Dental curable composition

Abstract

To provide a dental curable composition containing a radically polymerizable monomer having a urethane bond excellent in biological safety without using an organotin catalyst.SOLUTION: The dental curable composition contains a polymerizable monomer (A), wherein the polymerizable monomer (A) contains a radically polymerizable monomer (a- 1) having a urethane bond and containing substantially no organotin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a dental hardenable composition. More specifically, the present invention relates to a dental hardenable composition comprising a radically polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin. [Background technology]

[0002] As an example of a monomer contained in a curable composition, urethane (meth)acrylate, which is a (meth)acrylate compound having a urethane bond, is known. Conventionally, urethane (meth)acrylates have been synthesized using Sn (tin)-based catalysts. For example, Patent Document 1 discloses a dental composite filler which is a mixture of a fine inert inorganic filler powder and a reaction product of an organic diisocyanate with an oxyalkyl acrylate or oxyalkyl methacrylate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 51-36960 Summary of the Invention [Problem to be solved by the invention]

[0004] In the examples of Patent Document 1, dibutyltin dilaurate is used as a catalyst to react oxypropyl methacrylate with 2,2,4-trimethylhexamethylene diisocyanate to form diurethane dimethacrylate. However, in recent years, from the viewpoint of reducing the amount of heavy metals used, there has been a demand for catalysts to replace Sn-based catalysts (for example, dibutyltin dilaurate (DBTDL)) as catalysts used in the formation of urethane (meth)acrylates. In particular, when it comes to dental materials used in the oral cavity, it has been pointed out that dental materials used in the oral cavity may affect certain diseases, and there has been a demand for the development of dental materials with higher biosafety, taking safety into consideration in the manufacturing of materials.

[0005] An object of the present invention is to provide a dental curable composition containing a radically polymerizable monomer having a urethane bond, which does not use an organotin catalyst and has excellent biological safety. [Means for solving the problem]

[0006] As a result of intensive research to solve the above problems, the present inventors have found that by producing a radical polymerizable monomer having a urethane bond using a bismuth-based catalyst, it is possible to produce a radical polymerizable monomer having a urethane bond that has sufficient properties as a dental material when blended into a dental curable composition and that is substantially free of organotin. Based on this finding, the present inventors have conducted further research and have completed the present invention.

[0007] That is, the present invention includes the following inventions. [1] Contains a polymerizable monomer (A), A dental hardenable composition, wherein the polymerizable monomer (A) comprises a radical polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin. [2] A dental curable composition, wherein the radical polymerizable monomer (A-1) having a urethane bond is a compound represented by the following general formula [a]: X 1 -Y 1 -ZY 2 -ZY 3 -X 2 [a] (In the formula, X 1 and X 2 are the same or different and each represents a (meth)acryloyloxy group; Z represents a carbamoyloxy group; Y 2 represents a linear, branched, or cyclic divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; Y 1 and Y3 are the same or different and each represents a divalent hydrocarbon group having 1 to 12 carbon atoms which may have a linear, branched, or cyclic substituent. [3] The dental curable composition according to [1], wherein the radical polymerizable monomer (A-1) having a urethane bond is a compound represented by the following formula [a-1]: [ka] [4] The dental curable composition according to [3], wherein the polymerizable monomer (A) further contains a radical polymerizable monomer (A-2) having an acidic group. [5] The dental curable composition according to [4], wherein the radical polymerizable monomer (A-2) having an acidic group is 10-(meth)acryloyloxydecyl dihydrogen phosphate. [6] The dental curable composition according to [5], wherein the polymerizable monomer (A) further contains a radical polymerizable monomer (A-3) having no acidic group. [7] The dental curable composition according to any one of [1] to [6], further comprising a polymerization initiator (B), the polymerization initiator (B) comprising a photopolymerization initiator (B-1), and used for a dental bonding material. [8] The dental curable composition according to any one of [1] to [6], further comprising a solvent (D), a fourth-period transition metal compound (E), and optionally a silane coupling agent (F), and is for use as a dental primer. [9] Further comprising a polymerization initiator (B) and a filler (C), The dental curable composition according to any one of [1] to [6], wherein the content of the polymerization initiator (B) is 0.1 to 10 parts by mass and the content of the filler (C) is 80 to 900 parts by mass, relative to 100 parts by mass of the polymerizable monomers (A) in total.

[10] A dental composite resin comprising the dental hardenable composition according to [9].

[11] A dental cement comprising the dental hardenable composition according to [9].

[12] A dental hardenable composition in a divided package containing a first agent and a second agent, At least one of the first agent and the second agent contains a radically polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin and a filler (C), the first agent contains a radical polymerizable monomer (A-2) having an acidic group, an organic peroxide (B-2), and a fourth period transition metal compound (E), The dental hardenable composition, wherein the second agent comprises an aromatic sulfinic acid compound (G).

[13] A composition comprising a radical polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin, an organic peroxide (B-2), a filler (C), a fourth-period transition metal compound (E), and a cyclic thiourea compound (H), The dental hardenable composition, wherein the cyclic thiourea compound (H) is at least one selected from the group consisting of substituted ethylene thiourea compounds and substituted propylene thiourea compounds.

[14] A dental core build-up material comprising the dental curable composition according to [9].

[15] A dental mill blank comprising the dental hardenable composition according to [9].

[16] A method for producing a polymerizable monomer-containing composition comprising a step of contacting an inorganic filler molded body obtained by press-molding an inorganic filler (C-1) with the polymerizable monomer-containing composition, A method for producing a dental mill blank, wherein the polymerizable monomer-containing composition contains a radically polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin.

[17] A polymerizable monomer (A) and a polymerization initiator (B), the polymerizable monomer (A) comprises a radical polymerizable monomer (A-1) having a urethane bond and substantially not containing an organotin, and a radical polymerizable monomer (A-3) having no acidic group; the polymerization initiator (B) contains a photopolymerization initiator (B-1), A dental hardenable composition for photolithography for intraoral applications. [Effects of the Invention]

[0008] The present invention can provide a dental curable composition containing a radically polymerizable monomer having a urethane bond, which does not use an organotin catalyst and has excellent biosafety. DETAILED DESCRIPTION OF THE INVENTION

[0009] The dental curable composition of the present invention contains a polymerizable monomer (A), and the polymerizable monomer (A) contains a radical polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin.

[0010] In this specification, the term "(meth)acrylic" is used to mean both methacryl and acrylic, and the same applies to similar expressions ((meth)acrylate, (meth)acrylamide, etc.). In this specification, "100 parts by mass of the total amount of polymerizable monomer (A)" means the sum of the polymerizable monomer (A) contained in the dental curable composition converted into 100 parts by mass, and in the case of a dental curable composition in a separate package consisting of a first agent and a second agent, means the sum of the polymerizable monomer (A) contained in the first agent and the polymerizable monomer (A) contained in the second agent converted into 100 parts by mass. In this specification, the upper and lower limits of the numerical ranges (contents of each component, values ​​calculated from each component, and each physical property, etc.) can be combined as appropriate.

[0011] The dental curable composition of the present invention does not use an organotin catalyst, and therefore the radical polymerizable monomer (A-1) having a urethane bond that is synthesized does not substantially contain organotin. The phrase "the radically polymerizable monomer (A-1) having a urethane bond is substantially free of organotin" means that the amount of organotin detected by ICP analysis or gas chromatographic analysis is less than 1 ppm.

[0012] The radical polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin (hereinafter also referred to as "radical polymerizable monomer (A-1) having a urethane bond" or "radical polymerizable monomer (A-1)") may be used alone or in combination of two or more.

[0013] The radical polymerizable monomer (A-1) having a urethane bond can be produced by a known method, except that an organotin catalyst is not used as the catalyst. It can be easily synthesized by subjecting a compound having an isocyanate group (-NCO) to an addition reaction with a (meth)acrylic compound having a hydroxyl group (-OH) (e.g., 2-hydroxyethyl methacrylate). The catalyst is preferably a bismuth-based catalyst. Examples of bismuth catalysts include bismuth (III) 2-ethylhexanoate.

[0014] As the radical polymerizable monomer (A-1) having a urethane bond, a compound represented by the following general formula [a] is preferred because it has excellent properties (mechanical strength, toughness, etc.) as a dental material. X 1 -Y 1 -ZY 2 -ZY 3 -X 2 [a] (In the formula, X 1 and X 2 are the same or different and each represents a (meth)acryloyloxy group; Y represents a carbamoyloxy group; Y 2 represents a linear, branched, or cyclic divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; Y 1 and Y 3 are the same or different and each represents a divalent hydrocarbon group having 1 to 12 carbon atoms which may have a linear, branched, or cyclic substituent.

[0015] Y 2 When the dental curable composition to be obtained is in a paste form, the number of carbon atoms in the hydrocarbon group is preferably 2 to 26, more preferably 3 to 20, and even more preferably 4 to 16, in terms of providing good paste workability and excellent mechanical strength after curing.

[0016] Y 2 Examples of the hydrocarbon group include a divalent aliphatic group and a divalent aromatic group.

[0017] The divalent aliphatic group includes an alkylene group, a cycloalkylene group, an alkenylene group, and an alkynylene group, with an alkylene group and a cycloalkylene group being preferred, and an alkylene group being more preferred.

[0018] Examples of alkylene groups include methylene, ethylene, n-propylene, isopropylene, butylene, pentylene, hexylene, heptylene, octylene, 2,2,4-trimethylhexamethylene, nonylene, decylene, dodecylene, tetradecylene, hexadecylene, octadecylene, and eicosanylene groups. Examples of the cycloalkylene group include a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, and a cycloheptylene group.

[0019] The divalent aromatic group may be a monocyclic group containing only carbon atoms, or a heterocyclic group. Examples of heteroatoms contained in the heterocyclic group include a nitrogen atom, a sulfur atom, and an oxygen atom. The number of heteroatoms contained in the heterocyclic group is preferably 1 to 3. The number of carbon atoms in the aromatic group is 6 or more, preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more. The number of carbon atoms in the aromatic group is preferably 35 or less, more preferably 20 or less, and even more preferably 16 or less. Examples of the divalent aromatic group include an arylene group having an alkylene group and an arylene group. Examples of the arylene group include a phenylene group; and polycyclic aromatic groups such as a naphthylene group, an anthracenylene group, a phenanthrylene group, a biphenylene group, and a fluorenylene group. Examples of the alkylene group of the arylene group having an alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, etc. In addition, both of the two bonds of the aromatic group may be bonded to an alkylene group. Examples of the arylene group having an alkylene group include an ethylenephenylene group, a diethylenephenylene group, a triethylenephenylene group, a propylenephenylene group, a butylenephenylene group, etc. When the aromatic group is an arylene group having an alkylene group and the aromatic group has a substituent, the substituent may be on the aromatic ring or on the alkylene group. The aromatic group is preferably an arylene group having an alkylene group. In order to further enhance the hydrophobicity of the adhesive interface, the bond of the divalent aromatic group is preferably located at the para position of the aromatic ring.

[0020] Y 2 Examples of the substituent in the hydrocarbon group include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms, and an amino group. The number of the substituents is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 4. Y 2 The hydrocarbon group may be unsubstituted.

[0021] Y 1 and Y 3 When the dental curable composition to be obtained is in a paste form, the number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6, in terms of providing good paste workability and excellent mechanical strength after curing.

[0022] As a specific example of the radical polymerizable monomer (A-1) having a urethane bond, a compound represented by formula [a-1] is preferred because it has better properties (mechanical strength, toughness, etc.) as a dental material. [ka]

[0023] The content of the radical polymerizable monomer (A-1) having a urethane bond can be changed depending on the specific application, and is not particularly limited as long as the effects of the present invention are achieved. However, from the viewpoint of superior adhesion (particularly adhesion durability) to tooth structure, the content is preferably in the range of 1 to 100 parts by mass, more preferably 2 to 99 parts by mass, and even more preferably 2 to 98 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer (A) in the dental curable composition of the present invention. In another embodiment, the content of the radical polymerizable monomer (A-1) having a urethane bond is preferably in the range of 1 to 50 parts by mass, more preferably in the range of 2 to 40 parts by mass, and even more preferably in the range of 2 to 30 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer (A) in the dental curable composition of the present invention.

[0024] Polymerizable monomers other than the radical polymerizable monomer (A-1) having a urethane bond include a radical polymerizable monomer (A-2) having an acidic group and a radical polymerizable monomer (A-3) not having an acidic group. The radical polymerizable monomer (A-2) having an acidic group and the radical polymerizable monomer (A-3) not having an acidic group do not have a urethane bond.

[0025] A preferred embodiment includes a dental hardenable composition in which the polymerizable monomer (A) further contains a radical polymerizable monomer (A-2) having an acidic group.

[0026] The radical polymerizable monomer (A-2) having an acidic group is a polymerizable monomer having at least one acidic group such as a phosphoric acid group, a phosphonic acid group, a pyrophosphate group, a thiophosphate group, a carboxylic acid group, or a sulfonic acid group, and having at least one polymerizable group such as an acryloyl group, a methacryloyl group, an acrylamide group, or a methacrylamide group. The radical polymerizable monomer (A-2) having an acidic group may be used alone or in combination of two or more kinds.

[0027] Examples of the polymerizable monomer having a phosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, and 11-(meth)acryloyloxyundecyl dihydrogen phosphate. monofunctional (meth)acrylate compounds having a phosphate group such as hydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-(4-methoxyphenyl)hydrogen phosphate, and 2-(meth)acryloyloxypropyl-(4-methoxyphenyl)hydrogen phosphate, and acid chlorides, alkali metal salts, ammonium salts, and amine salts thereof;Examples of the difunctional (meth)acrylate compound having a phosphate group include bis[2-(meth)acryloyloxyethyl]hydrogenphosphate, bis[4-(meth)acryloyloxybutyl]hydrogenphosphate, bis[6-(meth)acryloyloxyhexyl]hydrogenphosphate, bis[8-(meth)acryloyloxyoctyl]hydrogenphosphate, bis[9-(meth)acryloyloxynonyl]hydrogenphosphate, bis[10-(meth)acryloyloxydecyl]hydrogenphosphate, and 1,3-di(meth)acryloyloxypropyl dihydrogenphosphate, as well as their acid chlorides, alkali metal salts, ammonium salts, and amine salts;

[0028] 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 phosphonoacetate, 10-(meth)acryloyloxydecyl phosphonoacetate, acid chlorides, alkali metal salts, ammonium salts, and amine salts thereof.

[0029] 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, and acid chlorides, alkali metal salts, ammonium salts, and amine salts thereof.

[0030] Examples of the polymerizable monomer having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogen thiophosphate, 3-(meth)acryloyloxypropyl dihydrogen thiophosphate, 4-(meth)acryloyloxybutyl dihydrogen thiophosphate, 5-(meth)acryloyloxypentyl dihydrogen thiophosphate, 6-(meth)acryloyloxyhexyl dihydrogen thiophosphate, 7-(meth)acryloyloxyheptyl dihydrogen thiophosphate, 8-(meth)acryloyloxyoctyl dihydrogen thiophosphate, 9-(meth)acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, 20-(meth)acryloyloxyeicosyl dihydrogen thiophosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

[0031] Examples of the polymerizable monomer having a carboxylic acid group include (meth)acrylic acid, 4-[2-[(meth)acryloyloxy]ethoxycarbonyl]phthalic acid, 4-(meth)acryloyloxyethyltrimellitic acid, 4-(meth)acryloyloxybutyloxycarbonylphthalic acid, 4-(meth)acryloyloxyhexyloxycarbonylphthalic acid, 4-(meth)acryloyloxyoctyloxycarbonylphthalic acid, 4-(meth)acryloyloxydecyloxy Examples of suitable carboxylic acids include acryloylcarbonylphthalic acid and its acid anhydrides; 5-(meth)acryloylaminopentylcarboxylic acid, 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 8-(meth)acryloyloxyoctane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, and their acid chlorides, alkali metal salts, ammonium salts, and amine salts.

[0032] Examples of polymerizable monomers having a sulfonic acid group include 2-(meth)acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl(meth)acrylate, and acid chlorides, alkali metal salts, ammonium salts, and amine salts thereof.

[0033] Among the radical polymerizable monomers (A-2) having an acidic group, polymerizable monomers having a phosphate group, polymerizable monomers having a pyrophosphate group, and polymerizable monomers having a carboxylic acid group are preferred because they exhibit better adhesion to tooth structure and have better adhesion to CAD / CAM resins, particularly better adhesion durability, and polymerizable monomers having a phosphate group and polymerizable monomers having a carboxylic acid group are more preferred. Among these, (meth)acrylate-based monofunctional polymerizable monomers having a phosphate group and an alkyl group having 6 to 20 carbon atoms or an alkylene group having 6 to 20 carbon atoms as the main chain in the molecule, or (meth)acrylate-based polymerizable monomers having a carboxylic acid group are more preferred, and (meth)acrylate-based monofunctional polymerizable monomers having a phosphate group and an alkylene group having 8 to 12 carbon atoms as the main chain in the molecule are even more preferred. Furthermore, 10-methacryloyloxydecyl dihydrogen phosphate, 4-(meth)acryloyloxyethyl trimellitic acid and 4-(meth)acryloyloxyethyl trimellitic anhydride are particularly preferred, and 10-methacryloyloxydecyl dihydrogen phosphate is the most preferred.

[0034] The content of the radical polymerizable monomer (A-2) having an acidic group can be changed depending on the specific application, and is not particularly limited as long as the effects of the present invention are achieved. However, from the viewpoint of superior adhesion (particularly adhesion durability) to tooth structure, the content is preferably in the range of 1 to 50 parts by mass, more preferably 2 to 25 parts by mass, and even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the total amount of polymerizable monomer (A) in the dental curable composition of the present invention.

[0035] A preferred embodiment of the dental hardenable composition includes a composition in which the polymerizable monomer (A) further contains a radical polymerizable monomer (A-3) that does not have an acidic group. Another preferred embodiment includes a dental hardenable composition, in which the polymerizable monomer (A) comprises a radical polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin, a radical polymerizable monomer (A-2) having an acidic group, and a radical polymerizable monomer (A-3) not having an acidic group.

[0036] Suitable examples of the radical polymerizable monomer (A-3) having no acidic group include a hydrophilic polymerizable monomer (A-3-a) and a hydrophobic polymerizable monomer (A-3-b). The polymerizable monomer (A-3) having no acidic group may be used alone or in combination of two or more kinds.

[0037] The hydrophilic polymerizable monomer (A-3-a) means a polymerizable monomer having a solubility in water at 25°C of 10% by mass or more. Those with a solubility of 30% by mass or more are preferred, and those that can be dissolved in water at 25°C in any proportion are more preferred. The hydrophilic polymerizable monomer (A-3-a) promotes the penetration of the components of the dental hardenable composition into the tooth structure, and also penetrates into the tooth structure itself to adhere to the organic components (collagen) in the tooth structure.

[0038] Examples of the hydrophilic polymerizable monomer (A-3-a) include monofunctional (meth)acrylic acid ester polymerizable monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter sometimes abbreviated as "HEMA"), 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and 2-((meth)acryloyloxy)ethyltrimethylammonium chloride; N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N,N-bis(2-hydroxyethyl) (meth)acrylamide, and N-methoxymethyl (meth)acrylamide; Examples of suitable polymerizable monomers include monofunctional (meth)acrylamide polymerizable monomers such as diethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, diacetone(meth)acrylamide, 4-(meth)acryloylmorpholine, N-trihydroxymethyl-N-methyl(meth)acrylamide, N,N-dimethylacrylamide, and N,N-diethylacrylamide; and bifunctional (meth)acrylic acid ester polymerizable monomers such as polyethylene glycol di(meth)acrylate (average number of added moles of oxyethylene groups: 9 or more). Of these, 2-hydroxyethyl methacrylate is preferred because it exhibits better adhesion to tooth tissue and has better adhesion to CAD / CAM resins, especially better adhesion durability.

[0039] The hydrophobic polymerizable monomer (A-3-b) refers to a crosslinkable polymerizable monomer having a solubility in water at 25°C of less than 10% by mass. Examples of the hydrophobic polymerizable monomer (A-3-b) include monofunctional and bifunctional polymerizable monomers of aromatic compounds, monofunctional and bifunctional polymerizable monomers of aliphatic compounds, trifunctional or higher functional polymerizable monomers, etc. The hydrophobic polymerizable monomer (A-3-b) improves the mechanical strength and handleability of the cured product of the dental curable composition.

[0040] Examples of aromatic compound-based monofunctional polymerizable monomers include aliphatic compound-based monofunctional (meth)acrylate monomers such as n-stearyl methacrylate; ether bond-containing aliphatic compound-based monofunctional (meth)acrylate monomers such as butoxydiethylene glycol methacrylate and methoxypolyethylene glycol methacrylate (average number of moles of oxyethylene groups added: 9); alicyclic compound-based monofunctional (meth)acrylate monomers such as cyclohexyl methacrylate, isobornyl methacrylate, and dicyclopentanyl methacrylate; and benzyl methacrylate (commonly known as BEMA). monofunctional (meth)acrylate monomers having an aromatic ring group, such as 2-phenoxyethyl methacrylate (commonly known as PEMA), phenoxybenzyl acrylate (commonly known as POB-A), phenoxybenzyl methacrylate (commonly known as POB-MA), p-cumyl-phenoxyethylene glycol (meth)acrylate, 1-naphthylmethyl (meth)acrylate, or 2-naphthylmethyl (meth)acrylate; and (meth)acrylate monomers containing a heterocyclic group (for example, a cyclic ether group), such as tetrahydrofurfuryl methacrylate (commonly known as "THF-MA"). The monofunctional (meth)acrylate monomer having an aromatic ring group is preferably one having one or two phenyl groups. The (meth)acrylate monomer containing a heterocyclic group is preferably one having one or two heterocyclic groups (for example, a cyclic ether group).

[0041] Examples of aromatic compound-based bifunctional polymerizable monomers include aromatic di(meth)acrylates. Specific examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(2-hydroxy-3-acryloyloxypropoxy)phenyl]propane, 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (hereinafter sometimes abbreviated as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetra ... 2-(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitate, and the like. Among these, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane and 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethoxy groups added: 2.6) (hereinafter sometimes abbreviated as "D2.6E") are preferred.

[0042] Examples of the aliphatic compound-based monofunctional polymerizable monomer include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, dicyclopentanyl (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, etc. Among these, isobornyl methacrylate is preferred.

[0043] Examples of the aliphatic compound-based bifunctional polymerizable monomer include erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate (hereinafter sometimes abbreviated as "TEGDMA"), propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and 1,3-butanediol. Examples of the polymerizable monomer include bifunctional (meth)acrylic acid ester polymerizable monomers such as di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, N-methacryloyloxyethyl acrylamide (commonly known as "MAEA"), and 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane; and (meth)acrylamide polymerizable monomers such as N-methacryloyloxyethyl acrylamide, N-methacryloyloxypropyl acrylamide, N-methacryloyloxybutyl acrylamide, N-(1-ethyl-(2-methacryloyloxy)ethyl)acrylamide, and N-(2-(2-methacryloyloxyethoxy)ethyl)acrylamide.

[0044] Among these, triethylene glycol diacrylate, TEGDMA, neopentyl glycol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 1,10-decanediol dimethacrylate (commonly known as "DD"), and 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate are preferred from the viewpoint of mechanical strength and fluidity. 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane and DD are preferred from the viewpoint of reducing polymerization shrinkage stress. MAEA and N-methacryloyloxypropylacrylamide are preferred from the viewpoint of adhesion to tooth structures, especially dentin.

[0045] Examples of trifunctional or higher polymerizable monomers include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, and 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxaheptane.

[0046] Among the radical polymerizable monomers (A-3) not having an acidic group, HEMA, Bis-GMA, D2.6E, and TEGDMA are more preferred from the viewpoint of the adhesive strength and polymerization curability of the dental curable composition of the present invention.

[0047] The content of the radical polymerizable monomer (A-3) not having an acidic group can be changed depending on the specific application, and is not particularly limited as long as the effects of the present invention are achieved. However, from the viewpoints of high penetration into tooth structure and excellent adhesion of the composition, and of the cured product having sufficient mechanical strength, the content is preferably in the range of 1 to 98 parts by mass, more preferably 1 to 95 parts by mass, and even more preferably 1 to 90 parts by mass, relative to 100 parts by mass of the total amount of polymerizable monomer (A) in the dental curable composition of the present invention. In another embodiment, the content of the radical polymerizable monomer (A-3) having no acidic group is preferably in the range of 50 to 98 parts by mass, more preferably in the range of 60 to 95 parts by mass, and even more preferably in the range of 70 to 90 parts by mass.

[0048] [Polymerization initiator (B)] In a preferred embodiment of the present invention, the dental hardenable composition further comprises a polymerization initiator (B). The polymerization initiator (B) may be a photopolymerization initiator (B-1), a thermal polymerization initiator, or a chemical polymerization initiator. The chemical polymerization initiator may be an organic peroxide (B-2) or an inorganic peroxide, as described below, and the organic peroxide (B-2) is preferably used. The polymerization initiator (B) may be used alone or in combination of two or more kinds.

[0049] Examples of inorganic peroxides include peroxodisulfates and peroxodiphosphates, among which peroxodisulfates are preferred in terms of curability. Specific examples of peroxodisulfates include sodium peroxodisulfate, potassium peroxodisulfate (hereinafter sometimes abbreviated as KPS), aluminum peroxodisulfate, and ammonium peroxodisulfate.

[0050] Another preferred embodiment of the present invention includes a dental curable composition for use as a dental bonding material, further comprising a polymerization initiator (B), wherein the polymerization initiator (B) comprises a photopolymerization initiator (B-1).

[0051] The photopolymerization initiator (B-1) is classified into a water-soluble photopolymerization initiator and a water-insoluble photopolymerization initiator. As the photopolymerization initiator (B-1), only a water-soluble photopolymerization initiator may be used, only a water-insoluble photopolymerization initiator may be used, or a water-soluble photopolymerization initiator and a water-insoluble photopolymerization initiator may be used in combination.

[0052] The water-soluble photopolymerization initiator improves the polymerization hardening property at the hydrophilic tooth surface interface, and can realize high adhesive strength. The water-soluble photopolymerization initiator has a solubility in water at 25° C. of 10 g / L or more, preferably 15 g / L or more, more preferably 20 g / L or more, and even more preferably 25 g / L or more. When the solubility is 10 g / L or more, the water-soluble photopolymerization initiator dissolves sufficiently in the water in the tooth substance at the adhesive interface, making it easier for the polymerization-promoting effect to be realized.

[0053] Examples of the water-soluble photopolymerization initiator include water-soluble thioxanthones; water-soluble acylphosphine oxides; 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one in which a (poly)ethylene glycol chain is introduced to the hydroxyl group, 1-hydroxycyclohexyl phenyl ketone in which a (poly)ethylene glycol chain is introduced to the hydroxyl group and / or phenyl group, and 1-hydroxycyclohexyl phenyl ketone in which -OCHCOO - Na + those in which a (poly)ethylene glycol chain has been introduced into the hydroxyl group and / or phenyl group of 2-hydroxy-2-methyl-1-phenylpropan-1-one; those in which -OCH2COO has been introduced into the phenyl group of 2-hydroxy-2-methyl-1-phenylpropan-1-one - Na + and α-aminoalkylphenones such as 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-(dimethylamino)-1-[(4-morpholino)phenyl]-1-butanone in which the amino group is converted into a quaternary ammonium salt.

[0054] Examples of the water-soluble thioxanthones include 2-hydroxy-3-(9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(1-methyl-9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2- Hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(3,4-dimethyl-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(1,3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, and the like can be used.

[0055] Examples of the water-soluble acylphosphine oxides that can be used include sodium phenyl(2,4,6-trimethylbenzoyl)phosphinate, lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate, sodium bis(2,4,6-trimethylbenzoyl)phosphinate, and lithium bis(2,4,6-trimethylbenzoyl)phosphinate.

[0056] Among these water-soluble photopolymerization initiators, sodium bis(2,4,6-trimethylbenzoyl)phosphinate is preferred from the viewpoint of polymerization curing properties. The water-soluble photopolymerization initiator may be used alone or in combination of two or more kinds.

[0057] The content of the water-soluble photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total of the polymerizable monomers (A) from the viewpoint of the curability of the resulting dental curable composition, and is more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, from the viewpoint of superior adhesion to tooth structure. When the content of the water-soluble photopolymerization initiator is equal to or greater than the lower limit, polymerization at the adhesive interface proceeds sufficiently, and sufficient adhesive strength is likely to be obtained. On the other hand, when the content of the water-soluble photopolymerization initiator is equal to or less than the upper limit, sufficient adhesive strength is likely to be obtained.

[0058] In a preferred embodiment, the dental hardenable composition contains a water-insoluble photopolymerization initiator having a solubility in water at 25°C of less than 10 g / L (hereinafter, may be referred to as a water-insoluble photopolymerization initiator). In another preferred embodiment, the dental hardenable composition contains, in addition to the water-insoluble photopolymerization initiator, a water-insoluble photopolymerization initiator having a solubility of less than 10 g / L in water at 25°C, from the viewpoints of hardenability and mechanical strength. The water-insoluble photopolymerization initiator used in the present invention may be a known photopolymerization initiator. One type of water-insoluble photopolymerization initiator may be used alone, or two or more types may be used in combination.

[0059] Examples of the water-insoluble photopolymerization initiator include (bis)acylphosphine oxides, thioxanthones, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, and α-aminoketone compounds other than water-soluble photopolymerization initiators.

[0060] Among the (bis)acylphosphine oxides, examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, and benzoyldi(2,6-dimethylphenyl)phosphonate. Examples of bisacylphosphine oxides include bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0061] Examples of the thioxanthones include thioxanthone and 2-chlorothioxanthen-9-one.

[0062] Examples of the ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

[0063] Examples of the α-diketones include diacetyl, benzil, dl-camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzil, and acenaphthenequinone.

[0064] Examples of the coumarins include 3,3'-carbonylbis(7-diethylaminocoumarin), 3-(4-methoxybenzoyl)coumarin, 3-thienoylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3-(p-nitrobenzoyl)coumarin, 3-(p-nitrobenzoyl)coumarin, 3,5-carbonylbis(7-methoxycoumarin), 3-benzoyl-6-bromo Coumarin, 3,3'-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo[f]coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo[f]coumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin, 7-dimethylamino-3-(4-methoxybenzoyl)coumarin, 7-diethylamino-3-(4-methoxybenzoyl) )coumarin, 7-diethylamino-3-(4-diethylamino)coumarin, 7-methoxy-3-(4-methoxybenzoyl)coumarin, 3-(4-nitrobenzoyl)benzo[f]coumarin, 3-(4-ethoxycinnamoyl)-7-methoxycoumarin, 3-(4-dimethylaminocinnamoyl)coumarin, 3-(4-diphenylaminocinnamoyl)coumarin, 3-[(3-dimethylbenzothiazol-2-ylidene)acetyl]coumarin, 3-[(1-methylnaphtho[1,2-d]thiazol-2-ylidene)acetyl]coumarin, 3,3'-carbo Nylbis(6-methoxycoumarin), 3,3'-carbonylbis(7-acetoxycoumarin), 3,3'-carbonylbis(7-dimethylaminocoumarin), 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dibutylamino)coumarin, 3-(2-benzimidazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dioctylamino)coumarin, 3-acetyl-7-(dimethylamino)coumarin, 3,3'-carbonylbis(7-dibutylaminocoumarin), 3,Examples of compounds include those described in JP-A-9-3109 and JP-A-10-245525, such as 3'-carbonyl-7-diethylaminocoumarin-7'-bis(butoxyethyl)aminocoumarin, 10-[3-[4-(dimethylamino)phenyl]-1-oxo-2-propenyl]-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one, and 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one.

[0065] Among the above-mentioned coumarins, 3,3'-carbonylbis(7-diethylaminocoumarin) and 3,3'-carbonylbis(7-dibutylaminocoumarin) are particularly preferred.

[0066] Examples of the anthraquinones include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, and 1-hydroxyanthraquinone.

[0067] Examples of the benzoin alkyl ether compounds include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0068] Examples of the α-aminoketone compounds include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one.

[0069] Among these water-insoluble photopolymerization initiators, it is preferable to use at least one selected from the group consisting of (bis)acylphosphine oxides, α-diketones, and coumarins. Among these, dl-camphorquinone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are particularly preferable because they have a maximum absorption wavelength in the visible light region. This allows for the production of a dental curable composition that has excellent photocurability in the visible and near-ultraviolet regions and exhibits sufficient photocurability whether using a halogen lamp, light-emitting diode (LED), or xenon lamp as a light source.

[0070] In an embodiment further comprising a filler (C), the content of the polymerization initiator (B) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total of the polymerizable monomers (A) from the viewpoint of the curability of the resulting dental curable composition, and is more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, from the viewpoint of superior adhesion to tooth structure. When the content of the polymerization initiator (B) is equal to or greater than the lower limit, polymerization at the adhesive interface proceeds sufficiently, and sufficient adhesive strength is likely to be obtained. On the other hand, when the content of the polymerization initiator (B) is equal to or less than the upper limit, sufficient adhesive strength is likely to be obtained.

[0071] Filler In a preferred embodiment, the dental hardenable composition contains a filler (C) to adjust fluidity, increase the mechanical strength (such as bending strength) of the hardened product, and improve adhesion to tooth structure.

[0072] Another preferred embodiment includes a polymerizable monomer (A), a polymerization initiator (B), and a filler (C), The dental curable composition may include a composition in which the polymerizable monomer (A) includes a radical polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin.

[0073] Another preferred embodiment includes a polymerizable monomer (A), a polymerization initiator (B), and a filler (C), the polymerizable monomer (A) comprises a radical polymerizable monomer (A-1) having a urethane bond and substantially not containing an organotin; The dental curable composition may include a composition in which the content of the polymerization initiator (B) is 0.1 to 10 parts by mass and the content of the filler (C) is 80 to 900 parts by mass relative to 100 parts by mass of the polymerizable monomers (A) in total.

[0074] The dental hardenable composition in another preferred embodiment described above can be used as a dental composite resin, a dental cement, a dental core build-up material, or a dental mill blank.

[0075] Examples of the filler (C) include inorganic fillers (C-1), organic-inorganic composite fillers (C-2), and organic fillers (C-3). The filler (C) may be used alone or in combination of two or more kinds.

[0076] Inorganic filler (C-1) The inorganic filler (C-1) preferably contains various glasses (containing silica as the main component (containing 30% by mass or more of silica, preferably 40% by mass or more, and more preferably 50% by mass or more of silica), and optionally containing oxides of heavy metals, boron, aluminum, etc.). Examples of inorganic fillers include glass powders of common compositions such as fused silica, quartz, soda lime silica glass, E glass, C glass, and borosilicate glass (Pyrex (registered trademark) glass); barium glass, strontium borosilicate glass, lanthanum glass ceramics, fluoroaluminosilicate glass, various ceramics, alumina, silica-titania, silica-zirconia, ytterbium oxide, silica-coated ytterbium fluoride, aluminosilicate glass, barium boroaluminosilicate glass, and calcium fluoroalumina. Examples of the inorganic filler include composite oxides such as luminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass, diatomaceous earth, kaolin, clay minerals (montmorillonite, etc.), activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, yttrium fluoride, calcium phosphate, barium sulfate, zirconium oxide, titanium oxide, and hydroxyapatite. These may be used alone or in combination of two or more. Among these, inorganic fillers containing metal elements such as aluminum, strontium, zirconium, barium, lanthanum, ytterbium, titanium, and bismuth as constituent elements, which have high X-ray contrast properties, are preferred (for example, barium glass, alumina, silica-titania, silica-zirconia, and silica-coated ytterbium fluoride). The inorganic filler (C-1) can be used as an inorganic filler having a relatively high refractive index. These may also be used alone or in combination of two or more. Among these, quartz, silica, silica-titania, silica-zirconia, barium glass, ytterbium oxide, and silica-coated ytterbium fluoride are preferred, and quartz, silica, silica-titania, silica-zirconia, barium glass, and silica-coated ytterbium fluoride are more preferred, in terms of excellent mechanical strength and transparency of the resulting cured product. From the viewpoint of the radiopacity of the dental hardenable composition, silica-zirconia, barium glass, and silica-coated ytterbium fluoride are preferred, and silica-zirconia and barium glass are more preferred.

[0077] The inorganic filler (C-1) may be amorphous, crystalline, or a mixture of both, but preferably contains at least an amorphous portion.

[0078] As the inorganic filler (C-1), a commercially available product may be used. Examples of commercially available products include silica such as Aerosil (registered trademark) 90, Aerosil (registered trademark) 130, Aerosil (registered trademark) 150, Aerosil (registered trademark) 200, Aerosil (registered trademark) 255, Aerosil (registered trademark) 300, Aerosil (registered trademark) 380, Aerosil (registered trademark) OX50, and Aerosil (registered trademark) R972 (all manufactured by Nippon Aerosil Co., Ltd.); barium glass such as GM27884 and 8235 (manufactured by Schott), product code "E-3000" (manufactured by Esstech), strontium borosilicate glass (E-4000, manufactured by Esstech), lanthanum glass ceramics (GM31684, manufactured by Schott), and fluoroaluminosilicate glass (GM35429, G018-091, G018-117, manufactured by Schott).

[0079] The inorganic filler (C-1) is preferably surface-treated in advance with a known surface treatment agent such as a silane coupling agent in order to adjust the mechanical strength and fluidity of the cured product. For example, by surface-treating the hydroxyl groups present on the surface of the inorganic filler with a surface treatment agent, an inorganic filler with the hydroxyl groups surface-treated can be obtained.

[0080] Examples of surface treatment agents include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane, of which vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, and γ-aminopropyltriethoxysilane are preferred.

[0081] The surface treatment method can be any known method without any particular limitation, and examples thereof include a method in which the surface treatment agent is sprayed onto the inorganic filler while vigorously stirring it; a method in which the inorganic filler and the surface treatment agent are dispersed or dissolved in a suitable solvent, and then the solvent is removed; and a method in which the alkoxy groups of the surface treatment agent are hydrolyzed in an aqueous solution with an acid catalyst to convert them to silanol groups, which are then attached to the inorganic filler surface in the aqueous solution, and then the water is removed. In any of these methods, the reaction between the inorganic filler surface and the surface treatment agent is completed, usually by heating in the range of 50 to 150°C, and the surface treatment can be performed. The amount of surface treatment is not particularly limited, and for example, 0.1 to 40 parts by mass of the surface treatment agent can be used per 100 parts by mass of the inorganic filler before treatment.

[0082] The inorganic particles used as the inorganic filler (C-1) are not particularly limited in shape, and may have various shapes, such as crushed, plate-like, scale-like, fibrous (short fibers, long fibers), needle-like, whisker-like, spherical, etc. Primary particles of these shapes may be aggregated, or different shapes may be combined. The inorganic particles used as the inorganic filler (C-1) may be those that have been subjected to some treatment (for example, pulverization) to have the above-mentioned shape.

[0083] Organic-inorganic composite filler (C-2) The organic-inorganic composite filler (C-2) is obtained by adding a monomer to the inorganic filler described above in advance, forming a paste, polymerizing it, and pulverizing it. The organic-inorganic composite filler (C-2) refers to a filler containing an inorganic filler and a polymer of a monomer. For example, the organic-inorganic composite filler (C-2) can be obtained by mixing and polymerizing a radical polymerizable monomer (A-3) (e.g., Bis-GMA and TEGDMA) that does not have an acidic group with a surface-treated silica filler, followed by pulverization. The organic-inorganic composite filler (C-2) may also be used alone or in combination of two or more, and the organic-inorganic composite filler (C-2) is also preferably surface-treated from the viewpoint of mechanical strength. Examples and preferred types of surface treatment agents are the same as those for the inorganic filler. From the viewpoint of the fluidity and mechanical strength of the resulting dental curable composition, the average particle size of the organic-inorganic composite filler (C-2) is preferably 0.001 to 50 μm, more preferably 0.001 to 20 μm, and even more preferably 0.005 to 15 μm.

[0084] Organic filler (C-3) Examples of materials for the organic filler (C-3) include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and the like, and these may be used alone or as a mixture of two or more.

[0085] The average particle size of the organic filler (C-3) is preferably 0.001 to 50 μm, more preferably 0.001 to 20 μm, and even more preferably 0.005 to 15 μm, from the viewpoints of the fluidity and mechanical strength of the resulting dental curable composition.

[0086] In this specification, the average particle size of the filler can be determined by laser diffraction scattering or electron microscope observation of the particles. Specifically, laser diffraction scattering is convenient for measuring particle sizes of 0.1 μm or more, while electron microscope observation is convenient for measuring the particle size of ultrafine particles less than 0.1 μm. The value of 0.1 μm is measured by laser diffraction scattering.

[0087] Specifically, the laser diffraction scattering method can be performed by, for example, measuring on a volume basis using a laser diffraction particle size distribution analyzer (SALD-2300, manufactured by Shimadzu Corporation) and a 0.2% aqueous solution of sodium hexametaphosphate as a dispersion medium.

[0088] Specifically, electron microscope observation can be performed by taking a photograph of particles using an electron microscope (S-4000 model, manufactured by Hitachi, Ltd.) and measuring the particle diameters of particles (200 or more) observed within a unit field of view of the photograph using image analysis particle size distribution measurement software (Mac-View, manufactured by Mountec Co., Ltd.). In this case, the particle diameter is determined as the arithmetic mean value of the longest and shortest lengths of the particles, and the average primary particle diameter is calculated from the number of particles and their particle diameters.

[0089] The content of the filler (C) is not particularly limited as long as the effects of the present invention are achieved, but is preferably in the range of 80 to 900 parts by mass, more preferably 100 to 600 parts by mass, and even more preferably 120 to 500 parts by mass, relative to 100 parts by mass of the total polymerizable monomer (A) in the dental curable composition of the present invention. Within these ranges, sufficient radiopacity or sufficient mechanical strength of the cured product can be obtained.

[0090] [Solvent (D)] In some preferred embodiments of the present invention, the dental hardenable composition further comprises a solvent (D).

[0091] Another preferred embodiment of the present invention includes a dental hardenable composition for use as a dental primer, further comprising a solvent (D), a fourth-row transition metal compound (E), and optionally a silane coupling agent (F).

[0092] Examples of the solvent (D) include water and organic solvents. The solvent (D) may be used alone or in combination of two or more kinds.

[0093] Examples of the organic solvent include water-soluble organic solvents. When the dental curable composition is used as a dental primer composition, the water-soluble organic solvent can improve the adhesive strength, application properties, and penetration into tooth structure, as well as the solubility of the polymerizable monomer (A) in water. The water-soluble organic solvent is typically one having a boiling point of 150°C or less under normal pressure and a solubility in water of 5 parts by mass or more at 25°C, with one having a solubility of 30% by mass or more being more preferred, and one that can be dissolved in water at any ratio being even more preferred. Among organic solvents, water-soluble organic solvents having a boiling point of 100°C or less under normal pressure are particularly preferred. Specific examples of the water-soluble organic solvent include ethanol, methanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane, and tetrahydrofuran.

[0094] [Fourth Period Transition Metal Compounds (E)] In certain preferred embodiments of the present invention, the dental hardenable composition further comprises a Period 4 transition metal compound (E).

[0095] The fourth period transition metal compound (E) may be any of vanadium compounds, copper compounds, and other fourth period transition metal compounds (fourth period transition metal compounds other than vanadium compounds and copper compounds). The fourth period transition metal compound (E) may be used alone or in combination of two or more.

[0096] Examples of vanadium compounds include vanadyl acetylacetonate(IV), vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, vanadyl oxalate, bis(maltolato)oxovanadium(IV), oxobis(1-phenyl-1,3-butanedionato)vanadium(IV), vanadium(V) oxytriisopropoxide, ammonium(V) metavanadate, sodium(V) metavanadate, vanadium(V) pentoxide, divanadium(IV) tetroxide, and vanadyl(IV) sulfate. Among these, vanadyl acetylacetonate(IV) and bis(maltolato)oxovanadium(IV) are preferred from the viewpoint of solubility in the solvent (D), and vanadyl acetylacetonate(IV) and bis(maltolato)oxovanadium(IV) are more preferred. The vanadium compounds may be used alone or in combination of two or more.

[0097] As an example of the copper compound, a compound soluble in the radical polymerizable monomer is preferred. Examples of copper compounds include copper(II) carboxylate, copper(II) β-diketone, copper(II) β-ketoester, copper alkoxide, copper dithiocarbamate, and salts of copper and inorganic acids. Examples of copper(II) carboxylates include copper(II) citrate, copper(II) acetate, copper(II) phthalate, copper(II) tartrate, copper(II) oleate, copper(II) octoate, copper(II) octenoate, copper(II) naphthenate, copper(II) methacrylate, and copper(II) 4-cyclohexylbutyrate. Examples of β-diketone copper(II) include acetylacetonate copper(II), trifluoroacetylacetonate copper(II), hexafluoroacetylacetonate copper(II), 2,2,6,6-tetramethyl-3,5-heptanedionato copper(II), and benzoylacetonate copper(II). Examples of β-ketoester copper(II) include ethyl acetoacetate copper(II). Examples of copper alkoxides include copper(II) methoxide, copper(II) ethoxide, copper(II) isopropoxide, copper(II) 2-(2-butoxyethoxy)ethoxide, and copper(II) 2-(2-methoxyethoxy)ethoxide. Examples of copper dithiocarbamates include copper(II) dimethyldithiocarbamate. Salts of copper with inorganic acids include copper(II) nitrate, copper(II) bromide, and copper(II) chloride. These may be used alone or in combination of two or more. Among these, from the viewpoint of solubility and reactivity with the polymerizable monomer (A), copper(II) carboxylate, copper(II) β-diketone, and copper(II) β-ketoester are preferred, and copper(II) acetate and copper(II) acetylacetonate are more preferred. Among these, copper carboxylate, copper β-diketone and copper β-ketoester are preferred, with copper acetate and copper acetylacetonate being particularly preferred, from the viewpoint of solubility and reactivity with the polymerizable monomer (A).

[0098] Examples of other fourth-period transition metal compounds include scandium isopropoxide, yttrium isopropoxide, lanthanum methoxide, lanthanum ethoxide, lanthanum isopropoxide, lanthanum butoxide, lanthanum hydroxide, lanthanum carbonate, lanthanum fluoride, cerium isopropoxide, praseodymium isopropoxide, promethium isopropoxide, neodymium isopropoxide, samarium isopropoxide, europium isopropoxide, gadolinium isopropoxide, terbium ethoxide, terbium methoxide, and dysprosium isopropoxide. Examples of the titanium fluoride include titanium isopropoxide, holmium isopropoxide, erbium isopropoxide, thulium isopropoxide, ytterbium isopropoxide, iron(III) ethoxide, actinium ethoxide, titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium butoxide, titanium hydroxide, titanium fluoride, zirconium ethoxide, zirconium isopropoxide, zirconium butoxide, tungsten(IV) methoxide, tungsten(IV) isopropoxide, and tungsten(IV) butoxide. Among these, divanadium(IV) tetroxide, vanadyl acetylacetonate(IV), vanadyl oxalate(IV), vanadyl sulfate(IV), oxobis(1-phenyl-1,3-butanedionato)vanadium(IV), bis(maltolato)oxovanadium(IV), vanadium(V) pentoxide, sodium metavanadate(V), ammonium metavanadate(V), and the like are preferably used. Among these fourth period transition metal compounds (E), vanadyl acetylacetonate(IV) and bis(maltolato)oxovanadium(IV) are preferred from the viewpoint of the curability of the composition, and vanadyl acetylacetonate(IV) is most preferably used.

[0099] The content of the fourth period transition metal compound (E) in the dental hardenable composition is preferably 0.0001 part by mass or more, more preferably 0.0005 part by mass or more, and even more preferably 0.001 part by mass or more, relative to 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental hardenable composition, so as not to delay the hardening rate. Furthermore, since there is no risk of polymerization initiator residue elution from the cured product of the dental curable composition, the content of the fourth period transition metal compound (E) is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 1.0 part by mass or less, relative to the total amount of 100 parts by mass.

[0100] [Silane coupling agent (F)] In some preferred embodiments of the present invention, the dental hardenable composition further comprises a silane coupling agent (F). The silane coupling agent (F) may be used alone or in combination of two or more kinds.

[0101] As the silane coupling agent (F), any known agent can be used without any limitation. Specific examples of the silane coupling agent (F) include vinyl group-containing silane coupling agents such as vinylhexyltrimethoxysilane, vinylheptyltrimethoxysilane, and vinyloctyltrimethoxysilane; 3-methacryloyloxypropyltrimethoxysilane, 5-(meth)acryloyloxypentyltrimethoxysilane, 6-(meth)acryloyloxyhexyltrimethoxysilane, 7-(meth)acryloyloxyheptyltrimethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 9-(meth)acryloyloxypropyltrimethoxysilane, 5-(meth)acryloyloxypentyltrimethoxysilane, 6-(meth)acryloyloxyhexyltrimethoxysilane, 7-(meth)acryloyloxyheptyltrimethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, and 9-(meth)acryloyloxypropyltrimethoxysilane. Examples of (meth)acryloyloxy group-containing silane coupling agents include acryloyloxynonyltrimethoxysilane, 10-(meth)acryloyloxydecyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, 8-(meth)acryloyloxyoctylmethyldimethoxysilane, 10-(meth)acryloyloxydecylmethyldimethoxysilane, 11-(meth)acryloyloxyundecylmethyldimethoxysilane, and (meth)acryloyloxymethylphenethyltrimethoxysilane.

[0102] Among these silane coupling agents (F), 3-methacryloyloxypropyltrimethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 9-(meth)acryloyloxynonyltrimethoxysilane, 10-(meth)acryloyloxydecyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, and (meth)acryloyloxymethylphenethyltrimethoxysilane are particularly preferred from the viewpoints of adhesion durability and ease of handling.

[0103] The content of the silane coupling agent (F) is preferably 0.1 to 10.0 mass% of the total amount of the dental curable composition of the present invention in terms of excellent adhesive strength, and more preferably 0.5 to 9.0 mass%, even more preferably 1.0 to 8.0 mass%, and particularly preferably 1.2 to 7.0 mass%, in terms of excellent adhesive durability to tooth structures, CAD / CAM resins, and ceramic materials.

[0104] The dental curable composition of the present invention may also be used in the form of individual packets. In one preferred embodiment, the dental hardenable composition is a divided-packet type dental hardenable composition comprising a first agent and a second agent, At least one of the first agent and the second agent contains a radically polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin and a filler (C), the first agent contains a radical polymerizable monomer (A-2) having an acidic group, an organic peroxide (B-2), and a fourth period transition metal compound (E), The second agent may include an aromatic sulfinic acid compound (G) in a dental hardenable composition.

[0105] [Organic peroxide (B-2)] In a preferred embodiment of the present invention, the dental hardenable composition further comprises an organic peroxide (B-2). Examples of the organic peroxide (B-2) include diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy ketals, ketone peroxides, and hydroperoxides. The organic peroxide (B-2) may be used alone or in combination of two or more kinds.

[0106] Specific examples of diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluoyl peroxide. Specific examples of peroxyesters include t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxy-2-ethylhexanoate, and t-butylperoxyisopropyl carbonate. Specific examples of dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, and lauroyl peroxide. Specific examples of peroxyketals include 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, and the like. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl acetoacetate peroxide. Specific examples of hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, p-diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0107] Among the organic peroxides (B-2), hydroperoxides and peroxyesters are particularly preferred. Among the hydroperoxides, t-butyl hydroperoxide, cumene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide are preferred. Furthermore, among the peroxyesters, t-butyl peroxybenzoate is preferred.

[0108] The organic peroxide (B-2), when combined with other components, exhibits excellent polymerization hardening properties, adhesion to tooth structure and CAD / CAM resins, and particularly excellent adhesion durability. From the viewpoints of polymerization curability, adhesion to CAD / CAM resins, and particularly adhesion durability, the content of the organic peroxide (B-2) is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the total polymerizable monomer (A) in the dental curable composition of the divided package embodiment of the present invention. Furthermore, by having the content of the organic peroxide (B-2) within the above range, the working time of the dental curable composition can be adjusted to a desired working time.

[0109] [Aromatic sulfinic acid compounds (G)] In certain preferred embodiments of the present invention, the dental hardenable composition further comprises an aromatic sulfinic acid compound (G). The aromatic sulfinic acid compound (G) includes aromatic sulfinic acids and salts thereof. The aromatic sulfinic acid compound (G) may be used alone or in combination of two or more kinds.

[0110] Examples of aromatic sulfinic acids and salts thereof include lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, calcium salts, strontium salts, iron salts, zinc salts, ammonium salts, tetramethylammonium salts, and tetraethylammonium salts of benzenesulfinic acid, p-toluenesulfinic acid, o-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, 2,4,6-triisopropylbenzenesulfinic acid (sodium salt may be abbreviated as "TPSS" hereinafter), p-chlorobenzenesulfinic acid, naphthalenesulfinic acid, and the like. Among these, in terms of the curability and storage stability of the resulting dental curable composition, the lithium salt, sodium salt, potassium salt, magnesium salt, and calcium salt of 2,4,6-trimethylbenzenesulfinic acid and 2,4,6-triisopropylbenzenesulfinic acid are preferred, and the lithium salt, sodium salt, potassium salt, magnesium salt, and calcium salt of 2,4,6-triisopropylbenzenesulfinic acid are more preferred.

[0111] The content of the aromatic sulfinic acid and its salt is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total polymerizable monomer (A) in the dental curable composition of the present invention. When the content is 0.01 parts by mass or more and 5 parts by mass or less, the resulting dental hardenable composition has excellent mechanical strength in its cured product.

[0112] In the individually packaged dental curable composition, at least one of the first and second parts may further contain a radical polymerizable monomer (A-3) having no acidic group. In the above-mentioned individually packaged dental curable composition, the radical polymerizable monomer (A-2) having an acidic group is preferably at least one selected from the group consisting of polymerizable monomers having a phosphate group, polymerizable monomers having a pyrophosphate group, and polymerizable monomers having a carboxylic acid group, from the viewpoint of superior adhesiveness; polymerizable monomers having a phosphate group and polymerizable monomers having a carboxylic acid group are more preferred; (meth)acrylate-based monofunctional polymerizable monomers having a phosphate group and an alkyl group having 6 to 20 carbon atoms or an alkylene group having 6 to 20 carbon atoms as the main chain in the molecule are even more preferred; (meth)acrylate-based monofunctional polymerizable monomers having a phosphate group and an alkylene group having 8 to 12 carbon atoms as the main chain in the molecule are particularly preferred; and 10-methacryloyloxydecyl dihydrogen phosphate is most preferred.

[0113] [Cyclic thiourea compounds (H)] In certain preferred embodiments of the present invention, the dental hardenable composition further comprises a cyclic thiourea compound (H). Examples of the cyclic thiourea compound (H) include substituted ethylene thiourea compounds, substituted propylene thiourea compounds, and substituted butylene thiourea compounds, with substituted ethylene thiourea compounds and substituted propylene thiourea compounds being preferred. The cyclic thiourea compound (H) may be used alone or in combination of two or more kinds.

[0114] In one preferred embodiment, the composition includes a radical polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin, an organic peroxide (B-2), a filler (C), a fourth-row transition metal compound (E), and a cyclic thiourea compound (H), The dental hardenable composition may be one in which the cyclic thiourea compound (H) is at least one selected from the group consisting of substituted ethylene thiourea compounds and substituted propylene thiourea compounds.

[0115] The substituted ethylene thiourea compound has a structure represented by the following formula (I):

[0116] [ka] (In the formula, R1, R2, R3, R4, R5, and R6 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkoxyl group, an optionally substituted aryl group, an optionally substituted acyl group, an optionally substituted alkenyl group, an optionally substituted aralkyl group, or an optionally substituted monovalent heterocyclic group containing an oxygen atom, a sulfur atom, or a nitrogen atom (except when all of R1, R2, R3, R4, R5, and R6 are hydrogen atoms), and R4 and R5, together with the carbon atoms to which they are bonded, may form a ring which may be substituted.)

[0117] The substituted propylene thiourea compound used in the present invention has a structure represented by the following formula (II):

[0118] [ka] (In the formula, R7, R8, R9, R 10 , R 11 , R 12 , R 13 , and R 14 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkoxyl group, an optionally substituted aryl group, an optionally substituted acyl group, an optionally substituted alkenyl group, an optionally substituted aralkyl group, or an optionally substituted monovalent heterocyclic group containing an oxygen atom, a sulfur atom, or a nitrogen atom (provided that R7, R8, R9, R 10 , R 11 , R 12 , R 13 , and R 14 (except when all of R are hydrogen atoms), R and R 11 , and R9 and R 13may be joined together with the carbon atom to which they are attached to form a ring which may have a substituent.

[0119] The substituted butylene thiourea compound used in the present invention has a structure represented by the following formula (III).

[0120] [ka] (In the formula, R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkoxyl group, an optionally substituted aryl group, an optionally substituted acyl group, an optionally substituted alkenyl group, an optionally substituted aralkyl group, or an optionally substituted monovalent heterocyclic group containing an oxygen atom, a sulfur atom, or a nitrogen atom (provided that R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 (except when all of R are hydrogen atoms), 17 and R 19 , R 17 and R 21 , R 17 and R 23 , and R 19 and R 21 may be joined together with the carbon atom to which they are attached to form a ring which may have a substituent.

[0121] Examples of the cyclic thiourea compound (H) having these structures include, from the viewpoints of improving adhesive strength, improving curing properties, easy availability, and solubility in radical polymerizable monomers, 4-methyl-2-imidazolidinethione, 4,4-dimethyl-2-imidazolidinethione, 4,5-dimethyl-2-imidazolidinethione, 4-ethyl-2-imidazolidinethione, 4,4-diethyl-2-imidazolidinethione, 4,5- Diethyl-2-imidazolidinethione, 4-methyl-3,4,5,6-tetrahydropyrimidine-2(1H)-thione, 4-ethyl-3,4,5,6-tetrahydropyrimidine-2(1H)-thione, 5-methyl-3,4,5,6-tetrahydropyrimidine-2(1H)-thione, 5-ethyl-3,4,5,6-tetrahydropyrimidine-2(1H)-thione, 4,4-dimethyl-3,4,5,6-tetrahydropyrimidine-2(1H)-thione dropyrimidine-2(1H)-thione, 4,5-dimethyl-3,4,5,6-tetrahydropyrimidine-2(1H)-thione, 4,6-dimethyl-3,4,5,6-tetrahydropyrimidine-2(1H)-thione, 5,5-dimethyl-3,4,5,6-tetrahydropyrimidine-2(1H)-thione, 5-(2-chlorophenyl)-3,4,5,6-tetrahydropyrimidine-2(1H)-thione, and 5, It is preferable to use at least one selected from the group consisting of 6-dimethyl-3,4,5,6-tetrahydropyrimidine-2(1H)-thione, and it is more preferable to use at least one selected from the group consisting of 4-methyl-2-imidazolidinethione, 4,4-dimethyl-2-imidazolidinethione, 4-ethyl-2-imidazolidinethione, and 4,4-diethyl-2-imidazolidinethione.

[0122] The cyclic thiourea compounds (H) having these structures have planar molecular structures, which allows them to have high reactivity with the organic peroxide (B-2), and as a result, the dental curable composition can achieve both high adhesion and appropriate curability.

[0123] The content of the cyclic thiourea compound (H) is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of the dental curable composition of the present invention. If the content is less than 0.01% by mass, the function as a redox polymerization initiator may be insufficient, whereas if it exceeds 20% by mass, the curing start time may be too early, making it difficult to obtain an appropriate operating time.

[0124] Another preferred embodiment is a dental hardenable composition containing a thiourea compound.

[0125] The thiourea compounds include thiourea, methylthiourea, ethylthiourea, ethylenethiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, N,N'-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, and tetracyclohexylthiourea. thiourea, 1-(2-pyridyl)-2-thiourea (hereinafter sometimes abbreviated as "PTU"), 4,4-dimethylethylenethiourea, phenylthiourea, N-(2-hydroxyphenyl)thiourea, N-(2,6-dihydroxyphenyl)thiourea, N-(2,4-dihydroxyphenyl)thiourea, N-(2-hydroxy-4-methoxyphenyl)thiourea, N-(2-hydroxy-4-ethoxyphenyl)thiourea, N-(2-hydroxy-4-dimethylphenyl)thiourea N-(2-hydroxy-4-diethylaminophenyl)thiourea, N-(2-methoxyphenyl)thiourea, N-(2-ethoxyphenyl)thiourea, N-(2,6-dimethoxyphenyl)thiourea, N-(2,4-dimethoxyphenyl)thiourea, N-(2-methoxy-4-hydroxyphenyl)thiourea, N-(2-methoxy-4-dimethylaminophenyl)thiourea, N-(2-methoxy-3-hydroxyphenyl)thiourea N-(2-dimethylaminophenyl)thiourea, N-(2-dimethylaminophenyl)thiourea, N-(2-diethylaminophenyl)thiourea, N-(2-dimethylamino-4-methoxyphenyl)thiourea, N-(2-dimethylamino-4-hydroxyphenyl)thiourea, N-(2-aminophenyl)thiourea, N-(2,4-diaminophenyl)thiourea, N-(2,6-diaminophenyl)thiourea, and N-(2-amino-4-hydroxyphenyl)thiourea. The thiourea compounds may be used alone or in combination of two or more.

[0126] The content of the thiourea compound is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total polymerizable monomer (A) in the dental curable composition of the present invention. When the content is 0.01 part by mass or more, a decrease in the adhesive strength of the resulting dental curable composition to a wet material such as tooth tissue can be suppressed. On the other hand, when the content is 15 parts by mass or less, the mechanical strength of the cured product of the resulting dental curable composition is excellent.

[0127] In addition, in certain preferred embodiments of the present invention, the dental hardenable composition further comprises a tertiary amine.

[0128] Examples of tertiary amines include N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, and N,N-bis(2- N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-di(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-diisopropylaniline, N,N-bis(2-hydroxyethyl) aromatic amines such as 2-n-butoxyethyl 4-(N,N-dimethylamino)benzoate, (2-methacryloyloxy)ethyl 4-(N,N-dimethylamino)benzoate, ethyl 4-(N,N-dimethylamino)benzoate, butyl 4-(N,N-dimethylamino)benzoate, and 4-(N,N-dimethylamino)benzophenone; and aliphatic amines such as N,N-dimethylaminoethyl methacrylate, N-methyldiethanolamine, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2-(dimethylamino)ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, and triethanolamine trimethacrylate. The tertiary amines may be used alone or in combination of two or more.

[0129] Another preferred embodiment is a dental hardenable composition containing an aldehyde compound. Examples of the aldehyde compound include dimethylaminobenzaldehyde and terephthalaldehyde. The aldehyde compounds may be used alone or in combination of two or more.

[0130] Another preferred embodiment is a dental hardenable composition containing a compound having a thiol group. Examples of compounds having a thiol group include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid. The compound having a thiol group may be used alone or in combination of two or more kinds.

[0131] Another preferred embodiment includes a dental hardenable composition comprising a benzotriazole compound and / or a benzimidazole compound.

[0132] Benzotriazole compounds and benzimidazole compounds include compounds represented by the following general formulas (8) and (9): The benzotriazole compounds and benzimidazole compounds may each be used alone or in combination of two or more. [ka] [ka]

[0133] In each general formula, A1 to A8 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an alkenyl group, an aralkyl group, or a halogen atom. The alkyl groups represented by A1 to A8 may be linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, cycloheptanyl, n-octyl, 2-ethylhexyl, cyclooctyl, n-nonyl, cyclononyl, and n-decyl. Of these, methyl and ethyl groups are particularly preferred. The aryl group represented by A1 to A8 preferably has a carbon number of 6 to 14. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. The alkoxy groups represented by A1 to A8 may be linear, branched, or cyclic, and preferably have a carbon number of 1 to 8. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an n-hexyloxy group, a cyclohexyloxy group, an n-octyloxy group, and a 2-ethylhexyloxy group. The alkenyl groups represented by A1 to A8 may be linear, branched, or cyclic, and preferably have a carbon number of 2 to 6. Examples of the alkenyl group include a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group. Examples of the aralkyl group represented by A1 to A8 include an alkyl group (particularly, an alkyl group having 1 to 10 carbon atoms) substituted with an aryl group (particularly, an aryl group having 6 to 10 carbon atoms), and specific examples include a benzyl group. Examples of the halogen atom represented by A1 to A8 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. A1 to A8 are preferably a hydrogen atom or a methyl group.

[0134] The benzotriazole compounds and benzimidazole compounds may be used alone or in combination of two or more. Specific examples of the benzotriazole compound and the benzimidazole compound include 1H-benzotriazole, 5-methyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazole, benzimidazole, 5-methylbenzimidazole, 5,6-dimethylbenzimidazole, etc. Among these, 1H-benzotriazole and 5-methyl-1H-benzotriazole are preferred in terms of the color tone and storage stability of the composition.

[0135] From the viewpoint of the mechanical strength of the cured product and adhesion to tooth structure, the content of the benzotriazole compound and the benzimidazole compound is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the total of the polymerizable monomers (A) in the dental curable composition.

[0136] Another preferred embodiment includes a dental hardenable composition containing a reducing inorganic compound having sulfur.

[0137] Examples of reducing inorganic compounds containing sulfur include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, and dithionites, with sulfites and bisulfites being preferred. Specific examples of sulfur-containing reducing inorganic compounds include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, and potassium hydrogen sulfite. The sulfur-containing reducing inorganic compound may be used alone or in combination of two or more kinds.

[0138] The content of the reducing inorganic compound is preferably 0.01 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total of the polymerizable monomers (A) in the dental curable composition of the present invention. When the content is 0.01 parts by mass or more, a decrease in the adhesive strength of the resulting dental hardenable composition to a wet material such as tooth tissue can be suppressed, whereas when the content is 15 parts by mass or less, there is no risk of a decrease in the mechanical strength of the cured product of the resulting dental hardenable composition.

[0139] In addition, another preferred embodiment includes a step of contacting an inorganic filler molded product obtained by press-molding the inorganic filler (C-1) with a polymerizable monomer-containing composition, The method for producing a dental mill blank may include a method in which the polymerizable monomer-containing composition contains a radically polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin.

[0140] The method for producing the dental mill blank can be the method described in WO 2014 / 021343. In the method for manufacturing the dental mill blank, a method is exemplified in which a radical polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin is blended with the polymerizable monomer-containing composition described in WO 2014 / 021343.

[0141] The method for manufacturing a dental mill blank includes a step of producing an inorganic filler molded body by press-molding an inorganic filler (C-1), and contacting the obtained inorganic filler molded body with a polymerizable monomer-containing composition, and polymerizing and curing the polymerizable monomer, thereby allowing the polymerizable monomer-containing composition to penetrate into the gaps between the inorganic particles in the inorganic filler molded body. More specifically, the inorganic filler (C-1) is press-molded to prepare a bulk-shaped molded body of appropriate size, in which the inorganic filler (C-1) is aggregated. Such a molded body does not have a porous structure, such as that obtained by sintering an inorganic filler, but rather is filled with individual inorganic fillers in close contact with each other. The molded body is then contacted with a polymerizable monomer, which penetrates into the gaps between the primary particles of the inorganic filler constituting the molded body. Polymerization and curing in this state allows a dental mill blank to be obtained, in which the inorganic filler is densely packed. In this respect, this method is completely different from conventional manufacturing methods in which an inorganic filler and a polymerizable monomer are uniformly mixed and kneaded to form a fluid, paste-like polymerizable composition (composite resin), which is then polymerized and cured to obtain a dental mill blank. Furthermore, the dental mill blank obtained by the present invention can give a cured product with an inorganic filler content that far exceeds that achieved in conventional dental composite resins.

[0142] As the inorganic filler (C-1) used in the method for producing a dental mill blank, those mentioned above can be used. In order to impart X-ray contrast, inorganic oxides containing heavy metal elements such as zirconium, barium, titanium, lanthanum, and strontium are used as the inorganic filler (C-1). The refractive index of such inorganic filler (C-1) containing a heavy metal element is usually high, within the range of 1.5 to 1.6. Therefore, in the present invention, for example, when a (meth)acrylate-based monomer is used as the polymerizable monomer, the refractive index of the (meth)acrylate-based monomer is usually within the range of 1.5 to 1.6, so even when combined with such inorganic particles with a high refractive index and X-ray contrast properties, the refractive index difference can be adjusted to be small, and the resulting dental mill blank is useful because it is likely to have high transparency.

[0143] In a more preferred embodiment of the method for producing a dental mill blank, the inorganic filler (C-1) preferably contains inorganic particles (submicron filler) having an average particle size in the range of 0.1 to 1 μm and a particle size in the range of 0.05 to 5 μm. Among these, inorganic particles having the above particle size range and an average particle size of preferably 0.1 to 0.5 μm, more preferably 0.1 to 0.3 μm, are preferred. That is, inorganic particles having an average particle size of 0.1 to 1 μm and a particle size range of 0.05 to 5 μm are preferred, inorganic particles having an average particle size of 0.1 to 0.5 μm and a particle size range of 0.05 to 5 μm are more preferred, and inorganic particles having an average particle size of 0.1 to 0.3 μm and a particle size range of 0.05 to 5 μm are even more preferred. The use of inorganic particles having particle sizes within this range can provide dental mill blanks that provide dental prostheses that adequately combine mechanical strength and aesthetics (wear resistance and smoothness). When the submicron filler is used, the content of the submicron filler in the inorganic filler (C-1) is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably substantially 100% by mass.

[0144] In another preferred embodiment of the method for producing a dental mill blank, the inorganic filler (C-1) has an average particle diameter of 0.001 to 0.1 μm and a specific surface area of ​​500 to 30 m 2 / g (hereinafter also referred to as "ultrafine inorganic particles"), and the average particle size is 0.005 to 0.05 μm, the specific surface area is 400 to 40 m 2 / g, and the average particle size is 0.005 to 0.05 μm, and the specific surface area is 200 to 50 m 2 / g range or inorganic ultrafine particles with an average particle diameter of 0.01 to 0.04 μm and a specific surface area of ​​400 to 40 m 2 / g, and the average particle size is 0.01 to 0.04 μm, and the specific surface area is 200 to 50 m 2 / g range of inorganic ultrafine particles is particularly preferred. Such inorganic ultrafine particles are so-called nanoparticles (ultrafine particle fillers), and can provide dental mill blanks with excellent transparency and polishing smoothness. When the inorganic ultrafine particles are used, the content of the inorganic ultrafine particles in the inorganic filler (C-1) is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably substantially 100% by mass.

[0145] Furthermore, in the method for producing a dental mill blank, agglomerated particles formed by agglomeration of the ultrafine particle filler (nanoparticles) can also be suitably used in the present invention. In particular, when the particle diameter of the agglomerated particles is in the range of 1 to 20 μm, preferably 2 to 10 μm, a mill blank with excellent mechanical strength can be obtained. The average particle size of the aggregated particles is measured on a volume basis using a laser diffraction particle size distribution analyzer (SALD-2300, manufactured by Shimadzu Corporation) and a 0.2% aqueous solution of sodium hexametaphosphate as a dispersion medium.

[0146] In another preferred embodiment, the inorganic filler (C-1) has an average particle size of 0.001 to 0.1 μm and a specific surface area of ​​500 to 30 m 2 / g, and inorganic particles having an average particle size in the range of 0.2 to 2 μm and a particle size in the range of 0.1 to 10 μm. In this way, a composition in which both inorganic ultrafine particles and inorganic particles of 0.2 to 2 μm are blended (mixed) is called hybrid inorganic particles, and can provide a dental mill blank with superior mechanical strength. When the hybrid inorganic particles are used, the content of the hybrid inorganic particles in the inorganic filler (C-1) is preferably 90 mass % or more, more preferably 95 mass % or more, and even more preferably substantially 100 mass %. Hereinafter, inorganic particles having an average particle size in the range of 0.2 to 2 μm and a particle size in the range of 0.1 to 10 μm may be simply referred to as "hybrid inorganic particles of 0.2 μm or larger." The inorganic ultrafine particles used in the hybrid type are the same as those used in the ultrafine particle filler.

[0147] In another preferred embodiment, the dental mill blank manufacturing method of the present invention can also produce mill blanks with layered structures that differ in physical properties, transparency, color, etc. by press-molding two or more different types of inorganic particles, or the same inorganic particles, into layers. Dental mill blanks with such layered structures can provide clinically useful dental prostheses. For example, if inorganic particles adjusted to increase the transparency of the cured product are arranged in the first layer and inorganic particles adjusted to the color tone of dentin are arranged in the second layer, a crown obtained by cutting such a mill blank can be produced that has an enamel-colored layer on top and a dentin-colored layer on the bottom, resulting in an aesthetically excellent crown. The color tone can be adjusted by mixing and dispersing a pigment (colored particles) into the inorganic particles. As the pigment, any known pigment used in dental compositions can be used without any limitation.

[0148] Furthermore, inorganic particles that have been surface-treated in advance can be used as the inorganic filler (C-1). Surface treatment improves the mechanical strength of the resulting mill blank. Furthermore, when the inorganic filler (C-1) is pressure-molded and the resulting aggregate of inorganic particles (inorganic filler molding) is brought into contact with a polymerizable monomer (described below) to allow the polymerizable monomer to penetrate into the gaps between the aggregates of the inorganic particles, there is an advantage in that the compatibility between the inorganic particle surface and the polymerizable monomer improves, facilitating the penetration of the polymerizable monomer into the gaps between the aggregates. When surface-treating hybrid inorganic particles, the hybrid inorganic ultrafine particles and the hybrid inorganic particles of 0.2 μm or larger may be surface-treated separately and then mixed to form hybrid inorganic particles, or the mixture of the inorganic ultrafine particles and the inorganic particles of 0.2 μm or larger may be surface-treated.

[0149] As such a surface treatment agent, a known surface treatment agent can be used, and an organometallic compound such as an organosilicon compound, an organotitanium compound, an organozirconium compound, or an organoaluminum compound, or an acidic group-containing organic compound having at least one acidic group such as a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonate group, a sulfonate group, or a carboxylic acid group, can be used. When two or more surface treatment agents are used, the surface treatment layer may be a mixture of two or more surface treatment agents, or may be a multi-layered surface treatment layer in which multiple surface treatment agent layers are laminated. Furthermore, the surface treatment method can be a known method without any particular limitation.

[0150] The inorganic filler (C-1) can be press-molded by any known method without limitation. For example, a suitable method is to fill the inorganic filler (C-1) into a press mold (die) of a desired size and apply pressure by uniaxial pressing using an upper punch and a lower punch. The pressure applied at this time is set to an optimum value depending on the size of the desired molded body and the type and particle size of the inorganic particles, and is usually 10 MPa or more. If the pressing pressure is low, the inorganic particles will not be packed densely and the gaps between the inorganic particles will not be narrow enough, so the inorganic particle content per unit volume of the resulting mill blank cannot be increased, and as a result, the mechanical strength, wear resistance, and surface smoothness of the dental prosthesis obtained from the mill blank may be insufficient. From this viewpoint, the higher the pressing pressure, the better. However, taking into consideration productivity aspects such as the size of the press-molded product and equipment factors, the pressing pressure in a uniaxial press is usually 200 MPa or less, preferably 10 MPa or more, more preferably 20 MPa or more, even more preferably 25 MPa or more, and is preferably 180 MPa or less, more preferably 150 MPa or less, even more preferably 100 MPa or less, and particularly preferably 80 MPa or less. In one embodiment, the pressure is preferably in the range of 10 to 200 MPa, more preferably 20 to 100 MPa, and even more preferably 25 to 80 MPa. The pressing time can be set appropriately depending on the pressing pressure, but is usually 1 to 120 minutes.

[0151] The press molding method in the manufacturing method of the present invention is preferably a cold isostatic pressing (CIP) step / or includes a CIP step. Specifically, it is preferable to perform press molding by a CIP step without performing the above-mentioned uniaxial press, or to further perform CIP molding on the molded body after the above-mentioned uniaxial press. CIP molding typically allows for higher press pressures than uniaxial pressing, and pressure can be applied uniformly to the compact from three directions. Therefore, CIP molding can eliminate undesirable microvoids and uneven inorganic particle aggregation within the compact, further increasing the compressed density of the inorganic particles and resulting in a mill blank with an extremely high inorganic particle content. When press molding is a CIP process, a press-molded product can also be obtained by filling an elastic container such as silicone rubber or polyisoprene rubber with the inorganic filler (C-1) without the uniaxial pressing step, and subjecting the container to CIP treatment either directly or under vacuum. High pressure during CIP molding is also desirable. Alternatively, when CIP molding is performed after uniaxial pressing, the press-molded product can be CIP-treated either directly or under vacuum. For such CIP processing, a CIP device capable of applying a pressure of approximately 1000 MPa, manufactured by Kobe Steel, Ltd., can be used. High pressure is preferable during CIP molding, regardless of whether uniaxial pressing is used or not. However, taking productivity into consideration, when uniaxial pressing is used, the pressure is preferably 30 MPa or more, more preferably 50 MPa or more, even more preferably 100 MPa or more, and preferably 500 MPa or less, more preferably 400 MPa or less, and even more preferably 300 MPa or less. A pressure of 30 to 500 MPa is preferred, with 50 to 400 MPa being more preferred, and 100 to 300 MPa being even more preferred. When CIP treatment is performed without uniaxial pressing, the pressure is preferably 30 MPa or more, more preferably 50 MPa or more, even more preferably 100 MPa or more, and preferably 1000 MPa or less, more preferably 800 MPa or less, and even more preferably 700 MPa or less. A pressure of 30 to 1000 MPa is preferred, with 50 to 800 MPa being more preferred, and 100 to 700 MPa being even more preferred. The CIP molding time can be appropriately set depending on the pressing pressure, but is typically 1 to 60 minutes.

[0152] In addition, examples of methods for stacking and press-molding two or more different types of inorganic particles include the following. For example, a first inorganic particle powder is filled into a uniaxial press die fitted with a lower punch, and an upper punch is set in the die to press the powder. Next, the upper punch is removed, and a second inorganic powder is filled on top of the pressed first inorganic powder aggregate, and the upper punch is set again to press the second inorganic powder. The press-molded product is then removed from the die to obtain a press-molded product in which the first inorganic particles and the second inorganic particles are layered. The pressing pressure during the pressing is set to an optimal value depending on the type and amount of inorganic particles used, and the pressing pressure for each layer may be different or the same. Alternatively, after filling the die with the first inorganic powder, the surface may be flattened, and without pressing, the second inorganic powder may be filled on top of it, and the first and second inorganic powders may be pressed together.

[0153] The press-molded body can be processed into dental mill blanks of various shapes, as described below, and therefore, its size is not particularly limited. The inorganic filler molded body may be a molded body obtained by pressing the inorganic filler (C-1) all at once, or may be a molded body obtained by stacking separately molded bodies and then pressing them together to form a single molded body, or may be a molded body obtained by pressing a new inorganic filler (C-1) onto a separately molded body.

[0154] The inorganic filler molding obtained in this way, in which inorganic filler (C-1) is aggregated, is brought into contact with the polymerizable monomer described below, so that the polymerizable monomer penetrates into the gaps between the powder primary particles, and as a result, a composition having a structure in which inorganic particles are extremely densely dispersed in the polymerizable monomer is obtained.Therefore, in the present invention, it is preferable to use the inorganic filler (C-1) as it is after press molding, and for example, it is not preferable to use the inorganic filler (C-1) as a porous body that is sintered and interconnected.That is, it is preferable to use a molding that is a densely packed body of inorganic filler (C-1).

[0155] Generally, in particle-dispersed composite materials such as those of the present invention, the smaller the particle size of the inorganic particles dispersed in the resin, the better the polishing smoothness and the longer the luster in the oral cavity that can be maintained. On the other hand, the smaller the particle size of the inorganic particles, the more difficult it becomes to densely pack the inorganic particles into the composite material, and the cured product tends to have reduced mechanical strength and abrasion resistance. However, in the present invention, dental mill blanks are produced by press-molding inorganic fillers, so high-density packing is possible even with small particle sizes of inorganic particles, and dental prostheses obtained from the mill blanks have excellent luster and improved strength and abrasion resistance.

[0156] The content of inorganic filler (C-1) in the dental mill blank obtained by the present invention varies depending on the particle size and shape of the inorganic particles used, but even if inorganic particles with a small particle size are used, it is usually blended in at 60 mass% or more of the total amount of the dental mill blank of the present invention, preferably 70 mass% or more, more preferably 80 mass% or more, even more preferably 82 mass% or more, particularly preferably 85 mass% or more, and preferably 96 mass% or less, more preferably 95 mass% or less. The content of the inorganic filler (C-1) is preferably 60 to 96 mass%, more preferably 70 to 96 mass%, even more preferably 80 to 95 mass%, and particularly preferably 85 to 95 mass%. The content of the inorganic filler (C-1) here is a value measured based on the ignition residue of the cured product.

[0157] Specifically, the ignition residue of a cured product can be measured by, for example, placing the cured product in a crucible and heating it in an electric furnace at 575°C for a predetermined time to burn off the organic resin component, and then measuring the mass of the remaining inorganic particles. In this method, in the case of a mill blank obtained using surface-treated inorganic particles, the applied surface treatment agent is calculated as the burned organic resin component. Next, the obtained inorganic filler molded article is brought into contact with a composition containing a polymerizable monomer (polymerizable monomer-containing composition).

[0158] The polymerizable monomer-containing composition contains a radical polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin, as well as a radical polymerizable monomer (A-2) having an acidic group and / or a radical polymerizable monomer (A-3) not having an acidic group.

[0159] The content of the polymerizable monomer in the dental mill blank can be appropriately adjusted depending on the degree of contact of the polymerizable monomer-containing composition. In addition, the content of the inorganic filler (C-1) in the dental mill blank of the present invention varies depending on the average particle size of the inorganic particles constituting the inorganic filler (C-1) and the press molding method, so the content of the polymerizable monomer cannot be determined in general.

[0160] The dental mill blank of the present invention is produced by polymerizing and curing a polymerizable monomer impregnated into the internal gaps of an inorganic filler molded body. Therefore, the polymerizable monomer-containing composition may contain a polymerization initiator (B) to facilitate polymerization and curing.

[0161] In addition to the above components, the polymerizable monomer-containing composition may further contain, depending on the purpose, a pH adjuster, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a colorant, a pigment, an antibacterial agent, an X-ray contrast agent, a thickener, a fluorescent agent, and the like.

[0162] The method for contacting the polymerizable monomer-containing composition with the inorganic filler molding is not particularly limited as long as the polymerizable monomer-containing composition can penetrate into the gaps between the inorganic particles in the inorganic filler molding. However, a simple and preferred method is to immerse the inorganic filler molding in the polymerizable monomer-containing composition. By immersion, the monomer can gradually penetrate into the interior of the aggregate due to capillary action. In this case, placing the surrounding environment under a reduced pressure atmosphere is a preferred method, as it promotes the penetration of the liquid monomer. In addition, repeating the operation of reducing pressure and then returning to normal pressure (reduced pressure / normal pressure operation) multiple times is effective in shortening the process time for completely penetrating the monomer into the molding. The degree of pressure reduction at this time is appropriately selected depending on the viscosity of the monomer and the particle size of the inorganic filler, but is usually 100 hectopascals (10 kPa) or less, preferably 50 to 0.001 hectopascals (5 to 0.0001 kPa), and more preferably 20 to 0.1 hectopascals (2 to 0.01 kPa). -1 ~1×10 -8 Pa).

[0163] As a method other than immersion, a method of applying pressure to the inorganic filler molding in a mold while the molding is in a press-molded state can be considered. This method allows the polymerization and curing process to be carried out in the mold as well. The pressure conditions are preferably 2 MPa or higher, more preferably 10 MPa or higher, and even more preferably 20 MPa or higher.

[0164] Furthermore, as a method for allowing the polymerizable monomer to penetrate into the inorganic filler molded body without leaving any gaps, there is a method in which the inorganic filler molded body apparently impregnated with the polymerizable monomer is placed under pressurized conditions for a certain period of time. That is, it is desirable to place the inorganic filler molded body impregnated with the polymerizable monomer together with the polymerizable monomer under pressurized conditions using a CIP device or the like. The pressure conditions are preferably 20 MPa or more, more preferably 50 MPa or more, and even more preferably 100 MPa or more. Furthermore, it is more preferable to repeat the process of releasing the pressure, returning to normal pressure, and then applying pressure again.

[0165] The viscosity of the polymerizable monomer-containing composition also affects the penetration rate; typically, the lower the viscosity, the faster the penetration. The preferred viscosity range (at 25°C) is 10 Pa·s or less, more preferably 5 Pa·s or less, and even more preferably 2 Pa·s or less. However, the selection of the polymerizable monomer must take into account not only viscosity but also mechanical strength and refractive index. Alternatively, the polymerizable monomer-containing composition may be diluted with a solvent and then the solvent removed by subsequent vacuum distillation. In addition, by raising the temperature to a range of preferably 25°C or higher, more preferably 30°C or higher, and preferably 70°C or lower, more preferably 60°C or lower, the viscosity of the polymerizable monomer-containing composition can be reduced, thereby accelerating penetration.

[0166] The time for which the polymerizable monomer-containing composition is brought into contact with the inorganic filler molded product is not necessarily determined, but can be adjusted appropriately depending on the type of inorganic filler (C-1), the size of the molded product, the degree of penetration of the monomer, the contacting method, etc. For example, when the contact is made by immersion, the time is usually 1 to 120 hours, when the contact is made by immersion under reduced pressure, the time is usually 0.5 to 12 hours, and when the contact is made under pressure, the time is usually 0.2 to 6 hours.

[0167] Next, in a state where the polymerizable monomer has penetrated into the molded article, the polymerizable monomer is polymerized and cured. Polymerization and curing can be carried out by thermal polymerization and / or photopolymerization and / or chemical polymerization under conditions according to known methods.

[0168] Furthermore, by heat treating the hardened material after polymerization at preferably 80 to 150°C for 10 to 120 minutes, stress strain generated inside the hardened material can be alleviated, and damage to the dental prosthesis that occurs during cutting or clinical use can be suppressed.

[0169] In addition, another preferred embodiment includes a polymerizable monomer (A) and a polymerization initiator (B), the polymerizable monomer (A) comprises a radical polymerizable monomer (A-1) having a urethane bond and substantially not containing an organotin, and a radical polymerizable monomer (A-3) having no acidic group; The dental curable composition may be one in which the polymerization initiator (B) contains a photopolymerization initiator (B-1) and is used for stereolithography for intraoral applications.

[0170] In the above embodiment, the radical polymerizable monomer (A-3) having no acidic group preferably includes a monofunctional hydrophobic polymerizable monomer, and more preferably includes a monofunctional (meth)acrylate polymerizable monomer having an aromatic ring group.

[0171] By using the dental curable composition for producing a three-dimensional object for intraoral use, it is possible to produce a three-dimensional object having excellent toughness, water resistance, and mechanical strength as a cured product.

[0172] <Fluoride ion-releasing substances> The dental hardenable composition may further contain a fluoride ion-releasing substance. By containing the fluoride ion-releasing substance, a dental hardenable composition capable of imparting acid resistance to tooth structure can be obtained. Examples of fluoride ion-releasing substances include fluoride ion-releasing polymers such as copolymers of methyl methacrylate and methacrylic acid fluoride; and metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride. The above fluoride ion releasing substances may be used alone or in combination of two or more.

[0173] The dental curable composition may contain known additives within the range that does not impair performance. Examples of such additives include polymerization inhibitors, antioxidants, colorants (pigments, dyes), ultraviolet absorbers, fluorescent agents, solvents such as organic solvents, thickeners, etc. One type of additive may be used alone, or two or more types may be used in combination. In one embodiment, the content of a solvent (e.g., water, organic solvent) in the dental hardenable composition is preferably less than 1 mass %, more preferably less than 0.1 mass %, and even more preferably less than 0.01 mass %, relative to the total amount (100 mass %) of the dental hardenable composition.

[0174] The dental hardenable composition of the present invention preferably contains a polymerization inhibitor from the viewpoints of storage stability and adjustment of hardenability. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, 3,5-di-t-butyl-4-hydroxytoluene, etc. These may be used alone or in combination of two or more. The content of the polymerization inhibitor is preferably 0.001 to 1.0 part by mass relative to 100 parts by mass of the polymerizable monomer (A).

[0175] The dental curable composition of the present invention may contain an ultraviolet absorber from the viewpoint of photostability against ambient light such as fluorescent lamps and LEDs, and from the viewpoint of suppressing discoloration of the cured product.

[0176] The dental curable composition of the present invention preferably contains a fluorescent agent from the viewpoint of aesthetics, in order to reproduce a color tone similar to that of tooth tissue. As the fluorescent agent, any known fluorescent agent can be used without any limitation, but a phthalate ester-based fluorescent agent is preferred.

[0177] Specific examples of phthalate ester-based fluorescent agents include dimethyl 2,5-dihydroxyterephthalate, diethyl 2,5-dihydroxyterephthalate, dimethylaminoterephthalate, and diethylaminoterephthalate, and phthalate ester-based fluorescent agents substituted with a hydroxyl group, such as diethyl 2,5-dihydroxyterephthalate, are more preferred. The fluorescent agent may be used alone or in combination of two or more kinds.

[0178] The content of the fluorescent agent is not particularly limited, but a certain amount is necessary to ensure fluorescence, and conversely, if the content is too high, it tends to be difficult to ensure photostability. To achieve a good balance between photostability and fluorescence, the content of the fluorescent agent is preferably 0.005 to 0.5 parts by mass, and more preferably 0.01 to 0.1 parts by mass, relative to 100 parts by mass of the polymerizable monomer (A).

[0179] The dental curable composition of the present invention preferably contains a colorant to reproduce a color tone similar to that of tooth structure. The type of the colorant is not particularly limited, and any inorganic pigment and / or organic pigment can be used without limitation depending on the color tone of the dental curable composition and its cured product. The colorant may be used alone or in combination of two or more types.

[0180] The colorant is a component added in a small amount to the dental hardenable composition, and the content of one type of colorant is less than 1.0 mass % relative to the total amount (100 mass %) of the dental hardenable composition.

[0181] The colorant used may have a refractive index of more than 2.00. The refractive index of the colorant may be 2.05 or more, or 2.10 or more.

[0182] The shape of the colorant is not particularly limited, and any particle shape such as spherical, needle-like, plate-like, crushed, or scaly may be used without any restrictions, and either inorganic or organic pigments may be used without any restrictions.

[0183] Among these colorants, inorganic pigments such as titanium white, red iron oxide, iron black, and yellow iron oxide are more preferred because they are superior in heat resistance and light resistance to organic pigments.

[0184] The method for producing the dental curable composition of the present invention is not particularly limited, and the composition can be produced by mixing the above-mentioned components by a known method.

[0185] The present invention includes embodiments in which all or part of the above-described configurations are combined in various ways within the scope of the technical concept of the present invention, as long as the effects of the present invention are achieved. [Example]

[0186] Next, the present invention will be explained in more detail by way of examples, but the present invention is not limited to these examples in any way, and many modifications within the technical scope of the present invention are possible by those skilled in the art.

[0187] The abbreviations for the components of the dental hardenable composition in Table 1 are listed below.

[0188] [Polymerizable monomer (A)] [Radically polymerizable monomer (A-1) having a urethane bond and substantially free of organotin] UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate [Radical polymerizable monomer (A-2) having an acidic group] MDP: 10-methacryloyloxydecyl dihydrogen phosphate [Radical polymerizable monomer (A-3) having no acidic group] [Hydrophilic polymerizable monomer (A-3-a)] DEAA: N,N-diethylacrylamide HEMA: 2-hydroxyethyl methacrylate [Hydrophobic polymerizable monomer (A-3-b)] EDMA: Erythritol dimethacrylate [1,4-bis(methacryloyloxy)-2,3-butanediol] MAEA: N-methacryloyloxyethyl acrylamide Bis-GMA: 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane NPG: Neopentyl glycol dimethacrylate

[0189] [Photopolymerization initiator (B-1)] BAPO: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide CQ: Camphorquinone

[0190] Filler R972: AEROSIL (registered trademark) R972, a fine particle silica manufactured by Nippon Aerosil Co., Ltd. Ar380: Nippon Aerosil Co., Ltd., fine particle silica "Aerosil (registered trademark) 380", average particle size: 7 nm [Polymerization inhibitor] BHT: 3,5-di-t-butyl-4-hydroxytoluene MEHQ: p-hydroquinone monomethyl ether [Tertiary amine] PDE: ethyl 4-(N,N-dimethylamino)benzoate TEA: Triethanolamine DEPT: p-Tolyldiethanolamine [UV absorber] TN326: Tinuvin 326 (manufactured by Chiba Specialty Chemicals Co., Ltd.)

[0191] [Production Example 1: Production of radical polymerizable monomer (A-1)] The UDMA in the examples herein was prepared in the following manner. A four-neck flask equipped with a thermometer, reflux condenser, and stirrer was charged with 54.0 g of 2-hydroxyethyl methacrylate (HEMA) and 41.5 g of 2,2,4-trimethylhexamethylene diisocyanate (TMHDI), and 0.01 g of a bismuth(III) 2-ethylhexanoate solution was added. The mixture was gradually heated to 60°C with stirring, and the reaction was carried out for 4 hours while maintaining the internal temperature at 60°C. Analysis by infrared absorption (IR) spectroscopy revealed the absorption (2270 cm) characteristic of the isocyanate group derived from TMHDI. -1 The disappearance of the radical polymerizable monomer (A-1) was confirmed, and UDMA was obtained.

[0192] [Examples 1-1 to 1-13] The components listed in Table 1 below except for the filler (C) were mixed, and then the filler (C) was mixed to produce a dental curable composition intended for use as a dental bonding material.

[0193] [Table 1]

[0194] The abbreviations for the components of the dental hardenable compositions in Table 2 are listed below. [Polymerizable monomer (A)] [Radically polymerizable monomer (A-1) having a urethane bond and substantially free of organotin] UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate [Radical polymerizable monomer (A-2) having an acidic group] MDP: 10-methacryloyloxydecyl dihydrogen phosphate [Radical polymerizable monomer (A-3) having no acidic group] [Hydrophilic polymerizable monomer (A-3-a)] HEMA: 2-hydroxyethyl methacrylate [Hydrophobic polymerizable monomer (A-3-b)] #801: 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane

[0195] [Fourth Period Transition Metal Compounds (E)] VOAA: Vanadyl acetylacetonate(IV) [Silane coupling agent (F)] 3-MPS: 3-methacryloyloxypropyltrimethoxysilane [Polymerization inhibitor] BHT: 3,5-di-t-butyl-4-hydroxytoluene

[0196] [Examples 2-1 to 2-4] The components shown in Table 2 below were mixed to produce dental curable compositions intended for use as dental primers.

[0197] [Table 2]

[0198] The abbreviations for the components of the dental hardenable compositions in Table 3 are listed below. [Polymerizable monomer (A)] [Radically polymerizable monomer (A-1) having a urethane bond and substantially free of organotin] UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate [Radical polymerizable monomer (A-2) having an acidic group] MDP: 10-methacryloyloxydecyl dihydrogen phosphate [Radical polymerizable monomer (A-3) having no acidic group] [Hydrophobic polymerizable monomer (A-3-b)] MAEA: N-methacryloyloxyethyl acrylamide Bis-GMA: 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane D2.6E: 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethoxy groups added: 2.6) 1-NMMA: 1-naphthylmethyl methacrylate DD: 1,10-decanediol dimethacrylate POB-MA: m-phenoxybenzyl methacrylate

[0199] [Photopolymerization initiator (B-1)] BAPO-ONa: sodium bis(2,4,6-trimethylbenzoyl)phenylphosphinate TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide CQ: Camphorquinone

[0200] Filler Surface treatment Ar130: 100 g of Ar130 (Nihon Aerosil Co., Ltd., hydrophilic fumed silica, ultrafine silica "Aerosil (registered trademark) 130", average particle size: 16 nm, refractive index: 1.46), 30 g of 3-methacryloyloxypropyltrimethoxysilane, and 200 mL of 0.3% by mass acetic acid aqueous solution were placed in a three-necked flask and stirred for 2 hours under ultrasonic dispersion at room temperature. After removing water by freeze-drying, the mixture was heated at 90°C for 3 hours to obtain "surface-treated Ar130." Surface-treated ytterbium fluoride: Surface-treated silica-coated ytterbium fluoride (SG-YBF100WSCMP10, average particle size of primary particles: 110 nm, average particle size of secondary particles: 1.2 μm, refractive index: 1.53, manufactured by Sukgyung AT) Surface treatment quartz powder: Silica powder (manufactured by Nichitsu Corporation, product name: Hi-Silica, refractive index: 1.55) was ground in a dry ball mill (Φ10 mm alumina balls) to obtain ground silica powder. The average particle size of the resulting ground silica powder was measured on a volume basis using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model "SALD-2300") and found to be 2.2 μm. 100 g of this ground silica powder, 4 g of γ-methacryloyloxypropyltrimethoxysilane, and 200 mL of aqueous acetic acid solution were placed in a three-neck flask and stirred for 2 hours under ultrasonic dispersion at room temperature. Water was removed by freeze-drying, and then the mixture was heated at 90°C for 3 hours to obtain "surface-treated quartz powder." Surface treatment barium glass 1: A dispersion was obtained by adding 80 parts by weight of distilled water to 100 parts by weight of GM27884 UF2.0 grade (barium glass manufactured by SCHOTT, average particle size: 2.0 μm) and mixing at room temperature (approximately 25°C). 3.0 parts by weight of 3-methacryloyloxytrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-503") and 200 parts by weight of 0.3% by weight aqueous acetic acid solution were added to this dispersion in a three-necked flask and stirred at room temperature for 1 hour. After removing water by freeze-drying, the mixture was heat-treated at 90°C for 3 hours to obtain "Surface-treated barium glass 1." Surface treated SiO2-ZrO2 agglomerate filler: Commercially available surface-treated SiO2-ZrO2 agglomerated filler (SG-SZ200G151CMP8, average particle size of primary particles: 200 nm, average particle size of secondary particles: 5.2 μm, refractive index: 1.51, manufactured by Sukgyung AT Co., Ltd.) Light-diffusing organic-inorganic composite filler 1: 70 parts by weight of Bis-GMA, 30 parts by weight of TEGDMA, and 0.5 parts by weight of benzoyl peroxide were mixed and uniformly dissolved to obtain a polymerizable monomer-containing composition. Meanwhile, colloidal silica powder (Aerosil® OX50, manufactured by Nippon Aerosil Co., Ltd.) with an average particle size of 0.04 μm was surface-treated with 3-methacryloyloxypropyltrimethoxysilane by standard methods. 100 parts by weight of the surface-treated colloidal silica and 100 parts by weight of the polymerizable monomer were kneaded to obtain a paste-like composition. The composition was heated under reduced pressure at 130°C for 3 hours to polymerize, and the resulting cured product was further pulverized in a ball mill to obtain a surface-untreated organic-inorganic composite filler. Furthermore, 100 parts by weight of the surface-untreated organic-inorganic composite filler was surface-treated with 1 part by weight of 3-methacryloyloxypropyltrimethoxysilane to obtain "light-diffusing organic-inorganic composite filler 1." The light-diffusing organic-inorganic composite filler 1 had an average particle size of 11 μm and a refractive index of 1.50. Light-diffusing organic-inorganic composite filler 2: 70 parts by weight of UDMA, 30 parts by weight of DD, and 0.5 parts by weight of benzoyl peroxide were mixed and uniformly dissolved to obtain a polymerizable monomer-containing composition. Meanwhile, colloidal silica powder (Aerosil® OX50, manufactured by Nippon Aerosil Co., Ltd.) with an average particle size of 0.04 μm was surface-treated with 3-methacryloyloxypropyltrimethoxysilane using standard methods. 100 parts by weight of the surface-treated colloidal silica and 100 parts by weight of the polymerizable monomer were kneaded to obtain a paste-like composition. The composition was heated under reduced pressure at 130°C for 3 hours to polymerize, and the resulting cured product was further pulverized in a ball mill to obtain a surface-untreated organic-inorganic composite filler. Furthermore, 100 parts by weight of the surface-untreated organic-inorganic composite filler was surface-treated with 1 part by weight of 3-methacryloyloxypropyltrimethoxysilane to obtain "light-diffusing organic-inorganic composite filler 2." The light-diffusing organic-inorganic composite filler 2 had an average particle size of 15 μm and a refractive index of 1.49. Titanium oxide: (Wako Pure Chemical Industries, Ltd., Japanese Pharmacopoeia "Titanium oxide" (TiO2)), average particle size: 0.5 μm Surface treatment of lantern glass powder: Lanthanum glass ceramics (GM31684 SM3.5, average particle size: 3.5 μm, refractive index: 1.58, specific surface area: 2.5 m) manufactured by Schott 2 550 g of (aluminum oxide C, average particle size 13 nm, refractive index 1.65, specific surface area 100 m) was added to a 3.6 L alumina grinding pot containing 350 φ20 mm alumina balls, and the mixture was ground for 12 hours in a vibration grinder (MEIDEN, manufactured by Chuo Kakoki Co., Ltd.) at an amplitude of 8 mm and a vibration frequency of 1120 rpm to obtain a dental inorganic filler. 2 16.5 g of 3-methacryloyloxypropyltrimethoxysilane (KBM-503) was added to 100 parts by mass of this mixed powder in accordance with a conventional method, to obtain a surface-treated lanthanum glass powder (average particle size: 1.73 μm). AluC: Aluminum oxide manufactured by Nippon Aerosil Co., Ltd., trade name "AEROXIDE (registered trademark) Alu C", average particle size: 13 nm

[0201] [Polymerization inhibitor] BHT: 3,5-di-t-butyl-4-hydroxytoluene

[0202] [Tertiary amine] PDE: ethyl 4-(N,N-dimethylamino)benzoate Kurzeramine: 2-n-butoxyethyl 4-(N,N-dimethylamino)benzoate DMAEMA: N,N-dimethylaminoethyl methacrylate

[0203] [UV absorber] TN326: Tinuvin 326 (manufactured by Chiba Specialty Chemicals Co., Ltd.)

[0204] [Examples 3-1 to 3-21] The components listed in Table 3 below except for the filler (C) were mixed, and then the filler (C) was mixed to prepare the target dental curable composition.

[0205] [Table 3]

[0206] The abbreviations for the components of the dental hardenable compositions in Table 4 are listed below. [Polymerizable monomer (A)] [Radically polymerizable monomer (A-1) having a urethane bond and substantially free of organotin] UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate [Radical polymerizable monomer (A-2) having an acidic group] MDP: 10-methacryloyloxydecyl dihydrogen phosphate [Radical polymerizable monomer (A-3) having no acidic group] [Hydrophilic polymerizable monomer (A-3-a)] HEMA: 2-hydroxyethyl methacrylate [Hydrophobic polymerizable monomer (A-3-b)] Bis-GMA: 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane D2.6E: 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethoxy groups added: 2.6) POB-MA: m-phenoxybenzyl methacrylate NPG: Neopentyl glycol dimethacrylate TEGDMA: Triethylene glycol dimethacrylate #801: 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane

[0207] [Photopolymerization initiator (B-1)] CQ: Camphorquinone [Organic peroxide (B-2)] BPO: Benzoyl peroxide BPB: t-butyl peroxybenzoate THP: 1,1,3,3-tetramethylbutyl hydroperoxide

[0208] [Fourth Period Transition Metal Compounds (E)] VOAA: Vanadyl acetylacetonate(IV) CA: Copper(II) acetate [Silane coupling agent (F)] 11-MPS: 11-methacryloyloxyundecyltrimethoxysilane

[0209] Filler Surface-treated barium glass 2: Barium glass (manufactured by Estec Co., Ltd., product code "E-3000") was pulverized in a ball mill to obtain barium glass powder. The average particle size of the obtained barium glass powder was measured on a volume basis using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model "SALD-2300") and found to be 2.4 μm. 100 parts by mass of this barium glass powder was surface-treated with 3 parts by mass of 3-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain "surface-treated barium glass 2," a silane-treated barium glass powder. Ar380: Nippon Aerosil Co., Ltd., fine particle silica "Aerosil (registered trademark) 380", average particle size: 7 nm AluC: Aluminum oxide manufactured by Nippon Aerosil Co., Ltd., trade name "AEROXIDE (registered trademark) Alu C", average particle size: 13 nm FAS: The raw materials for each component, such as oxides, fluorides, carbonates, nitrates, and hydroxides, were prepared and weighed to yield a vitrified composition of 11.2% by mass of Si, 6% by mass of Al, 22.7% by mass of Sr, 7% by mass of Zn, 4.8% by mass of B, 23.7% by mass of F, and 24.6% by mass of O. The materials were thoroughly mixed and placed in a platinum crucible and melted in an electric furnace. The melting temperature was adjusted appropriately within the range of 1000–1500°C to ensure sufficient degassing. The mixture was then stirred appropriately to homogenize, clarified, and rapidly cooled to obtain glass "FAS." YBF: Silane-treated silica coated ytterbium fluoride Surface-treated silica coated ytterbium fluoride (SG-YBF100WSCMP10, average particle size of primary particles: 110 nm, average particle size of secondary particles: 1.2 μm, refractive index: 1.53, manufactured by Sukgyung AT) Spherical silica: YC100C-SM1: spherical fine particle silica (manufactured by Admatechs Co., Ltd., Admanano YC100C-SM1, average particle size 0.1 μm, amorphous, refractive index 1.460) R972: AEROSIL® R972 fine particle silica, manufactured by Nippon Aerosil Co., Ltd. Surface-treated barium glass 3: 3-methacryloyloxypropyltrimethoxysilane-treated barium glass "SCHOTT (registered trademark) 8235 UF2.0" (manufactured by SCHOTT, average primary particle size: 2.0 μm) Surface treatment barium glass 1: A dispersion was obtained by adding 80 parts by weight of distilled water to 100 parts by weight of GM27884 UF2.0 grade (barium glass manufactured by SCHOTT, average particle size: 2.0 μm) and mixing at room temperature (approximately 25°C). 3.0 parts by weight of 3-methacryloyloxytrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-503") and 200 parts by weight of 0.3% by weight aqueous acetic acid solution were added to this dispersion in a three-necked flask and stirred at room temperature for 1 hour. After removing water by freeze-drying, the mixture was heat-treated at 90°C for 3 hours to obtain "Surface-treated barium glass 1."

[0210] [Aromatic sulfinic acid compounds (G)] TPSS: 2,4,6-triisopropylbenzenesulfinic acid [Thiourea compounds] PTU: 1-(2-pyridyl)-2-thiourea [Cyclic thiourea compounds (H)] DMETU: 4,4-dimethyl-2-imidazolidinethiol [Polymerization inhibitor] BHT: 3,5-di-t-butyl-4-hydroxytoluene

[0211] [Tertiary amine] PDE: ethyl 4-(N,N-dimethylamino)benzoate TEA: Triethanolamine DEPT: p-Tolyldiethanolamine [Benzotriazole compounds] BTA: 1H-benzotriazole [Sulfur-containing reducing inorganic compounds] NAA: sodium sulfite KPS: potassium peroxodisulfate [UV absorber] TN326: Tinuvin 326 (manufactured by Chiba Specialty Chemicals Co., Ltd.)

[0212] [Examples 4-1 to 4-13] The components listed in Table 4 below were mixed in the first part (referred to as "A" in Table 4) and the second part (referred to as "B" in Table 4) to produce the desired dental hardenable composition.

[0213] [Table 4]

[0214] The abbreviations for the components of the dental hardenable compositions in Table 5 are listed below. [Polymerizable monomer (A)] [Radically polymerizable monomer (A-1) having a urethane bond and substantially free of organotin] UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate [Radical polymerizable monomer (A-3) having no acidic group] [Hydrophobic polymerizable monomer (A-3-b)] Bis-GMA: 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane TEGDMA: Triethylene glycol dimethacrylate NPG: Neopentyl glycol dimethacrylate [Organic peroxide (B-2)] BPO: Benzoyl peroxide THP: 1,1,3,3-tetramethylbutyl hydroperoxide

[0215] Filler Block Filler 1: 100 g of commercially available barium boroaluminosilicate glass powder (manufactured by SCHOTT, 8235, average particle size: 1.5 μm, particle size range: 0.1 to 5.0 μm) and 100 g of commercially available ultrafine silica particles (manufactured by Nippon Aerosil Co., Ltd., Aerosil (registered trademark) OX50, average primary particle size: 0.04 μm, BET specific surface area: 50 m 220 g of / g) was dispersed together in 300 mL of toluene, and 4 g of 3-methacryloyloxypropyltrimethoxysilane was added thereto, followed by heating under reflux for 2 hours. Toluene was distilled off under reduced pressure using an evaporator, and the obtained powder was pulverized to obtain a hybrid-type surface-treated powder in which barium borosilicate glass powder and ultrafine silica powder were uniformly mixed. This was designated as "Filler 1 for blocks". Filler 2 for blocks: 100 parts by mass of a mixture of 80 parts by mass of UF0.4 (barium glass; average primary particle diameter: 0.4 μm, manufactured by Shot Co., Ltd.) and 20 parts by mass of Ox-50 was dispersed in 300 parts by mass of ethanol, and ultrasonic dispersion was carried out for 60 minutes under the conditions of an output of 720 W and a frequency of 40 kHz using an ultrasonic oscillator. 11 parts by mass of 3-MPS (3-methacryloyloxypropyltrimethoxysilane), 0.15 parts by mass of acetic acid, and 5 parts by mass of water were added thereto, and stirring was carried out at room temperature for 2 hours. The solvent was distilled off under reduced pressure, and further drying was carried out at 90 °C for 3 hours to obtain "Filler 2 for blocks" surface-treated with a surface treatment agent.

[0216] [Examples 5-1 to 5-6] Regarding the components described in Table 5 below, the components other than filler (C) were mixed, and then filler (C) was mixed to produce the target dental curable composition.

[0217]

Table 5

[0218] The abbreviations of the components of the dental curable composition in Table 6 are described below. [Polymerizable monomer (A)] [Radical polymerizable monomer (A-1) having a urethane bond substantially free of organic tin] UDMA: 2,2,4-trimethylhexamethylene bis(2-carbamoyloxyethyl) dimethacrylate [Radical polymerizable monomer (A-3) having no acidic group] [Hydrophilic polymerizable monomer (A-3-a)] ACMO: N-acryloylmorpholine [Hydrophobic polymerizable monomer (A-3-b)] 7PG: heptapropylene glycol dimethacrylate (NOF Corporation, "Blenmer (registered trademark)" PDP-400N)

[0219] [Photopolymerization initiator (B-1)] BAPO: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide [Polymerization inhibitor] BHT: 3,5-di-t-butyl-4-hydroxytoluene [UV absorber] 9,10-Dibutoxyanthracene

[0220] [Examples 6-1 to 6-2] The components shown in Table 6 below were mixed together to produce the desired dental hardenable compositions.

[0221] [Table 6] [Industrial Applicability]

[0222] The dental curable composition of the present invention does not use an organotin catalyst and contains a radically polymerizable monomer having a urethane bond that is substantially free of organotin, and therefore has excellent biological safety.

Claims

1. Contains a polymerizable monomer (A), The dental curable composition, wherein the polymerizable monomer (A) comprises a radical polymerizable monomer (A-1) having a urethane bond and substantially not containing an organotin.

2. The dental curable composition, wherein the radical polymerizable monomer (A-1) having a urethane bond is a compound represented by the following general formula [a]: X 1 -Y 1 -Z-Y 2 -Z-Y 3 -X 2 [a] (In the formula, X 1 and X 2 are the same or different and each represents a (meth)acryloyloxy group; Z represents a carbamoyloxy group; Y 2 represents a linear, branched, or cyclic divalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; Y 1 and Y 3 are the same or different and each represents a divalent hydrocarbon group having 1 to 12 carbon atoms which may have a linear, branched, or cyclic substituent.

3. 2. The dental curable composition according to claim 1, wherein the radical polymerizable monomer (A-1) having a urethane bond is a compound represented by the following formula [a-1]: 【Chemistry 1】

4. 4. The dental curable composition according to claim 3, wherein the polymerizable monomer (A) further comprises a radical polymerizable monomer (A-2) having an acidic group.

5. 5. The dental hardenable composition according to claim 4, wherein the radical polymerizable monomer (A-2) having an acidic group is 10-(meth)acryloyloxydecyl dihydrogen phosphate.

6. 6. The dental curable composition according to claim 5, wherein the polymerizable monomer (A) further comprises a radical polymerizable monomer (A-3) having no acidic group.

7. 3. The dental curable composition according to claim 1, further comprising a polymerization initiator (B), wherein the polymerization initiator (B) comprises a photopolymerization initiator (B-1), and wherein the dental curable composition is for use in a dental bonding material.

8. 3. The dental curable composition according to claim 1, further comprising a solvent (D), a fourth period transition metal compound (E), and optionally a silane coupling agent (F), and is used as a dental primer.

9. Further comprising a polymerization initiator (B) and a filler (C), 3. The dental curable composition according to claim 1, wherein a content of the polymerization initiator (B) is 0.1 to 10 parts by mass and a content of the filler (C) is 80 to 900 parts by mass, relative to 100 parts by mass of the polymerizable monomers (A) in total.

10. A dental composite resin comprising the dental hardenable composition according to claim 9.

11. A dental cement comprising the dental hardenable composition according to claim 9.

12. A dental hardenable composition in a divided package type, comprising a first agent and a second agent, At least one of the first agent and the second agent contains a radically polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin and a filler (C), the first agent contains a radical polymerizable monomer (A-2) having an acidic group, an organic peroxide (B-2), and a fourth period transition metal compound (E), A dental hardenable composition, wherein the second agent comprises an aromatic sulfinic acid compound (G).

13. The composition comprises a radical polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin, an organic peroxide (B-2), a filler (C), a fourth period transition metal compound (E), and a cyclic thiourea compound (H), The dental hardenable composition, wherein the cyclic thiourea compound (H) is at least one selected from the group consisting of substituted ethylene thiourea compounds and substituted propylene thiourea compounds.

14. A dental core build-up material comprising the dental hardenable composition according to claim 9.

15. A dental mill blank comprising the dental hardenable composition of claim 9.

16. The method includes a step of contacting an inorganic filler molded body obtained by press-molding an inorganic filler (C-1) with a polymerizable monomer-containing composition, The method for producing a dental mill blank, wherein the polymerizable monomer-containing composition contains a radically polymerizable monomer (A-1) having a urethane bond that is substantially free of organotin.

17. containing a polymerizable monomer (A) and a polymerization initiator (B), the polymerizable monomer (A) comprises a radical polymerizable monomer (A-1) having a urethane bond and substantially not containing an organotin, and a radical polymerizable monomer (A-3) having no acidic group, the polymerization initiator (B) contains a photopolymerization initiator (B-1), A dental hardenable composition for photolithography for intraoral applications.

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