Dental hardening composition

Abstract

To provide a dental curable composition which has an operation time within a reasonable range and is excellent in the adhesion to dentin and the mechanical strength of a cured material.SOLUTION: A dental curable composition contains a polymerizable monomer (A) having an acidic group, a polymerizable monomer (B) having no acidic group, a hydroperoxide (C), and a thiourea compound (D) represented by general formula (1). (In the formula, A1 and / or A5 are any of a hydroxy group, an alkoxy group, an amino group and a dialkylamino group; and A2 to A4 are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an amino group, a dialkylamino group, a hydrocarbon group, a carboxy group, or a halogen atom.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a dental hardenable composition used in dental treatment for bonding dental prostheses such as crowns, inlays, and bridges to tooth structures, and for core construction, etc. More specifically, the present invention relates to a dental hardenable composition that requires an appropriate working time and has excellent adhesion to tooth structures and mechanical strength of the cured product. [Background technology]

[0002] Adhesive materials and filling and restorative materials are widely used for restoring missing parts of teeth damaged by caries, fractures, etc. Resin-based dental curable compositions comprising polymerizable monomers, polymerization initiators, fillers, etc. are widely used as adhesive materials and filling and restorative materials used for tooth restoration.

[0003] Among resin-based dental hardenable compositions, materials used to bond dental prostheses to tooth structure are called dental resin cements. Furthermore, in restorative treatment for deep caries that reach the dental pulp, it is necessary to remove the pulp and construct an abutment tooth. The materials used for this are called dental core construction composite resins. Dental resin cements and dental core construction composite resins are both paste-like compositions, generally produced by mixing a liquid polymerizable monomer-containing composition in which a polymerizable monomer, a polymerization initiator system, a stabilizer, etc. are dissolved with a powdered filler, etc., and are provided to dentists in a container. Dental hardenable compositions are required to maintain a certain level of performance within their expiration date.

[0004] (Meth)acrylates are commonly used as polymerizable monomers in dental resin cements or composite resins for dental core construction. Furthermore, to impart adhesive properties to tooth structures or prostheses, dental resin cements contain polymerizable monomers with acidic groups such as phosphate groups or carboxyl groups. Dental resin cements that contain polymerizable monomers with acidic groups and have adhesive properties are called self-adhesive dental resin cements.

[0005] To polymerize and harden these dental hardenable compositions, a redox-type polymerization initiator system consisting of an oxidizing agent, a reducing agent, etc. may be used. In this case, the oxidizing agent and the reducing agent of the polymerization initiator system are packaged, for example, as a first agent containing an oxidizing agent and a second agent containing a reducing agent, and the dental hardenable composition is provided to the user, i.e., a dentist, in the form of a packaged dental hardenable composition. Just before using the packaged dental hardenable composition, the dentist mixes the first agent containing the oxidizing agent and the second agent containing the reducing agent, generating radicals through a redox reaction and causing the polymerization and hardening of the dental hardenable composition to proceed.

[0006] Conventionally, redox-type polymerization initiator systems used in dental curable compositions have generally been polymerization initiator systems consisting of benzoyl peroxide and an aromatic amine compound. However, the use of this initiator system has presented the problem of poor storage stability of the composition due to the low thermal stability of benzoyl peroxide. Specifically, when a composition containing benzoyl peroxide is stored for a long period of time in a temperature environment above room temperature, problems such as a decrease in curability due to decomposition of benzoyl peroxide and solidification of the composition before use can occur. Therefore, when providing a composition containing benzoyl peroxide to users such as dentists, measures such as specifying a storage temperature below room temperature or setting a short expiration date are necessary, and there is room for improvement in terms of usability and quality stability.

[0007] Therefore, in recent years, chemical polymerization initiator systems containing more stable organic peroxides have been used as chemical polymerization initiators instead of benzoyl peroxide. Specifically, dental curable compositions containing redox polymerization initiators that combine highly stable peroxides with thiourea derivatives have been used. These chemical polymerization initiator systems have high thermal stability, and dental curable compositions containing them have high storage stability at room temperature. However, they suffer from the problem of low curability. To solve this problem, polymerization initiator systems have been developed that incorporate transition metal compounds into the chemical polymerization initiator systems.

[0008] Patent Document 1 discloses a chemical polymerization initiator system containing a hydroperoxide, a thiourea derivative, and a copper compound as a transition metal compound. It is stated that this chemical polymerization initiator system achieves high storage stability and curability. Patent Document 2 discloses a chemical polymerization initiator system containing t-butyl hydroperoxide, a thiourea derivative, and a vanadium compound as a transition metal compound. It is stated that this chemical polymerization initiator system further improves storage stability.

[0009] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-056020 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-144054 Summary of the Invention [Problem to be solved by the invention]

[0010] As a result of investigations by the present inventors, it was found that some of the dental hardenable compositions disclosed in Patent Documents 1 and 2 are indeed superior in storage stability and hardening properties compared to conventional techniques, but when the content of the chemical polymerization initiator system described in these patent documents is adjusted to provide an appropriate operation time, there is still room for improvement in adhesion to tooth structure and mechanical strength.

[0011] Therefore, an object of the present invention is to provide a dental curable composition which has an appropriate working time, excellent adhesion to tooth structure, and excellent mechanical strength of the cured product. [Means for solving the problem]

[0012] The present inventors have conducted extensive research into dental curable compositions that have an appropriate working time, excellent adhesion to tooth structure, and excellent mechanical strength of the cured product. As a result, they have found that the above-mentioned problems can be solved by using a thiourea compound with a specific structure, and have completed the present invention after further research.

[0013] That is, the present invention includes the following inventions. [1] A dental curable composition comprising a polymerizable monomer (A) having an acidic group, a polymerizable monomer (B) not having an acidic group, a hydroperoxide (C), and a thiourea compound (D) represented by the following general formula (1): [ka] (In the formula, A1 and / or A5 are either a hydroxy group, an alkoxy group, an amino group, or a dialkylamino group, and A2 to A4 are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an amino group, a dialkylamino group, a hydrocarbon group, a carboxy group, or a halogen atom.) be.) [2] The dental curable composition according to [1], wherein A1 and / or A5 is a hydroxy group, an amino group, or a dialkylamino group, and A2 to A4 are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an amino group, a dialkylamino group, a hydrocarbon group, a carboxy group, or a halogen atom. [3] The dental curable composition according to [1], wherein A1 and / or A5 is a hydroxy group, and A2 to A4 are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an amino group, a dialkylamino group, a hydrocarbon group, or a halogen atom. [4] The dental hardenable composition according to any one of [1] to [3], wherein the thiourea compound (D) is in a powder form and is dispersed in the dental hardenable composition. [5] The dental curable composition according to any one of [1] to [4], further comprising a transition metal compound (E). [6] The dental hardenable composition according to [5], wherein the transition metal compound (E) is a copper compound or a vanadium compound. [7] Further containing a ligand compound (F), The dental curable composition according to any one of [1] to [6], wherein the ligand compound (F) is at least one compound selected from the group consisting of a ligand containing a phosphorus atom and a ligand containing a nitrogen atom. [8] The ligand compound (F) is a ligand containing a phosphorus atom, The dental curable composition according to [7], wherein the phosphorus atom-containing ligand is at least one compound selected from the group consisting of a compound represented by general formula (2), a compound represented by general formula (3), a compound represented by general formula (4), and a compound represented by the following general formula (5): [ka] (R1~R 15 each independently has a hydrogen atom, a halogen atom, a polar group, or a substituent represents an alkyl group which may have a substituent, or an alkoxy group which may have a substituent. [ka] (R 16 ~R 35 each independently has a hydrogen atom, a halogen atom, a polar group, or a substituent. represents an optionally substituted alkyl group or an optionally substituted alkoxy group, and X1 represents a substituent represents a divalent aliphatic group which may have the following structure: [ka] (Each Ar independently represents a group represented by the following general formula (4-a).) [ka] (Z1 to Z3 each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and at least one of Z1 to Z3 is a hydrogen atom.) P(OY1)3(5) (Y1's each independently represent an alkyl group which may have a substituent, or a represents an aryl group which may be [9] The ligand compound (F) is a ligand containing a nitrogen atom, the nitrogen atom-containing ligand is at least one compound selected from the group consisting of a compound represented by general formula (6), a compound represented by general formula (7), and a multidentate ligand containing a nitrogen-containing heterocycle (8), The dental curable composition according to [7], wherein the polydentate ligand (8) is a bidentate or higher ligand compound containing a heterocycle including a 5- or 6-membered ring containing a nitrogen atom, having two or more nitrogen atoms in the molecule. R 36 R 37 N-X2-NR 38 R 39 (6) (R 36 ~R 39 each independently represents an alkyl group which may have a substituent, and X2 represents a divalent aliphatic group which may have a substituent. [ka] (R 40 , R 41 , and R 42 each independently represent an alkyl group which may have a substituent; X3 and X4 each independently represent a divalent aliphatic group which may have a substituent and which may contain an oxygen atom and / or a nitrogen atom; m and n each independently represent an integer of 1 or more; Y2 is a monoalkylamino group or a dialkylamino group which may have a substituent; represents an amino group, and R 40 , R 41 , R 42 Any two or more of Y and Y2 together form a ring. R 41 , R 42 When a plurality of X, X3, and X4 are present, they may be the same or different.)

[10] The dental curable composition according to any one of [1] to [9], further comprising a filler (G).

[11] A two-paste type with a first agent and a second agent, [1] to

[10] The dental hardenable composition described above.

[12] The first agent contains a polymerizable monomer (A) having an acidic group, a polymerizable monomer (B) not having an acidic group, and a hydroperoxide (C), The dental curable composition according to

[11] , wherein the second agent contains a polymerizable monomer (B) having no acidic group and a thiourea compound (D) represented by general formula (1).

[13] The dental hardenable composition according to

[11] or

[12] , which is a dental resin cement. [Effects of the Invention]

[0014] According to the present invention, there is provided a dental hardenable composition which has an appropriate working time, excellent adhesion to tooth structure, and excellent mechanical strength of the hardened product. DETAILED DESCRIPTION OF THE INVENTION

[0015] The dental curable composition of the present invention contains a polymerizable monomer (A) having an acidic group, a polymerizable monomer (B) not having an acidic group, a hydroperoxide (C), and a thiourea compound (D) represented by the following general formula (1): [ka] (In the formula, A1 and / or A5 is any one of a hydroxy group, an alkoxy group, an amino group, and a dialkylamino group, and A2 to A4 are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an amino group, a dialkylamino group, a hydrocarbon group, a carboxy group, or a halogen atom.)

[0016] Although the mechanism by which the dental curable composition of the present invention exerts the effects of the present invention is unclear, it is presumed that the activity of the polymerization initiator system is improved by containing a thiourea compound (D) having a specific substituent represented by general formula (1) at the ortho position of the benzene ring. That is, among the substituents A1 and / or A5 in general formula (1), the atom directly bonded to the benzene ring has an unshared electron pair, which is presumed to exert various effects. For example, among the substituents A1 and / or A5, the unshared electron pair possessed by the atom directly bonded to the benzene ring interacts intramolecularly with the hydrogen atom bonded to the nitrogen atom of the thiourea, thereby enhancing the reactivity of the thiourea compound. In addition, the nitrogen atom of the thiourea compound and A1 and / or Among the substituents of A5, an atom having an unshared electron pair is The dental hardenable composition of the present invention is characterized by its ability to interact with the Ca atoms of hydroxyapatite, a component constituting the tooth, thereby enhancing the ability to initiate polymerization in the vicinity of the tooth. Each of the components contained in the dental hardenable composition of the present invention will be described below.

[0017] The dental curable composition of the present invention contains a polymerizable monomer (A) having an acidic group. The polymerizable monomer (A) having an acidic group has the effect of demineralizing tooth structure. The polymerizable monomer (A) having an acidic group is a polymerizable monomer having at least one acidic group such as a phosphate group, a phosphonate group, a pyrophosphate group, a thiophosphate group, a carboxylic acid group, or a sulfonic acid group, and at least one polymerizable group such as an acryloyl group, a methacryloyl group, an acrylamide group, or a methacrylamide group. From the viewpoint of adhesion to tooth structure, the polymerizable monomer (A) having an acidic group is any of an acryloyl group, a methacryloyl group, an acrylamide group, or a methacrylamide group. It is preferable that the polymerizable group is monofunctional, having only one polymerizable group. Specific examples include the following:

[0018] 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;

[0019] 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.

[0020] 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.

[0021] 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, and 6-(meth)acryloyloxyhexyl dihydrogen thiophosphate. ester, 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.

[0022] 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 acryloylphthalic acid and its acid anhydrides; 5-(meth)acryloylaminopentylcarboxylic acid, 6-(meth)acryloyloxy-1,1-hexanedicarboxylic acid, 8-(meth)acryloyloxy-1,1-octanedicarboxylic acid, 10-(meth)acryloyloxy-1,1-decanedicarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, and their acid chlorides, alkali metal salts, ammonium salts, and amine salts.

[0023] 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.

[0024] Among the polymerizable monomers (A) 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 superior adhesiveness to tooth structure, and polymerizable monomers having a phosphate group and polymerizable monomers having a carboxylic acid group are particularly preferred. 20 or C6-C 20 More preferred are (meth)acrylate-based monofunctional polymerizable monomers having a phosphate group or (meth)acrylate-based polymerizable monomers having a carboxylic acid group, each of which has an alkylene group of the formula (I) or (II) above, and the main chain in the molecule is a C8 to C 12 alkylene group More preferred are (meth)acrylate-based monofunctional polymerizable monomers having a phosphate group. Also preferred are 10-methacryloyloxydecyl dihydrogen phosphate, 4-(meth)acryloyloxyethyl trimellitic acid and 4-(meth)acryloyloxyethyl trimellitic anhydride, with 10-methacryloyloxydecyl dihydrogen phosphate being most preferred.

[0025] The polymerizable monomer (A) having an acidic group may be blended alone or in combination of two or more. The content of the polymerizable monomer (A) having an acidic group is not particularly limited as long as the effects of the present invention are exhibited, but from the viewpoint of better adhesiveness, it 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 the polymerizable monomer components in the dental curable composition of the present invention.

[0026] The dental curable composition of the present invention contains a polymerizable monomer (B) having no acidic group. The polymerizable monomer (B) having no acidic group is a polymerizable monomer that undergoes a radical polymerization reaction in the presence of a polymerization initiator system to become a polymer. The polymerizable monomer (B) having no acidic group may be used alone or in combination of two or more. Suitable examples of the polymerizable monomer (B) having no acidic group include the following water-soluble polymerizable monomer (B-1) and hydrophobic polymerizable monomer (B-2). It can be obtained.

[0027] The water-soluble polymerizable monomer (B-1) refers to a polymerizable monomer having a solubility in water of 10% by mass or more at 25° C. A solubility of 30% by mass or more is preferred, and one that can dissolve in water at any ratio at 25° C. is more preferred. The water-soluble polymerizable monomer (B-1) not only promotes the penetration of the components of the dental hardenable composition into the tooth structure, but also penetrates into the tooth structure itself and adheres to collagen, an organic component in the tooth structure. Examples of the water-soluble polymerizable monomer (B-1) 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; and bifunctional (meth)acrylic acid ester polymerizable monomers such as polyethylene glycol di(meth)acrylate (having 9 or more oxyethylene groups), with 2-hydroxyethyl (meth)acrylate being preferred. In this specification, "(meth)acrylic" refers to both acrylic and methacrylic, and the same applies to expressions such as "(meth)acryloyl" and "(meth)acrylate."

[0028] The hydrophobic polymerizable monomer (B-2) refers to a crosslinkable polymerizable monomer having a solubility in water of less than 10% by mass at 25°C. Examples of the crosslinkable polymerizable monomer (B-2) include monofunctional and bifunctional polymerizable monomers of aromatic compounds, monofunctional and bifunctional polymerizable monomers of aliphatic compounds, and trifunctional or higher functional polymerizable monomers. The hydrophobic polymerizable monomer (B-2) improves the mechanical strength and handleability of the dental curable composition.

[0029] Examples of aromatic compound-based monofunctional polymerizable monomers include benzyl (meth)acrylate, p-cumyl-phenoxyethylene glycol (meth)acrylate, 2-phenoxybenzyl (meth)acrylate, etc. Among these, benzyl methacrylate and p-cumyl-phenoxyethylene glycol methacrylate are preferred.

[0030] 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-(3-acryloyloxy-2-hydroxypropoxy)phenyl]propane, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)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 ...tetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2 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.

[0031] 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.

[0032] 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 di(meth)acrylate (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, 1,3-butanediol di(meth)acrylate, 1, Examples of the polymerizable monomer include bifunctional (meth)acrylic acid ester polymerizable monomers such as 5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate, 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. Among these, glycerol dimethacrylate, triethylene glycol di(meth)acrylate, neopentyl glycol dimethacrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate, and 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane are preferred.

[0033] Examples of the aliphatic compound-based 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.

[0034] Among the polymerizable monomers (B) 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.

[0035] The polymerizable monomer (B) having no acidic group (water-soluble polymerizable monomer (B-1) and hydrophobic The acidic polymerizable monomer (B-2)) may be contained alone or in combination of two or more. The content of the acidic group-free polymerizable monomer (B) is not particularly limited as long as the effects of the present invention are achieved, but from the viewpoints of high penetration into tooth structure, excellent adhesion, and sufficient strength of the composition, the content is preferably in the range of 50 to 99 parts by mass, more preferably 60 to 98 parts by mass, and even more preferably 70 to 95 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer components in the dental curable composition of the present invention.

[0036] Next, the polymerization initiator system will be described. The dental hardenable composition of the present invention contains a hydroperoxide (C) as an oxidizing agent of the polymerization initiator system and a thiourea compound (D) having a specific structure as a reducing agent. By using the hydroperoxide (C) and the thiourea compound (D) and further combining them with other components, a dental hardenable composition having a desired working time and excellent adhesion to tooth structure and mechanical strength of the cured product can be obtained.

[0037] Examples of the hydroperoxide (C) include t-butyl hydroperoxide, cumene hydroperoxide, p-diisopropylbenzene dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-amyl hydroperoxide, p-menthane hydroperoxide, p-isopropylcumyl hydroperoxide, diisopropylbenzene hydroperoxide, etc. Among these, t-butyl hydroperoxide, cumene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide are particularly preferred.

[0038] The hydroperoxide (C) may be used alone or in combination of two or more. From the viewpoints of curability, mechanical strength of the cured product, adhesion to tooth structure, and storage stability, the content of the hydroperoxide (C) is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass, and even more preferably in the range of 0.5 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer components in the dental curable composition of the present invention.

[0039] The thiourea compound (D) is preferably a compound represented by general formula (1) in which A1 and / or A5 is a hydroxy group, an amino group, or a dialkylamino group, and A2 to A4 are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an amino group, a dialkylamino group, a hydrocarbon group, a carboxy group, or a halogen atom. From the viewpoints of achieving the desired working time, achieving superior adhesion to tooth substrate, and achieving superior mechanical strength of the cured product, a compound in which A1 and / or A5 is a hydroxy group, and A2 to A4 are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an amino group, a dialkylamino group, a hydrocarbon group, a carboxy group, or a halogen atom is more preferred.

[0040] The alkoxy groups A1 to A5 may be either linear or branched. The alkoxy group of A5 preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and More preferred are 1 to 3, and particularly preferred are 1 to 3. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert- Butoxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, neopentyloxy group, n-hexyloxy group, isohexyl Examples thereof include an oxy group.

[0041] The dialkylamino groups of A1 to A5 may have either a linear or branched alkyl group. The number of carbon atoms in each alkyl group of the dialkylamino group is preferably 1 to 8, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 to 3. Examples of the dialkylamino group include a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group, a dibutylamino group, a diisobutylamino group, a dipentylamino group, a dihexylamino group, and an ethylmethylamino group. The alkyl of the dialkylamino group The group may be substituted with a substituent, such as a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxy group, etc.

[0042] Examples of the hydrocarbon groups of A2 to A4 include aliphatic hydrocarbon groups and alicyclic hydrocarbon groups. Examples of the aliphatic hydrocarbon groups include alkyl groups and alkenyl groups. Examples of the alicyclic hydrocarbon groups include cycloalkyl groups. The alkyl groups may be either linear or branched. The number of carbon atoms in the alkyl groups of A2 to A4 is preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 3. Examples of the alkyl groups of A2 to A4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-pentyl groups. Alkenyl groups may be either linear or branched. The alkyl groups A2 to A4 preferably have 2 to 8 carbon atoms, more preferably 2 to 6, even more preferably 2 to 4, and particularly preferably 2 to 3. Examples of the alkenyl groups A2 to A4 include a vinyl group, an allyl group, a 1-propenyl group, a 1-methylethenyl group, and a 1-butenyl group. The cycloalkyl groups A2 to A4 preferably have 3 to 10 carbon atoms, more preferably 3 to 9, even more preferably 3 to 8, and particularly preferably 3 to 6. Examples of the cycloalkyl groups A2 to A4 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

[0043] Examples of the thiourea compound (D) include 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-dimethylaminophenyl)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, and N-(2-methoxy-4 -hydroxyphenyl)thiourea, N-(2-methoxy-4-dimethylaminophenyl)thiourea, N-(2-methoxy-3-hydroxyphenyl)thiourea, N-(2-dimethylaminophenyl)thiourea, N-(2-diethylaminophenyl)thiourea, N-(2-dimethylamino-4-methoxyphenyl)thiourea, N-(2-dimethylamino-4-hydroxyphenyl)thiourea, N-(2-ethoxyphenyl)thiourea, N-(2-aminophenyl)thiourea, N-(2,4-diaminophenyl)thiourea, N-(2,6-diaminophenyl)thiourea, and N-(2-amino-4-hydroxyphenyl)thiourea. Among these, 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-dimethylaminophenyl)thiourea, and N-(2-hydroxy-4-diethylaminophenyl)thiourea are preferred, and N-(2-hydroxyphenyl)thiourea Urea, N-(2,6-dihydroxyphenyl)thiourea, N-(2,4-dihydroxyphenyl)thiourea, N-(2-hydroxy-4-methoxyphenyl)thiourea, and N-(2-hydroxy-4-ethoxyphenyl)thiourea are more preferred, and N-(2-hydroxyphenyl)thiourea, N-(2,6-dihydroxyphenyl)thiourea, N-(2,4-dihydroxyphenyl)thiourea, and N-(2-hydroxy-4-methoxyphenyl)thiourea are particularly preferred.

[0044] The thiourea compound (D) is preferably in a powder form, since this can increase the reactivity of the thiourea compound near the adhesive interface of the tooth, obtain a desired operation time, and provide better adhesion to the tooth. By dispersing the powdered thiourea compound (D) in the dental hardenable composition, when the dental hardenable composition is applied to the tooth surface, the thiourea compound dissolves in the moisture present at the adhesive interface of the tooth, and the concentration increases locally, thereby further increasing the reactivity at the adhesive interface. The thiourea compound (D) has an excessively large particle size. If the particle size is too large, the curing reaction will be delayed, but if the particle size is too small, the specific surface area of ​​the powder will be too large, reducing the amount that can be dispersed in the composition. Therefore, the average particle size is preferably 0.01 to 50 μm, more preferably 0.01 to 20 μm. The average particle size can be measured using the same method as that for the filler (G). The shape of the powdered thiourea compound (D) can be various, such as spherical, acicular, plate-like, or crushed, but is not particularly limited. In addition, the powdered thiourea compound (D) can be prepared by conventional methods such as pulverization, freeze-drying, or reprecipitation.

[0045] From the viewpoints of curability, mechanical strength of the cured product, adhesion to tooth structure, and storage stability, the content of the thiourea compound (D) is preferably in the range of 0.005 to 10 parts by mass, more preferably in the range of 0.01 to 5 parts by mass, and even more preferably in the range of 0.1 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer components in the dental curable composition of the present invention.

[0046] The dental curable composition of the present invention may contain a transition metal compound (E). The transition metal compound (E) has the effect of accelerating the redox reaction between the hydroperoxide (C) and the thiourea compound (D) having a specific structure. As the transition metal compound (E), a copper compound or a vanadium compound is preferably used.

[0047] Examples of copper compounds include copper(II) carboxylates, β-diketones, β-ketoesters, copper(II), copper alkoxides, copper dithiocarbamates, and salts of copper with 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) octylate, copper(II) octenoate, copper(II) naphthenate, copper(II) methacrylate, and copper(II) 4-cyclohexylbutyrate. Examples of copper(II) β-diketones include copper(II) acetylacetonate, copper(II) trifluoroacetylacetonate, copper(II) hexafluoroacetylacetonate, copper(II) 2,2,6,6-tetramethyl-3,5-heptanedionatocopper(II), and copper(II) benzoylacetone. Examples of copper(II) β-ketoesters include copper(II) ethyl acetoacetate. 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. Examples of salts of copper with inorganic acids include copper(II) nitrate, copper(II) bromide, and copper(II) chloride. These salts may be used alone or in combination of two or more. Among these, copper(II) carboxylate, β-diketone copper(II), and β-ketoester copper(II) are preferred, with copper(II) acetate and copper(II) acetylacetonate being more preferred, from the viewpoints of solubility and reactivity with polymerizable monomers.

[0048] The vanadium compound is preferably a tetravalent and / or pentavalent vanadium compound. Examples of the tetravalent and / or pentavalent vanadium compound include divanadium(IV) tetroxide, vanadyl acetylacetonate(IV), vanadium oxide stearate(IV), oxovanadium(IV) oxalate, vanadyl(IV) sulfate, vanadium naphthenate, vanadium benzoylacetonate, bis(maltolate)oxovanadium(IV), oxobis(1-phenyl-1,3-butanedionate)vanadium(IV), pentavalent vanadium tetraoxide, vanadyl acetylacetonate(IV), vanadyl oxovanadium ... Examples of vanadium compounds include vanadium(V) oxide, vanadium(V) oxytriisopropoxide, sodium metavanadate(V), and ammonium metavanadate(V). Among these, vanadium acetylacetonate, vanadyl acetylacetonate(IV), and bis(maltolate)oxovanadium(IV) are preferred from the viewpoint of adhesiveness, with vanadyl acetylacetonate(IV) and bis(maltolate)oxovanadium(IV) being more preferred. The vanadium compounds can be used singly or in combination of two or more.

[0049] From the viewpoints of curability, mechanical strength of the cured product, and adhesion to tooth structure, the content of the transition metal compound (E) is preferably in the range of 0.0001 to 1 part by mass, more preferably in the range of 0.0003 to 0.5 parts by mass, and even more preferably in the range of 0.0005 to 0.2 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer components in the dental curable composition of the present invention.

[0050] The dental curable composition of the present invention may contain a ligand compound (F). The ligand compound (F) is preferably at least one compound selected from the group consisting of phosphorus-atom-containing ligands and nitrogen-atom-containing ligands, because it acts on the polymerization initiator system of the hydroperoxide (C) and the thiourea compound (D), improving the activity of the polymerization initiator system and providing excellent curability, mechanical strength of the cured product, and adhesion to tooth structure. The phosphorus-atom-containing ligand contains a phosphorus atom as a coordinating atom. The nitrogen-atom-containing ligand contains a nitrogen atom as a coordinating atom. A preferred embodiment of the dental curable composition includes a ligand compound (F) containing a nitrogen atom-containing ligand. Another preferred embodiment of the dental curable composition includes a ligand compound (F) containing a phosphorus-atom-containing ligand and a nitrogen atom-containing ligand.

[0051] Examples of the phosphorus atom-containing ligand include phosphine ligands and phosphite ligands. Specific examples of the phosphorus atom-containing ligand include compounds represented by the following general formula (2), compounds represented by general formula (3), compounds represented by general formula (4), and compounds represented by the following general formula (5). The phosphorus atom-containing ligands may be used alone or in combination of two or more.

[0052] [ka] (R1~R 15 each independently has a hydrogen atom, a halogen atom, a polar group, or a substituent represents an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.

[0053] [ka] (R 16 ~R 35 each independently represents a hydrogen atom, a halogen atom, a polar group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and X1 is a substituent represents a divalent aliphatic group which may have the following structure:

[0054] [ka] (Each Ar independently represents a group represented by the following general formula (4-a).)

[0055] [ka] (Z1 to Z3 each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and at least one of Z1 to Z3 is a hydrogen atom.)

[0056] P(OY1)3(5) (Y1's each independently represent an alkyl group which may have a substituent, or a represents an aryl group which may be

[0057] R1~R 15 The alkyl group which may have a substituent may be either a straight chain or a branched chain. It is acceptable. R1~R 15 The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 12. R1 to R2 are preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 3. 15 Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- Butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group ethyl group, sec-pentyl group, neopentyl group, n-hexyl group, isohexyl group, n-hexyl group Examples of the alkyl groups include a butyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, and an n-dodecyl group. 15 The alkyl groups R to R may be unsubstituted. 15Examples of the substituent on the alkyl group include a halogen 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.

[0058] R1~R 15 The halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples include:

[0059] R1~R 15 The polar groups include an acid anhydride group, a carboxylic acid group, a carboxylic acid ester group, Examples of such groups include carboxylic acid chloride groups, carboxylic acid amide groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid ester groups, sulfonic acid chloride groups, sulfonic acid amide groups, sulfonic acid salt groups, aldehyde groups, epoxy groups, cyano groups, amino groups, monoalkyl-substituted amino groups, dialkyl-substituted amino groups, imide groups, and oxazoline groups. From the viewpoints of curability and the mechanical strength of the cured product, carboxylic acid groups, carboxylic acid ester groups, carboxylic acid chloride groups, carboxylic acid amide groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid ester groups, sulfonic acid chloride groups, sulfonic acid amide groups, sulfonic acid salt groups, and aldehyde groups are preferred, and carboxylic acid groups and carboxylic acid ester groups are More preferred are carboxylic acid chloride groups, carboxylic acid bases, sulfonic acid groups, sulfonate ester groups, sulfonic acid chloride groups, sulfonate bases, and aldehyde groups, and even more preferred are carboxylic acid groups, carboxylic acid ester groups, carboxylic acid chloride groups, carboxylic acid bases, sulfonic acid groups, sulfonate ester groups, sulfonic acid chloride groups, and sulfonate bases. Salts of carboxylic acid bases and sulfonate bases include alkali metal salts such as lithium, sodium, and potassium; and alkaline earth metal salts such as magnesium, calcium, strontium, barium, and radium. R1 to R 15 In the case where the polar group is a group represented by the formula (I), the number of polar groups is preferably 1 to 9, and more preferably 1 to 5. is more preferable, and 1 to 3 are even more preferable. 15 is an alkyl group having a substituent In the case where the aryl group is substituted, specific examples thereof include a trifluoromethyl group.

[0060] R1~R 15 The alkoxy group, which may have a substituent, may be either a straight chain or branched chain. R1 to R 15 The number of carbon atoms in the alkoxy group is not particularly limited, and is preferably 1 to 12. R1 is preferably 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 3. ~R 15 Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, and an n-pentyloxy group. group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, neopentyloxy group n-hexyloxy group, isohexyloxy group, sec-hexyloxy group group, a tert-hexyloxy group, a neohexyloxy group, etc. 15 Al The substituents of the koxy group include R1 to R 15 The substituents of the alkyl group in the above formula (I) are the same as those of the alkyl group in the above formula (I). .

[0061] R1~R 15 may be the same or different. 15 may be, for example, partly the same hydrogen atom, alkyl group or alkoxy group.

[0062] R 16 ~R 35 The alkyl group which may have a substituent is R1 to R 15 It has the following substituents: The same applies to alkyl groups that may be used. 16 ~R 35 The alkoxy group which may have a substituent is R1 to R 15 The same applies to the alkoxy group optionally having a substituent as defined above. 16 ~R 35 Noha The halogen atoms are R1 to R 15The same applies to halogen atoms in R. 16 ~R 35 The polar groups are R1 to R 15 The polar groups are the same as those of the above.

[0063] The optionally substituted divalent aliphatic group of X1 is either linear or branched. The divalent aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 16, still more preferably 1 to 12, and particularly preferably 1 to 8. Examples of the divalent aliphatic group include an alkylene group, an alkenylene group, and an alkynylene group, and an alkylene group is preferred. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a methylpropylene group, a dimethylpropylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, and a dodecamethylene group. Examples of the substituent of the divalent aliphatic group of X1 include R1 to R 15 The substituents for the alkyl group are the same as those for the alkyl group.

[0064] In formula (4), multiple Ar may be the same or different. In the group represented by general formula (4-a), Z1 to Z3 may be the same or different. The alkyl groups of Z1 to Z3, which may have a substituent, are each independently selected from R1 to R 15 It has a substituent of The same applies to the alkyl group which may be used. At least one of Z1 to Z3 may be a hydrogen atom, and all of Z1 to Z3 may be hydrogen atoms. Specific examples of Ar include the following groups. [ka]

[0065] In one embodiment, one or two of Z1 to Z3 are hydrogen atoms, and the other one or two of Z1 to Z3 may be a linear or branched alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a fluorine atom, or a trifluoromethyl group. The alkoxy groups optionally having a substituent of Z1 to Z3 are R1 to R 15 The same as an alkoxy group which may have a substituent, A preferred embodiment is a phosphine compound in which all Ar in the compound represented by general formula (4) are 3,5-dimethylphenyl groups. Another preferred embodiment is a phosphine compound in which all Ar in the compound represented by general formula (4) are 4-methylphenyl groups.

[0066] In the phosphite ligand represented by the general formula (5), three Y1 may be the same or different. The alkyl group of Y1, which may have a substituent, may be any of R1 to R2. 15 The alkyl group which may have a substituent is the same as the alkyl group which may have a substituent of Y1. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10. The substituents of the aryl group of Y1 include R1 to R 15 The aryl group of Y1 which may have a substituent is a phenyl group, Examples include a biphenyl group, an indenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a pyrenyl group, and a phenyl group substituted with an alkyl group such as a tolyl group, a xylyl group, a trimethylphenyl group, an ethylphenyl group, an isopropylphenyl group, or a tetramethylphenyl group. In one preferred embodiment, three Y1s are 1,1,1,3,3 ,3-hexafluoro-2-propyl group. Another preferred embodiment includes a phosphite compound in which three Y1 are 2,4-di-tert-butylphenyl groups.

[0067] Examples of the monodentate phosphine compound represented by the general formula (2) include phosphine compounds having an electron-donating group, such as triphenylphosphine (hereinafter sometimes abbreviated as "TPP"), diphenyl(o-tolyl)phosphine, tri(o-tolyl)phosphine, tri(p-tolyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(2-methoxyphenylphosphine), tris(4-methoxyphenylphosphine), tris(2,6-dimethoxyphenyl)phosphine (hereinafter sometimes abbreviated as "DMPP"), diphenyl(2-methoxyphenyl)phosphine, and 4-(dimethylamino)triphenylphosphine; (2-fluorophenyl)diphenylphosphine, and (2-chlorophenyl)diphenylphosphine. Examples of phosphine compounds having an electron-withdrawing group include (2-bromophenyl)diphenylphosphine, (pentafluorophenyl)diphenylphosphine, bis(pentafluorophenyl)phenylphosphine (hereinafter sometimes abbreviated as "BPFPP"), tris(pentafluorophenyl)phosphine (hereinafter sometimes abbreviated as "TPFPP"), tris(4-fluorophenyl)phosphine (hereinafter sometimes abbreviated as "TFPP"), tris(4-chlorophenyl)phosphine, tris(4-bromophenyl)phosphine, tris(4-trifluoromethylphenyl)phosphine, tris(4-carboxyphenyl)phosphine, sodium diphenylphosphinobenzene-3-sulfonate, and trisodium triphenylphosphine-3,3',3"-trisulfonate.

[0068] Examples of the bidentate phosphine compound of the general formula (3) include phosphine compounds such as bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane, and 1,2-bis[bis(pentafluorophenyl)-phosphino]ethane.

[0069] Examples of the bidentate phosphine ligand of the above general formula (4) include (±)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (hereinafter sometimes abbreviated as “BINAP”), (±)-2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl, (±)-2,2′-bis(di-p-fluorophosphino)-1,1′-binaphthyl, (±)-2,2′-bis(di-p-trifluoromethylphosphino)-1,1′-binaphthyl, (±)-2,2′-bis[di(3,5-xylyl)phosphino]-1,1′-binaphthyl, and the like.

[0070] Examples of the phosphite ligand of the above general formula (5) include trimethyl phosphite, triethyl phosphite, tris(1,1,1,3,3,3-hexafluoro-2-propyl) phosphite, triphenyl phosphite, and tris(2,4-di-t-butylphenyl) phosphite.

[0071] Examples of the nitrogen atom-containing ligand include compounds represented by general formula (6), compounds represented by general formula (7), and multidentate ligands containing a nitrogen-containing heterocycle (8). The nitrogen atom-containing ligands may be used alone or in combination of two or more.

[0072] R 36 R 37 N-X2-NR 38 R 39 (6) (R 36 ~R 39 each independently represents an alkyl group which may have a substituent, and X2 is represents a divalent aliphatic group which may have a substituent.

[0073] [ka] (R 40 , R 41 , and R 42each independently represent an alkyl group which may have a substituent; X3 and X4 each independently represent a divalent aliphatic group which may have a substituent and which may contain an oxygen atom and / or a nitrogen atom; m and n each independently represent an integer of 1 or more; Y2 is a monoalkylamino group or a dialkylamino group which may have a substituent; represents an amino group, and R 40 , R 41 , R 42 Any two or more of Y and Y2 together form a ring. R 41 , R 42 When a plurality of X, X3, and X4 are present, they may be the same or different.)

[0074] R 36 ~R 39 The alkyl group which may have a substituent is R1 to R 15 It has the following substituents: The same applies to the alkyl group which may be used.

[0075] The optionally substituted divalent aliphatic group of X2 is the same as the optionally substituted divalent aliphatic group of X1.

[0076] R 40 , R 41 , and R 42 The alkyl group which may have a substituent is R1 to R 15 Substituents of The alkyl group (-NHR) of Y2 is the same as the alkyl group (-NHR) of Y2. a (R a represents an alkyl group) and dialkylamino groups (-NR b R c (R b and R c Is Alki The number of carbon atoms in the monoalkylamino group represented by Y2 is not particularly limited, but is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 3. The alkyl group of the dialkylamino group is R1 to R15 an arsenic compound optionally having a substituent of Examples of alkyl groups include those having the above number of carbon atoms. In the case of a dialkylamino group, each alkyl group may have the above number of carbon atoms. Examples of the monoalkylamino group that may be present include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, an isobutylamino group, a t-butylamino group, a pentylamino group, and a hexylamino group. Suitable dialkylamino groups include dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, dipentylamino, dihexylamino, and ethylmethylamino groups. The alkyl group of the alkylamino group and the dialkylamino group may be substituted with a substituent. The substituent includes R1 to R 15 The substituents for the alkyl group are the same as those for the alkyl group.

[0077] The divalent aliphatic groups of X3 and X4 may be either linear or branched. The number of carbon atoms in the divalent aliphatic group is preferably 1 to 20, more preferably 1 to 16, still more preferably 1 to 12, and particularly preferably 1 to 8. Examples of the divalent aliphatic group include an alkylene group, an alkenylene group, and an alkynylene group, and an alkylene group is preferred. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a methylpropylene group, a dimethylpropylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, and a dodecamethylene group. Examples of the substituent of the divalent aliphatic groups of X3 and X4 include the substituent of the divalent aliphatic group of X1. The same as the substituents can be mentioned. The divalent aliphatic groups of X3 and X4 may contain an oxygen atom and / or a nitrogen atom. X3 and X4 may be the same or different.

[0078] m and n each independently represent an integer of 1 or greater, preferably an integer of 1 to 8, more preferably an integer of 1 to 6, even more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3. m and n may be the same or different.

[0079] R 40 , R 41 , R 42 Any two or more of Y and Y2 may be joined together to form a ring. For example, R 40 , R 41 , or R 42 and Y2 may be taken together to form a ring. Also, R 40 and Y2, R 41 and R 42 are joined together to form a ring, and as a compound there are two Furthermore, the nitrogen atom of the amino group of Y and R 40 and R may be taken together to form a ring. The ring may contain an oxygen atom and / or a nitrogen atom. Furthermore, in some embodiments, the compound represented by general formula (7) may be a compound having a bicyclo ring. For example, in other embodiments, in the compound represented by general formula (7), Y and R 40 and R form a ring together. 41 or R 42 and a ring formed by combining with Y2.

[0080] In one preferred embodiment, R 41 and R 42 is a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent.

[0081] Another preferred embodiment is a dental hardenable composition containing a ligand compound (F), wherein the ligand compound (F) is at least one selected from the group consisting of a compound represented by general formula (2) and a compound represented by general formula (6).

[0082] In another preferred embodiment, the compound contains a ligand compound (F), and the ligand compound (F) is a compound represented by general formula (7), and in the compound represented by general formula (7), R 40 , R 41 and R 42 represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent; the divalent aliphatic groups of X3 and X4 represent alkylene groups which do not contain oxygen atoms or nitrogen atoms; m and n each independently represent an integer of 1 or more; Y2 represents a monoalkylamino group or a dialkylamino group which may have a substituent, and R 40 , R 41 , or R 42 and Y2 may be taken together to form a ring. Things include:

[0083] Another preferred embodiment is a dental curable composition containing a ligand compound (F), wherein the ligand compound (F) is a compound represented by general formula (7), in which m is 1, n is 2, and the compound as a whole contains four nitrogen atoms.

[0084] The multidentate ligand (8) containing a nitrogen-containing heterocycle contains a heterocycle containing a 5- or 6-membered ring containing a nitrogen atom, has two or more nitrogen atoms in the molecule, and represents a bidentate or higher ligand compound. The number of nitrogen atoms contained in the molecule of the multidentate ligand (8) is two or more, and may be three or more. The number of heterocycles contained in the multidentate ligand (8) may be one or two or more. Examples of the nitrogen-containing heterocycle include a nitrogen-containing 5-membered ring such as a pyrrole ring, a pyrazole ring, or an imidazole ring; and a nitrogen-containing 6-membered ring such as a pyridine ring, a pyrazine ring, a pyridazine ring, a piperazine ring, a pyrimidine ring, or a triazine ring. The nitrogen-containing heterocycle may be a fused ring of the nitrogen-containing 5- or 6-membered ring with another ring (e.g., an aromatic ring), or may be a fused ring of two nitrogen-containing 5- or 6-membered rings. Examples of the fused ring of a 5- or 6-membered ring containing a nitrogen atom and an aromatic ring include a quinoline ring, an isoquinoline ring, an indole ring, a benzimidazole ring, and a benzotriazole ring. The multidentate ligand (8) may contain a heterocyclic ring containing a 5- or 6-membered ring containing a nitrogen atom, and examples thereof include ligand compounds containing a fused ring such as an indole ring, a benzimidazole ring, or a benzotriazole ring and a heterocyclic ring containing a 5- or 6-membered ring containing a nitrogen atom. The multidentate nature of the multidentate ligand (8) may be two or more, and may be tridentate, tetradentate, or the like.

[0085] Examples of the polydentate amine compound represented by the general formula (6) above include bidentate polydentate amine compounds such as N,N,N',N'-tetramethylethylenediamine (hereinafter sometimes abbreviated as "TMEDA"), N,N,N',N'-tetramethylpropylenediamine (hereinafter sometimes abbreviated as "TMPDA"), N,N,N',N'-tetramethyl-1,4-diaminobutane, N,N,N',N'-tetraethylethylenediamine (hereinafter sometimes abbreviated as "TEEDA"), and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine.

[0086] Examples of the compound represented by the general formula (7) include compounds having a cyclo ring such as 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; compounds having a bicyclo ring such as 4,11-dimethyl-1,4,8,11-tetraazabicyclohexadecane; 2,5,9,12-tetramethyl-2,5,9,12-tetraazatetradecane, 2,6,9,13-tetramethyl-2,6,9,13-tetraazatetradecane, 2,5,8,12-tetramethyl-2,5,8, Polydentate amines such as compounds without a ring, such as 12-tetraazatetradecane, N,N,N,N',N'',N''-pentamethyldiethylenetriamine (hereinafter sometimes abbreviated as "PMDETA"), hexamethyltris(2-aminoethyl)amine, N,N-bis(2-dimethylaminoethyl)-N,N'-dimethylethylenediamine (hereinafter sometimes abbreviated as "HMTETA"), and tris[2-(dimethylamino)ethyl]amine (hereinafter sometimes abbreviated as "Me6TREN"). Compounds include:

[0087] Examples of the polydentate ligand (8) containing a nitrogen-containing heterocycle include polydentate ligands having one nitrogen-containing heterocycle, such as N-(n-propyl)pyridylmethanimine and N-(n-octyl)pyridylmethanimine; 2,2-bipyridine, 4,4'-di-(5-nonyl)-2,2'-bipyridine, N-propyl-N,N-di(2-pyridylmethyl)amine, N',N''-dimethyl-N',N''-bis((pyridin-2-yl)methyl)ethane-1,2-diamine, ... Examples of the heterocyclic ring include polydentate ligands having two or more nitrogen-containing heterocycles, such as N,6-bis(1-pyrazole)-pyridine (hereinafter sometimes abbreviated as "DPP"), 2-(2-pyridyl)benzimidazole, tris[(2-pyridyl)methyl]amine, 3,6-di(2-pyridyl)-1,2,4,5-tetrazine, N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine, and 2,4,6-tri(2-pyridyl)-1,3,5-triazine.

[0088] Among these, tri(o-tolyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, TMEDA, TMPDA, TEEDA, PMDETA, Me6TREN are preferably used. The ligand compound (F) may be blended singly or in combination of two or more. The ligand compound (F) is used to enhance the catalytic activity of the transition metal compound (E) in the dental curable composition of the present invention. From the viewpoints of curability, mechanical strength of the cured product, and adhesion to tooth structure, the content of the ligand compound (F) is preferably in the range of 0.005 to 10 parts by mass, more preferably in the range of 0.01 to 5 parts by mass, and even more preferably in the range of 0.05 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer components in the dental curable composition of the present invention,

[0089] The dental hardenable composition of the present invention may contain a filler (G) in order to obtain sufficient workability of the composition and sufficient radiopacity and mechanical strength of the cured product.

[0090] As the filler (G), any filler can be used as long as it does not impair the effects of the present invention, and examples thereof include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers. The filler (G) may be blended singly or in combination of two or more types. The average particle size of the filler (G) is preferably 0.001 to 10 μm, and more preferably 0.001 to 5 μm.

[0091] Inorganic fillers include silica; silica-based minerals such as kaolin, clay, mica, and mica; and ceramics and glasses based on silica and containing Al2O3, BO3, TiO2, ZrO2, BaO, La2O3, SrO, ZnO, CaO, PO5, Li2O, and Na2O. Glasses include lithium borosilicate glass, borosilicate glass, bioglass, lanthanum glass, barium glass, strontium glass, soda glass, zinc glass, and fluoroaluminosilicate glass. Suitable inorganic fillers include crystalline quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride. Particulate silica with an average particle size of 0.001 to 0.1 μm is preferred for its adhesive properties and ease of handling. Commercially available products include "Aerosil (registered trademark) OX50," "Aerosil (registered trademark) 50," "Aerosil (registered trademark) 200," "Aerosil (registered trademark) 380," "Aerosil (registered trademark) R972," "Aerosil (registered trademark) 130," and "AEROXIDE (registered trademark) Alu C" (all of which are trade names manufactured by Nippon Aerosil Co., Ltd.). In the present invention, when the inorganic filler is surface-treated as described below, the average particle size of the inorganic filler means the average particle size before the surface treatment.

[0092] Examples of organic fillers include polymethyl methacrylate and polyethyl methacrylate. Examples of the rubber include acrylate, polyfunctional methacrylate polymer, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.

[0093] Examples of composite fillers of inorganic and organic fillers include those in which inorganic fillers are dispersed in organic fillers, and inorganic / organic composite fillers in which inorganic fillers are coated with various polymers.

[0094] To improve curability, mechanical strength, and handling properties, the filler (G) may be surface-treated with a known surface treatment agent such as a silane coupling agent before use. Examples of surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane.

[0095] The average particle size (average primary particle size) can be determined by laser diffraction scattering or electron microscope observation of the particles. Specifically, laser diffraction scattering is convenient for measuring the particle size of particles 0.1 μm or larger, while electron microscope observation is convenient for measuring the particle size of ultrafine particles less than 0.1 μm. In the present invention, 0.1 μm is a value measured by laser diffraction scattering. For example, the laser diffraction scattering method can be used to measure the particle size distribution on a volume basis using a 0.2% aqueous solution of sodium hexametaphosphate as a dispersion medium with a laser diffraction particle size distribution analyzer (SALD-2300, manufactured by Shimadzu Corporation). For electron microscope observation, a scanning electron microscope (SU3800, S-4000, etc., manufactured by Hitachi High-Technologies Corporation) can be used. For electron microscope observation, the particle size can be determined by taking an electron microscope photograph of the particles and measuring the particle size 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 (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.

[0096] The content of the filler (G) is not particularly limited as long as the effects of the present invention are achieved, but is preferably in the range of 50 to 300 parts by mass, and more preferably in the range of 100 to 250 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer components 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, and sufficient paste workability can be obtained.

[0097] The dental curable composition of the present invention contains a redox-type polymerization initiator. If necessary, the dental curable composition of the present invention may further contain a conventionally known photopolymerization initiator as a component separate from the above-described polymerization initiator system in order to form a dual-cure composition that also initiates polymerization upon irradiation with light.

[0098] Examples of the photopolymerization initiator include α-diketones, ketals, thioxanthones, (bis)acylphosphine oxides, and α-aminoacetophenones.

[0099] Examples of α-diketones include dl-camphorquinone (commonly known as "CQ"), benzil, and 2,3-pentanedione.

[0100] Examples of ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

[0101] Examples of thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone. Examples include oxanthone.

[0102] Among the (bis)acylphosphine oxides, examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, benzoylbis(2,6-dimethylphenyl)phosphine oxide, water-soluble acylphosphine oxide compounds disclosed in JP-B-3-57916, and salts thereof (for example, sodium salts, potassium salts, ammonium salts). Examples of bisacylphosphine oxides include bis(2,4,6-trimethylbenzoyl)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, dibenzoylphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, tris(2,4-dimethylbenzoyl)phosphine oxide, tris(2-methoxybenzoyl)phosphine oxide, and salts thereof (e.g., sodium salts, potassium salts, ammonium salts), and the like. Among these (bis)acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are preferred.

[0103] Examples of α-aminoacetophenones include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)-1-butanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-propanone, 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-pentanone, and 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)-1-pentanone.

[0104] The photopolymerization initiator may be used alone or in combination of two or more. The content of the photopolymerization initiator is not particularly limited, but from the viewpoint of the curability of the obtained dental curable composition, it is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 5 parts by mass, and even more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer components.

[0105] To enhance photocurability, the photopolymerization initiator may be used in combination with a polymerization accelerator for the photopolymerization initiator, such as tertiary amines, aldehydes, thiol compounds, and triazine compounds substituted with a trihalomethyl group.

[0106] 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, and N,N-dimethyl-4-isopropylaniline. N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, 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)-3,5-di-t-butylaniline, n-butoxyethyl 4-(N,N-dimethylamino)benzoate, 4-(N,N-dimethylamino) Examples of the aldehyde include 2-(methacryloyloxy)ethyl benzoate, ethyl 4-(N,N-dimethylamino)benzoate, butyl 4-(N,N-dimethylamino)benzoate, N-methyldiethanolamine, 4-(N,N-dimethylamino)benzophenone, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2-(dimethylamino)ethyl(meth)acrylate, N-methyldiethanolamine di(meth)acrylate, N-ethyldiethanolamine di(meth)acrylate, triethanolamine mono(meth)acrylate, triethanolamine di(meth)acrylate, triethanolamine tri(meth)acrylate, etc. Examples of the aldehyde include terephthalaldehyde and benzaldehyde derivatives. Examples of benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, p-n-octyloxybenzaldehyde, etc. Examples of thiol compounds include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, thiobenzoic acid, etc.As the trihalomethyl-substituted triazine compound, any known s-triazine compound having at least one trihalomethyl group such as a trichloromethyl group or a tribromomethyl group can be used without any limitation.

[0107] The polymerization accelerator for the photopolymerization initiator may be used alone or in combination of two or more. The content of the polymerization accelerator for the photopolymerization initiator is not particularly limited, but from the viewpoint of the curability of the obtained dental curable composition, it is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 5 parts by mass, and even more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer components in the dental curable composition of the present invention.

[0108] The dental curable composition of the present invention may further contain a polymerization accelerator for other chemical polymerization initiators. Examples of the polymerization accelerator for other chemical polymerization initiators include sulfinic acid and its salts, sulfites, hydrogen sulfites, borate compounds, barbituric acid and its derivatives, etc. These may be used alone or in combination of two or more.

[0109] Examples of sulfinic acids and salts thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethyl ...ate, triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, etc. Among these, sodium benzenesulfinate, sodium p-toluenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, and sodium 2,4,6-triisopropylbenzenesulfinate are preferred.

[0110] Examples of sulfites include sodium sulfite, potassium sulfite, calcium sulfite, and ammonium sulfite. Examples of hydrogen sulfites include sodium hydrogen sulfite and potassium hydrogen sulfite. Examples of borate compounds include arylborate compounds having 1 to 4 aryl groups per molecule (e.g., tetraphenylboron, tetrakis(p-chlorophenyl)boron, etc.) and salts thereof. Examples of barbituric acid and its derivatives include barbituric acid, 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and salts thereof.

[0111] The dental curable composition of the present invention may further contain a fluoride ion-releasing substance. By incorporating a fluoride ion-releasing substance, a dental resin cement capable of imparting acid resistance to tooth structure can be obtained. Examples of such fluoride ion-releasing substances include fluoride ion-releasing polymers such as copolymers of methyl methacrylate and methacrylic acid fluoride; hydrofluorides of aliphatic or alicyclic primary, secondary, or tertiary amines such as cetylamine hydrofluoride, cyclohexylamine hydrofluoride, diisobutylamine hydrofluoride, and triethylamine trihydrofluoride; and metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride. The fluoride ion-releasing substances may be used alone or in combination.

[0112] In addition, the dental curable composition of the present invention may contain polymerization inhibitors, ultraviolet absorbers, thickeners, solvents (e.g., water, organic solvents), pH adjusters, colorants, antibacterial agents, fragrances, etc., as long as the effects of the present invention are not impaired. These may be used alone or in combination of two or more. Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, dibutyl hydroquinone, dibutyl hydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, and 2,6-di-t-butyl-4-methylphenol. In some embodiments, the content of solvents (e.g., water, organic solvents) in the dental curable composition is preferably less than 1% by mass, more preferably less than 0.1% by mass, and even more preferably less than 0.01% by mass, based on the total amount of the dental curable composition.

[0113] The dental hardenable composition of the present invention may be prepared according to a conventional method depending on the types and amounts of the components. The dental hardenable composition of the present invention is preferably used in a two-component form. The two-component form can be appropriately selected from a powder and liquid form, a paste and liquid form, a two-paste form, etc., but in a more preferred embodiment from the viewpoint of operability, it is used in a two-paste form. It is preferable to store each paste in a state where the pastes are isolated from each other, and to knead the two pastes just before use to promote chemical polymerization and harden them. The paste is usually prepared by kneading a liquid component prepared by mixing components other than the filler (G) with the filler (G) (powder). One preferred embodiment is a two-paste dental hardenable composition comprising a first component and a second component. The two-component form is preferably used in a two-paste form. In a preferred embodiment, the dental hardenable composition is a paste-type dental hardenable composition, wherein the first part contains a polymerizable monomer (A) having an acidic group, a polymerizable monomer (B) not having an acidic group, and a hydroperoxide (C), and the second part contains a polymerizable monomer (B) not having an acidic group and a thiourea compound (D) represented by general formula (1). Another preferred embodiment is a two-paste dental hardenable composition, wherein at least one of the first part and the second part contains a transition metal compound (E). Another preferred embodiment is a two-paste dental hardenable composition, wherein at least one of the first part and the second part contains a ligand compound (F).

[0114] The dental curable composition of the present invention is used for bonding dental prostheses such as crowns, inlays, and bridges to tooth structures in damaged areas of teeth, and for core construction, and is particularly suitable as a dental resin cement, particularly as a self-adhesive dental resin cement.

[0115] The present invention includes embodiments in which 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]

[0116] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The abbreviations used below are as follows. The compounds and fillers used in the following examples and comparative examples were commercially available products, unless the production method was specifically described.

[0117] [Polymerizable monomer (A) having an acidic group] MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[0118] [Polymerizable monomer (B) having no acidic group] HEMA: 2-hydroxyethyl methacrylate Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane D2.6E: 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethoxy groups added: 2.6) TEGDMA: Triethylene glycol dimethacrylate

[0119] [Hydroperoxide (C)] THP: 1,1,3,3-tetramethylbutyl hydroperoxide

[0120] [Thiourea compound (D)] N-(2-hydroxyphenyl)thiourea N-(2,6-dihydroxyphenyl)thiourea N-(2,4-dihydroxyphenyl)thiourea N-(2-dimethylaminophenyl)thiourea N-(2-Methoxyphenyl)thiourea N-(2-Methoxy-3-hydroxyphenyl)thiourea PhTU: N-phenylthiourea AHETU: 1-allyl-3-(2-hydroxyethyl)-2-thiourea HEETU: 1-(2-hydroxyethyl)imidazolidine-2-thione m-HPTU: N-(3-hydroxyphenyl)thiourea p-HPTU: N-(4-hydroxyphenyl)thiourea m-CPTU: N-(3-carboxyphenyl)thiourea

[0121] [Transition metal compound (E)] CuA: Copper(II) acetate VOAA: Vanadyl acetylacetonate(IV)

[0122] [Ligand compound (F)] TPP: Triphenylphosphine BPFPP: bis(pentafluorophenyl)phenylphosphine TEEDA: N,N,N',N'-tetraethylethylenediamine

[0123] [Filler (G)] Surface-treated barium glass: 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 was found to be 2.4 μm. 100 parts by mass of this barium glass powder was surface-treated with 3 parts by mass of γ-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain surface-treated Ba glass powder. R972: Fine particle silica manufactured by Nippon Aerosil Co., Ltd., trade name "Aerosil (registered trademark) R972", average particle size: 16 nm Alumina: Aluminum oxide manufactured by Nippon Aerosil Co., Ltd., trade name "AEROXIDE (registered trademark) Alu C", average particle size: 20 nm

[0124] [Polymerization inhibitor] BHT: 2,6-di-t-butyl-4-methylphenol

[0125] (Examples 1 to 12 and Comparative Examples 1 to 8) The dental hardenable compositions of Examples 1 to 12 and Comparative Examples 1 to 8 were prepared by mixing the components listed in Tables 1 and 2, except for the filler, at room temperature to form a uniform liquid component, and then kneading the resulting liquid component with the filler. These dental hardenable compositions were then used to measure the working time at 23°C, bond strength to bovine dentin, and flexural strength immediately after production, according to the methods described below. Tables 1 and 2 show the compounding ratios (parts by mass) of the dental hardenable compositions and the test results.

[0126] [Working time of dental hardenable composition at 23°C] The first and second parts were mixed in a mass ratio of 1:1 in a thermostatic chamber at 23°C and mixed thoroughly with a spatula to form one part. The time (operation time) from the time of mixing to the time when the temperature began to rise due to the start of hardening of the paste was measured using a thermocouple (manufactured by Okazaki Manufacturing Co., Ltd.) connected to a recorder (manufactured by Yokogawa Electric Corporation). The operation time is the average value of the measured values ​​for five test samples. From the viewpoint of operation time that allows ample time for operation using the composition and for hardening after operation, the operation time suitable for practical use is 2 to 8 minutes.

[0127] [Adhesion strength of dental hardenable composition to bovine dentin] The labial surface of a bovine mandibular anterior tooth was polished with #80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to expose a flat surface of dentin. The exposed flat surface was further polished with #1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water. After polishing, the water on the surface was dried by air blowing. An adhesive tape with a thickness of approximately 150 μm and a round hole with a diameter of 3 mm was attached to the dried smooth surface to determine the adhesive area. Equal amounts of the first and second agents of each dental curable composition of the Examples and Comparative Examples were taken and kneaded for 10 seconds, and then the resulting kneaded product was placed on a stem. The dental curable composition was applied to one end (circular cross section) of a stainless steel cylindrical rod (7 mm diameter, 2.5 cm length). The end of the applied dental curable composition was then placed on the smooth surface (adhesion surface) of the circular hole so that the center of the circular hole and the center of the stainless steel cylindrical rod were approximately aligned. The stainless steel cylindrical rod was then pressed perpendicularly against the smooth surface to adhere the composition to prepare a test sample. Five test samples were prepared. The test samples were allowed to stand at 25°C for 30 minutes and then immersed in distilled water. The immersed test samples were then placed in an incubator maintained at 37°C for 24 hours. The tensile bond strength of the test samples to bovine dentin after standing at 37°C for 24 hours was measured. The tensile bond strength was measured using a universal testing machine (Shimadzu Corporation, Autograph "AG-I 100kN") at a crosshead speed of 2 mm / min. The tensile bond strength to dentin in the table is the average value of the measured tensile bond strength to bovine dentin for five test samples after leaving them to stand at 37°C for 24 hours.

[0128] [Flexural Strength and Flexural Modulus of Cured Product of Dental Curable Composition] A polyester film was laid on a glass slide, and a stainless steel mold measuring 2 mm long, 25 mm wide, and 2 mm deep was placed on top of it. A mixture of the first and second parts of the dental curable composition of the present invention was then filled into the mold. The surface of the composition in the mold was pressed against a glass slide via the polyester film, and the two glass slides were secured together using a 25 mm-wide double clip. The sample secured with the double clip was left in an incubator at 37°C for 1 hour to polymerize and harden, after which the sample was removed from the incubator and the polymerized and cured composition was removed from the mold. The polymerized and cured product was immersed in distilled water at 37°C for 24 hours and then used as a test specimen for a bending test. Flexural strength was measured using a universal testing machine (Shimadzu Corporation, Autograph "AG-I 100kN"), performing a three-point bending test with a span of 20 mm and a crosshead speed of 1 mm / min. The average flexural strength of five test specimens was recorded as the flexural strength of the sample. The average value of the flexural modulus of the five test pieces was taken as the flexural modulus of that test piece.

[0129] [Table 1]

[0130] [Table 2]

[0131] As shown in Table 1, the dental hardenable compositions of the present invention (Examples 1 to 12) had an appropriate working time at 23°C immediately after preparation (in the table, "Working time at 23°C"), and resulted in excellent adhesive strength and bending strength to bovine dentin.

[0132] On the other hand, as shown in Table 2, in Comparative Examples 1 to 8, which used compositions in which a thiourea compound without a specific structure was used and the operation time was adjusted to an appropriate level, the adhesive strength and / or bending strength to bovine dentin was lower than in the Examples. [Industrial Applicability]

[0133] The dental curable composition of the present invention can be suitably used in dental treatment for bonding dental prostheses such as crowns, inlays and bridges to tooth structures, and for building abutments.

Claims

1. A polymerizable monomer (A) having an acidic group, a polymerizable monomer (B) not having an acidic group, a hydrophilic monomer (B) and a thiourea compound (D) represented by the following general formula (1): the polymerizable monomer (A) having an acidic group includes a polymerizable monomer having a phosphate group, The polymerizable monomer (B) having no acidic group has a solubility in water at 25°C of 10% by mass. The water-soluble polymerizable monomer (B-1) and a water-soluble polymerizable monomer (B-2) having a solubility of 10% by mass in water at 25°C. a hydrophobic polymerizable monomer (B-2) which is a crosslinkable polymerizable monomer of less than The hydroperoxide (C) is t-butyl hydroperoxide, cumene hydroperoxide, p-Diisopropylbenzene dihydroperoxide, 1,1,3,3-tetramethyl Butyl hydroperoxide, t-amyl hydroperoxide, p-menthane hydroperoxide oxide, p-isopropyl cumyl hydroperoxide, and diisopropyl benzene hydroperoxide A dental hardenable composition comprising at least one selected from the group consisting of hydroxyperoxides. 【Chemical 1】 (In the formula, A 1 and / or A 5 is a hydroxy group, an alkoxy group, an amino group, a dialkylamino group groups, and satisfying either (i) or (ii) below: (i) A 1 or A 5 is a hydroxy group, an alkoxy group, an amino group, or a dialkylamino group If either of them is true, the other A 1 or A 5 is a hydrogen atom, or (ii) A 1 and A 5 are each a hydroxy group, an alkoxy group, an amino group, or a dialkylamino group. Either A 2 ~A 4 are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an amino group, a diamine group, alkylamino group, hydrocarbon group, carboxy group, or halogen atom.

2. A 1 and / or A 5 is a hydroxy group, an amino group, or a dialkylamino group, Either (iii) or (iv) below is satisfied: (iii) A 1 or A 5 is a hydroxy group, an amino group, or a dialkylamino group. In this case, the other A 1 or A 5 is a hydrogen atom, or (iv) A 1 and A 5 are either a hydroxy group, an amino group, or a dialkylamino group; A 2 ~A 4 are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an amino group, a diamine group, 2. The compound according to claim 1, wherein the aryl group is an alkylamino group, a hydrocarbon group, a carboxy group, or a halogen atom. A dental hardenable composition.

3. A 1 and / or A 5 is a hydroxy group, and satisfies either (v) or (vi) below: death, (v) A 1 or A 5 is a hydroxy group, the other A 1 or A 5 is a hydrogen atom, or (vi) A 1 and A 5 are hydroxy groups; A 2 ~A 4 are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an amino group, a diamine group, 2. The dental curable composition according to claim 1, wherein the curable composition is an alkylamino group, a hydrocarbon group, or a halogen atom. composition.

4. The thiourea compound (D) is in powder form, and the dental hardenable composition contains the thiourea compound (D). The dental hardenable composition according to any one of claims 1 to 3, wherein the substance (D) is dispersed in the dental hardenable composition.

5. The dental composition according to any one of claims 1 to 4, further comprising a transition metal compound (E). Curable composition.

6. 6. The method according to claim 5, wherein the transition metal compound (E) is a copper compound or a vanadium compound. A dental hardenable composition.

7. Further containing a ligand compound (F), The ligand compound (F) comprises a ligand containing a phosphorus atom and a ligand containing a nitrogen atom. The compound according to any one of claims 1 to 6, which is at least one compound selected from the group consisting of Dental curable composition.

8. the ligand compound (F) is a ligand containing a phosphorus atom, The phosphorus atom-containing ligand is a compound represented by general formula (2), a compound represented by general formula (3), a compound represented by the general formula (4), and a compound represented by the following general formula (5):

8. The dental hardenable composition of claim 7, wherein the compound is at least one compound selected from the group consisting of: thing. 【Chemistry 2】 (R 1 ~R 15 each independently has a hydrogen atom, a halogen atom, a polar group, or a substituent represents an alkyl group which may have a substituent, or an alkoxy group which may have a substituent. 【Chemistry 3】 (R 16 ~R 35 each independently has a hydrogen atom, a halogen atom, a polar group, or a substituent. X represents an alkyl group which may have a substituent, or an alkoxy group which may have a substituent; 1 is a substituent represents a divalent aliphatic group which may have the formula: 【Chemistry 4】 (Each Ar independently represents a group represented by the following general formula (4-a).) 【Chemistry 5】 (Z 1 ~Z 3 are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an alkyl group or an alkoxy group which may have a substituent; Z 1 ~Z 3 At least one of One of them is a hydrogen atom.) P(OY 1 ) 3 (5) (Y 1 are each independently an alkyl group which may have a substituent, or represents an aryl group which may be

9. the ligand compound (F) is a ligand containing a nitrogen atom, The nitrogen atom-containing ligand is a compound represented by general formula (6), a compound represented by general formula (7), and a multidentate ligand containing a nitrogen-containing heterocycle (8). is one compound, The polydentate ligand (8) contains a heterocycle containing a 5- or 6-membered ring containing a nitrogen atom, and the molecule 8. The dental compound according to claim 7, which is a bidentate or higher ligand compound having two or more nitrogen atoms therein. Curable composition. R 36 R 37 N-X 2 -NR 38 R 39 (6) (R 36 ~R 39 each independently represents an alkyl group which may have a substituent, and X 2 teeth represents a divalent aliphatic group which may have a substituent. 【Chemistry 6】 (R 40 , R 41 , and R 42 each independently represents an alkyl group which may have a substituent. S, X 3 , and X 4 may each independently have a substituent, and may be an oxygen atom and / or represents a divalent aliphatic group which may contain a nitrogen atom, and m and n each independently represent 1. represents an integer equal to or greater than Y 2 is a monoalkylamino group or a dialkylamino group which may have a substituent. represents an amino group, and R 40 , R 41 , R 42 and Y 2 Any two or more of these together form a ring. It may be formed. 41 , R 42 , X 3 , and X 4 If there are multiple may be the same or different.)

10. The dental curable composition according to any one of claims 1 to 9, further comprising a filler (G). composition.

11. The adhesive composition according to any one of claims 1 to 10, which is a two-paste type adhesive comprising a first agent and a second agent. A dental hardenable composition.

12. The first agent is a polymerizable monomer (A) having an acidic group, a polymerizable monomer (B) having no acidic group, (B) and a hydroperoxide (C), The second agent is a polymerizable monomer (B) having no acidic group and a group represented by general formula (1) The dental hardenable composition according to claim 11, comprising an oleic acid compound (D).

13. The dental hardenable composition according to claim 11 or 12, which is a dental resin cement.

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