.05 to 0.5 parts by mass, per 100 parts by mass of the total amount of (A) polymerizable monomers contained in the dental photocurable composition. If the amount of (B) photosensitizer is less than 0.02 parts by mass, the polymerization activity in response to irradiation light may be poor, resulting in insufficient curing. If the amount is greater than 1.0 part by mass, sufficient curing properties are achieved, but the ambient light stability is shortened and the yellowing increases. The dental photocurable composition of the present invention may contain only α-diketone compounds as (B) photosensitizer.

[0042] [(C) Photoacid Generator] The (C) photoacid generator used in the dental photocurable composition of the present invention can be any known compound without limitation. Specifically, examples include triazine compounds, iodonium salt compounds, sulfonium salt compounds, and sulfonic acid ester compounds. Among these, triazine compounds and iodonium salt compounds are preferred due to their high polymerizability when used in combination with a sensitizer. Iodonium salt compounds are more preferably preferred. Iodonium salt compounds are easily sensitized by photosensitizers that have absorption in the visible light region.

[0043] Specific examples of triazine compounds include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine. 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine s(trichloromethyl)-s-triazine, 2-[2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4, 6-bis(trichloromethyl)-s-triazine, 2-(1-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis(2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,Examples include 6-bis(trichloromethyl)-s-triazine and 2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine. Among these, 2,4,6-tris(trichloromethyl)-s-triazine is preferred.

[0044] Any known iodonium salt compound can be used. For example, the structural formula of an iodonium salt compound can be represented by the following formula (2). [Formula (2)] [(R1)2I] + [A] - ([(R1)2I] in the formula) + [A] is the cation part. - R1 is the anionic part, and in formula (2), R1 represents the organic group bonded to I. R1 may be the same or different. R1 represents, for example, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms. These may be substituted with at least one selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogens.

[0045] Examples of aryl groups having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl groups and condensed polycyclic aryl groups such as naphthyl, anthracenyl, phenanthrenyl, pyrenyl, crisenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, and anthraquinone.

[0046] Examples of heterocyclic groups having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 heteroatoms such as oxygen, nitrogen, and sulfur, which may be the same or different. Specific examples include monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, and pyrazinyl, as well as condensed polycyclic heterocyclic groups such as indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl.

[0047] Specific examples of alkyl groups having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl, and octadecyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0048] Furthermore, specific examples of alkenyl groups having 2 to 30 carbon atoms include linear or branched groups such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 1-methyl-1-propenyl.

[0049] Furthermore, specific examples of alkynyl groups having 2 to 30 carbon atoms include linear or branched groups such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl, and 1-methyl-2-propynyl.

[0050] The above C6-C30 aryl groups, C4-C30 heterocyclic groups, C1-C30 alkyl groups, C2-C30 alkenyl groups, or C2-C30 alkynyl groups may have at least one substituent. Specific examples of substituents include: C1-C18 linear alkyl groups such as methyl, ethyl, propyl, butyl, and octadecyl; C1-C18 branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; C3-C18 cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; hydroxyl groups; C1-C18 linear or branched alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and dodecyloxy; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanol, 2-methylbutanoyl, 3-methylbutanoyl, and o Linear or branched alkylcarbonyl groups with 2 to 18 carbon atoms, such as kutanoyl; arylcarbonyl groups with 7 to 11 carbon atoms, such as benzoyl and naphthoyl; linear or branched alkoxycarbonyl groups with 2 to 19 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, and tert-butoxycarbonyl; phenoxycarbonyl Aryloxycarbonyl groups with 7 to 11 carbon atoms, such as naphthoxycarbonyl; Arylthiocarbonyl groups with 7 to 11 carbon atoms, such as phenylthiocarbonyl and naphthoxythiocarbonyl; Linear or branched acyloxy groups with 2 to 19 carbon atoms, such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, and octadecylcarbonyloxy;Arylthio groups with 6 to 20 carbon atoms, such as phenylthio, biphenylylthio, 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-(ptert-butylbenzoyl)phenylthio, etc.; linear or branched alkylthio groups with 1 to 18 carbon atoms, such as methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, dodecylthio, etc.; Aryl groups with 6 to 10 carbon atoms, such as nyl, tolyl, dimethylphenyl, and naphthyl; heterocyclic groups with 4 to 20 carbon atoms, such as thienyl, furanyl, pyranyl, xanthenyl, chromanyl, isochromanyl, xanthonyl, tioxanthonyl, and dibenzofuranyl; aryloxy groups with 6 to 10 carbon atoms, such as phenoxy and naphthyloxy; linear or branched alkylsulfinyl groups with 1 to 18 carbon atoms, such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, and octylsulfinyl; arylsulfinyl groups with 6 to 10 carbon atoms, such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl; linear or branched alkylsulfonyl groups with 1 to 18 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and octylsulfonyl; Examples include aryl sulfonyl groups with 6 to 10 carbon atoms, such as phenylsulfonyl, tolylsulfonyl (tosyl group), and naphthylsulfonyl; alkylene oxy groups; cyano groups; nitro groups; and halogens such as fluorine, chlorine, bromine, and iodine.

[0051] Among iodonium salt compounds, aryliodonium salts are preferred due to their high stability. Furthermore, it is preferable that the aryl group has substituents to improve lipophilicity. Specifically, suitable substituents include linear alkyl groups such as methyl, propyl, octyl, decyl, undecyl, dodecyl, and tridecyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl; functional groups in which one or more H atoms of these hydrocarbon groups are substituted with F; perfluoroalkyl groups; and halogens.

[0052] The structure of the anionic portion of iodonium salt compounds is not particularly limited, but examples include those having atoms such as halogens, P, S, B, Al, and Ga. From a safety standpoint, anions containing As or Sb can be used, but they are not preferred for dental applications. Furthermore, it is preferable that the anion has an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group, and most preferably an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which at least one H is substituted with F. Iodonium salt compounds having such anions have high solubility in dental photocurable compositions, which can prevent precipitation during low-temperature storage and long-term storage, and can be expected to shorten manufacturing time because they dissolve in the composition in a short time. Furthermore, iodonium salt compounds consisting of anions having an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which one or more H is substituted with F can be expected to have even higher solubility. Precipitation of the photoacid generator is undesirable because it may cause a decrease in photochromic stability and flexural strength. Such anions, which have organic groups such as alkyl groups and / or alkoxy groups and / or aryl groups, in which at least one H may be substituted with F, can be anions with any atoms, but from the viewpoint of versatility and safety, those having P, S, B, Al, and Ga are preferred.

[0053] Anions that do not have alkyl groups and / or alkoxy groups and / or aryl groups include halogens such as chlorides and bromides, perhalates such as perchloric acid, aromatic sulfonic acids such as p-toluenesulfonate, camphorsulfonic acid, nitrates, acetates, chloroacetates, carboxylates, phenolates, tetrafluoroborates, hexafluorophosphates, hexafluoroantimonates, and hexafluoroarsenates. Among these, p-toluenesulfonate, camphorsulfonic acid, and carboxylates are preferably used.

[0054] [A] of the iodonium salt compound of formula (2) - The anionic portion of [A] of the iodonium salt compound of formula (2) is preferable because it improves solubility in dental photocurable compositions, and therefore it is preferable that the anionic portion has an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which at least one H is substituted with F. Specifically, [A] of the iodonium salt compound of formula (2) - The preferred number of carbon atoms in the alkyl group of the anionic portion is 1 to 8, preferably 1 to 4. Specific examples include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutylsec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The ratio of hydrogen atoms to fluorine atoms in the alkyl group (F / H) is 4 or more, preferably 9 or more. More preferably, all hydrogen atoms of the hydrocarbon are substituted with fluorine. The dental photocurable composition may also contain an iodonium salt comprising an anion having alkyl groups with different ratios of hydrogen atoms to fluorine atoms.

[0055] Furthermore, specific examples of alkyl groups include linear or branched perfluoroalkyl groups such as CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C.

[0056] The [A] of the iodonium salt compound of formula (2) - The preferred number of carbon atoms of the alkoxy group in the anion part is 1 to 8, preferably 1 to 4. Specific examples include linear alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentoxy, octoxy, and branched alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy, tert-butoxy. The ratio (F / H) of the number of hydrogen atoms to fluorine atoms in the alkyl group is 4 or more, preferably the ratio (F / H) of the number of hydrogen atoms to fluorine atoms in the alkyl group is 9 or more. More preferably, all hydrogen atoms of the hydrocarbon are substituted with fluorine. An iodonium salt composed of an anion having alkoxy groups with different ratios of hydrogen atoms to fluorine atoms may be incorporated into the dental photocurable composition.

[0057] Furthermore, specific examples of the alkoxy group include linear or branched perfluoroalkoxy groups such as CF3O, CF3CF2O, CF3CF2CF2O, (CF3)2CFO, CF3CF2CF2CF2O, (CF3)2CFCF2O, CF3CF2(CF3)CFO, CF3CF2CF2CF2CF2O, CF3CF2CF2CF2CF2CF2CF2CF2CF2O.

[0058] The [A] of the iodonium salt compound of formula (2) -The phenyl group in the anionic portion contains at least one hydrogen atom that is a fluorine atom, and / or a phenyl group that is substituted with an alkyl group and / or alkoxy group substituted with a fluorine atom. The alkyl group and / or alkoxy group substituted with a fluorine atom is preferably one of those described above. Particularly preferred phenyl groups include perfluorophenyl groups such as pentafluorophenyl group (C6F5), trifluorophenyl group (C6H2F3), tetrafluorophenyl group (C6HF4), trifluoromethylphenyl group (CF3C6H4), bis(trifluoromethyl)phenyl group ((CF3)2C6H3), pentafluoroethylphenyl group (CF3CF2C6H4), bis(pentafluoroethyl)phenyl group ((CF3CF2)2C6H3), trifluoromethylfluorophenyl group (CF3C6H3F), bistrifluoromethylfluorophenyl group ((CF3)2C6H2F), pentafluoroethylfluorophenyl group (CF3CF2C6H3F), and bispentafluoroethylfluorophenyl group ((CF3CF2)2C6H2F). The dental photocurable composition may also contain iodonium salts consisting of anions having phenyl groups with different ratios of hydrogen atoms to fluorine atoms.

[0059] [A] of the iodonium salt compound of formula (2) - As a specific example of the anion part, an anion containing P is [(CF3CF2)3PF3] - [(CF3CF2CF2)3PF3] - [((CF3)2CF)2PF4] - [((CF3)2CF)3PF3] - [((CF3)2CF)4PF2] - [((CF3)2CFCF2)2PF4] - [((CF3)2CFCF2)3PF3] - Examples include [(CF3SO2)3C]. Anions containing S include [(CF3SO2)3C]. - [(CF3CF2SO2)3C] - [(CF3CF2CF2SO2)3C] - [(CF3CF2CF2CF2SO2)3C] -[CF3CF2CF2CF2SO3] - [CF3CF2CF2SO3] - [(CF3CF2SO2)3C] - [(SO2CF3)3N] - [(SO2CF2CF3]2N] - [((CF3)C6H4)SO3] - [SO3((CF2CF2CF2CF2)SO3] 2- Examples include [B(C6F5)4], an anion containing B. - [(C6H5)B((CF3)2C6H3)3] - [(C6H5)B(C6F5)3] - Examples include [((CF3)4Ga)], an anion containing Ga. - [Ga(C6F5)4] - Examples include [((CF3)3CO)4Al], an anion containing Al. - [((CF3CF2)3CO)4Al] - These are some examples.

[0060] The dental photocurable composition of the present invention preferably contains 0.02 to 10 parts by mass of (C) a photoacid generator per 100 parts by mass of (A) polymerizable monomers, and more preferably 0.2 to 5 parts by mass. If the amount of photoacid generator is less than 0.02 parts by mass, the polymerization promoting ability may be poor and curing may be insufficient. If the amount is greater than 10 parts by mass, sufficient curing ability will be achieved, but the ambient light stability may be reduced, shortening the handling time, or discoloration such as browning of the cured product may increase.

[0061] The photoacid generators that can be used in the dental photocurable composition of the present invention are not limited to the photoacid generators shown in the specific examples, and two or more types can be used in combination.

[0062] 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 one or more atoms from among P, B, Al, S, and Ga, and an aryliodonium cation, as (C) a photoacid generator. 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 in which at least one or more H atoms are substituted with F, and an aryliodonium cation, as (C) a photoacid generator.

[0063] [(D) Polymerization accelerator] The polymerization accelerator (D) used in the dental photocurable composition of the present invention is not particularly limited as long as it has polymerization promoting ability, and any known polymerization accelerator commonly used in the dental field can be used without any restrictions. Examples of the polymerization accelerator (D) include aromatic amine compounds, primary to tertiary amine compounds such as aliphatic amine compounds, phosphine compounds, organometallic compounds, fourth-period transition metal compounds, thiourea derivatives, sulfinic acid and its salts, borate compounds, sulfur-containing reducing inorganic compounds, nitrogen-containing reducing inorganic compounds, barbituric acid derivatives, triazine compounds, halogen compounds, and the like.

[0064] Aromatic amine compounds refer to compounds in which one or more hydrogen atoms of ammonia (NH3) are substituted with aromatic rings. They can be classified as follows: aromatic primary amines are those in which one hydrogen atom of NH3 is substituted with an aromatic ring; aromatic secondary amines are those in which one hydrogen atom of NH3 is substituted with an aromatic ring and one other hydrogen atom is substituted with an aromatic ring or an alkyl group; and aromatic tertiary amines are those in which one hydrogen atom of NH3 is substituted with an aromatic ring and two other hydrogen atoms are substituted with aromatic rings or alkyl groups.

[0065] Examples of primary aromatic amine compounds include aniline, examples of secondary aromatic amine compounds include N-phenylbenzylamine, N-benzyl-p-anisidine, N-benzyl-o-phenethidine, N-phenylglycine ethyl, and N-phenylglycine (N-protected amino acids / esters), and examples of tertiary aromatic amine compounds include N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline, pN,N-dimethyltoluidine, mN,N-dimethyltoluidine, pN,N-diethyltoluidine, p-bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, and p-dimethylaminobenzoic acid. Examples include p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid 2-butoxyethyl, p-dimethylaminobenzoic acid 2-ethylhexyl, p-dimethylaminobenzoic acid amino ester, N,N-dimethylanthranic acid methyl ester, N,N-dihydroxyethylaniline, N,N-diisopropanolaniline, pN,N-dihydroxyethyl-toluidine, pN,N-dihydroxypropyl-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N,N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine, and N,N-dimethyl-β-naphthylamine. Among these, p-dimethylaminobenzoic acid ethyl ester is preferred.

[0066] A phosphine compound refers to a compound in which a phosphorus atom is substituted with three organic groups, while an aromatic phosphine compound refers to a compound in which a phosphorus atom is substituted with one or more phenyl groups that may have one or more substituents. Specific examples of phosphine compounds include trimethylphosphine, tributylphosphine, trihexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tri(2-thienyl)phosphine, diphenylpropylphosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, methyldiphenylphosphine, triphenylphosphine, 2-(diphenylphosphino)styrene, 3-(diphenylphosphino)styrene, 4-(diphenylphosphino)styrene, allyldiphenylphosphine, 2-(diphenylphosphino)benzaldehyde, 3-(diphenylphosphino)benzaldehyde, 4-(diphenylphosphino)benzaldehyde, and 2-(phenylphosphino)benzoic acid. Examples include acids, 3-(phenylphosphino)benzoic acid, 4-(phenylphosphino)benzoic acid, tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, 2-(diphenylphosphino)biphenyl, tris(4-fluorophenyl)phosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, 2-(dimethylamino)phenyldiphenylphosphine, 3-(dimethylamino)phenyldiphenylphosphine, 4-(dimethylamino)phenyldiphenylphosphine, 2,2'-bis(diphenylphosphino)biphenyl, and bis[2-(diphenylphosphino)phenyl]ether. Among these, triphenylphosphine, 4-(phenylphosphino)benzoic acid, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, and tri(p-tolyl)phosphine are preferred.

[0067] Aliphatic amine compounds refer to compounds in which one or more hydrogen atoms of ammonia (NH3) are substituted with alkyl groups. Alkyl groups are classified as follows: primary alkyl groups are those with CH3- or -CH2-; secondary alkyl groups are those with one substituted hydrogen atom of -CH2-; and tertiary alkyl groups are those with two substituted hydrogen atoms of -CH2-. Aliphatic amines are further classified as aliphatic primary amine compounds if one hydrogen atom of NH3 is substituted with an alkyl group; aliphatic secondary amine compounds if two hydrogen atoms of NH3 are substituted with alkyl groups; and aliphatic tertiary amine compounds if three hydrogen atoms of NH3 are substituted with alkyl groups.

[0068] Examples of aliphatic primary amine compounds include benzhydrylamine, triphenylmethylamine, glycine, and other amino acids or amino acid esters; examples of aliphatic secondary amine compounds include dibenzylamine, N-benzyl-1-phenylethylamine, bis(1-phenylethyl)amine, bis(4-cyanobenzyl)amine, N-benzyl-protected amino acids or N-benzyl-protected amino acid esters; and examples of aliphatic tertiary amine compounds include tributylamine, tripropylamine, triethylamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethylstearylamine, N-[3-(dimethylamino)propyl]acrylamide, N,N-dimethylformamide dimethylacetal, N,N-dimethylacetamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dimethylformamide dipropylacetal, N,N-dimethylformamide di-tert-butylacetal, 1-(2-hydroxyethyl)ethyleneimine, N,N-dimethylethanolamine, N,N- Dimethylisopropanolamine, N,N-diisopropylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, N-stearyldiethanolamine, triethanolamine, triisopropanolamine, trynzylamine, dibenzylglycine ethyl ester, N'-(2-hydroxyethyl)-N,N,N'-trimethylethylenediamine, 2-(dimethylamino)-2-methyl-1-propanol, N ,N-dimethyl-2,3-dihydroxypropylamine, N,N-diethylethanolamine, 1-methyl-3-pyrrolidinol, 1-(2-hydroxyethyl)pyrrolidinol, 1-isopropyl-3-pyrrolidinol, 1-piperidineethanol, 2-[2-(dimethylamino)ethoxy]ethanol, N,N-dimethylglycine, N,N-dimethylglycinemethyl, N,N-diethylglycinemethyl, N,N-dimethylglycineethyl, N,N-diethylglycinesodium, 2-(dimethylamino)ethyl acetate, N-methyliminodiacetic acid, N,Examples include N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diisopropylaminoethyl methacrylate, N,N-dibutylaminoethyl methacrylate, N,N-dibenzylaminoethyl methacrylate, 3-dimethylaminopropionitrile, tris(2-cyanoethyl)amine, N,N-dimethylallylamine, N,N-diethylallylamine, and triallylamine.

[0069] Specific examples of the above organometallic compounds include 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 organometallic compounds containing tin (Sn) include dibutyl-tin-diacetate, dibutyl-tin-dimareate, dioctyl-tin-dimareate, dioctyl-tin-dilaureate, dibutyl-tin-dilaureate, dioctyl-tin-dibersate, dioctyl-tin-S,S'-bis-isooctyl mercaptoacetate, and tetramethyl-1,3-diacetoxydistanoxane. Specific examples of organometallic compounds containing vanadium (V) include acetylacetate. Examples include vanadium tetraphosphate, divanadium tetroxide, vanadylacetylacetonate, vanadium stearate oxide, vanadyl oxalate, vanadyl sulfate, oxobis(1-phenyl-1,3-butanedione)vanadium, bis(maltrate)oxovanadium, vanadium pentoxide, and sodium metavanadate. Specific examples of organometallic compounds containing copper (Cu) include copper acetylacetone, copper naphthenate, copper octoate, copper stearate, and copper acetate.

[0070] Among these, trivalent or tetravalent vanadium compounds and divalent copper compounds are preferred, with trivalent or tetravalent vanadium compounds having higher polymerization promoting ability being more preferred, and most preferably tetravalent vanadium compounds. Multiple types of these fourth-period transition metal compounds may be used in combination as needed. The amount of transition metal compound to be blended is preferably 0.0001 to 1 part by mass per 100 parts by mass of the total amount of polymerizable monomers (A). If it is less than 0.0001 parts by mass, the polymerization promoting effect may be insufficient, and if it exceeds 1 part by mass, it may cause discoloration or gelation of the dental photocurable composition, reducing storage stability.

[0071] Any known thiourea derivative can be used without restriction. Specific examples include dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl)thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, N-benzylthiourea, 1,3-dicyclohexylthiourea, N,N'-diphenylthiourea, 1,3-di(p-tolyl)thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea, and dicyclohexylthiourea. Among these, (2-pyridyl)thiourea, N-acetylthiourea, and N-benzoylthiourea are preferred. Multiple types of these thiourea derivatives may be used in combination as needed. The amount of thiourea derivative added is preferably 0.1 to 5 parts by mass per 100 parts by mass of the total amount of polymerizable monomers (A). If it is less than 0.1 parts by mass, the polymerization promoting ability may be insufficient, and if it exceeds 5 parts by mass, the storage stability may decrease.

[0072] Sulfinic acid and its salts include p-toluenesulfinic acid, p-toluenesulfinate sodium, p-toluenesulfinate potassium, p-toluenesulfinate lithium, p-toluenesulfinate calcium, benzenesulfinic acid, benzenesulfinate sodium, benzenesulfinate potassium, benzenesulfinate lithium, benzenesulfinate calcium, 2,4,6-trimethylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinate sodium, 2,4,6-trimethylbenzenesulfinate potassium, 2,4,6-trimethylbenzenesulfinate lithium, 2,4,6-trimethylbenzenesulfinate calcium, 2,4,6-triethylbenzenesulfinic acid, 2, Examples include sodium 4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, etc., with sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate being particularly preferred.

[0073] Specific examples of borate compounds having one aryl group per 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, and trialkyl(p-butylphenyl) Examples include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of trialkyl(m-octyloxyphenyl)boron, trialkyl(m-octyloxyphenyl)boron (where the alkyl group is selected from the group consisting of n-butyl, n-octyl, and n-dodecyl groups).Specific examples of borate compounds having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron, dialkyldi(3,5-bistrifluoromethyl)phenylboron, dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, dialkyldi(p-nitrophenyl)boron, dialkyldi(m-nitrophenyl)boron, dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron, and dialkyldi(p-butyloxyphenyl) Examples include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of boron, dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p-octyloxyphenyl)boron, and dialkyldi(m-octyloxyphenyl)boron (where the alkyl group is selected from the group consisting of n-butyl group, n-octyl group, and n-dodecyl group, etc.).Specific examples of borate compounds having three aryl groups in one molecule include 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( Examples include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of p-butyloxyphenyl)boron, monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(m-octyloxyphenyl)boron, and monoalkyltri(m-octyloxyphenyl)boron (where the alkyl group is selected from an n-butyl group, an n-octyl group, or an n-dodecyl group, etc.).Specific examples of borate compounds having four aryl groups in one molecule include, for example, 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-butyloxyphenyl)boron, tetrakis(m-butyloxyphenyl)boron, tetrakis(p-octyloxyphenyl)boron, and tetrakis(m Examples include (-octyloxyphenyl)boron, (p-fluorophenyl)triphenylboron, (3,5-bistrifluoromethyl)phenyltriphenylboron, (p-nitrophenyl)triphenylboron, (m-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron, and sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of (p-octyloxyphenyl)triphenylboron.

[0074] Among these arylborate compounds, it is more preferable to use borate compounds having three or four aryl groups in one molecule, from the viewpoint of storage stability. Furthermore, these arylborate compounds can be used individually or in combination of two or more types.

[0075] Examples of reducing inorganic compounds containing sulfur include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, and dithionites. Specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

[0076] Examples of nitrogen-containing reducing inorganic compounds include nitrites, specifically sodium nitrite, potassium nitrite, calcium nitrite, and ammonium nitrite.

[0077] Examples of barbituric acid derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 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, 1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, and 5-propylbarbituric acid. Examples of barbituric acid salts include pyrubarbituric 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 salts (alkali metals or alkaline earth metals are preferred). Specific examples of these barbituric acid salts include sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate.

[0078] Specific examples of halogen compounds include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, and dilauryldimethylammonium bromide.

[0079] The dental photocurable composition of the present invention contains (D1) a tertiary amine compound represented by formula (1) as a polymerization accelerator. [Formula (1)] [ka] (In the formula, R1 may be an ether bond, an ester bond, a urethane bond, an unsaturated double bond, an aromatic ring, an organic group that may have a halogen, or H, and may be the same or different from each other. R2 may be an organic group that may have a hydroxyl group, or an aromatic ring that may have a substituent. The compounds represented by formula (1) do not have a primary hydroxyl group at the α-carbon and / or β-carbon of N.)

[0080] Conventional dental photocurable compositions have used tertiary amine compounds having a primary hydroxyl group, such as methyldiethanolamine, triethanolamine, and p-tolyldiethanolamine. Compared to conventionally used amine compounds such as dimethylaminoethyl methacrylate and dimethyl-p-toluidine, amine compounds having a primary hydroxyl group may have less of the unpleasant odor characteristic of amines, making them suitable for dental materials. However, the cured bodies of dental photocurable compositions containing a photopolymerization initiator that combines (B) a photosensitizer, (C) a photoacid generator, and an amine compound having a primary hydroxyl group tended to show significant discoloration over time. This discoloration over time can be predicted by accelerated testing. For example, immersion in water at a high temperature of 50-70°C is used as an accelerated test to predict discoloration after long-term use and is used as an indicator to predict discoloration after long-term use. For these reasons, photopolymerization initiators containing (B) a photosensitizer, (C) a photoacid generator, and an amine compound having a primary hydroxyl group cause discoloration over time after curing of dental photocurable compositions, which is undesirable from an aesthetic standpoint. As a result of their investigation, the inventors found that when an amine compound represented by the structure of formula (1) was used in a photopolymerization accelerator for dental photocurable compositions, the color difference between the cured product immediately after curing and after a long period of time was small, and the degree of discoloration was reduced.

[0081] Discoloration of the cured product of a composition containing (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization initiator consisting of an amine compound having a primary hydroxyl group as a photopolymerization accelerator, tends to be particularly pronounced when the composition contains a compound having two or more primary hydroxyl groups. More specifically, this refers to an amine compound having two or more primary hydroxyl groups at the α-carbon and / or β-carbon, starting from the amine-derived N. Here, the α-carbon and β-carbon refer to the first carbon adjacent to the amine-derived N, and the second carbon next to it, respectively. Discoloration does not occur when the primary hydroxyl group is bonded to a carbon other than the α-carbon and / or β-carbon, starting from N. In this invention, amine-derived N refers to cases where the bond to N is hydrogen or a hydrocarbon group. For example, it is distinguished from amide bonds, urethane bonds, urea bonds, and azo group-derived N.

[0082] Compositions using a photopolymerization initiator containing an amine compound having a primary hydroxyl group tend to show significant discoloration of the cured product during long-term storage, not only when (C) photoacid generators are present, but also when they contain acidic compounds such as polymerizable monomers having acidic groups. Therefore, a similar effect can be expected when using a tertiary amine compound represented by formula (1) (D1) as the photopolymerization initiator in a composition containing acidic compounds. Since discoloration tends to be particularly significant when (C) photoacid generators are present among acidic compounds, combining (C) photoacid generators with a tertiary amine compound represented by formula (1) (D1) is useful.

[0083] (D1) The tertiary amine compounds represented by formula (1) can be those of known origin, such as triisopropanolamine, which is commercially available, or those that are not commercially available, which can be synthesized using known synthetic methods. As an example of the synthesis of tertiary amine compounds represented by formula (1) (D1), aliphatic tertiary amines corresponding to the tertiary amine compounds represented by formula (1) (D1) can be synthesized by reacting them with epoxide in a molar ratio of 3 times the amount of ammonia, or by reacting them with epoxide in a molar ratio of 2 times the amount of a primary aliphatic amine compound. Aromatic tertiary amines corresponding to the tertiary amine compounds represented by formula (1) (D1) (1) can be synthesized by reacting epoxide with primary aromatic amines such as p-methyltoluidine in a molar ratio of 2 times the amount of ammonia.

[0084] Specific examples of epoxides that can be used in the synthesis of tertiary amine compounds represented by formula (1) (D1) include propylene oxide, butadiene monoepoxide, isobutylene oxide, butylene oxide, pentylene oxide, desilene oxide, glycidyl methyl ether, ethyl glycidyl ether, glycidyl trityl ether, benzyl glycidyl ether, glycidyl phenyl ether, allyl glycidyl ether, glycidyl isopropyl ether, butyl glycidyl ether, t-butyl glycidyl ether, glycidyl phenyl ether, epichlorohydrin, 2-(chloromethyl)-1,2-propylene oxide, epibromohydrin, styrene oxide, glycidyl acrylate, and glycidyl methacrylate.

[0085] (D1) Tertiary amine compounds represented by formula (1) are divided into tertiary aliphatic amine compounds represented by formula (1) (D11) and tertiary aromatic amine compounds represented by formula (1) (D12).

[0086] Specific examples of tertiary aliphatic amine compounds represented by formula (1) (D11) include triisopropanolamine, N-methyl-N,N-bis(2-hydroxypropyl)amine, 3,3′-(butaneazandiyl)bis(1-butoxypropan-2-ol), 1,1′-((3-chlorobenzyl)azeandiyl)bis(propan-2-ol), 1,1′-(cyclohexylazeandiyl)bis(propan-2-ol), and N,N-bis(2-hydroxypropyl)ethanolamine. Among these, triisopropanolamine is preferred.

[0087] (D12)Specific examples of tertiary aromatic amine compounds represented by formula (1) include N,N-bis(2-hydroxypropyl)-p-toluidine, N,N-bis(2-hydroxypropyl)aniline, and 2-[(2-hydroxy-2-phenyl-ethyl)-p-tolyl-amino]-1-phenyl-ethanol. Among these, N,N-bis(2-hydroxypropyl)-p-toluidine is particularly preferred.

[0088] These polymerization initiators—(B) photosensitizers, (C) photoacid generators, and (D) photopolymerization accelerators—can be subjected to secondary treatments such as fine grinding, carrier adsorption, or microcapsule encapsulation as needed without any problems. Furthermore, these various types of photopolymerization initiators can be used individually or in combination of two or more, regardless of the polymerization mode or method.

[0089] (D) The photopolymerization accelerator is preferably present in an amount of 0.2 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers (A) contained in the dental photocurable composition. If the amount is less than 0.2 parts by mass, the mechanical strength may be insufficient. If the amount is greater than 10 parts by mass, although sufficient curability is achieved, the ambient light stability is shortened, and discoloration such as browning or yellowing of the cured product may increase, which is undesirable.

[0090] (D1) Among the tertiary amine compounds represented by formula (1), the photopolymerization initiator consisting of the tertiary aliphatic amine compound represented by formula (1) (D11), (B) a photosensitizer, and (C) a photoacid generator is preferred in terms of photochromic stability. It is preferred because, in addition to showing less color change after long-term use after curing compared to commonly used triethanolamine having a primary hydroxyl group, it may also improve ambient light stability and allow for longer operating time. In this case, the tertiary aliphatic amine compound represented by formula (1) (D11) is preferably present in an amount of 0.2 to 10 parts by mass, and more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the total amount of polymerizable monomer (A). If the amount is less than 0.2 parts by mass, the mechanical strength may be insufficient. If the amount is greater than 10 parts by mass, although sufficient curability is achieved, the ambient light stability is shortened, and discoloration such as browning or yellowing of the cured product may increase, which is undesirable.

[0091] Furthermore, compositions containing a tertiary aliphatic amine compound and a tertiary aromatic amine compound represented by formula (1) (D12), among the tertiary amine compounds represented by formula (1), are also preferred as (B) a photosensitizer, (C) a photoacid generator, and (D) a polymerization accelerator. When (B) a photosensitizer, (C) a photoacid generator, and a tertiary aliphatic amine compound are combined with a tertiary aromatic amine compound having a primary hydroxyl group, such as p-tolyldiethanolamine, it is expected that ambient light stability will be improved and the operating margin time will be extended compared to cases where a tertiary aromatic amine compound having a primary hydroxyl group is not included. However, when a tertiary aromatic amine compound having a primary hydroxyl group is used, the discoloration over time after curing is significant, which is aesthetically undesirable. Therefore, using a tertiary aromatic amine compound represented by formula (1) (D12) in combination with a tertiary aliphatic amine compound as a (D) polymerization accelerator is preferred because it is expected that both improved ambient light stability and good color stability, as well as good mechanical strength, can be achieved. In this case, it is preferable that the tertiary aliphatic amine compound to be added at the same time is a tertiary amine compound that does not have a primary hydroxyl group. Preferred compounds that can be used in combination include tertiary aliphatic amine compounds having a dibenzylamino group structure, such as tripenzylamine, and aliphatic tertiary amine compounds having a dialkylamino group, such as dimethylamino methacrylate. It is also acceptable to separately add tertiary aromatic amine compounds such as ethyl dimethylaminobenzoate, which is a dialkylaminobenzoic acid ester compound. On the other hand, when using a tertiary aromatic amine including the tertiary aromatic amine compound represented by formula (1) (D12), it is particularly good against long-term discoloration when not exposed to strong light, but the photochromic stability when exposed to strong light may decrease, so it is preferable to add an ultraviolet absorber. When adding the tertiary aromatic amine compound represented by formula (1) (D12), it is preferable that it be included in an amount of 0.02 to 1 part by mass, and more preferably 0.05 to 0.5 parts by mass, per 100 parts by mass of the total amount of polymerizable monomer (A).If the amount is less than 0.02 parts by mass, sufficient improvement in ambient light stability may not be observed. If the amount is greater than 1 part by mass, a significant decrease in light color stability may occur, or discoloration such as brownish or yellowish discoloration of the cured product may increase, which is undesirable.

[0092] [(E) Fillers] The filler (E) used in the present invention can be any commonly used, known filler without any limitations.

[0093] (E) There are no restrictions on the type of filler, as long as it is a known filler, and fillers can be blended according to their intended use. It is preferable to blend fillers such as inorganic fillers, organic fillers, organic-inorganic composite fillers, or ion-releasing glass. The dental photocurable composition of the present invention may use the exemplified fillers individually or in combination of two or more types.

[0094] While the chemical composition of inorganic fillers is not particularly limited, specific examples include silicon dioxide, alumina, titania, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramics, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. In particular, barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, and fluoroaluminosilicate glass, which are used in dental glass ionomer cement, resin-reinforced glass ionomer cement, and resin cement, can also be suitably used. The fluoroaluminosilicate glass referred to here has a basic framework of silicon oxide and aluminum oxide, and contains alkali metals for non-crosslinking oxygen introduction. Furthermore, it contains alkaline earth metals, including strontium, and fluorine as modifying and coordinating ions. In addition, it is a composition that incorporates elements from the lanthanide series into the framework to impart further X-ray opacity. These lanthanide series elements are also incorporated into the composition as modifying and coordinating ions depending on the composition range.

[0095] The inorganic filler may contain hydrophobic inorganic fine particles. The hydrophobic inorganic fine particles preferably have an average particle size of 0.1 to 50 nm for the primary particles, and the hydrophobicity is preferably achieved by treatment with a silane coupling agent and / or modified silicone oil. In addition to improving flexural strength, the inclusion of these particles can be expected to suppress sedimentation of the inorganic filler and impart rheological properties.

[0096] Specific examples of organic fillers include polymers such as polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, and polycarbonate.

[0097] Examples of organic-inorganic composite fillers include, but are not limited to, those in which the surface of the filler is polymerized and coated with a polymerizable monomer, those in which the filler and polymerizable monomer are mixed and polymerized and then pulverized to an appropriate particle size, those in which the filler is dispersed in a polymerizable monomer beforehand and subjected to emulsion polymerization or suspension polymerization, those in which the filler is dispersed in a polymerizable monomer and solvent beforehand, spray-dried and then polymerized, and those in which the filler is dispersed in a solvent beforehand, spray-dried, impregnated with a polymerizable monomer and then polymerized.

[0098] The ion-releasing glass is characterized by its ability to release at least one of the following ions: fluoride ions, strontium ions, borate ions, and aluminum ions. It is preferable that multiple of these ions are released simultaneously.

[0099] The ion-releasing glass used in this invention is not limited in any way, as long as it contains one or more glass skeleton-forming elements that form a glass skeleton and one or more glass-modifying elements that modify the glass skeleton. These ion-releasing glasses can be used individually or in combination with other ion-releasing glasses. Furthermore, in this invention, glass amphoteric elements that have the role of either a glass skeleton-forming element or a glass-modifying element depending on the glass composition are included in the category of glass skeleton-forming elements. Specific examples of glass skeleton-forming elements contained in ion-releasing glass include silica, aluminum, boron, and phosphorus, and these can be used individually or in combination with other elements. Specific examples of glass-modifying elements include halogen elements such as fluorine, bromine, and iodine, alkali metal elements such as sodium and lithium, and alkaline earth metal elements such as calcium and strontium, and these can be used individually or in combination with other elements. Among these, it is preferable that the glass contains silica, aluminum, and boron as glass framework forming elements, and fluorine, sodium, and strontium as glass modifying elements. Specifically, examples include silica glass containing strontium and sodium, fluoroaluminosilicate glass, fluoroborosilicate glass, and fluoroaluminoborosilicate glass. Furthermore, from the viewpoint of gradually releasing fluoride ions, strontium ions, borate ions, and aluminum ions, fluoroaluminoborosilicate glass containing strontium is more preferable. Specific examples of the glass composition range include SiO2: 15-35% by mass, Al2O3: 15-30% by mass, B2O3: 5-20% by mass, SrO: 20-45% by mass, F: 5-15% by mass, and Na2O: 0-10% by mass. This glass composition can be confirmed using instrumental analysis such as elemental analysis, Raman spectroscopy, and X-ray fluorescence analysis, but there is no problem as long as the measured values ​​match these composition ranges in any of the analytical methods.

[0100] There are no particular restrictions on the manufacturing method of these ion-releasing glasses, and they can be manufactured by methods such as melting or sol-gel processes. Among these, the melting method using a melting furnace is preferred in terms of the ease of designing the glass composition, including the selection of raw materials. The ion-releasing glasses used in the present invention have an amorphous structure, but there is no problem if they contain some crystalline structure, and there is no problem even if they are mixtures of glasses with amorphous structures and glasses with crystalline structures. Whether or not the glass structure is amorphous can be confirmed using analytical instruments such as X-ray diffraction analysis or transmission electron microscopes. Among these, the ion-releasing glasses used in the present invention are preferably amorphous in structure, as they release various ions in equilibrium with the ion concentration in the external environment.

[0101] Furthermore, in order to enhance the ion-releasing properties from ion-releasing glass, it is preferable to functionalize the glass surface by surface treatment to improve the ion-releasing properties. Specific examples of surface treatment materials used include surfactants, fatty acids, organic acids, inorganic acids, monomers, polymers, various coupling materials, silane compounds, metal alkoxide compounds and their partial condensates. Among these surface treatment materials, it is preferable to perform composite surface treatment using acidic polymers and silane compounds.

[0102] This composite surface treatment is a method in which the surface of an ion-releasing glass is coated with a silane compound, and then the surface is treated with an acidic polymer, which will be explained in detail below. A silane compound represented by formula (3) is mixed into an aqueous dispersion containing ion-releasing glass that has been finely ground to a desired average particle size (D50) by grinding or the like, and this is hydrolyzed or partially hydrolyzed in system to obtain a silanol compound, which is then condensed to obtain a polysiloxane, and the surface of the ion-releasing glass is coated with it to obtain a polysiloxane-coated ion-releasing glass.

[0103] [Formula (3)] [ka]

[0104] (In the formula, Z is RO - X is halogen, Y is OH - (R is an organic group with 8 or fewer carbon atoms, n, m, and L are integers from 0 to 4, and n+m+L=4)

[0105] Specific examples of silane compounds represented by formula (3) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraalyloxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, trimethoxychlorosilane, triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane, diethoxydichlorosilane, tetraphenoxysilane, tetrachlorosilane, silicon hydroxide (silicon oxide hydrate), and the like, with tetramethoxysilane and tetraethoxysilane being more preferred.

[0106] Furthermore, it is more preferable that the compound is a low-condensation compound of the silane compound represented by formula (3). For example, a low-condensation silane compound obtained by partially hydrolyzing and condensing tetramethoxysilane and tetraethoxysilane. These compounds can be used alone or in combination. In addition, an organosilane compound can be added as part of the silane compound represented by formula (3) during polysiloxane treatment.

[0107] The polysiloxane-coated ion-sustaining glass obtained in the previous step can be subjected to an acidic polymer treatment, in which an acidic polymer is reacted to produce ion-sustaining glass. The acidic polymer treatment can be carried out using any dry-flow type agitator commonly used in the industry, such as a Hensil mixer, super mixer, or high-speed mixer. The reaction of the acidic polymer with the polysiloxane-coated ion-sustaining glass can be carried out by contacting it with the acidic polymer solution through impregnation or spraying. For example, the polysiloxane-coated ion-sustaining glass can be dry-flowed, and the acidic polymer solution can be dispersed from above while it is flowing, followed by thorough stirring. While there are no particular restrictions on the dispersion method of the acidic polymer solution, a dropping or spraying method that allows for uniform dispersion is more preferable. Furthermore, the reaction is preferably carried out at around room temperature, as higher temperatures accelerate the reaction between the acid-reactive elements and the acidic polymer, resulting in uneven formation of the cement phase.

[0108] It is preferable to remove moisture from the cement reaction phase by performing heat treatment after the reaction. If moisture remains in the cement reaction phase, it will be disadvantageous in terms of strength, but since the filler of the present invention is covered and strengthened by a coupling agent condensate film, the decrease in mechanical strength is suppressed. The heat treatment method after acid polymer treatment is not particularly limited and can be carried out by known general methods. Preferred equipment for heat treatment is a box-type hot air dryer or a rotary heat treatment device that can heat uniformly. The heat treatment temperature is in the range of room temperature to 200°C, more preferably in the range of 40 to 150°C. If the temperature is lower than this range, the removal of the aqueous medium will be insufficient, and if it is higher than this range, the organic layer of the acid polymer may decompose or discolor. The heat treatment time depends on the capacity of the dryer, etc., so there is no problem as long as it is long enough to sufficiently remove the aqueous medium. After heat treatment, the heat-treated material can be easily crushed by applying shear force or impact force, and the crushing method can be carried out using the equipment used in the above reaction.

[0109] The solvent used to prepare the acidic polymer solution for the reaction can be any solvent that dissolves the acidic polymer, such as water, ethanol, acetone, etc. Of these, water is particularly preferred, as it allows the acidic groups of the acidic polymer to dissociate and react uniformly with the surface of the basic filler core.

[0110] The weight-average molecular weight of the polymer dissolved in the acidic polymer solution is in the range of 2,000 to 50,000, preferably in the range of 5,000 to 40,000. When treated with an acidic polymer having a weight-average molecular weight of less than 2,000, the acidic polymer reaction phase does not form in the polysiloxane-coated ion-sustaining glass, resulting in a tendency for low ion-sustaining performance. On the other hand, when treated with an acidic polymer having a weight-average molecular weight exceeding 50,000, the viscosity of the acidic polymer solution increases, making it difficult to treat the polysiloxane-coated ion-sustaining glass homogeneously. Furthermore, the concentration of the acidic polymer in the acidic polymer solution is preferably in the range of 3 to 25 parts by mass, more preferably in the range of 8 to 20 parts by mass. If the acidic polymer concentration is less than 3 parts by mass, the acidic polymer reaction phase described above becomes fragile, and the effect of improving ion-sustaining performance cannot be obtained. Furthermore, if the acidic polymer concentration exceeds 25 parts by mass, it becomes difficult to diffuse uniformly through the polysiloxane layer (porous), resulting in a non-homogeneous acidic polymer reaction phase. Additionally, the reaction occurs immediately upon contact with the polysiloxane-coated ion-releasing glass, leading to problems such as the formation of strongly reacted aggregates. The amount of acidic polymer solution added to the polysiloxane-coated ion-releasing glass is preferably in the range of 6 to 40 parts by mass, and more preferably 10 to 30 parts by mass. Based on this addition amount, the optimal amount of acidic polymer relative to the polysiloxane-coated ion-releasing glass is 1 to 7 parts by mass, and the optimal amount of water is in the range of 10 to 25 parts by mass.

[0111] The acidic polymer that can be used to form an acidic polymer reaction phase on the surface of polysiloxane-coated ion-releasing glass by the above method can be any copolymer or homopolymer of polymerizable monomers having acidic groups such as phosphate residues, pyrophosphate residues, thiophosphate residues, carboxylic acid residues, or sulfonic acid groups, without any problems. Specific examples of these polymerizable monomers include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic anhydride, 5-(meth)acryloylaminopentylcarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen Examples include phosphate, 20-(meth)acryloyloxyeicosyldihydrogenphosphate, 1,3-di(meth)acryloyloxypropyl-2-dihydrogenphosphate, 2-(meth)acryloyloxyethylphenyl phosphate, 2-(meth)acryloyloxyethyl-2'-bromoethyl phosphate, (meth)acryloyloxyethylphenyl phosphonate, di(2-(meth)acryloyloxyethyl) pyrophosphate, 2-(meth)acryloyloxyethyl dihydrogen dithiophosphophosphate, 10-(meth)acryloyloxydecyldihydrogenthiophosphate, etc. Among polymers (co)polymerized using these polymerizable monomers, it is preferable to use homopolymers or copolymers of α-β unsaturated carboxylic acids that undergo relatively slow acid-base reactions with acid-reactive elements contained in polysiloxane-coated ion-sustaining glass. Specifically, examples include acrylic acid polymers, acrylic acid-maleic acid copolymers, and acrylic acid-itaconic acid copolymers.

[0112] The above-mentioned (E) filler can be treated with a surface treatment material, such as a silane coupling material, for the purpose of improving its affinity with polymerizable monomers, dispersibility in polymerizable monomers, mechanical strength of the cured product, and water resistance. Such surface treatment materials and surface treatment methods are not particularly limited, and known methods can be used without limitation, such as a method of spraying the surface treatment material while stirring the powdered filler, a method of dispersing and mixing the filler and surface treatment material in a solvent, or a method of supplying a silane coupling material in vapor or gaseous form to the surface of the filler. Preferred silane coupling materials used for surface treatment of fillers include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, or hexamethyldisilazane. In addition to silane coupling materials, the surface treatment of fillers can also be performed using titanate-based coupling materials or aluminate-based coupling materials. The amount of surface treatment material applied to the filler is preferably 0.01 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the filler before treatment.

[0113] (E) The shape of the filler is not particularly limited, and fillers of any shape such as spherical, needle-shaped, plate-shaped, crushed, or flaky can be used. The average particle size of the filler is preferably in the range of 0.01 μm to 50 μm, more preferably 0.01 μm to 30 μm, even more preferably 0.05 μm to 20 μm, and more preferably 0.05 μm to 10 μm.

[0114] If the dental photocurable composition of the present invention contains (E) a filler, it is preferable that the amount of filler is 500 parts by mass or less per 100 parts by mass of (A) polymerizable monomer. When a filler is included, an improvement in physical strength can be expected, but if the amount of filler exceeds 500 parts by mass, the operability of the dental photocurable composition may decrease.

[0115] <Other ingredients> Furthermore, the dental photocurable composition of the present invention may contain components other than those listed in (A) to (E) above, as long as they do not hinder the effects of the present invention. For example, components such as excipients represented by fumed silica, benzophenone-based and benzotriazole-based ultraviolet absorbers, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and 2,5-diter-butyl-4-methylphenol, mercaptan compounds such as α-alkylstyrene compounds, n-butyl mercaptan, and n-octyl mercaptan, chain transfer agents such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, and α-pinene, metal adjuvants such as aminocarboxylic acid-based chelating agents and phosphonic acid-based chelating agents, anti-discoloration agents, antibacterial agents, coloring pigments, water and solvents that can be miscible with water in any ratio, and other conventionally known additives can be added as needed.

[0116] The method for producing the dental photocurable composition of the present invention is not particularly limited. A common method for producing the dental photocurable composition is to first prepare a matrix by mixing (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a polymerization accelerator, then knead this matrix with (E) a filler, remove air bubbles under reduced pressure, and prepare a uniform paste. The present invention can also be produced without any problems using the above production method.

[0117] The photocurable dental composition of the present invention can be used as a dental adhesive, dental composite resin, dental core buildup material, dental resin cement, dental coating material, dental pit and fissure sealing material, dental manicure material, dental tooth fixing adhesive, dental hard resin, dental cutting material, and dental 3D printer material.

[0118] The photocurable dental composition of the present invention is preferably used in dental adhesives, dental composite resins, dental core buildup materials, dental resin cements, dental coating materials, dental pit and fissure sealing materials, dental manicure materials, dental tooth fixation adhesives, dental cutting materials, and dental 3D printer materials, and is particularly preferably used in dental adhesives, dental composite resins, dental core buildup materials, dental resin cements, dental coating materials, dental pit and fissure sealing materials, dental manicure materials, and dental tooth fixation materials.

[0119] The dental photocurable composition of the present invention may contain only (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, (D) a photopolymerization accelerator, and (E) a filler. Alternatively, it may contain only one or more of the above-mentioned components as components other than (A) to (E). [Examples]

[0120] The following describes specific embodiments of the present invention, but the present invention is not limited to these embodiments.

[0121] The materials used in the examples and comparative examples, along with their abbreviations, are shown below. [(A) Polymerizable monomers] • Bis-GMA: 2,2-Bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane D2.6E: 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, which has an average number of moles of ethoxy groups added of 2.6. UDMA: N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)ethanol]methacrylate NPG: Neopentyl glycol dimethacrylate TEGDMA: Triethylene glycol dimethacrylate MDP: 10-Methacryloyloxydecyldihydrogen phosphate ·MHPA:6-Methacryloxyhexylphosphonoacetate • MET:4-methacryloxyethyl trimellitic acid

[0122] [(B) Photosensitizer] • CQ: Camphorquinone BAPO: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[0123] [(C) Photoacid Generator] <A salt of an aryliodnium cation with an organic group in which at least one H is substituted with F and an anion having one or more atoms from among P, B, Al, S, and Ga> • C1: Bis(4-tert-butylphenyl)iodonium nonafluorobutanesulfonate [ka] • C2: Bis(4-tert-butylphenyl)iodonium tris(pentafluoropropyl)trifluorophosphate [ka] • C3: p-Cumenyl(p-tolyl)iodonium tris(pentafluoroethyl)trifluorophosphate [ka] • C4: Bis(4-n-dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate [ka] C5: Bis[4-(tert-butyl)phenyl]iodonium tetra(nonafluoro-tert-butoxy)aluminate [ka] • C6: Bis[4-(tert-butyl)phenyl]iodonium tetra(pentafluorophenyl) gallate [ka] <A salt of an anion having an organic group and one or more atoms from P, B, Al, S, or Ga, and an aryliodonium cation> C11: Bis(4-tert-butylphenyl)iodonium-p-toluenesulfonate [ka] <A photoacid generator that is not a salt of an anion having an organic group and one or more atoms from P, B, Al, S, or Ga, and an aryliodonium cation.> C21: Bis(4-tert-butylphenyl)iodonium hexafluorophosphate [ka] C22:2,4,6,-Tris(trichloromethyl)-1,3,5-triazine [ka] C23: Diphenyliodonium-2-carboxylate monohydrate [ka]

[0124] [(D) Polymerization accelerator] [(D1) Tertiary amine represented by formula (1)] [(D11) Tertiary aliphatic amine represented by formula (1)] · D11-1: Triisopropanolamine [ka] ·D11-2: N-methyl-N,N-bis(2-hydroxypropyl)amine [ka] ·D11-3:3,3′-(butaneazandiyl)bis(1-butoxypropane-2-ol) [ka] ·D11-4:1,1′-((3-chlorobenzyl)azandiyl)bis(propan-2-ol) [ka] ·D11-5:1,1′-(cyclohexylazanediyl)bis(propan-2-ol) [ka] [(D12) Tertiary aromatic amine represented by formula (1)] ·D12-1:N,N-bis(2-hydroxypropyl)-p-toluidine [ka] · D12-2: N,N-bis(2-hydroxypropyl)aniline [ka] <Other aliphatic tertiary amines> <<Aliphatic tertiary amine compounds lacking a primary hydroxyl group>> • DMAEMA: N,N-dimethylaminoethyl methacrylate • DIAEMA: N,N-diisopropylaminoethyl methacrylate TBA: Tribenzylamine • DBMA: Dibenzylmethylamine <<Aliphatic tertiary amine compound having two primary hydroxyl groups>> • MDEOA: Methyldiethanolamine DEIPA: N,N-bis(2-hydroxyethyl)isopropanolamine <<Aromatic tertiary amine compounds having two primary hydroxyl groups>> • DEPT: N,N-dihydroxyethyl-p-toluidine <<Aliphatic tertiary amine compound having three primary hydroxyl groups>> TEA: Triethanolamine <Aromatic tertiary amine compounds> • DMBE: Ethyl N,N-dimethylaminobenzoate

[0125] [(E) Fillers] The manufacturing methods for each filler used in the preparation of the dental photocurable composition are shown below.

[0126] (Filler E1) To 100.0 g of fluoroaluminosilicate glass (average particle size 1.1 μm), 50.0 g of water, 35.0 g of ethanol, and 3.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours to obtain a silane coupling solution, which was then stirred and mixed for 30 minutes. Subsequently, the mixture was heat-treated at 100°C for 15 hours to obtain packing material E1.

[0127] (Filler E2) To 100.0 g of zirconium silicate filler (average particle size 0.8 μm: 85 wt% zirconia, 15 wt% silica), 50.0 g of water, 35.0 g of ethanol, and 5.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours to obtain a silane coupling solution, which was then stirred and mixed for 30 minutes. Subsequently, the mixture was heat-treated at 100°C for 15 hours to obtain filler E2.

[0128] (Filler E3) After mixing various raw materials including silicon dioxide, aluminum oxide, boron oxide, sodium fluoride, and strontium carbonate, the mixture was melted at 1400°C to obtain glass A (glass composition: SiO2: 22.5 mass%, Al2O3: 20.0 mass%, B2O3: 12.3 mass%, SrO: 35.7 mass%, Na2O: 2.5 mass%, F: 7.0 mass%). Next, the obtained glass A was pulverized using a vibratory mill for 100 hours, and then further pulverized using a wet bead mill for 3 hours. To 100 g of the obtained pulverized material, 4.5 g of the low condensate of silane compounds "MKC Silicate MS56S" (SiO2 content 56.0 mass%, degree of polymerization 2-100, manufactured by Mitsubishi Chemical Corporation) was added and stirred and mixed for about 90 minutes. After mixing for a predetermined time, the resulting processed slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and left to stand for 6 hours, and then cooled to obtain a heat-treated product. The obtained heat-treated product was placed in a Henschel mixer and crushed at 1800 rpm for 5 minutes. After crushing, a polysiloxane-treated product with good fluidity was obtained. (Acid polymer treatment) 100 g of polysiloxane-treated material was placed in a Henschel mixer and, while stirring, 16.0 g of polyacrylic acid aqueous solution (polymer concentration 13% by mass, weight-average molecular weight 20,000: manufactured by Nakalai) was sprayed from above. After spraying, the powder was removed from the mixer and heated in a hot air dryer at 100°C for 3 hours to obtain a polysiloxane-polyacrylic acid treated product. (Silane treatment) To 100 g of polysiloxane-polyacrylic acid treated material, 100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 8-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours to obtain a silane coupling solution, which was then stirred and mixed for 30 minutes. Subsequently, the mixture was heat-treated at 100°C for 15 hours to obtain filler E3.

[0129] (Filler E4) To 100 g of the above polysiloxane-treated material, 100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 8-methacryloyloxyoctyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours to obtain a silane coupling solution, which was then stirred and mixed for 30 minutes. Subsequently, the mixture was heat-treated at 100°C for 15 hours to obtain packing material E4.

[0130] (Filler E5) Aerosil R-711

[0131] [UV absorber] BT:2-(2-hydroxy-5-methylphenyl)benzotriazole [Polymerization inhibitor] • MeHQ: p-methoxyphenol [Fluorescent dye] • FA: 2.5-Diethyl dihydroxyterephthalate

[0132] <Production method of dental photocurable composition> All components except for filler (E) shown in Table 1 were placed in a wide-mouthed poly container and mixed using a VMRC-5 mix rotor at 100 rpm for 48 hours to obtain the matrix. The matrix and filler (E) were then placed in a rotary-type kneader, uniformly stirred, and degassed under vacuum to obtain a paste. This paste was then filled into a 2 mL PP syringe to prepare a dental photocurable composition. In Table 1, the mass of each component is indicated in parentheses after its abbreviation.

[0133] [Table 1]

[0134] [Table 2]

[0135] (1) Bending strength After filling a stainless steel mold with the prepared dental photocurable composition, cover glass was placed on both sides, and the mold was pressed with a glass mixing plate. Then, the composition was cured by irradiating it with light at five locations for 10 seconds each using a light curing lamp (Penbright: manufactured by Shofu). After curing, the cured material was removed from the mold, and the back side was irradiated with light again in the same manner to obtain a test specimen (25 × 2 × 2 mm: rectangular parallelepiped). The test specimen was immersed in water at 37°C for 24 hours, and then a bending test was performed. The bending test was performed using an Instron universal testing machine (manufactured by Instron) with a support distance of 20 mm and a crosshead speed of 1 mm / min. The bending strength of the dental photocurable composition was judged as good if it was 100 MPa or more, suitable if it was between 90 and 100 MPa, slightly low if it was between 80 and 90 MPa, and insufficient if it was below 80 MPa.

[0136] (2) Environmental light stability Using an illuminometer, the height of the dental lamp (Luna-Vue S, manufactured by Morita Seisakusho) was adjusted so that the sample placement area received light with an illuminance of 8000 ± 1000 lx. A glass slide (26 × 16 mm, 2 mm thick) was placed on a glass mixing plate covered with matte black paper, and approximately 30 mg of the sample was placed on top of it. After exposing the sample to light in the sample placement area, the sample was removed from the sample placement area, and another glass slide was immediately pressed onto the sample to create a thin layer. If the state of the sample at this time was not physically uniform, it was determined that hardening had begun, and the time until hardening was evaluated in 5-second increments. A longer time is preferable because it allows more time to remove the composition from the light-shielding container and apply it. Ambient light stability was judged as follows: 150 seconds or more was particularly good, 100 seconds to less than 150 seconds was good, 80 seconds to less than 100 seconds was suitable, 60 seconds to less than 80 seconds was somewhat poor, and less than 60 seconds was insufficient.

[0137] (3) Thermochromic stability The prepared dental photocurable composition was filled into a stainless steel mold (15φ × 1 mm: disc-shaped), and a cover glass was placed on top and pressed down with a glass plate. Light curing was performed for 1 minute using a light curing incubator (Griplight II: manufactured by Shofu) over the cover glass to cure it. After removing the cured material from the mold, the cover glass was removed and the color tone of the test specimen was measured. The color measurement was performed by placing the test specimen on a standard white plate (D65 / 10° X=81.07, Y=86.15, Z=93.38) background and using a spectrocolorimeter (manufactured by Vic Chemie) under predetermined conditions (light source: C, field of view: 2°, measurement area: 11 mm). After that, the test specimen was immersed in a container of 10 mL of water in a constant temperature oven set to 70°C and left to stand for one week. The color tone of the test specimen was measured again, and the difference in color change was expressed as ΔE calculated from the following formula. ΔE = {(ΔL*)} 2 +(Δa*) 2 +(Δb*) 2} 1 / 2 ΔL* = L1* - L2* Δa* = a1* - a2* Δb* = b1* - b2* Here, L1* is the lightness index before immersion and standing, L2* is the lightness index after immersion and standing, a1* and b1* are the color quality indices before immersion and standing, and a2* and b2* are the color quality indices after immersion and standing. A ΔE of less than 5 is considered good (A), a ΔE of 5 to less than 8 is considered suitable (B), a ΔE of 8 to less than 10 is considered somewhat poor (C), and a ΔE of 10 or more is considered insufficient (D). Thermal color stability is performed to predict the change in color tone when the cured material is used for a long period of time, and the smaller the ΔE, the smaller the change in color when the cured material is used for a long period of time.

[0138] (4) Light color stability The prepared dental photocurable composition was filled into a stainless steel mold (15φ × 1 mm: disc-shaped), and a cover glass was placed on top and pressed down with a glass plate. Light curing was performed for 1 minute using a light curing incubator (Griplight II: manufactured by Shofu) from above the cover glass to cure it. After removing the cured material from the mold, the cover glass was removed and the color tone of the test specimen was measured. The color measurement was performed by placing the test specimen on a standard white plate (D65 / 10° X=81.07, Y=86.15, Z=93.38) background and using a spectrocolorimeter (manufactured by Vic Chemie) under predetermined conditions (light source: C, field of view: 2°, measurement area: 11 mm). After that, the test specimen was exposed to light for 24 hours using a xenon lamp light exposure tester (Suntest CPS+), and the color tone of the test specimen was measured again, and the difference in color change was expressed as ΔE calculated from the following formula. ΔE = {(ΔL*)} 2 +(Δa*) 2 +(Δb*) 2} 1 / 2 ΔL* = L1* - L2* Δa* = a1* - a2* Δb* = b1* - b2* Here, L1* is the lightness index before light exposure, L2* is the lightness index after light exposure, a1* and b1* are the color quality indices before light exposure, and a2* and b2* are the color quality indices after light exposure. A ΔE of less than 5 is considered good (A), a ΔE of 5 to less than 8 is considered suitable (B), a ΔE of 8 to less than 10 is considered suitable (C), and a ΔE of 10 or more is considered insufficient. Photochromic stability is performed to predict the change in color tone when the cured material is used for a long period of time in an area that is exposed to light. The smaller the ΔE, the less the color change even when the cured material is exposed to light for a long period of time.

[0139] The results in Table 2 are discussed below.

[0140] The compositions described in the examples were confirmed to have sufficient flexural strength and color stability.

[0141] Examples 2, 4, and 9, which contained low amounts of the photosensitizer camphorquinone, 4, and 9 respectively, tended to have slightly lower flexural strength. Examples 4, 3, and 2, which contained high amounts of the photosensitizer and relatively high amounts of the photoacid generator respectively, tended to have lower photochromic stability. Example 10, which contained a high amount of the tertiary amine compound represented by formula (1) (D1), tended to have lower thermal color stability.

[0142] Example 33, which included BAPO as a photosensitizer, showed good bending strength, but had low ambient light stability and tended to have reduced color stability.

[0143] Among the examples that did not include a photoacid generator consisting of an organic group with at least one H substituted with F and an anion having one or more atoms from P, B, Al, S, or Ga, and an aryliodonium cation, Example 5, which included a C11 photoacid generator that was a salt of an organic group with one or more atoms from P, B, Al, S, or Ga, and an aryliodonium cation, showed slightly reduced photochromic stability, and Examples 6-8, which included other photoacid generators, tended to have even lower photochromic stability.

[0144] Examples 18-24, which contained the tertiary aromatic amine compound represented by formula (1) (D12), showed particularly good ambient light stability. Examples 26-30, which contained DMBE, another tertiary aromatic amine compound, tended to show decreased ambient light stability. Aromatic amine compounds having a dialkylamino group and an electron-withdrawing group at the p-position, such as DMBE, can be expected to exhibit good curability when used in combination with camphorquinone, but this may result in decreased ambient light stability and decreased color stability. Among Examples 26-30, Examples 27 and 30, which contained the tertiary aromatic amine compound represented by formula (1) (D12), tended to show slightly improved ambient light stability. In addition, Examples 26 and 27, which contained an ultraviolet absorber, also tended to show improved color stability despite containing aromatic amine compounds.

[0145] Example 31 tended to have slightly lower bending strength because it did not contain any filler. Although Example 32 had no problems with its physical properties, its workability was somewhat poor due to the large amount of filler it contained.

[0146] Comparative Examples 1 and 2, which did not contain photosensitizers or photoacid generators, tended to have low flexural strength. Comparative Examples 4 to 7, which contained amine compounds having two or more primary hydroxyl groups, tended to have low thermal color stability. Comparative Example 8 had sufficient flexural strength, but its ambient light stability was insufficient due to the relatively large amount of DMBE it contained. [Industrial applicability]

[0147] According to the present invention, it is possible to provide a dental photocurable composition that can achieve both sufficient mechanical strength and color stability after curing.

Claims

1. (A) A polymerizable monomer, (B) A photosensitizer, (C) A photoacid generator, and (D) A polymerization accelerator comprising (D1) a tertiary amine compound represented by formula (1), A dental photocurable composition in which the tertiary amine compound represented by formula (1) (D1) is the tertiary aliphatic amine compound represented by formula (1) (D11). [Formula (1)] 【Chemistry 1】 (In the formula, R １ R is an ether bond, ester bond, urethane bond, unsaturated double bond, aromatic ring, halogen, or H, and may be the same or different from each other. ２ This is an organic group that may have a hydroxyl group. The compound represented by formula (1) does not have a primary hydroxyl group at the α-carbon and / or β-carbon of N.

2. (C) Contains an aryliodonium salt as a photoacid generator, The dental photocurable composition according to claim 1, wherein the aryliodonium salt is a salt of an aryliodonium cation with an anion having an organic group and one or more atoms selected from P, B, Al, S, and Ga.

3. (C) Contains an aryliodonium salt as a photoacid generator, The dental photocurable composition according to claim 1, wherein the aryliodonium salt is a salt of an aryliodonium cation with an anion having an organic group in which at least one or more H atoms are substituted with F and one or more atoms from among P, B, Al, S, and Ga.

4. A dental photocurable composition according to any one of claims 1 to 3, comprising a tertiary aliphatic amine compound.

5. (A) Per 100 parts by mass of polymerizable monomer, (B) Containing 0.02 to 1 part by mass of a photosensitizer, (C) Containing 0.02 to 10 parts by mass of a photoacid generator, (D11) Contains 0.2 to 10 parts by mass of a tertiary aliphatic amine compound represented by formula (1), The dental photocurable composition according to claim 1.

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