Dental curable composition containing ultraviolet absorber

Abstract

To provide a dental curable composition with excellent solubility of an ultraviolet absorber, as well as sunlight stability, fluorescence characteristics, and mechanical strength.SOLUTION: The present invention provides a dental curable composition comprising (A) a polymerizable monomer, (B) a polymerization initiator, (C) a fluorescent agent, and (D) an ultraviolet absorber, wherein, the dental curable composition comprises, as (D) the ultraviolet absorber, a compound having at least one first absorption maximum in (D-1) a wavelength region of 250 to 320 nm and at least one second absorption maximum in a wavelength region of 320 to 400 nm, wherein a ratio of an absorbance of the first absorption maximum to an absorbance of the second absorption maximum is within a range of 1 to 4.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to dental hardenable compositions. [Background technology]

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

[0003] Patent Document 1 discloses a photopolymerizable composition containing an α-diketone and an aromatic tertiary amine as a photopolymerization initiator, and a benzotriazole compound as an ultraviolet absorber.

[0004] Patent Document 2 discloses a photopolymerizable composition containing a visible light polymerization initiator, a phthalate ester-based fluorescent agent, and a benzotriazole compound as an ultraviolet absorber.

[0005] Patent Document 3 discloses a dental photopolymerizable composition containing a photopolymerization initiator and two types of ultraviolet absorbers having an absorption maximum in a specific wavelength range.

[0006] Patent Document 4 discloses a dental composition containing a fluorescent agent and an ultraviolet absorbing agent that does not have an absorption maximum in a specific wavelength range. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent Publication No. 2004-231913 [Patent Document 2] Patent Publication 2014-15408 [Patent Document 3] Patent Publication No. 2016-166138 [Patent Document 4] WO2020-066099 Summary of the Invention [Problem to be solved by the invention]

[0008] However, dental curable compositions using the ultraviolet absorbents described in Patent Documents 1 to 4 have problems with the solubility of the ultraviolet absorbent in the polymerizable monomer, sunlight stability, fluorescence, and mechanical properties.

[0009] An object of the present invention is to provide a dental hardenable composition which has excellent solubility of an ultraviolet absorber, sunlight stability, fluorescence, and mechanical strength. [Means for solving the problem]

[0010] The dental curable composition of the present invention comprises (A) a polymerizable monomer, (B) a polymerization initiator, (C) a fluorescent agent, and (D) an ultraviolet absorber, and the ultraviolet absorber (D) comprises (D-1) a compound having at least one first absorption maximum in a wavelength range of 250 to 320 nm and at least one second absorption maximum in a wavelength range of 320 to 400 nm, and having a ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum of 1 to 4. Effect of the Invention

[0011] According to the present invention, it is possible to provide a dental curable composition having excellent solubility of an ultraviolet absorber, stability in sunlight, fluorescence, and mechanical strength. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] In the present invention, (D-1) a compound having at least one first absorption maximum in a wavelength range of 250 to 320 nm, at least one second absorption maximum in a wavelength range of 320 to 400 nm, and a ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum of 1 to 4 can be a benzophenone compound represented by formula (1).

[0013] [Formula (1)] [ka] (In the formula, R1 is an organic group having 2 to 10 carbon atoms.)

[0014] In the present invention, the polymerization initiator (B) includes a combination of a photosensitizer (B-1), a photoacid generator (B-2), and a polymerization accelerator (B-3), (B-2) A photoacid generator containing a diaryliodonium salt compound (B-3) A tertiary amine compound may be included as a polymerization accelerator.

[0015] In the present invention, the polymerization accelerator (B-3) may be substantially free of an aromatic amine compound.

[0016] In the present invention, (D-1) can include only compounds having at least one first absorption maximum in the wavelength range of 250 to 320 nm, at least one second absorption maximum in the wavelength range of 320 to 400 nm, and a ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum of 1 to 4.

[0017] In the present invention, the ultraviolet absorber (D) may contain only one kind of compound (D-1) which has at least one first absorption maximum in the wavelength range of 250 to 320 nm and at least one second absorption maximum in the wavelength range of 320 to 400 nm, and in which the ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum is 1 to 4.

[0018] In the present invention, the fluorescent agent (C) may include a terephthalic acid ester compound represented by formula (3). [Formula (3)] [ka]

[0019] In the present invention, the (C) fluorescent agent may contain only the terephthalic acid ester compound represented by formula (3). [Formula (3)] [ka]

[0020] In the present invention, the composition may contain, relative to 100 parts by mass of (A) polymerizable monomer, 0.5 to 10 parts by mass of (B) polymerization initiator, 0.001 to 0.1 parts by mass of (C) fluorescent agent, and 0.01 to 2 parts by mass of (D-1) an ultraviolet absorber having at least one first absorption maximum in a wavelength range of 250 to 320 nm and at least one second absorption maximum in a wavelength range of 320 to 400 nm, and having a ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum of 1 to 4.

[0021] The dental hardenable composition of the present invention is applied to dental adhesives, dental composite resins, dental core construction materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicure materials, dental adhesives for fixing loose teeth, dental glass ionomer cements, dental hard resins, dental cutting materials, dental 3D printer materials, orthodontic materials, etc.

[0022] In dental clinical practice, in order to restore the aesthetics and functionality of teeth that have been lost due to caries, fractures, etc., treatments are performed using direct methods, such as restoration using dental adhesives and composite resins, and indirect methods, such as restoration using prosthetic devices made of ceramics and dental hard resins with dental resin cement. In addition, dental adhesives for attaching dental composite resins to various dental materials and natural teeth, dental adhesives for fixing loose teeth, dental coating materials for protecting sensitive teeth and vital teeth after formation from external irritation and secondary caries, dental pit and fissure sealants for preventing caries by filling deep fissures in molars, dental manicure materials for temporarily restoring aesthetics by masking discoloration of teeth, and dental core construction materials for forming abutment teeth when the crown of a tooth collapses due to caries are also used. In recent years, new composite materials have been developed, such as dental cutting materials for making prosthetic devices by CAD / CAM processing, dental 3D printer materials for making prosthetic devices by 3D printers, and orthodontic materials used to treat malocclusion, and various dental materials are used in treatment. The above-mentioned 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 according to the purpose. As an example of some materials, dental filling composite resin is filled into teeth in an unhardened paste state, and after giving the anatomical form of natural teeth with dental instruments and other dental tools, it is used by irradiating it with light from a dental light irradiator or the like to harden it. The light irradiated from the light irradiator generally has a light intensity of 100 to 3500 mW / cm in the wavelength range of about 360 to 500 nm. 2 On the other hand, dental resin cement is used when bonding a prosthesis to a cavity or an abutment tooth, and is hardened by irradiating the prosthesis with light after the prosthesis is attached to the cavity or the abutment tooth.

[0023] As photopolymerization initiators used in dental materials, photosensitizers or systems combining photosensitizers with suitable photopolymerization accelerators are widely used. As photosensitizers, acylphosphine oxide compounds and α-diketone compounds are known, and α-diketone compounds in particular have polymerization initiation ability in the visible light wavelength range that has little effect on the human body. In addition, photoacid generators and tertiary amine compounds are well known as compounds to be combined with photosensitizers. The combination of α-diketone compounds, photoacid generators, and tertiary amine compounds has high polymerization activity against irradiated light, and is therefore used in the dental material field. Dental curable compositions containing the photopolymerization initiators exhibit excellent mechanical properties such as hardness, bending strength, and compressive strength required for various materials.

[0024] Representative tertiary amine compounds used in such photopolymerization initiators include aliphatic tertiary amines such as methyldiethanolamine, triethanolamine, and dimethylaminoethyl methacrylate, and aromatic tertiary amines such as ethyl dimethylaminobenzoate and p-tolylethanolamine. Since a photosensitizer, a photoacid generator, and an aromatic tertiary amine compound alone do not fully satisfy the various properties required for dental materials, such as sufficient mechanical strength, environmental light stability, and color stability, a photopolymerization initiator consisting of a photosensitizer, a photoacid generator, and an aliphatic tertiary amine compound is suitable because it can satisfy the various properties required for dental materials in a well-balanced manner.

[0025] However, dental curable compositions containing these photopolymerization initiators have a problem in that the cured product significantly discolors when exposed to ultraviolet light contained in sunlight, etc. When the polymerized cured product discolors, the color match with the surrounding tooth structure where the product is filled decreases, causing a problem of impaired aesthetics. Therefore, JIS T 6514 and ISO 4049 stipulate tests regarding sunlight stability, and require that the cured product does not significantly discolor even when exposed to ultraviolet light for a long period of time.

[0026] In order to prevent discoloration of the cured product due to exposure to ultraviolet light, an ultraviolet absorber is blended into the dental curable composition. Examples of ultraviolet absorbers that can be blended into dental curable compositions include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers, and among them, benzotriazole-based ultraviolet absorbers are known to have excellent stability against sunlight.

[0027] In addition, since natural teeth emit fluorescence by absorbing ultraviolet light, dental hardenable compositions are also formulated with fluorescent agents. Phthalate ester fluorescent agents are commonly used among fluorescent agents, and these fluorescent agents emit fluorescence by absorbing ultraviolet light in the wavelength range of 320 to 400 nm. When these fluorescent agents are formulated together with the ultraviolet absorbers, the ultraviolet light absorption of the fluorescent agent is inhibited, resulting in a problem of weakened fluorescence. In particular, many benzotriazole ultraviolet absorbers have the largest absorption maximum in the near ultraviolet range of 320 to 400 nm among the wavelength range of 250 to 400 nm, so there is a problem that they tend to inhibit fluorescence. When the amount of ultraviolet absorber is reduced or the amount of fluorescent agent is increased to compensate for fluorescence, the function of the ultraviolet absorber becomes insufficient, resulting in a problem of reduced solar light stability.

[0028] In order to solve this problem, the present inventors investigated the use of an ultraviolet absorber that does not have an absorption maximum in the near ultraviolet range of 320 to 400 nm, but has an absorption maximum in the wavelength range of 250 to 320 nm. It was found that, although the absorption of the fluorescent agent in the near ultraviolet range is not inhibited and excellent fluorescence is exhibited, the ultraviolet absorption in the wavelength range of 320 to 400 nm is insufficient, resulting in reduced solar light stability.

[0029] Furthermore, in order to achieve both solar light stability and fluorescence, a first ultraviolet absorber having an absorption maximum in the wavelength range of 250 to 320 nm and a second ultraviolet absorber having an absorption maximum in the wavelength range of 320 to 400 nm were used to combine and blend two or more ultraviolet absorbers having different absorption maximum wavelengths. However, as a result of the study by the present inventors, it was found that ultraviolet absorbers usually have low solubility in polymerizable monomers, and when two or more ultraviolet absorbers are dissolved in a polymerizable monomer, the solubility of each of the ultraviolet absorbers in the polymerizable monomer is different, so that the solubility in the polymerizable monomer is further reduced compared to when the ultraviolet absorbers are blended alone. As a result, the time required for production is increased, and when the dissolution of the ultraviolet absorber in the polymerizable monomer is insufficient, a phenomenon such as uneven coloring of the curable composition is observed.

[0030] As a result of further investigations by the present inventors, it was found that a dental curable composition having excellent solar stability, fluorescence, and mechanical properties can be obtained by using a compound having at least one first absorption maximum in the wavelength range of 250 to 320 nm, at least one second absorption maximum in the wavelength range of 320 to 400 nm, and a ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum of 1 to 4 as an ultraviolet absorber. It was also found that there is no need to blend multiple ultraviolet absorbers, and the solubility in the polymerizable monomer is good, so that there are effects such as less color unevenness and a short time required for production. The present invention is based on these findings.

[0031] The dental curable composition of the present invention is excellent in sunlight stability, fluorescence, and mechanical strength. In addition, the ultraviolet absorber of the present invention has excellent solubility in polymerizable monomers, so that it is possible to achieve effects such as a short production time and less occurrence of color unevenness.

[0032] Next, an embodiment of the present invention will be described.

[0033] [(A) Polymerizable monomer] The polymerizable monomer (A) contained in the dental curable composition of the present invention can be used without any restriction as long as it is a known one. In the polymerizable monomer or compound having a polymerizable group described in the present invention, the polymerizable group is preferably one that exhibits radical polymerizability, and specifically, from the viewpoint of easiness of radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. In this specification, "(meth)acrylic" means acrylic and / or methacrylic, "(meth)acryloyl" means acryloyl and / or methacryloyl, "(meth)acrylate" means acrylate and / or methacrylate, and "(meth)acrylamide" means acrylamide and / or methacrylamide. Polymerizable monomers having a substituent at the α-position of the acrylic group and / or acrylamide group can also be preferably used. Examples of the polymerizable monomers include those having one radical polymerizable group, those having two radical polymerizable groups, those having three or more radical polymerizable groups, those having an acidic group, an alkoxysilyl group, and those having a sulfur atom.

[0034] Specific examples of polymerizable monomers having one radical polymerizable group and no acidic group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, propylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, erythritol mono(meth)acrylate, N-methylol (meth)acrylamide, N -hydroxyethyl (meth)acrylamide, N,N-(dihydroxyethyl) (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, 3-(meth)acryloyloxypropyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, (meth)acrylamide, and the like.

[0035] 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, and 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)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"), 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, etc.

[0036] 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, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like.

[0037] Specific examples of polymerizable monomers having an alkoxysilyl group include (meth)acrylic compounds and (meth)acrylamide compounds having one alkoxysilyl group in the molecule, and (meth)acrylic compounds and (meth)acrylamide compounds having multiple alkoxysilyl groups in the molecule. Examples of the silane include 2-(meth)acryloxyethyl trimethoxysilane, 3-(meth)acryloxypropyl trimethoxysilane, 3-(meth)acryloxypropyl triethoxysilane, 3-(meth)acryloxypropyl methyl dimethoxysilane, 4-(meth)acryloxybutyl trimethoxysilane, 5-(meth)acryloxypentyl trimethoxysilane, 6-(meth)acryloxyhexyl trimethoxysilane, 7-(meth)acryloxyheptyl trimethoxysilane, 8-(meth)acryloxyoctyl trimethoxysilane, 9-(meth)acryloxynonyl trimethoxysilane, 10-(meth)acryloxydecyl trimethoxysilane, and 11-(meth)acryloxyundecyl trimethoxysilane.Furthermore, examples of compounds having a urethane group or an ether group include 3,3-dimethoxy-8,37-dioxo-2,9,36-trioxa-7,38-diaza-3-silatetracontan-40-yl(meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,18-trioxa-7-aza-3-silanonadecan-19-oyl)amino)-2-methylpropane-1,3-diyldi(meth)acrylate, and 3,3-dimethoxy-8,19-dioxo-2,9,18-trioxa-7,20-diaza-3-siladocosan-22-yl(meth)acrylate. acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21-hexaoxa-7,23-diaza-3-silapentacosan-25-yl (meth)acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21,26-heptaoxa-7,23-diaza-3-silaoctacosan-28-yl (meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18-pentaoxa-7,20-diaza-3-siladocosane-22-yl (meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18-pentaoxa-7,20-diaza-3-siladocosane-22-yl (meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,12,15,18-pentaoxa-7-aza-3-silanonadecane-19-yl)amino)-2-methylpropane-1,3-diyl di(meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosane-23-yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosane-23-yl (meth)acrylate 4,4-diethoxy-13-oxo-3,12,17-trioxa-14-aza-4-silanonadecan-19-yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silaicosan-20-yl (meth)acrylate, and 2-methyl-2-((11-(triethoxysilyl)undecyloxy)carbonylamino)propane-1,3-diyl di(meth)acrylate.

[0038] The dental curable composition of the present invention may contain a polymerizable monomer having a sulfur atom as a polymerizable monomer (A) in order to impart adhesion to precious metals. The polymerizable monomer having a sulfur atom may be any known compound without any restrictions, so long as it is a polymerizable monomer having one or more sulfur atoms and a polymerizable group. Specifically, it refers to a compound having a partial structure such as -SH, -SS-, >C=S, >CSC<, >P=S, or a compound resulting from tautomerization. Specific examples include 10-methacryloxydecyl-6,8-dithiooctanate, 6-methacryloxyhexyl-6,8-dithiooctanate, 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate, 2-(11-methacryloyloxyundecylthio)-5-mercapto-1,3,4-thiadiazole, and 10-(meth)acryloyloxydecyl dihydrogen thiophosphate.

[0039] In addition to these polymerizable monomers, there is no limitation in using oligomers or prepolymers having at least one polymerizable group in the molecule. In addition, there is no problem in having a substituent such as a fluoro group in the same molecule. The above-mentioned polymerizable monomers can be used alone or in combination.

[0040] The dental curable composition of the present invention may contain a silane coupling agent as a polymerizable monomer (A) in order to impart adhesion to glass ceramics. Any known silane coupling agent may be used without limitation, but 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 11-methacryloxyundecyltrimethoxysilane, etc. are preferred. From the viewpoint of imparting adhesion, the blending amount is 1 part by mass or more, more preferably 5 parts by mass or more and less than 20 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers in the composition. The silane coupling agent as a polymerizable monomer is blended separately from the surface treatment agent for the filler, since the purpose of the silane coupling agent is to impart adhesion to glass ceramics or resin materials containing a filler made of glass ceramics.

[0041] The dental curable composition of the present invention may contain a polymerizable monomer having a sulfur atom as a polymerizable monomer (A) in order to impart adhesiveness to precious metals. The 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 and less than 20 parts by mass, based on the total amount of 100 parts by mass of the polymerizable monomers contained in the dental curable composition, from the viewpoint of imparting adhesiveness.

[0042] Although the polymerizable monomer contained in the dental hardenable composition of the present invention may contain a polymerizable monomer having a cationic polymerizable functional group, it is preferable that the composition contains only a polymerizable monomer having a radical polymerizable functional group. When the composition contains a cationic polymerizable monomer, the storage stability may be reduced.

[0043] Examples of the polymerizable monomer having a cationic polymerizable functional group include vinyl ether compounds, epoxy compounds, oxetane compounds, cyclic ether compounds, and cyclic carbonate compounds.

[0044] The dental curable composition of the present invention can contain (A1) a polymerizable monomer having an acidic group. 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 phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, or a carboxylic acid group. By containing a polymerizable monomer having an acidic group, it is possible to impart adhesion to teeth and prosthetic devices.

[0045] Specific examples of polymerizable monomers 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)acryloyloxyethyl dihydrogen phosphate, 9-(meth)acryloyloxypropyl dihydrogen phosphate, 10-(meth)acryloyloxybutyl dihydrogen phosphate, 11-(meth)acryloyloxybutyl dihydrogen phosphate, 12-(meth)acryloyloxybutyl dihydrogen phosphate, 13-(meth)acryloyloxypentyl 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-(meth)acrylo 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]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di( Examples of the 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.

[0046] 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.

[0047] 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)acryloyloxyhexyl dihydrogen thiophosphate. Examples of the acryloyloxynonyl dihydrogen thiophosphate include 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 of these compounds is replaced with an amide bond. Polymerizable monomers having a thiophosphate group are also classified as polymerizable monomers having a sulfur atom.

[0048] Specific examples of the polymerizable monomer having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenyl phosphonate, 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.

[0049] Specific examples of the polymerizable monomer having a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid, 2-sulfoethyl(meth)acrylate, and the like.

[0050] 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 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen malate; acid halides thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.Specific examples of (meth)acrylic compounds having multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)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 of the acid anhydride and acid halide of these compounds 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; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0051] Preferred examples of the polymerizable monomer having an acidic group (A1) include (meth)acrylic acid, 10-methacryloyloxydecyl dihydrogen phosphate, 6-methacryloxyhexyl phosphonoacetate, 4-(meth)acryloyloxyethyl trimellitate, and acid anhydrides thereof. The amount of the polymerizable monomer having an acidic group (A1) to be blended is preferably 1 part by mass or more and 20 parts by mass or less in 100 parts by mass of the polymerizable monomer (A) from the viewpoint of imparting adhesiveness. If the amount is less than 1 part by mass, sufficient adhesiveness may not be exhibited, and if the amount exceeds 20 parts by mass, storage stability or curing property may decrease.

[0052] [(B) Polymerization initiator] The polymerization initiator used in the dental curable composition of the present invention is not particularly limited, and known radical generators can be used. Polymerization initiators are generally broadly classified into those that initiate polymerization by mixing immediately before use (chemical polymerization initiators), those that initiate polymerization by heating or warming (thermal polymerization initiators), and those that initiate polymerization by light irradiation (photopolymerization initiators), and can be selected from these depending on the method of use and purpose. In addition, these polymerization initiators can be used alone or in combination, regardless of the polymerization mode or polymerization method. Furthermore, these polymerization initiators can be used without any problem even if they are subjected to secondary treatment such as encapsulation in microcapsules to achieve polymerization stabilization or polymerization delay.

[0053] Examples of the chemical polymerization initiator include a redox-type polymerization initiation system consisting of an organic peroxide / amine compound, an organic peroxide / amine compound / sulfinate salt, an organic peroxide / amine compound / borate compound, or the like, and an organometallic polymerization initiator system which reacts with oxygen or water to initiate polymerization. Furthermore, sulfinate salts and borate compounds can also initiate polymerization by reacting with a polymerizable monomer having an acidic group.

[0054] Specific examples of organic peroxides include benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, 2,5-dihydroperoxide, methyl ethyl ketone peroxide, and tertiary butyl peroxybenzoate.

[0055] Specific examples of the amine compound include secondary or tertiary amines in which an amine group is bonded to an aryl group, and specific examples include pN,N-dimethyl-toluidine, N,N-dimethylaniline, N-β-hydroxyethyl-aniline, N,N-di(β-hydroxyethyl)-aniline, pN,N-di(β-hydroxyethyl)-toluidine, N-methyl-aniline, and pN-methyl-toluidine.

[0056] Specific examples of sulfinic acid salts include sodium benzenesulfinate, lithium benzenesulfinate, and sodium p-toluenesulfinate.

[0057] Specific examples of borate compounds include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, and tetramethylammonium salts of trialkylphenylboron and trialkyl(p-fluorophenyl)boron (wherein the alkyl group is an n-butyl group, an n-octyl group, an n-dodecyl group, or the like).

[0058] Specific examples of organometallic polymerization initiators include organoboron compounds such as triphenylborane, tributylborane, and tributylborane partial oxide, and fourth period transition metal compounds.

[0059] As the thermal polymerization initiator by heating or warming, in addition to the above organic peroxides, azo compounds such as azobisisobutyronitrile, methyl azobisisobutyrate, and azobiscyanovaleric acid are preferably used.

[0060] The photopolymerization initiator may be a photosensitizer, a combination of a photosensitizer / photopolymerization accelerator, or a combination of a photosensitizer / photoacid generator / photopolymerization accelerator. Among them, the photopolymerization initiator used in the dental hardenable composition of the present invention preferably includes a combination of (B-1) a photosensitizer, (B-2) a photoacid generator, and (B-3) a polymerization accelerator. Any known compound that is generally used may be used without any restrictions.

[0061] [(B-1) Photosensitizer] Specific examples of the photosensitizer (B-1) that can be used in the present invention include α-diketones such as benzil, camphorquinone, camphorquinonecarboxylic acid, camphorquinonesulfonic acid, α-naphthyl, acetonaphthene, p,p'-dimethoxybenzyl, p,p'-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, and naphthoquinone; benzoins such as benzoin methyl ether and benzoin ethyl ether; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones; benzophenone, p-chlorobenzophenone, p-methoxybenzophenone and other benzophenones; bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl) )phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzo yl)(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-dimethoxybenzoyl benzyl 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, α-aminoacetophenones such as α-propanone-1, ketals such as benzyl dimethyl ketal, benzyl diethyl ketal, and benzyl (2-methoxyethyl ketal), and titanocenes such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]-titanium, bis(cyclopentadienyl)-bis(pentanefluorophenyl)-titanium, and bis(cyclopentadienyl)-bis(2,3,5,6-tetrafluoro-4-disiloxyphenyl)-titanium.

[0062] (B-1) Photosensitizer can be appropriately selected according to the wavelength, intensity, and light irradiation time of the light used for polymerization, and the type and amount of other components to be combined. The photosensitizer can be used alone or in combination of two or more kinds. Among them, α-diketone compounds having an absorption maximum wavelength in the visible light region are preferably used, and camphorquinone compounds such as camphorquinone, camphorquinone carboxylic acid, and camphorquinone sulfonic acid are more preferably used, and camphorquinone is particularly preferred because it is easily available.

[0063] The dental hardenable composition of the present invention may contain only an α-diketone compound as the photosensitizer (B-1).

[0064] [(B-2) Photoacid generator] The photoacid generator (B-2) used in the dental curable composition of the present invention can be any known compound without limitation. Specific examples include triazine compounds, iodonium salt compounds, sulfonium salt compounds, and sulfonic acid ester compounds. Among these, triazine compounds and iodonium salt compounds are preferred because of their high polymerizability when used in combination with a sensitizer. More preferred are iodonium salt compounds. Iodonium salt compounds are easily sensitized by photosensitizers that have absorption in the visible light region.

[0065] Specific examples of triazine compounds include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine. , 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis s-triazine, 2-[2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4, 6-bis(trichloromethyl)-s-triazine, 2-(1-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis(2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,Examples of the 6-bis(trichloromethyl)-s-triazine include 2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine. Among these, 2,4,6-tris(trichloromethyl)-s-triazine is preferred.

[0066] Any known iodonium salt compound can be used. To give a specific example, the structural formula of an iodonium salt compound can be represented by the following formula (2). [Formula (2)] [(R1)2I] + [A] - (In the formula, [(R1)2I] + is the cationic portion, [A] - is an anion moiety, and R1 in formula (2) represents an organic group bonded to I, and R1 may be the same or different. R1 represents, for example, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms, which may be substituted with at least one selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, and nitro groups, and halogen.

[0067] In the above, examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as a phenyl group, and condensed polycyclic aryl groups such as naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, and anthraquinone.

[0068] Examples of the heterocyclic group having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 heteroatoms such as oxygen, nitrogen, and sulfur, which may be the same or different. Specific examples include monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, and pyrazinyl, and condensed polycyclic heterocyclic groups such as indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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 type of 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, aryl ... Linear or branched alkylcarbonyl groups having 2 to 18 carbon atoms, such as kutanoyl; arylcarbonyl groups having 7 to 11 carbon atoms, such as benzoyl and naphthoyl; linear 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; linear or branched alkylthio groups having 1 to 18 carbon atoms, such as methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, and dodecylthio; 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 of the arylsulfonyl group include arylsulfonyl groups having 6 to 10 carbon atoms, such as phenylsulfonyl, tolylsulfonyl (tosyl group), and naphthylsulfonyl; alkyleneoxy groups; cyano groups; nitro groups; and halogens such as fluorine, chlorine, bromine, and iodine.

[0073] Among the iodonium salt compounds, aryl iodonium salts are preferred because they are highly stable. In addition, it is preferred that the aryl group has a substituent in order to improve fat solubility. 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, or functional groups in which one or more H of these hydrocarbon groups are replaced with F, perfluoroalkyl groups, and halogens are preferred as the substituent.

[0074] The structure of the anion portion of the iodonium salt compound is not particularly limited, but examples include those having atoms such as halogen, P, S, B, Al, and Ga. Anions having As or Sb can be used, but are not preferred for dental applications from the viewpoint of safety. In addition, the anion preferably has an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group, and more preferably has an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which at least one H is substituted with F. Since the iodonium salt compound having such an anion has high solubility in the dental hardenable composition, it is expected to prevent precipitation during low-temperature storage or long-term storage, and to shorten the manufacturing time because it dissolves in the composition in a short time. In addition, an iodonium salt compound consisting of an anion having an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which one or more H is substituted with F can be expected to have even higher solubility. If the photoacid generator precipitates, it may cause a decrease in light color stability and a decrease in bending strength, which is not preferred. The anion having an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which at least one H may be substituted with F 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 preferable.

[0075] 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.

[0076] [A] of the iodonium salt compound of formula (2) - In order to improve the solubility in the dental hardenable composition, the anion part of the formula (2) is preferably an anion having an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which at least one H is substituted with F. Specifically, [A] of the iodonium salt compound of the formula (2) is - The alkyl group in the anion portion preferably has 1 to 8 carbon atoms, 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 (F / H) of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group is 4 or more, and preferably the ratio (F / H) of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group is 9 or more. More preferably, all hydrogen atoms of the hydrocarbon are substituted with fluorine. The dental curable composition may contain an iodonium salt consisting of an anion having an alkyl group with a different ratio of hydrogen atoms to fluorine atoms.

[0077] Further specific examples of the alkyl group include linear or branched perfluoroalkyl groups such as CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C.

[0078] [A] of the iodonium salt compound of formula (2) - The number of carbon atoms of the alkoxy group in the anion portion is preferably 1 to 8, more preferably 1 to 4. 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 (F / H) of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group is 4 or more, and preferably the ratio (F / H) of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group is 9 or more. More preferably, all of the hydrogen atoms in the hydrocarbon are substituted with fluorine. The dental curable composition may contain an iodonium salt consisting of an anion having an alkoxy group with a different ratio of hydrogen atoms to fluorine atoms.

[0079] Further specific examples of alkoxy groups include linear or branched perfluoroalkoxy groups such as CF3O, CF3CF2O, CF3CF2CF2O, (CF3)2CFO, CF3CF2CF2CF2O, (CF3)2CFCF2O, CF3CF2(CF3)CFO, CF3CF2CF2CF2CF2O, CF3CF2CF2CF2CF2CF2CF2CF2CF2CF2O.

[0080] [A] of the iodonium salt compound of formula (2) -The phenyl group in the anion moiety has at least one hydrogen atom substituted with a fluorine atom, and / or an alkyl group and / or an alkoxy group substituted with a fluorine atom. The alkyl group and / or alkoxy group substituted with a fluorine atom are preferably those described above. Particularly preferred specific examples of the phenyl group include perfluorophenyl groups such as pentafluorophenyl group (CF5), trifluorophenyl group (CHF3), tetrafluorophenyl group (CHHF4), trifluoromethylphenyl group (CF3C6H4), bis(trifluoromethyl)phenyl group ((CF3)2C6H3), pentafluoroethylphenyl group (CF3CF2C6H4), bis(pentafluoroethyl)phenyl group ((CF3CF2)2C6H3), trifluoromethylfluorophenyl group (CF3C6H3F), bistrifluoromethylfluorophenyl group ((CF3)2C6H2F), pentafluoroethylfluorophenyl group (CF3CF2C6H3F), and bispentafluoroethylfluorophenyl group ((CF3CF2)2C6H2F). The dental hardenable composition may contain an iodonium salt consisting of an anion having a phenyl group with a different ratio of hydrogen atoms to fluorine atoms.

[0081] [A] of the iodonium salt compound of formula (2) - A specific example of the anion portion of the anion having P is [(CF3CF2)3PF3] - , [(CF3CF2CF2)3PF3] - , [((CF3)2CF)2PF4] - , [((CF3)2CF)3PF3] - , [((CF3)2CF)4PF2] - , [((CF3)2CFCF2)2PF4] - , [((CF3)2CFCF2)3PF3] - The anion containing S is [(CF3SO2)3C] - , [(CF3CF2SO2)3C] - , [(CF3CF2CF2SO2)3C] - , [(CF3CF2CF2CF2SO2)3C] -, [CF3CF2CF2CF2SO3] - , [CF3CF2CF2SO3] - , [(CF3CF2SO2)3C] - , [(SO2CF3)3N] - , [(SO2CF2CF3]2N] - , [((CF3)C6H4)SO3] - , [SO3((CF2CF2CF2CF2)SO3] 2- Examples of anions containing B include [B(C6F5)4] - , [(C6H5)B((CF3)2C6H3)3] - , [(C6H5)B(C6F5)3] - , etc. An anion having Ga is [((C6F5)3(C6H5)Ga)] - , [((C6F5)3(C4F9)Ga)] - , [((C6H2F3)4Ga)] - , [((CF3)2C6H3)4Ga)] - , [[((CF3)4Ga)] - , [Ga(C6F5)4] - Examples of anions containing Al include [((CF3)3CO)4Al] - , [((CF3CF2)3CO)4Al] - etc.

[0082] The photoacid generator that can be used in the dental hardenable composition of the present invention is not limited to the photoacid generators shown as specific examples, and two or more types can be used in combination.

[0083] [(B-3) Polymerization accelerator] The polymerization accelerator (B-3) used in the dental hardenable composition of the present invention is not particularly limited as long as it has the ability to accelerate polymerization, and known polymerization accelerators generally used in the dental field can be used without any restrictions. As the polymerization accelerator (B-3), primary to tertiary amine compounds such as aromatic amine compounds and aliphatic amine compounds, phosphine compounds, organometallic compounds, transition metal compounds of the fourth period, thiourea derivatives, sulfinic acid and its salts, borate compounds, reducing inorganic compounds containing sulfur, reducing inorganic compounds containing nitrogen, barbituric acid derivatives, triazine compounds, halogen compounds, etc. can be used.

[0084] Aromatic amine compounds refer to compounds in which one or more H of ammonia (NH3) is substituted with an aromatic ring. Compounds in which one H of NH3 is substituted with an aromatic ring are classified as aromatic primary amine compounds, compounds in which one H of NH3 is substituted with an aromatic ring and another H is substituted with an aromatic ring or an alkyl group are classified as aromatic secondary amine compounds, and compounds in which one H of NH3 is substituted with an aromatic ring and two different H are substituted with aromatic rings or alkyl groups are classified as aromatic tertiary amine compounds.

[0085] Specific examples of aromatic primary amine compounds include aniline, etc., specific examples of aromatic secondary amine compounds include N-phenylbenzylamine, N-benzyl-p-anisidine, N-benzyl-o-phenetidine, N-phenylglycine ethyl, N-phenylglycine and other N-protected amino acids (esters), etc., 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, 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-dihydroxyethyl aniline, N,N-diisopropanol aniline, pN,N-dihydroxyethyl-toluidine, pN,N-dihydroxypropyl-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N,N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine, N,N-dimethyl-β-naphthylamine, etc. Among these, p-dimethylaminobenzoic acid ethyl ester is preferred.

[0086] The phosphine compound refers to a compound in which the P atom is substituted with three organic groups, and the aromatic phosphine compound refers to a compound in which the P atom is substituted with a phenyl group which may have one or more substituents. 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)benzoic acid. 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, bis[2-(diphenylphosphino)phenyl]ether, etc. Among these, triphenylphosphine, 4-(phenylphosphino)benzoic acid, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, and tri(p-tolyl)phosphine are preferred.

[0087] Aliphatic amine compounds refer to compounds in which one or more H of ammonia (NH3) is replaced by an alkyl group. The alkyl group is classified as follows: CH3- or CH2- is a primary alkyl group, -CH2- with one H substituted as a secondary alkyl group, -CH2- with two H substituted as a tertiary alkyl group. Aliphatic amines are classified as aliphatic primary amine compounds in which one H of NH3 is replaced by an alkyl group, aliphatic secondary amine compounds in which two H of NH3 are replaced by alkyl groups, and aliphatic tertiary amine compounds in which three H of NH3 are replaced by alkyl groups.

[0088] Specific examples of aliphatic primary amine compounds include benzhydrylamine, triphenylmethylamine, amino acids such as glycine, and 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, and 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-Dimethyl Methylisopropanolamine, 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 of the amines 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.

[0089] Specific examples of the organometallic compounds include organometallic compounds containing scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), tin (Sn), zinc (Zn), and zirconium (Zr), and preferably organometallic compounds containing tin (Sn), vanadium (V), and copper (Cu). Specific examples of organometallic compounds containing tin (Sn) include dibutyl-tin-diacetate, dibutyl-tin-dimaleate, dioctyl-tin-dimaleate, dioctyl-tin-dilaurate, dibutyl-tin-dilaurate, dioctyl-tin-diversatate, dioctyl-tin-S,S'-bis-isooctylmercaptoacetate, and tetramethyl-1,3-diacetoxydistannoxane. Specific examples of organometallic compounds containing vanadium (V) include acetylacetate. Examples of the organometallic compounds containing copper (Cu) include copper acetylacetonate, copper naphthenate, copper octylate, copper stearate, and copper acetate.

[0090] Among these, trivalent or tetravalent vanadium compounds and divalent copper compounds are preferred, and trivalent or tetravalent vanadium compounds having higher polymerization promoting ability are more preferred, and tetravalent vanadium compounds are most preferred. These fourth period transition metal compounds may be used in combination of a plurality of types as necessary. The blending amount of the transition metal compound is preferably 0.0001 to 1 part by mass relative to 100 parts by mass of the total amount of the polymerizable monomer (A). If the blending amount is less than 0.0001 part by mass, the polymerization promoting effect may be insufficient, and if the blending amount exceeds 1 part by mass, discoloration or gelation of the dental curable composition may occur, resulting in reduced storage stability.

[0091] As the thiourea derivative, any known thiourea derivative can be used without limitation. Specific examples include dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl)thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, N-benzylthiourea, 1,3-dicyclohexylthiourea, N,N'-diphenylthiourea, 1,3-di(p-tolyl)thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea, dicyclohexylthiourea, etc. Among these, (2-pyridyl)thiourea, N-acetylthiourea, and N-benzoylthiourea are preferred. These thiourea derivatives may be used in combination as necessary. 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.

[0092] 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 of the sulfinic acid salt 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. Of these, sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferred.

[0093] Specific examples of borate compounds having one aryl group per molecule include trialkylphenyl boron, trialkyl(p-chlorophenyl) boron, trialkyl(p-fluorophenyl) boron, trialkyl(3,5-bistrifluoromethyl) phenyl boron, 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 the alkyl group 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), as well as 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.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 the 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 (p-butyloxyphenyl)boron, 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, and the like).Specific examples of borate compounds having four aryl groups in one molecule include tetraphenyl boron, tetrakis(p-chlorophenyl) boron, tetrakis(p-fluorophenyl) boron, tetrakis(3,5-bistrifluoromethyl)phenyl boron, 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 suitable aryloxyphenyl)boron 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.

[0094] Among these aryl borate compounds, it is more preferable to use a borate compound having 3 or 4 aryl groups in one molecule from the viewpoint of storage stability. In addition, these aryl borate compounds can be used alone or in combination of two or more kinds.

[0095] Examples of reducing inorganic compounds containing sulfur include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, and dithionites. Specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

[0096] The nitrogen-containing reducing inorganic compound may be a nitrite, and specific examples thereof include sodium nitrite, potassium nitrite, calcium nitrite, and ammonium nitrite.

[0097] 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 propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and salts of thiobarbituric acids (preferably salts of alkali metals or alkaline earth metals). Specific examples of the salts of barbituric acids include sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate.

[0098] Specific examples of the halogen compound include dilauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, benzyl trimethyl ammonium chloride, tetramethyl ammonium chloride, benzyl dimethyl cetyl ammonium chloride, and dilauryl dimethyl ammonium bromide.

[0099] These polymerization initiators (B-1) photosensitizer, (B-2) photoacid generator, and (B-3) polymerization accelerator may be subjected to secondary treatment such as fine grinding, carrier adsorption, encapsulation in microcapsules, etc. 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.

[0100] The amount of the polymerization initiator (B) is preferably 0.5 to 10 parts by mass per 100 parts by mass of the total amount of the polymerizable monomer (A). If it is less than 0.5 parts by mass, the mechanical strength may be insufficient. If it is more than 10 parts by mass, although sufficient curability is obtained, the ambient light stability may be shortened and discoloration may increase, such as the cured body becoming brownish or yellowish, which is not preferable.

[0101] Among the (B) polymerization initiators, it is preferable that the (B) polymerization initiator contains a combination of (B-1) a photosensitizer, (B-2) a photoacid generator, and (B-3) a polymerization accelerator. In this case, it is preferable that the (B-2) photoacid generator contains a diaryliodonium salt compound. It is also preferable that the (B-3) polymerization accelerator contains a tertiary amine compound. By containing a (B-2) photoacid generator containing a diaryliodonium salt compound and a (B-3) polymerization accelerator containing a tertiary amine compound, it is possible to obtain excellent photocuring properties.

[0102] More preferably, the composition is substantially free of aromatic amine compounds as the polymerization accelerator (B-3). Substantially free means that the composition is not intentionally blended. For example, when aromatic amines are included in the impurities of the components contained in the dental curable composition, or when the dental curable composition contains only a trace amount of less than 0.1 parts by mass relative to 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental curable composition, the composition is deemed substantially free if it does not affect the properties of the dental curable composition. When an aromatic amine compound is used as a polymerization accelerator, the photopolymerization promoting ability tends to be higher than when an aliphatic amine compound is used, but there is a problem that the solar stability is significantly reduced. Therefore, when an aromatic amine compound is used, it is necessary to blend a large amount of an ultraviolet absorber in order to ensure solar stability, which may reduce the fluorescence and mechanical properties. When the dental curable composition of the present invention contains an amine compound as the polymerization accelerator (B-3), it is preferably an aliphatic amine compound.

[0103] [(C) Fluorescent agent] The dental curable composition of the present invention contains a fluorescent agent (C). As the fluorescent agent (C), any known fluorescent agent that is generally used can be used without any limitation.

[0104] Specific examples of the fluorescent agent (C) that can be used in the present invention include terephthalic acid ester compounds such as dimethyl-2,5-dihydroxyterephthalate, diethyl-2,5-dihydroxyterephthalate, dimethyl-2,5-diaminoterephthalate, diethyl-2,5-diaminoterephthalate, dimethylaminoterephthalate, and diethylaminoterephthalate; benzoxazole compounds such as 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole) and 2,2'-(1,2-ethylenediyldi-4,1-phenylene)bisbenzoxazole; and phthalic acid derivatives such as o-phthalaldehyde.

[0105] Among these fluorescent agents, the terephthalic acid ester compound represented by formula (3) is preferred because it is relatively easy to obtain, does not affect the color tone when mixed into a dental hardenable composition, and emits fluorescence similar to that of natural teeth, and it is particularly preferred to use diethyl-2,5-dihydroxyterephthalate, which corresponds to the structure represented by formula (3). These fluorescent agents may be used alone or in combination of two or more. The fluorescent agent may contain only the terephthalic acid ester compound represented by formula (3), or may contain only diethyl-2,5-dihydroxyterephthalate. [Formula (3)] [ka] (In the formula, R1 and R2 are each independently an alkyl group, R3 is a hydrogen atom, an amino group, or a hydroxyl group, and R4 is an amino group or a hydroxyl group. The alkyl group has 1 to 3 carbon atoms and is, for example, a methyl group, an ethyl group, an n-propyl group, or an i-propyl group.)

[0106] The dental curable composition of the present invention preferably contains 0.001 to 0.1 parts by mass of the fluorescent agent (C) relative to 100 parts by mass of the total amount of the polymerizable monomer (A). If the amount of the fluorescent agent is less than 0.001 parts by mass, the fluorescence may be poor. If the amount of the fluorescent agent is more than 0.1 parts by mass, the fluorescence may be too strong compared to natural teeth and may look unnatural.

[0107] [(D) Ultraviolet absorber] The dental hardenable composition of the present invention includes an ultraviolet light absorber.

[0108] In the present invention, the ultraviolet absorbent (D) includes a compound (D-1) having at least one first absorption maximum in the wavelength range of 250 to 320 nm, at least one second absorption maximum in the wavelength range of 320 to 400 nm, and a ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum of 1 to 4. Compounds that fall under this category of (D-1) do not include compounds that do not have at least one first absorption maximum in the wavelength range of 250 to 320 nm. Compounds that fall under this category of (D-1) do not include compounds that do not have at least one second absorption maximum in the wavelength range of 320 to 400 nm. Compounds that fall under this category of (D-1) can be selected from known ultraviolet absorbents that are commonly used.

[0109] The dental curable composition of the present invention may contain only a compound (D-1) having at least one first absorption maximum in a wavelength range of 250 to 320 nm and at least one second absorption maximum in a wavelength range of 320 to 400 nm, and the ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum is 1 to 4. The dental curable composition of the present invention may not contain a compound that does not fall under (D-1) as the ultraviolet absorbent (D). As the ultraviolet absorbent (D) consisting of such a compound that does not fall under (D-1), a commonly used known ultraviolet absorbent can be used.

[0110] Furthermore, the dental curable composition of the present invention may contain, as the ultraviolet absorbent (D), only one kind of compound (D-1) having at least one first absorption maximum in the wavelength range of 250 to 320 nm and at least one second absorption maximum in the wavelength range of 320 to 400 nm, and having a ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum of 1 to 4.

[0111] The dental curable composition of the present invention may contain, as the ultraviolet absorbent (D), two or more kinds of compounds (D-1) having at least one first absorption maximum in a wavelength range of 250 to 320 nm and at least one second absorption maximum in a wavelength range of 320 to 400 nm, and having a ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum of 1 to 4.

[0112] Many of the fluorescent agents blended in dental curable compositions absorb near-ultraviolet light of 320 to 400 nm and emit fluorescence. In addition, some polymerization initiators blended in dental curable compositions have absorption in the near-ultraviolet region of 320 to 400 nm. In the study by the present inventors, it was found that when a compound having at least one first absorption maximum in the wavelength region of 250 to 320 nm, at least one second absorption maximum in the wavelength region of 320 to 400 nm, and a ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum is 1 to 4, is used as an ultraviolet absorbent, the compound has excellent fluorescence, mechanical properties, and solar light stability, and the present invention has been completed. In the present invention, the absorption maximum refers to a point in the absorption spectrum of the ultraviolet absorbent where the absorbance curve is convex upward and becomes 0 when differentiated. In the present invention, the first absorption maximum is an absorption maximum present in the wavelength region of 320 to 400 nm, and the second absorption maximum is an absorption maximum present in the wavelength region of 320 to 400 nm. The compound corresponding to (D-1) contained in the ultraviolet absorbent (D) of the present invention has at least one first absorption maximum and at least one second absorption maximum. In addition, the compound may have multiple first absorption maximums and / or multiple second absorption maximums.

[0113] In the compound corresponding to (D-1) contained in the ultraviolet absorber (D) of the present invention, the ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum is 1 to 4, preferably 1.1 to 3, and more preferably 1.2 to 2. When a compound having an absorbance ratio of less than 1 is used as the ultraviolet absorber (D), the absorption of the fluorescent agent and the polymerization initiator in the near ultraviolet region is inhibited, and the fluorescence and mechanical properties of the curable composition tend to decrease, and the distribution of ultraviolet absorption in the wavelength region of 250 to 400 nm is biased, so that the solar stability is also decreased. On the other hand, when a compound having an absorbance ratio of more than 4 is used as the ultraviolet absorber (D), although excellent fluorescence is exhibited, the distribution of ultraviolet absorption in the wavelength region of 250 to 400 nm is biased, so that the solar stability is decreased.

[0114] The compound corresponding to (D-1) contained in the ultraviolet absorber (D) used in the present invention preferably has a second absorption maximum wavelength of less than 350 nm. When the second absorption maximum wavelength of the compound corresponding to (D-1) contained in the ultraviolet absorber (D) is less than 350 nm, it exhibits particularly excellent fluorescence, mechanical properties, and solar light stability. When the second absorption maximum wavelength is 350 nm or more, it overlaps greatly with the ultraviolet absorption range of the fluorescent agent and the polymerization initiator, and the fluorescence and mechanical properties may be slightly reduced.

[0115] The absorbance at the absorption maximum wavelength of the ultraviolet absorbent containing the compound corresponding to (D-1) can be obtained by dissolving the ultraviolet absorbent in an organic solvent in which the ultraviolet absorbent is soluble and measuring with a spectrophotometer. The organic solvent is not particularly limited as long as each compound is soluble in the organic solvent, but it is necessary to select an organic solvent having a transmittance of 50% or more in the ultraviolet range of 250 to 400 nm so as not to inhibit the absorbance in the ultraviolet range of the ultraviolet absorbent containing the compound corresponding to (D-1). Examples of organic solvents having a transmittance of 50% or more in the ultraviolet range of 250 to 400 nm include acetonitrile, n-hexane, methanol, ethanol, etc., and from these, an organic solvent in which the ultraviolet absorbent containing the compound corresponding to (D-1) is soluble can be arbitrarily selected. Among these organic solvents, acetonitrile, which has a high transmittance in the ultraviolet range of 250 to 400 nm, is particularly preferable.

[0116] For the measurement of absorbance of a compound corresponding to (D-1), a cell that does not absorb in the ultraviolet region of 250 to 400 nm is used. A quartz cell is generally used as such a cell.

[0117] The concentration of the ultraviolet absorber containing the compound corresponding to (D-1) in the organic solvent may be appropriately adjusted so that both the first absorption maximum and the second absorption maximum have an absorbance in the range of 0.2 to 2. If the absorbance is out of this range, it will be out of the effective range of transmittance, resulting in a large measurement error. In addition, since the absorption coefficient differs depending on the type of ultraviolet absorber, the concentration in the organic solvent when the absorbance is adjusted to be in the range of 0.2 to 2 differs for each ultraviolet absorber. However, the ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum derived from the absorbance measurement result of the ultraviolet absorber of the present invention (containing the compound corresponding to (D-1)) is not affected by the concentration of the ultraviolet absorber in the organic solvent as long as the absorbance is appropriately adjusted to be in the range of 0.2 to 2.

[0118] The ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum of the ultraviolet absorber is calculated by dividing the absorbance of the peak top of the first absorption maximum present in the wavelength range of 250 to 320 nm by the absorbance of the peak top of the second absorption maximum present in the wavelength range of 320 to 400 nm. When multiple absorption maxima exist in the wavelength range of 250 to 320 nm and / or the wavelength range of 320 to 400 nm, the total absorbance of the peak tops of all the absorption maxima present in each wavelength range is used.

[0119] Specific examples of compounds corresponding to (D-1) that can be used in the present invention include benzotriazole compounds such as 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)-ethyl]phenyl]-2H-benzotriazole, and 2-(5-chloro-2-benzotriazolyl)-6-tert-butyl-p-cresol; benzophenone compounds such as 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2-hydroxy-4-n-octyloxybenzophenone; and triazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol.

[0120] Among these compounds, benzophenone compounds are preferred because they have excellent solar stability, fluorescence, and mechanical properties, as well as excellent solubility in polymerizable monomers. From the results of the studies by the present inventors, it has become clear that benzophenone compounds have excellent solubility in polymerizable monomers compared to triazine compounds. It has also become clear that benzophenone compounds tend to show good mechanical properties and high fluorescence compared to benzotriazole compounds.

[0121] Among the benzophenone compounds, benzophenone compounds having a hydroxy group are more preferred, and even more preferred are benzophenone compounds represented by formula (1) which are excellent in solubility in polymerizable monomers, fluorescence, mechanical properties, and sunlight stability, and are therefore particularly preferred. [Formula (1)] [ka] (In the formula, R1 is an organic group having 2 to 10 carbon atoms.)

[0122] Any organic group having 2 to 10 carbon atoms can be used as R1 in the benzophenone compound represented by formula (1) without any problems. A more specific example of the structure of R1 is a linear alkyl group having 2 to 10 carbon atoms.

[0123] Specific examples of the benzophenone compound represented by formula (1) include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, etc. Among these, 2-hydroxy-4-n-octyloxybenzophenone is particularly preferred due to its high solubility.

[0124] When an aromatic amine compound is used as a polymerization accelerator, it is necessary to add a large amount of an ultraviolet absorber to ensure solar stability, but the compound corresponding to (D-1) of the present invention represented by chemical formula (1) has excellent solubility in polymerizable monomers, so it can be added in a large amount, and even when an aromatic amine compound is used as a polymerization accelerator, it is possible to sufficiently reduce the solar stability. However, if an excessive amount of a compound corresponding to (D-1) is added as an ultraviolet absorber, the fluorescence and mechanical properties may be reduced, so that a particularly preferred embodiment of the present invention is preferably one in which the polymerization accelerator does not substantially contain an aromatic amine compound. In particular, by using (B-1) a photosensitizer, (B-2) a photoacid generator containing a diaryliodonium salt compound, and (B-3) a polymerization accelerator containing a tertiary amine compound as the polymerization initiator (B), sufficiently high mechanical properties are exhibited even when no aromatic amine compound is included, so it is possible to reduce the solar stability without adding a large amount of a compound corresponding to (D-1) as an ultraviolet absorber.

[0125] Therefore, the compound (D-1) as the ultraviolet absorber (D) in the present invention has excellent sunlight stability, fluorescence, and mechanical properties, as well as excellent solubility in polymerizable monomers, and therefore has the effects of being highly versatile in producing a dental curable composition, shortening the time required for production, and making the curable composition less prone to color unevenness.

[0126] The dental curable composition of the present invention preferably contains 0.01 to 2 parts by mass, more preferably 0.1 to 1 part by mass, of the compound (D-1) contained as the ultraviolet absorber (D) relative to 100 parts by mass of the total amount of the polymerizable monomer (A). If the total amount of ultraviolet absorbers is less than 0.01 parts by mass, the solar stability is insufficient and discoloration may occur due to exposure to ultraviolet light. If more than 2 parts by mass is blended, the solar stability is sufficient, but the mechanical properties may be reduced.

[0127] The compound corresponding to (D-1) contained as the ultraviolet absorber (D) in the present invention exhibits excellent fluorescence, sunlight stability, and mechanical properties even when blended alone in the dental curable composition. Therefore, the dental curable composition of the present invention does not contain a compound not corresponding to (D-1) as an ultraviolet absorber. When a combination of a plurality of compounds not corresponding to (D-1) is blended to have at least one first absorption maximum in the wavelength range of 250 to 320 nm, at least one second absorption maximum in the wavelength range of 320 to 400 nm, and the ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum is adjusted to 1 to 4, the solubility of additives such as ultraviolet absorbers, polymerization initiators, fluorescent agents, and other polymerization inhibitors in the polymerizable monomer decreases, and these components precipitate after long-term storage, and the effects of the present invention are not fully exhibited.

[0128] [(E) Filler] The dental hardenable composition of the present invention may contain a filler (E). As the filler (E), any known filler that is generally used can be used without any limitation.

[0129] (E) The type of filler is not limited as long as it is a known filler, and a filler according to its application can be blended, and it is preferable to blend a filler such as an inorganic filler, an organic filler, an organic-inorganic composite filler, or an ion-releasing glass. The dental hardenable composition of the present invention may use the exemplified fillers alone or in combination of two or more kinds.

[0130] The inorganic filler is not particularly limited in its chemical composition, but specific examples include silicon dioxide, alumina, titania, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. In particular, fluoroaluminosilicate barium glass, fluoroaluminosilicate strontium glass, fluoroaluminosilicate glass, etc., which are used in dental glass ionomer cement, resin-reinforced glass ionomer cement, resin cement, etc., can also be suitably used. The fluoroaluminosilicate glass referred to here has a basic skeleton of silicon oxide and aluminum oxide, and contains an alkali metal for the introduction of non-bridging oxygen. It also contains alkaline earth metals including strontium and fluorine as modifying and coordinating ions. It is also a composition in which a lanthanide series element is incorporated into the skeleton to provide further X-ray opacity. This lanthanide series element is also incorporated into the composition as a modifying and coordinating ion depending on the composition range.

[0131] The inorganic filler may contain hydrophobic inorganic fine particles. The hydrophobic inorganic fine particles preferably have an average primary particle size of 0.1 to 50 nm, and are preferably hydrophobized by treatment with a silane coupling agent and / or modified silicone oil. By blending, it is expected to suppress sedimentation of the inorganic filler and impart rheological properties in addition to improving bending strength.

[0132] Specific examples of organic fillers include polymers such as polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, and polycarbonate.

[0133] Examples of organic / inorganic composite fillers include fillers whose surfaces are polymerized and coated with a polymerizable monomer, fillers which are mixed and polymerized with a polymerizable monomer and then pulverized to an appropriate particle size, fillers in which a filler is previously dispersed in a polymerizable monomer and then emulsion-polymerized or suspension-polymerized, fillers in which a filler is previously dispersed in a polymerizable monomer and then spray-dried and then polymerized, fillers in which a filler is previously dispersed in a solvent and then spray-dried, then impregnated with a polymerizable monomer and then polymerized, and the like, but the fillers are not limited to these.

[0134] The ion-releasing glass is characterized by releasing at least one of fluorine ions, strontium ions, borate ions, aluminum ions, and silicate ions. It is preferable to release a plurality of these ions at the same time.

[0135] The ion-releasing glass used in the present invention can be any ion-releasing glass without any limitation as long as it contains one or more glass skeleton forming elements that form a glass skeleton and one or more glass modifying elements that modify the glass skeleton. These ion-releasing glasses can be used alone or in combination of a plurality of ion-releasing glasses. In addition, in the present invention, glass amphoteric elements that play the role of either a glass skeleton forming element or a glass modifying element depending on the glass composition are included in the category of glass skeleton forming elements. Specific examples of glass skeleton forming elements contained in ion-releasing glass include silica, aluminum, boron, phosphorus, etc., and these can be used alone or in combination of a plurality of elements. Specific examples of glass modifying elements include halogen elements such as fluorine, bromine, and iodine, alkali metal elements such as sodium and lithium, and alkaline earth metal elements such as calcium and strontium, and these can be used alone or in combination of a plurality of elements. Among these, it is preferable to include silica, aluminum, and boron as glass skeleton forming elements, and fluorine, sodium, and strontium as glass modifying elements. Specific examples include silica glass, fluoroaluminosilicate glass, fluoroborosilicate glass, and fluoroaluminoborosilicate glass containing strontium and sodium. Furthermore, from the viewpoint of gradually releasing fluorine ions, strontium ions, borate ions, and aluminum ions, fluoroaluminoborosilicate glass containing strontium is more preferable. Specific examples of the glass composition range are SiO2: 15-35 mass%, Al2O3: 15-30 mass%, B2O3: 5-20 mass%, SrO: 20-45 mass%, F: 5-15 mass%, and Na2O: 0-10 mass%. This glass composition can be confirmed by using instrumental analysis such as elemental analysis, Raman spectrum, and fluorescent X-ray analysis, but there is no problem if the actual measured value matches these composition ranges in any of the analysis methods.

[0136] The manufacturing method of these ion-releasing glasses is not particularly limited, and they can be manufactured by a manufacturing method such as a melting method or a sol-gel method. Among them, the manufacturing method using a melting furnace is preferable from the viewpoint of ease of glass composition design including the selection of raw materials. The ion-releasing glass used in the present invention has an amorphous structure, but there is no problem even if it contains a part of a crystalline structure, and there is no problem even if it is a mixture of glass having an amorphous structure and glass having a crystalline structure. The judgment of whether the glass structure is amorphous or not can be confirmed using an analytical instrument such as X-ray diffraction analysis or a transmission electron microscope. Among them, the ion-releasing glass used in the present invention is preferably an amorphous structure, which is a homogeneous structure, since various ions are gradually released due to the equilibrium relationship with the ion concentration in the external environment.

[0137] Furthermore, in order to enhance the ion release from the ion-releasing glass, it is preferable to perform a surface treatment on the glass surface to functionalize it and improve the ion release. Specific examples of surface treatment materials used for the surface treatment include surfactants, fatty acids, organic acids, inorganic acids, monomers, polymers, various coupling materials, silane compounds, metal alkoxide compounds, and partial condensates thereof. Among these surface treatment materials, it is preferable to perform a composite surface treatment using an acidic polymer and a silane compound.

[0138] This composite surface treatment is a method in which the surface of the ion-releasing glass is coated with a silane compound, and then the surface is treated with an acidic polymer, as will be specifically described below. A silane compound represented by formula (4) is mixed into an aqueous dispersion containing ion-releasing glass that has been finely pulverized to a desired average particle size (D50) by grinding or the like, and this is hydrolyzed or partially hydrolyzed in the system to form a silanol compound, which is then condensed to form a polysiloxane, which is then coated on the surface of the ion-releasing glass to form polysiloxane-coated ion-releasing glass.

[0139] [Formula (4)] [ka]

[0140] (Wherein, Z is RO - , X is halogen, Y is OH - , R is an organic group having 8 or less carbon atoms, n, m, and L are integers from 0 to 4, and n+m+L=4.

[0141] Specific examples of the silane compound represented by formula (4) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraallyloxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, trimethoxychlorosilane, triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane, diethoxydichlorosilane, tetraphenoxysilane, tetrachlorosilane, silicon hydroxide (silicon oxide hydrate), and the like, with tetramethoxysilane and tetraethoxysilane being more preferred.

[0142] Also, it is more preferable that the silane compound is a low condensate of the silane compound represented by formula (4). For example, it is a low condensate silane compound obtained by partially hydrolyzing and condensing tetramethoxysilane and tetraethoxysilane. These compounds can be used alone or in combination. In addition, an organosilane compound can be added as a part of the silane compound represented by formula (4) during the polysiloxane treatment.

[0143] The polysiloxane-coated ion-releasing glass obtained in the previous step can be subjected to an acidic polymer treatment to react with an acidic polymer to obtain an ion-releasing glass. The acidic polymer treatment can be performed using equipment commonly used in the industry as long as it is a dry-fluidized mixer, such as a Henschel mixer, a super mixer, or a high-speed mixer. The reaction of the acidic polymer with the ion-releasing glass on which the polysiloxane coating has been formed can be performed by contacting the glass with an acidic polymer solution by impregnation or spraying. For example, the polysiloxane-coated ion-releasing glass is dry-fluidized, and the acidic polymer solution is dispersed from the top while the glass is in the fluidized state, and the glass is sufficiently stirred. There is no particular restriction on the method of dispersing the acidic polymer solution, but a dripping or spraying method that allows uniform dispersion is more preferable. The reaction is preferably performed at around room temperature, and as the temperature increases, the reaction between the acid-reactive element and the acidic polymer becomes faster, resulting in non-uniform formation of the cement phase.

[0144] It is preferable to remove moisture in the cement reaction phase by performing heat treatment after the reaction. If moisture remains in the cement reaction phase, it is disadvantageous in terms of strength, but the filler of the present invention is covered and reinforced by the coupling agent condensate film, so that the decrease in mechanical strength is suppressed. The heat treatment method after the acidic polymer treatment is not particularly limited and can be performed by a known general method. The equipment used for the heat treatment is preferably a box-type hot air dryer or a rotary heat treatment device capable of uniform heating. The heat treatment temperature is in the range of room temperature to 200°C, more preferably in the range of 40 to 150°C. If the temperature is lower than this range, the aqueous medium is not sufficiently removed, and if the temperature is higher than this range, the organic layer of the acidic polymer may decompose or discolor. Since the heat treatment time depends on the capacity of the dryer, etc., there is no problem as long as the aqueous medium can be sufficiently removed. After the heat treatment, the heat-treated product can be easily crushed by applying a shear force or an impact force, and the crushing method can be performed using the equipment used in the above reaction.

[0145] The solvent used in the preparation of the acidic polymer solution used in the reaction can be any solvent that dissolves the acidic polymer, including water, ethanol, acetone, etc. Among these, water is particularly preferred, since it allows the acidic groups of the acidic polymer to dissociate and react uniformly with the surface of the basic filler, which is the core.

[0146] The weight-average molecular weight of the polymer dissolved in the acidic polymer solution is in the range of 2000 to 50000, preferably in the range of 5000 to 40000. When treated with an acidic polymer having a weight-average molecular weight of less than 2000, an acidic polymer reaction phase is not formed in the polysiloxane-coated ion-release glass, and as a result, the ion-release property tends to be reduced. On the other hand, when treated with an acidic polymer having a weight-average molecular weight of more than 50000, the viscosity of the acidic polymer solution increases, making it difficult to uniformly treat the polysiloxane-coated ion-release glass. In addition, the acidic polymer concentration per 100 parts by mass of the acidic polymer solution is preferably in the range of 3 to 25 parts by mass, more preferably in the range of 8 to 20 parts by mass. When the acidic polymer concentration is less than 3 parts by mass, the acidic polymer reaction phase described above becomes fragile, and the effect of improving the ion-release property cannot be obtained. Furthermore, if the acidic polymer concentration exceeds 25 parts by mass, it is difficult to uniformly diffuse the polysiloxane layer (porous), and a homogeneous acidic polymer reaction phase cannot be obtained. In addition, since the reaction occurs immediately upon contact with the polysiloxane-coated ion-releasing glass, problems such as the formation of strongly reacted aggregates occur. Furthermore, the amount of the acidic polymer solution added to the polysiloxane-coated ion-releasing glass is preferably in the range of 6 to 40 parts by mass, more preferably 10 to 30 parts by mass. Converted based on this amount of addition, the optimal amount of acidic polymer and the optimal amount of water are 1 to 7 parts by mass and 10 to 25 parts by mass, respectively, relative to the polysiloxane-coated ion-releasing glass.

[0147] The acidic polymer that can be used to form an acidic polymer reaction phase on the surface of the polysiloxane-coated ion-releasing glass by the above-mentioned method can be any copolymer or homopolymer of a polymerizable monomer having an acidic group such as a phosphate residue, a pyrophosphate residue, a thiophosphate residue, a carboxylic acid residue, or a sulfonic acid group as the acidic group. Specific examples of these polymerizable monomers include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic anhydride, 5-(meth)acryloylaminopentylcarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, and the like. Examples of the dihydrogen phosphate include 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, 1,3-di(meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl phosphate, 2-(meth)acryloyloxyethyl-2'-bromoethyl phosphate, (meth)acryloyloxyethyl phenyl phosphonate, di(2-(meth)acryloyloxyethyl) pyrophosphate, 2-(meth)acryloyloxyethyl dihydrogen dithiophosphorate, and 10-(meth)acryloyloxydecyl dihydrogen thiophosphate. Among the polymers (co)polymerized using these polymerizable monomers, it is preferable to use a homopolymer or copolymer of an α-β unsaturated carboxylic acid, which has a relatively slow acid-base reaction with the acid-reactive element contained in the polysiloxane-coated ion-releasing glass, and specifically, examples thereof include an acrylic acid polymer, an acrylic acid-maleic acid copolymer, and an acrylic acid-itaconic acid copolymer.

[0148] The above-mentioned (E) filler can be treated with a surface treatment material, typically a silane coupling material, for the purpose of improving the affinity with the polymerizable monomer, dispersibility in the polymerizable monomer, and mechanical strength and water resistance of the cured product. Such a surface treatment material and surface treatment method are not particularly limited, and known methods can be used without limitation, such as a method of spraying the surface treatment material while stirring the powdered filler, a method of dispersing and mixing the filler and the surface treatment material in a solvent, and a method of supplying the silane coupling material in a vapor or gaseous state to the surface of the filler. As the silane coupling agent used for the surface treatment of the filler, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, or hexamethyldisilazane is preferable. In addition to the silane coupling agent, the surface treatment of the filler can be performed by a method using a titanate-based coupling agent or an aluminate-based coupling agent. The amount of the surface treatment agent in the filler is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the filler before treatment.

[0149] The shape of the (E) filler is not particularly limited, and fillers of any shape such as spheres, needles, plates, crushed pieces, scales, etc. may be used. The average particle size of the filler is preferably in the range of 0.01 μm to 50 μm, more preferably 0.01 μm to 30 μm, still more preferably 0.05 μm to 20 μm, and even more preferably 0.05 μm to 10 μm.

[0150] The shape of the (E) filler is not particularly limited, and fillers of any shape such as spheres, needles, plates, crushed pieces, scales, etc. may be used. The average particle size of the filler is preferably in the range of 0.01 μm to 50 μm, more preferably 0.01 μm to 30 μm, still more preferably 0.05 μm to 20 μm, and even more preferably 0.05 μm to 10 μm.

[0151] The dental curable composition of the present invention preferably contains hydrophobized silica fine particles having an average particle size of 1 to 40 nm as a filler (E) in order to impart rheological properties. The primary particle size refers to the diameter of one particle (primary particle) constituting the powder. The average particle size in the present invention can be the average particle size calculated based on the volume-based particle size distribution measured by, for example, a laser diffraction type particle size distribution measuring device, and can be measured, for example, by a laser diffraction type particle size measuring device (Microtrac MT3300EXII: manufactured by Nikkiso Co., Ltd.). In addition, the primary particle size can be measured by dynamic light scattering particle size measurement, or, for those in which primary particles are strongly aggregated to form secondary particles, by using an electron microscope photograph. The average particle size of the primary particles of the silica fine particles is preferably 1 to 40 nm. Examples of a method for hydrophobizing the silica fine particles include surface treatment with modified silicone oil such as dimethyl silicone oil, and / or surface treatment with a silane coupling agent having an alkylsilyl group that may have a trimethylsilyl group, a dimethylsilyl group, a methylsilyl group, or a (meth)acryloyl group having an alkyl chain with a carbon number of 3 to 18.

[0152] Specific examples of hydrophobized silica microparticles include those manufactured and sold under the trade name Aerosil by Nippon Aerosil Co., Ltd., such as Aerosil R972, Aerosil R974, Aerosil R976, Aerosil R711, Aerosil R7200, Aerosil R976S, Aerosil R202, Aerosil R812, Aerosil R812S, Aerosil R805, Aerosil R8200, Aerosil R104, Aerosil R106, Aerosil RY200, Aerosil RX200, Aerosil RY200S, Aerosil RA200H, and Aerosil RA200HS.

[0153] By including hydrophobic silica fine particles having an average particle size of 1 to 40 nm, the dental hardenable composition exhibits moderate thixotropy, and thus has good operability. Since the dental hardenable composition of the present invention itself exhibits good storage stability, good storage stability can be expected even if the amount of filler in the dental hardenable composition is small. In general, when the amount of filler is large, the transparency and the elasticity and flexibility may decrease. Transparency, elasticity and flexibility may be required for dental coating materials, dental lining materials, dental cements, dental bonding materials, dental adhesive materials for fixing loose teeth, and dental manicure materials. In order to avoid such cases, if the amount of filler in the dental hardenable composition is reduced, the operability may decrease. In such cases, hydrophobic silica fine particles having an average particle size of 1 to 40 nm, which can be expected to impart rheological properties and improve operability with a small amount of filling, can be suitably used. The hydrophobized silica fine particles having an average primary particle size of 1 to 40 nm are preferably contained in an amount of 1 to 30 parts by mass relative to 100 parts by mass of the polymerizable monomer (A). If the amount is less than 1 part by mass, the rheological properties may not be exhibited, and if the amount is 30 parts by mass or more, the operability of the dental curable composition may decrease.

[0154] In the present invention, a matrix, which is a medium with a lower viscosity than the paste containing a polymerizable monomer, a photopolymerization initiator, a fluorescent agent, an ultraviolet absorber, and, if necessary, a part of the filler, may be prepared and then mixed with the filler to prepare a dental hardenable composition in the form of a paste. By preparing in this manner, it is possible to dissolve the photopolymerization initiator, the fluorescent agent, the ultraviolet absorber, etc. in the polymerizable monomer and uniformly disperse the photopolymerization initiator in the paste. In particular, if a solid at room temperature is not dissolved in the matrix, it will cause sedimentation and performance variations. If the matrix is ​​uniformly dispersed without sedimentation, a filler with a primary particle size of 100 nm or less may be mixed with a filler with a size exceeding 100 nm. In terms of manufacturing, it is preferable to create a process to confirm that the matrix has been dissolved, so it is preferable that the matrix does not contain a filler that does not dissolve in the matrix.

[0155] The dental curable composition of the present invention may contain 0 to 900 parts by mass of the filler (E) relative to 100 parts by mass of the polymerizable monomer (A). In the case of a dental filling composite resin as one embodiment of the present invention, the amount of the filler (E) is preferably 100 to 900 parts by mass. When the filler is 100 parts by mass or less, the mechanical properties may decrease and the operability may become poor, and when the filler exceeds 900 parts by mass, the operability of the dental curable composition may decrease.

[0156] <Other ingredients> In addition, the dental hardenable composition of the present invention may contain components other than the above components (A) to (D) as long as the effects of the present invention are not impaired. For example, excipients such as fumed silica, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and 2,5-ditertiary butyl-4-methylphenol, mercaptan compounds such as α-alkylstyrene compounds, n-butyl mercaptan, and n-octyl mercaptan, chain transfer agents such as 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 chelating agents and phosphonic acid chelating agents, discoloration inhibitors, antibacterial agents, coloring pigments, water and solvents that can be mixed with water in any ratio, and other conventionally known additives can be added as necessary.

[0157] The dental curable composition of the present invention may contain only the polymerizable monomer (A), the polymerization initiator (B), the fluorescent agent (C), and the ultraviolet absorbing agent (D), or may contain only one or more of the above-mentioned components as components other than (A) to (D).

[0158] The method for producing the dental hardenable composition of the present invention is not particularly limited. A general method for producing a dental hardenable composition includes a method in which (A) a polymerizable monomer, (B) a polymerization initiator, (C) a fluorescent agent, and (D) an ultraviolet absorbing agent are mixed in advance by a known method such as a rotation-revolution mixer, a tumbler mixer, a mix rotor, a dissolver, or a planetary mixer to prepare a matrix, and then this matrix and (E) a filler are kneaded by a known method such as a rotation-revolution mixer, a tumbler mixer, a mix rotor, a dissolver, or a planetary mixer, and air bubbles are removed under reduced pressure to prepare a uniform paste. In the present invention, the composition can also be produced without any problems by the above-mentioned production method.

[0159] The dental hardenable composition of the present invention is preferably used in dental adhesives, dental composite resins, dental core construction materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicure materials, dental adhesives for fixing loose teeth, dental cutting materials, and dental 3D printer materials, and is particularly preferably used in dental adhesives, dental composite resins, dental core construction materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicure materials, dental adhesives for fixing loose teeth, and orthodontic materials. EXAMPLES

[0160] Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

[0161] The materials used in the examples and comparative examples and their abbreviations are shown below. [(A) Polymerizable monomer] <Radical 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 NPG: Neopentyl glycol dimethacrylate TEGDMA: Triethylene glycol dimethacrylate ·HEMA: Hydroxyethyl methacrylate

[0162] <(A1) Polymerizable monomer having an acidic group> ·MDP: 10-Methacryloyloxydecyl dihydrogen phosphate ·MHPA: 6-Methacryloxyhexylphosphonoacetate

[0163] [(B) Polymerization initiator] [(B-1) Photosensitizer] CQ: Camphorquinone BAPO: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[0164] [(B-2) Photoacid generator] DPI: Diphenyliodonium hexafluorophosphate [ka] IFP: p-Cumenyl(p-tolyl)iodonium tris(pentafluoroethyl)trifluorophosphate [ka] IFB: Bis(4-tert-butylphenyl)iodonium tetrakispentafluorophenylborate [ka] IFG: Bis(4-tert-butylphenyl)iodonium tetrakispentafluorophenylgallate [ka]

[0165] [(B-3) Polymerization accelerator] <Aliphatic tertiary amine> TBA: Tribenzylamine DM: 2-(N,N-dimethylamino)ethyl methacrylate <Aromatic tertiary amine> DMBE: Ethyl N,N-dimethylaminobenzoate

[0166] [(C) Fluorescent agent] DHT: Diethyl-2,5-dihydroxyterephthalate TB: 2,5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole)

[0167] [(D) Ultraviolet absorber] Samples were prepared by dissolving various UV absorbents in acetonitrile to a concentration of 100 ppm, and the absorbance of each sample was measured at wavelengths of 250 nm to 400 nm using a UV-Visible Spectrophotometer (V-750, JASCO Corporation). Each UV absorbent was classified based on the absorbance measurement results.

[0168] <<UV absorber with absorption maximum only in the range of 250 nm to 320 nm>> D1: Benzophenone D2: 4-tert-butylphenyl salicylate

[0169] <<UV absorber with absorption maximum only in the range of 320 nm to less than 400 nm>> D3: 1,4-naphthoquinone

[0170] <<An ultraviolet absorber having a ratio of the absorbance at the first absorption maximum to the absorbance at the second absorption maximum of less than 1.0>> D4: 2,2'-dihydroxy-4,4'-dimethoxybenzophenone (ratio of absorbance of first absorption maximum to second absorption maximum: 0.73) D5: 2-[2-hydroxy-5-[2-(methacryloyloxy)-ethyl]phenyl]-2H-benzotriazole (ratio of absorbance of first absorption maximum to second absorption maximum: 0.79) D6: 2-(2H-benzotriazol-2-yl)-p-cresol (ratio of absorbance of first absorption maximum to second absorption maximum: 0.84)

[0171] <<An ultraviolet absorber having a ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum of 1 to 4>> D7: 2-hydroxy-4-n-octyloxybenzophenone (ratio of absorbance of first absorption maximum to second absorption maximum: 1.47) D8: 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (ratio of absorbance of first absorption maximum to second absorption maximum: 2.09)

[0172] [(E) Filler] The manufacturing method of each filler used in the preparation of the dental hardenable composition is shown below.

[0173] (Filler E1) To 100.0 g of fluoroaluminoborosilicate glass (average particle size 1.0 μm), 50.0 g of water, 35.0 g of ethanol, and 3.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours, and the resulting silane coupling treatment liquid was added and mixed for 30 minutes. After that, the mixture was heat-treated at 100°C for 15 hours to obtain filler E1.

[0174] (Filler E2) To 100.0g of zirconium silicate filler (average particle size 0.8μm: zirconia 85wt%, silica 15wt%), 50.0g of water, 35.0g of ethanol, and 5.0g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours, and the silane coupling treatment liquid obtained was added and stirred for 30 minutes. After that, heat treatment was performed at 100℃ for 15 hours to obtain filler E2.

[0175] (Filler E3) After mixing various raw materials of silicon dioxide, aluminum oxide, boron oxide, sodium fluoride, and strontium carbonate, the mixture was melted at 1400°C to obtain glass A (glass composition: SiO2: 22.5% by mass, Al2O3: 20.0% by mass, B2O3: 12.3% by mass, SrO: 35.7% by mass, Na2O: 2.5% by mass, F: 7.0% by mass). Next, the obtained glass A was pulverized for 100 hours using a vibration mill, and then further pulverized for 3 hours using a wet bead mill. 4.5 g of a low condensation product of a silane compound "MKC Silicate MS56S" (SiO2 content 56.0% by mass, polymerization degree 2 to 100, manufactured by Mitsubishi Chemical Corporation) was added to 100 g of the obtained pulverized material, and the mixture was stirred and mixed for about 90 minutes. After mixing for a predetermined time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours, and then cooled to obtain a heat-treated product. The resulting heat-treated product was placed in a Henschel mixer and crushed at 1800 rpm for 5 minutes. After crushing, a polysiloxane-treated product with good fluidity was obtained. (Acid polymer treatment) 100 g of the polysiloxane-treated product was placed in a Henschel mixer, and while stirring, 16.0 g of an aqueous polyacrylic acid solution (polymer concentration 13% by mass, weight average molecular weight 20,000: manufactured by Nakarai, Inc.) was sprayed from above. After spraying, the powder removed from the mixer was heated in a hot air dryer at 100°C for 3 hours to obtain a polysiloxane-polyacrylic acid-treated product. (Silane treatment) To 100 g of polysiloxane-polyacrylic acid treated product, add 100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 8-methacryloyloxypropyltrimethoxysilane as a silane coupling agent, which was stirred at room temperature for 2 hours, and add the silane coupling treatment liquid obtained, and stir and mix for 30 minutes. After that, heat treatment was performed at 100°C for 15 hours to obtain filler E3.

[0176] To 100 g of the polysiloxane treatment, add 100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 8-methacryloyloxyoctyltrimethoxysilane as a silane coupling agent, which was stirred at room temperature for 2 hours, and add the silane coupling treatment liquid obtained, and stir and mix for 30 minutes. After that, heat treatment was performed at 100°C for 15 hours to obtain filler E3.

[0177] (Filler E4) A uniform matrix was prepared by mixing 60 parts by mass of BisGMA, 40 parts by mass of TEGDMA, and 0.2 parts by mass of BPO. The matrix was mixed with 300 parts by mass of fluoroboroaluminosilicate glass (average primary particle size 0.5 μm), 20 parts by mass of Aerosil R7200, and 15 parts by mass of γ-methacryloxypropyltrimethoxysilane in a kneader under a nitrogen atmosphere and polymerized to obtain a cured product. The cured product was coarsely crushed with a roll crusher and finely crushed with a vibration mill to obtain a finely crushed product with an average particle size of 20 μm. 100 parts by mass of the sieved product of the finely crushed product was mixed with 1 part by mass of water, 1 part by mass of ethanol, and 6 parts by mass of γ-methacryloxypropyltrimethoxysilane, and dried at 90° C. for 10 hours to obtain an organic-inorganic composite filler.

[0178] (Filler E5) Aerosil R8200 (Evonik) (Filler E6) Aerosil R711 (Evonik) (Filler E7) Aerosil AluC805 (Evonik)

[0179] [Polymerization inhibitor] MeHQ: p-Methoxyphenol BHT: Dibutyl hydroxytoluene

[0180] [Chemical polymerization initiator] ·BPO: Benzoyl peroxide TMBH: 1,1,3,3-tetramethylbutyl hydroperoxide PTU: Pyridylthiourea ·DEPT: p-tolyldiethanolamine VOA: Vanadyl acetylacetonate CAA: Copper acetylacetone ·KPS: Potassium peroxodisulfate

[0181] <Matrix manufacturing method> All ingredients except for the (E) filler shown in Tables 1 and 2 were placed in a wide-mouth plastic container and mixed for 48 hours at 50°C and 100 rpm using a VMRC-5 mix rotor to obtain a matrix. In Tables 1 and 2, the abbreviation for each ingredient is followed by the mass part of each ingredient in parentheses.

[0182] <Method for producing one-part dental photocurable composition> A matrix prepared by mixing everything except for the filler (E) shown in Tables 1 and 2 was kneaded with the filler (E) in a planetary mixer and filled into a PP syringe to prepare a dental curable composition. In Tables 1 and 2, the abbreviation of each component is followed by the mass part of each component in parentheses.

[0183] <Method for producing two-component dental hardenable composition> The matrix prepared by mixing all of the ingredients except for the filler (E) shown in Table 3 and the filler (E) were kneaded in a planetary mixer to obtain the first and second pastes separately, and then filled into a double syringe (5 mL) manufactured by Mixpack Co., Ltd. to prepare a dental photocurable composition. In Table 3, the abbreviation of each component is followed by the mass part of each component in parentheses. In addition, when the two-component dental curable composition was evaluated in the examples, it was all kneaded using a Matsukaze mixer tip (Matsukaze Co., Ltd.).

[0184] [Table 1]

[0185] [Table 2]

[0186] [Table 3]

[0187] (1) Fluorescence The dental hardenable composition thus prepared was filled into a stainless steel mold (15φ×1mm: disk-shaped), and then a cover glass was placed on top and pressed with a glass plate. The cover glass was irradiated with light using a photopolymerization irradiator (Penbright, manufactured by Matsukaze) for 1 minute to harden the composition, and the cover glass was removed before removing the hardened product from the mold. This hardened product was used as a test specimen for fluorescence evaluation. This test specimen and natural teeth were irradiated with ultraviolet light with a wavelength of 366 nm, and the fluorescence state of each was observed and evaluated by three evaluators. The evaluation was judged according to the following criteria, with the most common evaluation being adopted. A: Good, with fluorescence equivalent to that of natural teeth B: Slightly less fluorescent than natural teeth, or slightly more fluorescent, but suitable for use without any problems. C: Inappropriate due to poorer or stronger fluorescence than natural teeth and problems with use. D: The fluorescence is obviously inferior to that of natural teeth, or is obviously too strong, making it unnatural and problematic to use, making it unsuitable. It was decided. If the fluorescence is too strong or too weak compared to natural teeth, when viewed under sunlight or other light sources that contain ultraviolet light, the restoration will emit light differently from natural teeth and make the restored area stand out, which is not aesthetically pleasing.

[0188] (2) Bending strength The dental curable composition thus prepared was filled into a stainless steel mold, and then cover glass was placed on both sides and pressed with a glass plate. Then, light was irradiated at 5 locations for 10 seconds each using a photopolymerization irradiator (Penbright: manufactured by Matsukaze) to cure the composition. After curing, the cured product was removed from the mold, and the back side was irradiated with light in the same manner, and this was used as a test specimen (25×2×2 mm: rectangular parallelepiped type). The test specimen was immersed in water at 37° C. for 24 hours, and then subjected to a bending test. The bending test was performed using an Instron universal testing machine (manufactured by Instron) with a support distance of 20 mm and a crosshead speed of 1 mm / min. The bending strength of the dental curable composition was judged to be particularly good when it was 120 MPa or more, good when it was 120 to less than 100 MPa, and insufficient when it was less than 100 MPa.

[0189] (3) Solar stability The dental hardenable composition thus prepared was filled into a stainless steel mold (15φ×1mm: disk-shaped), and then a cover glass was placed from above and pressed with a glass plate. The cover glass was irradiated with light for 1 minute using a photopolymerization irradiator (Penbright: Matsukaze Co., Ltd.) to harden the composition, and the cover glass was removed and the hardened product was removed from the mold. The color tone of this hardened product was measured. The color measurement was performed by placing a test specimen on a background of a standard white plate (D65 / 10°X=81.07, Y=86.15, Z=93.38) and using a spectrophotometer (BYK-Chemie Co., Ltd.) under a certain set of conditions (light source: C, viewing angle: 2°, measurement area: 11mm). After that, the test specimen was exposed to light for 24 hours using a xenon lamp light exposure tester (Suntest CPS+), and the color tone of the test specimen was measured again, and the difference in color change was expressed as ΔE calculated from the following formula. ΔE={(ΔL*) 2 +(Δa*) 2 +(Δb*) 2} 1 / 2 ΔL*=L1*-L2* Δa*=a1*-a2* Δb*=b1*-b2* Here, L1* is the lightness index before light exposure, L2* is the lightness index after light exposure, a1* and b1* are the color quality index before light exposure, and a2* and b2* are the color quality index after light exposure. ΔE of less than 3 was considered to be good, ΔE of less than 5 was considered to be applicable, and ΔE of 5 or more was considered to be poor stability. The solar light stability was measured to predict the color change when the cured body was used for a long period of time in a place exposed to light, and the smaller ΔE is, the smaller the color change of the cured body even when exposed to light for a long period of time. Dental curable compositions with small color change can be suitably used for dental materials where aesthetics are important.

[0190] (4)Solubility When manufacturing the matrix, all ingredients except for the (E) filler and chemical polymerization initiator of each example were placed in a wide-mouthed plastic container and mixed with a mixer (Mix Rotor: VMRC-5, AS ONE) set at 50°C. After mixing started, visual inspection was performed at 3, 36, and 48 hours to see if any solid matter remained. Evaluation was as follows: A: No solid matter remains after 3 hours. B: Solid matter is present after 3 hours, but no solid matter is present after 36 hours. C: Solids are present after 36 hours, but no solids are present after 48 hours. It was decided. Good solubility is preferable because it can be produced in a short time. Furthermore, it is preferable because there is a low risk of the photoacid generator precipitating during low-temperature storage. On the other hand, ultraviolet absorbers with poor solubility may precipitate after long-term storage even when uniformly dissolved in the composition, which is not preferable. In addition, it is not preferable because it takes a long time to produce the composition and it is necessary to expose the composition to high temperatures for a long time, which may cause deterioration of materials during preparation.

[0191] The results of each test are shown in Tables 4 and 5.

[0192] [Table 4]

[0193] [Table 5]

[0194] It was confirmed that the compositions described in the examples had good fluorescence, bending strength, solar light stability, and solubility.

[0195] Examples 9 to 10, which had a small amount of polymerization initiator, tended to have poor bending strength. Examples 16 to 18 and 42, which had a large amount of polymerization initiator, had good bending strength but tended to have poor sunlight stability.

[0196] Examples 24, 33, 34, and 48, which contained a small amount of fluorescent agent, tended to have slightly inferior fluorescence. Examples 27, 37, and 50, which contained a large amount of fluorescent agent, tended to have too much fluorescence, resulting in unnatural emission or slightly inferior physical properties.

[0197] Examples 1, 2, and 38, which contained a small amount of ultraviolet absorber, tended to have poor sunlight stability. Examples 31, 32, and 47, which contained a large amount of ultraviolet absorber, tended to have excellent sunlight stability but poor bending strength.

[0198] Examples 1 to 37, which contain D7, a benzophenone compound represented by formula 1, tended to have particularly excellent solubility.

[0199] Examples 7, 20, and 44, which contained the aliphatic amines TBA and DM, tended to have better results in terms of sunlight stability than Examples 23, 45, and 55, which contained the aromatic amine DMBE.

[0200] Examples 20 and 23, which did not contain the photoacid generator (B-2), tended to have inferior bending strength compared to Examples 21 and 22, which contained the photoacid generator (B-2).

[0201] Comparative Examples 1 and 2, which used an ultraviolet absorbent having an absorption maximum in only one of the wavelength regions of 250 to 320 nm or 320 to 400 nm, tended to have significantly poor sunlight stability.

[0202] Comparative Examples 3 to 10, which used ultraviolet absorbents in which the ratio of the absorbance at the first absorption maximum to the absorbance at the second absorption maximum was less than 1, tended to have significantly inferior fluorescence.

[0203] In Comparative Examples 6 to 10, in which an ultraviolet absorber having a ratio of the absorbance at the first absorption maximum to the absorbance at the second absorption maximum of less than 1 was used, the solar light stability could be improved by increasing the amount of ultraviolet absorber added, but the fluorescence tended to decrease significantly.

[0204] Comparative Examples 5 and 11, in which ultraviolet absorbents having an absorption maximum in only one of the wavelength regions of 250 to 320 nm or 320 to 400 nm were used in combination, tended to have significantly inferior solubility.

[0205] It was confirmed that Examples 101 to 110, which are examples of two-component dental curable compositions, also have good fluorescence, bending strength, sunlight stability, and solubility. Among Examples 101 to 103 containing the aromatic amine compound p-tolyldiethanolamine, Example 103, which contains an excessive amount of ultraviolet absorber, tended to have excellent results in sunlight stability, but tended to have reduced bending strength and fluorescence. On the other hand, Examples 101 and 103 tended to have inferior sunlight stability compared to Examples 104 to 110, which do not contain an aromatic amine compound.

[0206] These are Comparative Examples 101 and 102 of two-component dental hardenable compositions. Comparative Example 101, which contains D4, an ultraviolet absorber having a ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum of less than 1.0 as an ultraviolet absorber, was inferior in fluorescence, bending strength, and solar stability, and the solubility of the ultraviolet absorber in the matrix also tended to be somewhat low. Comparative Example 102, which contains D1 and D3, a combination of ultraviolet absorbers having a ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum of more than 4.0 as an ultraviolet absorber, had good fluorescence, but was inferior in solar stability and tended to be inferior in solubility of the ultraviolet absorber in the matrix. [Industrial Applicability]

[0207] According to the present invention, it is possible to provide a dental hardenable composition that is excellent in solubility and stability to sunlight without sacrificing fluorescence and mechanical properties.

Claims

1. (A) A polymerizable monomer, (B) A polymerization initiator, (C) A fluorescent agent, and (D) A UV absorber, A dental curable composition characterized by comprising (D) a UV absorber comprising (D-1) a compound having at least one first absorption maximum in the wavelength range of 250 to 320 nm and at least one second absorption maximum in the wavelength range of 320 to 400 nm, wherein the ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum is 1.0 to 4.0, and B) a polymerization initiator comprising (B-3) a polymerization accelerator.

2. (D-1) The dental curable composition according to claim 1, wherein the compound having at least one first absorption maximum in the wavelength range of 250 to 320 nm and at least one second absorption maximum in the wavelength range of 320 to 400 nm, and the ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum to 1.0 to 4.0 is a benzophenone compound represented by formula (1). [Formula (1)] 【Chemistry 1】 (In the formula, R １ (This refers to an organic group with 2 to 10 carbon atoms.)

3. (B) The polymerization initiator includes a combination of (B-1) a photosensitizer, (B-2) a photoacid generator, and (B-3) a polymerization accelerator. (B-2) Contains a diaryliodonium salt compound as a photoacid generator, (B-3) The dental curable composition according to claim 1, comprising a tertiary amine compound as a polymerization accelerator.

4. (B-3) The dental curable composition according to claim 1, which substantially does not contain an aromatic amine compound as a polymerization accelerator.

5. (D) The dental curable composition according to claim 1, comprising only compounds as ultraviolet absorbers, (D-1) having at least one first absorption maximum in the wavelength range of 250 to 320 nm and at least one second absorption maximum in the wavelength range of 320 to 400 nm, wherein the ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum is 1.0 to 4.

0.

6. (C) The dental curable composition according to claim 1, comprising a terephthalate ester compound represented by formula (3) as a fluorescent agent. [Formula (3)] 【Chemistry 2】

7. (B) The polymerization initiator includes a combination of (B-1) a photosensitizer, (B-2) a photoacid generator, and (B-3) a polymerization accelerator. (B-2) Contains diaryliodonium salt compounds as photoacid generators (B-3) The dental curable composition according to claim 2, comprising a tertiary amine compound as a polymerization accelerator.

8. (B-3) The dental curable composition according to claim 2, which substantially does not contain an aromatic amine compound as a polymerization accelerator.

9. (B-3) The dental curable composition according to claim 3, which substantially does not contain an aromatic amine compound as a polymerization accelerator.

10. (D) The dental curable composition according to claim 2, comprising only one compound as an ultraviolet absorber, wherein (D-1) has at least one first absorption maximum in the wavelength range of 250 to 320 nm and at least one second absorption maximum in the wavelength range of 320 to 400 nm, and the ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum is 1 to 4.

11. (D) The dental curable composition according to claim 3, comprising only one compound as an ultraviolet absorber, wherein (D-1) has at least one first absorption maximum in the wavelength range of 250 to 320 nm and at least one second absorption maximum in the wavelength range of 320 to 400 nm, and the ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum is 1 to 4.

12. (D) The dental curable composition according to claim 4, comprising only one compound as an ultraviolet absorber, wherein (D-1) has at least one first absorption maximum in the wavelength range of 250 to 320 nm and at least one second absorption maximum in the wavelength range of 320 to 400 nm, and the ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum is 1 to 4.

13. (D) The dental curable composition according to claim 5, comprising only one compound as an ultraviolet absorber, wherein (D-1) has at least one first absorption maximum in the wavelength range of 250 to 320 nm and at least one second absorption maximum in the wavelength range of 320 to 400 nm, and the ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum is 1 to 4.

14. (C) The dental curable composition according to claim 2, comprising only a terephthalate ester compound represented by formula (3) as a fluorescent agent. [Formula (3)] 【Transformation 3】

15. (C) The dental curable composition according to claim 3, comprising only a terephthalate ester compound represented by formula (3) as a fluorescent agent. [Formula (3)] 【Chemistry 4】

16. (C) The dental curable composition according to claim 4, comprising only a terephthalate ester compound represented by formula (3) as a fluorescent agent. [Formula (3)] 【Transformation 5】

17. (C) The dental curable composition according to claim 6, comprising only a terephthalate ester compound represented by formula (3) as a fluorescent agent. [Formula (3)] 【Transformation 6】

18. (A) Per 100 parts by mass of polymerizable monomer, (B) Polymerization initiator: 0.5 to 10 parts by mass (C) 0.001 to 0.1 parts by mass of fluorescent agent (D) (D-1) 0.01 to 2 parts by mass of a compound having at least one first absorption maximum in the wavelength range of 250 to 320 nm, at least one second absorption maximum in the wavelength range of 320 to 400 nm, and a ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum of 1 to 4, as an ultraviolet absorber. A dental curable composition according to any one of claims 1 to 17, comprising:

19. (D) The dental curable composition according to any one of claims 1 to 17, wherein the compound corresponding to (D-1) included as an ultraviolet absorber has a second absorption maximum wavelength of less than 350 nm.

20. (B-3) A dental curable composition according to any one of claims 1 to 17, comprising tripenzylamine as a polymerization accelerator.

21. A dental curable composition according to any one of claims 1 to 17, comprising 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol as a compound having at least one first absorption maximum in the wavelength range of 250 to 320 nm and at least one second absorption maximum in the wavelength range of 320 to 400 nm, wherein the ratio of the absorbance of the first absorption maximum to the absorbance of the second absorption maximum is 1.0 to 4.

0.

22. (B-3) A dental curable composition according to any one of claims 1 to 3, 5 to 7, 10 to 11, 13 to 15, or 17, comprising only an aromatic amine compound as a polymerization accelerator.

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