Dental hardening composition

Abstract

To provide a dental curable composition which is excellent in the mechanical strength of a cured material even when the pH is 7 or more.SOLUTION: A dental curable composition contains a polymerizable monomer (A) having no acidic group, a polymerization initiator (B), a transition metal compound (C), and a ligand compound (D), where the ligand compound (D) is at least one compound selected from the group consisting of ligands comprising phosphorus atoms and ligands comprising nitrogen atoms, and has a pH of 7 or more. Preferably, the ligands comprising phosphorus atoms are at least one compound selected from the group consisting of compounds represented by general formula (1), compounds represented by general formula (2), compounds represented by general formula (3), and compounds represented by general formula (4). Preferably, the ligands comprising nitrogen atoms are at least one compound selected from the group consisting of compounds represented by general formula (5), compounds represented by general formula (6), and multidentate ligands (7) comprising a nitrogen-containing heterocyclic ring.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a dental curable composition used for adhesion between dental prostheses such as crowns, inlays, and bridges and dental substances, abutment construction, etc. in dental treatment. More specifically, the present invention relates to a dental curable composition having excellent mechanical strength of a cured product in a state where the pH is 7 or higher.

Background Art

[0002] For the restorative treatment of defective parts of teeth damaged by dental caries, fracture, etc., adhesive materials or filling restorative materials are widely used. As adhesive materials and filling restorative materials used for tooth restoration, resin-based dental curable compositions composed of polymerizable monomers, polymerization initiators, fillers, etc. are widely used.

[0003] In order to polymerize and cure these dental curable compositions, a redox type polymerization initiator system composed 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, for example, packaged into a first agent containing the oxidizing agent and a second agent containing the reducing agent, and provided to a dentist who is a user in the state of the dental curable composition. Immediately before the dentist uses this dental curable composition, the first agent containing the oxidizing agent and the second agent containing the reducing agent are mixed, radicals are generated by a redox reaction, and the polymerization and curing of the dental curable composition proceed.

[0004] In recent years, a polymerization initiator system using an organic peroxide as an oxidizing agent has been proposed. For example, in Patent Document 1, a combination of an organic peroxide, an aryl borate compound, and a vanadium compound is used, and it is described that high adhesive strength to dental substances can be obtained.

[0005] Further, in Patent Document 2, a combination of an organic peroxide, a sulfinate, a vanadium compound, and an aromatic amine compound is used, and as a result, it is described that storage stability in which no significant delay occurs in the curing time even after long-term storage at room temperature or higher can be obtained.

Prior Art Documents

Patent Document

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] As a result of investigations by the present inventors, in the polymerization initiator systems of the dental curable compositions disclosed in Patent Documents 1 and 2, a polymerizable monomer containing an acidic group is included, and the pH after mixing is less than 7, and curing proceeds favorably. However, it was confirmed that there is room for improvement in curability under conditions where the pH is 7 or higher. On the other hand, as the functionality of dental curable compositions is enhanced, when imparting effects of promoting remineralization of tooth substance and promoting healing of dental pulp tissue, dental curable compositions need to contain a large amount of calcium-containing compounds or fluorides. When a large amount of calcium-containing compounds or fluorides are contained, the pH after mixing becomes 7 or higher, and good curability under such conditions is required. Therefore, it can be said that there is room for improvement in the mechanical strength of the cured product under the condition that the pH after mixing is 7 or higher in the polymerization initiator systems disclosed in Patent Documents 1 and 2.

[0008] Therefore, an object of the present invention is to provide a dental curable composition having excellent mechanical strength of the cured product even in a state where the pH is 7 or higher.

Means for Solving the Problems

[0009] As a result of intensive investigations by the present inventors, it has been found that the above problems can be solved by combining a polymerizable monomer having no acidic group, a polymerization initiator, a transition metal compound, and a predetermined ligand compound, and further investigations have been repeated to complete the present invention.

[0010] That is, the present invention includes the following inventions. [1] A dental curable composition containing a polymerizable monomer (A) having no acidic group, a polymerization initiator (B), a transition metal compound (C), and a ligand compound (D), wherein the ligand compound (D) is at least one compound selected from the group consisting of a ligand containing a phosphorus atom and a ligand containing a nitrogen atom, and the pH is 7 or higher. [2] The ligand compound (D) is a ligand containing a phosphorus atom, and the ligand containing a phosphorus atom is at least one compound selected from the group consisting of a compound represented by the following general formula (1), a compound represented by general formula (2), a compound represented by general formula (3), and a compound represented by general formula (4). The dental curable composition according to [1]. [Chemical formula] (R1 to R 15 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.) [Chemical formula] (R 16 to 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 represents a divalent aliphatic group which may have a substituent.) [Chemical formula] (Ar each independently represents a group represented by the following general formula (3-a).) [Chemical formula] (Z1 to Z3 each independently represents 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(4) (Y1 each independently represents an alkyl group which may have a substituent, or an aryl group which may have a substituent.) )( [3] The dental curable composition according to [2], wherein the ligand containing the phosphorus atom is a compound represented by the general formula (1). [4] The ligand compound (D) is a ligand containing a nitrogen atom, and the ligand containing the nitrogen atom is at least one compound selected from the group consisting of a compound represented by the general formula (5), a compound represented by the general formula (6), and a polydentate ligand (7) containing a nitrogen-containing heterocyclic ring, and the dental curable composition according to [1], wherein the polydentate ligand (7) contains a heterocyclic ring containing a 5-membered or 6-membered ring containing a nitrogen atom, has two or more nitrogen atoms in the molecule, and is a bidentate or higher polydentate ligand compound. R 36 R 37 N-X2-NR 38 R 39 (5) (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.)

Chemical formula

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

[11] The dental curable composition according to any one of [1] to

[10] , which is of the two-paste type.

[12] Subpackaged into a first agent and a second agent, the first agent contains a polymerizable monomer (A) having no acidic group and a polymerization initiator (B), The first agent and / or the second agent contain the transition metal compound (C) and the ligand compound (D), The dental curable composition according to any one of [1] to

[11] , wherein all of the polymerization initiator (B), the transition metal compound (C), and the ligand compound (D) do not coexist in either the first agent or the second agent.

[13] Either the first agent or the second agent further contains a polymerizable monomer having an acidic group, the content of the polymerizable monomer having an acidic group is more than 0 part by mass and 5 parts by mass or less in 100 parts by mass of the total amount of the polymerizable monomer component, or neither the first agent nor the second agent contains a polymerizable monomer having an acidic group, the dental curable composition according to

[12] .

Advantages of the Invention

[0011] According to the present invention, it is possible to provide a dental curable composition having excellent mechanical strength of the cured product even in a state where the pH is 7 or higher. Further, according to the present invention, a dental curable composition having a pH of 7 or higher containing a component that imparts an effect of promoting the remineralization of dental tissue and the healing of dental pulp tissue also has excellent mechanical strength.

Mode for Carrying Out the Invention

[0012] The dental curable composition of the present invention contains a polymerizable monomer (A) having no acidic group, a polymerization initiator (B), a transition metal compound (C), and a ligand compound (D). The ligand compound (D) is at least one compound selected from the group consisting of a ligand containing a phosphorus atom and a ligand containing a nitrogen atom, and the pH is 7 or higher.

[0013] Although the mechanism by which the dental curable composition of the present invention exhibits the effects of the present invention is not clear, it is presumed that the activity of the transition metal compound (C) is improved by the coordination of the ligand compound (D) to the transition metal compound (C) under the condition of pH 7 or higher, and the cured product has excellent mechanical strength by reacting with the polymerization initiator (B). Hereinafter, each of the components contained in the dental curable composition of the present invention will be described.

[0014] The dental curable composition of the present invention contains a polymerizable monomer (A) having no acidic group. The polymerizable monomer (A) having no acidic group is a polymerizable monomer in which a radical polymerization reaction proceeds by a polymerization initiator system to form a polymer. The polymerizable monomer constituting the polymerizable monomer (A) having no acidic group in the present invention is not limited to one kind and may be two or more kinds. As the polymerizable monomer (A) having no acidic group, the following hydrophilic polymerizable monomer (A-1) and hydrophobic polymerizable monomer (A-2) are preferably exemplified.

[0015] The hydrophilic polymerizable monomer (A-1) means a polymerizable monomer having a solubility in water at 25°C of 10% by mass or more. Those having a solubility of 30% by mass or more are preferred, and those soluble in water at any ratio at 25°C are more preferred. The hydrophilic polymerizable monomer (A-1) promotes the penetration of the components of the dental curable composition into dentin, and also penetrates into dentin and adheres to the organic components (collagen) in dentin. Examples of the hydrophilic polymerizable monomer (A-1) include monofunctional (meth)acrylic acid ester-based 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, 2-((meth)acryloyloxy)ethyltrimethylammonium chloride, etc.; bifunctional (meth)acrylic acid ester-based polymerizable monomers such as polyethylene glycol di(meth)acrylate (having 9 or more oxyethylene groups), etc. Among them, 2-hydroxyethyl (meth)acrylate is preferred. In this specification, "(meth)acryl" means acrylic and methacrylic, and expressions such as "(meth)acryloyl" and "(meth)acrylate" are the same. Examples of the bifunctional (meth)acrylic acid ester-based polymerizable monomers include polyethylene glycol di(meth)acrylate (having 9 or more oxyethylene groups), etc. Among them, 2-hydroxyethyl (meth)acrylate is preferred. In this specification, "(meth)acryl" means acrylic and methacrylic, and expressions such as "(meth)acryloyl" and "(meth)acrylate" are the same.

[0016] The hydrophobic polymerizable monomer (A-2) means a crosslinkable polymerizable monomer having a solubility in water at 25°C of less than 10% by mass. Examples of the crosslinkable polymerizable monomer (A-2) include aromatic compound-based monofunctional and bifunctional polymerizable monomers, aliphatic compound-based monofunctional and bifunctional polymerizable monomers, trifunctional or higher-functional polymerizable monomers, etc. The hydrophobic polymerizable monomer (A-2) improves the mechanical strength, handleability, etc. of the dental curable composition.

[0017] Examples of the aromatic compound-based monofunctional polymerizable monomer include benzyl (meth)acrylate, p-cumyl-phenoxyethylene glycol (meth)acrylate, 2-phenoxybenzyl (meth)acrylate, and the like. Among these, benzyl methacrylate and p-cumyl-phenoxyethylene glycol methacrylate are preferred.

[0018] Examples of the aromatic compound-based bifunctional polymerizable monomer include aromatic di(meth)acrylates. Specific examples of the aromatic compound-based bifunctional polymerizable monomer 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)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(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 added ethoxy groups: 2.6) (hereinafter sometimes abbreviated as "D-2.6E") are preferred.

[0019] Examples of aliphatic monofunctional polymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobornyl (meth)acrylate, 2-phenoxybenzyl (meth)acrylate, stearyl (meth)acrylate, dicyclopentanyl (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, and the like. Among these, isobornyl methacrylate is preferred.

[0020] Examples of the aliphatic compound-based bifunctional polymerizable monomer include bifunctional (meth)acrylic acid ester-based polymerizable monomers such as 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, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2,2,4-trimethylhexamethylene bis(2-carbamoyloxyethyl) dimethacrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane; (meth)acrylamide-based polymerizable monomers such as N-methacryloyloxyethyl acrylamide, N-methacryloyloxypropyl acrylamide, N-methacryloyloxybutyl acrylamide, N-(1-ethyl-(2-methacryloyloxy)ethyl) acrylamide, N-(2-(2-methacryloyloxyethoxy)ethyl) acrylamide. Among these, glycerol dimethacrylate, triethylene glycol di(meth)acrylate, neopentyl glycol dimethacrylate, 2,2,4-trimethylhexamethylene bis(2-carbamoyloxyethyl) dimethacrylate, and 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane are preferred.

[0021] Examples of the polymerizable monomer having trifunctionality or higher 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, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxaheptane, and the like.

[0022] Among the polymerizable monomers (A) having no acidic group, HEMA, Bis-GMA, D-2.6E, and TEGDMA are more preferable from the viewpoints of the adhesive strength and the polymerization curability of the dental curable composition of the present invention.

[0023] Any of the above polymerizable monomers (A) having no acidic group (hydrophilic polymerizable monomer (A-1) and hydrophobic polymerizable monomer (A-2)) may be contained alone or in combination of two or more. The content of the polymerizable monomer (A) containing no acidic group is not particularly limited as long as the effects of the present invention are exhibited. However, from the viewpoints that the composition has high penetrability into dentin and excellent adhesiveness and the cured product has sufficient mechanical strength, in 100 parts by mass of the total amount of the polymerizable monomer component in the dental curable composition of the present invention, the range of 50 to 99 parts by mass is preferable, the range of 60 to 98 parts by mass is more preferable, and the range of 70 to 95 parts by mass is even more preferable. In the present specification, "100 parts by mass of the total amount of the polymerizable monomer component in the dental curable composition" means the case where, when divided into a first agent and a second agent, the total of the polymerizable monomer contained in the first agent and the polymerizable monomer contained in the second agent is converted to 100 parts by mass.

[0024] Next, the polymerization initiator system will be described. The dental curable composition of the present invention contains a polymerization initiator (B), a transition metal compound (C), and a ligand compound (D) as the polymerization initiator system. The ligand compound (D) is at least one compound selected from the group consisting of a ligand containing a phosphorus atom and a ligand containing a nitrogen atom.

[0025] Examples of the polymerization initiator (B) of the present invention include organic peroxides and inorganic peroxides. Known chemical polymerization initiators can be used without particular limitation. The organic peroxide and the inorganic peroxide may each be blended alone or in combination of two or more. By blending the polymerization initiator (B), together with the transition metal compound (C) and the ligand compound (D), the dental curable composition is excellent in curability, mechanical strength of the cured product, etc.

[0026] Typical organic peroxides include diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy ketals, ketone peroxides, and hydroperoxides.

[0027] Specific examples of diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, and benzoyl peroxide.

[0028] As peroxyesters, any known ones can be used without any limitation as long as one of the peroxy groups (-OO- groups) has an acyl group and the other has a hydrocarbon group (or a similar group). Specific examples include α,α-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-bis(m-toluoylperoxy)hexane, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butyl peroxyacetate, t-butyl peroxy-m-toluoylbenzoate, t-butyl peroxybenzoate (hereinafter sometimes abbreviated as "BPB"), bis(t-butylperoxy)isophthalate, and the like. Among these, from the viewpoints of storage stability and reactivity, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, and t-butyl peroxyacetate are preferred, and t-butyl peroxybenzoate is more preferred.

[0029] Specific examples of dialkyl peroxides include α,α-bis(t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, t-butyl cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy) 3-hexyne, and the like.

[0030] Specific examples of peroxyketals include 1,1-bis(t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy) cyclohexane, 1,1-bis(t-butylperoxy) 3,3,5-trimethylcyclohexanone, 1,1-bis(t-butylperoxy) cyclohexane, 1,1-bis(t-butylperoxy) cyclodecane, 2,2-bis(t-butylperoxy) butane, n-butyl-4,4-bis(t-butylperoxy) valerate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl) propane, and the like.

[0031] Specific examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, and the like.

[0032] Specific examples of hydroperoxides include cumene hydroperoxide, t-butyl hydroperoxide, t-hexyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide (hereinafter sometimes abbreviated as "THP"), and the like.

[0033] Examples of the inorganic peroxide include peroxodisulfates and peroxodiphosphates. Among these, peroxodisulfates are preferred in terms of curability. Specific examples of peroxodisulfates include sodium peroxodisulfate, potassium peroxodisulfate (hereinafter sometimes abbreviated as KPS), aluminum peroxodisulfate, and ammonium peroxodisulfate.

[0034] Among the polymerization initiators (B), hydroperoxides and peroxy esters are particularly preferred. Among the hydroperoxides, t-butyl hydroperoxide, cumene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide are preferably used. Among the peroxy esters, t-butyl peroxybenzoate is preferably used.

[0035] The polymerization initiator (B) may be blended alone or in combination of two or more. From the viewpoints of curability, mechanical strength, and adhesion to dentin, the content of the polymerization initiator (B) is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the dental curable composition.

[0036] As the transition metal compound (C), a copper compound and / or a vanadium compound is preferably used. By coordinating the ligand compound (D) to the transition metal compound (C), the dental curable composition is excellent in curability, mechanical strength of the cured product, etc. The transition metal compound (C) may be used alone or in appropriate combination of two or more.

[0037] Examples of the copper compound include copper(II) carboxylate, copper(II) β-diketone, copper(II) β-ketoester, copper alkoxide, copper dithiocarbamate, salts of copper and inorganic acids, and the like. Examples of copper(II) carboxylate 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, copper(II) 4-cyclohexylbutyrate, and the like. Examples of copper(II) β-diketone include copper(II) acetylacetonate, copper(II) trifluoroacetylacetonate, copper(II) hexafluoroacetylacetonate, copper(II) 2,2,6,6-tetramethyl-3,5-heptanedionate, copper(II) benzoylacetonate, and the like. Examples of copper(II) β-ketoester include copper(II) ethyl acetoacetate, and the like. Examples of copper alkoxide include copper(II) methoxide , copper(II) ethoxide, copper(II) isopropoxide, copper(II) 2-(2-butoxyethoxy)ethoxide, copper(II) 2-(2-methoxyethoxy)ethoxide, and the like. Examples of copper dithiocarbamate include copper(II) dimethyldithiocarbamate, and the like. Examples of salts of copper and inorganic acids include copper(II) nitrate, copper(II) bromide, and copper(II) chloride. These may be used alone or in appropriate combinations of two or more. Among these, from the viewpoints of solubility and reactivity with the polymerizable monomer, copper(II) carboxylate, copper(II) β-diketone, and copper(II) β-ketoester are preferred, and copper(II) acetate and copper(II) acetylacetonate are particularly preferred.

[0038] The vanadium compound is preferably a tetravalent and / or pentavalent vanadium compound. Examples of the tetravalent and / or pentavalent vanadium compounds include compounds described in JP-A-2003-96122 such as vanadium(IV) dioxide, vanadyl acetylacetonate(IV), vanadyl oxalate(IV), vanadyl sulfate(IV), oxobis(1-phenyl-1,3-butanedionato)vanadium(IV), bis(maltolato)oxovanadium(IV), vanadium(V) pentoxide, sodium metavanadate(V), ammonium metavanadate(V), etc. The vanadium compound may be used alone or in appropriate combination of two or more kinds.

[0039] From the viewpoints of curability, mechanical strength, and adhesion to dentin, the content of the transition metal compound (C) is preferably in the range of 0.0001 to 1 part by mass, more preferably in the range of 0.0005 to 0.5 part by mass, and even more preferably in the range of 0.001 to 0.2 part by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the dental curable composition of the present invention.

[0040] The dental curable composition of the present invention contains a ligand compound (D) capable of coordinating to a metal. The ligand compound (D) is at least one compound selected from the group consisting of a ligand containing a phosphorus atom and a ligand containing a nitrogen atom. The ligand containing a phosphorus atom contains a phosphorus atom as a coordinating atom. The ligand containing a nitrogen atom contains a nitrogen atom as a coordinating atom. In a preferred embodiment, since the basicity of the paste of the obtained dental curable composition is increased and a higher pH is obtained, the ligand compound (D) includes a dental curable composition containing a ligand containing a nitrogen atom. In another preferred embodiment, since the basicity of the paste of the obtained dental curable composition is increased and a higher pH is obtained, the ligand compound (D) includes a dental curable composition containing a ligand containing a phosphorus atom and a ligand containing a nitrogen atom.

[0041] Examples of the ligand containing a phosphorus atom include a phosphine ligand and a phosphite ligand. Specific examples of the ligand containing a phosphorus atom include a compound represented by the following general formula (1), a compound represented by general formula (2), a compound represented by general formula (3), and a compound represented by general formula (4). The ligand containing a phosphorus atom may be used alone or in combination of two or more kinds.

[0042] [ka] (R1~R 15 each independently represents 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.

[0043] [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; X1 is a substituent represents a divalent aliphatic group which may have the following formula:

[0044] [ka] (Each Ar independently represents a group represented by the following general formula (3-a).)

[0045] [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.)

[0046] P(OY1)3(4) (Y1 each independently represents an alkyl group which may have a substituent, or an aryl group which may have a substituent.) (.)

[0047] R1 to R 15 The alkyl group which may have a substituent may be linear or branched. R1 to R 15 The number of carbon atoms of the alkyl group is not particularly limited, preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 3. Examples of the alkyl group of R1 to R 15 include methyl group, ethyl group, n-propyl group, isopropyl group, n- butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, n-hexyl group, isohexyl group, n-he ptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like. The alkyl group of R1 to R 15 may be unsubstituted. Examples of the substituent of the alkyl group of R1 to R 15 include halogen atom, hydroxy group, alkoxy group having 1 to 6 carbon atoms, amino group, monoalkylamino group or dialkylamino group having a linear or branched alkyl group having 1 to 6 carbon atoms, and the like.

[0048] R1 to R 15 Examples of the halogen atom of R1 to R include fluorine atom, chlorine atom, bromine atom, iodine atom. (.)

[0049] R1 to R 15 Examples of the polar group of R1 to R include acid anhydride group, carboxylic acid group, carboxylic acid ester group, ca Examples include a rubonic acid chloride group, a carboxylic acid amide group, a carboxylic acid group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid amide group, a sulfonic acid group, an aldehyde group, an epoxy group, a cyano group, an amino group, a monoalkyl-substituted amino group, a dialkyl-substituted amino group, an imide group, an oxazoline group, etc. From the viewpoints of curability and the mechanical strength of the cured product, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid chloride group, a carboxylic acid amide group, a carboxylic acid group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid amide group, a sulfonic acid group, an aldehyde group are preferable, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid chloride group, a carboxylic acid group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid group, an aldehyde group are more preferable, and a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid chloride group, a carboxylic acid group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid group are even more preferable. Examples of the salts of the carboxylic acid group and the sulfonic acid group include alkali metal salts such as lithium, sodium, and potassium; alkaline earth metal salts such as magnesium, calcium, strontium, barium, and radium, etc. R1~R 15 When it is a polar group of, the number of polar groups is preferably 1 to 9, more preferably 1 to 5 and even more preferably 1 to 3. R1~R 15 When it is an alkyl group having a substituent specific examples include a trifluoromethyl group, etc.

[0050] R1~R 15 The alkoxy group which may have a substituent of R1~R may be either linear or branched R1~R 15 The carbon number of the alkoxy group of R1~R is not particularly limited, preferably 1 to 12 , more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 to 3. R1 ~R 15 Examples of the alkoxy group of R1~R 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, an n-pentyloxy groups, isopentyloxy groups, sec-pentyloxy groups, tert-pentyloxy groups, neopentyloxy groups, n-hexyloxy groups, isohexyloxy groups, sec-hexyloxy groups, tert-hexyloxy groups, neohexyloxy groups, and the like. Substituents of the alkoxy groups of R1 to R are the same as those of the alkyl groups of R1 to R and include those mentioned above. 15 alkyl Substituents of the alkoxy groups of R1 to R 15 are the same as those of the alkyl groups of R1 to R .

[0051] R1 to R 15 may be the same or different. R1 to R 15 may, for example, partly be the same hydrogen atom, alkyl group, or alkoxy group.

[0052] R 16 to R 35 The alkyl group that may have substituents of R to R 15 is the same as the alkyl group that may have substituents of R1 to R . R 16 to R 35 The alkoxy group that may have substituents of R to R 15 is the same as the alkoxy group that may have substituents of R1 to R 16 to R 35 The halogen atoms of R to R 15 are the same as the halogen atoms of R1 to R 16 to R 35 The polar groups of R 15 to R

[0053] The divalent aliphatic group that may have substituents of X1 may be linear or branched. The number of carbon atoms of 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 ​Examples include an alkylene group, an alkenylene group, and an alkynylene group, with the alkylene group being 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, a dodecamethylene group, and the like. Examples of the substituent of the divalent aliphatic group of X1 include the same as those of the substituent of the alkyl group of R1 to R 15 and are the same as those of the substituent of the alkyl group of R.

[0054] In formula (3), the plurality of Ar may be the same or different. In the group represented by general formula (3-a), Z1 to Z3 may be the same or different. The alkyl group which may have a substituent of Z1 to Z3 is the same as the alkyl group which may have a substituent of R1 to R 15 and may have a substituent of R. At least one of Z1 to Z3 is a hydrogen atom, and all of Z1 to Z3 may be hydrogen atoms. Specific examples of Ar include, for example, the following groups. [Chemical formula]

[0055] In a certain 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, may be a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a fluorine atom, or may be a trifluoromethyl group. The alkoxy group which may have a substituent of Z1 to Z3 is the same as the alkoxy group which may have a substituent of R1 to R 15 and may have a substituent of R. In a certain preferred embodiment, examples of the phosphine compound include a compound represented by general formula (3) in which all Ar are 3,5-dimethylphenyl groups. In another preferred embodiment, examples of the phosphine compound include a compound represented by general formula (3) in which all Ar are 4-methylphenyl groups.

[0056] Regarding the phosphite ligand represented by the general formula (4), the three Y1s may be the same or may be different. The alkyl group which may have a substituent of Y1 is the same as the alkyl group which may have a substituent of R1 to R 15 . The carbon number of the aryl group which may have a substituent of Y1 is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10. Examples of the substituent of the aryl group of Y1 include the same ones as the substituent of the alkyl group of R1 to R . Examples of the aryl group which may have a substituent of Y1 include phenyl group, 15 biphenyl group, indenyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, pyrenyl group; phenyl group substituted with an alkyl group such as tolyl group, xylyl group, trimethylphenyl group, ethylphenyl group, isopropylphenyl group, tetramethylphenyl group, etc. A preferred embodiment includes a phosphite compound in which the three Y1s are 1,1,1,3,3 ,3-hexafluoro-2-propyl group. Another preferred embodiment includes a phosphite compound in which the three Y1s are 2,4,-di-tert-butylphenyl group.

[0057] A preferred embodiment includes a dental curable composition in which the ligand compound (D) is a compound represented by the general formula (1).

[0058] Examples of the monodentate phosphine ligand of the general formula (1) include triphenylphosphine (hereinafter, may be abbreviated as "TPP"), diphenyl(o-tolyl)phosphine, tri(o- Phosphine compounds having an electron-donating group such as trill) phosphine, tri(p-tolyl) phosphine, tris(2,4,6-trimethylphenyl) phosphine, tris(2,6-dimethylphenyl) phosphine, tris(2-methoxyphenylphosphine), tris(4-methoxyphenylphosphine) (hereinafter may be abbreviated as "TMOPP"), tris(2,6-dimethoxyphenyl) phosphine (hereinafter may be abbreviated as "DMPP"), diphenyl(2-methoxyphenyl) phosphine, 4-(dimethylamino) triphenylphosphine; (2-fluorophenyl) diphenylphosphine, (2-chlorophenyl) diphenylphosphine, (2-bromophenyl) diphenylphosphine, (pentafluorophenyl) diphenylphosphine, bis(pentafluorophenyl) phenylphosphine (hereinafter may be abbreviated as "BPFPP"), tris(pentafluorophenyl) phosphine (hereinafter may be abbreviated as "TPFPP"), tris(4-fluorophenyl) phosphine (hereinafter may be abbreviated as "TFPP"), tris(4-chlorophenyl) phosphine, tris(4-bromophenyl) phosphine, tris(4-trifluoromethylphenyl) phosphine, tris(4-carboxyphenyl) phosphine, sodium diphenylphosphinobenzene-3-sulfonate, trisodium triphenylphosphine-3,3',3''-trisulfonate and other phosphine compounds having an electron-withdrawing group.

[0059] Examples of the bidentate phosphine ligand of the general formula (2) 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, 1,2-bis[bis(pentafluorophenyl)-phosphino]ethane.

[0060] Examples of the bidentate phosphine ligand of the general formula (3) 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.

[0061] Examples of the phosphite ligand of the general formula (4) include trimethyl phosphite, triethyl phosphite, tris(1,1,1,3,3,3-hexafluoro-2-propyl) phosphite, triphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, and the like.

[0062] Examples of the ligand containing a nitrogen atom include, for example, a compound represented by the general formula (5), a compound represented by the general formula (6), and a polydentate ligand (7) containing a nitrogen-containing heterocyclic ring. The ligand containing a nitrogen atom may be used alone or in combination of two or more. In a preferred embodiment, the dental curable composition is such that the ligand containing a nitrogen atom is a compound represented by the general formula (5).

[0063] R 36 R 37 N-X2-NR 38 R 39 (5) (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.)

Chemical formula

[0064] The alkyl group which may have a substituent of R 36 ~R 39 is the same as the alkyl group which may have a substituent of R1~R 15 . The divalent aliphatic group which may have a substituent of X2 is the same as the divalent aliphatic group which may have a substituent of X1.

[0065] The divalent aliphatic group which may have a substituent of X2 is the same as the divalent aliphatic group which may have a substituent of X1.

[0066] The alkyl group which may have a substituent of R 40 , R 41 , and R 42 is the same as the alkyl group which may have a substituent of R1~R 15 . The carbon number of the alkyl group of the monoalkylamino group (-NHR (R a (R a represents an alkyl group)) and the dialkylamino group (-NR b R c (R b and R c represent an alkyl group)) of Y2 is not particularly limited, preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 3. The alkyl groups of the monoalkyl amino group and the dialkylamino group of Y2 are the same as those of R1~R15 which may have a substituent Among the alkyl groups which may have a substituent, those satisfying the above carbon number are included. As the dialkylamino group, each alkyl group may have the above carbon number. The substituent of Y2 Examples of the monoalkylamino group which may have a substituent of Y2 include methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, t-butylamino group, pentylamino group, hexylamino group and the like. The substituent of Y2 Examples of the dialkylamino group which may have a substituent of Y2 include dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, dipentylamino group, dihexylamino group, ethylmethylamino group. The alkyl groups of the monoalkylamino group and dialkylamino group of Y2 may be substituted with a substituent Examples of the substituent include the same ones as the substituent of the alkyl group of R1 to R 15 . In a certain preferred embodiment, Y2 is a dialkylamino group having two alkyl groups with 1 to 6 carbon atoms . In another certain preferred embodiment, in the compound represented by the general formula (6), R and R 40 and R 41 are unsubstituted alkyl groups with 1 to 3 carbon atoms, R 42 is an alkyl group with 1 to 3 carbon atoms substituted with a dialkylamino group having two alkyl groups with 1 to 3 carbon atoms, Y2 is an alkyl group with 1 to 3 carbon atoms substituted with a dialkylamino group having two alkyl groups with 1 to 3 carbon atoms , m and n are 1, and X3 and X4 are unsubstituted alkylene groups with 1 to 3 carbon atoms

[0067] The divalent aliphatic groups of X3 and X4 are the same as the divalent aliphatic groups which may have a substituent of X1, except that they may contain an oxygen atom and / or a nitrogen atom. X3 and X4 are They may be the same or different. The number of oxygen atoms and nitrogen atoms contained in the divalent aliphatic groups of X3 and X4 is 1 or more, and may be 2 or more. When the divalent aliphatic groups of X3 and X4 contain a nitrogen atom, the divalent aliphatic groups of X3 and X4 may contain -NH-, and -NR d -(R d represents an alkyl group having 1 to 6 carbon atoms) may be included.

[0068] m and n each independently represent an integer of 1 or more, preferably an integer of 1 to 6, more preferably an integer of 1 to 5, still more preferably an integer of 1 to 3, and particularly preferably 1 or 2. m and n may be the same or different.

[0069] R 40 、R 41 、R 42 and any two or more of Y2 may combine to form a ring if desired. For example, R 40 、R 41 、or R 42 and Y2 may combine to form a ring. In addition, R 40 and Y2, R 41 and R 42 may each combine to form a ring, and the compound may have two rings. Further, the nitrogen atom of the amino group of Y2 and R 40 may combine to form a ring . The ring may contain an oxygen atom and / or a nitrogen atom. Further, in another embodiment, the compound represented by the general formula (6) may be a compound having a bicyclo ring. For example, in one embodiment, in the compound represented by the general formula (6), the ring formed by combining Y2 and R 40 and the ring formed by combining R 41 or R 42 and Y2 may be a compound having a bicyclo ring.

[0070] In a preferred embodiment, in the compound represented by formula (6), 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.

[0071] In another preferred embodiment, the ligand compound (D) is a compound represented by general formula (6), and in the compound represented by general formula (6), 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; X3 and the divalent aliphatic group of X4 represents an alkylene group containing no oxygen or nitrogen atoms, m and n each independently represents an integer of 1 or more, and Y2 is a monocyclic group which may have a substituent. represents an alkylamino group or a dialkylamino group, R 40 , R 41 , or R 42 And Y2 are one The dental hardenable compositions include those which come together to form a ring.

[0072] In another preferred embodiment, the ligand compound (D) is a compound represented by general formula (6), and in the general formula (6), R 40 , R 41 , and R 42 each independently represents an alkyl group which may have a substituent, X3 and X4 each independently represent an alkylene group which does not contain an oxygen atom or a nitrogen atom, and Y2 is a monocyclic group which may have a substituent. Examples of dental hardenable compositions include a compound which represents an alkylamino group or a dialkylamino group, in which m is 1 and n is 2, and which contains four nitrogen atoms as a whole compound.

[0073] The polydentate ligand (7) containing the nitrogen-containing heterocyclic ring contains a heterocyclic ring including a 5-membered or 6-membered ring containing a nitrogen atom, has two or more nitrogen atoms in the molecule, and represents a ligand compound having two or more coordination sites. The number of nitrogen atoms that the polydentate ligand (7) has in the molecule is two or more, and may be three or more. The number of heterocyclic rings contained in the polydentate ligand (7) may be one, or may be two or more. Examples of the nitrogen-containing heterocyclic ring include nitrogen-containing 5-membered rings such as pyrrole ring, pyrazole ring, imidazole ring; nitrogen-containing 6-membered rings such as pyridine ring, pyrazine ring, pyridazine ring, piperazine ring, pyrimidine ring, triazine ring, etc. The nitrogen-containing heterocyclic ring may be a condensed ring of a 5-membered or 6-membered ring containing the nitrogen atom and another ring (for example, an aromatic ring), or may be a condensed ring of 5-membered or 6-membered rings containing the nitrogen atom. Examples of the condensed ring of a 5-membered or 6-membered ring containing the nitrogen atom and an aromatic ring include quinoline ring, isoquinoline ring, indole ring, benzimidazole ring, benzotriazole ring, etc. The polydentate ligand (7) only needs to contain a heterocyclic ring including a 5-membered or 6-membered ring containing a nitrogen atom. For example, ligand compounds containing a condensed ring such as indole ring, benzimidazole ring, benzotriazole ring and a heterocyclic ring including a 5-membered or 6-membered ring containing a nitrogen atom can be mentioned. The polydenticity of the polydentate ligand (7) only needs to be two or more, and may be tridentate, tetradentate, etc.

[0074] Examples of the polydentate amine ligand of the general formula (5) include bidentate coordination 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”), N,N,N’,N’-tetrakis(2-hydroxyethyl)ethylenediamine, etc.

[0075] Examples of the multi-dentate amine ligand of the general formula (6) 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-2,5,8,12-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"), tris[2-(dimethylamino)ethyl]amine (hereinafter sometimes abbreviated as "Me6TREN"), and other multi-dentate amine compounds such as compounds having no ring. Examples thereof include multi-dentate amine compounds.

[0076] Examples of the multi-dentate ligand (7) containing the nitrogen-containing heterocyclic ring include multi-dentate ligands having one nitrogen-containing heterocyclic ring such as N-(n-propyl)pyridylmethanimine and N-(n-octyl)pyridylmethanimine; multi-dentate ligands having two or more nitrogen-containing heterocyclic rings such as 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, 2,6-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, 2,4,6-tri(2-pyridyl)-1,3,5-triazine.

[0077] Among these, BPFPP, TPFPP, TMEDA, TMPDA, TEEDA, PMDETA, and Me6TREN are preferably used. The ligand compound (D) may be used alone or in combination of two or more. The ligand compound (D) is used to enhance the catalytic activity of the transition metal compound in the dental curable composition of the present invention. From the viewpoints of curability, mechanical strength, and adhesion to dental tissue, the content of the ligand compound (D) is preferably in the range of 0.001 to 10 parts by mass, more preferably in the range of 0.01 to 8 parts by mass, and even more preferably in the range of 1 to 6 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the dental curable composition of the present invention. The ligand compound (D) may be used alone or in combination of two or more. The ligand compound (D) is used to enhance the catalytic activity of the transition metal compound in the dental curable composition of the present invention. From the viewpoints of curability, mechanical strength, and adhesion to dental tissue, the content of the ligand compound (D) is preferably in the range of 0.001 to 10 parts by mass, more preferably in the range of 0.01 to 8 parts by mass, and even more preferably in the range of 1 to 6 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the dental curable composition of the present invention.

[0078] When only a pH adjuster is added to a composition that substantially contains a polymerizable monomer containing an acidic group and has a pH of less than 7 after mixing to make the pH 7 or more, instead of the multidentate ligand (7) containing the nitrogen-containing heterocycle, many inhibitory factors that do not contribute to polymerization promotion will be incorporated, resulting in a decrease in the mechanical strength of the cured product.

[0079] The dental curable composition of the present invention may further contain a filler (E) in order to obtain sufficient workability of the composition, sufficient radiopacity of the cured product, and mechanical strength.

[0080] As the filler (E), any filler can be used as long as the effects of the present invention are not impaired, and examples include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers. The filler (E) may be blended alone or in combination of two or more. The average particle size of the filler (E) is preferably 0.001 to 10 μm, and more preferably 0.001 to 5 μm.

[0081] Examples of inorganic fillers include silica; minerals based on silica such as kaolin, clay, mica, and mica; ceramics and glasses based on silica and containing Al2O3, B2O3, TiO2, ZrO2, BaO, La2O3, SrO, ZnO, CaO, P2O5, Li2O, Na2O, etc. Examples of glasses include lithium borosilicate glass, borosilicate glass, bioglass, lanthanum glass, barium glass, strontium glass, soda glass, zinc glass, and fluoroaluminosilicate glass. As inorganic fillers, crystalline quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride are also preferably used. In terms of adhesiveness and handleability, fine particle silica with an average particle diameter of 0.001 to 10 μm is preferably used. 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 product names manufactured by Nippon Aerosil Co., Ltd.). In the present invention, when the inorganic filler is surface-treated as described below, the average particle diameter of the inorganic filler means the average particle diameter before the surface treatment.

[0082] Examples of organic fillers include, for example, polymers of polymethyl methacrylate, polyethyl methacrylate, polyfunctional methacrylate, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.

[0083] Examples of composite fillers of inorganic fillers 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.

[0084] In order to improve the hardness, mechanical strength, and handleability, the filler (E) may be used after being surface-treated in advance with a known surface treatment agent such as a silane coupling agent. Examples of the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like. When surface-treated, the average particle size represents the average particle size of the particles before surface treatment.

[0085] The average particle size (average primary particle size) can be determined by the laser diffraction scattering method or electron microscope observation of the particles. Specifically, the laser diffraction scattering method is convenient for measuring the particle size of particles of 0.1 μm or more, and electron microscope observation is convenient for measuring the particle size of ultrafine particles of less than 0.1 μm. In the present invention, 0.1 μm is a value measured by the laser diffraction scattering method. The laser diffraction scattering method can be measured, for example, by using a 0.2% sodium hexametaphosphate aqueous solution as a dispersion medium and a laser diffraction particle size distribution measuring device (SALD-2300, manufactured by Shimadzu Corporation) based on volume. For electron microscope observation, a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, SU3800, S-4000, etc.) can be used. For electron microscope observation, an electron micrograph of the particles is taken, and the particle size of the particles (200 or more) observed within the unit visual field of the photograph is measured by using image analysis type particle size distribution measurement software (Mac-View (manufactured by Mount ck)). At this time, the particle size is obtained as the arithmetic mean value of the longest length and the shortest length of the particles, and the average primary particle size is calculated from the number of particles and their particle sizes.

[0086] The content of the filler (E) is not particularly limited as long as the effects of the present invention can be achieved. However, the range of 50 to 300 parts by mass is preferable, and the range of 100 to 250 parts by mass is more preferable with respect to 100 parts by mass of the polymerizable monomer of 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.

[0087] The dental curable composition of the present invention may further contain a calcium-containing compound (F). Examples of the calcium-containing compound (F) include calcium silicate and calcium salts. The calcium-containing compound (F) may be used alone or in combination of two or more. Calcium silicate is used to impart calcium ion sustained release property and induce the formation of dentin-like hard tissue in the exposed pulp. Examples of calcium silicate include tricalcium silicate, dicalcium silicate, and calcium silicate hydrate. Among these, tricalcium silicate is more preferably used in terms of calcium ion sustained release property. Calcium salts are used to assist the calcium ion sustained release property. As the calcium salt, calcium oxide, calcium hydroxide, calcium chloride, calcium carbonate, calcium sulfate, calcium sulfite, calcium phosphate, calcium pyrophosphate, etc. are preferably used. Calcium oxide and calcium hydroxide are particularly preferable because they have the ability to assist and enhance the calcium ion sustained release property and do not inhibit the polymerization curability.

[0088] The dental curable composition of the present invention may further contain a thiourea compound (G). Examples of the thiourea compound (G) include thiourea, methylthiourea, ethylthiourea, ethylene thiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, N,N'-dicyclohexylthiourea, N-acetylthiourea, N-benzoylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, tetracyclohexylthiourea, 1-(2-pyridyl)-2-thiourea, 4,4-dimethylethylene thiourea, diphenylthiourea, N-(6-methyl-2-pyridyl)-thiourea, 1-(2-(6-ethylpyridyl))-2-thiourea, 1-(2-(6-methoxypyridyl))-2-thiourea, 1-(2-(6-chloropyridyl))-2-thiourea, 1-(2-(5-methylpyridyl))-2-thiourea, 1-(2-(5-ethylpyridyl))-2-thiourea, 1-(2-(5-methoxypyridyl))-2-thiourea, 1-(2-(5-chloropyridyl))-2-thiourea, 1-(2-(5-fluoropyridyl))-2-thiourea, 1-(2-(5,6-dimethylpyridyl))-2-thiourea, 4-methyl-2-imidazolidinethione, 4,4-dimethyl-2-imidazolidinethione, 4-ethyl-2-imidazolidinethione, and 4,4-diethyl-2-imidazolidinethione, etc.

[0089] Any of the thiourea compounds (G) may be used alone, or two or more thereof may be used in combination. From the viewpoint of curability, the blending amount of the thiourea compound (G) is preferably in the range of 0.05 to 5 parts by mass, more preferably in the range of 0.1 to 3 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer component in the dental curable composition.

[0090] The dental curable composition of the present invention may further contain a polymerizable monomer having an acidic group within a range that does not become less than pH 7. In a certain preferred embodiment, there is provided a dental curable composition that further contains a polymerizable monomer having an acidic group, and the content of the polymerizable monomer having an acidic group is more than 0 part by mass and 5 parts by mass or less in 100 parts by mass of the total amount of the polymerizable monomer component. In another preferred embodiment, from the viewpoint of being easy to adjust the pH to 7 or more, there is provided a dental curable composition that does not contain a polymerizable monomer having an acidic group. In another preferred embodiment, from the viewpoint of being easy to adjust the pH to 7 or more, there is provided a dental curable composition that substantially does not contain a polymerizable monomer having an acidic group. "Substantially does not contain a polymerizable monomer having an acidic group" means that in 100 parts by mass of the total amount of the polymerizable monomer component in the dental curable composition, the content of the polymerizable monomer having an acidic group is less than 1 part by mass, preferably less than 0.5 part by mass, more preferably less than 0.1 part by mass, and even more preferably less than 0.01 part by mass.

[0091] The polymerizable monomer having an acidic group is a polymerizable monomer having at least one acidic group and at least one polymerizable group such as an acryloyl group, a methacryloyl group, an acrylamide group, or a methacrylamide group. In the present invention, examples of the acidic group include a phosphoric acid group, a phosphonic acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a carboxylic acid group, and a sulfonic acid group. From the viewpoint of adhesion to dentin, the polymerizable monomer having an acidic group is preferably monofunctional having any one of an acryloyl group, a methacryloyl group, an acrylamide group, or a methacrylamide group as a polymerizable group. Specific examples include the following.

[0092] Examples of the polymerizable monomer having a phosphate group include monofunctional (meth)acrylate compounds having a phosphate group such as 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, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-(4-methoxyphenyl) hydrogen phosphate, 2-(meth)acryloyloxypropyl-(4-methoxyphenyl) hydrogen phosphate, their acid chlorides, alkali metal salts, ammonium salts, and amine salts;Bifunctional (meth)acrylate compounds having a phosphate group such as bis[2-(meth)acryloyloxyethyl] hydrogen phosphate, bis[4-(meth)acryloyloxybutyl] hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl] hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl] hydrogen phosphate, bis[9-(meth)acryloyloxynonyl] hydrogen phosphate, bis[10-(meth)acryloyloxydecyl] hydrogen phosphate, 1,3-di(meth)acryloyloxypropyldihydrogen phosphate, their acid chlorides, alkali metal salts, ammonium salts, and amine salts, etc. are included.;

[0093] Examples of the polymerizable monomer having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl phosphonoacetate, 10-(meth)acryloyloxydecyl phosphonoacetate, their acid chlorides, alkali metal salts, ammonium salts, and amine salts, etc. are included.

[0094] Examples of the polymerizable monomer 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, their acid chlorides, alkali metal salts, ammonium salts, and amine salts, etc. are included.

[0095] Examples of the polymerizable monomer having a thiophosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogen thiophosphate, 3-(meth)acryloyloxypropyl dihydrogen thiophosphate, 4-(meth)acryloyloxybutyl dihydrogen thiophosphate, 5-(meth)acryloyloxypentyl dihydrogen thiophosphate, 6-(meth)acryloyloxyhexyl dihydrogen thiophosphate, 7-(meth)acryloyloxyheptyl dihydrogen thiophosphate, 8-(meth)acryloyloxyoctyl dihydrogen thiophosphate, 9-(meth)acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, 20-(meth)acryloyloxyeicosyl dihydrogen thiophosphate, and acid chlorides, alkali metal salts, ammonium salts, etc. thereof.

[0096] Examples of the polymerizable monomer having a carboxylic acid group include (meth)acrylic acid, 4-[2-[(meth)acryloyloxy]ethoxycarbonyl]phthalic acid, 4-(meth)acryloyloxyethyl trimellitic acid, 4-(meth)acryloyloxybutyloxycarbonyl phthalic acid, 4-(meth)acryloyloxyhexyloxycarbonyl phthalic acid, 4-(meth)acryloyloxyoctyloxycarbonyl phthalic acid, 4-(meth)acryloyloxydecyloxycarbonyl phthalic acid, and acid anhydrides thereof; 5-(meth)acryloylaminopentyl carboxylic 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, acid chlorides, alkali metal salts, ammonium salts, amine salts, etc. thereof.

[0097] Examples of the polymerizable monomer having a sulfonic acid group include 2-(meth)acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate, their acid chlorides, alkali metal salts, ammonium salts, and amine salts.

[0098] Among the polymerizable monomers having the acidic group, polymerizable monomers having a phosphate group, a pyrophosphate group, and a carboxylic acid group are preferable because they exhibit better adhesiveness to dentin. In particular, polymerizable monomers having a phosphate group and polymerizable monomers having a carboxylic acid group are preferable. Among them, (meth)acrylate-based monofunctional polymerizable monomers having a phosphate group having an alkyl group of C6~ C 20 or an alkylene group of C6~C 20 in the molecule are more preferable, and (meth)acrylate-based polymerizable monomers having a phosphate group having an alkylene group of C8~C in the molecule are even more preferable. Also, 10-methacryloyloxydecyl dihydrogen phosphate, 4-(meth)acryloyloxyethyl trimellitic acid, and 4-(meth)acryloyloxyethyl trimellitic 12 anhydride are preferable, and 10-methacryloyloxydecyl dihydrogen phosphate is most preferable. The dental curable composition of the present invention contains a redox type polymerization initiator. However, in order to make it a dual cure type composition that also starts polymerization by light irradiation, or in order to make it a kit with a dental adhesive that starts polymerization by light irradiation, a conventionally known photoinitiator system may be further contained in the dental curable composition as a component different from the above polymerization initiator system. The dental curable composition of the present invention contains a redox type polymerization initiator. However, in order to make it a dual cure type composition that also starts polymerization by light irradiation, or in order to make it a kit with a dental adhesive that starts polymerization by light irradiation, a conventionally known photoinitiator system may be further contained in the dental curable composition as a component different from the above polymerization initiator system.

[0099] The dental curable composition of the present invention contains a redox type polymerization initiator. However, in order to make it a dual cure type composition that also starts polymerization by light irradiation, or in order to make it a kit with a dental adhesive that starts polymerization by light irradiation, a conventionally known photoinitiator system may be further contained in the dental curable composition as a component different from the above polymerization initiator system.

[0100] Examples of the photoinitiator system include α-diketones, ketals, thioxanthones, (bis)acylphosphine oxides, and α-aminoacetophenones.

[0101] Examples of α-diketones include, for example, dl-camphorquinone (hereinafter sometimes abbreviated as "CQ"), benzil, and 2,3-pentanedione.

[0102] Examples of ketals include, for example, benzyldimethyl ketal and benzyldiethyl ketal.

[0103] Examples of thioxanthones include, for example, 2-chlorothioxanthone and 2,4-diethylthioxanthone.

[0104] Among the above-mentioned (bis)acylphosphine oxides, examples of 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, the water-soluble acylphosphine oxide compound disclosed in Japanese Patent Publication No. 3-57916, and salts thereof (e.g., sodium salt, potassium salt, ammonium salt), etc. 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 salt, potassium salt, ammonium salt), etc. Among these (bis)acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and sodium 2,4,6-trimethylbenzoylphenylphosphine oxide are preferred.

[0105] Examples of α-aminoacetophenones include, for example, 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-dimethyl amino-1-(4-morpholinophenyl)-1-pentanone, and 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)-1-pentanone.

[0106] In addition, in the dental curable composition of the present invention, a photopolymerization initiator and a polymerization accelerator for the photopolymerization initiator may be used in combination to enhance the photocurability. Further, the polymerization initiator (B) may be used in combination with a polymerization accelerator. Examples of the polymerization accelerator used together with the polymerization initiator (B) and / or the photopolymerization initiator include tertiary amines, aldehydes, thiol compounds, triazine compounds substituted with a trihalomethyl group, sulfinic acids, benzotriazole compounds, benzimidazole compounds, sulfites, bisulfites, borate compounds, barbituric acid compounds, and the like. The polymerization accelerator may be used alone or in combination of two or more.

[0107] Examples of the tertiary amines include aromatic tertiary amines such as N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(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, 2-(methacryloyloxy)ethyl 4-(N,N-dimethylamino)benzoate, ethyl 4-(N,N-dimethylamino)benzoate, butyl 4-(N,N-dimethylamino)benzoate, 4-(N,N-dimethylamino)benzophenone; and aliphatic tertiary amines such as N-methyldiethanolamine, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-n-butyldiethanolamine, N-lauryl diethanolamine, 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.

[0108] Examples of the aldehydes include terephthalaldehyde, benzaldehyde derivatives and the like. Examples of the benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, p-n-octyloxybenzaldehyde and the like. Examples of the thiol compounds include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, decanethiol, thiobenzoic acid and the like. As the triazine compound substituted with a trihalomethyl group, any known compound can be used without any limitation as long as it is an s-triazine compound having at least one trihalomethyl group such as a trichloromethyl group or a tribromomethyl group.

[0109] Examples of the sulfinic acids include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, benzen Calcium sulfinate, 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-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, and the like can be mentioned. Among these, sodium benzenesulfinate, sodium p-toluenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, and sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferred.

[0110] Examples of the benzotriazole compound include 1H-benzotriazole (hereinafter sometimes abbreviated as "BTA"), 5-methyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazole, and the like. Examples of the benzimidazole compound include benzimidazole, 5-methylbenzimidazole, 5,6-dimethylbenzimidazole, and the like. Examples of the sulfite include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, and the like. Examples of the bisulfite include sodium bisulfite, potassium bisulfite, and the like. Examples of the borate compound include aryl borate compounds having 1 to 4 aryl groups in one molecule (for example, tetraphenylboron, tetrakis(p-chlorophenyl)boron, etc.) and salts thereof. Examples of the barbituric acid compound 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 blending a fluoride ion-releasing substance, a dental cement capable of imparting acid resistance to dental tissue can be obtained. Examples of the fluoride ion-releasing substance include fluoride ion-releasing polymers such as copolymers of methyl methacrylate and methacrylic fluoride; hydrogen fluoride salts of aliphatic or alicyclic primary, secondary or tertiary amines such as cetylamine hydrogen fluoride salt, cyclohexylamine hydrogen fluoride salt, diisobutylamine hydrogen fluoride salt, triethylamine trihydrogen fluoride salt; metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, ytterbium fluoride, and the like. The fluoride ion-releasing substance may be used alone or in combination of two or more.

[0112] In addition, in the dental curable composition of the present invention, a polymerization inhibitor, a pH adjuster, an ultraviolet absorber, an organic solvent, a solvent such as water, a thickener, a colorant, an antibacterial agent, a fragrance, etc. may be blended as long as the effects of the present invention are not inhibited. These may be blended individually by one type or in combination of two or more types. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, etc. The content of the polymerization inhibitor is preferably 0.001 to 1.0 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomers in the dental curable composition. Examples of the pH adjuster include the tertiary amines exemplified as the polymerization accelerator for the photopolymerization initiator (for example, N-methyldiethanolamine, triethanol amine, etc.). In one embodiment, the content of the solvent (for example, water, organic solvent) 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 mass of the dental curable composition. In another embodiment, from the viewpoint of achieving the effects of the present invention, the dental curable composition preferably contains substantially no water. That the dental curable composition contains substantially no water means that the water content is preferably 1% by mass or less, more preferably 0.1% by mass or less, even more preferably 0.01% by mass or less, and may even be 0% by mass with respect to the total mass of the dental curable composition.

[0113] The dental curable composition of the present invention may be prepared according to a conventional method according to the above-mentioned components. The dental curable composition of the present invention is used in the form of a two-component type and can be appropriately selected and implemented from forms such as a powder material and a liquid material, a paste and a liquid material, and a two-paste type. However, from the viewpoint of operability, in a more preferable embodiment, it is used in the form of a two-paste type. It is preferable to store each paste in a state where the pastes are isolated from each other, and immediately before use, knead the two pastes to allow chemical polymerization to proceed and cure. The paste is usually prepared by kneading a liquid component prepared by mixing components other than the filler (E) and the filler (E) (powder).

[0114] The two-paste type dental curable composition of the present invention is packaged into a first agent and a second agent. The first agent contains a polymerizable monomer (A) having no acidic group and a polymerization initiator (B). And / or the second agent contains a transition metal compound (C) and a ligand compound (D). It is preferable that all of the polymerization initiator (B), the transition metal compound (C), and the ligand compound (D) do not coexist in either the first agent or the second agent. As a certain preferred embodiment, either the first agent or the second agent further contains a polymerizable monomer having an acidic group, and the content of the polymerizable monomer having an acidic group is more than 0 part by mass and 5 parts by mass or less in 100 parts by mass of the total amount of the polymerizable monomer component, or neither the first agent nor the second agent contains a polymerizable monomer having an acidic group. Examples of the dental curable composition include those. As another certain preferred embodiment, there is provided the two-paste type dental curable composition in which the first agent and the second agent substantially do not contain a polymerizable monomer having an acidic group.

[0115] The dental curable composition of the present invention is used for adhesion between a dental prosthesis such as a crown, inlay, or bridge and dentin, abutment construction, etc. to a defect part of a tooth affected part. In particular, it is preferably used as a dental resin cement.

[0116] The present invention includes embodiments in which the above configurations are variously combined within the scope of the technical idea of the present invention as long as the effects of the present invention are achieved.

Examples

[0117] Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The abbreviations and symbols used hereinafter are as follows. Compounds and fillers used in the following Examples and Comparative Examples were commercial products, unless otherwise specified for the production method.

[0118] [Polymerizable monomer having an acidic group] MDP: 10-Methacryloyloxydecyl dihydrogen phosphate

[0119] [Polymerizable monomer (A) having no acidic group] HEMA: 2-Hydroxyethyl methacrylate Bis-GMA: 2,2-Bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane D-2.6E: 2,2-Bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of added moles of ethoxy group is 2.6) TEGDMA: Triethylene glycol dimethacrylate

[0120] [Polymerization initiator (B)] THP: 1,1,3,3-Tetramethylbutyl hydroperoxide BPB: t-Butyl peroxybenzoate

[0121] [Inorganic peroxide] KPS: Potassium peroxydisulfate

[0122] [Transition metal compound (C)] CuA: Copper(II) acetate VOAA: Vanadyl acetylacetonate(IV)

[0123] [Ligand compound (D)] BPFPP: Bis(pentafluorophenyl)phenylphosphine TPFPP: Tris(pentafluorophenyl)phosphine PPh3: Triphenylphosphine TEEDA: Tetraethylethylenediamine TMPDA: Tetramethylpropylenediamine

[0124] 〔Filler (E)〕 Surface-treated Ba glass powder: Barium glass (manufactured by Estec Co., Ltd., product code "E-3000") was pulverized by a ball mill to obtain barium glass powder. When the average particle diameter of the obtained barium glass powder was measured by volume basis using a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation, model "SALD-2300"), it was 2.4 μm. The surface of 100 parts by mass of this barium glass powder was 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 diameter: 16 nm Alumina: Aluminum oxide, manufactured by Nippon Aerosil Co., Ltd., trade name "AEROXIDE (registered trademark) Alu C", average particle diameter: 20 nm

[0125] 〔Calcium-containing compound (F)〕 Tricalcium silicate: Ca3SiO5 Calcium oxide: CaO

[0126] 〔Thiourea compound (G)〕 PyTU: 1-(2-Pyridyl)-2-thiourea 6MPyTU: N-(6-Methyl-2-pyridyl)-thiourea 5FPyTU: 1-(2-(5-Fluoropyridyl))-2-thiourea

[0127] 〔pH adjuster〕 TTA: Triethanolamine

[0128] 〔Polymerization inhibitor〕 BHT: 2,6-Di-t-butyl-4-methylphenol

[0129] [Polymerization accelerator] DEPT: N,N-Bis(2-hydroxyethyl)-p-toluidine TPSS: 2,4,6-Triisopropylbenzenesulfinic acid Sodium sulfite: Na2SO3 BTA: 1H-Benzotriazole

[0130] (Examples 1 - 15 and Comparative Examples 1 - 5) Among the components described in Tables 1 and 2, the components other than the filler were mixed at room temperature to form a uniform liquid component, and then the obtained liquid component and the filler were kneaded to prepare the dental curable compositions of Examples 1 - 15 and Comparative Examples 1 - 5. Next, using these dental curable compositions, according to the method described below, the pH of the paste after kneading, the flexural strength of the cured product, and the flexural modulus were measured. Tables 1 and 2 show the compounding ratios (parts by mass) and test results of this dental curable composition.

[0131] [Table 1]

[0132] [Table 2]

[0133] [pH of the paste after mixing] The mixture of the first agent and the second agent of the dental curable composition of the present invention was applied to a moistened pH test paper (Universal Indikatorpapier pH 1 - 14), and the pH of the paste after mixing was visually observed. When it is difficult to determine whether the pH is 7 or higher, it may be measured using Johnson Test Papers Comparator Paper pH6.4 - 8.0 pH Paper. The average value of the results of three pH measurements of the paste was taken as the pH of the paste after mixing.

[0134] [Flexural Strength and Flexural Modulus during Chemical Curing of the Hardened Product of the Dental Curable Composition] A polyester film was laid on a slide glass plate, and a stainless steel mold with a length of 2 mm, a width of 25 mm, and a depth of 2 mm was placed thereon. Next, the mixture of the first agent and the second agent of the dental curable composition of the present invention was filled into the mold, the surface of the composition in the mold was pressure-bonded with a slide glass through the polyester film, and the two slide glasses were fixed using a double clip with a width of 25 mm. The sample fixed with the double clip was allowed to stand in a thermostat at 37°C for 1 hour for polymerization curing, then the sample was taken out from the thermostat, and the polymerized cured product of the composition was removed from the mold. After the polymerized cured product was immersed in distilled water at 37°C for 24 hours for storage, a bending test was performed using this as a test piece. The flexural strength was measured by performing a three-point bending test with a support span of 20 mm and a crosshead speed of 1 mm / min using a universal testing machine (manufactured by Shimadzu Corporation, Autograph "AG-I 100kN"). The average value of the flexural strengths of 5 test pieces was taken as the flexural strength of the test piece. Also, the average value of the flexural moduli of 5 test pieces was taken as the flexural modulus of the test piece.

[0135] As shown in Tables 1 and 2, in the case where the pH of the paste after mixing of the dental curable composition of the present invention (Examples 1 to 15) is 7 or more, the flexural strength of the hardened product is 80 MPa or more, and the flexural modulus is 5.0 GPa or more, which is an excellent result. In particular, even in the case of the dental curable composition containing the calcium-containing compound (F) component that imparts the effect of promoting the remineralization of dental tissue and the healing of pulp tissue shown in Example 15, the flexural strength was 80 MPa and the flexural modulus was 5.0 GPa, which is an excellent result. In Comparative Examples 1 to 3, although the paste pH after mixing is 7 or more, the flexural strength is very low or uncured. In Comparative Examples 4 and 5, the flexural strength is 80 MPa or more, but it is the performance obtained by the functioning of the polymerization initiator system in the composition because the pH of the paste after mixing is less than 7. When the pH after mixing in Comparative Examples 4 and 5 is set to 7 or more, the curability decreases, so data similar to those with a pH less than 7 cannot be obtained. [Industrial Applicability]

[0136] The curable dental composition of the present invention can be suitably used for adhesion between dental prostheses such as crowns, inlays, and bridges and tooth substance, and for abutment construction, etc. in dental treatment.

Claims

1. It contains a polymerizable monomer (A) having no acidic group and a polymerization initiator system, does not contain an ascorbic acid component, the polymerization initiator system contains a polymerization initiator (B), a transition metal compound (C), and a ligand compound (D), the transition metal compound (C) is a copper compound and / or a vanadium compound, the ligand compound (D) is at least one compound selected from the group consisting of a ligand containing a phosphorus atom and a ligand containing a nitrogen atom, the ligand containing a phosphorus atom is at least one compound selected from the group consisting of a compound represented by the following general formula (1), a compound represented by general formula (2), a compound represented by general formula (3), and a compound represented by general formula (4), 【Chemical Formula 1】 (R1 to R15 each independently represent 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.) 【Chemical Formula 2】 (R16 to R35 each independently represent 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 represents a divalent aliphatic group which may have a substituent.) [Chemical Formula 3] (Ar each independently represents a group represented by the following general formula (3-a).) 【Chemical Formula 4】 (Z1 to Z3 each independently are 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 (4) (Y1 each independently represents an alkyl group which may have a substituent, or an aryl group which may have a substituent.) the ligand containing a nitrogen atom is at least one compound selected from the group consisting of a compound represented by general formula (5), a compound represented by general formula (6), and a polydentate ligand (7) containing a nitrogen-containing heterocyclic ring, the polydentate ligand (7) contains a heterocyclic ring containing a 5-membered or 6-membered ring containing a nitrogen atom, has two or more nitrogen atoms in the molecule, and is a bidentate or more ligand compound, A dental curable composition having a pH of 7 or higher. R36R37N-X2-NR38R39 (5) (R36 to R39 each independently represent an alkyl group which may have a substituent, and X2 represents a divalent aliphatic group which may have a substituent.) 【Chemical Formula 5】 (R40, R41, and R42 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 may contain an oxygen atom and / or a nitrogen atom, 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 any two or more of R40, R41, R42, and Y2 may combine to form a ring. When there are a plurality of R40, R41, X3, and X4, they may be the same or different from each other.)

2. The ligand compound (D) is a ligand containing a phosphorus atom, The ligand containing a phosphorus atom is at least one compound selected from the group consisting of a compound represented by the following general formula (1), a compound represented by general formula (2), a compound represented by general formula (3), and a compound represented by general formula (4). The dental curable composition according to claim 1. 【Chemical 1】 (R 1 ~ R 15 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.) 【Chemical Formula 2】 (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 X 1 represents a divalent aliphatic group which may have a substituent.) 【Chemical Formula 3】 (Ar each independently represents a group represented by the following general formula (3-a).) [Chemical Formula 4] (Z 1 to Z 3 are each independently 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 Z 1 to Z 3 is a hydrogen atom.) P(OY 1 ) 3 (4) (Y 1 each independently represents an alkyl group which may have a substituent or an aryl group which may have a substituent.)

3. The ligand containing a phosphorus atom is a compound represented by general formula (1). The dental curable composition according to claim 1.

4. The ligand compound (D) is a ligand containing a nitrogen atom, The ligand containing a nitrogen atom is at least one compound selected from the group consisting of a compound represented by general formula (5), a compound represented by general formula (6), and a multidentate ligand (7) containing a nitrogen-containing heterocyclic ring, The multidentate ligand (7) contains a heterocyclic ring containing a 5-membered or 6-membered ring containing a nitrogen atom, has two or more nitrogen atoms in the molecule, and is a bidentate or higher multidentate ligand compound. The dental curable composition according to claim 1. R 36 R 37 N−X 2 −NR 38 R 39 (5) (R 36 ~R 39 each independently represents an alkyl group which may have a substituent, and X 2 represents a divalent aliphatic group which may have a substituent.) 【Chemical Formula 5】 (R 40 , R 41 , and R 42 each independently represents an alkyl group which may have a substituent, X 3 , and X 4 each independently represents a divalent aliphatic group which may have a substituent and may contain an oxygen atom and / or a nitrogen atom, m and n each independently represent an integer of 1 or more, Y 2 represents a monoalkylamino group or a dialkylamino group which may have a substituent, R 40 , R 41 , R 42 and Y 2 among any two or more of them may combine together to form a ring. R 40 , R 41 , X 3 and X 4 may be the same or different from each other when there are a plurality of them.)

5. The ligand containing a nitrogen atom is a compound represented by the above general formula (5). The dental curable composition according to claim 1.

6. The copper compound is at least one selected from the group consisting of copper(II) carboxylate, copper(II) β-diketone, copper(II) β-ketoester, copper alkoxide, copper dithiocarbamate, and salts of copper with inorganic acids, The vanadium compound is a tetravalent and / or pentavalent vanadium compound. The dental curable composition according to any one of claims 1 to 5.

7. The dental curable composition according to any one of claims 1 to 6, which further contains a polymerizable monomer having an acidic group, and the content of the polymerizable monomer having an acidic group is more than 0 part by mass and 5 parts by mass or less in 100 parts by mass of the total amount of the polymerizable monomer components, or which does not contain a polymerizable monomer having an acidic group.

8. The dental curable composition according to any one of claims 1 to 7, which further contains a filler (E).

9. The dental curable composition according to any one of claims 1 to 8, which further contains a calcium-containing compound (F).

10. The dental curable composition according to any one of claims 1 to 9, which further contains a thiourea compound (G).

11. The dental curable composition according to any one of claims 1 to 10, which is of a two-paste type.

12. It is sub-packaged into a first agent and a second agent. The first agent contains a polymerizable monomer (A) having no acidic group and a polymerization initiator (B). The first agent and / or the second agent contains the transition metal compound (C) and the ligand compound (D). The dental curable composition according to any one of claims 1 to 11, wherein all of the polymerization initiator (B), the transition metal compound (C), and the ligand compound (D) do not coexist in either the first agent or the second agent.

13. Either the first agent or the second agent further contains a polymerizable monomer having an acidic group, and the content of the polymerizable monomer having an acidic group is more than 0 part by mass and 5 parts by mass or less in 100 parts by mass of the total amount of the polymerizable monomer components, or neither the first agent nor the second agent contains a polymerizable monomer having an acidic group. The dental curable composition according to claim 12.

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