Photocurable composition excellent in hardening depth

Abstract

To provide a photocurable composition excellent in curing depth.SOLUTION: There is provided a photocurable composition which comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator and (D) a photopolymerization accelerator and comprises an amine compound as (D) the photopolymerization accelerator, wherein the amine compound preferably is an aminoacid (ester) protected with two or more benzyl groups such as dibenzylaminoalkyl(meth)acrylate such as dibenzylaminoethyl(meth)acrylate and dibenzylaminopropyl(meth)acrylate, dibenzylaminoalkyl(meth)acrylamide, dibenzylaminoethanol, dibenzylaminopropanol and N,N-dibenzylglycine ethyl and a tribenzylamine.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photocurable composition.

Background Art

[0002] The present invention relates to a dental material, a printing plate-making material, and a photoresist material containing an initiator system for curing a polymerizable monomer. In particular, specifically, it relates to a photocurable composition suitable for dental materials.

[0003] In the dental field, dental photocurable compositions are used and applied to dental adhesives, dental composite resins, dental abutment construction materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicure materials, dental loose tooth fixing adhesives, dental glass ionomer cements, dental 3D printer materials, and the like.

[0004] In Patent Documents 1 and 2, a photopolymerization initiator comprising a photoacid generator (a triazine compound or a specific aryliodonium salt), a sensitizer, and an electron donor compound has been proposed, and in Patent Document 3, a dental curable composition containing a photoinitiator system containing a color-stable amine electron donor has been proposed.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, conventional photocurable compositions, particularly dental photocurable compositions, have problems in terms of the curing depth for curing to a deep part.

[0007] An object of the present invention is to provide a photocurable composition having a high curing depth.

Means for Solving the Problems

[0008] The photocurable composition of the present invention is a photocurable composition containing (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, and is a photocurable composition containing (D-1) an amine compound represented by the formula (1) as the (D) photopolymerization accelerator. [Formula (1)]

Chemical formula

Chemical formula

[0009] The photocurable composition of the present invention has a high curing depth. [Embodiments for Carrying Out the Invention]

[0010] In the present invention, the amine compound represented by the formula (1) in (D-1) can be an aliphatic tertiary amine.

[0011] In the present invention, it can include an amine compound represented by the formula (1) in (D-1) wherein R2 in the formula (1) is a substituent represented by the formula (2).

[0012] In the present invention, the amine compound represented by the formula (1) in (D-1) can be such that R2 in the formula (1) is a substituent represented by the formula (2) and is an aliphatic tertiary amine.

[0013] In the present invention, it includes an aryl iodonium salt as the (C) photoacid generator, and the aryl iodonium salt can be a salt of an aryl iodonium cation and an anion having an organic group and one or more atoms selected from P, B, Al, S, and Ga.

[0014] In the present invention, it includes an aryl iodonium salt as the (C) photoacid generator, and the aryl iodonium salt can be a salt of an aryl iodonium cation and an anion having an organic group in which at least one or more H are substituted by F and one or more atoms selected from P, B, Al, S, and Ga.

[0015] In the present invention, the (B) photosensitizer can be used for dental applications including the (B-1) α-diketone compound.

[0016] In the present invention, it can be a one-component type or a two-component type for dental use.

[0017] In the present invention, there is a photocurable composition of one dosage form, which contains (B) a photosensitizer in an amount of 0.001 to 1 part by mass, (C) a photoacid generator in an amount of 0.01 to 10 parts by mass, and (D-1) an amine compound represented by the formula (1) in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

[0018] In the present invention, there is a photocurable composition of two dosage forms, which consists of a first paste and a second paste. The specific gravity of the first paste and the second paste is 1:0.8 to 1.2. With respect to a total of 200 parts by mass of the (A) polymerizable monomer contained in the first paste and the second paste, (B) a photosensitizer is contained in an amount of 0.002 to 2 parts by mass, (C) a photoacid generator is contained in an amount of 0.02 to 20 parts by mass, and (D-1) an amine compound represented by the formula (1) can be contained in an amount of 0.02 to 40 parts by mass.

[0019] Hereinafter, each component of the photocurable composition of the present invention will be described in detail. The photocurable composition of the present invention can be used as a dental material, a printing plate-making material, a photoresist material, and is particularly applied as a dental adhesive, a dental primer, a dental composite resin, a dental abutment construction material, a dental resin cement, a dental coating material, a dental pit and fissure sealant, a dental manicure material, a dental room-temperature polymerizable resin, a dental loose tooth fixing adhesive, a dental glass ionomer cement, a dental hard resin, a dental cutting material, a material for a dental 3D printer, etc.

[0020] In dental clinics, for the aesthetic and functional restoration of tooth defects caused by dental caries, fractures, etc., treatments such as direct restoration with dental composite resin or indirect restoration of prosthetic devices made of ceramics or dental hard resin using dental resin cement are performed. In addition, dental adhesives for bonding dental composite resin to various dental materials and natural teeth, dental loose tooth fixing adhesives for fixing loose teeth, dental coating materials for protecting sensitive or formed vital teeth from external stimuli and secondary dental caries, dental pit and fissure sealants for preventing dental caries by filling complex grooves such as primary teeth, dental manicure materials for temporarily restoring aesthetics by masking tooth discoloration, and dental abutment building materials for forming abutment teeth when the crown part collapses due to dental caries are used. In recent years, composite materials such as dental cutting materials for making prosthetic devices by CAD / CAM processing and dental 3D printer materials for making prosthetic devices by 3D printers have been developed, and various dental materials are used in treatments. The above materials are prepared in a uniform paste form by mixing a resin matrix composed of several kinds of polymerizable monomers, various fillers such as inorganic fillers and organic-inorganic composite fillers, and a polymerization initiator according to their uses. Taking some materials as examples, dental filling composite resin is filled into teeth in the state of uncured paste, and after imparting the anatomical form of natural teeth with dental instruments such as instruments, it is used by irradiating light with a dental light irradiator or the like to cure it. The irradiation light from the light irradiator generally uses a light source with an output of about 100 - 2000 mW / cm 2 in the light intensity range of light with a wavelength of about 360 - 500 nm. On the other hand, dental resin cement is used when bonding a prosthetic device to a cavity or an abutment tooth, and is cured by irradiating light after mounting the prosthetic device on the cavity or the abutment tooth.

[0021] As the photoinitiators used in such dental materials, systems combining photosensitizers and appropriate photo-polymerization accelerators for photosensitizers are widely used. As photosensitizers, acylphosphine oxide compounds and α-diketone compounds are known, and in particular, α-diketone compounds have the ability to initiate polymerization in the visible light wavelength range with less impact on the human body.

[0022] In addition, as a polymerization accelerator combined with a photosensitizer, tertiary amine compounds are well known. Since the combination of an α-diketone compound and a tertiary amine compound has high polymerization activity with respect to irradiated light, it is used in the field of dental materials. The dental photocurable composition containing the photoinitiator exhibits excellent mechanical properties such as hardness, flexural strength, and compressive strength required for various materials.

[0023] However, the photoinitiators conventionally used have room for improvement in terms of curing depth. The curing depth is an index for evaluating the ability to cure to a deep part. Curing to a deep part has various advantages such as not requiring laminating and curing a photocurable composition and being able to shorten the light irradiation time.

[0024] In order to solve the above problems, the photocurable composition of the present invention has found that excellent curing depth is exhibited when an amine compound having a specific structure is used, and thus the present invention has been completed.

[0025] In addition, since it exhibits excellent curing depth, it can be used for photocurable compositions such as dental materials, printing plate-making materials, and photoresist materials, and is particularly preferably used for dental materials. Specifically, when used for dental adhesives, dental composite resins, dental abutment construction materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicure materials, dental loose tooth fixing adhesives, dental cutting materials, and dental 3D printer materials, a dental photocurable composition having excellent curing depth can be provided.

[0026] [(A) Polymerizable monomer] The (A) polymerizable monomer of the present invention can be used without limitation as long as it is a known one. In the polymerizable monomer or the compound having a polymerizable group described in the present invention, the polymerizable group preferably exhibits radical polymerizability. Specifically, from the viewpoint of easy radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. In the present specification, "(meth)acrylic" 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. A polymerizable monomer having a substituent at the α-position of the acrylic group and / or acrylamide group can also be preferably used. There are those having one radical polymerizable group, those having two radical polymerizable groups, those having three or more radical polymerizable groups, those having an acidic group, an alkoxysilyl group, those having a sulfur atom, and the like.

[0027] Specific examples of the polymerizable monomer having one radical polymerizable group and no acidic group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, propylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, erythritol mono(meth)acrylate, N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N,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, and the like.

[0028] Specific examples of the polymerizable monomer having two radically polymerizable groups and no acidic group include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxydiethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyditrioethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytrioethoxyphenyl)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 thereof include 4-trimethylhexamethylene bis(2-carbamoyloxyethyl) dimethacrylate (commonly known as "UDMA"), 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy) ethane, etc.

[0029] Specific examples of the polymerizable monomer having three or more radical polymerizable groups and no acidic group 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, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, etc.

[0030] The polymerizable monomer having an acidic group can be used without limitation as long as it has at least one radical polymerizable group and at least one acidic group such as a phosphoric acid group, pyrophosphoric acid group, thiophosphoric acid group, phosphonic acid group, sulfonic acid group, carboxylic acid group, etc.

[0031] Specific examples of the polymerizable monomer 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, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate, bis[2-(meth)acryloyloxyethyl] 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(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl] hydrogen phosphate; acid chlorides, alkali metal salts, ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond, and the like.

[0032] Specific examples of the polymerizable monomer having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate; acid chlorides, alkali metal salts, ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond, and the like.

[0033] Specific examples of the polymerizable monomer having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogen thiophosphate, 3-(meth)acryloyloxypropyl dihydrogen thiophosphate, 4-(meth)acryloyloxybutyl dihydrogen thiophosphate, 5-(meth)acryloyloxypentyl dihydrogen thiophosphate, 6-(meth)acryloyloxyhexyl dihydrogen thiophosphate, 7-(meth)acryloyloxyheptyl dihydrogen thiophosphate, 8-(meth)acryloyloxyoctyl dihydrogen thiophosphate, 9-(meth)acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, 20-(meth)acryloyloxyicosyl dihydrogen thiophosphate; acid chlorides, alkali metal salts, ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond, and the like. The polymerizable monomer having a thiophosphate group is also classified as a polymerizable monomer having a sulfur atom.

[0034] Specific examples of the polymerizable monomer having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phosphonoacetate; acid chlorides, alkali metal salts, ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond, and the like.

[0035] Specific examples of the polymerizable monomer having a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate, and the like.

[0036] The polymerizable monomer having a carboxylic acid group is classified into a (meth)acrylic compound having one carboxyl group in the molecule and a (meth)acrylic compound having a plurality of carboxyl groups in the molecule. Specific examples of the (meth)acrylic compound having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen maleate; acid halides thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond, and the like.Specific examples of the (meth)acrylic compound having a plurality of carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytetradecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate; acid anhydrides and acid halides thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond, etc.

[0037] Specific examples of the polymerizable monomer having an alkoxysilyl group include (meth)acrylic compounds having one alkoxysilyl group in the molecule and (meth)acrylic compounds having a plurality of alkoxysilyl groups in the molecule. Examples include 2-(meth)acryloxyethyl trimethoxysilane, 3-(meth)acryloxypropyl trimethoxysilane, 3-(meth)acryloxypropyl triethoxysilane, 3-(meth)acryloxypropyl methyldimethoxysilane, 4-(meth)acryloxybutyl trimethoxysilane, 5-(meth)acryloxypropyl trimethoxysilane, 6-(meth)acryloxyhexyl trimethoxysilane, 7-(meth)acryloxyheptyl trimethoxysilane, 8-(meth)acryloxyoctyl trimethoxysilane, 9-(meth)acryloxyoctyl trimethoxysilane, 10-(meth)acryloxydecyl trimethoxysilane, 11-(meth)acryloxyundecyl trimethoxysilane.

[0038] As long as the polymerizable monomer having a sulfur atom is a polymerizable monomer having one or more sulfur atoms and a polymerizable group, known compounds can be used without any limitation. Specifically, it refers to compounds having partial structures such as -SH, -S-S-, >C=S, >C-S-C<, >P=S or those generated by tautomerism. Specific examples include 10-methacryloxydecyl-6,8-dithiaoctanoate, 6-methacryloxyhexyl-6,8-dithiaoctanoate, 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate, 2-(11-methacryloyloxyundecylthio)-5-mercapto-1,3,4-thiadiazole, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate.

[0039] There is no restriction whatsoever in using an oligomer or prepolymer having at least one or more polymerizable groups in the molecule other than these polymerizable monomers. Also, there is no problem even if it has a substituent such as a fluoro group in the same molecule. The polymerizable monomers described above can be used alone or in combination of a plurality.

[0040] The photocurable composition of the present invention can contain a known polymerizable monomer containing an acidic group as the (A) polymerizable monomer in order to impart adhesiveness to dental substances and prosthetic devices. Preferably, it is 10-methacryloyloxydecyl dihydrogen phosphate or 6-methacryloxyhexyl phosphonoacetate. The blending amount of the polymerizable monomer containing an acidic group is 1 part by mass or more, more preferably 10 parts by mass or more, based on 100 parts by mass of the total amount of the polymerizable monomers contained in the photocurable composition from the viewpoint of imparting adhesiveness.

[0041] In the photocurable composition of the present invention, a silane coupling agent can be included as a (A) polymerizable monomer in order to impart adhesiveness to glass ceramics. Any known silane coupling agent can be used without limitation, but 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, and 11-methacryloxyundecyltrimethoxysilane are preferred. From the viewpoint of imparting adhesiveness, the blending amount is 1 part by mass or more, more preferably 10 parts by mass or more and less than 20 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomers in the composition. Since the silane coupling agent as a polymerizable monomer is for the purpose of imparting adhesiveness to resin materials containing glass ceramics or fillers made of glass ceramics, it is blended separately from the surface treatment agent for fillers.

[0042] The photocurable composition of the present invention can contain a polymerizable monomer having a sulfur atom as a (A) polymerizable monomer in order to impart adhesiveness to noble metals. The blending amount of the polymerizable monomer having a sulfur atom is 0.01 part by mass or more, more preferably 0.1 part by mass or more and less than 10 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomers contained in the photocurable composition, from the viewpoint of imparting adhesiveness.

[0043] [(Photoinitiator)] The photoinitiator used in the photocurable composition of the present invention includes (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, and these are not particularly limited, and any generally used known compounds can be used without any limitation.

[0044] [(B) Photosensitizer] Specific examples of the (B) photosensitizer that can be used in the present invention include α-diketones such as benzyl, camphorquinone, camphorquinone carboxylic acid, camphorquinone sulfonic acid, α-naphthyl, acetonaphthone, p,p'-dimethoxybenzyl, p,p'-dichlorobenzyl acetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, naphthoquinone; benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether; 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-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylprop-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)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide and 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide, acylgermanium compounds such as bisbenzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis(4-methoxybenzoyl)dimethylgermanium, and bis(4-methoxybenzoyl)diethylgermanium, α-aminoacetophenones such as 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-butanone-1 and 2-benzyl-diethylamino-1-(4-morpholinophenyl)-propanone-1, ketals such as benzyldimethylketal, benzyldiethylketal, and benzyl(2-methoxyethylketal), titanocenes such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]-titanium, bis(cyclopentadienyl)-bis(pentafluorophenyl)-titanium, and bis(cyclopentadienyl)-bis(2,3,5,6-tetrafluoro-4-disyloxyphenyl)-titanium, etc.

[0045] (B) The photosensitizer can be appropriately selected according to the wavelength, intensity, light irradiation time of the light used for polymerization, and the types and blending amounts of other components to be combined. Also, the photosensitizer can be used alone or in combination of two or more. Among them, 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. Camphorquinone is particularly preferred because it is easily available.

[0046] Generally, the blending amount of (B) the photosensitizer is preferably 0.001 to 1.0 parts by mass, more preferably 0.01 to 1.0 parts by mass, and even more preferably 0.05 to 1.0 parts by mass, based on 100 parts by mass of the total amount of (A) the polymerizable monomer contained in the photocurable composition. When the blending amount of the photosensitizer is less than 0.001 parts by mass, the polymerization activity with respect to the irradiated light is poor and the curing is insufficient. When more than 1.0 parts by mass is blended, although sufficient curability is exhibited, the environmental light stability becomes short and the yellowness increases. The photocurable composition of the present invention may contain only (B-1) an α-diketone compound as (B) the photosensitizer.

[0047] [(C) Photoacid generator] As the (C) photoacid generator used in the photocurable composition of the present invention, known compounds can be used without limitation. Specifically, triazine compounds, iodonium salt compounds, sulfonium salt compounds, sulfonic acid ester compounds, etc. can be mentioned. Among these, triazine compounds and iodonium salt compounds are preferred because of their high polymerizability when used in combination with a sensitizer. More preferably, iodonium salt compounds are preferred. Iodonium salt compounds are easily sensitized by photosensitizers having absorption in the visible light region.

[0048] Specific examples of the triazine compound include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(1-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis(2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,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.,

[0049] Any known iodonium salt compound can be used. As a specific example, the structural formula of the iodonium salt compound can be represented by the following formula (3). [Formula (3)] [(R1)2I] + [A] - (In the formula, [(R1)2I] + is the cationic part, and [A] - is the anionic part. R1 shown in formula (3) represents an organic group bonded to I, and 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, and 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, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogen.)

[0050] Examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl group, and condensed polycyclic aryl groups such as naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, and anthraquinone.

[0051] Examples of the complex cyclic group 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 complex cyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, and condensed polycyclic complex cyclic 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, dibenzofuranyl, etc.

[0052] Specific examples of the alkyl group having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl, octadecyl, etc., branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, etc., and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0053] In addition, specific examples of the alkenyl group having 2 to 30 carbon atoms include linear or branched ones such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, etc.

[0054] Furthermore, specific examples of the alkynyl group having 2 to 30 carbon atoms include linear or branched ones such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl, 1-methyl-2-propynyl, etc.

[0055] The above aryl group having 6 to 30 carbon atoms, heterocyclic group having 4 to 30 carbon atoms, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms or alkynyl group having 2 to 30 carbon atoms may have at least one substituent, and specific examples of the substituent include linear alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, octadecyl; branched alkyl groups having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl; cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; hydroxy group; linear or branched alkoxy groups having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, dodecyloxy; linear or branched alkylcarbonyl groups having 2 to 18 carbon atoms such as acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl; arylcarbonyl groups having 7 to 11 carbon atoms such as benzoyl, naphthoyl; linear or branched alkoxycarbonyl groups having 2 to 19 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl; aryloxycarbonyl groups having 7 to 11 carbon atoms such as phenoxycarbonyl, naphthoxycarbonyl; arylthiocarbonyl groups having 7 to 11 carbon atoms such as phenylthiocarbonyl, naphthoxythiocarbonyl; linear or branched acyloxy groups having 2 to 19 carbon atoms such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octadecylcarbonyloxy;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., arylthio groups having 6 to 20 carbon atoms; methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, dodecylthio, etc., linear or branched alkylthio groups having 1 to 18 carbon atoms; phenyl, tolyl, dimethylphenyl, naphthyl, etc., aryl groups having 6 to 10 carbon atoms; thienyl, furanyl, pyranyl, xanthenyl, chromanyl, isochromanyl, xanthonyl, thioxanthonyl, dibenzofuranyl, etc., heterocyclic groups having 4 to 20 carbon atoms; phenoxy, naphthyloxy, etc., aryloxy groups having 6 to 10 carbon atoms; methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, octylsulfinyl, etc., linear or branched alkylsulfinyl groups having 1 to 18 carbon atoms; phenylsulfinyl, tolylsulfinyl, naphthylsulfinyl, etc., arylsulfinyl groups having 6 to 10 carbon atoms; methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, octylsulfonyl, etc., linear or branched alkylsulfonyl groups having 1 to 18 carbon atoms; phenylsulfonyl, tolylsulfonyl (tosyl group), naphthylsulfonyl, etc., arylsulfonyl groups having 6 to 10 carbon atoms; alkyleneoxy groups; cyano groups; nitro groups; halogens such as fluorine, chlorine, bromine, iodine, etc. are exemplified.;

[0056] Among the iodonium salt compounds, aryl iodonium salts are preferred because of their high stability. Further, in order to improve the fat solubility, the aryl group preferably has a substituent. Specifically, linear alkyl groups such as methyl, propyl, octyl, decyl, undecyl, dodecyl, tridecyl, branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, or functional groups in which one or more Hs of these are substituted with F, perfluoroalkyl groups, halogens, etc. are suitable as substituents.

[0057] The structure of the anion part of the iodonium salt compound is not particularly limited, but examples include those having atoms such as halogen, P, S, B, Al, Ga. From the viewpoint of safety, anions having As or Sb can be used, but they are not preferred for dental applications. Further, the anion preferably has an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group, and more preferably has an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which at least one or more Hs are substituted with F. The iodonium salt compound having such an anion has high solubility in the photocurable composition, so it can be expected to prevent precipitation during low-temperature storage or long-term storage, and to dissolve in the composition in a short time, thus shortening the production time. Further, an iodonium salt compound composed of an anion having an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which one or more Hs are substituted with F can be expected to have even higher solubility. When the photoacid generator precipitates, it may cause a decrease in photo-color stability and a decrease in flexural strength, so it is not preferred. Such an anion having an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which at least one or more Hs may be substituted with F can use an anion having any atom, but those having P, S, B, Al, Ga are preferred from the viewpoints of versatility and safety.

[0058] Examples of anions having no alkyl group, alkoxy group, and / or aryl group include halogens such as chloride and bromide, perhalogenic acids such as perchloric acid, aromatic sulfonic acids such as p-toluenesulfonate, camphorsulfonic acid, nitrate, acetate, chloroacetate, carboxylate, phenolate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, and the like. Among these, p-toluenesulfonate, camphorsulfonic acid, and carboxylate are preferably used.

[0059] [A] of the iodonium salt compound of formula (3) - Since the solubility of the anion moiety in the photopolymerizable composition is improved, it is preferably an anion having an organic group such as an alkyl group, an alkoxy group, and / or an aryl group in which at least one or more Hs are substituted with F. Specifically, [A] of the iodonium salt compound of formula (3) - The preferred number of carbon atoms of the alkyl group in the anion moiety is 1 to 8, preferably 1 to 4. Specific examples include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, octyl, and branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. 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 of the hydrogen atoms of the hydrocarbon are substituted with fluorine. An iodonium salt composed of an anion having an alkyl group with different ratios of hydrogen atoms to fluorine atoms may be blended in the photocurable composition.

[0060] Furthermore, specific examples of the alkyl group include linear or branched perfluoroalkyl groups such as CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, (CF3)3C.

[0061] [A] of the iodonium salt compound of formula (3) - The preferred number of carbon atoms of the alkoxy group in the anion moiety is from 1 to 8, preferably from 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 blended in the photocurable composition.

[0062] 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.

[0063] [A] of the iodonium salt compound of formula (3) -At least one or more hydrogen atoms in the phenyl group of the anion moiety are substituted with a fluorine atom, and / or an alkyl group substituted with a fluorine atom and / or a phenyl group substituted with an alkoxy group. The alkyl group and / or alkoxy group substituted with a fluorine atom are preferably those described above. Specific examples of particularly preferred phenyl groups include 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), bispentafluoroethylfluorophenyl group (CF3CF2)2C6H2F), and other perfluorophenyl groups. An iodonium salt composed of an anion having phenyl groups with different ratios of hydrogen atoms and fluorine atoms may be incorporated in the photocurable composition.

[0064] The [A] of the iodonium salt compound of formula (3) - As specific examples of the anion moiety of, the anion having P is [(CF3CF2)3PF3] - , [(CF3CF2CF2)3PF3] - , [((CF3)2CF)2PF4] - , [((CF3)2CF)3PF3] - , [((CF3)2CF)4PF2] - , [((CF3)2CFCF2)2PF4] - , [((CF3)2CFCF2)3PF3] - and the like. The anion having S is [(CF3SO2)3C] - , [(CF3CF2SO2)3C] - , [(CF3CF2CF2SO2)3C] - , [(CF3CF2CF2CF2SO2)3C] -, [[CF3CF2CF2CF2SO3]] - , [[CF3CF2CF2SO3]] - , [[(CF3CF2SO2)3C]] - , [[(SO2CF3)3N]] - , [[(SO2CF2CF3)2N]] - , [[((CF3)C6H4)SO3]] - , [[SO3((CF2CF2CF2CF2)SO3]] 2- etc. Anions having B include [[B(C6F5)4]] - , [[(C6H5)B((CF3)2C6H3)3]] - , [[(C6H5)B(C6F5)3]] - etc. Anions having Ga include [[((CF3)4Ga]] - , [[Ga(C6F5)4]] - etc. Anions having Al include [[((CF3)3CO)4Al]] - , [[((CF3CF2)3CO)4Al]] - etc.

[0065] The photocurable composition of the present invention preferably contains 0.01 to 10 parts by mass, more preferably 0.2 to 5 parts by mass of (C) photoacid generator with respect to the total amount of 100 parts by mass of the total amount of polymerizable monomers. When the blending amount of the photoacid generator is less than 0.01 part by mass, the polymerization promoting ability may be poor and the curing may be insufficient. When blending more than 10 parts by mass, sufficient curability is exhibited, but the environmental light stability may be shortened and discoloration such as the cured product turning brown may increase.

[0066] The photoacid generator that can be used in the photocurable composition of the present invention is not limited to the photoacid generators shown in the specific examples, and two or more kinds can be used in combination.

[0067] The 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 of any one of P, B, Al, S, and Ga and an aryliodonium cation as the (C) photoacid generator. The photocurable composition of the present invention may contain only a salt of an anion having an organic group in which at least one or more Hs are substituted with F and one or more atoms of any one of P, B, Al, S, and Ga and an aryliodonium cation as the (C) photoacid generator.

[0068] [(D) Photopolymerization accelerator] The (D) photopolymerization accelerator used in the photocurable composition of the present invention is not particularly limited as long as it has the ability to promote polymerization, and known photopolymerization accelerators generally used in the dental field can be used without any limitation. As the photopolymerization accelerator, aromatic amine compounds, primary to tertiary amine compounds such as aliphatic amine compounds, organometallic compounds, phosphine compounds, etc. can be used. Among these, tertiary aliphatic amine compounds and organometallic compounds are preferred because of their good photo-color stability.

[0069] The aromatic amine compound refers to a compound in which one or more Hs of ammonia (NH3) are substituted with an aromatic ring. A compound in which one H of NH3 is substituted with an aromatic ring is an aromatic primary amine compound, a compound in which one H of NH3 is substituted with an aromatic ring and a different one H is substituted with an aromatic ring or an alkyl group is an aromatic secondary amine compound, and a compound in which one H of NH3 is substituted with an aromatic ring and two different Hs are substituted with an aromatic ring or an alkyl group can be classified as an aromatic tertiary amine compound.

[0070] Specific examples of the aromatic primary amine compound include aniline and the like. Specific examples of the aromatic secondary amine compound include N-protected amino acids (esters) such as N-phenylbenzylamine, N-benzyl-p-anisidine, N-benzyl-o-phenetidine, N-phenylglycine ethyl, and N-phenylglycine. Specific examples of the aromatic tertiary amine compound include N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline, p-N,N-dimethyl-toluidine, m-N,N-dimethyl-toluidine, p-N,N-diethyl-toluidine, p-bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid 2-butoxyethyl, p-dimethylaminobenzoic acid 2-ethylhexyl, p-dimethylaminobenzoic acid amino ester, N,N-dimethylanthranilic acid methyl ester, N,N-dihydroxyethylaniline, N,N-diisopropanol aniline, p-N,N-dihydroxyethyl-toluidine, p-N,N-diisopropanol-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N,N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine, N,N-dimethyl-β-naphthylamine, and the like.

[0071] Specific examples of the above-mentioned 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), zirconium (Zr), and preferably organometallic compounds containing tin (Sn), vanadium (V), and copper (Cu). Specific examples of the organometallic compound containing tin (Sn) include dibutyl-tin-diacetate, dibutyl-tin-dimaleate, dioctyl-tin-dimaleate, dioctyl-tin-dilaurate, dibutyl-tin-dilaurate, dioctyl-tin-diversatate, dioctyl-tin-S,S'-bis-isooctylmercaptoacetate, tetramethyl-1,3-diacetoxydistannoxane, etc. Specific examples of the organometallic compound containing vanadium (V) include vanadium acetylacetonate, vanadium dioxide, vanadyl acetylacetonate, vanadium stearate, vanadyl oxalate, vanadyl sulfate, oxobis(1-phenyl-1,3-butanedionate)vanadium, bis(maltolato)oxovanadium, vanadium pentoxide, sodium metavanadate, etc. Specific examples of the organometallic compound containing copper (Cu) include copper acetylacetonate, copper naphthenate, copper octylate, copper stearate, copper acetate.

[0072] A phosphine compound refers to a compound in which the P atom is trisubstituted with organic groups, and an aromatic phosphine compound refers to a compound in which a phenyl group that may have one or more substituents is substituted on the P atom. 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, 2-(phenylphosphino)benzoic acid, 3-(phenylphosphino)benzoic acid, 4-(phenylphosphino)benzoic acid, tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, 2-(diphenylphosphino)biphenyl, tris(4-fluorophenyl)phosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, 2-(dimethylamino)phenyl diphenylphosphine, 3-(dimethylamino)phenyl diphenylphosphine, 4-(dimethylamino)phenyl diphenylphosphine, 2,2'-bis(diphenylphosphino)biphenyl, bis[2-(diphenylphosphino)phenyl]ether, and the like. Among these, triphenylphosphine, 4-(phenylphosphino)benzoic acid, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, and tri(p-tolyl)phosphine are preferred.

[0073] An aliphatic amine compound refers to a compound in which one or more H atoms of ammonia (NH3) are substituted by alkyl groups. The alkyl group is classified as a primary alkyl group when it is CH3- or -CH2-, a secondary alkyl group when one H of -CH2- has a substituent, and a tertiary alkyl group when two H atoms of -CH2- have substituents. Aliphatic amines are classified as aliphatic primary amine compounds in which one H of NH3 is substituted by an alkyl group, aliphatic secondary amine compounds in which two H atoms of NH3 are substituted by alkyl groups, and aliphatic tertiary amine compounds in which three H atoms of NH3 are substituted by alkyl groups.

[0074] Specific examples of the aliphatic primary amine compound include amino acids such as benzhydrylamine, triphenylmethylamine, glycine, or amino acid esters, etc. Specific examples of the aliphatic secondary amine compound include dibenzylamine, N-benzyl-1-phenylethylamine, bis(1-phenylethyl)amine, bis(4-cyanobenzyl)amine, N-benzyl-protected amino acids or N-benzyl-protected amino acid esters, etc. Specific examples of the aliphatic tertiary amine compound 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-lauryl diethanolamine, N-stearyl diethanolamine, triethanolamine, triisopropanolamine, tribenzylamine, dibenzylglycine ethyl ester, N'-(2-hydroxyethyl)-N,N,N'-trimethylethylenediamine, 2-(dimethylamino)-2-methyl-1-propanol, N,N-dimethyl-2,3-dihydroxypropylamine, N,N-diethylethanolamine, 1-methyl-3-pyrrolidinol, 1-(2-hydroxyethyl)pyrrolidine, 1-isopropyl-3-pyrrolidinol, 1-piperidineethanol, 2-[2-(dimethylamino)ethoxy]ethanol, N,N-dimethylglycine, N,N-dimethylglycine methyl, N,N-diethylglycine methyl, N,N-dimethylglycine ethyl, N,N-diethylglycine sodium, 2-(dimethylamino)ethyl acetate, N-methyliminodiacetic acid, N,Examples thereof 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, triallylamine and the like.,

[0075] (D) It is particularly preferable to use an aliphatic tertiary amine compound as the photopolymerization accelerator. Since aromatic amine compounds are inferior in light color stability, it is not preferable to use them in prosthetic devices, restorative materials, and adhesives in areas where light is likely to hit, such as anterior teeth, because the color tone may change over time. It can be expected to suppress discoloration over time due to light by using an ultraviolet absorber in combination. However, since ultraviolet absorbers are usually used as additives, improvement in mechanical properties by blending cannot be expected, and further, it may increase the yellowness of the photocurable composition before curing, so it is not preferable to blend a large amount. For these reasons, it is preferable to use an aliphatic tertiary amine compound. In addition, depending on the composition of the photocurable composition, high storage stability and high mechanical strength can be expected when an aliphatic primary amine compound and an aliphatic secondary amine compound are included, so known ones can be used without any limitation.,

[0076] Furthermore, among aliphatic tertiary amine compounds, it is preferably not an amine compound having two or more primary hydroxy groups in the molecule, and more preferably an amine compound having no primary hydroxy group in the molecule. Specific examples of amine compounds having two or more primary hydroxy groups in the molecule include triethanolamine and methyldiethanolamine. Amine compounds having a primary hydroxy group may cause discoloration when the cured product of the photocurable composition is stored for a long time. The discoloration tends to increase as the number of primary hydroxy groups in the molecule increases, and is particularly remarkable when there are two or more in the molecule. Discoloration during long-term storage of the cured product can be confirmed in a short period by storing it under high-temperature water conditions. When the discoloration under high-temperature water conditions is small, that is, when the thermochromic stability is high, the discoloration when the cured product of the photocurable composition is used for a long time is small.

[0077] The photocurable composition of the present invention contains, as a (D) photopolymerization accelerator, an (D-1) amine compound represented by formula (1). [Formula (1)] [Chemical formula] (In formula (1), R1 is a substituent represented by formula (2), and R2 and R3 are substituents represented by formula (2), or a -OH group, -O- group, -S- group, -NH-C(O)-NH- group, -C(O)-O- group, -O-C(O)- group, -O-C(O)-NH- group, -NH-C(O)-O- group, halogen, an organic group which may have an alkoxysilyl group, an aromatic ring which may have a substituent or an alicyclic heterocyclic ring which may have a substituent. However, when at least one or more of R4 in formula (2) is an aromatic ring, R2 and R3 may be H, and when R2 is a substituent represented by formula (2), R3 may be H.) [Formula (2)] [Chemical formula] (In formula (2), X is C or N, and two or more X's are not N. When X is N, there is no R5 bonded to N. R4 is a hydrocarbon chain, an aromatic ring, or H, and they may be the same as or different from each other. R5 is an organic group that may have an -OH group, an -O- group, an -S- group, an -NH-C(O)-NH- group, a -C(O)-O- group, an -O-C(O)- group, an -O-C(O)-NH- group, or an -NH-C(O)-O- group, a halogen, or H, and they may be the same as or different from each other.)

[0078] (D-1) The photocurable composition of the present invention containing the amine compound represented by formula (1) cures to a deep part when irradiated with light. Further, since it is superior in curing depth to conventional photocurable compositions, it is possible to exhibit the same curing depth with light irradiation for a shorter time than before. For example, among photocurable compositions, when used for dental composite resins, it is expected to shorten the working time of the operator by reducing the number of resin laminations during filling or by reducing the number and time of light irradiations. When used for dental adhesives, since it can be cured to a deep part with short-time light irradiation, it is expected to shorten the working time of the operator by reducing the light irradiation time.)

[0079] (D-1) The amine compound represented by formula (1) can be divided into an aromatic amine compound in which N is bonded to an aromatic ring and an aliphatic amine compound in which N is bonded to an alkyl group. Further, the amine compound represented by formula (1) in (D-1) includes a primary amine compound in which N is bonded to one aromatic ring or alkyl group, a secondary amine compound in which N is bonded to two aromatic rings and / or alkyl groups, and a tertiary amine compound in which N is bonded to three aromatic rings and / or alkyl groups.)

[0080] (D-1) Specific examples of the amine compound represented by formula (1) include, as primary amine compounds, benzhydrylamine, 4,4'-dimethoxybenzhydrylamine, triphenylmethylamine, etc.; as aromatic secondary amine compounds, N-phenylbenzylamine, N-benzyl-p-anisidine, N-benzylanthranilic acid, N-benzyl-o-phenetidine, N-benzyl-2-naphthylamine, α,α'-dianilino-p-xylene, etc.; as aliphatic secondary amine compounds, dibenzylamine, N-benzyl-1-phenylethylamine, bis(1-phenylethyl)amine, bis(4-cyanobenzyl)amine, etc.; as aromatic tertiary amines, N,N-dibenzylaniline, N,N-dibenzyl-4-bromoaniline, etc.; as aliphatic tertiary amine compounds, N,N-dimethylbenzylamine, N-ethyl-N-methylbenzylamine, N,N-dimethyl-1-phenylethylamine, N,N-dimethylaminomethylphenol, N-methyl-N-(2-propyn-1-yl)benzylamine, 3-benzyloxazolidine, N,N-diethylbenzylamine, 3-[1-(dimethylamino)ethyl]phenol, N-benzyldiethanolamine, N-cyanodibenzylamine, N-benzyliminodiacetic acid, N-benzyl-3,3'-iminodipropionic acid, 1-benzhydryl-3-azetidinone, 1-(diphenylmethyl)-3-azetidinol, N,N-dibenzylaminoethanol, N,N-dibenzylaminopropanol, 2,6-Di-tert-butyl-4-dimethylaminomethylphenol, dibenzylaminopropionaldehyde, tribenzylamine, dibenzylaminoethyl (meth)acrylate, dibenzylaminopropyl (meth)acrylate, benzylaminodiethyl (meth)acrylate, tris(2-picolyl)amine, N-(4-tert-butylbenzyl)-N-methyl-1-naphthalenemethanamine, (S)-(-)-2-(dibenzylamino)propionaldehyde, (S)-(+)-2-(dibenzylamino)-1-propanol, (S)-2-(dibenzylamino)-3-methylbutanol, 1-[(dibenzylamino)methyl]-2-naphthol, (2S)-2-(dibenzylamino)-4-methyl-1-pentanol, (S)-(+)-2-(dibenzylamino)-3-phenyl-1-propanol, etc. And those having a heterocyclic structure include 1-benzyl-3-pyrrolidone, N-benzoylmetholquine tert-butyl, ethyl 1-benzyl-4-piperidinecarboxylate, N-benzylnortropinone, 1-benzyl-3-methyl-4-piperidone, 1-benzyl-4-piperidinecarboxaldehyde, 1-benzyl-4-piperidone, 1-benzylpiperidine, etc. Also, benzyl group-protected amino acids and benzyl-protected amino acid esters, such as N,N-dibenzylglycine ethyl, etc. are included.,

[0081] Among the compounds listed above, those having a benzyl group can be easily synthesized by benzyl-protecting a commercially available compound having NH3 or NH2 - , NH 2- . For the benzyl protection of amines, benzyl chloride, benzyl bromide, etc. are used, but any known benzyl protection method can be used. Furthermore, in addition to benzyl protection, amine compounds protected with a protecting group having a substitution on the aromatic ring, such as a p-methoxybenzyl protecting group, can be used in the same way.,

[0082] (D-1) The amine compound shown in formula (1) can be one having a polymerizable group. The amine compound having a polymerizable group introduced therein can be synthesized by a known method. For example, by reacting dibenzylaminoalkyl alcohol and alkyl (meth)acrylate in the presence of a transesterification catalyst such as an alkali metal alcoholate, a magnesium alcoholate, a titanium alcoholate, a tin-based catalyst, or an acetylacetone metal complex compound, an amine compound having an ester bond can be obtained. Further, by subjecting dibenzylaminoalkyl alcohol and isocyanatoalkyl (meth)acrylate to a urethanization reaction in the absence of a catalyst or in the presence of a urethanization catalyst such as a tin-based catalyst or a bismuth-based catalyst, an amine compound having a urethane bond can be obtained. Further, by reacting a compound having a benzyl group and a primary or secondary amine with isocyanatoalkyl (meth)acrylate in the absence of a catalyst, an amine compound having a urea bond can be obtained. By reacting a benzyl-protected amino acid with an alcohol or hydroxyalkyl (meth)acrylate in the presence of a transesterification catalyst, an amine compound having an ester bond can be obtained. The above reactions are known synthetic methods, and the amine compound shown in formula (1) of the present invention (D-1) can be synthesized using a known synthetic method. Further, since it is synthesized using benzyl protection and each synthetic catalyst, the raw materials or catalysts used in the synthesis and the by-products generated in the reaction can be used without problem even if they are contained in the photocurable composition of the present invention.

[0083] A compound having both a benzylamino group and an alkoxysilyl group can also be used as a surface treatment agent for fillers. For example, 3-(N,N-dibenzylamino)propyltriethoxysilane can be synthesized by benzyl-protecting aminopropyltriethoxysilane. Similar to the photocurable composition containing 3-(N,N-dibenzylamino)propyltriethoxysilane, a photocurable composition containing a filler surface-treated with 3-(N,N-dibenzylamino)propyltriethoxysilane can be expected to exhibit a high curing depth.

[0084] (D-1) If it is a compound having the structure of the amine compound shown in formula (1) or a compound having an amine skeleton partially having the substituent shown in formula (2), the same effect can be expected regardless of the molecular weight such as a polymer. Furthermore, there is no problem even if secondary treatments such as encapsulating these in microcapsules, physically adsorbing them on a carrier, or chemically immobilizing them by covalent bonding are performed. Also, even in the case shown above, when the amine compound shown in formula (1) of (D-1) has two or more substituents shown in formula (2) or when it has an amine skeleton having two or more substituents shown in formula (2), it tends to exhibit good photocuring depth.

[0085] Among the amine compounds shown in formula (1) of (D-1), it is preferable that R1 and R2 in formula (1) are aliphatic tertiary amines having the structure of formula (2). Specifically, dibenzylaminoalkyl (meth) acrylates such as dibenzylaminoethyl (meth) acrylate and dibenzylaminopropyl (meth) acrylate, dibenzylaminoalkyl (meth) acrylamide, dibenzylaminoethanol, dibenzylaminopropanol, amino acids (esters) protected by two or more benzyl groups such as N,N-dibenzylglycine ethyl, and tribenzylamine can be mentioned. Aliphatic tertiary amines having two or more structures of formula (2) show a more remarkable improvement in curing depth, and furthermore, when using aliphatic tertiary amines, the light color stability is higher than when using aromatic amines.

[0086] The amine compound shown in formula (1) of (D-1) is preferably contained in an amount of 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer. If it is less than 0.01 part by mass, the ability to improve the curing depth tends to be insufficient. When blended in an amount more than 20 parts by mass, although sufficient curing depth is exhibited, the environmental light stability may be shortened, which is not preferable.

[0087] In addition, the type of the (D) photoinitiator containing the amine compound represented by the formula (1) in (D-1) can be appropriately selected according to the types and blending amounts of other components to be combined. Further, the (D) photoinitiator can be used alone or in combination of two or more kinds.

[0088] The (D) photoinitiator is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total amount of the (A) polymerizable monomer contained in the photocurable composition. When the blending amount of the (D) polymerization accelerator is less than 0.01 part by mass, the polymerization accelerating ability is poor and curing tends to be insufficient. When the blending amount is more than 10 parts by mass, although sufficient curability is exhibited, the environmental light stability may be shortened and the discoloration of the cured body may increase.

[0089] The photocurable composition of the present invention may contain only the amine compound represented by the formula (1) in (D-1) as the (D) photoinitiator. The photocurable composition of the present invention may contain only the amine compound represented by the formula (1) in (D-1), which is an aliphatic tertiary amine, as the (D) photoinitiator. The photocurable composition of the present invention may contain only the amine compound represented by the formula (1) in (D-1), in which R2 in the formula (1) is a substituent represented by the formula (2), as the (D) photoinitiator.

[0090] These (B) photosensitizers, (C) photoacid generators, and (D) photoinitiators, which are polymerization initiators, may be subjected to secondary treatments such as fine pulverization, carrier adsorption, and encapsulation in microcapsules as necessary, without any problems. Further, these various types of photoinitiators can be used alone or in combination of two or more kinds, regardless of the polymerization mode and polymerization method.

[0091] [(E) filler] The (E) filler that can be used in the present invention can be used without any limitation to known fillers that are generally used.

[0092] (E) The type of the filler is not limited as long as it is a known filler, and a filler suitable for its use can be blended. It is preferable to blend fillers such as inorganic fillers, organic fillers, or organic-inorganic composite fillers. These can be used not only alone but also in combination of a plurality regardless of the type of the filler.

[0093] Regarding the above-mentioned inorganic fillers, their chemical compositions are not particularly limited. Specific examples include silicon dioxide, alumina, silica - titania, silica - titania - barium oxide, silica - zirconia, silica - alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium borosilicate aluminosilicate glass, strontium borosilicate aluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. In particular, barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, fluoroaluminosilicate glass, etc. used in dental glass ionomer cement, resin - reinforced glass ionomer cement, resin cement, etc. can also be preferably used. The fluoroaluminosilicate glass mentioned here has silicon dioxide and aluminum oxide as a basic skeleton, contains an alkali metal for introducing non - crosslinked oxygen, further contains an alkaline earth metal containing strontium and fluorine as modified and coordinated ions, and is a composition in which an element of the lanthanoid series is incorporated into the skeleton to impart further X - ray impermeability. This lanthanoid series element is incorporated into the composition as a modified and coordinated ion depending on the composition range.

[0094] Specific examples of the organic filler 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.

[0095] Examples of the organic-inorganic composite filler include those obtained by polymer coating the surface of the filler with a polymerizable monomer, those obtained by mixing and polymerizing the filler and the polymerizable monomer and then pulverizing to an appropriate particle size, or those obtained by previously dispersing the filler in the polymerizable monomer and subjecting to emulsion polymerization or suspension polymerization, but are not limited thereto.

[0096] The above-mentioned (E) filler can be treated with a surface treatment material typified by a silane coupling agent for the purpose of improving the affinity with the polymerizable monomer, the dispersibility in the polymerizable monomer, the mechanical strength and water resistance of the cured body. Such a surface treatment material and surface treatment method are not particularly limited, and known methods can be adopted without limitation. Examples of the silane coupling agent used for the surface treatment of the filler 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, etc. are preferable. In addition to the silane coupling agent, the surface treatment of the filler can be performed by a method using a titanate-based coupling agent or an aluminate-based coupling agent. The amount of the surface treatment material used for the filler is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the filler before treatment.

[0097] The shape of the filler is not particularly limited, and fillers of any shape such as amorphous, spherical, needle-like, plate-like, crushed, or flaky can be used. Also, the average particle diameter of the filler preferably has an average particle diameter in the range of 0.01 μm to 50 μm, more preferably 0.01 μm to 30 μm, still more preferably 0.05 μm to 20 μm, and even more preferably 0.05 μm to 10 μm.

[0098] When compounding (E) filler in the photocurable composition, it is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the (A) polymerizable monomer, and preferably less than 500 parts by mass in consideration of formability and the like. When the compounding amount of the filler is less than 10 parts by mass, the effect of improving the mechanical strength and expressing thixotropy when the filler is compounded may be poor. When compounding more than 1000 parts by mass, the paste properties of the composition become hard, which may make it difficult to handle. However, depending on the type of filler and the surface treatment conditions of the filler, it may contain 1000 parts by mass or more. For example, it refers to the case where the filler has a high specific gravity, the amount of the surface treatment agent on the filler is large, or a surface treatment agent having good affinity with the polymerizable monomer is used. The composition of the present invention exhibits an effect regardless of the compounding amount of the filler.

[0099] The photocurable composition of the present invention may contain a chemical polymerization initiator. Examples of the organic peroxide as the chemical polymerization initiator include diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy ketals, ketone peroxides, peroxydicarbonates, and hydroperoxides. Specific examples of diacyl peroxides include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. Specific examples of peroxy esters include α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 2,2,4-trimethylpentyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxylisophthalate, di-t-butyl peroxyhexahydroterephthalate, t-butyl peroxy-3,3,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butyl peroxymaleic acid. Specific examples of dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne. Specific examples of peroxy ketals include 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, n-butyl 4,4-(t-butylperoxy)pelleate, and 1,1-di(t-amylperoxy)cyclohexane. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methyl cyclohexanone peroxide, and cyclohexanone peroxide.Specific examples of peroxydicarbonates include di-3-methoxyp peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, diallyl peroxydicarbonate, and the like. Specific examples of hydroperoxides include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide, and the like.

[0100] As the organic peroxide, the above-mentioned organic peroxides may be used alone, or two or more kinds of organic peroxides may be used in combination. Among these organic peroxides, benzoyl peroxide and cumene hydroperoxide are preferable from the viewpoint of curability. The organic peroxide as a chemical polymerization initiator is preferably set to 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer, from the viewpoint of improving curability. When the blending amount of the organic peroxide exceeds 5 parts by mass, it may be difficult to ensure a sufficient operation time. On the other hand, when the blending amount of the organic peroxide is less than 0.1 part by mass, the mechanical strength may be insufficient.

[0101] A chemical polymerization accelerator may be further blended in the photocurable composition of the present invention to improve curability. Examples of the chemical polymerization accelerator include transition metal compounds of the fourth period, thiourea derivatives, aliphatic amines, aromatic amines, sulfinic acids and their salts, borate compounds, sulfur-containing reducing inorganic compounds, nitrogen-containing reducing inorganic compounds, barbituric acid derivatives, triazine compounds, halogen compounds, and the like. The blending amount of the chemical polymerization accelerator is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer.

[0102] The transition metal compounds of the fourth period as chemical polymerization accelerators refer to metal compounds of Groups 3 to 12 in the fourth period of the periodic table. Specifically, any metal compounds of scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn) can be used without limitation. Each of the above transition metal elements can take multiple valences, but as long as it is a valence in which it can stably exist, it can be added to the photocurable composition of the present invention. For example, Sc (trivalent), Ti (tetravalent), V (trivalent, tetravalent, or pentavalent), Cr (divalent, trivalent, or hexavalent), Mn (divalent to heptavalent), Fe (divalent or trivalent), Co (divalent or trivalent), Ni (divalent), Cu (monovalent or divalent), Zn (divalent). Specific examples of transition metal compounds include scandium iodide (trivalent) as a scandium compound, titanium chloride (tetravalent), titanium (tetravalent) tetraisopropoxide, etc. as titanium compounds, acetylacetone vanadium (trivalent), vanadium dioxide (tetravalent), vanadyl acetylacetonate (tetravalent), stearic acid vanadium oxide (tetravalent), vanadyl oxalate (tetravalent), vanadyl sulfate (tetravalent), oxobis(1-phenyl-1,3-butanedionate) vanadium (tetravalent), bis(maltrate) oxovanadium (tetravalent), vanadium pentoxide (pentavalent), sodium metavanadate (pentavalent), etc. as vanadium compounds, manganese acetate (divalent), manganese naphthenate (divalent), etc. as manganese compounds, iron acetate (divalent), iron chloride (divalent), iron acetate (trivalent), iron chloride (trivalent), etc. as iron compounds, cobalt acetate (divalent), cobalt naphthenate (divalent), etc. as cobalt compounds, nickel chloride (divalent), etc. as nickel compounds, copper chloride (monovalent), copper bromide (monovalent), copper chloride (divalent), copper acetate (divalent), etc. as copper compounds, zinc chloride (divalent), zinc acetate (divalent), etc. as zinc compounds.

[0103] Among these, trivalent or tetravalent vanadium compounds and divalent copper compounds are preferred. Among them, trivalent or tetravalent vanadium compounds having a higher polymerization promoting ability are more preferred, and tetravalent vanadium compounds are most preferred. These transition metal compounds of the fourth period may be used in combination of a plurality of types as necessary. The compounding amount of the transition metal compound is preferably 0.0001 to 1 part by mass with respect to 100 parts by mass of the total amount of the (A) polymerizable monomer. If it is less than 0.0001 part by mass, the polymerization promoting effect may be insufficient, and if it exceeds 1 part by mass, it may cause discoloration and gelation of the photocurable composition, resulting in a decrease in storage stability.

[0104] As the thiourea derivative as a chemical polymerization accelerator, any known thiourea derivative can be used without limitation. Specific examples include dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl)thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, N-benzylthiourea, 1,3-dicyclohexylthiourea, N,N'-diphenylthiourea, 1,3-di(p-tolyl)thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea, dicyclohexylthiourea and the like. Among these, (2-pyridyl)thiourea, N-acetylthiourea, and N-benzoylthiourea are preferred. These thiourea derivatives may be used in combination of a plurality of types as necessary. The compounding amount of the thiourea derivative is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the (A) polymerizable monomer. If it is less than 0.1 part by mass, the polymerization promoting ability may be insufficient, and if it exceeds 5 parts by mass, the storage stability may decrease.

[0105] Examples of sulfinic acids and their salts include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, etc. Among them, sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferred.

[0106] As borate compounds, specific examples of borate compounds having one aryl group in one molecule 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 trialkylphenylboron, trialkyl(p-chlorophenyl)boron, trialkyl(p-fluorophenyl)boron, trialkyl(3,5-bistrifluoromethyl)phenylboron, trialkyl[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, trialkyl(p-nitrophenyl)boron, trialkyl(m-nitrophenyl)boron, trialkyl(p-butylphenyl)boron, trialkyl(m-butylphenyl)boron, trialkyl(p-butyloxyphenyl)boron, trialkyl(m-butyloxyphenyl)boron, trialkyl(p-octyloxyphenyl)boron, and trialkyl(m-octyloxyphenyl)boron (the alkyl group is at least one selected from the group consisting of an n-butyl group, an n-octyl group, an n-dodecyl group, etc.).Specific examples of the borate compound having two aryl groups in the molecule include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methyquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of 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, dialkyldi(p-butyloxyphenyl)boron, dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p-octyloxyphenyl)boron, and dialkyldi(m-octyloxyphenyl)boron (the alkyl group is at least one selected from the group consisting of an n-butyl group, an n-octyl group, and an n-dodecyl group, etc.).Specific examples of the borate compound having three aryl groups in the molecule 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, butylquinolinium salts, etc. of monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron, monoalkyltri(p-fluorophenyl)boron, monoalkyltri(3,5-bistrifluoromethyl)phenylboron, monoalkyltri[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, monoalkyltri(p-nitrophenyl)boron, monoalkyltri(m-nitrophenyl)boron, monoalkyltri(p-butylphenyl)boron, monoalkyltri(m-butylphenyl)boron, monoalkyltri(p-butyloxyphenyl)boron, monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(p-octyloxyphenyl)boron, and monoalkyltri(m-octyloxyphenyl)boron (the alkyl group is one selected from an n-butyl group, an n-octyl group, an n-dodecyl group, etc.).Specific examples of the borate compound 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, tetrakis(m-octyloxyphenyl)boron, (p-fluorophenyl)triphenylboron, (3,5-bistrifluoromethyl)phenyltriphenylboron, (p-nitrophenyl)triphenylboron, (m-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron, and (p-octyloxyphenyl)triphenylboron, 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 thereof.

[0107] Among these aryl borate compounds, from the viewpoint of storage stability, it is more preferable to use a borate compound having three or four aryl groups in one molecule. Further, these aryl borate compounds can be used alone or in admixture of two or more.

[0108] Examples of the sulfur-containing reducing inorganic compounds include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, dithionites, etc. Specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, thiobenzoic acid, and the like.

[0109] Examples of the nitrogen-containing reducing inorganic compounds include nitrites. Specific examples include sodium nitrite, potassium nitrite, calcium nitrite, ammonium nitrite, and the like.

[0110] 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, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and salts of thiobarbituric acids (preferably alkali metals or alkaline earth metals). Specific examples of these salts of barbituric acids include sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate, etc.

[0111] Specific examples of the halogen compounds include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide, and the like.

[0112] The photocurable composition of the present invention can be made to contain no chemical polymerization initiator and chemical polymerization accelerator. The photocurable composition of the present invention can be made to contain no polymerization initiator system of a polymerization system other than the photopolymerization system.

[0113] <Other components> In addition, the photocurable composition of the present invention may contain components other than the components (A) to (D) above as long as the effects of the present invention are not inhibited. For example, excipients typified by fumed silica, ultraviolet absorbers such as benzophenone-based and benzotriazole-based, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, 2,5-di-tert-butyl-4-methylphenol, α-alkylstyrene compounds, mercaptan compounds such as n-butyl mercaptan and n-octyl mercaptan, chain transfer agents such as terpeneoid compounds such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, and α-pinene, metal scavengers such as aminocarboxylic acid-based chelating agents and phosphonic acid-based chelating agents, discoloration inhibitors, antibacterial agents, coloring pigments, water, solvents that can be mixed with water in any ratio, and other components such as conventionally known additives can be arbitrarily added as needed.

[0114] When the photocurable composition of the present invention contains a colorant such as a pigment, the curing depth may be lower than that in the case of not containing the colorant, but in any case, it can be expected to exhibit an excellent curing depth compared with conventional photoinitiators.

[0115] The method for preparing the photocurable composition of the present invention is not particularly limited. As a general production method of a photocurable composition, after preparing a matrix in which (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator are mixed in advance, this matrix and (E) a filler are kneaded, and bubbles are removed under vacuum to prepare a uniform paste-like form. Even in the present invention, it can be produced without any problem by the above production method.

[0116] The composition of the present invention can be used in dental materials, printing plate-making materials, and photoresist materials, and is particularly preferably used in dental materials. Specifically, it is used in dental adhesives, dental composite resins, dental abutment construction materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicure materials, dental loose tooth fixing adhesives, dental glass ionomer cements, dental cutting materials, dental 3D printer materials, etc.

[0117] <One-component photocurable composition> When the present invention is used in a one-component photocurable composition, particularly as a dental material, it is preferably used in dental adhesives, dental composite resins, dental abutment construction materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicure materials, dental loose tooth fixing adhesives, dental cutting materials, dental 3D printer materials. Particularly preferably, it is preferably used in dental adhesives, dental composite resins, dental abutment construction materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicure materials, dental loose tooth fixing adhesives. In the case of a one-component photocurable composition, it can be expected that there are fewer technical errors and the risk of air bubble entrainment is reduced.

[0118] <Two-component photocurable composition> When the present invention is used in a two-component type photocurable composition, particularly as a dental material, it is preferably used in dental adhesives, dental composite resins, dental abutment building materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicure materials, dental loose tooth fixing adhesives, dental cutting materials, and dental 3D printer materials. Particularly preferably, it is used in dental composite resins, dental abutment building materials, and dental resin cements. The two-component type dental material is used by kneading immediately before use with two components divided into a first paste and a second paste. The kneading is preferably performed at a volume ratio of 0.9 to 1.1:1.0 or a mass ratio of 0.8 to 1.2:1.0, preferably an equal volume ratio, of the first paste and the second paste. The kneading method can be performed by a known method such as manual kneading using a dedicated shaking device or spatula, or automatic kneading through a static mixer. Since the components can be divided into two components, compounds that cannot be blended in the same paste can be separately blended, so that the storage stability is excellent.

[0119] The photocurable composition of the present invention may contain only (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator. Further, as components other than (A) to (D), only one or more of the above-described components may be contained.

Examples

[0120] Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. [(A) Polymerizable monomer] · Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane · D2.6E: 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane having an average addition mole number of 2.6 of ethoxy groups · UDMA: N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)ethanol]methacrylate · NPG: Neopentyl glycol dimethacrylate ·TEGDMA: Triethylene glycol dimethacrylate ·GDMA: Glycerin dimethacrylate ·HEMA: 2-Hydroxyethyl methacrylate ·MDP: 10-Methacryloyloxydecyl dihydrogen phosphate ·6-MHPA: 6-Methacryloxyhexyl phosphonoacetate ·4-MET: 4-Methacryloxyethyl trimellitic acid ·TMODS: 8-Methacryloxyoctyl trimethoxysilane

[0121] [(B) Photosensitizer] ·CQ: Camphorquinone ·BAPO: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[0122] [(C) Photoacid generator] ·C1: Bis(4-tert-butylphenyl)iodonium nonafluorobutanesulfonate

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[0123] [(D) Photoinitiator] [Aliphatic tertiary amine] [<Aliphatic tertiary amine compound without primary hydroxyl group>] ·DMAEMA: N,N-Dimethylaminoethyl methacrylate [<Aliphatic tertiary amine compound with two or more primary hydroxyl groups>] ·MDEOA: Methyldiethanolamine ·TEA: Triethanolamine [Aromatic tertiary amine compound] ·DMBE: Ethyl N,N-dimethylaminobenzoate ·DEPT: N,N-Dihydroxyethyl-p-toluidine [Organometallic compound] ·DBTL: Dibutyl-tin-dilaurate

[0124] [(D-1) Amine compound represented by formula (1)] [Aliphatic primary amine compound] ·D1: Benzhydrylamine [Chemical formula] ·D2: Triphenylmethylamine [Chemical formula] [Aliphatic secondary amine compound] ·D3: N-(Triphenylmethyl)glycine [Chemical formula] ·D4: N-(diphenylmethyl)methylamine

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[0125] [(E) Filler] The manufacturing method of each filler used for the preparation of the photocurable composition is 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 added, and the mixture was stirred at room temperature for 2 hours to obtain a silane coupling treatment solution. Then, the mixture was stirred and mixed for 30 minutes. Thereafter, heat treatment was performed at 100 °C for 15 hours to obtain Filler E1.

[0127] (Filling material 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 added and stirred at room temperature for 2 hours to obtain a silane coupling treatment solution, which was then stirred and mixed for 30 minutes. Thereafter, heat treatment was performed at 100 °C for 15 hours to obtain filling material E2

[0128] [Chemical polymerization initiator] ·CHP: Cumene hydroperoxide ·BPO: Benzoyl peroxide [Chemical polymerization accelerator] ·PTU: (2-Pyridyl)thiourea ·BTU: N-Benzoylthiourea ·DEPT: N,N-Dihydroxyethyl-p-toluidine ·CAA: Copper acetylacetonate ·VAA: Vanadyl acetylacetonate

[0129] [UV absorber] ·BT: 2-(2-Hydroxy-5-methylphenyl)benzotriazole [Polymerization inhibitor] ·BHT: 2,6-Di-t-butyl-4-methylphenol ·MeHQ: p-Methoxyphenol [Fluorescent agent] ·FA: Diethyl 2,5-dihydroxyterephthalate

[0130] <Method for producing a one-component photocurable composition> All except the (E) filler shown in Tables 1 to 3 were put into a wide-mouth poly container and mixed for 48 hours at 100 rpm using a mix rotor VMRC-5 to obtain a matrix. Thereafter, the matrix and the (E) filler were put into a kneader, uniformly stirred, and then degassed under vacuum to prepare a photocurable composition. In Tables 1 to 3, the parts by mass of each component are described in parentheses after the abbreviation of each component.

[0131]

Table 1

[0132]

Table 2

[0133]

Table 3

[0134] <Method for producing two-component photocurable composition> All except the (E) filler shown in Tables 4 to 7 were put into a wide-mouth poly container and mixed for 48 hours at 100 rpm using a mix rotor VMRC-5 to obtain a matrix. Thereafter, the matrix and the (E) filler were put into a kneader, uniformly stirred, and then degassed under vacuum to obtain Pastes 1 and 2. Then, Pastes 1 and 2 were filled into a double syringe (5 mL) manufactured by Mix Pack to prepare a photocurable composition. In Tables 4 to 7, the parts by mass of each component are described in parentheses after the abbreviation of each component.

[0135]

Table 4

[0136]

Table 5

[0137]

Table 6

[0138]

Table 7

[0139] The test methods adopted in the examples and comparative examples are as follows. For the one-component photocurable composition, it was directly sampled. For the two-component photocurable composition, the paste obtained by mixing Paste 1 and 2 using a mixing tip manufactured by Mixpac was used. When using, the paste obtained by mixing Paste 1 and 2 using a mixing tip manufactured by Mixpac was used. The mixing tip manufactured by Mixpac can be mixed through a static mixer. When this was used, Paste 1 and Paste 2 could be kneaded at a volume ratio of 0.9 to 1.1:1.0, ideally at an equal volume. When converted to a mass ratio, Paste 1 and Paste 2 were kneaded and used so that the ratio was 0.8 to 1.2:1.0.

[0140] (1) Flexural strength After filling the prepared photocurable composition into a stainless steel mold, cover glasses were placed on both sides and pressed against with a glass leveling plate, and then light irradiation was performed 5 times for 10 seconds each using a photopolymerization irradiator (Penbright: manufactured by Matsuura) to cure it. After curing, the cured product was taken out of the mold, and then the back surface was similarly irradiated with light again to obtain a test specimen (25×2×2 mm: rectangular parallelepiped shape). For the type 1 photocurable composition, after immersing the test specimen in water at 37°C for 24 hours, a bending test was conducted. For the type 2 photocurable composition, a bending test was performed within 1 hour after light irradiation. The bending test was carried out using an Instron universal testing machine (manufactured by Instron) with a span length of 20 mm and a crosshead speed of 1 mm / min. The flexural strength of the type 1 and type 2 photocurable compositions containing 100 parts by mass or more of (E) filler based on 100 parts by mass of the polymerizable monomer was judged to be good when greater than 100 MPa, acceptable when 80 - 100 MPa, and insufficient when less than 80 MPa. The flexural strength of the type 1 and type 2 photocurable compositions containing less than 100 parts by mass of (E) filler based on 100 parts by mass of the polymerizable monomer was judged to be good when greater than 90 MPa, acceptable when 60 - 90 MPa, and insufficient when less than 60 MPa. Since the flexural strength varies depending on the blending amount of the filler, different criteria were set.

[0141] (2) Environmental light stability The height of the dental lamp (Luna-Vue S manufactured by Morita Manufacturing Co., Ltd.) was adjusted using an illuminometer so that light with an illuminance of 8000 ± 1000 lx was incident on the sample placement part. After placing a slide glass (26×16 mm, thickness 2 mm) on a glass leveling plate covered with dull black paper, about 30 mg of the sample was collected on it. After exposing the sample at the sample placement part for 60 ± 5 seconds, the sample was taken out from the sample placement part, and immediately another slide glass was pressed against the sample to form a thin layer. If the state of the sample at this time did not maintain a physically uniform state, it was determined that curing had started, and the time until curing was evaluated in 5-second increments. The longer this time is, the more preferable it is because the time from taking the composition out of the light-shielding container to application is longer. The environmental light stability was judged to be good when more than 90 seconds, acceptable when 60 - 90 seconds, and insufficient when less than 60 seconds.

[0142] (3) Hardening depth One side of a cylindrical mold made of stainless steel with a hole of 12 mm in length and 4 mm in diameter was covered with a cover glass, and the prepared photocurable composition was filled in. After filling the photocurable composition into the mold and covering it with the cover glass, it was rubbed and then irradiated with light for 20 seconds using a photopolymerization irradiator (Grip Light II: manufactured by Matsuura) from above the cover glass to cure it. After taking out the cured product from the mold, the height of the cured product was measured with a micrometer, and half of the obtained value was taken as the hardening depth. The measurement of the cured product was carried out within 1 minute after the light irradiation. It was judged that a hardening depth of more than 4 mm was good, 3.5 - 4 mm was acceptable, and less than 3.5 mm was insufficient. The larger the hardening depth, the more preferable it is because it can be cured deeper.

[0143] (4) Thermal color stability Each of the prepared photocurable compositions was filled in a stainless steel mold (15φ×1 mm: disc-shaped), and then a cover glass was placed on top and pressed using a glass plate. After irradiating with light for 1 minute using a photopolymerization irradiator (Grip Light II: manufactured by Matsuura) from above the cover glass to cure it, and taking out the cured product from the mold, the cover glass was removed, and the color tone of this specimen was measured. The color measurement was carried out by placing the specimen on the background of a standard white plate (D65 / 10° X = 81.07, Y = 86.15, Z = 93.38) and using a spectrocolorimeter (manufactured by BYK-Chemie) under predetermined constant conditions (light source: C, viewing angle: 2°, measurement area: 11 mm). Then, the specimen was immersed in a container containing 10 mL of water in a thermostat set at 70°C and left standing for one week, and then the color tone of the specimen was measured again, and the color change difference was expressed by 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 dipping and standing, L2* is the lightness index after dipping and standing, a1* and b1* are the color quality indices before dipping and standing, and a2* and b2* are the color quality indices after dipping and standing. Since those with ΔE less than 5 are considered good as A, those with ΔE between 5 and 10 are considered adaptable as B, and those with ΔE exceeding 10 are judged as insufficient as C. The thermal color stability is carried out to predict the color tone change when the cured body is used for a long time. The smaller the ΔE, the smaller the color change when the cured body is used for a long time.

[0144] (5) Photochromic stability After filling the prepared photocurable composition into a stainless steel mold (15φ × 1 mm: disk-shaped) respectively, a cover glass was placed from above and pressed using a glass plate. Using a photopolymerization irradiator (Grip Light II: manufactured by Matsuura) from above the cover glass, light irradiation was performed for 1 minute to cure it. After taking out the cured product from the mold, the cover glass was removed, and the color tone of this specimen was measured. For color measurement, the specimen was placed on the background of a standard white plate (D65 / 10° X = 81.07, Y = 86.15, Z = 93.38), and it was carried out under predetermined fixed conditions (light source: C, viewing angle: 2°, measurement area: 11 mm) using a spectrophotometer (manufactured by BYK-Chemie). Then, after exposing the specimen to xenon lamp light for 24 hours using a xenon lamp light exposure tester (Sun Test CPS+), the color tone of the specimen was measured again, and the color change difference was represented by 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 chromaticity indices before light exposure, and a2* and b2* are the chromaticity indices after light exposure. Those with ΔE less than 5 were judged to be good, those with ΔE between 5 and 10 were judged to be acceptable, and those with ΔE exceeding 10 were judged to be insufficient. The light color stability was carried out to predict the color tone change when the cured body was used for a long time at the exposed part. The smaller the ΔE, the smaller the color change of the cured body even after long-term exposure.

[0145] The results in Tables 8 to 14 will be described.

[0146]

Table 8

[0147]

Table 9

[0148]

Table 10

[0149]

Table 11

[0150]

Table 12

[0151]

Table 13

[0152]

Table 14

[0153] The composition described in the examples was confirmed to have sufficient flexural strength and good curing depth.

[0154] When the amount of the amine compound represented by the formula (1) of (D-1) is less than 0.1 part by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer, as in Examples A1, A9, A12, B1, B9, and B12, the flexural strength and the curing depth were slightly inferior. When the amount of the amine compound represented by the formula (1) of (D-1) was more than 10 parts by mass, as in Examples A3, A10, A11, B3, B10, and B11, the environmental light stability tended to be slightly inferior. In Examples A55 and B42 containing DMBE as a photopolymerization accelerator, a decrease in environmental light stability and a decrease in photochromic stability occurred. However, in the compositions containing an ultraviolet absorber simultaneously, such as Examples A60, A66, and B47, although the environmental light stability decreased, the decrease in photochromic stability was suppressed. Further, the compositions containing MDEOA or TEA, which are amine compounds having two or more primary hydroxy groups in the molecule, as in Examples A57, A58, B44, and B45, tended to be slightly inferior in thermochromic stability. Regardless of the photopolymerization accelerator, Examples B14 to B17, which are compositions containing an amine compound having two or more primary hydroxy groups, such as DEPT, as a chemical polymerization accelerator, also tended to be slightly inferior in thermochromic stability.

[0155] Among the compositions containing only the amine compound having one substituent represented by the formula (2) among the amine compounds represented by the formula (1) of (D-1), as in Examples A28 to A31, A34 to A37, B28 to B31, and B34 to B37, the compositions containing the amine compound having two or more substituents represented by the formula (2) tended to have a higher curing depth.

[0156] Among the compositions containing the amine compound represented by the formula (1) of (D-1), as in Examples A34, A39, A40, B34, B39, and B40, the compositions containing an aromatic amine compound tended to be slightly inferior in photochromic stability to the compositions containing an aliphatic amine compound.

[0157] Compositions such as Example A8 and B8, which contain more than 1 part by mass of (B) photosensitizer with respect to 100 parts by mass of the total amount of the polymerizable monomer (A), tended to be slightly inferior in environmental light stability and light color stability. Compositions such as Example A7, A12, B7, and B12, which contained less than 0.01 part by mass of (B) photosensitizer with respect to 100 parts by mass of the total amount of the polymerizable monomer (A), tended to be slightly inferior in flexural strength and curing depth. In addition, Example A53, which used only BAPO instead of an α-diketone compound as (B) photosensitizer, tended to be slightly inferior in flexural strength and curing depth.

[0158] Compositions such as Example A6, A79, B6, and B51, which contained 10 parts by mass or more of (C) photoacid generator with respect to 100 parts by mass of the total amount of the polymerizable monomer (A), tended to have a decrease in environmental light stability, and were slightly inferior in light color stability and thermal color stability. Compositions such as Example A5, A12, B5, and B12, which contained less than 0.01 part by mass of (C) photoacid generator, tended to be slightly inferior in flexural strength and curing depth. Furthermore, Examples A23 to A27 and B19, B23 to B27, which were compositions containing an aryl iodonium salt compound or a triazine compound with an anion having no organic group such as C11 to C15 as the photoacid generator, tended to be slightly inferior in light color stability.

[0159] Comparative Examples CA1 and CB1 did not cure or had extremely low flexural strength and curing depth because they did not contain (B) photosensitizer. Comparative Examples CA2, CA6, CB2, and CB6 had extremely low flexural strength and curing depth because they did not contain (C) photoacid generator. Comparative Examples CA3 to CA5 and CB3 to CB5 had extremely low flexural strength and curing depth because they did not contain (D) photopolymerization accelerator. Comparative Examples CA6 to 10 and CB6 to 11 had extremely low curing depth because they did not contain the amine compound represented by formula (1) of (D-1).

[0160] The photocurable composition of the present invention evaluated in the examples can be used without any problems in any known photocurable composition. The photocurable composition is a dental material, a printing plate-making material, a photoresist material, and can be preferably used particularly in a photocurable composition which is a dental material. The dental photocurable composition includes a dental adhesive, a dental primer, a dental composite resin, a dental abutment building material, a dental resin cement, a dental coating material, a dental pit and fissure sealing material, a dental manicure material, a dental room temperature polymerizable resin, a dental loose tooth fixing adhesive, a dental glass ionomer cement, a dental hard resin, a dental cutting material, a dental 3D printer material, and the like.

Industrial Applicability

[0161] According to the present invention, a photocurable composition having a high curing depth can be provided.

Claims

1. A photocurable composition comprising (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, wherein (D) the photopolymerization accelerator contains (D-1) an amine compound represented by formula (1), and the photocurable composition wherein the amine compound represented by formula (1) is an aliphatic tertiary amine. [Formula (1)] 【Chemical 1】 (In formula (1), R １ is a substituent represented by formula (2), R ２ and R ３ are substituents represented by formula (2), or a -OH group, -O- group, -S- group, -NH-C(O)-NH- group, -C(O)-O- group, -O-C(O)- group, -O-C(O)-NH- group, -NH-C(O)-O- group, halogen, an organic group which may have an alkoxysilyl group, an aromatic ring which may have a substituent or an alicyclic heterocyclic ring which may have a substituent. However, when at least one or more of R ４ in formula (2) is an aromatic ring, R ２ and R ３ may be H, and when R ２ is a substituent represented by formula (2), R ３ may be H.) [Formula (2)] [Chemical Formula 2] (In formula (2), X is C or N, and two or more X's are not N. When X is N, R that binds to N does not exist. R is a hydrocarbon chain, an aromatic ring, or H, and they may be the same as or different from each other. R is an organic group that may have an -OH group, an -O- group, an -S- group, an -NH-C(O)-NH- group, a -C(O)-O- group, an -O-C(O)- group, an -O-C(O)-NH- group, or an -NH-C(O)-O- group, a halogen, or H, and they may be the same as or different from each other.) ５ does not exist. R ４ is a hydrocarbon chain, an aromatic ring, or H, and may be the same as or different from each other. R ５ is an organic group that may have an -OH group, an -O- group, an -S- group, an -NH-C(O)-NH- group, a -C(O)-O- group, an -O-C(O)- group, an -O-C(O)-NH- group, or an -NH-C(O)-O- group, a halogen, or H, and may be the same as or different from each other.)

2. R in formula (1) ２ is a substituent represented by formula (2). The photocurable composition according to claim 1, comprising an amine compound represented by formula (1) (D-1).

3. wherein (C) the photoacid generator contains an aryliodonium salt, and the aryliodonium salt is a salt of an anion having an organic group and one or more atoms of P, B, Al, S, or Ga and an aryliodonium cation, and the photocurable composition according to any one of Claims 1 to 2.

4. wherein (C) the photoacid generator contains an aryliodonium salt, and the aryliodonium salt is a salt of an anion having an organic group in which at least one or more H's are substituted with F and one or more atoms of P, B, Al, S, or Ga and an aryliodonium cation, and the photocurable composition according to any one of Claims 1 to 3.

5. The photocurable composition according to any one of Claims 1 to 4, wherein (B) the photosensitizer contains (B-1) an α-diketone compound and is used for dental applications.

6. The photocurable composition according to any one of Claims 1 to 5, which is a one-component type or a two-component type for dental use.

7. A one-component type photocurable composition, wherein, based on 100 parts by mass of (A) the polymerizable monomer, it contains 0.001 to 1 part by mass of (B) the photosensitizer, it contains 0.01 to 10 parts by mass of (C) the photoacid generator, and it contains 0.01 to 20 parts by mass of (D-1) the amine compound represented by formula (1), and the photocurable composition according to any one of Claims 1 to 5.

8. A two-component type photocurable composition, comprising a first paste and a second paste, wherein the mass ratio of the first paste to the second paste is 1:0.8 to 1.2, and based on a total of 200 parts by mass of (A) the polymerizable monomer contained in the first paste and the second paste, it contains 0.002 to 2 parts by mass of (B) the photosensitizer, it contains 0.02 to 20 parts by mass of (C) the photoacid generator, and it contains 0.02 to 40 parts by mass of (D-1) the amine compound represented by formula (1), and the photocurable composition according to any one of Claims 1 to 5.

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