Dental photocurable components

Abstract

To provide a dental photocurable composition having sufficient mechanical properties and excellent color tone stability.SOLUTION: A dental photocurable composition contains (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, (D) a photopolymerization accelerator. The (C) photoacid generator (C1) includes an iodonium salt compound having a structure represented by formula (1). Relative to the (A) polymerizable monomer 100 pts.mass, the content of the iodonium salt compound having the structure represented by formula (1) is 0.5 pt.mass or more. [Formula (1)] (where R1 and R2 each denote an organic group, where there may be a plurality of R1 and R2. All organic groups constituting R1 and R2 as substituents include carbon atoms of 6 more in total).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a dental light-curable composition. [Background technology]

[0002] In the dental field, dental photocurable compositions are used for oral treatment and are applied to dental adhesives, dental composite resins, dental core construction materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicure materials, dental materials for fixing loose teeth, dental glass ionomer cements, dental cutting materials, and dental 3D printer materials.

[0003] Patent Documents 1 and 2 propose a photopolymerization initiator comprising a photoacid generator (a triazine compound or a specific aryliodonium salt), a sensitizer, and an electron donor compound. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 4093974 [Patent Document 2] Patent No. 4596786 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the dental photocurable compositions using the conventional photopolymerization initiators described in Patent Documents 1 and 2 have had a problem in achieving both mechanical strength and color stability.

[0006] An object of the present invention is to provide a dental photocurable composition having excellent mechanical properties and good color stability. [Means for solving the problem]

[0007] The dental photocurable composition of the present invention comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, wherein the (C) photoacid generator comprises (C1) an iodonium salt compound having a structure represented by formula (1), and the dental photocurable composition comprises 0.5 parts by mass or more of the iodonium salt compound having a structure represented by formula (1) per 100 parts by mass of the (A) polymerizable monomer. [Formula (1)] [ka] (In the formula, R1 and R2 are organic groups, and a plurality of R1 and R2 may be present. The total number of carbon atoms in the organic groups constituting all of the R1 and R2 substituents is 6 or more.) [Effects of the Invention]

[0008] The dental photocurable composition of the present invention exhibits excellent mechanical properties and good color stability. DETAILED DESCRIPTION OF THE INVENTION

[0009] In the present invention, the total number of carbon atoms in the organic groups constituting R1 and R2 of the iodonium salt compound having the structure represented by formula (1) (C1) can be 8 or more.

[0010] In the present invention, R1 and / or R2 of the iodonium salt compound having the structure represented by formula (1) (C1) can be an organic group having an alkyl chain with 8 or more carbon atoms.

[0011] In the present invention, (C1) an iodonium salt compound having a structure represented by formula (1) can be contained in an amount of 1 part by mass or more per 100 parts by mass of (A) polymerizable monomer.

[0012] In the present invention, the anion of the iodonium salt compound having the structure represented by formula (1) (C1) can be an anion having an organic group.

[0013] In the present invention, the anion of the iodonium salt compound having the structure represented by formula (1) (C1) can have an organic group in which at least one H is substituted with F, and one or more atoms of P, B, Al, S, and Ga.

[0014] In the present invention, (D1) a tertiary aliphatic amine compound having no primary hydroxy group at the α-position carbon and / or β-position carbon of N can be contained as the photopolymerization accelerator (D).

[0015] In the present invention, the photopolymerization accelerator (D) may be substantially free of an aromatic amine compound.

[0016] In the present invention, the (D) photopolymerization accelerator may substantially not contain a tertiary amine compound having a primary hydroxy group at the α-position carbon and / or β-position carbon starting from an amine-derived N atom.

[0017] In the present invention, the composition may be substantially free of water and organic solvents.

[0018] In the present invention, a dental photocurable composition (A) relative to 100 parts by mass of the polymerizable monomer, (B) 0.02 to 1 parts by mass of a photosensitizer (C1) 0.5 to 10 parts by mass of an iodonium salt compound having a structure represented by formula (1) (D) 0.1 to 10 parts by mass of a photopolymerization accelerator may include:

[0019] Each component of the dental photocurable composition of the present invention will be described in detail below. The dental photocurable composition of the present invention is applied as a dental adhesive, 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 adhesive for fixing loose teeth, a dental glass ionomer cement, a dental hard resin, a dental cutting material, a dental 3D printer material, etc.

[0020] In clinical dentistry, various treatments are performed to restore the aesthetic and functional appearance of teeth missing due to caries, fractures, etc., using direct methods, such as restoration with dental adhesives and composite resins, and indirect methods, such as restoration with prosthetic devices made of ceramics or dental hard resins using dental resin cement. In addition, dental adhesives are used to attach dental composite resins to various dental materials and natural teeth, dental adhesives for fixing loose teeth, dental coating materials to protect sensitive and formed vital teeth from external irritation and secondary caries, dental pit and fissure sealants to prevent caries by filling deep fissures in molars, dental nail polish to temporarily restore aesthetics by masking tooth discoloration, and dental core buildup materials to form abutment teeth when the crown of a tooth has collapsed due to caries. In recent years, new composite materials have been developed, such as dental cutting materials for creating prosthetic devices using CAD / CAM processing and dental 3D printing materials for creating prosthetic devices using 3D printers, and a variety of dental materials are used in treatment. These materials are prepared into a uniform paste by mixing a resin matrix consisting of several types of polymerizable monomers, various fillers such as inorganic fillers and organic-inorganic composite fillers, and a polymerization initiator, depending on the application. To cite some examples, dental filling composite resins are filled into teeth in an uncured paste state, and then shaped to the anatomical shape of natural teeth using dental instruments and other dental tools. They are then cured by exposure to light using a dental light curing device or similar device. The light emitted from the light curing device generally has a wavelength range of approximately 360 to 500 nm and an intensity of 100 to 2000 mW / cm. 2 On the other hand, dental resin cement is used to bond a prosthetic device to a cavity or an abutment tooth, and is hardened by irradiating it with light after the prosthetic device is attached to the cavity or the abutment tooth.

[0021] Photopolymerization initiators used in such dental materials include photosensitizers and systems combining photosensitizers with appropriate photopolymerization accelerators. Known photosensitizers include acylphosphine oxide compounds and α-diketone compounds. α-diketone compounds, in particular, have the ability to initiate polymerization in the visible light wavelength range, which has minimal impact on the human body. Tertiary amine compounds are also well known as polymerization accelerators combined with photosensitizers. The combination of an α-diketone compound and a tertiary amine compound has high polymerization activity when exposed to light, and is therefore used in the dental material field. Dental photocurable compositions containing such photopolymerization initiators exhibit excellent mechanical properties, such as hardness, flexural strength, and compressive strength, required for various materials.

[0022] However, when the above-mentioned combination of α-diketone compounds and tertiary amine compounds is used as a photopolymerization initiator, the problem of poor ambient light stability arises. In other words, although the procedure is performed under white light (ambient light) such as a dental light used by the surgeon to illuminate the oral cavity or indoor light such as a fluorescent lamp, when the above-mentioned combination of α-diketone compounds and tertiary amine compounds is used alone as a photopolymerization initiator, it exhibits high sensitivity not only to the irradiated light but also to ambient light, resulting in gradual curing during operations such as filling, building up, and fitting, which increases the viscosity of the paste and makes operation difficult.

[0023] In order to solve the above problems, a photopolymerization initiator comprising an aryl iodonium salt, which is a photoacid generator, a sensitizer, and an electron donor compound has been proposed, but this has resulted in problems with the color stability of dental photocurable compositions.

[0024] The present inventors have found that the dental photocurable composition of the present invention exhibits excellent color stability when a photoacid generator with a specific structure is used, and furthermore, that the use of a specific amount of the photoacid generator results in excellent mechanical strength, leading to the present invention.

[0025] [(A) Polymerizable Monomer] The polymerizable monomer (A) contained in the dental photocurable composition of the present invention can be any known polymerizable monomer. In the polymerizable monomer or compound having a polymerizable group described in the present invention, the polymerizable group preferably exhibits radical polymerization. Specifically, from the viewpoint of ease of radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. In this specification, "(meth)acrylic" refers to acrylic and / or methacrylic, "(meth)acryloyl" refers to acryloyl and / or methacryloyl, "(meth)acrylate" refers to acrylate and / or methacrylate, and "(meth)acrylamide" refers to acrylamide and / or methacrylamide. Polymerizable monomers having a substituent at the α-position of the acrylic and / or acrylamide group are also preferred. Examples of suitable polymerizable monomers include those having one radically polymerizable group, two radically polymerizable groups, three or more radically polymerizable groups, an acidic group, an alkoxysilyl group, and a sulfur atom.

[0026] Specific examples of polymerizable monomers having one radically 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, and (meth)acrylamide.

[0027] Specific examples of polymerizable monomers having two radical 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)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2-(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxydiethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyditriethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitate, glycerol di(meth)acrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate , triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,Examples include 4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA") and 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane.

[0028] Specific examples of polymerizable monomers having three or more radically polymerizable groups and no acidic group include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, and 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane.

[0029] The polymerizable monomer having an acidic group can be used without limitation as long as it has one or more polymerizable groups and at least one acidic group such as a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonate group, a sulfonic acid group, a carboxylic acid group, etc. By including a polymerizable monomer having an acidic group, it is possible to impart adhesiveness to tooth structures and prosthetic devices.

[0030] Specific examples of the polymerizable monomer having a phosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyhexyl dihydrogen phosphate, 9-(meth)acryloyloxyheptyl dihydrogen phosphate, 10-(meth)acryloyloxyhexyl dihydrogen phosphate, 11-(meth)acryloyloxyhexyl dihydrogen phosphate, 12-(meth)acryloyloxyhexyl dihydrogen phosphate, 13-(meth)acryloyloxyhexyl dihydrogen phosphate, 14-(meth)acryloyloxyhexyl dihydrogen phosphate, 15-(meth)acryloyloxyhexyl dihydrogen phosphate, 16-(meth)acryloyloxyhexyl dihydrogen phosphate, 17-(meth)acryloyloxyheptyl dihydrogen phosphate, 18-(meth)acryloyloxyhexyl dihydrogen phosphate, 19-(meth)acryloyloxyhexyl dihydrogen phosphate, 20-(meth)acryloyloxyhexyl dihydrogen phosphate, 21-(meth)acryloyloxyhexyl dihydrogen phosphate, 22-(meth)acryloyloxyhexyl dihydrogen phosphate, 23-(meth)acryloyloxyhexyl dihydrogen phosphate, 24-(meth)acryloyloxyhexyl dihydrogen phosphate, 25-(meth)acryloyloxyhexyl dihydrogen phosphate, 26-(meth)acryloyloxyhexyl dihydrogen phosphate, 27- 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 phosphate, bis[2-(meth)acryloyloxyethyl]hydrogenphosphate, bis[4-(meth)acryloyloxybutyl]hydrogenphosphate, bis[6-(meth)acryloyloxyhexyl]hydrogenphosphate, bis[8-(meth)acryloyloxyoctyl]hydrogenphosphate, bis[9-(meth)acryloyloxynonyl]hydrogenphosphate, bis[10-(meth)acryloyloxydecyl]hydrogenphosphate, 1,3-di( Examples thereof include 2-(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, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0031] Specific examples of polymerizable monomers having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0032] Specific examples of polymerizable monomers 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, and 9-(meth)acryloyloxy. Examples of suitable thiophosphates include 1-(meth)acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, and 20-(meth)acryloyloxyicosyl dihydrogen thiophosphate; their acid chlorides, alkali metal salts, and ammonium salts; and (meth)acrylamide compounds in which the ester bond in these compounds is replaced with an amide bond. Polymerizable monomers having a thiophosphate group are also classified as polymerizable monomers having a sulfur atom.

[0033] 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, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0034] Specific examples of polymerizable monomers having a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid and 2-sulfoethyl(meth)acrylate.

[0035] Polymerizable monomers having a carboxylic acid group are classified into (meth)acrylic compounds having one carboxyl group in the molecule and (meth)acrylic compounds having multiple carboxyl groups in the molecule. Specific examples of (meth)acrylic compounds having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)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, and 4-(meth)acryloyloxybenzoic acid. Examples of the acryloyloxybenzoic acid include 2-(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, and 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.Specific examples of the (meth)acrylic compound having multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, 4 ...4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth Examples thereof include acryloyloxyethyl trimellitate, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate; acid anhydrides and acid halides thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0036] Preferably, 10-methacryloyloxydecyl dihydrogen phosphate or 6-methacryloxyhexyl phosphonoacetate is used. The amount of the polymerizable monomer having an acidic group is 1 part by mass or more, more preferably 10 parts by mass or more, per 100 parts by mass of the total amount of polymerizable monomers contained in the dental photocurable composition, from the viewpoint of imparting adhesiveness. If the amount is less than 1 part by mass, sufficient adhesiveness to tooth structure, metals, and metal oxides may not be exhibited.

[0037] Specific examples of polymerizable monomers having an alkoxysilyl group include (meth)acrylic compounds and (meth)acrylamide compounds having one alkoxysilyl group in the molecule, and (meth)acrylic compounds and (meth)acrylamide compounds having multiple alkoxysilyl groups in the molecule. Examples of the silane include 2-(meth)acryloxyethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane, 5-(meth)acryloxypentyltrimethoxysilane, 6-(meth)acryloxyhexyltrimethoxysilane, 7-(meth)acryloxyheptyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 9-(meth)acryloxynonyltrimethoxysilane, 10-(meth)acryloxydecyltrimethoxysilane, and 11-(meth)acryloxyundecyltrimethoxysilane.Furthermore, examples of compounds having a urethane group or an ether group include 3,3-dimethoxy-8,37-dioxo-2,9,36-trioxa-7,38-diaza-3-silatetracontan-40-yl(meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,18-trioxa-7-aza-3-silanonadecan-19-oyl)amino)-2-methylpropane-1,3-diyldi(meth)acrylate, and 3,3-dimethoxy-8,19-dioxo-2,9,18-trioxa-7,20-diaza-3-siladocosan-22-yl(meth)acrylate. acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21-hexaoxa-7,23-diaza-3-silapentacosan-25-yl(meth)acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21,26-heptaoxa-7,23-diaza-3-silaoctacosan-28-yl(meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18-pentaoxa-7,20-diaza-3-siladocosan-22-yl(meth)acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21,26-heptaoxa-7,23-diaza-3-silaoctacosan-28-yl(meth)acrylate 2-((3,3-dimethoxy-8-oxo-2,9,12,15,18-pentaoxa-7-aza-3-silanonadecan-19-yl)amino)-2-methylpropane-1,3-diyldi(meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosan-23-yl(meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosan-23-yl(meth)acrylate 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silahexacosan-26-yl (meth)acrylate, 4,4-diethoxy-13-oxo-3,12,17-trioxa-14-aza-4-silanonadecan-19-yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silaicosan-20-yl (meth)acrylate, 2-methyl-2-((11-(triethoxysilyl)undecyloxy)carbonylamino)propane-1,3-diyl di(meth)acrylate.

[0038] The dental photocurable composition of the present invention may contain a sulfur-containing polymerizable monomer (A) to impart adhesion to precious metals. Known compounds containing one or more sulfur atoms and a polymerizable group can be used without limitation. Specifically, the sulfur-containing polymerizable monomer refers to compounds having partial structures such as -SH, -SS-, >C=S, >CSC<, and >P=S, or compounds resulting from tautomerization. Specific examples include 10-methacryloxydecyl-6,8-dithiooctanate, 6-methacryloxyhexyl-6,8-dithiooctanate, 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate, 2-(11-methacryloyloxyundecylthio)-5-mercapto-1,3,4-thiadiazole, and 10-(meth)acryloyloxydecyl dihydrogen thiophosphate.

[0039] In addition to these polymerizable monomers, oligomers or prepolymers having at least one polymerizable group in the molecule may be used without any limitation. Furthermore, there is no problem even if the same molecule has a substituent such as a fluoro group. The above-described polymerizable monomers may be used alone or in combination.

[0040] The dental photocurable composition of the present invention may contain a silane coupling agent as a polymerizable monomer (A) to impart adhesion to glass ceramics. While any known silane coupling agent can be used without limitation, preferred are 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, and 11-methacryloxyundecyltrimethoxysilane. To impart adhesion, the silane coupling agent is blended in an amount of at least 1 part by mass, more preferably at least 5 parts by mass but less than 20 parts by mass, per 100 parts by mass of the total polymerizable monomers in the composition. Because the silane coupling agent as a polymerizable monomer is intended to impart adhesion to glass ceramics and resin materials containing glass ceramic fillers, it is blended separately from the surface treatment agent for the filler.

[0041] The dental photocurable composition of the present invention may contain a polymerizable monomer having a sulfur atom as polymerizable monomer (A) to impart adhesiveness to precious metals. From the viewpoint of imparting adhesiveness, the blending amount of the polymerizable monomer having a sulfur atom is 0.01 parts by mass or more, more preferably 0.1 parts by mass or more but less than 20 parts by mass, based on 100 parts by mass of the total amount of polymerizable monomers contained in the dental photocurable composition.

[0042] Although there is no problem if the polymerizable monomer contained in the dental photocurable composition of the present invention contains a polymerizable monomer having a cationically polymerizable functional group, it is preferable that the composition contains only polymerizable monomers having a radically polymerizable functional group.

[0043] <Photopolymerization initiator> The dental photocurable composition of the present invention contains a photopolymerization initiator. A photopolymerization initiator is a polymerization initiator that can initiate polymerization by irradiating light. The photopolymerization initiator used in the dental photocurable composition of the present invention includes (B) a photosensitizer, (C) a photoacid generator, and (D) a polymerization accelerator, but these are not particularly limited, and commonly used known compounds can be used without any restrictions.

[0044] [(B) Photosensitizer] Specific examples of the photosensitizer (B) that can be used in the present invention include α-diketones such as benzil, camphorquinone, camphorquinonecarboxylic acid, camphorquinonesulfonic acid, α-naphthyl, acetonaphthene, p,p'-dimethoxybenzyl, p,p'-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, and naphthoquinone; benzoins such as benzoin methyl ether and benzoin ethyl ether; Alkyl ethers, thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone, benzophenones such as benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, and 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 Bis(2,6-diethoxybenzoyl)(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-dimethoxy 2,6-Dimethoxybenzoylbenzyl phosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropyl phosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethyl phosphine oxide, 2,6-dimethoxybenzoylbenzyl butyl phosphine oxide, 2,6-dimethoxybenzoylbenzyl octyl phosphine oxide, bis(2,4,6-trimethylbenzoyl) isobutyl phosphine oxide and 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl acylphosphine oxides such as n-butylphosphine oxide, acylgermanium compounds such as bisbenzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis(4-methoxybenzoyl)dimethylgermanium, and bis(4-methoxybenzoyl)diethylgermanium, 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-2, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-3, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-4, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-5, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-6, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-7, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-8, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-9, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-1 ...1, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-2, 2-benzyl α-aminoacetophenones such as α-propanone-1; ketals such as benzil dimethyl ketal, benzil diethyl ketal, and benzil (2-methoxyethyl ketal); and titanocenes such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]-titanium, bis(cyclopentadienyl)-bis(pentanefluorophenyl)-titanium, and bis(cyclopentadienyl)-bis(2,3,5,6-tetrafluoro-4-disiloxyphenyl)-titanium.

[0045] (B) The photosensitizer can be appropriately selected depending on the wavelength, intensity, and irradiation time of the light used for polymerization, as well as the types and amounts of other components to be combined. The photosensitizers can be used alone or in combination of two or more. Among these, α-diketone compounds having a maximum absorption wavelength in the visible light region are preferably used, and camphorquinone compounds such as camphorquinone, camphorquinonecarboxylic acid, and camphorquinonesulfonic acid are more preferred. Camphorquinone is particularly preferred because of its easy availability.

[0046] The photosensitizer (B) contained in the dental photocurable composition of the present invention may be an α-diketone compound alone, which may result in excellent ambient light stability and color tone of the cured product.

[0047] Typically, the amount of (B) photosensitizer is preferably 0.02 to 1.0 part by mass, more preferably 0.05 to 0.5 part by mass, per 100 parts by mass of the total amount of (A) polymerizable monomer contained in the dental photocurable composition. If the amount of (B) photosensitizer is less than 0.02 part by mass, the polymerization activity with respect to the irradiated light is poor, resulting in insufficient curing. If the amount is more than 1.0 part by mass, sufficient curing is achieved, but the ambient light stability and light color stability may be reduced.

[0048] [(C) Photoacid generator] The dental photocurable composition of the present invention contains (C) an iodonium salt compound having a structure represented by formula (1) as a photoacid generator. In the dental photocurable composition of the present invention, other known photoacid generators can be used without limitation together with the iodonium salt compound having a structure represented by formula (1) (C1). Specific examples include triazine compounds, iodonium salt compounds, sulfonium salt compounds, and sulfonate ester compounds. Among these, triazine compounds and iodonium salt compounds are preferred because of their high polymerizability when used in combination with a sensitizer. Iodonium salt compounds are more preferred. Iodonium salt compounds are easily sensitized by photosensitizers that absorb light in the visible light region.

[0049] 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, and 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine. 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine s(trichloromethyl)-s-triazine, 2-[2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4, 6-bis(trichloromethyl)-s-triazine, 2-(1-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis(2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,6-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. Of these, 2,4,6-tris(trichloromethyl)-s-triazine is preferred.

[0050] Any known iodonium salt compound can be used. To give a specific example, the structural formula of an iodonium salt compound can be represented by the following formula (2): [Formula (2)] [(R1)2I] + [A] - (In the formula [(R1)2I] + is the cationic moiety, [A] - is an anion moiety, and R1 in formula (2) 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, which may be substituted with at least one selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogen.

[0051] 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.

[0052] Examples of heterocyclic groups having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 heteroatoms such as oxygen, nitrogen, and sulfur, which may be the same or different. Specific examples include monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, and pyrazinyl, and fused polycyclic heterocyclic groups such as indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl.

[0053] Specific examples of the alkyl group having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl, and octadecyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0054] Specific examples of alkenyl groups having 2 to 30 carbon atoms include straight-chain or branched ones such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 1-methyl-1-propenyl.

[0055] Furthermore, specific examples of the alkynyl group having 2 to 30 carbon atoms include straight-chain or branched ones such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl, and 1-methyl-2-propynyl.

[0056] The above-mentioned aryl group having 6 to 30 carbon atoms, heterocyclic group having 4 to 30 carbon atoms, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, or alkynyl group having 2 to 30 carbon atoms may 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, and octadecyl; branched alkyl groups having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, and tert-butyl; cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; hydroxy groups; linear or branched alkoxy groups having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and dodecyloxy; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, and octadecyl. Straight-chain or branched alkylcarbonyl groups having 2 to 18 carbon atoms, such as octanoyl; arylcarbonyl groups having 7 to 11 carbon atoms, such as benzoyl and naphthoyl; straight-chain or branched alkoxycarbonyl groups having 2 to 19 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, and tert-butoxycarbonyl; phenoxycarbonyl aryloxycarbonyl groups having 7 to 11 carbon atoms, such as phenylthiocarbonyl and naphthoxythiocarbonyl; arylthiocarbonyl groups having 7 to 11 carbon atoms, such as phenylthiocarbonyl and naphthoxythiocarbonyl; linear or branched acyloxy groups having 2 to 19 carbon atoms, such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, and octadecylcarbonyloxy;Arylthio groups having 6 to 20 carbon atoms, such as phenylthio, biphenylylthio, methylphenylthio, chlorophenylthio, bromophenylthio, fluorophenylthio, hydroxyphenylthio, methoxyphenylthio, naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl-chlorophenylthio, 4-benzoyl-methylthiophenylthio, 4-(methylthiobenzoyl)phenylthio, and 4-(ptert-butylbenzoyl)phenylthio; straight-chain or branched alkylthio groups having 1 to 18 carbon atoms, such as methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, and dodecylthio; phenylthio aryl groups having 6 to 10 carbon atoms, such as phenyl, tolyl, dimethylphenyl, and naphthyl; heterocyclic groups having 4 to 20 carbon atoms, such as thienyl, furanyl, pyranyl, xanthenyl, chromanyl, isochromanyl, xanthonyl, thioxanthonyl, and dibenzofuranyl; aryloxy groups having 6 to 10 carbon atoms, such as phenoxy and naphthyloxy; linear or branched alkylsulfinyl groups having 1 to 18 carbon atoms, such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, and octylsulfinyl; arylsulfinyl groups having 6 to 10 carbon atoms, such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl; linear or branched alkylsulfonyl groups having 1 to 18 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and octylsulfonyl; Examples include arylsulfonyl groups having 6 to 10 carbon atoms, such as phenylsulfonyl, tolylsulfonyl (tosyl), and naphthylsulfonyl; alkyleneoxy groups; cyano groups; nitro groups; and halogens such as fluorine, chlorine, bromine, and iodine.

[0057] Among iodonium salt compounds, aryliodonium salts are preferred because of their high stability. Furthermore, the aryl group preferably has a substituent to improve liposolubility. Specifically, linear alkyl groups such as methyl, propyl, octyl, decyl, undecyl, dodecyl, and tridecyl, branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl, and functional groups in which one or more H atoms in these groups are replaced with F, perfluoroalkyl groups, and halogens are preferred as the substituent.

[0058] The structure of the anion moiety of the iodonium salt compound is not particularly limited, but examples include those containing atoms such as halogen, P, S, B, Al, and Ga. From a safety perspective, anions containing As or Sb can be used, but are not preferred for dental applications. Furthermore, the anion preferably contains an organic group such as an alkyl group, an alkoxy group, and / or an aryl group, and most preferably an organic group such as an alkyl group, an alkoxy group, and / or an aryl group in which at least one H is substituted with F. Iodonium salt compounds containing such an anion have high solubility in dental photocurable compositions, preventing precipitation during low-temperature storage or long-term storage, and dissolving in the composition in a short time, thereby shortening production time. Furthermore, iodonium salt compounds containing an anion containing an organic group such as an alkyl group, an alkoxy group, and / or an aryl group in which at least one H is substituted with F are expected to have even higher solubility. Precipitation of the photoacid generator is undesirable because it can cause a decrease in photocolor stability and bending strength. The anion having an organic group such as an alkyl group, an alkoxy group, and / or an aryl group in which at least one H may be substituted with F can be an anion having any atom, but from the viewpoints of versatility and safety, an anion having P, S, B, Al, or Ga is preferred.

[0059] Examples of anions having no alkyl group and / or alkoxy group and / or aryl group include halogens such as chloride and bromide, perhalogen acids such as perchloric acid, aromatic sulfonic acids such as p-toluenesulfonate, camphorsulfonic acid, nitrate, acetate, chloroacetate, carboxylate, phenolate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, etc. Among these, p-toluenesulfonate, camphorsulfonic acid, and carboxylate are preferably used.

[0060] [A] of the iodonium salt compound of formula (2) - The anion moiety of the iodonium salt compound of formula (2) 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 H is substituted with F, because this improves the solubility in the dental photocurable composition. - The alkyl group in the anion moiety preferably has 1 to 8 carbon atoms, and more preferably 1 to 4. Specific examples include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The ratio of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group (F / H) is 4 or more, and preferably the ratio of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group (F / H) is 9 or more. It is more preferable that all hydrogen atoms in the hydrocarbon are substituted with fluorine. The dental photocurable composition may contain an iodonium salt having an anion having an alkyl group with a different ratio of hydrogen atoms to fluorine atoms.

[0061] Specific examples of the alkyl group include straight-chain or branched perfluoroalkyl groups such as CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C.

[0062] [A] of the iodonium salt compound of formula (2) - The alkoxy group in the anion moiety preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples include linear alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentoxy, and octoxy, and branched alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy, and tert-butoxy. The ratio of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group (F / H) is 4 or more, and preferably the ratio of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group (F / H) is 9 or more. It is more preferable that all hydrogen atoms in the hydrocarbon are substituted with fluorine. The dental photocurable composition may contain an iodonium salt composed of an anion having an alkoxy group with a different ratio of hydrogen atoms to fluorine atoms.

[0063] 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, CF3CF2CF2CF2CF2CF2CF2CF2CF2CF2O.

[0064] [A] of the iodonium salt compound of formula (2) -The phenyl group in the anion moiety has at least one hydrogen atom substituted with a fluorine atom and / or an alkyl group and / or an alkoxy group substituted with a fluorine atom. The alkyl group and / or alkoxy group substituted with a fluorine atom are preferably those described above. Particularly preferred examples of the phenyl group include perfluorophenyl groups such as pentafluorophenyl (CF), trifluorophenyl (CHF), tetrafluorophenyl (CHF), trifluoromethylphenyl (CF), bis(trifluoromethyl)phenyl ((CF)CH), pentafluoroethylphenyl (CFCFCH), bis(pentafluoroethyl)phenyl ((CFCF)CH), trifluoromethylfluorophenyl (CFCHF), bistrifluoromethylfluorophenyl ((CF)CHF), pentafluoroethylfluorophenyl (CFCFCHF), and bispentafluoroethylfluorophenyl ((CFCF)CHF). The dental photocurable composition may contain an iodonium salt containing an anion having a phenyl group with a different ratio of hydrogen atoms to fluorine atoms.

[0065] [A] of the iodonium salt compound of formula (2) - A specific example of the anion portion 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] - Anions containing S include [(CF3SO2)3C] - , [(CF3CF2SO2)3C] - , [(CF3CF2CF2SO2)3C] - , [(CF3CF2CF2CF2SO2)3C] -, [CF3CF2CF2CF2SO3] - , [CF3CF2CF2SO3] - , [(CF3CF2SO2)3C] - , [(SO2CF3)3N] - , [(SO2CF2CF3]2N] - , [((CF3)C6H4)SO3] - , [SO3((CF2CF2CF2CF2)SO3] 2- Examples of anions containing B include [B(C6F5)4] - , [(C6H5)B((CF3)2C6H3)3] - , [(C6H5)B(C6F5)3] - Examples of Ga-containing anions include [((CF3)4Ga)] - , [Ga(C6F5)4] - Examples of anions containing Al include [((CF3)3CO)4Al] - , [((CF3CF2)3CO)4Al] - Examples include:

[0066] The dental photocurable composition of the present invention contains (C) an iodonium salt compound having a structure represented by formula (1) as a photoacid generator. [Formula (1)] [ka] (In the formula, R1 and R2 are organic groups, and a plurality of R1 and R2 may be present. The total number of carbon atoms in the organic groups constituting all of the R1 and R2 substituents is 6 or more.)

[0067] The structure of formula (1) represents the structure of a diaryliodonium cation, with the aryl group having substituents R1 and / or R2. In the structure of formula (1), R1 and R2 are organic groups. Dental light-curable compositions containing 0.5 parts by mass or more of an iodonium salt compound, in which the total carbon number of the organic groups constituting R1 and R2 is less than 6, per 100 parts by mass of polymerizable monomer (A) tend to have reduced color stability. More specifically, when subjected to immersion tests in high-temperature water simulating long-term use or light resistance tests to check the effects of discoloration due to light, the compositions tend to show significant discoloration, uneven coloring, and black spots, impairing aesthetics. On the other hand, we have found that dental photocurable compositions containing 0.5 parts by mass or more of a photoacid generator containing an iodonium salt compound in which the total carbon number of the organic groups constituting R1 and R2 is 6 or more per 100 parts by mass of polymerizable monomer (A) can maintain aesthetics without causing significant discoloration, uneven color, or black spots when subjected to immersion tests in high-temperature water and light resistance tests simulating long-term use, and can exhibit good mechanical strength.

[0068] In the iodonium salt compound having the structure represented by formula (1) (C1), R1 and R2 are organic groups. Specific examples of the organic group include hydrocarbon groups, alkoxy groups, functional groups in which some of the hydrogen atoms in the hydrocarbon and alkoxy groups have been replaced with fluorine, and perfluoro groups in which all hydrogen atoms have been replaced with fluorine. The organic group may also contain an ester group, an ether group, a urethane group, and / or a urea group. The iodonium salt compound having the structure represented by formula (1) (C1) may contain substituents in addition to R1 and R2. Examples include fluoro, chloro, bromo, nitro, hydroxy, and amino groups. However, dental photocurable compositions containing iodonium salt compounds having nitro or amino groups as substituents on the aryl group are not preferred because they may exhibit a strong brownish or yellowish tinge after curing or may have poor color stability in light or heat.

[0069] The total carbon number of the organic groups constituting all of the R1 and R2 substituents is 6 or more, preferably 8 to 26. Furthermore, within the range of 8 to 26, the larger the total carbon number, the more preferable. A larger carbon number improves solubility in the composition, shortening the time required to prepare the dental photocurable composition. It also improves storage stability, staining resistance, and resistance to elution from the composition. Furthermore, the safety of the compound itself is improved, which can be expected to reduce harmful effects to living organisms, such as acute toxicity, thereby improving biological safety. On the other hand, a carbon number greater than 26 may result in a decrease in the reaction rate during photopolymerization. Among iodonium salt compounds having a structure represented by formula (1) (C1), it is particularly preferred that the organic chain of R1 and / or R2 has an alkyl chain containing 8 or more carbon atoms. Examples of such alkyl chains include octyl, nonyl, decyl, octadecyl, icosyl, and octyloxy groups. As long as the alkyl chain contains 8 or more carbon atoms, it can be linear, branched, or cyclic. Such compounds are expected to have high solubility regardless of the anion species, and furthermore, are expected to have excellent color stability when used in the dental photocurable composition of the present invention.

[0070] The anion of the iodonium salt compound having the structure represented by formula (C1) is preferably an anion having an organic group, more preferably an anion having an organic group in which at least one H is substituted with F and one or more atoms of P, B, Al, S, and Ga. Iodonium salt compounds having such an anion may provide dental photocurable compositions with good color stability immediately after preparation and high storage stability.

[0071] The dental light-curable composition of the present invention may contain only the iodonium salt compound (C1) as the photoacid generator (C). The dental light-curable composition of the present invention may contain only an aryliodonium salt, which is a salt of an aryliodonium cation with an anion having an organic group and one or more atoms of P, B, Al, S, or Ga. The dental light-curable composition of the present invention may contain only a salt of an aryliodonium cation with an organic group in which at least one H is substituted with F and an anion having one or more atoms of P, B, Al, S, or Ga.

[0072] The dental photocurable composition of the present invention contains 0.5 parts by mass or more of (C) photoacid generator per 100 parts by mass of the total amount of (A) polymerizable monomer, preferably 1 part by mass or more, and more preferably 1 to 5 parts by mass. If the amount of (C) photoacid generator is less than 0.5 parts by mass, sufficient mechanical strength may not be obtained. If the amount of (C) photoacid generator other than (C1) is 0.5 parts by mass or more, color stability may decrease. If the amount of photoacid generator other than (C1) is less than 0.5 parts by mass, color stability may not decrease. However, using (C1) and photoacid generators other than (C1) in combination is complicated and not preferred.

[0073] The photoacid generators that can be used in the dental photocurable composition of the present invention are not limited to the photoacid generators exemplified above, and two or more types can be used in combination.

[0074] [(D) Photopolymerization accelerator] The photopolymerization accelerator (D) used in the dental photocurable composition of the present invention is not particularly limited as long as it has the ability to accelerate polymerization, and known photopolymerization accelerators commonly used in the dental field can be used without any restrictions. Examples of photopolymerization accelerators that can be used include primary to tertiary amine compounds such as aromatic amine compounds and aliphatic amine compounds, organometallic compounds, and phosphine compounds. Among these, tertiary aliphatic amine compounds, organometallic compounds, and phosphine compounds are preferred because of their excellent color stability in light.

[0075] Specific examples of the organometallic compounds include those containing scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), tin (Sn), zinc (Zn), and zirconia (Zr), and preferably those containing tin (Sn), vanadium (V), and copper (Cu). Specific examples of organometallic compounds containing tin (Sn) include dibutyltin diacetate, dibutyltin dimaleate, dioctyltin dimaleate, dioctyltin dilaurate, dibutyltin dilaurate, dioctyltin diversatate, dioctyltin S,S'-bis-isooctylmercaptoacetate, and tetramethyl-1,3-diacetoxydistannoxane. Specific examples of organometallic compounds containing vanadium (V) include acetylacetone. Examples of organic metal compounds containing copper (Cu) include vanadium tetraoxide, vanadium tetroxide, vanadyl acetylacetonate, vanadium oxide stearate, vanadyl oxalate, vanadyl sulfate, oxobis(1-phenyl-1,3-butanedionate)vanadium, bis(maltolate)oxovanadium, vanadium pentoxide, and sodium metavanadate. Specific examples of organometallic compounds containing copper (Cu) include copper acetylacetonate, copper naphthenate, copper octoate, copper stearate, and copper acetate.

[0076] A phosphine compound refers to a compound in which three organic groups are substituted on the P atom, and an aromatic phosphine compound refers to a compound in which a phenyl group which may have one or more substituents is substituted on the P atom. Specific examples of the phosphine compound include trimethylphosphine, tributylphosphine, trihexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tri(2-thienyl)phosphine, diphenylpropylphosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, methyldiphenylphosphine, triphenylphosphine, 2-(diphenylphosphino)styrene, 3-(diphenylphosphino)styrene, 4-(diphenylphosphino)styrene, allyldiphenylphosphine, 2-(diphenylphosphino)benzaldehyde, 3-(diphenylphosphino)benzaldehyde, 4-(diphenylphosphino)benzaldehyde, and 2-(phenylphosphino)benzoin. Examples of suitable benzoates include benzoic acid, 3-(phenylphosphino)benzoic acid, 4-(phenylphosphino)benzoic acid, tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, 2-(diphenylphosphino)biphenyl, tris(4-fluorophenyl)phosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, 2-(dimethylamino)phenyldiphenylphosphine, 3-(dimethylamino)phenyldiphenylphosphine, 4-(dimethylamino)phenyldiphenylphosphine, 2,2'-bis(diphenylphosphino)biphenyl, and bis[2-(diphenylphosphino)phenyl]ether. Among these, triphenylphosphine, 4-(phenylphosphino)benzoic acid, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, and tri(p-tolyl)phosphine are preferred.

[0077] Aromatic amine compounds are compounds in which one or more H atoms in ammonia (NH3) are substituted with an aromatic ring. They can be classified as aromatic primary amine compounds when one H atom in NH3 is substituted with an aromatic ring, aromatic secondary amine compounds when one H atom in NH3 is substituted with an aromatic ring and another H atom is substituted with an aromatic ring or an alkyl group, and aromatic tertiary amine compounds when one H atom in NH3 is substituted with an aromatic ring and two other H atoms are substituted with aromatic rings or alkyl groups.

[0078] Specific examples of aromatic primary amine compounds include aniline, etc., specific examples of aromatic secondary amine compounds include N-protected amino acids (esters) such as N-phenylbenzylamine, N-benzyl-p-anisidine, N-benzyl-o-phenetidine, N-phenylglycine ethyl, and N-phenylglycine, and specific examples of aromatic tertiary amine compounds include N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline, pN,N-dimethyl-toluidine, mN,N-dimethyl-toluidine, pN,N-diethyl-toluidine, p-bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, and 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-diisopropanolaniline, pN,N-dihydroxyethyl-toluidine, pN,N-dihydroxypropyl-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N,N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine, N,N-dimethyl-β-naphthylamine, etc. Among these, p-dimethylaminobenzoic acid ethyl ester is preferred.

[0079] Aliphatic amine compounds are compounds in which one or more H groups in ammonia (NH3) are substituted with alkyl groups. Alkyl groups are classified as primary alkyl groups (CH3- or -CH2-), secondary alkyl groups (-CH2- with one H substituted), and tertiary alkyl groups (-CH2- with two H groups substituted). Aliphatic amines are classified as primary amines when one H group in NH3 is substituted with an alkyl group, secondary amines when two H groups in NH3 are substituted with alkyl groups, and tertiary amines when three H groups in NH3 are substituted with alkyl groups.

[0080] Specific examples of aliphatic primary amine compounds include benzhydrylamine, triphenylmethylamine, amino acids such as glycine, or amino acid esters. Specific examples of aliphatic secondary amine compounds include dibenzylamine, N-benzyl-1-phenylethylamine, bis(1-phenylethyl)amine, bis(4-cyanobenzyl)amine, N-benzyl-protected amino acids, or N-benzyl-protected amino acid esters. Specific examples of aliphatic tertiary amine compounds include tributylamine, tripropylamine, triethylamine, N,N-Dimethylhexylamine, N,N-Dimethyldodecylamine, N,N-Dimethylstearylamine, N-[3-(dimethylamino)propyl]acrylamide, N,N-Dimethylformamide dimethyl acetal, N,N-Dimethylacetamide dimethyl acetal, N,N-Dimethylformamide diethyl acetal, N,N-Dimethylformamide dipropyl acetal, N,N-Dimethylformamide di-tert-butyl acetal, 1-(2-hydroxyethyl)ethyleneimine, N,N-Dimethylethanolamine, N,N- Dimethylisopropanolamine, N,N-diisopropylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, N-stearyldiethanolamine, triethanolamine, triisopropanolamine, tribenzylamine, dibenzylglycine ethyl ester, N'-(2-hydroxyethyl)-N,N,N'-trimethylethylenediamine, 2-(dimethylamino)-2-methyl-1-propanol, N ,N-Dimethyl-2,3-dihydroxypropylamine, N,N-Diethylethanolamine, 1-Methyl-3-pyrrolidinol, 1-(2-hydroxyethyl)pyrrolidine, 1-Isopropyl-3-pyrrolidinol, 1-Piperidineethanol, 2-[2-(dimethylamino)ethoxy]ethanol, N,N-Dimethylglycine, N,N-Dimethylglycine Methyl, N,N-Diethylglycine Methyl, N,N-Dimethylglycine Ethyl, N,N-Diethylglycine Sodium, 2-(Dimethylamino)ethyl Acetate, N-Methyliminodiacetic Acid, N,Examples include N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diisopropylaminoethyl methacrylate, N,N-dibutylaminoethyl methacrylate, N,N-dibenzylaminoethyl methacrylate, 3-dimethylaminopropionitrile, tris(2-cyanoethyl)amine, N,N-dimethylallylamine, N,N-diethylallylamine, and triallylamine.

[0081] The dental photocurable composition of the present invention preferably contains an aliphatic amine compound. Aromatic amine compounds have poor color stability in light, and therefore are undesirable when used in prosthetic devices, restorative materials, or adhesives used in areas prone to light exposure, as this may cause color changes over time. The combined use of an ultraviolet absorber is expected to suppress discoloration over time due to light. However, since ultraviolet absorbers are typically used as additives, their incorporation is unlikely to improve mechanical properties. Furthermore, their incorporation in large amounts is undesirable because they may increase the yellowish color of the dental photocurable composition before curing. For these reasons, the use of an aliphatic amine compound is preferred. Furthermore, from the perspective of reactivity with photoacid generators, tertiary aliphatic amine compounds are preferred among primary to tertiary aliphatic amine compounds. Depending on the composition of the dental photocurable composition, the combined use of an aliphatic primary amine compound and an aliphatic secondary amine compound can be expected to achieve high storage stability and high mechanical strength, and therefore, known compounds can be used without any restrictions.

[0082] Furthermore, it is preferable to include (D) a photopolymerization accelerator (D1) that does not have a primary hydroxy group at the α- and / or β-position carbon of the amine-derived N. Here, the α- and β-position carbons refer to the carbons adjacent to the amine-derived N as the α- and β-position carbons as the β-position carbons. Furthermore, the amine-derived N in a tertiary amine compound is distinguished from N derived from a urethane bond, urea bond, or amide bond. When a tertiary aliphatic amine compound having a primary hydroxy group at the α- and / or β-position carbon of N is used in the dental photocurable composition of the present invention, the cured product of the dental photocurable composition may discolor during long-term storage. Therefore, it is preferable to use (D1) a tertiary aliphatic amine compound that does not have a primary hydroxy group at the α- and / or β-position carbon of N as the photopolymerization accelerator (D).

[0083] (D1) Examples of tertiary aliphatic amine compounds not having a primary hydroxy group at the α-carbon and / or β-carbon of N include tributylamine, tripropylamine, triethylamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethylstearylamine, N-[3-(dimethylamino)propyl]acrylamide, N,N-dimethylisopropanolamine, triisopropanolamine, tribenzylamine, dibenzylmethylamine, dibenzylglycine ethyl ester, N,N-dimethylglycine methyl ester, N,N-diethylglycine methyl ester, N,N-dimethylglycine ethyl ester, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diisopropylaminoethyl methacrylate, N,N-dibutylaminoethyl methacrylate, and N,N-dibenzylaminoethyl methacrylate. Of these, N,N-dimethylaminoethyl acrylate, N-diisopropylaminoethyl methacrylate, N,N-dibutylaminoethyl methacrylate, N,N-dibenzylaminoethyl methacrylate, triisopropanolamine, tribenzylamine, dibenzylmethylamine, dibenzylglycine ethyl ester, and the like are preferred.

[0084] The dental photocurable composition of the present invention preferably does not substantially contain a tertiary amine compound having a primary hydroxy group at the α- and / or β-position carbon starting from an amine-derived N atom. The inclusion of such a compound may cause discoloration of the cured product of the dental photocurable composition over a long period of use. Examples of such aliphatic amine compounds include N,N-dimethylethanolamine, N,N-diisopropylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, N-stearyldiethanolamine, triethanolamine, and N,N-diethylethanolamine. Examples of aromatic amine compounds include N,N-bis(2-hydroxyethyl)-p-toluidine.

[0085] "Substantially free" means 0.1 parts by mass or less, preferably 0.01 parts by mass or less, per 100 parts by mass of (A) polymerizable monomer. When the amount is 0.1 parts by mass or less, it is expected that the cured product will not undergo significant discoloration during long-term use. On the other hand, when the amount exceeds 0.1 parts by mass, the cured product may undergo discoloration during long-term use. The dental light-curable composition of the present invention can be free of tertiary amine compounds having a primary hydroxy group at the α-position carbon and / or β-position carbon starting from the amine-derived N atom.

[0086] The dental photocurable composition of the present invention is preferably substantially free of aromatic amine compounds. Although the inclusion of an aromatic amine compound can be expected to further improve mechanical strength, it may result in a decrease in photocolor stability. "Substantially free" means that the content is 0.1 parts by mass or less, preferably 0.01 parts by mass or less, per 100 parts by mass of the (A) polymerizable monomer. The dental photocurable composition of the present invention may be free of aromatic amine compounds.

[0087] It is preferable that the raw materials do not contain impurities such as tertiary amine compounds and / or aromatic amine compounds having a primary hydroxy group at the α-carbon and / or β-carbon of N, but this is not limited to this as long as the properties of the dental photocurable composition are not affected.

[0088] The (D) photopolymerization accelerator is preferably contained in an amount of 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total amount of the (A) polymerizable monomer contained in the dental photocurable composition. If the amount is less than 0.2 parts by mass, the mechanical strength may be insufficient. If the amount is more than 10 parts by mass, although sufficient curability is obtained, it may be undesirable because the ambient light stability may be shortened or discoloration, such as browning of the cured product, may increase.

[0089] The dental photocurable composition of the present invention may contain only an aliphatic tertiary amine compound as the photopolymerization accelerator (D). The dental photocurable composition of the present invention may contain only a tertiary aliphatic amine compound (D1) that does not have a primary hydroxy group at the α-carbon and / or β-carbon of N as the photopolymerization accelerator (D).

[0090] These polymerization initiators (B) photosensitizer, (C) photoacid generator, and (D) photopolymerization accelerator may be subjected to secondary treatment such as fine pulverization, carrier adsorption, or encapsulation in microcapsules, if necessary. Furthermore, these various types of photopolymerization initiators can be used alone or in combination of two or more types, regardless of the polymerization mode or polymerization method.

[0091] [(E) Filler] The dental photocurable composition of the present invention may contain a filler (E), and any known filler that is commonly used may be used without any limitation.

[0092] (E) The type of filler is not limited as long as it is a known filler, and a filler appropriate for the intended use can be blended, and it is preferable to blend a filler such as an inorganic filler, an organic filler, an organic-inorganic composite filler, or an ion-releasing glass. The dental photocurable composition of the present invention may use the exemplified fillers alone or in combination of two or more.

[0093] Specific examples of organic fillers include polymers such as polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, and polycarbonate.

[0094] The inorganic filler is not particularly limited in terms of its chemical composition, and specific examples include silicon dioxide, alumina, titania, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. In particular, barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, fluoroaluminosilicate glass, etc., which are used in dental glass ionomer cements, resin-reinforced glass ionomer cements, resin cements, etc., can also be suitably used. The fluoroaluminosilicate glass referred to here has a basic skeleton of silicon oxide and aluminum oxide, and contains alkali metals for the introduction of non-bridging oxygen. It also contains alkaline earth metals, including strontium, and fluorine as modifying and coordinating ions. Furthermore, it is a composition in which lanthanide series elements are incorporated into the skeleton to impart further radiopacity. Depending on the composition range, these lanthanide series elements are also incorporated into the composition as modifying and coordinating ions.

[0095] The inorganic filler may contain inorganic fine particles with an average primary particle size of 0.1 to 50 nm. Specific examples include alumina fine particles and silica fine particles. The hydrophobic inorganic fine particles preferably have an average particle size of 0.1 to 50 nm, and are preferably hydrophobized by treatment with a silane coupling agent and / or modified silicone oil. Adding these particles is expected to not only improve bending strength, but also inhibit sedimentation of the inorganic filler and impart rheological properties.

[0096] Examples of organic-inorganic composite fillers include, but are not limited to, fillers whose surfaces are polymerized and coated with a polymerizable monomer; fillers obtained by mixing and polymerizing a filler and a polymerizable monomer and then pulverizing the mixture to an appropriate particle size; fillers in which a filler is previously dispersed in a polymerizable monomer and then emulsion-polymerized or suspension-polymerized; fillers in which a filler is previously dispersed in a polymerizable monomer and a solvent and then spray-dried and polymerized; and fillers in which a filler is previously dispersed in a solvent and then spray-dried, then impregnated with a polymerizable monomer and then polymerized.

[0097] The ion-releasing glass is characterized by releasing at least one of fluorine ions, strontium ions, borate ions, and aluminum ions, and it is preferable that more than one of these ions be released simultaneously.

[0098] The ion-releasing glass used in the present invention can be any ion-releasing glass without any limitations, as long as it contains one or more glass-skeleton-forming elements that form the glass skeleton and one or more glass-modifying elements that modify the glass skeleton. These ion-releasing glasses can be used alone or in combination. Furthermore, in the present invention, glass amphoteric elements that function as both glass-skeleton-forming elements and glass-modifying elements depending on the glass composition are included in the category of glass-skeleton-forming elements. Specific examples of glass-skeleton-forming elements contained in ion-releasing glasses include silica, aluminum, boron, phosphorus, etc., and these can be used alone or in combination. Specific examples of glass-modifying elements include halogen elements such as fluorine, bromine, and iodine, alkali metal elements such as sodium and lithium, and alkaline earth metal elements such as calcium and strontium, and these can be used alone or in combination. Among these, glass containing silica, aluminum, and boron as glass framework elements and fluorine, sodium, and strontium as glass modifiers is preferred. Specific examples include silica glass, fluoroaluminosilicate glass, fluoroborosilicate glass, and fluoroaluminoborosilicate glass containing strontium and sodium. Furthermore, from the viewpoint of sustained release of fluorine ions, strontium ions, borate ions, and aluminum ions, strontium-containing fluoroaluminoborosilicate glass is more preferred. Specific examples of glass composition ranges include SiO2: 15-35 mass%, Al2O3: 15-30 mass%, BO3: 5-20 mass%, SrO: 20-45 mass%, F: 5-15 mass%, and Na2O: 0-10 mass%. This glass composition can be confirmed using instrumental analysis such as elemental analysis, Raman spectroscopy, and X-ray fluorescence analysis. There is no problem with any of these analytical methods as long as the measured values ​​match these composition ranges.

[0099] The manufacturing method of these ion-releasing glasses is not particularly limited, and they can be manufactured by manufacturing methods such as a melting method or a sol-gel method. Among these, a manufacturing method using a melting furnace is preferred from the viewpoint of ease of glass composition design, including raw material selection. The ion-releasing glasses used in the present invention have an amorphous structure, but there is no problem if they contain a partial crystalline structure. Furthermore, there is no problem if they are a mixture of glass having an amorphous structure and glass having a crystalline structure. Whether the glass structure is amorphous or not can be confirmed using analytical equipment such as X-ray diffraction analysis or a transmission electron microscope. Among these, the ion-releasing glasses used in the present invention preferably have an amorphous structure, which is a homogeneous structure, because various ions are gradually released in an equilibrium relationship with the ion concentration in the external environment.

[0100] Furthermore, in order to enhance the ion release from the ion-releasing glass, it is preferable to functionalize the glass surface by surface treatment to improve the ion release. Specific examples of surface treatment materials used for the surface treatment include surfactants, fatty acids, organic acids, inorganic acids, monomers, polymers, various coupling agents, silane compounds, metal alkoxide compounds, and partial condensates thereof. Among these surface treatment materials, it is preferable to perform a composite surface treatment using an acidic polymer and a silane compound.

[0101] This composite surface treatment is a method in which the surface of ion-releasing glass is coated with a silane compound, and then surface-treated with an acidic polymer, as described in detail below. A silane compound represented by formula (3) is mixed into an aqueous dispersion containing ion-releasing glass that has been finely pulverized to a desired average particle size (D50) by grinding or other methods, and this is hydrolyzed or partially hydrolyzed in the system to form a silanol compound, which is then condensed to form a polysiloxane, which is then coated on the surface of the ion-releasing glass to form polysiloxane-coated ion-releasing glass.

[0102] [Formula (3)] [ka]

[0103] (wherein Z is RO - , X is halogen, Y is OH - , R is an organic group having 8 or less carbon atoms, n, m, and L are integers from 0 to 4, and n+m+L=4.

[0104] Specific examples of the silane compound represented by formula (3) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraallyloxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, trimethoxychlorosilane, triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane, diethoxydichlorosilane, tetraphenoxysilane, tetrachlorosilane, and silicon hydroxide (silicon oxide hydrate), with tetramethoxysilane and tetraethoxysilane being more preferred.

[0105] A low-condensation silane compound represented by formula (3) is more preferred. For example, a low-condensation silane compound obtained by partially hydrolyzing and condensing tetramethoxysilane and tetraethoxysilane is preferred. These compounds can be used alone or in combination. Furthermore, an organosilane compound can also be added as part of the silane compound represented by formula (3) during polysiloxane treatment.

[0106] The polysiloxane-coated ion-releasing glass obtained in the previous step can be subjected to an acidic polymer treatment to react with an acidic polymer to obtain ion-releasing glass. The acidic polymer treatment can be performed using equipment commonly used in the industry, as long as it is a dry-fluidized mixer, such as a Henschel mixer, super mixer, or high-speed mixer. The reaction of the acidic polymer with the polysiloxane-coated ion-releasing glass can be achieved by contacting the glass with the acidic polymer solution by impregnation or spraying. For example, the polysiloxane-coated ion-releasing glass can be dry-fluidized, and the acidic polymer solution can be dispersed from above while still fluidized, followed by thorough stirring. There are no particular restrictions on the method for dispersing the acidic polymer solution, but a drip or spray method is preferred to ensure uniform dispersion. The reaction is preferably performed near room temperature; as temperatures increase, the reaction between the acid-reactive element and the acidic polymer becomes more rapid, resulting in non-uniform formation of the cement phase.

[0107] It is preferable to remove moisture from the cement reaction phase by heat treatment after the reaction. Residual moisture in the cement reaction phase is detrimental to strength, but the filler of the present invention is reinforced by the covering of the coupling agent condensate film, thereby preventing a decrease in mechanical strength. The heat treatment method after the acidic polymer treatment is not particularly limited and can be carried out by a known, general method. Equipment used for the heat treatment is preferably a box-type hot air dryer or a rotary heat treatment device capable of uniform heating. The heat treatment temperature is in the range of room temperature to 200°C, more preferably 40 to 150°C. Temperatures below this range may result in insufficient removal of the aqueous medium, while temperatures above this range may result in decomposition or discoloration of the organic layer of the acidic polymer. The heat treatment time depends on the capacity of the dryer, etc., so there is no problem as long as the time allows sufficient removal of the aqueous medium. After the heat treatment, the heat-treated product can be easily crushed by applying shear or impact force. Crushing can be carried out using equipment such as that used for the above reaction.

[0108] The solvent used to prepare the acidic polymer solution to be used in the reaction is not limited in any way as long as it dissolves the acidic polymer, and examples include water, ethanol, acetone, etc. Among these, water is particularly preferred, as it allows the acidic groups of the acidic polymer to dissociate and react uniformly with the polysiloxane-coated ion-releasing glass.

[0109] The weight-average molecular weight of the polymer dissolved in the acidic polymer solution is in the range of 2,000 to 50,000, preferably in the range of 5,000 to 40,000. Treatment with an acidic polymer having a weight-average molecular weight of less than 2,000 tends to result in an acidic polymer reaction phase not being formed in the polysiloxane-coated ion-release glass, resulting in poor ion-release properties. Treatment with an acidic polymer having a weight-average molecular weight of more than 50,000 increases the viscosity of the acidic polymer solution, making it difficult to uniformly treat the polysiloxane-coated ion-release glass. The acidic polymer concentration in the acidic polymer solution is preferably in the range of 3 to 25% by mass, more preferably 8 to 20% by mass. If the acidic polymer concentration is less than 3% by mass, the acidic polymer reaction phase described above becomes fragile, and the effect of improving ion-release properties is not achieved. Furthermore, if the acidic polymer concentration exceeds 25% by mass, it becomes difficult to uniformly diffuse the polysiloxane layer (porous), making it difficult to obtain a homogeneous acidic polymer reaction phase. Furthermore, the reaction occurs immediately upon contact with the polysiloxane-coated ion-releasing glass, resulting in problems such as the formation of strongly reacted aggregates. Furthermore, the amount of acidic polymer solution added to the polysiloxane-coated ion-releasing glass is preferably in the range of 6 to 40% by mass, more preferably 10 to 30% by mass. Converted based on this addition amount, the optimal amount of acidic polymer and the optimal amount of water relative to the polysiloxane-coated ion-releasing glass are 1 to 7% by mass and 10 to 25% by mass, respectively.

[0110] The acidic polymer that can be used to form an acidic polymer reaction phase on the surface of the polysiloxane-coated ion-releasing glass by the above method can be any copolymer or homopolymer of a polymerizable monomer having an acidic group such as a phosphate residue, a pyrophosphate residue, a thiophosphate residue, a carboxylic acid residue, or a sulfonic acid group as the acidic group. Specific examples of these polymerizable monomers include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic anhydride, 5-(meth)acryloylaminopentylcarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, and 11-(meth)acryloyloxydecyl dihydrogen phosphate. Examples of suitable polymers include 2-(meth)acryloyloxyethylphenyl phosphate, 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, 1,3-di(meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl phosphate, 2-(meth)acryloyloxyethyl-2'-bromoethyl phosphate, (meth)acryloyloxyethylphenyl phosphonate, di(2-(meth)acryloyloxyethyl)pyrophosphate, 2-(meth)acryloyloxyethyl dihydrogendithiophosphophosphate, and 10-(meth)acryloyloxydecyl dihydrogenthiophosphate. Among the polymers (co)polymerized using these polymerizable monomers, it is preferable to use a homopolymer or copolymer of an α-β unsaturated carboxylic acid, which undergoes a relatively slow acid-base reaction with the acid-reactive element contained in the polysiloxane-coated ion-releasing glass, and specific examples thereof include an acrylic acid polymer, an acrylic acid-maleic acid copolymer, and an acrylic acid-itaconic acid copolymer.

[0111] The above-mentioned (E) filler can be treated with a surface treatment material, typically a silane coupling material, for the purpose of improving its affinity with the polymerizable monomer, its dispersibility in the polymerizable monomer, and the mechanical strength and water resistance of the cured product. The surface treatment material and the surface treatment method are not particularly limited, and known methods can be used without limitation, such as a method of spraying the surface treatment material while stirring the powdered filler, a method of dispersing and mixing the filler and surface treatment material in a solvent, or a method of supplying the silane coupling material in vapor or gas form to the surface of the filler. Preferred silane coupling agents used for surface treatment of fillers include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, and hexamethyldisilazane. In addition to silane coupling agents, surface treatment of fillers can also be performed using titanate-based coupling agents or aluminate-based coupling agents. The amount of surface treatment agent used on the filler is preferably 0.01 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, per 100 parts by weight of the filler before treatment.

[0112] The shape of the (E) filler is not particularly limited, and fillers of any shape such as spheres, needles, plates, crushed particles, scales, etc. The average particle size of the filler is preferably in the range of 0.01 μm to 50 μm, more preferably 0.01 μm to 30 μm, still more preferably 0.05 μm to 20 μm, and even more preferably 0.05 μm to 10 μm.

[0113] When the dental photocurable composition of the present invention contains a filler (E), the amount is preferably 500 parts by mass or less per 100 parts by mass of the polymerizable monomer (A). When the filler is contained, an improvement in the strength of the physical properties can be expected, but when the filler exceeds 500 parts by mass, the operability of the dental photocurable composition may decrease.

[0114] The dental photocurable composition of the present invention may contain a chemical polymerization initiator. Examples of organic peroxides as chemical polymerization initiators include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, peroxydicarbonates, and hydroperoxides. Specific examples of diacyl peroxides include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. Specific examples of peroxyesters include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, and t-butylperoxymaleic acid. Specific examples of dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl 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 peroxyketals include 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, n-butyl 4,4-(t-butylperoxy)pallate, and 1,1-di(t-amylperoxy)cyclohexane. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.Specific examples of peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate. Specific examples of hydroperoxides include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0115] The organic peroxide may be one of the above organic peroxides, or two or more organic peroxides may be used in combination. Among these organic peroxides, benzoyl peroxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate are preferred from the viewpoint of curability. To improve curability, the amount of organic peroxide used 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, per 100 parts by mass of the total amount of polymerizable monomer (A). If the amount of organic peroxide exceeds 5 parts by mass, it may be difficult to ensure sufficient operating time. On the other hand, if the amount of organic peroxide is less than 0.1 part by mass, mechanical strength may be insufficient.

[0116] The dental photocurable composition of the present invention may further contain a chemical polymerization accelerator to improve curability. Examples of chemical polymerization accelerators include fourth-period transition metal compounds, thiourea derivatives, aliphatic amines, aromatic amines, sulfinic acid and its salts, borate compounds, sulfur-containing reducing inorganic compounds, nitrogen-containing reducing inorganic compounds, barbituric acid derivatives, triazine compounds, and halogen compounds. The amount of the chemical polymerization accelerator is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers.

[0117] The fourth period transition metal compound used as a chemical polymerization accelerator refers to a metal compound of Groups 3 to 12 of the fourth period of the periodic table. Specifically, any metal compound of scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), or zinc (Zn) can be used without limitation. Each of the above transition metal elements can have multiple valences, but any valence that allows stable existence can be added to the dental photocurable composition of the present invention. Examples include Sc (trivalent), Ti (tetravalent), V (tri-, tetra-, or pentavalent), Cr (di-, tri-, or hexavalent), Mn (di- to heptavalent), Fe (di- or trivalent), Co (di- or trivalent), Ni (divalent), Cu (mono- or divalent), and Zn (divalent). Specific examples of transition metal compounds include scandium compounds such as scandium iodide (trivalent), titanium compounds such as titanium chloride (tetravalent) and titanium (tetravalent) tetraisopropoxide, and vanadium compounds such as vanadium acetylacetonate (trivalent), divanadium tetroxide (tetravalent), vanadyl acetylacetonate (tetravalent), vanadium stearate oxide (tetravalent), vanadyl oxalate (tetravalent), vanadyl sulfate (tetravalent), oxobis(1-phenyl-1,3-butanedionate)vanadium (tetravalent), and bis(maltolato)oxovanadium (tetravalent). ), vanadium pentoxide (5), sodium metavanadate (5), etc.; manganese compounds include manganese acetate (2), manganese naphthenate (2); iron compounds include iron acetate (2), iron chloride (2), iron acetate (3), iron chloride (3); cobalt compounds include cobalt acetate (2), cobalt naphthenate (2); nickel compounds include nickel chloride (2); copper compounds include copper chloride (1), copper bromide (1), copper chloride (2), copper acetate (2); zinc compounds include zinc chloride (2), zinc acetate (2).

[0118] Among these, trivalent or tetravalent vanadium compounds and divalent copper compounds are preferred, with trivalent or tetravalent vanadium compounds being more preferred due to their higher polymerization-promoting ability, and tetravalent vanadium compounds being most preferred. These fourth-period transition metal compounds may be used in combination with one another as needed. The amount of transition metal compound added is preferably 0.0001 to 1 part by mass per 100 parts by mass of the total amount of (A) polymerizable monomer. If the amount is less than 0.0001 part by mass, the polymerization-promoting effect may be insufficient, while if the amount is more than 1 part by mass, discoloration or gelation of the dental photocurable composition may occur, resulting in reduced storage stability.

[0119] Any known thiourea derivative can be used as a chemical polymerization accelerator 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, and dicyclohexylthiourea. Among these, (2-pyridyl)thiourea, N-acetylthiourea, and N-benzoylthiourea are preferred. If necessary, multiple types of these thiourea derivatives may be used in combination. The amount of the thiourea derivative to be blended is preferably 0.1 to 5 parts by mass per 100 parts by mass of the total amount of the polymerizable monomer (A). If the amount is less than 0.1 part by mass, the polymerization-promoting ability may be insufficient, and if the amount is more than 5 parts by mass, the storage stability may decrease.

[0120] 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, 2, Examples thereof include sodium 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, and calcium 2,4,6-triisopropylbenzenesulfinate, with sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate being particularly preferred.

[0121] Specific examples of borate compounds having one aryl group per molecule include trialkylphenylboron, trialkyl(p-chlorophenyl)boron, trialkyl(p-fluorophenyl)boron, trialkyl(3,5-bistrifluoromethyl)phenylboron, trialkyl[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, trialkyl(p-nitrophenyl)boron, trialkyl(m-nitrophenyl)boron, trialkyl(p-butylphenyl)boron, trialkyl(m-butylphenyl)boron, trialkyl(p-butylphenyl)boron, Examples of suitable alkyl groups include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of trialkyl(m-butyloxyphenyl)boron, trialkyl(p-octyloxyphenyl)boron, and trialkyl(m-octyloxyphenyl)boron (wherein 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, and the like).Specific examples of borate compounds having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron, dialkyldi(3,5-bistrifluoromethyl)phenylboron, dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, dialkyldi(p-nitrophenyl)boron, dialkyldi(m-nitrophenyl)boron, dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron, and dialkyldi(p-butyloxyphenyl). )boron, dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p-octyloxyphenyl)boron, and dialkyldi(m-octyloxyphenyl)boron (wherein 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, and the like), sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, and butylquinolinium salt.Specific examples of borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron, monoalkyltri(p-fluorophenyl)boron, monoalkyltri(3,5-bistrifluoromethyl)phenylboron, monoalkyltri[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, monoalkyltri(p-nitrophenyl)boron, monoalkyltri(m-nitrophenyl)boron, monoalkyltri(p-butylphenyl)boron, monoalkyltri(m-butylphenyl)boron, monoalkyltri( Examples of suitable alkyl groups 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 monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(p-octyloxyphenyl)boron, and monoalkyltri(m-octyloxyphenyl)boron (wherein the alkyl group is one selected from an n-butyl group, an n-octyl group, an n-dodecyl group, etc.).Specific examples of borate compounds having four aryl groups in one molecule include tetraphenylboron, tetrakis(p-chlorophenyl)boron, tetrakis(p-fluorophenyl)boron, tetrakis(3,5-bistrifluoromethyl)phenylboron, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, tetrakis(p-nitrophenyl)boron, tetrakis(m-nitrophenyl)boron, tetrakis(p-butylphenyl)boron, tetrakis(m-butylphenyl)boron, tetrakis(p-butyloxyphenyl)boron, tetrakis(m-butyloxyphenyl)boron, tetrakis(p-octyloxyphenyl)boron, and tetrakis(m Examples of the methyl quinolinium salt 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 (m-octyloxyphenyl)triphenylboron, (p-octyloxyphenyl)triphenylboron, (p-fluorophenyl)triphenylboron, (3,5-bistrifluoromethyl)phenyltriphenylboron, (p-nitrophenyl)triphenylboron, (m-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron, and (p-octyloxyphenyl)triphenylboron.

[0122] Among these aryl borate compounds, it is more preferable to use a borate compound having three or four aryl groups in one molecule from the viewpoint of storage stability. Furthermore, these aryl borate compounds can be used alone or in combination of two or more.

[0123] Examples of sulfur-containing reducing inorganic compounds include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, and dithionites. Specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

[0124] Examples of the nitrogen-containing reducing inorganic compound include nitrites, and specific examples include sodium nitrite, potassium nitrite, calcium nitrite, and ammonium nitrite.

[0125] 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-propyl ... Examples of the salts of barbituric acids include pyrubarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and thiobarbituric acids (preferably salts of alkali metals or alkaline earth metals). Specific examples of the salts of these barbituric acids include sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate.

[0126] Specific examples of the halogen compound include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, and dilauryldimethylammonium bromide.

[0127] The dental photocurable composition of the present invention may be one that does not contain a chemical polymerization initiator or a chemical polymerization accelerator, and may be one that does not contain a polymerization initiator system of a polymerization system other than a photopolymerization system.

[0128] <Other ingredients> The dental photocurable composition of the present invention may contain components other than the components (A) to (E) above, as long as the effects of the present invention are not impaired. For example, the following components may be added as needed: fillers such as fumed silica; benzophenone-based and benzotriazole-based UV absorbers; polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and 2,5-ditertiarybutyl-4-methylphenol; chain transfer agents such as α-alkylstyrene compounds, mercaptan compounds such as n-butyl mercaptan and n-octyl mercaptan; terpenoid compounds such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, and α-pinene; metal capture agents such as aminocarboxylic acid-based chelating agents and phosphonic acid-based chelating agents; discoloration inhibitors; antibacterial agents; color pigments; water and solvents miscible with water in any ratio; and other conventionally known additives.

[0129] The dental photocurable composition of the present invention preferably contains substantially no water or organic solvent. Water and highly hydrophilic organic solvents may have poor compatibility with the photoacid generator (C1) suitable for the dental photocurable composition of the present invention. Furthermore, the inclusion of water or an organic solvent may result in a decrease in the mechanical strength of the dental photocurable composition. "Substantially free" means 1 part by mass or less, preferably 0.1 part by mass or less, per 100 parts by mass of the dental photocurable composition. For example, when an organic solvent or water is used to dissolve the raw materials to be incorporated into the dental photocurable composition, it is preferable to remove the organic solvent or water by heating and / or decompression. This does not apply if water or an organic solvent is intentionally not included in the dental photocurable composition and does not affect the physical properties, such as when it is present as an impurity in the raw materials. The organic solvent referred to here refers to solvents such as ethanol and acetone, not impurities or by-products in the raw materials. The dental photocurable composition of the present invention may be free of water or organic solvent.

[0130] The method for producing the dental photocurable composition of the present invention is not particularly limited. A typical method for producing a dental photocurable composition, for example, when the dental photocurable composition contains (E), is to first prepare a matrix by mixing (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, and then knead this matrix with (E) a filler and remove air bubbles under vacuum to prepare a uniform paste. The present invention can also be produced using the above-mentioned method without any problems.

[0131] The dental photocurable composition of the present invention is applied as a dental adhesive, 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 material for fixing loose teeth, a dental hard resin, a dental cutting material, and a dental 3D printer material.

[0132] <One-dose dental photocurable composition> When the present invention is used in a one-component dental photocurable composition, it is particularly preferred that the dental materials used be dental adhesives, dental composite resins, dental core buildup materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicures, dental materials for fixing loose teeth, dental hard resins, dental cutting materials, and dental 3D printer materials, and it is particularly preferred that the present invention be used in dental adhesives, dental composite resins, dental core buildup materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicures, dental materials for fixing loose teeth, and dental hard resins. When the present invention is used in a one-component dental photocurable composition, it is expected that there will be fewer technical errors and a lower risk of air bubbles being mixed in.

[0133] <Two-dose dental photocurable composition> When the present invention is used in a two-component dental photocurable composition, it is particularly preferred for dental materials such as dental adhesives, dental composite resins, dental core buildup materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicures, dental loose tooth fixation materials, dental hard resins, dental cutting materials, and dental 3D printer materials, and is particularly preferred for dental adhesives, dental composite resins, dental core buildup materials, and dental resin cements. Two-component dental materials are prepared by mixing the first and second pastes immediately before use. Mixing is performed by mixing the first and second pastes in a volume ratio of 0.9 to 1.1:1.0 or a mass ratio of 0.8 to 1.2:1.0, preferably in an equal volume ratio. Mixing can be performed by known methods, such as manual mixing using a dedicated shaker or spatula, or automatic mixing using a static mixer. Because the ingredients can be separated into two agents, compounds that cannot be mixed in the same paste can be mixed separately, resulting in excellent storage stability.

[0134] The dental photocurable composition of the present invention comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a polymerization accelerator, and the (C) photoacid generator may comprise only (C1) an iodonium salt compound having a structure represented by formula (1). Alternatively, the composition may comprise only one or more of the above components as components other than (A) to (D). [Example]

[0135] Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

[0136] The materials used in the examples and comparative examples and their abbreviations are shown below. [(A) Polymerizable Monomer] Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane D2.6E: 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane in which the average number of moles of ethoxy groups added is 2.6 UDMA: N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)ethanol]methacrylate TEGDMA: Triethylene glycol dimethacrylate NPG: Neopentyl glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate GDMA: Glycerin dimethacrylate MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[0137] [(B) Photosensitizer] CQ: Camphorquinone BAPO: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[0138] [(D) Photopolymerization accelerator] <Aliphatic tertiary amine> <<(D1) Tertiary aliphatic amine compounds having no primary hydroxy groups at the α- and / or β-carbon positions of N>> TBA: Tribenzylamine DBMA: N-methyldibenzylamine DEAEMA: N,N-diethylaminoethyl methacrylate DMAEMA: N,N-dimethylaminoethyl methacrylate DMAPAA: N,N-dimethylaminopropylacrylamide TIPA: Triisopropanolamine DBGE: N,N-Dibenzylglycine ethyl ester <<Aliphatic tertiary amine compounds that have a primary hydroxyl group at the α- and / or β-carbon positions starting from the N-position of the amine>> MDEOA: Methyldiethanolamine TEA: Triethanolamine <Aromatic tertiary amine compounds> <<Aromatic tertiary amine compounds that do not have a primary hydroxyl group at the α- and / or β-carbon positions starting from the N-position of the amine>> DMBE: Ethyl N,N-dimethylaminobenzoate DHPT: N,N-di(2-hydroxypropyl)-p-toluidine <<Aromatic tertiary amine compounds that have a primary hydroxyl group at the α- and / or β-carbon positions starting from the N-position of the amine>> DEPT: N,N-bis(2-hydroxyethyl)-p-toluidine <Organometallic compounds> DBTL: Dibutyl-tin-dilaurate

[0139] [Chemical polymerization initiator] TMBH: 1,1,3,3-tetramethylbutyl hydroperoxide TPE: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate BPO: Benzoyl peroxide [Chemical polymerization accelerator] PTU: (2-pyridyl)thiourea BTU: N-benzoylthiourea ATU: N-acetylthiourea DHPT: N,N-di(2-hydroxypropyl)-p-toluidine PTSA: Sodium p-toluenesulfinate tetrahydrate COA: Copper acetylacetonate VOA: Vanadyl acetylacetonate

[0140] [(E) Filler] The manufacturing method of each filler used in preparing the dental photocurable composition is shown below.

[0141] (Filler E1) To 100.0 g of zirconium silicate filler (average particle size 1.2 μm: zirconia 90 wt%, silica 10 wt%), 50.0 g of water, 35.0 g of ethanol, and 7.0 g of 3-methacryloxyoctyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours, and the resulting silane coupling treatment liquid was added and stirred for 30 minutes. Then, the mixture was heat-treated at 100 ° C for 5 hours to obtain filler E1.

[0142] (Filler E2) To 100.0 g of zirconium silicate filler (average particle size 0.8 μm: zirconia 85 wt%, silica 15 wt%), 50.0 g of water, 35.0 g of ethanol, and 7.0 g of 8-methacryloyloxyoctyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours, and the resulting silane coupling treatment liquid was added and stirred for 30 minutes. After that, the mixture was heat-treated at 100 ° C for 5 hours to obtain filler E2.

[0143] (Filler E3) The raw materials silicon dioxide, aluminum oxide, boron oxide, sodium fluoride, and strontium carbonate were mixed and then melted at 1400°C to obtain Glass A (glass composition: SiO2: 22.5% by mass, Al2O3: 20.0% by mass, BO3: 12.3% by mass, SrO: 35.7% by mass, Na2O: 2.5% by mass, F: 7.0% by mass). The resulting Glass A was then pulverized using a vibration mill for 100 hours and then further pulverized using a wet bead mill for 3 hours. To 100 g of the resulting pulverized material, 4.5 g of a low-condensation silane compound "MKC Silicate MS56S" (SiO2 content 56.0% by mass, degree of polymerization 2-100, manufactured by Mitsubishi Chemical Corporation) was added and mixed with stirring for approximately 90 minutes. After mixing for the specified time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours, then cooled to obtain a heat-treated product. The resulting heat-treated product was placed in a Henschel mixer and crushed at 1800 rpm for 5 minutes. After crushing, a polysiloxane-treated product with good fluidity and a surface coated with polysiloxane was obtained. (acidic polymer treatment) 100 g of the polysiloxane-treated product was placed in a Henschel mixer, and while stirring, 16.0 g of an aqueous polyacrylic acid solution (polymer concentration 13% by mass, weight-average molecular weight 20,000: manufactured by Nakarai, Inc.) was sprayed from above. After spraying, the powder was removed from the mixer and heated at 100°C for 3 hours in a hot air dryer to obtain a polysiloxane-polyacrylic acid-treated product. (Silane treatment) To 100 g of the polysiloxane-polyacrylic acid treated product, 100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 8-methacryloyloxyoctyltrimethoxysilane (silane coupling agent) were stirred at room temperature for 2 hours to obtain a silane coupling treatment solution, which was then added and stirred for 30 minutes. The mixture was then heat-treated at 100°C for 15 hours to obtain filler E3.

[0144] (Filler E4) To 100 g of the polysiloxane treatment product, 100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 8-methacryloyloxyoctyltrimethoxysilane (silane coupling agent) were stirred at room temperature for 2 hours, and the resulting silane coupling treatment solution was added and stirred for 30 minutes. Then, the mixture was heat-treated at 100°C for 15 hours to obtain filler E4.

[0145] (Filler E5) Filler E5 was obtained using the same materials and method as Filler E3, except that 3-methacryloyloxypropyltrimethoxysilane was used instead of 8-methacryloyloxyoctyltrimethoxysilane as the silane coupling agent.

[0146] (Filler E6) Filler E6 was obtained using the same materials and method as Filler E4, except that 3-methacryloyloxypropyltrimethoxysilane was used instead of 8-methacryloyloxyoctyltrimethoxysilane as the silane coupling agent.

[0147] (Filler E7) To 10 g of aluminum fine particles (primary particle diameter: 13 nm), 10 g of water, 20 g of ethanol, 0.001 g of phosphoric acid, and 5.0 g of 3-methacryloxyoctyltrimethoxysilane (silane coupling agent) were stirred at room temperature for 2 hours, and the resulting silane coupling treatment solution was added and stirred for 30 minutes. Then, the mixture was heat-treated at 100°C for 15 hours to obtain filler E7.

[0148] (Filler E8) To 10 g of zirconia fine particles (primary particle diameter: 10 nm), 10 g of water, 20 g of ethanol, 0.001 g of phosphoric acid, and 5.0 g of 3-methacryloxyoctyltrimethoxysilane (silane coupling agent) were stirred at room temperature for 2 hours, and the resulting silane coupling treatment solution was added and stirred for 30 minutes. Then, the mixture was heat-treated at 100°C for 15 hours to obtain filler E8.

[0149] (Filler E9) Aerosil R-8200

[0150] (Filler E10) Aerosil R-7200

[0151] [UV absorber] BP: 2-hydroxy-4-(octyloxy)benzophenone BT: 2-(2-hydroxy-5-methylphenyl)benzotriazole [Polymerization inhibitor] MeHQ: p-Methoxyphenol BHA: 3-tert-butyl-4-hydroxyanisole BHT: 2,6-di-t-butyl-4-methylphenol [Fluorescent agent] FA: Diethyl 2,5-dihydroxyterephthalate

[0152] [(C) Photoacid generator] [(C1) Iodonium salt compound having a structure represented by formula (1)] <The total number of carbon atoms in the organic groups that make up all of R1 and R2 is 8 or more> The anion has an organic group in which at least one H is substituted with F, and one or more atoms of P, B, Al, S, or Ga. C-1: Bis(4-tert-butylphenyl)iodonium tetra(nonafluoro-tert-butoxy)aluminate [ka] C-2: Diphenyliodonium tris(trifluoromethylsulfonyl)methide [ka] C-3: Bis(4-tert-butylphenyl)iodonium tris(pentafluoropropyl)trifluorophosphate [ka] C-4: Bis(4-tert-butylphenyl)iodonium nonafluorobutanesulfonate [ka] C-5: Bis(4-tert-butylphenyl)iodonium nonafluorobutanesulfonate [ka] C-6: Bis(4-tert-butylphenyl)iodonium bis(trifluoromethylsulfonyl)imide [ka] C-7: p-(octyloxyphenyl)phenyliodonium bis(trifluoromethylsulfonyl)imide [ka] C-8: Bis(4-tert-butylphenyl)iodonium tetra(pentafluorophenyl)gallate [ka] <<Anion has an organic group>> C-9: Bis(4-tert-butylphenyl)iodonium camphorsulfonate [ka] <<The anion does not have an organic group>> C-10: Bis(3-isopropyl-4-methoxyphenyl)iodonium tetrafluoroborate [ka] C-11: p-(octyloxyphenyl)phenyliodonium hexafluoroantimonate [ka] C-12: Bis(4-dodecylphenyl)iodonium hexafluorophosphate [ka] <The total number of carbon atoms in the organic groups that make up all of R1 and R2 is 6 or more and less than 8> C-13: Bis(4-isopropylphenyl)iodonium hexafluorophosphate [ka] C-14: (4-tert-butylphenyl)(2,4,6-trimethoxyphenyl)iodonium hexafluorophosphate [ka] <Other iodonium salt compounds> C-21: (4-methylphenyl)(4-(2-methylpropyl)phenyl)iodonium hexafluorophosphate [ka] C-22: p-Cumenyl(p-tolyl)iodonium chloride [ka] C-23: (4-methylphenyl)(2,4,6-trimethylphenyl)iodonium trifluoromethanesulfonate [ka]

[0153] <Confirmation of the solubility of the photoacid generator> After weighing out 60 parts by weight of Bis-GMA and 40 parts by weight of TEGDMA, they were mixed for 6 hours using a mixer (mix rotor: VMRC-5, AS ONE) set to 50°C to obtain a homogeneous solution. After confirming that the solution had returned to room temperature, 0.5 parts by weight of each photoacid generator was added and stirred to dissolve. Solubility was evaluated based on the stirring time at which dissolution was visually confirmed. Stirring times of within 6 hours were rated A, within 24 hours B, and within 48 hours C, indicating good solubility. For those that did not dissolve within 48 hours, stirring was continued for an additional 6 hours using a mixer set to 50°C until dissolution was confirmed. This was rated D, indicating somewhat poor solubility. Furthermore, those that did not dissolve even after 24 hours of stirring were rated E. Good solubility is preferred because it allows for rapid production. Furthermore, this is preferred because there is a low risk of the photoacid generator precipitating during low-temperature storage. On the other hand, photoacid generators with poor solubility may precipitate after long-term storage even when uniformly dissolved in the composition, and this tends to occur particularly when they are blended in a large amount of 0.5 parts by mass or more, or even 1.0 part by mass or more, per 100 parts by mass of the polymerizable monomer (A). Furthermore, the production of the composition takes time, and the composition must be exposed to high temperatures for a long time, which can cause deterioration of the materials during preparation, which is undesirable.

[0154] [Table 1]

[0155] The photoacid generators C-1 to C-12, in which the total carbon number of all R1 and R2 is 8 or more, exhibited good solubility. Among these, C-4, C-7, C-11, and C-12, in which R1 and / or R2 have an alkyl chain with 8 or more carbon atoms, exhibited particularly good solubility. Among photoacid generators in which R1 and / or R2 do not have an alkyl chain with 8 or more carbon atoms and in which all R1 and R2 have a total carbon number of 8 or more, photoacid generators in which the anion has an organic group in which at least one H is substituted with F and one or more atoms of P, B, Al, S, or Ga tended to exhibit good solubility. On the other hand, C-13 and C-14, in which the total carbon number of all R1 and R2 is 6 or more but less than 8, tended to exhibit slightly poorer solubility. On the other hand, C-21 to C-23, in which the carbon number is less than 6, exhibited poor solubility, sufficient to dissolve 0.5 parts by mass or more per 100 parts by mass of the (A) polymerizable monomer.

[0156] <Method for producing one-component dental photocurable composition> All components except for the filler (E) shown in Tables 2 and 3 were placed in a wide-mouth plastic container and mixed for 168 hours at 100 rpm using a VMRC-5 mix rotor to obtain a matrix. The matrix and filler (E) were then placed in a kneader, and after the filler was uniformly mixed, the mixture was degassed under vacuum to prepare a dental photocurable composition. In Tables 2 and 3, the abbreviation for each component is followed by the mass part of each component in parentheses.

[0157] <Method for producing two-component dental photocurable composition> All ingredients except for filler (E) shown in Table 4 were placed in a wide-mouth plastic container and mixed for 168 hours at 100 rpm using a VMRC-5 mix rotor to obtain a matrix. The matrix and filler (E) were then placed in a kneader, uniformly stirred, and degassed under vacuum to obtain pastes 1 and 2. Pastes 1 and 2 were then filled into a 5 mL double syringe (Mixpack) to prepare dental photocurable compositions. In Table 4, the abbreviation for each component is followed by the mass (parts) of each component in parentheses.

[0158] The test methods used in the examples and comparative examples are as follows. The one-component dental light-curable composition was used by discharging it from a syringe container. The two-component dental light-curable composition was a paste prepared by mixing pastes 1 and 2 using a Mixpack mixing tip. When used, a paste prepared by mixing pastes 1 and 2 using a Mixpack mixing tip was used. The Mixpack mixing tip can be mixed using a static mixer, and when used, paste 1 and paste 2 can be mixed at a volume ratio of 0.9 to 1.1:1.0, ideally at equal volumes. When converted to a mass ratio, paste 1 and paste 2 were mixed and used at a ratio of 0.8 to 1.2:1.0.

[0159] [Table 2]

[0160] [Table 3]

[0161] [Table 4]

[0162] <Evaluation 1: Bending strength> The dental photocurable composition was filled into a stainless steel mold, and cover glasses were placed on both sides. The composition was then pressed against a glass plate. The composition was then cured by irradiating the composition with light at five locations for 10 seconds each using a photopolymerization irradiator (Blue Shot, manufactured by Shofu). After curing, the cured product was removed from the mold, and the reverse side was irradiated with light in the same manner. This produced a test specimen (25 x 2 x 2 mm: rectangular parallelepiped). The test specimen was immersed in water at 37°C for 24 hours and then subjected to a bending test. The two-part photocurable composition was subjected to a bending test within 1 hour of irradiation. The bending test was performed using an Instron universal testing machine (manufactured by Instron) with a support distance of 20 mm and a crosshead speed of 1 mm / min. Flexural strength was evaluated as good if it was 100 MPa or higher, fair if it was 90 to 100 MPa, slightly poor if it was 80 to 90 MPa, and insufficient if it was less than 80 MPa. A high bending strength indicates excellent mechanical strength of the dental photocurable composition.

[0163] <Evaluation 2: Thermal color stability> The prepared dental photocurable compositions were filled into stainless steel molds (15φ×1mm: disc-shaped), and a cover glass was placed on top and pressed against the mold using a glass plate. The cover glass was irradiated with light for 1 minute using a photopolymerization irradiator (Grip Light II, manufactured by Matsufuku) to cure the composition. The cured product was then removed from the mold, the cover glass removed, and the color of the specimen was measured. The color was measured using a spectrophotometer (manufactured by BYK-Chemie) under specified conditions (light source: C, viewing angle: 2°, measurement area: 11 mm) with the specimen placed against a background of a standard white plate (D65 / 10°X=81.07, Y=86.15, Z=93.38). The specimen was then immersed in a container containing 10 mL of water in an incubator set at 70°C and allowed to stand for one week. The color of the specimen was then measured again, and the difference in color change was expressed as ΔE, calculated using the following formula: ΔE={(ΔL*) 2 +(Δa*) 2 +(Δb*) 2} 1 / 2 ΔL*=L1*-L2* Δa*=a1*-a2* Δb*=b1*-b2* Here, L1* is the lightness index before immersion and leaving it undisturbed, L2* is the lightness index after immersion and leaving it undisturbed, a1* and b1* are the color quality indices before immersion and leaving it undisturbed, and a2* and b2* are the color quality indices after immersion and leaving it undisturbed. A ΔE of less than 5 is considered the best, a ΔE of 5 to less than 7 is considered good, a ΔE of 7 to less than 10 is considered slightly poor, and a ΔE of 10 or more or significant color unevenness confirmed by visual inspection is considered N and not applicable. If the dental material has good thermal stability, there is little discoloration when used in the oral cavity for a long period of time, and it can maintain a highly aesthetic state over the long term.

[0164] <Evaluation 3: Light color stability> The prepared dental photocurable composition was filled into a stainless steel mold (15φ x 1mm: disc-shaped), and a cover glass was placed on top and pressed against the mold using a glass plate. The cover glass was irradiated with light for 1 minute using a photopolymerization irradiator (Grip Light II, manufactured by Matsufuku) to cure the composition. The cured product was then removed from the mold, the cover glass removed, and the color of the specimen was measured. The color was measured using a spectrophotometer (manufactured by BYK Chemie) under specified conditions (light source: C, viewing angle: 2°, measurement area: 11 mm) with the specimen placed against a standard white background (D65 / 10°, X = 81.07, Y = 86.15, Z = 93.38). The specimen was then exposed to light for 24 hours using a xenon lamp light exposure tester (Suntest CPS+), after which the color of the specimen was measured again. The difference in color change was expressed as ΔE, calculated using 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 color quality indices before light exposure, and a2* and b2* are color quality indices after light exposure. A ΔE of less than 5 is considered the best, a ΔE of 5 to less than 7 is considered good, a ΔE of 7 to less than 10 is considered slightly poor, and a ΔE of 10 or more or five or more black spots are found when visually inspecting the appearance is considered N, making it unsuitable. Good light color stability means that there is little discoloration when used, maintaining high aesthetics.

[0165] The results of each test are shown in Tables 5 and 6.

[0166] [Table 5]

[0167] [Table 6]

[0168] The compositions described in the examples were confirmed to exhibit a bending strength of 80 MPa or more at the preparation stage, and the light color stability and heat color stability were not significantly reduced.

[0169] Examples 10, 12 to 16, 26, 35 to 37, 39, and 40, in which the amount of the (C) photoacid generator was an iodonium salt compound having a structure represented by formula (1) (C1) was 0.5 parts by mass, tended to have slightly lower bending strength. Example 17, in which the amount of the photoacid generator exceeded 10 parts by mass, tended to have slightly lower light color stability. Example 17, in which the amount of the photosensitizer camphorquinone was 0.02 parts by mass or less, tended to have slightly lower bending strength. Example 18, in which the amount of the sensitizer camphorquinone exceeded 1 part by mass, tended to have slightly lower light color stability. Example 18, in which the amount of the photopolymerization accelerator was less than 0.2 parts by mass, tended to have slightly lower bending strength. Example 19, in which the amount of the photopolymerization accelerator exceeded 10 parts by mass, tended to have slightly lower light color stability.

[0170] Examples 15 and 16, which contained iodonium salt compounds C-13 and C-14, whose anions have the structure represented by formula (1) (C1), and whose anions do not have an organic group, as photoacid generators, tended to have slightly inferior color stability in light. Furthermore, among Examples 10 and 11, which contained a photoacid generator C-9, whose anion has an organic group, Example 11, which contained 1 part by mass of C-9, tended to have slightly inferior color stability in light. On the other hand, photoacid generators whose anions do not have an organic group, but whose R1 and / or R2 in formula (1) have an alkyl group with 8 or more carbon atoms, showed good color stability in light.

[0171] Examples 31, 32, 36, 37, 39, 41, and 42, which contain tertiary amine compounds having a primary hydroxy group at the α- and / or β-position carbon starting from an amine-derived N, such as triethanolamine (TEA), methyldiethanolamine (MDEOA), and N,N-bis(2-hydroxyethyl)-p-toluidine (DEPT), tended to exhibit reduced thermal color stability.

[0172] Furthermore, among Examples 33 to 42 containing aromatic amines such as DMBE and DEPT, Examples 38 to 41 containing an ultraviolet absorber tended to have excellent light color stability.

[0173] Example 43, which did not contain a tertiary aliphatic amine compound as a photopolymerization accelerator, tended to have slightly lower bending strength, and Example 44, which did not contain an α-diketone compound as a photosensitizer, tended to have slightly lower bending strength.

[0174] The two-paste type dental photocurable compositions of Examples 101 to 109 exhibited good physical properties similar to the one-paste type dental photocurable compositions.

[0175] Comparative Examples 1 to 4 and 9, which did not contain an iodonium salt compound having the structure represented by formula (1) (C1) and contained 0.5 parts by mass or more of a photoacid generator, were confirmed to have uneven color and black spots after tests of thermal color stability and photocolor stability, and were significantly inferior in aesthetics. Comparative Examples 5 to 8, which contained less than 0.5 parts by mass of an iodonium salt compound having the structure represented by formula (1) (C1), were significantly inferior in flexural strength. Comparative Example 10, which did not contain the photopolymerization accelerator (D), had significantly low flexural strength, and Comparative Example 11, which did not contain the photosensitizer (B), did not cure sufficiently.

[0176] The dental photocurable compositions of the present invention evaluated in the examples can be used without any problems with any known dental photocurable compositions, such as dental adhesives, dental composite resins, dental core buildup materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicures, dental materials for fixing loose teeth, dental glass ionomer cements, dental hard resins, dental cutting materials, and dental 3D printer materials. [Industrial Applicability]

[0177] According to the present invention, it is possible to provide a dental photocurable composition having excellent mechanical properties and good color stability.

Claims

1. (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, (C) the photoacid generator comprises (C1) an iodonium salt compound having a structure represented by formula (1), (A) relative to 100 parts by mass of the polymerizable monomer, (C1) A dental photocurable composition containing 0.5 parts by mass or more of an iodonium salt compound having a structure represented by formula (1). [Formula (1)] 【Chemistry 1】 (In the formula, R １ and R ２ is an organic group, and a plurality of R １ and R ２ The total number of carbon atoms in the organic groups constituting the formula (I) is 6 or more.

2. (C1) R of an iodonium salt compound having a structure represented by formula (1) １ and R ２ 2. The dental photocurable composition according to claim 1, wherein the total number of carbon atoms of the organic groups constituting the composition is 8 or more.

3. (C1) R of an iodonium salt compound having a structure represented by formula (1) １ and / or R ２ 3. The dental photocurable composition according to claim 1, wherein is an organic group having an alkyl chain having 8 or more carbon atoms.

4. The dental photocurable composition according to any one of claims 1 to 3, characterized in that it contains 1 part by mass or more of (C1) an iodonium salt compound having a structure represented by formula (1) per 100 parts by mass of (A) the polymerizable monomer.

5. The dental photocurable composition according to any one of claims 1 to 4, wherein the anion of the iodonium salt compound having the structure represented by formula (C1) is an anion having an organic group.

6. (C1) The dental photocurable composition according to any one of claims 1 to 5, wherein the anion of the iodonium salt compound having the structure represented by formula (1) has an organic group in which at least one H is substituted with F, and one or more atoms of P, B, Al, S, and Ga.

7. The dental photocurable composition according to any one of claims 1 to 6, comprising (D) a photopolymerization accelerator (D1) a tertiary aliphatic amine compound having no primary hydroxy group at the α-position carbon and / or the β-position carbon of N.

8. 8. The dental photocurable composition according to claim 1, which is substantially free of an aromatic amine compound as the photopolymerization accelerator (D).

9. The dental photocurable composition according to claim 1, which is substantially free of (D) a tertiary amine compound having a primary hydroxy group at the α-position carbon and / or the β-position carbon starting from an amine-derived N atom as a photopolymerization accelerator.

10. 2. The dental photocurable composition of claim 1, which is substantially free of water and organic solvents.

11. A dental photocurable composition comprising: (A) relative to 100 parts by mass of the polymerizable monomer, (B) 0.02 to 1 part by mass of a photosensitizer (C1) 0.5 to 10 parts by mass of an iodonium salt compound having a structure represented by formula (1) (D) 0.1 to 10 parts by mass of a photopolymerization accelerator The dental photocurable composition of claim 1 , comprising:

Images