Dental photocurable composition containing a highly soluble photoacid generator

Abstract

To provide a dental photocurable composition which can exhibit excellent mechanical characteristics even after put back to the room temperature from a low temperature.SOLUTION: A dental photocurable composition comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator and (D) a photopolymerization accelerator, and the (C) photoacid generator includes (C-1) an iodonium salt-based compound with an anion having log S of -4 or less.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 manicures, dental adhesives 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 were unable to provide sufficient physical properties after low-temperature storage.

[0006] An object of the present invention is to provide a dental photocurable composition that can exhibit excellent mechanical properties even after being cooled from a low temperature to room temperature. [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, and the (C) photoacid generator is a dental photocurable composition comprising (C-1) an iodonium salt-based compound with an anion having a logS of -4 or less. [Effects of the Invention]

[0008] The dental photocurable composition of the present invention exhibits excellent mechanical properties even after being cooled from a low temperature to room temperature. DETAILED DESCRIPTION OF THE INVENTION

[0009] In the present invention, (C-1) an iodonium salt compound with an anion having a logS of −4 or less may be contained in an amount of 0.5 parts by mass or more per 100 parts by mass of (A) the polymerizable monomer.

[0010] In the present invention, (C-1) the iodonium salt-based compound with an anion having a logS of -4 or less can include an aryl iodonium salt having an anion having an organic group and one or more atoms of P, B, Al, S, and Ga.

[0011] In the present invention, (C-1) the iodonium salt-based compound with an anion having a logS of -4 or less can include an aryl iodonium salt having an anion containing 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.

[0012] In the present invention, an aliphatic tertiary amine compound may be contained as the photopolymerization accelerator (D).

[0013] In the present invention, (D-1) an aliphatic tertiary amine compound having no two or more primary hydroxy groups can be contained as (D) a photopolymerization accelerator.

[0014] In the present invention, the dental photocurable composition is a one-component composition, which can contain, relative to 100 parts by mass of (A) polymerizable monomer, 0.005 to 0.5 parts by mass of (B) photosensitizer, 0.5 to 10.0 parts by mass of (C) photoacid generator, and 0.01 to 20 parts by mass of (D) photopolymerization accelerator.

[0015] In the present invention, a two-component dental photocurable composition is provided, which comprises a first paste and a second paste, the first paste and the second paste having a specific gravity of 1:0.8 to 1.2, and the first paste and the second paste contain 200 parts by mass of the total of (A) polymerizable monomers, and the first paste and the second paste contain 0.01 to 2.0 parts by mass of (B) photosensitizer, 1.0 to 20 parts by mass of (C) photoacid generator, and 0.02 to 40 parts by mass of (D) photopolymerization accelerator.

[0016] The components of the dental photocurable composition of the present invention are described in detail below. The dental photocurable composition of the present invention is used as a dental adhesive, a dental composite resin, a dental core 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 hard resin, a dental cutting material, and a dental 3D printer material.

[0017] In clinical dentistry, various treatments are performed to restore aesthetic and functional health to teeth missing due to caries, fractures, etc., including direct restoration with dental composite resin and indirect restoration with dental resin cement using prosthetic devices made of ceramics or dental hard resin. In addition, dental adhesives are used to bond dental composite resins to various dental materials and natural teeth, dental adhesives for fixing loose teeth, dental coatings to protect sensitive and formed vital teeth from external irritation and secondary caries, dental pit and fissure sealants to prevent caries by filling complex grooves, especially those found in primary teeth, dental nail polish to temporarily restore aesthetics by masking 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 printer 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.

[0018] 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.

[0019] 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.

[0020] In order to solve the above problems, a photopolymerization initiator comprising an aryliodonium salt, which is a photoacid generator, a sensitizer, and an electron donor compound has been proposed. However, this has problems with solubility in dental photocurable compositions, and precipitates when stored at low temperatures, so that when the dental photocurable composition is used after being transported to a cold region, sufficient physical properties may not be exhibited.

[0021] The present inventors discovered that the dental photocurable composition of the present invention, when containing a highly lipophilic photoacid generator, exhibits excellent physical properties without precipitation during low-temperature storage. This discovery led to the completion of the present invention. More specifically, the inventors discovered that the lipophilicity of the anion of the aryliodonium salt significantly affects its solubility in the polymerizable monomer. The inventors discovered that dental photocurable compositions containing aryliodonium salts with anions exhibiting specific values ​​of log S (Log Solubility), a measure of water solubility calculated by calculation, which is the opposite of lipophilicity, exhibit stable properties even when stored in a refrigerator or freezer. This discovery led to the completion of the present invention.

[0022] [(A) Polymerizable Monomer] The polymerizable monomer (A) 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 polymerizability. 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 group and / or acrylamide group are also preferably used. Examples of suitable polymerizable monomers include those having one radically polymerizable group, those having two radically polymerizable groups, those having three or more radically polymerizable groups, those having an acidic group, an alkoxysilyl group, and those having a sulfur atom.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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, or a carboxylic acid group.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] Specific examples of polymerizable monomers having a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid and 2-sulfoethyl(meth)acrylate.

[0032] 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.

[0033] Specific examples of polymerizable monomers having an alkoxysilyl group include (meth)acrylic compounds having one alkoxysilyl group in the molecule and (meth)acrylic 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.

[0034] The polymerizable monomer having a sulfur atom can be any known compound without any limitation, as long as it is a polymerizable monomer having one or more sulfur atoms and a polymerizable group. Specific examples include 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.

[0035] 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.

[0036] The dental photocurable composition of the present invention can contain a known acidic group-containing polymerizable monomer as the polymerizable monomer (A) to impart adhesiveness to teeth and prosthetic devices. 10-methacryloyloxydecyl dihydrogen phosphate or 6-methacryloxyhexyl phosphonoacetate is preferred. From the viewpoint of imparting adhesiveness, the amount of the acidic group-containing polymerizable monomer 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.

[0037] 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, 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, and 11-methacryloxyundecyltrimethoxysilane are preferred. To provide adhesion, the silane coupling agent is blended in an amount of at least 1 part by mass, more preferably at least 10 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.

[0038] The dental photocurable composition of the present invention may contain a polymerizable monomer having a sulfur atom as a 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 10 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers contained in the dental photocurable composition.

[0039] <Photopolymerization initiator> The photopolymerization initiator used in the dental photocurable composition of the present invention includes (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, and these are not particularly limited, and commonly used known compounds can be used without any restrictions.

[0040] [(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, acetonaphthone, 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.

[0041] (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.

[0042] Typically, the amount of (B) photosensitizer is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 1.0 part by mass, and even more preferably 0.05 to 1.0 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 photosensitizer is less than 0.005 part by mass, the polymerization activity in response to 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 is shortened and the composition becomes more yellow.

[0043] [(C) Photoacid generator] The dental photocurable composition of the present invention contains (C) an iodonium salt-based compound with an anion having a logS of -4 or less as a photoacid generator (C-1). In addition to (C-1) an iodonium salt-based compound with an anion having a logS of -4 or less, other known photoacid generators can be used without limitation in the dental photocurable composition of the present invention. Specific examples include triazine compounds, iodonium salt-based compounds, sulfonium salt-based compounds, and sulfonate ester compounds. Among these, triazine compounds and iodonium salt-based compounds are preferred because of their high polymerizability when used in combination with a sensitizer. Iodonium salt-based compounds are more preferred. Iodonium salt-based compounds are easily sensitized by photosensitizers that absorb light in the visible light region.

[0044] 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.

[0045] 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 (1): [Formula (1)] [(R1)2I] + [A] - (In the formula [(R1)2I] + is the cationic moiety, [A] - is an anion moiety, and R1 in formula (1) 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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 photocurable compositions, preventing precipitation during low-temperature storage or long-term storage. They also dissolve in the composition quickly, thereby shortening production times. 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, may 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.

[0054] 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.

[0055] [A] of the iodonium salt compound of formula (1) - The anion moiety of the iodonium salt compound of formula (1) 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 photopolymerizable composition. - The alkyl group in the anion moiety preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. 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 photocurable composition may contain an iodonium salt having an anion having an alkyl group with a different ratio of hydrogen atoms to fluorine atoms.

[0056] 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.

[0057] [A] of the iodonium salt compound of formula (1) - 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 photocurable composition may contain an iodonium salt consisting of an anion having an alkoxy group with a different ratio of hydrogen atoms to fluorine atoms.

[0058] 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.

[0059] [A] of the iodonium salt compound of formula (1) -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 photocurable composition may contain an iodonium salt consisting of an anion having a phenyl group with a different ratio of hydrogen atoms to fluorine atoms.

[0060] [A] of the iodonium salt compound of formula (1) - 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(C6F5)3] - , [(C6H5)B((CF3)2C6H3))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:

[0061] The dental photocurable composition of the present invention contains, as a photoacid generator (C), (C-1) an iodonium salt compound with an anion having a logS of −4 or less.

[0062] Log S is an index of a compound's solubility in water and is used to predict its water solubility. In this study, calculations were performed using ChemDraw Professional ver. 18.1. The higher the log S value, the higher the water solubility, and the lower the log S value, the lower the water solubility. Known indices for determining the properties of such compounds from their structure include partition coefficients such as Log P, CLog P, Alog P, and Log D, as well as Hansen Solubility Parameter (HSP) and topological polar surface area (tPSA). By comparing these indices with experimental results, a correlation was confirmed between the aforementioned solubility-related indices and experimental results. Specifically, investigations based on log S revealed that the use of iodonium salt-based compounds improves the storage stability of dental photocurable compositions during low-temperature storage. By incorporating a highly soluble photoacid generator into a dental photocurable composition, it is believed that the composition will not precipitate even during low-temperature storage and will maintain sufficient physical properties even after returning to room temperature. Furthermore, excellent storage stability was confirmed during high-temperature storage. Among the aforementioned indices, such iodonium salts exhibit a high correlation with Clog P, and generally, as the log S value increases, Clog P tends to decrease. When ClogP is used as an index, it is preferable to use an iodonium salt with an anion that exhibits a ClogP of 1 or more. In the present invention, it was determined that using logS as an index would be applicable to many compounds, and the present invention was developed by conducting studies using logS.

[0063] An example of an anion with a log S of -4 or less is [(CF3CF2)3PF3] - , [(CF3CF2CF2)3PF3] - , [((CF3)2CF)2PF4] - , [((CF3)2CF)3PF3] - , [((CF3)2CF)4PF2] - , [((CF3)2CFCF2)2PF4] - , [((CF3)2CFCF2)3PF3] - , [(CF3CF2SO2)3C] - , [(CF3CF2CF2SO2)3C] -, [(CF3CF2CF2CF2SO2)3C] - , [B(C6F5)4] - , [(C6H5)B(C6F5)3] - , [(C6H5)B((CF3)2C6H3))3] - , [((CF3)4Ga] - , [Ga(C6F5)4] - , [((CF3)3CO)4Al] - , [((CF3CF2)3CO)4Al] - Examples include:

[0064] On the other hand, examples of anions with a logS greater than -4, i.e., anions with low lipid solubility, include chloride, bromide, nitrate, perchlorate, tetrafluoroborate, hexafluoroantimonate, hexafluorophosphate, p-toluenesulfonate, and trifluoromethanesulfonate. These anions have high water solubility due to their high logS values, but low lipid solubility due to their low ClogP values. For example, the ClogP of the anions listed above is 1 or less.

[0065] The log S of the anion in the iodonium salt compound (C-1) is -4 or less, preferably -5 or less. When an iodonium salt with an anion having a log S of more than -4 is blended in a dental photocurable composition in an amount of 0.5 parts by mass or more per 100 parts by mass of the total amount of polymerizable monomer (A), precipitation may occur during storage at low temperatures, and particularly those with low solubility may not dissolve uniformly in the dental photocurable composition. If the photoacid generator does not dissolve uniformly in the dental photocurable composition or if precipitation of the photoacid generator occurs, sufficient mechanical properties may not be exhibited, photocolor stability may decrease, and the precipitated photoacid generator may be observed as black spots, affecting aesthetics.

[0066] The amount of (C-1) iodonium salt compound with an anion having a logS of -4 or less is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, per 100 parts by mass of the total amount of (A) polymerizable monomer. If the amount is less than 0.5 parts by mass, the bending strength may be insufficient, and if the amount is 0.5 to 1.0 parts by mass, the bending strength tends to be lower than when the amount is 1.0 part by mass or more. On the other hand, the amount of (C-1) iodonium salt compound with an anion having a logS of -4 or less is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of the total amount of (A) polymerizable monomer. If the amount is more than 10 parts by mass, deterioration in ambient light stability and light color stability may occur. Furthermore, if the amount of the iodonium salt compound (C-1) with an anion having a logS of -4 or less is increased between 5 and 10 parts by mass, a significant improvement in bending strength cannot be expected, and therefore the most preferred amount is 1.0 to 5.0 parts by mass per 100 parts by mass of the total amount of the polymerizable monomer (A). The iodonium salt compound (C-1) can be used alone or in combination of two or more types.

[0067] The (C) photoacid generator is not limited to the (C-1) iodonium salt-based compound, and a (C) photoacid generator other than the (C-1) iodonium salt-based compound can be used in combination. In this case, the dental photocurable composition of the present invention preferably contains the (C) photoacid generator (including the (C-1) iodonium salt-based compound in an amount of 0.5 to 10.0 parts by weight per 100 parts by weight of the total amount of the (A) polymerizable monomer. It is more preferably 1.0 to 5.0 parts by weight. If the amount is less than 0.5 parts by weight, the polymerization-accelerating ability may be poor, resulting in insufficient curing. If the amount is more than 10 parts by weight, sufficient curing is maintained, but the ambient light stability may be shortened and discoloration, such as browning, of the cured product may increase.

[0068] The dental light-curable composition of the present invention may contain only the iodonium salt compound (C-1) 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.

[0069] [(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 and organometallic compounds are preferred because of their excellent color stability in light.

[0070] 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.

[0071] 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-diisopropanol-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N,N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine, N,N-dimethyl-β-naphthylamine, and the like.

[0072] 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 zirconium (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.

[0073] 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.

[0074] Aliphatic amine compounds are compounds in which one or more H groups in ammonia (NH3) are substituted with alkyl groups. The 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.

[0075] 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.

[0076] It is particularly preferable to use an aliphatic tertiary amine compound as the (D) photopolymerization accelerator. Aromatic amine compounds have poor color stability in light, and therefore are undesirable when used in prosthetic devices, restorative materials, or adhesives in areas exposed to light, such as anterior teeth, because color tone may change 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, they may increase the yellowish color of the dental photocurable composition before curing, so incorporation in large amounts is undesirable. For these reasons, it is preferable to use an aliphatic tertiary amine compound. Furthermore, depending on the composition of the dental photocurable composition, the inclusion of an aliphatic primary amine compound and an aliphatic secondary amine compound can be expected to provide high storage stability and high mechanical strength, and known compounds can be used without any restrictions.

[0077] Furthermore, among aliphatic tertiary amine compounds, amine compounds having two or more primary hydroxy groups in the molecule are preferred, and amine compounds having no primary hydroxy groups in the molecule are even more preferred. Specific examples of amine compounds having two or more primary hydroxy groups in the molecule include triethanolamine and methyldiethanolamine. Amine compounds having primary hydroxy groups may cause discoloration of a cured product of a dental photocurable composition during long-term storage. Discoloration tends to increase with the number of primary hydroxy groups in the molecule, and is particularly pronounced when the molecule has two or more primary hydroxy groups. Discoloration during long-term storage of a cured product can be confirmed within a short period of time by storing the cured product in high-temperature water. If discoloration under high-temperature water conditions is small, i.e., if the thermal color stability is high, discoloration of a cured product of a dental photocurable composition during long-term use is small.

[0078] The (D) photopolymerization accelerator is preferably contained in an amount of 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total amount of the (A) polymerizable monomer contained in the dental photopolymerizable composition. If the amount is less than 0.01 part by mass, the mechanical strength may be insufficient. If the amount is more than 20 parts by mass, although sufficient curing ability 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.

[0079] 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.

[0080] The dental photocurable composition of the present invention may contain only an aliphatic tertiary amine compound as the (D) photopolymerization accelerator. The dental photocurable composition of the present invention may contain only an (D-1) aliphatic tertiary amine compound that does not have two or more primary hydroxy groups as the (D) photopolymerization accelerator. The dental photocurable composition of the present invention may contain only an aliphatic tertiary amine compound that does not have a primary hydroxy group in the molecule as the (D) photopolymerization accelerator.

[0081] [(E) Filler] The dental photopolymerizable composition of the present invention can contain a filler (E) as another component. The filler (E) used in the present invention can be any known filler that is commonly used, without any limitations.

[0082] The type of (E) filler is not limited as long as it is a known filler, and a filler suitable for the intended use can be blended, and it is preferable to blend fillers such as inorganic fillers, organic fillers, or organic-inorganic composite fillers. These may be used alone or in combination regardless of the type of filler.

[0083] The inorganic filler is not particularly limited in chemical composition, and specific examples include silicon dioxide, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium 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.

[0084] Specific examples of the organic filler include polymers such as polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, and polycarbonate.

[0085] Examples of organic-inorganic composite fillers include, but are not limited to, fillers whose surfaces are polymerized and coated with polymerizable monomers, fillers obtained by mixing and polymerizing a filler and a polymerizable monomer and then pulverizing the mixture to an appropriate particle size, and fillers obtained by dispersing a filler in a polymerizable monomer in advance and then emulsion-polymerizing or suspension-polymerizing the dispersed filler.

[0086] The filler (E) can be treated with a surface treatment agent, typically a silane coupling agent, to improve 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 agent and surface treatment method are not particularly limited, and known methods can be used without limitation. Preferred silane coupling agents used for the surface treatment of the filler include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, and hexamethyldisilazane. In addition to silane coupling agents, the filler can also be surface-treated using a titanate-based coupling agent or an aluminate-based coupling agent. The amount of the surface treatment agent on the filler is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the filler before treatment.

[0087] The shape of the filler is not particularly limited, and any shape such as amorphous, spherical, needle-like, plate-like, crushed, scale-like, etc. The average particle size of the filler is preferably 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.

[0088] When a dental photocurable composition contains a filler (E), the amount is preferably 10 to 1,000 parts by weight per 100 parts by weight of the total polymerizable monomer (A). Considering factors such as formability, the amount is preferably less than 500 parts by weight. If the amount of filler is less than 10 parts by weight, the effects of incorporating the filler in the composition, such as improving mechanical strength and exhibiting thixotropy, may be poor. If the amount of filler is greater than 1,000 parts by weight, the composition may become hard and difficult to handle. However, depending on the type of filler and the surface treatment conditions of the filler, the amount of filler may be greater than 1,000 parts by weight. For example, this refers to cases where the filler has a high specific gravity, where a large amount of surface treatment agent is applied to the filler, or where a surface treatment agent with good affinity with the polymerizable monomer is used. The composition of the present invention exhibits its effects regardless of the amount of filler.

[0089] 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.

[0090] 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 and cumene hydroperoxide 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 operation time. On the other hand, if the amount of organic peroxide is less than 0.1 part by mass, mechanical strength may be insufficient.

[0091] 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.

[0092] 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).

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] Examples of the nitrogen-containing reducing inorganic compound include nitrites, and specific examples thereof include sodium nitrite, potassium nitrite, calcium nitrite, and ammonium nitrite.

[0100] 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.

[0101] Specific examples of the halogen compound include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, and dilauryldimethylammonium bromide.

[0102] 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 for a polymerization system other than a photopolymerization system.

[0103] <Other ingredients> The dental photocurable composition of the present invention may contain components other than the components (A) to (D) above, as long as the effects of the present invention are not 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.

[0104] The method for preparing 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 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 without any problems using the above-mentioned production method.

[0105] 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 hard resin, a dental cutting material, and a dental 3D printer material.

[0106] <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 adhesives 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 adhesives 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.

[0107] <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 adhesives for loose teeth, dental hard resins, dental cutting materials, and dental 3D printer materials, with dental adhesives, dental composite resins, dental core buildup materials, and dental resin cements being particularly preferred. 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 at a volume ratio of 0.9-1.1:1.0 or a mass ratio of 0.8-1.2:1.0, preferably at 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.

[0108] The dental photocurable composition of the present invention comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, and the (C) photoacid generator may comprise only (C-1) an iodonium salt compound with an anion having a logS of −4 or less. Alternatively, the composition may comprise only one or more of the above-mentioned components as components other than (A) to (D). [Example]

[0109] Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

[0110] 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 2.6E: 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 MDP: 10-methacryloyloxydecyl dihydrogen phosphate MHPA: 6-methacryloxyhexylphosphonoacetate

[0111] [(B) Photosensitizer] CQ: Camphorquinone BAPO: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[0112] [(D) Photopolymerization accelerator] <Aliphatic tertiary amine> <<Aliphatic tertiary amine compounds that do not have a primary hydroxyl group>> TBA: Tribenzylamine DBGE: N,N-Dibenzylglycine ethyl ester DEAEMA: N,N-diethylaminoethyl methacrylate DMAEMA: N,N-dimethylaminoethyl methacrylate <<Aliphatic tertiary amine compound with one primary hydroxyl group>> DBAE: N,N-dibenzylaminoethanol <<Aliphatic tertiary amine compound with two primary hydroxyl groups>> MDEOA: Methyldiethanolamine <<Aliphatic tertiary amine compound with three primary hydroxyl groups>> TEA: Triethanolamine <Aromatic tertiary amine compounds> DMBE: Ethyl N,N-dimethylaminobenzoate <Organometallic compounds> DBTL: Dibutyl-tin-dilaurate

[0113] [(E) Filler] The manufacturing method of each filler used in preparing the photocurable composition is described below.

[0114] (filler 1) 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 8-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 140°C for 15 hours to obtain Filler 1.

[0115] (filler 2) 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 3-methacryloyloxypropyltrimethoxysilane 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 140 ° C for 15 hours to obtain Filler 2.

[0116] [Chemical polymerization initiator] CHP: Cumene hydroperoxide BPO: Benzoyl peroxide TPE: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate [Chemical polymerization accelerator] PTU: (2-pyridyl)thiourea DEPT: N,N-dihydroxyethyl-p-toluidine DMPT: N,N-dimethyl-p-toluidine COA: Copper acetylacetonate VOA: Vanadyl acetylacetonate

[0117] [UV absorber] BT: 2-(2-hydroxy-5-methylphenyl)benzotriazole [Polymerization inhibitor] BHT: 2,6-di-t-butyl-4-methylphenol MeHQ: p-Methoxyphenol [Fluorescent agent] FA: Diethyl 2,5-dihydroxyterephthalate

[0118] [(C) Photoacid generator] The log S of the hydrides of the anions of iodonium salts was calculated using ChemDraw Professional ver. 18.1. <(C-1) Iodonium salt compounds with anions having a logS of -4 or less> C1: Bis[4-(tert-butyl)phenyl]iodonium tetra(pentafluorophenyl)gallate (LogS: -15.1) [ka] C2: Di-p-tolyliodonium phenyltris(pentafluorophenyl)borate (LogS: -11.3) [ka] C3: Bis(4-tert-butylphenyl)iodonium tetra(nonafluoro-tert-butoxy)aluminate (LogS: -14.7) [ka] C4: p-Cumenyl(p-tolyl)iodonium tris(pentafluoroethanesulfonyl)methide (LogS: -5.3) [ka] ·C5: Diphenyliodonium tris(nonafluorobutanesulfonyl)methide (LogS: -9.4)

Chem.

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[0119] <Method for producing one-component dental photocurable composition> All ingredients except for the filler (E) shown in Table 1 were placed in a wide-mouth plastic container and mixed for 48 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 prepare a dental photocurable composition. In Table 1, the abbreviation for each component is followed by the mass part of each component in parentheses.

[0120] [Table 1]

[0121] <Method for producing two-component dental photocurable composition> All ingredients except for (E) filler shown in Table 2 were placed in a wide-mouth plastic container and mixed for 48 hours at 100 rpm using a VMRC-5 mix rotor to obtain a matrix. The matrix and (E) filler 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 Mixpack double syringe (5 mL) to prepare dental photocurable compositions. Two-component dental photocurable compositions were prepared by mixing pastes 1 and 2 using a Mixpack mixing tip. The Mixpack mixing tip is a static mixer, and when used, pastes 1 and 2 can be mixed at a volume ratio of 0.9-1.1:1.0, which translates to a mass ratio of 0.8-1.2:1.0. In Table 2, the abbreviations for each component are followed by the parts by mass in parentheses.

[0122] [Table 2]

[0123] <Accelerated test conditions> The one-component dental photocurable composition and the two-component dental photocurable composition filled in each container were placed in a storage cabinet set at 40°C (Yamato Scientific Co., Ltd.) and a storage cabinet set at -5°C (KGT-4010HC, Nippon Freezer Co., Ltd.) and stored for 6 months.

[0124] <Evaluation 1: Check appearance> The one-component dental photocurable compositions and two-component dental photocurable compositions stored at -5°C were removed from storage and left to stand at room temperature of 15 to 25°C for one week. 1 g of paste was then discharged from the container. If no precipitates were observed by visual inspection, the composition was judged as A: good; if one to five precipitates were observed, the composition was judged as B: within the acceptable range; and if five or more precipitates were observed, the composition was judged as C: problematic in appearance.

[0125] <Evaluation 2: Storage stability confirmed by 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 five locations for 10 seconds each using a photopolymerization irradiator (Penbrite, 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 to form a test specimen (25 × 2 × 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 bending test for the two-component photocurable composition was conducted 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. The storage stability of the composition was evaluated using the bending test results using Equation 2. A change of more than -5% from the value before storage indicated high storage stability. A change between -5% and -15% indicated slightly poor storage stability. A change of less than -15% indicated significantly poor storage stability. [(Formula 2)] (Bending strength after storage (MPa) - Bending strength before storage (MPa)) / (Bending strength before storage (MPa)) x 100 [%]

[0126] Furthermore, the flexural strength before the accelerated test was evaluated separately. For one-component photocurable compositions and two-component photocurable compositions containing 100 parts by mass or more of (E) filler per 100 parts by mass of polymerizable monomer, the flexural strength was judged to be good if it was greater than 100 MPa, acceptable if it was 80 to 100 MPa, and insufficient if it was less than 80 MPa. For one-component photocurable compositions and two-component photocurable compositions containing less than 100 parts by mass of (E) filler per 100 parts by mass of polymerizable monomer, the flexural strength was judged to be good if it was greater than 90 MPa, acceptable if it was 60 to 90 MPa, and insufficient if it was less than 60 MPa. Because the flexural strength varies depending on the amount of filler, different standards were established.

[0127] <Evaluation 3: Stability to ambient light> Using a light meter, the height of a dental lamp (Luna-Vue S, Morita Seisakusho) was adjusted so that light with an illuminance of 8000 ± 1000 lx hit the sample mounting area. A glass slide (26 × 16 mm, 2 mm thick) was placed on a glass mixing board covered with matte black paper, and approximately 30 mg of sample was placed on it. After the sample was exposed to light for 60 ± 5 seconds in the sample mounting area, it was removed from the sample mounting area and immediately pressed against another glass slide to form a thin layer. If the sample did not maintain a physically uniform state at this time, it was judged to have begun to cure, and the time until cure was evaluated in 5-second increments. The longer this time, the better the ambient light stability. Ambient light stability was judged as good for 90 seconds or more, acceptable for 60 to less than 90 seconds, and insufficient for less than 60 seconds. Ambient light stability refers to the time it takes for a dental photocurable composition to be discharged from its container and to be able to change shape sufficiently without curing under ambient light such as fluorescent light. The oral cavity is a small space, making it difficult to operate freely, and the shape of natural teeth varies from person to person, so a long ambient light stability is preferable in order to adapt to a variety of cases.

[0128] <Evaluation 4: Light color stability> The prepared dental photocurable compositions were filled into stainless steel molds (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+). 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 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 was judged to be the best, a ΔE of 5 to 10 was judged to be good, and a ΔE of more than 10 was judged to be applicable. If the color stability to light is good, there will be little discoloration when used, and high aesthetics can be maintained.

[0129] <Rating 5: 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 was judged to be the best, a ΔE of 5 to 10 was judged to be good, and a ΔE of more than 10 was judged to be applicable. If the dental material has good thermal stability, there will be little discoloration when used in the oral cavity for a long period of time, and it will be able to maintain a highly aesthetic state over the long term.

[0130] The results of each test shown in Tables 3 and 4 are described below.

[0131] [Table 3]

[0132] [Table 4]

[0133] The compositions described in the examples were confirmed to exhibit a bending strength of 80 MPa or more at the preparation stage, and the bending strength did not decrease significantly even after long-term storage at low temperatures.

[0134] Examples A8, A9, A15, A16, A23, B8, B9, B15, B16, and B17 had slightly low amounts of photoacid generator, and therefore showed slightly low flexural strength values. On the other hand, when the amount of photoacid generator was slightly high, as in Examples A12, A13, A14, and B14, the flexural strength tended to decrease when a storage test was conducted at a high temperature such as 40°C, and it was confirmed that the ambient light stability was shortened and the light color stability was reduced. When the photoacid generator contained iodonium salt compounds C8 and C9, which are salts of anions and iodonium cations with a logS of -4 to -5, low-temperature storage was not a problem when the amounts were small, as in Examples A8, A9, B8, and B9. In Examples A10, A11, B10, and B11, and in Examples A12, A13, B12, and B13, where the amounts were increased, storage stability tended to decrease slightly, with some precipitates observed and photocolor stability slightly worsening after low-temperature storage, but these changes were within the range of acceptable use. Furthermore, even when an iodonium salt compound, which is a salt of anions and iodonium cations with a logS of more than -4, was contained, as in Examples A16 and A17, a trace amount of approximately 0.1 parts by weight per 100 parts by weight of polymerizable monomer did not significantly affect storage stability.

[0135] Examples A22 and B22 tended to have low bending strength due to the slightly low amount of photosensitizer blended, while Examples A21, A47, and B21 tended to have high bending strength due to the slightly high amount of photosensitizer blended, but tended to have reduced environmental light stability and reduced light color stability. Furthermore, Examples A36 and B36, which contained BAPO, an acylphosphine oxide, as the photosensitizer, tended to have lower bending strength than compositions containing an α-diketone compound as the photosensitizer.

[0136] Examples A18, A48, and B18 tended to have low bending strength due to the relatively low amount of photopolymerization accelerator blended, while Examples A19, A20, and B20 tended to have high bending strength due to the relatively high amount of photopolymerization accelerator blended, but tended to have reduced environmental light stability and reduced light color stability.

[0137] Examples A26, A27, B26, and B27 contain dibenzylaminoethanol (DBAE), which has one primary hydroxy group, as a photopolymerization accelerator, Examples A28 and B28 contain methyldiethanolamine, which has two primary hydroxy groups, as a photopolymerization accelerator, and Examples A29 and B29 contain triethanolamine, which has three primary hydroxy groups. Comparing these, it was confirmed that the thermal color stability tends to decrease as the number of primary hydroxy groups increases, and that the thermal color stability decreases significantly when there are two or more primary hydroxy groups.

[0138] Examples A30, A31, A32, B30, B31, and B32 contain the aromatic amine DMBE as a photopolymerization accelerator. It was confirmed that the inclusion of an aromatic amine reduces color stability in light. On the other hand, compositions containing both an aromatic amine and a UV absorber, such as those in Examples A33, A34, B33, and B34, can prevent the reduction in color stability in light. However, UV absorbers can increase the yellow color of the cured product, and because they do not contribute to improving physical properties, adding them in large amounts can cause a reduction in mechanical strength, so it is preferable not to add them.

[0139] Examples B41, B42, B44, and B45 contain an aromatic amine as a chemical polymerization accelerator. Similar to the use of an aromatic amine as a photopolymerization accelerator, the photocolor stability tends to decrease. Furthermore, Examples B42, B44, and B45, which contain an aromatic amine with two primary hydroxyl groups in the molecule, such as DEPT, also tend to exhibit decreased thermal color stability.

[0140] Comparative Examples CA1 and CB1 either did not cure or exhibited significantly reduced flexural strength due to the absence of a photosensitizer. Comparative Examples CA2 and CB3 exhibited significantly lower flexural strength due to the absence of a photoacid generator. Comparative Examples CA3 and CB2 exhibited significantly lower flexural strength due to the absence of a photopolymerization accelerator. Comparative Examples CA4 to CA13 and CB4 to CB13 contained an iodonium salt compound, which is a salt of an anion with a logS exceeding -4 and an iodonium cation. Comparative Examples CA4, CA5, CB5, and CB6, which contained low amounts of such photoacid generator, did not exhibit a decrease in storage stability but exhibited insufficient flexural strength. Increasing the amount of photoacid generator, as in Comparative Examples CA6 to CA9 and Comparative Examples CB6 to CB9, improved flexural strength, but precipitates were observed during low-temperature storage, indicating a tendency for flexural strength to decrease. Furthermore, a decrease in photocolor stability was also observed. Furthermore, in Comparative Examples CA10 to CA13 and Comparative Examples CB10 to CB13, in which the amount of photoacid generator was increased, the bending strength was further improved, but a decrease in storage stability and photocolor stability during storage at low and high temperatures was confirmed. The solubility of the photoacid generator affects storage stability and color stability.

[0141] 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 adhesives for fixing loose teeth, dental glass ionomer cements, dental hard resins, dental cutting materials, and dental 3D printer materials. [Industrial Applicability]

[0142] According to the present invention, it is possible to provide a dental photocurable composition that exhibits excellent mechanical properties even after being cooled from a low temperature to room temperature.

Claims

1. (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator; (C) The photoacid generator (C-1) comprises an iodonium salt compound with an anion selected from [(CF3CF2)3PF3]-, [(CF3CF2CF2)3PF3]-, [(CF3CF2SO2)3C]-, [(CF3CF2CF2CF2SO2)3C]-, [(C6H5)B(C6F5)3]-, [Ga(C6F5)4]-, and [((CF3)3CO)4Al]-; (C-1) contains 1.0 to 5.0 parts by mass of an iodonium salt compound per 100 parts by mass of the (A) polymerizable monomer, A dental photocurable composition in which the blending amount of (C) a photoacid generator other than (C-1) an iodonium salt-based compound is less than the blending amount of (C-1) an iodonium salt-based compound.

2. The dental photocurable composition according to claim 1, comprising, as the iodonium salt compound (C-1), an aryl iodonium salt composed of an anion having an organic group and one or more atoms of P, B, Al, S, or Ga, and an aryl iodonium cation.

3. The dental photocurable composition according to claim 1, comprising, as the iodonium salt compound (C-1), an aryl iodonium salt composed of an aryl iodonium cation and 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.

4. 4. The dental photocurable composition according to claim 1, further comprising (D) an aliphatic tertiary amine compound as a photopolymerization accelerator.

5. 4. The dental photocurable composition according to claim 1, further comprising (D-1) an aliphatic tertiary amine compound having no two or more primary hydroxy groups as a photopolymerization accelerator (D).

6. A one-component dental light-curable composition, (A) relative to 100 parts by mass of the polymerizable monomer, (B) 0.005 to 1.0 parts by mass of a photosensitizer; 6. The dental photocurable composition according to claim 1, further comprising 0.01 to 20 parts by mass of (D) a photopolymerization accelerator.

7. A two-component dental light-curable composition, It consists of a first paste and a second paste, The mass ratio of the first paste to the second paste is 1:0.8 to 1.2; relative to a total of 200 parts by mass of the polymerizable monomer (A) contained in the first paste and the second paste, (B) 0.01 to 2.0 parts by mass of a photosensitizer; 6. The dental photocurable composition according to claim 1, further comprising 0.02 to 40 parts by mass of (D) a photopolymerization accelerator.

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