Subcontracted dental curable composition

Abstract

To provide a dental curable composition in a divided form that has an operation time within a reasonable range, is excellent in the adhesion to dentin and the mechanical strength of a cured material, hardly deteriorates in performance during long-term storage, and exhibits low discoloration and low solidification risk.SOLUTION: A dental curable composition in a divided form contains: a first agent containing a polymerizable monomer (A) having an acidic group, a polymerizable monomer (B) having no acidic group, and an ascorbic acid compound (C); and a second agent containing the polymerizable monomer (B) having no acidic group, an organic peroxide (D), and a transition metal compound (E), and not containing the polymerizable monomer (A) having an acidic group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a sub-packaged dental curable composition used for adhesion between dental prostheses such as crowns, inlays, and bridges and tooth substance, and for abutment construction in dental treatment. More specifically, the operation time is within an appropriate range, the adhesiveness to tooth substance and the mechanical strength of the cured product are excellent, and in addition to a small decrease in performance during long-term storage, the composition has less discoloration and a low solidification risk. The present invention relates to a sub-packaged dental curable composition.

Background Art

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

[0003] Among resin-based dental curable compositions, materials used for adhesion between dental prostheses and tooth substance are called dental resin cements. 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 a composite resin for dental abutment construction. Both dental resin cements and composite resins for dental abutment construction are paste-like compositions, and are generally manufactured 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. Dental curable compositions are required to maintain certain performance within their 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 dentin or a prosthesis in a dental resin cement, a polymerizable monomer having an acidic group such as a phosphate group or a carboxyl group is contained. A dental resin cement containing a polymerizable monomer having an acidic group and having adhesiveness imparted thereto 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. In this case, the oxidizing agent and the reducing agent of the polymerization initiator system are, for example, packaged into a first agent containing the oxidizing agent and a second agent containing the reducing agent, and are provided to a dentist who is a user in the state of a packaged type dental curable composition. Immediately before the dentist uses this packaged type dental curable composition, by mixing the first agent containing the oxidizing agent and the second agent containing the reducing agent, 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 initiator system, there has been 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 oxidizing agents have been proposed. For example, Patent Document 1 discloses a polymerization initiator system comprising an organic peroxide selected from hydroperoxide and diperoxide, a transition metal compound, and ascorbic acid or its derivative. 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.

[0008] Also, Patent Document 2 discloses a two-component self-adhesive dental composition comprising a polymerization initiator system consisting of an organic peroxide, a transition metal compound, and ascorbic acid or its derivative, and further containing a stabilizer selected from phosphite or sulfite that contributes to the stabilization of ascorbic acid or its derivative. Since ascorbic acid or its derivative is easily decomposed over time, conventionally, it has been necessary to blend it in excess when used in the polymerization initiator system of dental curable compositions, which has caused a problem of discoloration. However, by blending the stabilizer described in Patent Document 2, the decomposition of ascorbic acid or its derivative is suppressed, and it becomes possible to reduce the content. As a result, it is described that the aesthetic property of the composition is improved.

[0009]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0010] As a result of investigations by the present inventors, among the dental curable compositions disclosed in Patent Documents 1 and 2, there are compositions in which the working time is indeed within an appropriate range, the adhesiveness to dentin and the mechanical strength of the cured product are excellent, and even after storage for a certain period of time or longer, there is no significant decrease in these performances, and the discoloration of the composition is also suppressed. However, when storage was continued for a longer period, it was found that solidification occurred in all of the above compositions, making them substantially unusable. Therefore, in the dental curable compositions disclosed in Patent Documents 1 and 2, since there is a risk of paste solidification over a long storage period, when providing to users such as dentists, it is necessary to set a short usable period from after manufacture, etc., and it was found that there is room for further improvement from the viewpoint of storage stability.

[0011] Therefore, an object of the present invention is to provide a sub-packaged dental curable composition in which the working time is within an appropriate range, the adhesiveness to dentin and the mechanical strength of the cured product are excellent, the performance degradation during long-term storage is small, the composition has little discoloration, and the solidification risk is low.

Means for Solving the Problems

[0012] As a result of intensive investigations by the present inventors on a sub-packaged dental curable composition in which the working time is within an appropriate range, the adhesiveness to dentin and the mechanical strength of the cured product are excellent, the performance degradation during long-term storage is small, the composition has little discoloration, and the solidification risk is low, it was found that the above problems can be solved by setting a polymerizable monomer having an acidic group and a polymerization initiator system in a specific sub-packaged state, and further investigations were repeated to complete the present invention.

[0013] That is, the present invention includes the following inventions. [1] A first agent containing a polymerizable monomer (A) having an acidic group, a polymerizable monomer (B) not having an acidic group, and an ascorbic acid compound (C), A two - component dental curable composition, which comprises a second agent containing a polymerizable monomer (B) having no acidic group, an organic peroxide (D), and a transition metal compound (E), and not containing a polymerizable monomer (A) having an acidic group. [2] The two - component dental curable composition according to [1], wherein at least one of the first agent and the second agent contains a ligand compound (F), and the ligand compound (F) is at least one compound selected from the group consisting of a ligand containing a phosphorus atom and a ligand containing a nitrogen atom. [3] The ligand compound (F) is a ligand containing a phosphorus atom. The ligand containing a phosphorus atom is at least one compound selected from the group consisting of a compound represented by the following general formula (1), a compound represented by general formula (2), a compound represented by general formula (3), and a compound represented by general formula (4). The two - component dental curable composition according to [2].

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[10] The pH adjuster is a phosphate, and the sub-packaged dental curable composition according to [9].

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

[10] , which is a dental resin cement.

[12] The dental resin cement is a self-adhesive dental resin cement, and the sub-packaged dental curable composition according to

[11] .

Advantages of the Invention

[0014] According to the present invention, an operation time is within an appropriate range, adhesiveness to dentin and mechanical strength of a cured product are excellent, a decrease in performance during long-term storage is small, discoloration of the composition is small, and a sub-packaged dental curable composition with a low solidification risk can be provided.

Embodiments for Carrying Out the Invention

[0015] The two-component dental curable composition of the present invention comprises a first agent containing a polymerizable monomer (A) having an acidic group, a polymerizable monomer (B) having no acidic group, and an ascorbic acid compound (C), and a second agent containing a polymerizable monomer (B) having no acidic group, an organic peroxide (D), and a transition metal compound (E) and not containing the polymerizable monomer (A) having an acidic group.

[0016] Although the mechanism by which the two-component dental curable composition of the present invention exhibits the effects of the present invention is not clear, it is presumed that by blending the organic peroxide (D) into the second agent that does not contain the polymerizable monomer (A) having an acidic group, the stability of the organic peroxide is improved, and thus the risk of solidification associated with the decomposition of the organic peroxide is reduced. Hereinafter, the components contained in the two-component dental curable composition of the present invention will be described respectively.

[0017] The two-component dental curable composition of the present invention contains the polymerizable monomer (A) having an acidic group in the first agent and does not contain it in the second agent. The polymerizable monomer (A) having an acidic group is an essential component for the dental curable composition of the present invention to exhibit adhesiveness. On the other hand, when the second agent contains the polymerizable monomer (A) having an acidic group, problems such as a decrease in curability and an increase in the risk of solidification occur, so it is contained only in the first agent. The polymerizable monomer (A) having an acidic group has an action of demineralizing dental tissue. The polymerizable monomer (A) having an acidic group is a polymerizable monomer having 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 dental tissue, the polymerizable monomer (A) having an acidic group is preferably monofunctional having any one of an acryloyl group, a methacryloyl group, an acrylamide group or a methacrylamide group as a polymerizable group. Specific examples include the following.

[0018] Examples of the polymerizable monomer having a phosphate group include monofunctional (meth)acrylate compounds having a phosphate group such as 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-(4-methoxyphenyl) hydrogen phosphate, 2-(meth)acryloyloxypropyl-(4-methoxyphenyl) hydrogen phosphate, etc., acid chlorides, alkali metal salts, ammonium salts, and amine salts thereof;Bifunctional (meth)acrylate compounds having a phosphate group such as bis[2-(meth)acryloyloxyethyl] hydrogen phosphate, bis[4-(meth)acryloyloxybutyl] hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl] hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl] hydrogen phosphate, bis[9-(meth)acryloyloxynonyl] hydrogen phosphate, bis[10-(meth)acryloyloxydecyl] hydrogen phosphate, 1,3-di(meth)acryloyloxypropyldihydrogen phosphate, their acid chlorides, alkali metal salts, ammonium salts, amine salts, etc. can be mentioned.;

[0019] Examples of the polymerizable monomer having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl phosphonoacetate, 10-(meth)acryloyloxydecyl phosphonoacetate, their acid chlorides, alkali metal salts, ammonium salts, amine salts, etc.

[0020] Examples of the polymerizable monomer having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, their acid chlorides, alkali metal salts, ammonium salts, amine salts, etc.

[0021] Examples of the polymerizable monomer having a thiophosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogen thiophosphate, 3-(meth)acryloyloxypropyl dihydrogen thiophosphate, 4-(meth)acryloyloxybutyl dihydrogen thiophosphate, 5-(meth)acryloyloxypentyl dihydrogen thiophosphate, 6-(meth)acryloyloxyhexyl dihydrogen thiophosphate, 7-(meth)acryloyloxyheptyl dihydrogen thiophosphate, 8-(meth)acryloyloxyoctyl dihydrogen thiophosphate, 9-(meth)acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, 20-(meth)acryloyloxyeicosyl dihydrogen thiophosphate, and acid chlorides, alkali metal salts, ammonium salts, etc. thereof.

[0022] Examples of the polymerizable monomer having a carboxylic acid group include (meth)acrylic acid, 4-[2-[(meth)acryloyloxy]ethoxycarbonyl]phthalic acid, 4-(meth)acryloyloxyethyl trimellitic acid, 4-(meth)acryloyloxybutyloxycarbonyl phthalic acid, 4-(meth)acryloyloxyhexyloxycarbonyl phthalic acid, 4-(meth)acryloyloxyoctyloxycarbonyl phthalic acid, 4-(meth)acryloyloxydecyl oxycarbonyl phthalic acid, and acid anhydrides thereof; 5-(meth)acryloylaminopentyl carboxylic acid, 6-(meth)acryloyloxy-1,1-hexanedicarboxylic acid, 8-(meth)acryloyloxy-1,1-octanedicarboxylic acid, 10-(meth)acryloyloxy-1,1-decanedicarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, acid chlorides, alkali metal salts, ammonium salts, and amine salts, etc. thereof.

[0023] Examples of the polymerizable monomer having a sulfonic acid group include 2-(meth)acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth)acrylate, their acid chlorides, alkali metal salts, ammonium salts, and amine salts.

[0024] Among the polymerizable monomers (A) having an acidic group, polymerizable monomers having a phosphate group, polymerizable monomers having a pyrophosphate group, and polymerizable monomers having a carboxylic acid group are preferable because they exhibit better adhesiveness to dentin. In particular, polymerizable monomers having a phosphate group and polymerizable monomers having a carboxylic acid group are preferable. Among them, (meth)acrylate-based monofunctional polymerizable monomers having a phosphate group having an alkyl group with 6 to 20 carbon atoms or an alkylene group with 6 to 20 carbon atoms as the main chain in the molecule or (meth)acrylate-based polymerizable monomers having a carboxylic acid group are more preferable, and (meth)acrylate-based monofunctional polymerizable monomers having a phosphate group having an alkylene group with 8 to 12 carbon atoms as the main chain in the molecule are even more preferable. Also, 10-methacryloyloxydecyl dihydrogen phosphate, 4-(meth)acryloyloxyethyl trimellitic acid, and 4-(meth)acryloyloxyethyl trimellitic anhydride are preferable, and 10-methacryloyloxydecyl dihydrogen phosphate is most preferable.

[0025] The polymerizable monomer (A) having an acidic group may be blended alone or in combination of two or more. The content of the polymerizable monomer (A) having an acidic group is not particularly limited as long as the effects of the present invention are achieved. However, from the viewpoint of better adhesiveness, in 100 parts by mass of the total amount of the polymerizable monomer component of the subpackage type 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 10 parts by mass is even more 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.

[0026] The subcontracted dental curable composition of the present invention contains a polymerizable monomer (B) having no acidic group in both the first agent and the second agent. The polymerizable monomer (B) having no acidic group is a polymerizable monomer in which a radical polymerization reaction proceeds by a polymerization initiator system to form a polymer. The polymerizable monomer (B) having no acidic group may be used alone or in combination of two or more. As the polymerizable monomer (B) having no acidic group, the following hydrophilic polymerizable monomer (B-1) and hydrophobic polymerizable monomer (B-2) are preferably exemplified.

[0027] 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 preferable, and those that can be dissolved in water at any ratio at 25 ° C are more preferable. 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. are mentioned, and 2-hydroxyethyl (meth) acrylate is preferable. In the present specification, "(meth) acrylic" means acrylic and methacrylic, and expressions such as "(meth) acryloyl" and "(meth) acrylate" are the same.

[0028] 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 monofunctional and bifunctional polymerizable monomers of aromatic compound-based, monofunctional and bifunctional polymerizable monomers of aliphatic compound-based, and trifunctional or higher functional polymerizable monomers. The hydrophobic polymerizable monomer (B-2) improves the mechanical strength, handleability, etc. of the dental curable composition.

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

[0030] Examples of the aromatic compound-based bifunctional polymerizable monomer include aromatic di(meth)acrylate. Specific examples of the aromatic compound-based bifunctional polymerizable monomer include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]propane, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (hereinafter sometimes abbreviated as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitate, and the like. Among these, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane and 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of added ethoxy groups: 2.6) (hereinafter sometimes abbreviated as "D-2.6E") are preferred.

[0031] Examples of the aliphatic monofunctional polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, dicyclopentanyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and the like. Among these, isobornyl methacrylate is preferred.

[0032] Examples of the aliphatic compound-based bifunctional polymerizable monomer include bifunctional (meth)acrylic acid ester-based polymerizable monomers such as erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate (hereinafter sometimes abbreviated as "TEGDMA"), propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2,2,4-trimethylhexamethylene bis(2-carbamoyloxyethyl) dimethacrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane; (meth)acrylamide-based polymerizable monomers such as N-methacryloyloxyethyl acrylamide, N-methacryloyloxypropyl acrylamide, N-methacryloyloxybutyl acrylamide, N-(1-ethyl-(2-methacryloyloxy)ethyl) acrylamide, N-(2-(2-methacryloyloxyethoxy)ethyl) acrylamide, 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.

[0033] 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, and the like.

[0034] Among the polymerizable monomers (B) having no acidic group, from the viewpoints of the adhesive strength and polymerization curability of the dental curable composition of the present invention, HEMA, Bis-GMA, D-2.6E, and TEGDMA are more preferable.

[0035] Any of the above polymerizable monomers (B) having no acidic group (hydrophilic polymerizable monomer (B-1) and hydrophobic polymerizable monomer (B-2)) may be contained alone or in combination of two or more. The content of the polymerizable monomer (B) having no acidic group is not particularly limited as long as the effects of the present invention are exhibited. However, from the viewpoints that the composition has high permeability to dentin and excellent adhesiveness and the cured product has sufficient mechanical strength, in 100 parts by mass of the total amount of the polymerizable monomer component in the packaged 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.

[0036] Next, the polymerization initiator system will be described. The sub-packaged dental curable composition of the present invention contains an ascorbic acid compound (C) in the first agent, and an organic peroxide (D) and a transition metal compound (E) in the second agent as the polymerization initiator system. By combining such a polymerization initiator system and using it together with other components, the sub-packaged dental curable composition of the present invention can set the working time within an appropriate range, be excellent in adhesion to dentin and the mechanical strength of the cured product, have excellent storage stability, suppress the deterioration of performance during long-term storage, have little discoloration of the composition, and suppress the solidification risk.

[0037] Examples of the ascorbic acid compound (C) include salts, esters, ethers, etc. of ascorbic acid. Among these, salts and esters of ascorbic acid are preferred.

[0038] Examples of the salt 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 preferred.

[0039] Examples of the ester of ascorbic acid include those formed by reacting one or more of the hydroxy groups of ascorbic acid with a carboxylic acid. Suitable 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, in particular, the ester of stearic acid and ascorbic acid, and the ester of palmitic acid and ascorbic acid (ascorbyl palmitate) are preferably used.

[0040] Examples of the ether of ascorbic acid include ethyl ether of ascorbic acid and cetyl ether of ascorbic acid.

[0041] The ascorbic acid compound (C) 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 (C) 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 still more preferably in the range of 0.5 to 2 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the subpackage type dental curable composition of the present invention.

[0042] In the subpackage type dental curable composition of the present invention, the ascorbic acid compound (C) is blended in the same agent as the polymerizable monomer (A) having an acidic group. Although the ascorbic acid compound (C) undergoes oxidative decomposition under neutral or higher conditions, resulting in a problem that the composition turns yellow, discoloration (yellowing) of the composition can be suppressed by blending it in the first agent containing the polymerizable monomer (A) having an acidic group. The pH (pH when the paste is brought into contact with water) of the first agent containing the ascorbic acid compound (C) is optimally in the range of 3 to 7.

[0043] The ascorbic acid compound (C) is blended in the first agent from the viewpoint of storage stability. The ascorbic acid compound (C) may be dissolved in the first agent or dispersed as a powder in the composition of the first agent.

[0044] When the ascorbic acid compound (C) is dispersed as a powder, if its average particle diameter 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 still more preferably 5 μm or less.

[0045] The average particle diameter of the powder of the ascorbic acid compound (C) 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.

[0046] Regarding the shape of the particles when dispersing the ascorbic acid compound (C) in powder form, various shapes such as spherical, needle-like, plate-like, crushed, etc. can be mentioned, but it is not particularly limited. The ascorbic acid compound (C) can be produced by conventionally known methods such as a pulverization method, a freeze-drying method, a reprecipitation method, etc. From the viewpoint of the average particle diameter of the obtained powder, the pulverization method and the freeze-drying method are preferable.

[0047] Examples of the organic peroxide (D) include diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy ketals, ketone peroxides, and hydroperoxides. Specific examples of diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, etc. Specific examples of peroxy esters include t-butyl peroxybenzoate, bis(t-butylperoxy) isophthalate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisopropyl carbonate, etc. Specific examples of dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, etc. Specific examples of peroxy ketals include 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, etc. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide, etc. Specific examples of hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, p-diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, etc.

[0048] Among the organic peroxides (D), 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.

[0049] When the organic peroxide (D) is incorporated into the second agent and combined with other components, it suppresses the decomposition of the organic peroxide (D) while having a desired curability, so that the working time is within an appropriate range. It has excellent adhesion to dentin and mechanical strength of the cured product, and in addition, has a small decrease in performance during long-term storage, and can reduce the solidification risk. The organic peroxide (D) may be incorporated alone or in combination of two or more. From the viewpoints of curability, mechanical strength of the cured product, adhesion to dentin, and storage stability, the content of the organic peroxide (D) is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass, and even more preferably in the range of 0.5 to 3 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the sub-packaged dental curable composition of the present invention.

[0050] As the transition metal compound (E), copper compounds and vanadium compounds are preferably used.

[0051] 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.

[0052] As the vanadium compound, preferably vanadium compounds of tetravalent and / or pentavalent are used. Examples of the tetravalent and / or pentavalent vanadium compounds include vanadium(IV) dioxide, vanadyl acetylacetonate(IV), vanadium(IV) stearate, oxovanadium(IV) oxalate, vanadyl(IV) sulfate, 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), and the like. 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.

[0053] When the transition metal compound (E) is blended in the second agent and combined with other components, the operation time is within an appropriate range, and it is excellent in adhesiveness to dentin and mechanical strength of the cured product, and also excellent in storage stability during long-term storage. From the viewpoints of curability, mechanical strength, and adhesiveness to dentin, the content of the transition metal compound (E) is preferably in the range of 0.0001 to 1 part by mass, more preferably in the range of 0.0005 to 0.5 part by mass, and even more preferably in the range of 0.001 to 0.2 part by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the subpackage type dental curable composition of the present invention.

[0054] At least one of the first agent and the second agent of the dental curable composition of the present invention may contain a ligand compound (F). In a certain preferred embodiment, the ligand compound (F) is at least one compound selected from the group consisting of a ligand containing a phosphorus atom and a ligand containing a nitrogen atom. The ligand containing a phosphorus atom contains a phosphorus atom as a coordinating atom. The ligand containing a nitrogen atom contains a nitrogen atom as a coordinating atom.

[0055] As one embodiment, there is provided a unit-dose dental curable composition in which the first agent contains a ligand compound (F).

[0056] As a preferred embodiment, there is provided a unit-dose dental curable composition in which the ligand compound (F) contains a ligand containing a nitrogen atom.

[0057] As another preferred embodiment, there is provided a unit-dose dental curable composition in which the ligand compound (F) contains a ligand containing a phosphorus atom.

[0058] Examples of the ligand containing a phosphorus atom include a phosphine ligand and a phosphite ligand. Specifically, examples of the ligand containing a phosphorus atom include a compound represented by the following general formula (1), a compound represented by general formula (2), a compound represented by general formula (3), and a compound represented by general formula (4). The ligand containing a phosphorus atom may be used alone or in combination of two or more.

[0059]

Chemical formula

[0060]

Chemical formula

[0061]

Chemical formula

Chemical Formula

[0062] Among the ligands containing a phosphorus atom, from the viewpoints of curability, mechanical strength of the cured product, and adhesion to dentin, the compound represented by the above general formula (1) and the compound represented by general formula (2) are more preferable.)

[0063] R1 to R 15 are more preferably a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.)

[0064] R 16 to R 35 are more preferably a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.)

[0065] Each of Z1 to Z3 is more preferably a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.)

[0066] The alkyl group which may have a substituent of R1 to R 15 may be either linear or branched. The carbon number of the alkyl group of R1 to R 15 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. R1 to R 15Examples of the alkyl group 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. R1 to R 15 The alkyl group of R1 to R 15 Examples of the substituent of the alkyl group of R1 to R

[0067] R1 to R 15 Examples of the halogen atom of R1 to R

[0068] R1 to R 15As the polar group, examples include an acid anhydride group, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid chloride group, a carboxylic acid amide group, a carboxylic acid salt group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid amide group, a sulfonic acid salt group, an aldehyde group, an epoxy group, a cyano group, an amino group, a monoalkyl-substituted amino group, a dialkyl-substituted amino group, an imide group, an oxazoline group, etc. From the viewpoints of curability and mechanical strength of the cured product, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid chloride group, a carboxylic acid amide group, a carboxylic acid salt group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid amide group, a sulfonic acid salt group, an aldehyde group are preferable, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid chloride group, a carboxylic acid salt group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid salt group, an aldehyde group are more preferable, and a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid chloride group, a carboxylic acid salt group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid salt group are even more preferable. As the salts of the carboxylic acid salt group and the sulfonic acid salt group, examples include alkali metal salts such as lithium, sodium, potassium, etc.; alkaline earth metal salts such as magnesium, calcium, strontium, barium, radium, etc. R1~R 15 When it is the polar group of 15 , the number of polar groups is preferably 1 to 9, more preferably 1 to 5, and even more preferably 1 to 3. R1~R 15 When R1~R 15 is an alkyl group having a substituent, specifically, a trifluoromethyl group, etc. can be mentioned.

[0069] R1~R 15 The alkoxy group which may have a substituent of R1~R 15 may be either linear or branched. R1~R 15 The carbon number of the alkoxy group of R1~R 15 is not particularly limited, preferably 1 to 12, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 to 3. R1~R 15Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, neopentyloxy group, n-hexyloxy group, isohexyloxy group, sec-hexyloxy group, tert-hexyloxy group, neohexyloxy group, etc. R1 to R 15 Examples of the substituent of the alkoxy group include the same as those of the alkyl group of R1 to R 15 15

[0070] R1 to R 15 may be the same or different. R1 to R 15 For example, some of them may be the same hydrogen atom, alkyl group or alkoxy group.

[0071] R 16 to R 35 The alkyl group which may have a substituent of R to R 15 is the same as the alkyl group which may have a substituent of R1 to R 16 R to R 35 The alkoxy group which may have a substituent of R to R 15 is the same as the alkoxy group which may have a substituent of R1 to R 16 R to R 35 Examples of the halogen atom of R to R 15 are the same as those of the halogen atom of R1 to R 16 R to R 35 Examples of the polar group of R to R 15 are the same as those of the polar group of R1 to R

[0072] The divalent aliphatic group which may have a substituent for X1 may be either 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, with the alkylene group being preferred. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a methylpropylene group, a dimethylpropylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, etc. Examples of the substituent of the divalent aliphatic group for X1 include the same as those of the substituent of the alkyl group for R1 to R 15 The same as those of the substituent of the alkyl group of.

[0073] In formula (3), the plurality of Ars may be the same or different. In the group represented by general formula (3-a), Z1 to Z3 may be the same or different. The alkyl group which may have a substituent for Z1 to Z3 is the same as the alkyl group which may have a substituent for R1 to R 15 At least one of Z1 to Z3 is a hydrogen atom, and Z1 to Z3 may all be hydrogen atoms. Specific examples of Ar include, for example, the following groups. [Chemical formula]

[0074] In a certain embodiment, among Z1 to Z3, one or two are hydrogen atoms, and the other one or two of Z1 to Z3 may be a linear or branched alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, may be a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a fluorine atom, or may be a trifluoromethyl group. The alkoxy group which may have a substituent for Z1 to Z3 is R1 to R 15This is the same as an alkoxy group which may have a substituent. In a certain preferred embodiment, examples of the phosphine compound include those in which, in the compound represented by the general formula (3), all Ar are 3,5-dimethylphenyl groups. In another preferred embodiment, examples of the phosphine compound include those in which, in the compound represented by the general formula (3), all Ar are 4-methylphenyl groups.

[0075] Regarding the phosphite ligand represented by the general formula (4), the three Y1 may be the same or different. The alkyl group which may have a substituent of Y1 is the same as the alkyl group which may have a substituent of R1 to R 15 This is the same as the alkyl group which may have a substituent. The number of carbon atoms of the aryl group which may have a substituent of Y1 is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10. Examples of the substituent of the aryl group of Y1 include the same ones as the substituent of the alkyl group of R1 to R 15 Examples of the aryl group which may have a substituent of Y1 include phenyl group, biphenyl group, indenyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, pyrenyl group; phenyl group substituted with an alkyl group such as tolyl group, xylyl group, trimethylphenyl group, ethylphenyl group, isopropylphenyl group, tetramethylphenyl group, etc. In a certain preferred embodiment, examples of the phosphite compound include those in which the three Y1 are 1,1,1,3,3,3-hexafluoro-2-propyl groups. In another preferred embodiment, examples of the phosphite compound include those in which the three Y1 are 2,4,-di-tert-butylphenyl groups.

[0076] Examples of the monodentate phosphine compound represented by the general formula (1) include phosphine compounds having an electron-donating group such as triphenylphosphine, diphenyl(o-tolyl)phosphine, tri(o-tolyl)phosphine, tri(p-tolyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(2-methoxyphenylphosphine), tris(4-methoxyphenylphosphine), tris(2,6-dimethoxyphenyl)phosphine (hereinafter sometimes abbreviated as "DMPP"), diphenyl(2-methoxyphenyl)phosphine, 4-(dimethylamino)triphenylphosphine; phosphine compounds having an electron-withdrawing group such as (2-fluorophenyl)diphenylphosphine, (2-chlorophenyl)diphenylphosphine, (2-bromophenyl)diphenylphosphine, (pentafluorophenyl)diphenylphosphine, bis(pentafluorophenyl)phenylphosphine (hereinafter sometimes abbreviated as "BPFPP"), tris(pentafluorophenyl)phosphine (hereinafter sometimes abbreviated as "TPFPP"), tris(4-fluorophenyl)phosphine (hereinafter sometimes abbreviated as "TFPP"), tris(4-chlorophenyl)phosphine, tris(4-bromophenyl)phosphine, tris(4-trifluoromethylphenyl)phosphine, tris(4-carboxyphenyl)phosphine, sodium diphenylphosphinobenzene-3-sulfonate, trisodium triphenylphosphine-3,3',3''-trisulfonate.

[0077] Examples of the bidentate phosphine compound of the general formula (2) include phosphine compounds such as bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)pentane, 1,6-bis(diphenylphosphino)hexane.

[0078] Examples of the biphenylphosphine compound of the general formula (3) include (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (hereinafter sometimes abbreviated as "BINAP"), (±)-2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl, (±)-2,2'-bis(di-p-fluorophosphino)-1,1'-binaphthyl, (±)-2,2'-bis(di-p-trifluoromethylphosphino)-1,1'-binaphthyl, (±)-2,2'-bis[di(3,5-xylyl)phosphino]-1,1'-binaphthyl, and the like.

[0079] Examples of the phosphite compound of the general formula (4) include trimethyl phosphite, triethyl phosphite, tris(1,1,1,3,3,3-hexafluoro-2-propyl) phosphite, triphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, and the like.

[0080] Examples of the ligand containing a nitrogen atom include, for example, a compound represented by the general formula (5), a compound represented by the general formula (6), and a multidentate ligand (7) containing a nitrogen-containing heterocyclic ring. The ligand containing a nitrogen atom may be used alone or in combination of two or more.

[0081] R 36 R 37 N-X2-NR 38 R 39 (5) (R 36 ~R 39 (each independently represents an alkyl group which may have a substituent, and X2 represents a divalent aliphatic group which may have a substituent.)

[0082]

Chemical formula

[0083] R 36 ~R 39 the alkyl group which may have a substituent is the same as the alkyl group which may have a substituent of R1~R 15 .

[0084] The divalent aliphatic group which may have a substituent of X2 is the same as the divalent aliphatic group which may have a substituent of X1.

[0085] R 40 R 41 and R 42 the alkyl group which may have a substituent is the same as the alkyl group which may have a substituent of R1~R 15 . For the monoalkylamino group (-NHR a (R a represents an alkyl group)) and the dialkylamino group (-NR b R c (R b and R c represent alkyl groups)) of Y2, the number of carbon atoms is not particularly limited, preferably 1~12, more preferably 1~6, still more preferably 1~4, and particularly preferably 1~3. As the alkyl group of the monoalkylamino group and the dialkylamino group of Y2, R1~R 15Among the alkyl groups which may have a substituent, those satisfying the above carbon number are mentioned. As the dialkylamino group, each alkyl group may have the above carbon number. As the monoalkylamino group which may have a substituent of Y2, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, t-butylamino group, pentylamino group, hexylamino group and the like are mentioned. As the dialkylamino group which may have a substituent of Y2, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, dipentylamino group, dihexylamino group, ethylmethylamino group and the like are mentioned. The alkyl groups of the monoalkylamino group and dialkylamino group of Y2 may be substituted with a substituent. As the substituent, those similar to the substituent of the alkyl group of R1~R 15 are mentioned, which are the same as those of the substituent of the alkyl group.

[0086] The divalent aliphatic groups of X3 and X4 may be either linear or branched. As the carbon number of the divalent aliphatic group, 1 to 20 is preferable, 1 to 16 is more preferable, 1 to 12 is further preferable, and 1 to 8 is particularly preferable. As the divalent aliphatic group, an alkylene group, an alkenylene group, an alkynylene group are mentioned, and an alkylene group is preferable. As the alkylene group, methylene group, ethylene group, propylene group, butylene group, methylpropylene group, dimethylpropylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group and the like are mentioned. As the substituent of the divalent aliphatic group of X3 and X4, those similar to the substituent of the divalent aliphatic group of X1 are mentioned. The divalent aliphatic groups of X3 and X4 may contain an oxygen atom and / or a nitrogen atom. X3 and X4 may be the same or different.

[0087] m and n each independently represent an integer of 1 or more, preferably an integer of 1 to 8, more preferably an integer of 1 to 6, still more preferably an integer of 1 to 5, and particularly preferably 1 to 3. m and n may be the same or different.

[0088] R 40 、R 41 、R 42 Any two or more of Y2 may combine to form a ring. For example, R 40 、R 41 、or R 42 and Y2 may combine to form a ring. Also, R 40 and Y2, R 41 and R 42 may each combine to form a ring, and the compound may have two rings. Further, the nitrogen atom of the amino group of Y2 and R 40 may combine to form a ring. The ring may contain an oxygen atom and / or a nitrogen atom. Furthermore, in certain embodiments, the compound represented by general formula (6) may be a compound having a bicyclic ring. For example, in other embodiments, in the compound represented by general formula (6), the ring formed by Y2 and R 40 and the ring formed by Y2 and R 41 or R 42 may have a bicyclic ring.

[0089] In a preferred embodiment, R 41 and R 42 are a linear or branched alkyl group which may have a substituent having 1 to 6 carbon atoms.

[0090] Also, as another preferred embodiment, at least one of the first agent and the second agent contains a ligand compound (F), and the ligand compound (F) is at least one selected from the group consisting of a compound represented by general formula (1) and a compound represented by general formula (5), and a packaged dental curable composition is exemplified.

[0091] Also, in another preferred embodiment, at least one of the first agent and the second agent contains a ligand compound (F), the ligand compound (F) is a compound represented by the general formula (6), and in the compound represented by the general formula (6), R 40 , R 41 and R 42 represent a linear or branched alkyl group which may have a substituent having 1 to 6 carbon atoms, the divalent aliphatic group of X3 and X4 represents an alkylene group not containing an oxygen atom and a nitrogen atom, m and n each independently represent an integer of 1 or more, Y2 represents a monoalkylamino group or a dialkylamino group which may have a substituent, R 40 , R 41 , or R 42 and Y2 together form a ring, and an example is a two-package type dental curable composition.

[0092] Also, in another preferred embodiment, at least one of the first agent and the second agent contains a ligand compound (F), the ligand compound (F) is a compound represented by the general formula (6), and in the general formula (6), m is 1 and n is 2, and an example is a two-package type dental curable composition which is a compound containing 4 nitrogen atoms as a whole compound.

[0093] The polydentate ligand (7) containing the nitrogen-containing heterocyclic ring contains a heterocyclic ring including a 5-membered or 6-membered ring containing a nitrogen atom, has two or more nitrogen atoms in the molecule, and represents a ligand compound having two or more coordination sites. The number of nitrogen atoms that the polydentate ligand (7) has in the molecule is two or more, and may be three or more. The number of heterocyclic rings contained in the polydentate ligand (7) may be one, or may be two or more. Examples of the nitrogen-containing heterocyclic ring include nitrogen-containing 5-membered rings such as pyrrole ring, pyrazole ring, imidazole ring; nitrogen-containing 6-membered rings such as pyridine ring, pyrazine ring, pyridazine ring, piperazine ring, pyrimidine ring, triazine ring, etc. The nitrogen-containing heterocyclic ring may be a condensed ring of the 5-membered or 6-membered ring containing the nitrogen atom and another ring (for example, an aromatic ring), or may be a condensed ring of two 5-membered or 6-membered rings containing the nitrogen atom. Examples of the condensed ring of the 5-membered or 6-membered ring containing the nitrogen atom and the aromatic ring include quinoline ring, isoquinoline ring, indole ring, benzimidazole ring, benzotriazole ring, etc. The polydentate ligand (7) only needs to contain a heterocyclic ring including a 5-membered or 6-membered ring containing a nitrogen atom. For example, ligand compounds containing a condensed ring such as indole ring, benzimidazole ring, benzotriazole ring and a heterocyclic ring including a 5-membered or 6-membered ring containing a nitrogen atom can be mentioned. The polydentate property of the polydentate ligand (7) only needs to be two or more, and may be tridentate, tetradentate, etc.

[0094] Examples of the polydentate amine compound of the general formula (5) include bidentate coordination polydentate amine compounds such as N,N,N’,N’-tetramethylethylenediamine (hereinafter, may be abbreviated as “TMEDA”), N,N,N’,N’-tetramethylpropylenediamine (hereinafter, may be abbreviated as “TMPDA”), N,N,N’,N’-tetramethyl-1,4-diaminobutane, N,N,N’,N’-tetraethylethylenediamine (hereinafter, may be abbreviated as “TEEDA”), N,N,N’,N’-tetrakis(2-hydroxyethyl)ethylenediamine, etc.

[0095] Examples of the compound represented by the general formula (6) include compounds having a cyclo ring such as 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; compounds having a bicyclo ring such as 4,11-dimethyl-1,4,8,11-tetraazabicyclohexadecane; 2,5,9,12-tetramethyl-2,5,9,12-tetraazatetradecane, 2,6,9,13-tetramethyl-2,6,9,13-tetraazatetradecane, 2,5,8,12-tetramethyl-2,5,8,12-tetraazatetradecane, N,N,N,N’,N’’,N’’-pentamethyldiethylenetriamine (hereinafter sometimes abbreviated as “PMDETA”), hexamethyltris(2-aminoethyl)amine, N,N-bis(2-dimethylaminoethyl)-N,N’-dimethylethylenediamine (hereinafter sometimes abbreviated as “HMTETA”), tris[2-(dimethylamino)ethyl]amine (hereinafter sometimes abbreviated as “Me6TREN”), and other multi-dentate amine compounds such as compounds having no ring.

[0096] Examples of the multi-dentate ligand (7) containing the nitrogen-containing heterocyclic ring include 2,2-bipyridine, 4,4’-di-(5-nonyl)-2,2’-bipyridine, N-(n-propyl)pyridylmethanimine, N-(n-octyl)pyridylmethanimine, N-propyl-N,N-di(2-pyridylmethyl)amine, N’,N’’-dimethyl-N’,N’’-bis((pyridin-2-yl)methyl)ethane-1,2-diamine, 2,6-bis(1-pyrazole)-pyridine (hereinafter sometimes abbreviated as “DPP”), 2-(2-pyridyl)benzimidazole, tris[(2-pyridyl)methyl]amine, 3,6-di(2-pyridyl)-1,2,4,5-tetrazine, N,N,N’,N’-tetrakis(2-pyridylmethyl)ethylenediamine, 2,4,6-tri(2-pyridyl)-1,3,5-triazine, and the like.

[0097] Among these, tri(o-tolyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, TMEDA, TMPDA, TEEDA, PMDETA, and Me6TREN are preferably used. The ligand compound (F) may be blended alone or in combination of two or more. The ligand compound (F) is used to enhance the catalytic activity of the transition metal compound in the subpackage type dental curable composition of the present invention. From the viewpoints of curability, mechanical strength of the cured product, and adhesiveness to dentin, the content of the ligand compound (F) is preferably in the range of 0.005 to 10 parts by mass, more preferably in the range of 0.01 to 5 parts by mass, and even more preferably in the range of 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the subpackage type dental curable composition of the present invention.

[0098] In order to obtain sufficient workability of the composition and further sufficient radiopacity and mechanical strength of the cured product, at least one of the first agent and the second agent of the subpackage type dental curable composition of the present invention may contain a filler (G).

[0099] As the filler (G), any filler can be used as long as the effects of the present invention are not impaired, and examples include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers. The filler (G) may be blended alone or in combination of two or more. The average particle diameter of the filler (G) is preferably 0.001 to 10 μm, and more preferably 0.001 to 5 μm.

[0100] Examples of the inorganic filler include silica; minerals based on silica such as kaolin, clay, mica, and myca; ceramics and glasses based on silica and containing Al2O3, B2O3, TiO2, ZrO2, BaO, La2O3, SrO, ZnO, CaO, P2O5, Li2O, Na2O, etc. Examples of the glasses include lithium borosilicate glass, borosilicate glass, bioglass, lanthanum glass, barium glass, strontium glass, soda glass, zinc glass, and fluoroaluminosilicate glass. As the inorganic filler, crystalline quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride are also preferably used. In terms of adhesiveness and handleability, fine particle silica with an average particle diameter of 0.001 to 0.1 μm is preferably used. Commercially available products include "Aerosil (registered trademark) OX50", "Aerosil (registered trademark) 50", "Aerosil (registered trademark) 200", "Aerosil (registered trademark) 380", "Aerosil (registered trademark) R972", "Aerosil (registered trademark) 130", and "AEROXIDE (registered trademark) Alu C" (all of the above are product names manufactured by Nippon Aerosil Co., Ltd.). In the present invention, when the inorganic filler is surface-treated as described below, the average particle diameter of the inorganic filler means the average particle diameter before the surface treatment.

[0101] Examples of the organic filler include, for example, polymers of polymethyl methacrylate, polyethyl methacrylate, polyfunctional methacrylate, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.

[0102] 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.

[0103] In order to improve the hardness, mechanical strength, and handleability, the filler (G) 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.

[0104] The average particle diameter (average primary particle diameter) can be determined by the laser diffraction scattering method or electron microscope observation of the particles. Specifically, the laser diffraction scattering method is convenient for measuring the particle 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 the 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 measuring with 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. In electron microscope observation, an electron micrograph of the particles is taken, and the particle diameter of the particles (200 or more) observed in a unit visual field of the photograph can be determined by measuring using image analysis type particle size distribution measurement software (Mac-View (manufactured by Mountech 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.

[0105] The content of the filler (G) is not particularly limited as long as the effects of the present invention are achieved. However, in the total amount of 100 parts by mass of the polymerizable monomer component in the subpackage type dental curable composition of the present invention, a range of 50 to 300 parts by mass is preferable, and a range of 100 to 250 parts by mass is more preferable. Within these ranges, sufficient radiopacity or sufficient mechanical strength of the cured product can be obtained, and sufficient paste workability can be obtained.

[0106] In the subcontracted dental curable composition of the present invention, the first agent may further contain a thiourea compound, sulfinic acid and its salts, sulfites, bisulfites, borate compounds, barbituric acid and its derivatives.

[0107] Examples of the thiourea compound include thiourea, methylthiourea, ethylthiourea, ethylene thiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, N,N'-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, tetracyclohexylthiourea, 1-(2-pyridyl)-2-thiourea, 4,4-dimethylethylene thiourea and the like. The thiourea compound may be used alone or in combination of two or more.

[0108] 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, etc. Among these, sodium benzenesulfinate, sodium p-toluenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, and sodium 2,4,6-triisopropylbenzenesulfinate are preferred. The sulfinic acid and its salts may be used alone or in combination of two or more.

[0109] 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, tetraphenyl boron, tetrakis(p-chlorophenyl) boron and the like) and salts thereof. Examples of barbituric acid and its derivatives include barbituric acid, 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and salts thereof.

[0110] The sub-packaged dental curable composition of the present invention contains a redox type polymerization initiator. In order to make the sub-packaged dental curable composition of the present invention a dual-cure type composition that also starts polymerization by light irradiation as needed, at least one of the first agent and the second agent may further contain a conventionally known photoinitiator as a component different from the above polymerization initiator system.

[0111] Examples of the photoinitiator include α-diketones, ketals, thioxanthones, (bis)acylphosphine oxides, and α-aminoacetophenones.

[0112] Examples of the α-diketones include dl-camphorquinone (commonly known as "CQ"), benzil, and 2,3-pentanedione.

[0113] Examples of the ketals include benzyldimethyl ketal and benzyldiethyl ketal.

[0114] Examples of the thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

[0115] Among the above-mentioned (bis)acylphosphine oxides, examples of acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, benzoylbis(2,6-dimethylphenyl)phosphine oxide, the water-soluble acylphosphine oxide compound disclosed in Japanese Patent Publication No. 3-57916, and salts thereof (e.g., sodium salt, potassium salt, ammonium salt), etc. Examples of bisacylphosphine oxides include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, dibenzoylphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, tris(2,4-dimethylbenzoyl)phosphine oxide, tris(2-methoxybenzoyl)phosphine oxide, and salts thereof (e.g., sodium salt, potassium salt, ammonium salt), etc. Among these (bis)acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and sodium 2,4,6-trimethylbenzoylphenylphosphine oxide are preferred.

[0116] 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.

[0117] 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.

[0118] In addition, in order to enhance the photocurability, a photoinitiator and a polymerization accelerator for the photoinitiator may be used in combination. Examples of the polymerization accelerator for the photoinitiator include tertiary amines, aldehydes, thiol compounds, triazine compounds substituted with a trihalomethyl group, and the like.

[0119] Examples of the tertiary amines include N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-di(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-diisopropylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, n-butoxyethyl 4-(N,N-dimethylamino)benzoate, 2-(methacryloyloxy)ethyl 4-(N,N-dimethylamino)benzoate, ethyl 4-(N,N-dimethylamino)benzoate, butyl 4-(N,N-dimethylamino)benzoate, N-methyldiethanolamine, 4-(N,N-dimethylamino)benzophenone, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, 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. Examples of the aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of the benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, p-n-octyloxybenzaldehyde, and the like.Examples of the thiol compound 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 or a tribromomethyl group.

[0120] 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 0.001 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 in the subpackage type dental curable composition of the present invention.

[0121] 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, a dental resin cement capable of imparting acid resistance to dental tissue can be obtained. Examples of such fluoride ion-releasing substances 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 substances may be used alone or in combination of two or more.

[0122] 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. The pH adjuster may be used alone or in combination of two or more kinds.

[0123] Examples of phosphates include alkali metal phosphates such as trisodium phosphate and tripotassium phosphate; alkali metal hydrogen phosphates such as disodium hydrogen phosphate and dipotassium hydrogen phosphate; alkali metal dihydrogen phosphates such as sodium dihydrogen phosphate and potassium dihydrogen phosphate; alkyl alkali metal phosphates such as sodium dodecyl phosphate; sodium glycerophosphate and disodium glycerophosphate; alkaline earth metal phosphates such as tricalcium phosphate and trimagnesium phosphate; alkaline earth metal hydrogen phosphates such as calcium hydrogen phosphate and magnesium hydrogen phosphate; and alkaline earth metal dihydrogen phosphates such as calcium dihydrogen phosphate. Among these, disodium hydrogen phosphate, sodium dodecyl phosphate, sodium glycerophosphate, and disodium glycerophosphate are preferably used.

[0124] In addition, additives such as a polymerization inhibitor, an ultraviolet absorber, a thickener, a solvent (e.g., water, an organic solvent), a colorant, an antibacterial agent, and a fragrance may be incorporated into at least one of the first agent and the second agent as long as the effects of the present invention are not inhibited. These may be incorporated 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-t-butyl-4-methylphenol, and the like. In certain embodiments, the content of the solvent (e.g., water, an organic solvent) in the 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, based on the total amount of the two-component dental curable composition.

[0125] The two-component dental curable composition of the present invention may be prepared according to a conventional method depending on the types and amounts of the above components. The two-component dental curable composition of the present invention is used in a two-agent form. As the two-agent form, it can be appropriately selected and implemented from forms such as a powder material and a liquid material, a paste and a liquid material, and a two-paste form. From the viewpoint of operability, in a more preferred embodiment, it is used in a two-paste form. It is preferable to store each paste in a state where the pastes are isolated from each other, and to knead the two pastes immediately before use to allow chemical polymerization to proceed and cure. The paste is usually prepared by kneading a liquid component prepared by mixing components other than the filler (G) and the filler (G) (powder).

[0126] The two-component dental curable composition of the present invention is used for adhesion between a dental prosthesis such as a crown, inlay, or bridge and tooth substance to a defect part of a tooth affected part, and for abutment construction. In particular, it is preferably used as a self-adhesive dental resin cement.

[0127] 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.

Example

[0128] Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. The abbreviations and symbols used hereinafter are as follows. Compounds and fillers used in the following examples and comparative examples were commercially available products unless otherwise specified in the manufacturing method.

[0129] 〔Polymerizable monomer (A) having an acidic group〕 MDP: 10-Methacryloyloxydecyl dihydrogen phosphate

[0130] 〔Polymerizable monomer (B) having no acidic group〕 HEMA: 2-Hydroxyethyl methacrylate Bis-GMA: 2,2-Bis〔4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl〕propane D-2.6E: 2,2-Bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of added moles of ethoxy group: 2.6) TEGDMA: Triethylene glycol dimethacrylate

[0131] 〔Ascorbic acid compound (C)〕 PA: Ascorbyl palmitate ANa: Sodium L-ascorbate

[0132] 〔Organic peroxide (D)〕 THP: 1,1,3,3-Tetramethylbutyl hydroperoxide BPB: t-Butyl peroxybenzoate

[0133] 〔Transition metal compound (E)〕 CuA: Copper(II) acetate VOAA: Vanadyl acetylacetonate(IV)

[0134] [Ligand compound (F)] DMPP: Tris(2,6-dimethoxyphenyl)phosphine TEEDA: Tetraethylethylenediamine

[0135] [Filler (G)] Surface-treated barium glass: Barium glass (manufactured by Estec Co., Ltd., product code "E-3000") was pulverized with a ball mill to obtain barium glass powder. When the average particle diameter of the obtained barium glass powder was measured on a volume basis using a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation, model "SALD-2300"), it was 2.4 μm. 100 parts by mass of this barium glass powder was surface-treated with 3 parts by mass of γ-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain surface-treated Ba glass powder. R972: Fine silica manufactured by Nippon Aerosil Co., Ltd., trade name "Aerosil (registered trademark) R972", average particle diameter: 16 nm Alumina: Aluminum oxide manufactured by Nippon Aerosil Co., Ltd., trade name "AEROXIDE (registered trademark) Alu C", average particle diameter: 20 nm

[0136] [Polymerization inhibitor] BHT: 2,6-Di-t-butyl-4-methylphenol

[0137] [pH adjuster] Disodium hydrogen phosphate Sodium dodecyl phosphate

[0138] (Examples 1 to 10 and Comparative Examples 1 to 3) Among the components listed in Table 1, the components other than the filler and ascorbic acid compound were mixed at room temperature to obtain a uniform liquid component. Then, the obtained liquid component was kneaded with the ascorbic acid compound and the filler to prepare the unit-dose dental curable compositions of Examples 1 to 10 and Comparative Examples 1 to 3. Next, using these unit-dose dental curable compositions, the working time at 23°C, the adhesive strength to bovine dentin, and the flexural strength were measured immediately after production 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, the solidification of the paste, and the discoloration of the paste were measured. Table 1 shows the mixing ratio (parts by mass) and test results of this dental curable composition.

[0139] [Working Time at 23°C of Unit-Dose 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 well mixed with a spatula to form one agent. The time (working time) from the time of mixing to the time when the temperature began to rise due to the start of paste curing was measured with a thermocouple (manufactured by Okazaki Seisakusho Co., Ltd.) connected to a recording meter (manufactured by Yokogawa Electric Corporation). The working time is the average value of the measured values for 5 test samples. From the viewpoint of the working margin time, that is, the ability to operate with the composition with a margin and to cure after operation, the working time suitable for actual use is 2 to 10 minutes. Also, 4 g each of the first agent and the second agent of the unit-dose 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. Then, the working time was measured in the same manner using this.

[0140] [Adhesive Strength of Unit-Dose Dental Curable Composition to Bovine Dentin] The labial surface of the bovine mandibular anterior teeth was polished with #80 silicon carbide paper (manufactured by Nippon Kenji Co., Ltd.) under running water to expose the flat surface of the dentin. The exposed flat surface was further polished with #1000 silicon carbide paper (manufactured by Nippon Kenji Co., Ltd.) under running water. After polishing, the water on the surface was dried by air blowing. A pressure-sensitive tape with a thickness of about 150 μm and having a round hole with a diameter of 3 mm was adhered to the dried smooth surface to define the adhesive 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 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. 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 these test samples, the tensile adhesive strength to bovine dentin after standing at 37°C for 24 hours was measured. The tensile adhesive strength was measured using a universal testing machine (manufactured by Shimadzu Corporation, Autograph "AG-I 100kN") with the crosshead speed set at 2 mm / min. 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 five test samples. Also, 4 g each of the first agent and the second agent of the sub-packaged 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 them in a drying atmosphere at 60°C for 3 weeks, the adhesive strength was measured using them in the same manner as when stored at 37°C for 24 hours.

[0141] [Flexural Strength of the Cured Product of the Sub-Packaged Dental Curable Composition] A polyester film was laid on a slide glass plate, and a stainless steel mold with a length of 2 mm, a width of 25 mm, and a depth of 2 mm was placed thereon. Next, a mixture of the first agent and the second agent of the sub-packaged dental curable composition of the present invention was filled into the mold, the surface of the composition in the mold was pressed against the slide glass through the polyester film, and two slide glasses were fixed using a double clip with a width of 25 mm. The sample fixed with the double clip was allowed to stand in a thermostat at 37°C for 1 hour for polymerization and curing, then the sample was taken out of the thermostat, and the polymerized and cured product of the composition was removed from the mold. After the polymerized and cured product was immersed in distilled water at 37°C for 24 hours for storage, a bending test was performed using this as a test piece. The bending strength was measured by performing a three-point bending test with a span of 20 mm and a crosshead speed of 1 mm / min using a universal testing machine (manufactured by Shimadzu Corporation, Autograph "AG-I 100kN"). The average value of the bending strengths of 5 test pieces was taken as the bending strength of the sample.

[0142] [Solidification of Sub-packaged Dental Curable Composition] The first agent and the second agent of the sub-packaged dental curable composition of the present invention were each filled with 4 g into a product container of "SA ROUTING (registered trademark) Multi" (manufactured by Kuraray Noritake Dental Co., Ltd.), stored in a dry atmosphere at 60°C for 3 weeks, and the presence or absence of a cured product was confirmed for each of the first agent and the second agent. 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 performed for 5 samples, and samples for which the presence of a cured product was confirmed even in one were indicated as "present".

[0143] [Discoloration of Sub-packaged Dental Curable Composition] The first agent (or the second agent in the case of Comparative Examples 1 and 2) of the unit-dose dental curable composition of the present invention containing an ascorbic acid compound was sandwiched between two cover glasses, made into a disk shape with a thickness of 1 mm using a 1-mm gauge, and its color tone was measured with a color difference meter, which was taken as the initial value. Also, 4 g each of the first agent and the second agent of the unit-dose dental curable composition of the present invention were filled into a product container of "SA Routing (registered trademark) Multi" (manufactured by Kuraray Noritake Dental Co., Ltd.), stored for 3 weeks in a drying atmosphere at 60°C, and the color tone was measured in the same manner as the initial value. Discoloration is the average value of the measured values for two test samples. At this time, the difference from the initial value was defined as discoloration (ΔE*).

[0144] As shown in Table 1, the unit-dose dental curable compositions of the present invention (Examples 1 to 10) had an appropriate working time at 23°C immediately after preparation (the "23°C working time" of the refrigerated products in the table), and excellent results in terms of the adhesive strength and flexural strength to bovine dentin. Also, no solidification was observed in the paste after storage at 60°C for 3 weeks, and the discoloration of the paste was below the visually observable level (ΔE * ≦5). Also, the working time at 23°C after storage at 60°C for 3 weeks (the "23°C working time" of the temperature-accelerated products in the table) and the adhesive strength to bovine dentin showed little change compared to immediately after production.

[0145] On the other hand, the first agents of the dental curable compositions of Comparative Examples 1 and 2 in which the polymerizable monomer (A) having an acidic group, the organic peroxide (D), and the transition metal compound (E) were blended in the same agent solidified after storage at 60°C for 3 weeks. Also, in Comparative Example 1, when the ascorbic acid compound was blended in the second agent not containing the polymerizable monomer (A) having an acidic group, the discoloration of the second agent was very large. Furthermore, in Comparative Example 3 in which the polymerizable monomer (A) having an acidic group was contained in both the first agent and the second agent, solidification occurred in the second agent in which the polymerizable monomer (A) having an acidic group and the organic peroxide (D) coexisted after storage at 60°C for 3 weeks.

[0146]

Table 1

Industrial Applicability

[0147] The subcontracted dental curable composition of the present invention can be suitably used in dental treatment for adhesion between dental prostheses such as crowns, inlays, bridges and tooth substance, and for abutment construction and the like.

Claims

1. A first agent containing a polymerizable monomer (A) having an acidic group, a polymerizable monomer (B) having no acidic group, and an ascorbic acid compound (C), a second agent containing a polymerizable monomer (B) having no acidic group, an organic peroxide (D), and a transition metal compound (E) and not containing a polymerizable monomer (A) having an acidic group, wherein the ascorbic acid compound (C) is a photo-dissociable reducing agent represented by the following formula: [In the formula, each of R1 and R2 is H, alkyl, aryl, or RPhoto, provided that at least one of R1 and R2 is RPhoto, RPhoto is a photo-dissociable group, each of R3 and R4 is independently H, alkyl, aryl containing an ester, ether, urethane or carbonate functional group.], and does not contain a two-pack dental curable composition, wherein the transition metal compound (E) is a copper compound or a vanadium compound.

2. The two-pack dental curable composition according to claim 1, wherein at least one of the first agent and the second agent contains a ligand compound (F), and the ligand compound (F) is at least one compound selected from the group consisting of a ligand containing a phosphorus atom and a ligand containing a nitrogen atom.

3. The ligand compound (F) is a ligand containing a phosphorus atom, and the ligand containing a phosphorus atom is at least one compound selected from the group consisting of a compound represented by the following general formula (1), a compound represented by general formula (2), a compound represented by general formula (3), and a compound represented by general formula (4). The two-pack dental curable composition according to claim 2. 【Chemical 1】 (R 1 ~R 15 each independently represents a hydrogen atom, a halogen atom, a polar group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.) 【Chemical 2】 (R 16 ~R 35 each independently represents a hydrogen atom, a halogen atom, a polar group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and X 1 represents a divalent aliphatic group which may have a substituent.) 【Chemical Formula 3】 (Ar each independently represents a group represented by the following general formula (3-a).) 【Chemical Formula 4】 (Z 1 to Z 3 are each independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and at least one of Z 1 to Z 3 is a hydrogen atom.) P(OY 1 ) 3 (4) (Y 1 is each independently an alkyl group which may have a substituent, or an aryl group which may have a substituent)

4. The two-pack dental curable composition according to claim 3, wherein the ligand containing a phosphorus atom is at least one compound selected from the group consisting of a compound represented by general formula (1) and a compound represented by general formula (2).

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

6. The ascorbic acid compound (C) is at least one compound selected from the group consisting of salts and esters of ascorbic acid. The encapsulated dental curable composition according to any one of claims 1 to 5.

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

8. Furthermore, at least one of the first agent and the second agent contains a filler (G). The encapsulated dental curable composition according to any one of claims 1 to 7.

9. Furthermore, at least one of the first agent and the second agent contains a pH adjuster. The encapsulated dental curable composition according to any one of claims 1 to 8.

10. The pH adjuster is a phosphate. The encapsulated dental curable composition according to claim 9.

11. A dental resin cement. The encapsulated dental curable composition according to any one of claims 1 to 10.

12. The dental resin cement is a self-adhesive dental resin cement. The encapsulated dental curable composition according to claim 11.

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