Paste-like two-component dental curable composition

Abstract

To provide a pasty two-part dental curable composition that has an operation time within a reasonable range, is excellent in the strength of adhesion to noble metal and dentin, hardly deteriorates in the strength of adhesion to dentin during long-term storage, and exhibits low solidification risk of the paste, and low variation of the curing time.SOLUTION: A pasty two-part dental curable composition contains: a first agent containing a polymerizable monomer (A) containing an acidic group, a polymerizable monomer (B) having no acidic group, an organic peroxide (C), a filler (D), and a ligand (G) comprising a nitrogen atom; and a second agent containing the polymerizable monomer (B) having no acidic group, the filler (D), and an ascorbic acid compound (F), and containing substantially no thiourea compound; where at least one of the first and second agents contains a transition metal compound (E).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a paste-like two-component dental curable composition used for fitting dental prostheses such as crowns, inlays, and bridges to dentin and for constructing abutments in dental treatment. More specifically, the operation time is within an appropriate range, the adhesive strength to noble metals and dentin is excellent, and in addition to a small decrease in the adhesive strength to dentin during long-term storage, the solidification risk of the paste is low and the variation in the curing time is small. The present invention relates to a paste-like two-component dental curable composition.

Background Art

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

[0003] Among resin-based dental curable compositions, the material used for adhering dental prostheses to dentin is called dental resin cement. In the restorative treatment of deep dental caries reaching the dental pulp, it is necessary to remove the dental pulp and construct abutment teeth, and the material used for this is called composite resin for dental abutment construction. Both dental resin cement and composite resin for dental abutment construction are paste-like compositions, and are generally produced by mixing a liquid polymerizable monomer-containing composition in which a polymerizable monomer, a polymerization initiator system, a stabilizer, etc. are dissolved with a powdery filler, etc., and are provided to a dentist, who is the user, in a state filled in a container. A dental curable composition is required to maintain certain performance within its expiration date.

[0004] As a polymerizable monomer contained in a dental resin cement or a composite resin material for dental abutment construction, (meth)acrylate is generally used. In addition, in order to impart adhesiveness to dental hard tissues or prostheses, a polymerizable monomer having an acidic group such as a phosphate group or a carboxyl group is blended in the dental resin cement. The dental resin cement with adhesiveness imparted is called a self-adhesive dental resin cement.

[0005] 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. 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 are provided to a dentist who is a user in the state of a two-component dental curable composition. Immediately before the dentist uses this two-component dental curable composition, the first agent containing the oxidizing agent and the second agent containing the reducing agent are mixed, and radicals are generated by a redox reaction, and the polymerization and curing of the dental curable composition proceed.

[0006] Conventionally, as a redox-type polymerization initiator system used in dental curable compositions, a polymerization initiator system composed of benzoyl peroxide and an aromatic amine compound has been widely used. However, when using this polymerization initiator system, there is a problem that the storage stability of the composition is low due to the low thermal stability of benzoyl peroxide. Specifically, when a composition containing benzoyl peroxide is stored for a long time in a temperature environment of room temperature or higher, problems such as a decrease in curability due to the decomposition of benzoyl peroxide and solidification in the composition before use may occur. Therefore, when providing a composition containing benzoyl peroxide to a user such as a dentist, measures such as stipulating the storage temperature to be lower than room temperature and setting a short expiration date are necessary, and there is room for improvement from the viewpoints of usability and quality stability.

[0007] Therefore, in recent years, polymerization initiator systems using various organic peroxides with higher stability instead of benzoyl peroxide as an oxidizing agent have been proposed. For example, in Patent Document 1, a dental cement containing a polymerization initiator system composed of an organic peroxide, a vanadium compound, an ascorbate, and a thiourea derivative has been proposed.

[0008] In Patent Document 2, a polymerization initiator system composed of an organic peroxide selected from hydroperoxide and diperoxide, a transition metal compound, and ascorbic acid or its derivative has been proposed. It is described that a two-component self-adhesive dental composition containing this polymerization initiator system can obtain good mechanical properties, aesthetic properties, and good adhesiveness.

[0009] In addition, Patent Document 3 discloses a two-component self-adhesive dental composition further containing a stabilizer selected from phosphite or sulfite that contributes to the stabilization of ascorbic acid or its derivative in a polymerization initiator system composed of an organic peroxide, a transition metal compound, and ascorbic acid or its derivative.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

[0011] As a result of the study by the present inventors, it was found that the dental cement containing the thiourea derivative described in Patent Document 1 is inferior in adhesiveness to dental noble metals. It is considered that the thiourea derivative chemically adsorbs to the noble metal and inhibits the chemical adhesiveness to the noble metal by the acidic group-containing polymerizable monomer. Furthermore, it was found that there is still room for improvement in storage stability and adhesiveness to dentin.

[0012] In Patent Documents 2 and 3, it has been proposed to blend an organic peroxide in the same agent as a polymerizable monomer containing an acidic group and a transition metal component. The organic peroxide described as a preferred compound in Patent Documents 2 and 3 is a peroxide more stable than benzoyl peroxide. However, generally, the decomposition of an organic peroxide is promoted under acidic conditions, and radicals may be generated during storage, which may cause the paste to solidify. Furthermore, it has been found that when an organic peroxide and a transition metal component coexist under acidic conditions, the above decomposition reaction is further promoted, and the risk of the paste solidifying during storage increases. Therefore, in the compositions described in Patent Documents 2 and 3, there is a risk that the paste will solidify over a long storage period, and it is necessary to set a short storage period. From the viewpoint of storage stability, it has been found that there is room for further improvement.

Summary of the Invention

Problems to be Solved by the Invention

[0013] Therefore, in the present invention, the operation time is within an appropriate range, the adhesive strength to noble metals and dentin is excellent, and during long-term storage, in addition to a small decrease in the adhesive strength to dentin, the risk of paste solidification is low, and the variation in curing time is small. An object is to provide a paste-like two-component dental curable composition.

Means for Solving the Problems

[0014] That is, the present invention provides the following inventions. [1] A first agent containing a polymerizable monomer (A) containing an acidic group, a polymerizable monomer (B) having no acidic group, an organic peroxide (C), a filler (D), and a ligand (G) containing a nitrogen atom, A second agent containing a polymerizable monomer (B) having no acidic group, a filler (D), and an ascorbic acid compound (F), and substantially not containing a thiourea compound, At least one of the first agent or the second agent contains a transition metal compound (E), A paste-like two-component dental curable composition. [2] The paste-like two-component dental curable composition according to [1], wherein the ligand (G) containing a nitrogen atom contains a ligand having two or more nitrogen atoms in the molecule. [3] The ligand (G) containing a nitrogen atom is at least one compound selected from a compound represented by the following general formula (1), a compound represented by general formula (2), and a polydentate ligand (3) containing a nitrogen-containing heterocyclic ring. The paste-like two-component dental curable composition according to [2], wherein the polydentate ligand (3) containing a nitrogen-containing heterocyclic ring contains a 5-membered ring or a 6-membered ring containing a nitrogen atom, has two or more nitrogen atoms in the molecule, and is a bidentate or higher ligand compound. R1R2N-X1-NR3R4(1) (R1 to R4 each independently represent an alkyl group which may have a substituent, and X1 represents a divalent aliphatic group which may have a substituent.) [Chemical formula] (R5, R6, and R7 each independently represent an alkyl group which may have a substituent, X2 and X3 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, Y represents a monoalkylamino group or a dialkylamino group which may have a substituent, and any two or more of R5, R6, R7, and Y may combine to form a ring. When a plurality of R6, R7, X2, and X3 exist, they may be the same or different from each other.) [4] The paste-like two-component dental curable composition according to any one of [1] to [3], wherein the ascorbic acid compound (F) is at least one compound selected from the group consisting of salts and esters of ascorbic acid. [5] The paste-like two-component dental curable composition according to any one of [1] to [4], wherein the transition metal compound (E) is a copper compound and / or a vanadium compound. [6] The paste-like two-component dental curable composition according to any one of [1] to [5], wherein the first agent does not contain the transition metal compound (E). [7] A paste-like two-component dental curable composition according to any one of [1] to [6], which is a self-adhesive composition.

Advantages of the Invention

[0015] According to the present invention, there can be provided a paste-like two-component dental curable composition having an appropriate operation time, excellent adhesion strength to noble metals and dentin, a small decrease in adhesion strength to dentin during long-term storage, a low risk of paste solidification, and a small variation in curing time.

Modes for Carrying Out the Invention

[0016] The dental curable composition of the present invention comprises a first agent containing a polymerizable monomer (A) containing an acidic group, a polymerizable monomer (B) having no acidic group, an organic peroxide (C), a filler (D), and a ligand (G) containing a nitrogen atom, and a second agent containing a polymerizable monomer (B) having no acidic group, a filler (D), and an ascorbic acid compound (F) and substantially not containing a thiourea compound. The second agent substantially does not contain a thiourea compound. Further, at least one of the first agent or the second agent contains a transition metal compound (E). By the second agent substantially not containing a thiourea compound, the adhesiveness to noble metals is high, and by blending a ligand (G) containing a nitrogen atom into the first agent, the storage stability of the organic peroxide (C) contained in the first agent is improved. Even when a transition metal compound (E) is blended into the first agent, it is possible to provide a dental curable composition with a low risk of solidification due to decomposition and a small variation in curing time and high storage stability.

[0017] ·First Agent The first agent in the dental curable composition of the present invention contains a polymerizable monomer (A) containing an acidic group, a polymerizable monomer (B) not containing an acidic group, an organic peroxide (C), a filler (D), and a ligand (G) containing a nitrogen atom.

[0018] ​The polymerizable monomer (A) containing an acidic group is an essential component for the dental curable composition of the present invention to exhibit adhesiveness. The polymerizable monomer (A) containing an acidic group has an action of demineralizing dentin. The polymerizable monomer (A) containing an acidic group has at least one acidic group such as a phosphate group, a phosphonic acid group, a pyrophosphate group, a thiophosphate group, a carboxylic acid group, a sulfonic acid group, etc., and at least one polymerizable group such as an acryloyl group, a methacryloyl group, an acrylamide group, a methacrylamide group, etc. From the viewpoint of adhesiveness to dentin, the polymerizable monomer (A) containing 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.

[0019] Examples of the phosphate group-containing polymerizable monomer include phosphate group-containing monofunctional (meth)acrylate compounds 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, etc., acid chlorides, alkali metal salts, ammonium salts, and amine salts thereof;Phosphate group-containing difunctional (meth)acrylate compounds 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, etc., and their acid chlorides, alkali metal salts, ammonium salts, amine salts, etc. can be mentioned.;

[0020] Examples of the polymerizable monomer containing 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, and their acid chlorides, alkali metal salts, ammonium salts, amine salts, etc. can be mentioned.

[0021] Examples of the polymerizable monomer containing a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, and their acid chlorides, alkali metal salts, ammonium salts, amine salts, etc. can be mentioned.

[0022] Examples of the thiophosphoric acid group-containing polymerizable monomer 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 their acid chlorides, alkali metal salts, ammonium salts, etc.

[0023] Examples of the carboxylic acid group-containing polymerizable monomer include (meth)acrylic acid, 4-[2-[(meth)acryloyloxy]ethoxycarbonyl]phthalic acid, 4-(meth)acryloxyethyl trimellitic acid, 4-(meth)acryloyloxybutyloxycarbonyl phthalic acid, 4-(meth)acryloyloxyhexyloxycarbonyl phthalic acid, 4-(meth)acryloyloxyoctyloxycarbonyl phthalic acid, 4-(meth)acryloyloxydecyl oxycarbonyl phthalic acid, and their acid anhydrides; 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, their acid chlorides, alkali metal salts, ammonium salts, and amine salts, etc.

[0024] Examples of the sulfonic acid group-containing polymerizable monomer include 2-(meth)acrylamide-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate, their acid chlorides, alkali metal salts, ammonium salts, and amine salts.

[0025] Among the acidic group-containing polymerizable monomers (A), phosphoric acid group-containing polymerizable monomers, pyrophosphoric acid group-containing polymerizable monomers, and carboxylic acid group-containing polymerizable monomers are preferable because they exhibit better adhesion to dentin. In particular, phosphoric acid group-containing polymerizable monomers and carboxylic acid group-containing polymerizable monomers are preferable. Among them, phosphoric acid group-containing (meth)acrylate-based monofunctional polymerizable monomers or carboxylic acid group-containing (meth)acrylate-based polymerizable monomers having an alkyl group with 6 to 20 carbon atoms or an alkylene group with 6 to 20 carbon atoms as the main chain in the molecule are more preferable. More preferably, phosphoric acid group-containing (meth)acrylate-based monofunctional polymerizable monomers having an alkylene group with 8 to 12 carbon atoms as the main chain in the molecule are further preferable. Also, 10-methacryloyloxydecyl dihydrogen phosphate, 4-(meth)acryloxyethyl trimellitic acid, and 4-(meth)acryloxyethyl trimellitic anhydride are preferable, and 10-methacryloyloxydecyl dihydrogen phosphate is most preferable.

[0026] The acidic group-containing polymerizable monomer (A) may be blended alone or in combination of two or more. The content of the acidic group-containing polymerizable monomer (A) is not particularly limited as long as the effects of the present invention are achieved. However, from the viewpoint of better adhesion, in 100 parts by mass of the total amount of the polymerizable monomer component of the dental curable composition of the present invention, the range of 1 to 50 parts by mass is preferable, the range of 2 to 25 parts by mass is more preferable, and the range of 2 to 15 parts by mass is further preferable. In this specification, "100 parts by mass of the total amount of the polymerizable monomer component of the dental curable composition" means the case where 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.

[0027] The polymerizable monomer (B) that does not contain an acidic group is a polymerizable monomer in which a radical polymerization reaction proceeds by a polymerization initiator system to form a polymer. The polymerizable monomers constituting the polymerizable monomer (B) that does not contain an acidic group in the present invention are not limited to one type and may be two or more types. As the polymerizable monomer (B) that does not contain an acidic group, the following hydrophilic polymerizable monomer (B-1) and hydrophobic polymerizable monomer (B-2) are preferably exemplified.

[0028] The hydrophilic polymerizable monomer (B-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 that can be dissolved in water at any ratio at 25 °C are more preferred. The hydrophilic polymerizable monomer (B-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 (B-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; bifunctional (meth) acrylic acid ester-based polymerizable monomers such as polyethylene glycol di (meth) acrylate (having 9 or more oxyethylene groups), etc. From the viewpoint of dentin adhesiveness, 2-hydroxyethyl (meth) acrylate is preferred. In the present specification, "(meth) acrylic" means acrylic and methacrylic, and expressions such as "(meth) acryloyl" and "(meth) acrylate" are the same.

[0029] The hydrophobic polymerizable monomer (B-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 (B-2) include aromatic compound-based difunctional polymerizable monomers, aliphatic compound-based difunctional polymerizable monomers, trifunctional or higher functional polymerizable monomers, and the like. The hydrophobic polymerizable monomer (B-2) improves the mechanical strength, handleability, etc. of the dental curable composition.

[0030] Examples of the aromatic compound-based difunctional polymerizable monomer include aromatic di(meth)acrylates. Specific examples of the aromatic compound-based difunctional 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)acryloyloxy (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)acryloyloxipropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxoisopropoxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitate, etc. Among these, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane, 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.

[0031] Examples of aliphatic bifunctional polymerizable monomers include difunctional (meth)acrylic acid ester 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, etc. 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.

[0032] Examples of the polymerizable monomer having a functionality of 3 or more 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, etc. Examples thereof include .

[0033] Among the above hydrophobic polymerizable monomers (B-2), Bis-GMA, D-2.6E, and TEGDMA are preferably used from the viewpoints of the mechanical strength and the polymerization curability of the dental curable composition of the present invention.

[0034] Any of the above polymerizable monomers (B) that do not contain an acidic group (hydrophilic polymerizable monomer (B-1) and hydrophobic polymerizable monomer (B-2)) may be blended alone or in combination of two or more. The content of the polymerizable monomer (B) that does not contain an acidic group is not particularly limited as long as the effects of the present invention are exhibited. However, from the viewpoints that the dental curable composition has high permeability to dental tissue 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.

[0035] Examples of the organic peroxide (C) include diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy ketals, ketone peroxides, and hydroperoxides. Specific examples of the diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide and the like. Specific examples of the peroxy esters include t-butyl peroxybenzoate, bis(t-butyl peroxy) isophthalate, 2,5-dimethyl-2,5-bis(benzoyl peroxy) hexane, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisopropyl carbonate and the like. Specific examples of the dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide and the like. Specific examples of the peroxy ketals include 1,1-bis(t-butyl peroxy) 3,3,5-trimethylcyclohexane, 1,1-bis(t-butyl peroxy) cyclohexane, 1,1-bis(t-hexyl peroxy) cyclohexane and the like. Specific examples of the ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide and the like. Specific examples of the hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, p-diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide and the like.

[0036] Among the organic peroxides (C), 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. Also, among the peroxy esters, t-butyl peroxybenzoate is preferably used.

[0037] The organic peroxide (C) may be blended singly or in combination of two or more. From the viewpoints of curability, mechanical strength of the cured product, and adhesiveness to dentin, the content of the organic peroxide (C) is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass, and still more preferably in the range of 0.5 to 3 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the dental curable composition.

[0038] The first agent in the dental curable composition of the present invention is in paste form and contains a filler (D) in order to obtain sufficient workability of the composition and further sufficient radiopacity and mechanical strength of the cured product.

[0039] As the filler (D), any filler can be used as long as the effects of the present invention are not impaired. Examples thereof include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers. The filler (D) may be blended singly or in combination of two or more. The average particle size of the filler (D) is preferably 0.001 to 10 μm, and more preferably 0.001 to 5 μm.

[0040] Examples of the inorganic filler materials include quartz, silica, alumina, silica - titania, silica - titania - barium oxide, silica - zirconia, silica - alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium borosilicate aluminosilicate glass, strontium borosilicate aluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, ytterbium oxide, ytterbium fluoride coated with silica, etc. Further, as the inorganic filler, fine particle silica having an average particle diameter of 0.001 to 0.1 μm is preferably used in terms of handleability. 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", "AEROXIDE (registered trademark) Alu C" (all of the above are product names manufactured by Nippon Aerosil Co., Ltd.). In the present invention, when the inorganic filler is surface - treated as described later, the average particle diameter of the inorganic filler means the average particle diameter before the surface treatment.

[0041] Examples of the organic filler include polymers of polymethyl methacrylate, polyethyl methacrylate, polyfunctional methacrylate, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene - butadiene rubber.

[0042] Examples of the composite filler of the inorganic filler and the organic filler include those in which the inorganic filler is dispersed in the organic filler, and inorganic / organic composite fillers in which the inorganic filler is coated with various polymers.

[0043] Among the above fillers (D), from the viewpoints of the transparency and mechanical strength of the resulting dental curable composition, inorganic fillers such as quartz, silica, silica-zirconia, barium glass, ytterbium oxide, and ytterbium fluoride coated with silica are preferable, and quartz, silica, silica-zirconia, barium glass, and ytterbium fluoride coated with silica are more preferable.

[0044] In the first agent, from the viewpoint that the interaction with the above acidic group-containing polymerizable monomer (A) is small and the change in the paste properties is small even when stored for a long time, as the filler (D), a combination of either quartz or silica and ytterbium fluoride coated with silica is more preferably used. In this case, the X-ray contrast of the resulting first agent can be adjusted by appropriately adjusting the content of ytterbium fluoride coated with silica.

[0045] In order to improve curability, mechanical strength, and handleability, the filler (D) 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.

[0046] The average particle diameter (average primary particle diameter) can be determined by the laser diffraction scattering method or by observing the particles with an electron microscope. Specifically, the laser diffraction scattering method is convenient for measuring the particle diameter of particles of 0.1 μm or more, and electron microscope observation is convenient for measuring the particle diameter 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% aqueous sodium hexametaphosphate solution as a dispersion medium and a laser diffraction particle size distribution measuring device (SALD-2300, manufactured by Shimadzu Corporation) on a volume basis. For electron microscope observation, a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, SU3800, S-4000, etc.) can be used. Electron microscope observation can be determined by taking an electron micrograph of the particles and measuring the particle diameters of the particles (200 or more) observed within the unit visual field of the photograph using image analysis type particle size distribution measurement software (Mac-View (manufactured by Mount Tech Co., Ltd.)). At this time, the particle diameter is determined as the arithmetic mean value of the longest length and the shortest length of the particles, and the average primary particle diameter is calculated from the number of particles and their particle diameters.

[0047] The content of the filler (D) contained in the first agent is not particularly limited as long as the effects of the present invention are exhibited. However, based on 100 parts by mass of the total amount of the polymerizable monomer component contained in the first agent of the dental curable composition of the present invention, a range of 50 to 350 parts by mass is preferable, and a range of 100 to 300 parts by mass is more preferable. In the first agent, when ytterbium fluoride coated with silica is used as a part of the filler (D), from the viewpoint of X-ray contrast, the content of ytterbium fluoride coated with silica is preferably in the range of 2 to 40 parts by mass, more preferably in the range of 5 to 30 parts by mass, and even more preferably in the range of 10 to 25 parts by mass in 100 parts by mass of the total amount of the first agent.

[0048] The dental curable composition of the present invention contains an organic peroxide (C) in the first agent and an ascorbic acid compound (F) in the second agent as a polymerization initiator system, at least one of the first agent or the second agent contains a transition metal compound (E), and the first agent further contains a ligand (G) containing a nitrogen atom. The ligand (G) containing a nitrogen atom acts as a polymerization accelerator in the dental curable composition of the present invention, improves the adhesiveness to dentin, and contributes to reducing the solidification risk of the first agent and stabilizing the curing time during long-term storage.

[0049] The ligand (G) containing a nitrogen atom is a ligand having one or more nitrogen atoms in the molecule, preferably a ligand having two or more nitrogen atoms in the molecule, and more preferably a polydentate ligand having two or more nitrogen atoms in the molecule. Examples of the ligand (G) containing a nitrogen atom include a compound represented by the following general formula (1), a compound represented by the general formula (2), a polydentate ligand (3) containing a nitrogen-containing heterocyclic ring, and tertiary aliphatic amines having one amino group.

[0050] In a preferred embodiment, the first agent contains a ligand (G) containing a nitrogen atom, and the ligand (G) containing a nitrogen atom is at least one compound selected from a compound represented by the following general formula (1), a compound represented by the general formula (2), and a polydentate ligand (3) containing a nitrogen-containing heterocyclic ring, and a paste-like two-component dental curable composition is exemplified.

[0051] Regarding the reason why the effect of the polydentate ligand is high among the ligands (G) containing a nitrogen atom, it is considered as follows. That is, the ligand (G) containing a nitrogen atom is considered to contribute to the stabilization of the organic peroxide (C) by forming a salt with the acidic group-containing polymerizable monomer (A). However, among the molecules of the ligand (G) containing a nitrogen atom in the paste of the first agent, the movement of the molecules is restricted. The larger the number of nitrogen atoms contained per molecule, the higher the contact probability with the acidic group-containing polymerizable monomer (A), and the reaction is more advantageous physically and chemically.

[0052] R1R2N-X1-NR3R4(1) (R1 to R4 each independently represent an alkyl group which may have a substituent, and X1 represents a divalent aliphatic group which may have a substituent.)

[0053] [Chemical formula] (R5, R6, and R7 each independently represent an alkyl group which may have a substituent, X2 and X3 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, Y represents a monoalkylamino group or a dialkylamino group which may have a substituent, and any two or more of R5, R6, R7, and Y may combine to form a ring. When there are a plurality of R6, R7, X2, and X3, they may be the same or different from each other.)

[0054] The alkyl group which may have a substituent for R1 to R4 may be either linear or branched. The number of carbon atoms of the alkyl group for R1 to R4 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 for R1 to R4 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-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. The alkyl group for R1 to R4 may be unsubstituted. Examples of the substituent of the alkyl group for R1 to R4 include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxy group, alkoxy group having 1 to 6 carbon atoms, dialkylamino group having an alkyl group having 1 to 6 carbon atoms in each, amino group, etc.)

[0055] R1 to R4 may be the same or different. For example, a part (e.g., R1 and R3) of R1 to R4 may be the same alkyl group.

[0056] The divalent aliphatic group which may have a substituent 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 an alkylene group, an alkenylene group, and an alkynylene group, and an alkylene group is preferred. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a methylpropylene group, a dimethylpropylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, 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 R4. The same as those of the substituent of the alkyl group of R1 to R4 can be mentioned.

[0057] In a preferred embodiment, the ligand (G) containing a nitrogen atom is a compound represented by the general formula (1). In the general formula (1), R1 to R4 each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, and X1 represents a linear or branched alkylene group having 1 to 8 carbon atoms which may have a substituent. Examples of the paste-like two-component dental curable composition include those.

[0058] The alkyl group which may have a substituent of R5, R6, and R7 is the same as the alkyl group which may have a substituent of R1 to R4. The monoalkylamino group (-NHR (R a (represents an alkyl group)) and the dialkylamino group (-NR a is (R b R c (R b and R crepresents an alkyl group)), the number of carbon atoms 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. As the alkyl group of the monoalkylamino group and dialkylamino group of Y, those satisfying the above carbon number among the alkyl groups which may have substituents of R1 to R4 can be mentioned. As the dialkylamino group, each alkyl group may have the above carbon number. Examples of the monoalkylamino group which may have a substituent of Y include methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, t-butylamino group, pentylamino group, hexylamino group and the like. Examples of the dialkylamino group which may have a substituent of Y 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 Y may be substituted with a substituent. Examples of the substituent include the same as those of the substituents of the alkyl groups of R1 to R4.

[0059] The divalent aliphatic groups of X2 and X3 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. X2 and X3 may be the same or different. The number of oxygen atoms and nitrogen atoms contained in the divalent aliphatic groups of X2 and X3 is 1 or more, and may be 2 or more. When the divalent aliphatic groups of X2 and X3 contain a nitrogen atom, the divalent aliphatic groups of X2 and X3 may contain -NH-, -NR d (R d represents an alkyl group having 1 to 6 carbon atoms)- may be contained.

[0060] m and n each independently represent an integer of 1 or more, preferably an integer from 1 to 8, more preferably an integer from 1 to 6, even more preferably an integer from 1 to 5, and particularly preferably 1 to 3. m and n may be the same or different. When m and n are 2 or more and there are a plurality of X2 and X3, X2 and X3 may be the same or different from each other.

[0061] Any two or more of R5, R6, R7, and Y may combine to form a ring. For example, R5, R6, or R7 and Y may combine to form a ring. Also, R5 and Y, R6 and R7 may each combine to form a ring, and the compound may have two rings. Further, the nitrogen atom of the amino group of Y and R5 may combine to form a ring. This is acceptable. The ring may contain an oxygen atom and / or a nitrogen atom. Further, in certain embodiments, the compound represented by general formula (2) may be a compound having a bicyclic ring. For example, in other embodiments, in the compound represented by general formula (2), a ring formed by Y and R5 combined together, and a ring formed by R6 or R7 and Y combined together, may be a compound having a bicyclic ring. This is acceptable.

[0062] In a certain preferred embodiment, R5, R6, and R7 may be a linear or branched alkyl group which may have a substituent having 1 to 6 carbon atoms. This is acceptable.

[0063] Also, as another certain preferred embodiment, the ligand (G) containing a nitrogen atom is the compound represented by general formula (2), and in the compound represented by general formula (2), R5, R6, and R7 represent a linear or branched alkyl group which may have a substituent having 1 to 6 carbon atoms. Here, the divalent aliphatic groups of X2 and X3 represent an alkylene group that does not contain an oxygen atom or a nitrogen atom, m and n each independently represent an integer of 1 or more, Y represents a monoalkylamino group or a dialkylamino group which may have a substituent, and there is provided a paste-like two-component dental curable composition in which R5, R6, or R7 and Y together form a ring.

[0064] Further, as another preferred embodiment, a ligand (G) containing a nitrogen atom is a compound represented by the general formula (2) and in the general formula (2), m is 1, n is 2, and there is provided a paste-like two-component dental curable composition which is a compound containing 4 nitrogen atoms as a whole compound.

[0065] The polydentate ligand (3) containing the nitrogen-containing heterocyclic ring contains a heterocyclic ring containing a 5-membered ring or a 6-membered ring containing a nitrogen atom, has 2 or more nitrogen atoms in the molecule, and represents a bidentate or higher ligand compound. The number of nitrogen atoms that the polydentate ligand (3) has in the molecule is 2 or more, and may be 3 or more. The number of heterocyclic rings contained in the polydentate ligand (3) may be 1, or may be 2 or more. Examples of the nitrogen-containing heterocyclic ring include nitrogen-containing 5-membered rings such as a pyrrole ring, a pyrazole ring, and an imidazole ring; nitrogen-containing 6-membered rings such as a pyridine ring, a pyrazine ring, a pyridazine ring, a piperazine ring, a pyrimidine ring, and a triazine ring. The nitrogen-containing heterocyclic ring may be a condensed ring of the 5-membered ring 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 rings or 6-membered rings containing the nitrogen atom. Examples of the condensed ring of the 5-membered ring or 6-membered ring containing the nitrogen atom and the aromatic ring include a quinoline ring, an isoquinoline ring, an indole ring, a benzimidazole ring, and a benzotriazole ring. The polydentate ligand (3) only needs to contain a heterocyclic ring containing a 5-membered ring or a 6-membered ring containing a nitrogen atom. For example, there are provided ligand compounds containing a condensed ring such as an indole ring, a benzimidazole ring, and a benzotriazole ring and a heterocyclic ring containing a 5-membered ring or a 6-membered ring containing a nitrogen atom. The polydentate property of the polydentate ligand (3) only needs to be bidentate or higher, and may be tridentate, tetradentate, or the like.

[0066] Examples of the compound represented by the general formula (1) include bidentate coordinating polyamine 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, and the like.

[0067] Examples of the compound represented by the general formula (2) 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 polyamine compounds such as compounds having no ring. are included.

[0068] Examples of the polydentate ligand (3) containing the nitrogen-containing heterocyclic ring include polydentate ligands having one nitrogen-containing heterocyclic ring such as N-(n-propyl)pyridylmethanimine and N-(n-octyl)pyridylmethanimine; 2,2'-bipyridine, 4,4'-di-(5-nonyl)-2,2'-bipyridine, N-propyl-N,N-di(2-pyridylmethyl)amine, N',N''-dimethyl-N',N''-bis((pyridin-2-yl)methyl)ethane-1,2-diamine, 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)- Examples thereof also include polydentate ligands having two or more nitrogen-containing heterocyclic rings such as 1,3,5-triazine.

[0069] Examples of the tertiary aliphatic amines having one amino group include 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 and the like.

[0070] Among the ligands (G) containing the above nitrogen atom, at least one compound selected from the compound represented by the general formula (1), the compound represented by the general formula (2) and the nitrogen-containing heterocyclic ring-containing polydentate amine (3) is more preferable because it is excellent in reducing the solidification risk of the first agent during long-term storage. In particular, the compounds represented by the general formula (1) and the general formula (2) are more preferable because they are excellent in stabilizing the curing time.

[0071] In addition, the mixing ratio (mass ratio) of the polymerizable monomer (A) containing an acidic group and the ligand (G) containing a nitrogen atom in the first agent is preferably from 40:1 to 2:1, more preferably from 30:1 to 4:1, and even more preferably from 20:1 to 5:1.

[0072] The ligand (G) containing a nitrogen atom may be blended alone or in combination of two or more. From the viewpoints of curability, mechanical strength of the cured product, and adhesiveness to dentin, the content of the ligand (G) containing a nitrogen atom is preferably in the range of 0.05 to 10 parts by mass, more preferably in the range of 0.1 to 8 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the dental curable composition.

[0073] In a certain preferred embodiment, from the viewpoints of low risk of paste solidification and excellent storage stability, there is provided a paste-like two-component dental curable composition in which the first agent does not contain a transition metal compound (E). Examples of the transition metal compound (E) include copper compounds and vanadium compounds.

[0074] In another preferred embodiment, from the viewpoint of storage stability, there is provided a paste-like two-component dental curable composition in which the first agent contains a transition metal compound (E).

[0075] ·Second agent The second agent in the dental curable composition of the present invention contains a polymerizable monomer (B) that does not contain an acidic group, a filler (D), and an ascorbic acid compound (F), and substantially does not contain a thiourea compound.

[0076] The polymerizable monomer (B) that does not contain an acidic group in the second agent is the same as the polymerizable monomer (B) that does not contain an acidic group used in the first agent in terms of type and content.

[0077] In a certain preferred embodiment, from the viewpoint of further reducing the variation in curing time, there is provided a paste-like two-component dental curable composition in which the second agent does not contain a polymerizable monomer (A) containing an acidic group.

[0078] As the filler (D) in the second agent, the same filler (D) as that used in the above-mentioned first agent can be exemplified.

[0079] Similar to the case of being used in the first agent, the filler (D) may be surface-treated in advance with a known surface treatment agent such as a silane coupling agent in order to improve curability, mechanical strength, and handleability, and then used. Examples of the surface treatment agent include the same silane coupling agents as those exemplified for the first agent.

[0080] In the second agent, from the viewpoints of the transparency and mechanical strength of the resulting dental curable composition, quartz, silica, silica-zirconia, barium glass, and silica-coated ytterbium fluoride are preferable as the filler (D). Further, from the viewpoint of X-ray contrast, a combination of at least one selected from the group consisting of quartz, silica, and silica-zirconia and silica-coated ytterbium fluoride, or barium glass is more preferably used.

[0081] The content of the filler (D) contained in the second agent is not particularly limited as long as the effects of the present invention are achieved. However, it is preferably in the range of 50 to 350 parts by mass, more preferably in the range of 100 to 300 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer component contained in the second agent of the dental curable composition of the present invention.

[0082] Examples of the ascorbic acid compound (F) include salts, esters, ethers, etc. of ascorbic acid. Among these, salts and esters of ascorbic acid are preferable.

[0083] Examples of the salts of ascorbic acid include sodium L-ascorbate, calcium L-ascorbate, potassium ascorbate, and their stereoisomers (for example, sodium isoascorbate, etc.). Among these, sodium L-ascorbate is preferable.

[0084] Examples of esters of ascorbic acid include those formed by reacting one or more of the hydroxy groups of ascorbic acid with a carboxylic acid. Preferred examples of the carboxylic acid include fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolelaidic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid, which are saturated or unsaturated fatty acids having 6 to 30 carbon atoms. The number of carbon atoms of the fatty acid is preferably 10 to 28, more preferably 12 to 26, and even more preferably 14 to 24. Among these, esters of stearic acid and ascorbic acid and esters of palmitic acid and ascorbic acid (ascorbyl palmitate) are particularly preferably used.

[0085] Examples of ethers of ascorbic acid include ethyl ether of ascorbic acid and cetyl ether of ascorbic acid.

[0086] The ascorbic acid compound (F) may be blended alone or in combination of two or more. From the viewpoints of curability, mechanical strength of the cured product, and adhesiveness to dentin, the content of the ascorbic acid compound (F) is preferably in the range of 0.01 to 8 parts by mass, more preferably in the range of 0.1 to 5 parts by mass, and even more preferably in the range of 0.3 to 3 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the dental curable composition.

[0087] The ascorbic acid compound (F) is blended in the second agent from the viewpoint of storage stability. The ascorbic acid compound (F) may be dissolved in the second agent or dispersed as a powder in the composition of the second agent.

[0088] When the ascorbic acid compound (F) is dispersed as a powder, if its average particle size is too large, the operability or curability is likely to decrease. Therefore, it is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less.

[0089] The average particle diameter of the powder of the ascorbic acid compound (F) can be calculated as the volume average particle diameter after performing image analysis using image analysis type particle size distribution measurement software (Mac-View; manufactured by Mount Tech Co., Ltd.) based on electron micrographs of 100 or more particles.

[0090] Regarding the shape of the particles when the ascorbic acid compound (F) is dispersed in powder form, various shapes such as spherical, needle-like, plate-like, and crushed shapes can be mentioned, but it is not particularly limited. The ascorbic acid compound (F) can be produced by conventionally known methods such as a grinding method, a freeze-drying method, and a reprecipitation method. From the viewpoint of the average particle diameter of the obtained powder, the grinding method and the freeze-drying method are preferred.

[0091] The dental curable composition of the present invention substantially does not contain a thiourea compound. In the present invention, the content of the thiourea compound is preferably less than 0.1% by mass, more preferably less than 0.01% by mass, still more preferably less than 0.001% by mass, and particularly preferably 0% by mass in the total amount of the dental curable composition. When the thiourea compound is below the above lower limit value, excellent adhesiveness of the dental curable composition to noble metals can be easily obtained. The thiourea compound is not particularly limited, and examples thereof include ethylene thiourea, 4,4-dimethyl ethylene thiourea, N,N'-dimethyl thiourea, N,N'-diethyl thiourea, N,N'-di-n-propyl thiourea, dicyclohexyl thiourea, trimethyl thiourea, triethyl thiourea, tri-n-propyl thiourea, tricyclohexyl thiourea, tetramethyl thiourea, tetraethyl thiourea, tetra-n-propyl thiourea, dicyclohexyl thiourea, tetracyclohexyl thiourea, N-acetyl thiourea, N-benzoyl thiourea, diphenyl thiourea, pyridyl thiourea, and salts thereof (such as hydrochloride, sulfonate, and complex salt).

[0092] At least one of the first agent or the second agent contains a transition metal compound (E). The transition metal compound (E) is not particularly limited, and examples thereof include copper compounds and vanadium compounds.

[0093] 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, etc. Examples of the 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, etc. Examples of the 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, etc. Examples of the copper(II) β-ketoester include copper(II) ethyl acetoacetate, etc. Examples of the copper alkoxide include copper(II) methoxide, copper(II) ethoxide, copper(II) isopropoxide, copper(II) 2-(2-butoxyethoxy)ethoxide, copper(II) 2-(2-methoxyethoxy)ethoxide, etc. Examples of the copper dithiocarbamate include copper(II) dimethyldithiocarbamate, etc. Examples of the 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 combination 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 more preferred.

[0094] Examples of the vanadium compound preferably include vanadium compounds of tetravalent and / or pentavalent There are. Examples of tetravalent and / or pentavalent vanadium compounds include vanadium(IV) dioxide, vanadyl acetylacetonate(IV), vanadium(IV) stearate, oxovanadium(IV) oxalate, vanadyl sulfate(IV), vanadium naphthenate, vanadium benzoylacetonate, bis(maltolato)oxovanadium(IV), oxobis(1-phenyl-1,3-butanedionato)vanadium(IV), vanadium(V) pentoxide, vanadium(V) oxytris(isopropoxide), sodium metavanadate(V), ammonium metavanadate(V), etc. Among them, from the viewpoint of adhesiveness and the like, vanadium acetylacetonate, vanadyl acetylacetonate(IV), and bis(maltolato)oxovanadium(IV) are preferable, and vanadyl acetylacetonate(IV) and bis(maltolato)oxovanadium(IV) are more preferable. The vanadium compound can be used alone or in combination of two or more.

[0095] The transition metal compound (E) may be blended alone or in combination of two or more. From the viewpoint of storage stability, it is preferable to blend the transition metal compound in the second agent. The content thereof 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 0.3 part by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the dental curable composition from the viewpoints of curability, mechanical strength of the cured product, and adhesiveness to dentin.

[0096] Next, the optional components of the dental curable composition of the present invention will be described.

[0097] The dental curable composition of the present invention contains a redox-type polymerization initiator. However, in order to obtain a dual-cure type composition that also starts polymerization by light irradiation, as a component different from the above polymerization initiator system, a conventionally known photoinitiator may be further blended in at least one of the first agent and the second agent.

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

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

[0100] Examples of the ketals include benzyldimethyl ketal and benzyldiethyl ketal.

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

[0102] Among the (bis)acylphosphine oxides, examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, benzoylbis(2,6-dimethylphenyl)phosphine oxide, 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 the bisacylphosphine oxides include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, and 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, dibenzoyl phenylphosphine 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. are mentioned. Among these (bis)acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide are preferred.

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

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

[0105] In addition, in order to enhance the photocurability, a photopolymerization initiator and a polymerization accelerator for the photopolymerization initiator may be used in combination. Examples of the polymerization accelerator for the photopolymerization initiator include tertiary amines, aldehydes, thiol compounds, triazine compounds substituted with a trihalomethyl group, and the like.

[0106] 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, 4-(N,N-dimethylamino)benzoic acid n-butoxyethyl, 4-(N,N-dimethylamino)benzoic acid 2-(methacryloyloxy)ethyl, 4-(N,N-dimethylamino)benzoic acid ethyl, 4-(N,N-dimethylamino)benzoic acid butyl, 4-(N,N-dimethylamino)benzophenone; N-methyldiethanolamine, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-n-butyldiethanolamine, N-lauryl diethanolamine, triethanolamine, 2- Examples of the aliphatic tertiary amines include (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, and the like. However, only when the first agent contains a polymerization accelerator for a photopolymerization initiator and the polymerization accelerator is an aliphatic tertiary amine, the aliphatic tertiary amine belongs to the ligand (G) containing a nitrogen atom and is excluded from the polymerization accelerator for a photopolymerization initiator.

[0107] 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, 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 and a tribromomethyl group.

[0108] The polymerization accelerator for the photopolymerization initiator may be used alone or in combination of two or more. The content of the polymerization accelerator for the photopolymerization initiator is not particularly limited, but from the viewpoint of the curability of the resulting dental curable composition, etc., it is preferably 0.01 to 2 parts by mass, more preferably 0.02 to 1.5 parts by mass, and even more preferably 0.05 to 0.8 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component. When the content of the polymerization accelerator for the photopolymerization initiator is at least the lower limit value, photopolymerization easily proceeds sufficiently. On the other hand, when the content of the polymerization accelerator for the photopolymerization initiator is at most the upper limit value, discoloration of the cured product of the dental curable composition is easily suppressed within an allowable range.

[0109] The curable dental composition of the present invention may contain a polymerization accelerator for another chemical polymerization initiator. Examples of the polymerization accelerator for another chemical polymerization initiator include sulfinic acid and its salts, sulfites, bisulfites, borate compounds, barbituric acid compounds, and the like. These may be used alone, respectively, or two or more of them may be used in combination.

[0110] Examples of the sulfinic acid and its salts include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, 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. Among these, sodium benzenesulfinate, sodium p-toluenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, and sodium 2,4,6-triisopropylbenzenesulfinate are preferable.

[0111] 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.

[0112] In the dental curable composition of the present invention, the second agent may contain a ligand (G) containing a nitrogen atom. As an embodiment, there is provided a paste-like two-component dental curable composition in which the second agent further contains a ligand (G) containing a nitrogen atom as necessary. The ligand (G) containing a nitrogen atom contained in the second agent is the same as the ligand (G) containing a nitrogen atom contained in the first agent.

[0113] In the dental curable composition of the present invention, at least one of the first agent and the second agent may further contain a fluoride ion-releasing substance. By blending a fluoride ion-releasing substance, it can be used as a dental resin cement capable of imparting acid resistance to dentin. Examples of the fluoride ion-releasing substance include fluoride ion-releasing polymers such as copolymers of methyl methacrylate and methyl methacrylate fluoride; hydrogen fluoride salts of aliphatic or alicyclic primary, secondary or tertiary amines such as cetylamine hydrogen fluoride, cyclohexylamine hydrogen fluoride, diisobutylamine hydrogen fluoride, and triethylamine trihydrogen fluoride; metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride. The fluoride ion-releasing substance may be used alone or in combination of two or more.

[0114] In the sub-packaged dental curable composition of the present invention, at least one of the first agent and the second agent may contain a pH adjuster. The pH adjuster is used for the purpose of adjusting the pH and stabilizing the pH of the sub-packaged dental curable composition of the present invention. The pH adjuster is not particularly limited as long as it exhibits the effects of the present invention, but acids such as lactic acid, succinic acid, gluconic acid, citric acid, phosphoric acid, and carbonic acid, and their salts are preferably used.

[0115] Examples of phosphates include alkali metal phosphates such as trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate; alkyl alkali metal phosphates such as sodium dodecyl phosphate, sodium glycerophosphate, and disodium glycerophosphate; alkali metal hydrogen phosphates or alkali metal dihydrogen phosphates; alkaline earth metal phosphates such as tricalcium phosphate, calcium hydrogen phosphate, and calcium dihydrogen phosphate; alkaline earth metal hydrogen phosphates or alkaline earth metal dihydrogen phosphates; and trimagnesium phosphate and magnesium hydrogen phosphate. Among these, disodium hydrogen phosphate, sodium dodecyl phosphate, sodium glycerophosphate, and disodium glycerophosphate are preferably used.

[0116] In addition, additives such as a pH adjuster, a polymerization inhibitor, an ultraviolet absorber, a solvent (e.g., water, an organic solvent), a thickener, a coloring agent, an antibacterial agent, and a fragrance may be blended into at least one of the first agent and the second agent within a range that does not inhibit the effects of the present invention. These may be blended individually or in combination of two or more. 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- Examples thereof include t-butyl-4-methylphenol. 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 monomer component of the dental curable composition. In certain embodiments, the content of the solvent (e.g., water, organic solvent) in the paste-like two-component 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 in the total amount of the paste-like two-component dental curable composition. The dental curable composition of the present invention can also be suitably used as a self-adhesive composition. The dental curable composition of the present invention can also be suitably used, for example, as a dental resin cement or a composite resin for dental abutment construction.

[0117] 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

[0118] 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 below are as follows. Compounds and fillers used in the following Examples and Comparative Examples were commercially available products unless otherwise specified regarding the production method.

[0119] 〔Polymerizable monomer (A) containing an acidic group〕 MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[0120] 〔Polymerizable monomer (B) not containing an acidic group〕 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: 2.6) TEGDMA: Triethylene glycol dimethacrylate HEMA: 2-Hydroxyethyl methacrylate

[0121] [Organic peroxide (C)] THP: 1,1,3,3 - Tetramethylbutyl hydroperoxide CHP: Cumene hydroperoxide BPB: t - Butyl peroxybenzoate

[0122] [Filler (D)] Filler 1: Silane - treated silica Commercially available product (methacryl silane - treated spherical silica fine powder manufactured by Admatechs Co., Ltd., trade name "Admanano (registered trademark) YA010C - SM1", average primary particle size: 10 nm, BET specific surface area: 300 m 2 / g) was used as it was.

[0123] Filler 2: Silane - treated silica - coated ytterbium fluoride Commercially available product (SG - YBF100WSCMP10, average particle size: 110 nm, spherical, refractive index: 1.53, manufacturing company: Sukgyung AT Co., Ltd.) was used as it was.

[0124] Filler 3: Silane - treated barium glass: Barium glass (manufactured by Estec Co., product code "E - 3000") was pulverized with a ball mill to obtain barium glass powder. When the average particle size 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. Surface treatment was carried out on 100 parts by mass of this barium glass powder with 3 parts by mass of γ - methacryloyloxypropyltrimethoxysilane by a conventional method to obtain silane - treated barium glass powder.

[0125] Filler 4: Alumina Commercially available product (AEROXIDE (registered trademark) Alu C, average particle size: 20 nm, manufactured by Nippon Aerosil Co., Ltd.) was used as it was.

[0126] [Transition metal compound (E)] VOAA: Vanadyl acetylacetonate(IV) BMOV: Bis(maltolate)oxovanadium(IV) CuA: Copper(II) acetate

[0127] [Ascorbic acid compound (F)] PA: Ascorbyl palmitate ANa: Sodium L-ascorbate

[0128] [Ligand (G) containing a nitrogen atom] TTA: Triethanolamine TEEDA: N,N,N’,N’-Tetraethylethylenediamine TMPDA: N,N,N’,N’-Tetramethylpropylenediamine PMDETA: N,N,N,N’,N’’,N’’-Pentamethyldiethylenetriamine Me6TREN: Tris[2-(dimethylamino)ethyl]amine DPP: 2,6-Bis(1-pyrazol)-pyridine

[0129] [Polymerization inhibitor] BHT: 2,6-Di-t-butyl-4-methylphenol

[0130] (Examples 1 to 11 and Comparative Examples 1 to 3) Among the components listed in Table 1, components other than the filler and ascorbic acid compound were mixed at room temperature to obtain a uniform liquid component, and then the obtained liquid component, ascorbic acid compound, and filler were kneaded to prepare the dental curable compositions of Examples 1 to 11 and Comparative Examples 1 to 3. Next, using these dental curable compositions, immediately after production, the working time at 23°C, the adhesive strength to bovine dentin, the adhesive strength to gold alloy, and the adhesion durability were measured according to the method described below. Also, after storage at 60°C for 3 weeks, the working time at 23°C, the adhesive strength to bovine dentin, and the solidification of the paste were measured. Table 1 shows the compounding ratios (parts by mass) and test results of this dental curable composition. Note that for the dental curable composition of Comparative Example 2, since the first agent solidified after storage at 60°C for 3 weeks, measurements after storage at 60°C for 3 weeks could not be performed. Also, for the dental curable composition of Comparative Example 3, since the first agent solidified after preparation, all measurements could not be performed.

[0131] [Working Time at 23°C of Dental Curable Composition] In a constant temperature room at 23°C, the first agent and the second agent were mixed at a mass ratio of 1:1, and thoroughly mixed with a spatula to form a single agent. The time (working margin time) from the time of mixing to the time when the temperature began to rise due to the start of curing of the paste was measured with a thermocouple (manufactured by Okazaki Seisakusho Co., Ltd.) connected to a recording meter (manufactured by Yokogawa Electric Corporation). The working time (denoted as "23°C working time" in the following table) is the average value of the measured values for 5 test samples. Note that a practical working margin time is 2 to 8 minutes. Also, 4 g each of the first agent and the second agent of the two-component type dental curable composition of the present invention were filled into the product containers of "SA ROUTING (registered trademark) Multi" (manufactured by Kuraray Noritake Dental Co., Ltd.), and stored in a dry atmosphere at 60°C for 3 weeks, and then the working time was measured in the same manner using these.

[0132] [Adhesive Strength of Dental Curable Composition to Bovine Dentin] The labial surface of the bovine mandibular anterior tooth was polished with #80 silicon carbide paper (manufactured by Nippon Kenji Paper Co., Ltd.) under running water to expose a flat surface of dentin. The exposed flat surface was further polished with #1000 silicon carbide paper (manufactured by Nippon Kenji Paper Co., Ltd.) under running water. After polishing, the water on the surface was dried by air blowing. An adhesive tape with a thickness of about 150 μm having a round hole with a diameter of 3 mm was attached to the dried smooth surface to define the adhesion area. Equal amounts of the first agent and the second agent of each dental curable composition of the examples and comparative examples were collected and kneaded for 10 seconds. Then, the obtained kneaded product was placed on one end face (circular cross-section) of a stainless steel cylindrical bar (diameter 7 mm, length 2.5 cm). Next, with the center of the above-mentioned round hole and the center of the above-mentioned stainless steel cylindrical bar substantially coinciding, the end face on the side where the dental curable composition was placed was placed on the smooth surface (adhesion surface) inside the round hole, and a stainless steel cylindrical bar was pressed against and adhered perpendicularly to the smooth surface to prepare test samples. Five test samples were prepared. The test samples were allowed to stand at 25 °C for 30 minutes and then immersed in distilled water. The test samples immersed in distilled water were allowed to stand in a thermostat maintained at 37 °C for 24 hours. For this test sample, the tensile adhesive strength to bovine dentin after standing at 37 °C for 24 hours was measured. The tensile adhesive strength was measured with a universal testing machine (manufactured by Shimadzu Corporation, Autograph "AG-I 100kN") with the crosshead speed set at 2 mm / min. Regarding the properties immediately after preparation in the table, the tensile adhesive strength to dentin is the average value of the measured values of the tensile adhesive strength to bovine dentin after standing at 37 °C for 24 hours for 5 test samples. Also, 4 g each of the first agent and the second agent of the two-component dental curable composition of the present invention were filled into the product containers of "SA Routing (registered trademark) Multi" (manufactured by Kuraray Noritake Dental Co., Ltd.), and after storing for 3 weeks in a 60 °C dry atmosphere, the adhesive strength was measured in the same manner as after storing at 37 °C for 24 hours using this. Regarding the properties of the temperature-accelerated products in the table, the tensile adhesive strength to dentin is the average value of the measured values of the tensile adhesive strength to bovine dentin after storing for 3 weeks in a 60 °C dry atmosphere for 5 test samples.

[0133] [Tensile Adhesive Strength and Adhesion Durability of Dental Curable Composition to Gold Alloy] The surface of a gold alloy casting product in the shape of a cube with each side being 1 cm (manufactured by GC Corporation, trade name "Casting Gold M.C. Type IV") was polished with #1000 silicon carbide paper under running water to obtain a smooth surface, and then the water on the surface was dried by air blowing. An adhesive tape with a thickness of about 150 μm and having round holes with a diameter of 5 mm was adhered to the dried smooth surface to define the adhesion area. Equal amounts of the first agent and the second agent of each dental curable composition in the examples and comparative examples were collected and kneaded for 10 seconds. Then, the obtained kneaded product was placed on one end face (circular cross-section) of a stainless steel cylindrical bar (diameter 7 mm, length 2.5 cm). Next, with the center of the above-mentioned round hole and the center of the above-mentioned stainless steel cylindrical bar being substantially coincident, the end face on the side where the dental curable composition was placed was placed on the smooth surface (adherend surface) inside the round hole, and a stainless steel cylindrical bar was pressed against it perpendicularly to the smooth surface for adhesion to prepare test samples. Ten test samples were prepared. The test samples were allowed to stand at 25°C for 30 minutes, immersed in distilled water, and then allowed to stand in a thermostat maintained at 37°C for 24 hours. For 5 out of the 10 test samples, the tensile adhesion strength after standing at 37°C for 24 hours was examined. This tensile adhesion strength indicates the adhesion strength at the initial stage of adhesion. For the remaining 5 test samples, a thermal cycle load of immersing them alternately in a water bath at 4°C and a water bath at 60°C for 1 minute each for 4000 times was applied, and then the tensile adhesion strength was measured. The adhesion durability was evaluated by the tensile adhesion strength after this thermal cycle load. The tensile adhesion strength was measured with a universal testing machine (manufactured by Shimadzu Corporation, Autograph "AG-I 100kN") with the crosshead speed set at 2 mm / min. In the table, both the tensile adhesion strength to the gold alloy and the adhesion durability to the gold alloy (tensile adhesion strength after thermal cycle load) are the average values of the measured values for 5 test samples.

[0134] 〔Solidification of Dental Curable Composition (Paste)〕 The first agent and the second agent of the dental curable composition of the present invention are "SA Routing (Registered Trademark) Each product container of "Multi" (manufactured by Kuraray Noritake Dental Co., Ltd.) was filled with 4 g each, and stored for 3 weeks in a drying atmosphere at 60°C. For each of the first agent and the second agent, the presence or absence of a cured product was confirmed. When a cured product was present, it was determined as "solidification present", and when no cured product was present, it was determined as "no solidification". The confirmation of the presence or absence of solidification was carried out for 5 samples, and for any sample in which the presence of a cured product was confirmed even in one sample, it was determined as "present".

[0135]

Table 1

[0136] As shown in Table 1, the dental curable compositions according to the present invention (Examples 1 to 11) had an appropriate working time at 23°C immediately after preparation, and excellent results in terms of adhesive strength to bovine dentin, adhesive strength to gold alloy, and adhesive durability. Further, no solidification was observed in the paste after storage at 60°C for 3 weeks, and the change in the working time at 23°C and the adhesive strength to bovine dentin after storage was small compared to immediately after manufacture. In Examples 2 to 9, when the first agent contained a ligand having two or more nitrogen atoms in the molecule as the ligand (G) containing a nitrogen atom, and the second agent contained a transition metal compound (E), the change in the working time at 23°C and the adhesive strength to bovine dentin after storage was even smaller compared to immediately after manufacture. Further, in Examples 10 to 11, when the first agent contained a ligand having two or more nitrogen atoms in the molecule as the ligand (G) containing a nitrogen atom and a transition metal compound (E), although the variation in the working time at 23°C after storage at 60°C for 3 weeks was slightly larger in comparison with immediately after preparation, it was within the allowable range, and solidification of the paste after storage at 60°C for 3 weeks did not occur in the first agent as in Comparative Example 2.

[0137] On the other hand, the dental curable composition containing the thiourea compound of Comparative Example 1 was not excellent in either the adhesive strength to the gold alloy or the adhesive durability. Further, the first agent of the dental curable composition of Comparative Example 2 in which the acidic group-containing polymerizable monomer (A), the organic peroxide (C), and copper(II) acetate which is a transition metal compound were blended in the same agent without containing the ligand (G) containing a nitrogen atom was solidified after storage at 60 °C for 3 weeks. Furthermore, the first agent of the dental curable composition of Comparative Example 3 in which the acidic group-containing polymerizable monomer (A), the organic peroxide (C), and the transition metal compound (E) were blended in the same agent without containing the ligand (G) containing a nitrogen atom was solidified immediately after preparation.

Industrial Applicability

[0138] The dental curable composition of the present invention can be suitably used in dental treatment for the fitting of dental prostheses such as crowns, inlays, and bridges to dentin (for example, dental cements), abutment construction (for example, composite resins for dental abutment construction), and the like.

Claims

1. A first agent containing a polymerizable monomer (A) containing an acidic group, a polymerizable monomer (B) having no acidic group, an organic peroxide (C), a filler (D), and a ligand (G) containing a nitrogen atom, and A second agent containing a polymerizable monomer (B) having no acidic group, a filler (D), and an ascorbic acid compound (F) and substantially free of a thiourea compound, provided that At least one of the first agent or the second agent contains a transition metal compound (E), The transition metal compound (E) is a copper compound and / or a vanadium compound, 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 a salt of copper and an inorganic acid, The vanadium compound is a tetravalent and / or pentavalent vanadium compound, The ascorbic acid compound (F) is at least one compound selected from the group consisting of salts and esters of ascorbic acid, The salts of ascorbic acid are sodium L-ascorbate, calcium L-ascorbate, potassium ascorbate, and stereoisomers thereof, The esters of ascorbic acid are those obtained by reacting one or more of the hydroxy groups of ascorbic acid with a fatty acid such as a saturated or unsaturated fatty acid having 6 to 30 carbon atoms, The ligand (G) containing a nitrogen atom is at least one compound selected from a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a polydentate ligand (3) containing a nitrogen-containing heterocyclic ring, The polydentate ligand (3) containing a nitrogen-containing heterocyclic ring contains 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, R1R2N−X1−NR3R4 (1) (R1 to R4 each independently represent an alkyl group which may have a substituent, and X1 represents a divalent aliphatic group which may have a substituent.) 【Chemical 1】 (R5, R6, and R7 each independently represent an alkyl group which may have a substituent, X2 and X3 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, Y represents a monoalkylamino group or a dialkylamino group which may have a substituent, and any two or more of R5, R6, R7, and Y may combine together to form a ring. When there are a plurality of R6, R7, X2, and X3, they may be the same or different from each other.) A paste-like two-component dental curable composition.

2. The paste-like two-component dental curable composition according to claim 1, wherein the tetravalent and / or pentavalent vanadium compounds are at least one compound selected from vanadium(IV) oxide, vanadyl acetylacetonate(IV), vanadium(IV) stearate, oxovanadium(IV) oxalate, vanadyl sulfate(IV), vanadium naphthenate, vanadium benzoylacetonate, bis(maltolato)oxovanadium(IV), oxobis(1-phenyl-1,3-butanedionato)vanadium(IV), vanadium(V) oxide, vanadium(V) oxytris(isopropoxide), sodium metavanadate(V), and ammonium metavanadate(V).

3. The paste-like two-component dental curable composition according to claim 1 or 2, wherein the first component does not contain a transition metal compound (E).

4. The paste-like two-component dental curable composition according to any one of claims 1 to 3, which is a self-adhesive composition.

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