JP7708636B2 - Dental hardenable composition in individual packets - Google Patents

Description

The present invention relates to a sachet-type dental hardenable composition used in dental treatment for bonding dental prostheses such as crowns, inlays, and bridges to tooth structure, and for building abutments. More specifically, the present invention relates to a sachet-type dental hardenable composition that has an appropriate operating time, excellent adhesion to tooth structure, and mechanical strength of the hardened product, and that shows little deterioration in performance during long-term storage, as well as little discoloration of the composition and a low risk of hardening.

Adhesive materials and filling and restorative materials are widely used to repair missing parts of teeth damaged by caries, fractures, etc. Resin-based dental hardenable compositions consisting of polymerizable monomers, polymerization initiators, fillers, etc. are commonly used as adhesive materials and filling and restorative materials used to repair teeth.

Among the resin-based dental hardenable compositions, the material used to bond dental prostheses to tooth structure is called dental resin cement. In addition, in the repair treatment of deep caries that reaches the dental pulp, it is necessary to remove the dental pulp and construct an abutment tooth, and the material used for this is called a composite resin for dental core construction. Both dental resin cement and composite resin for dental core 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 powdered filler, etc., and are provided to the user, the dentist, in a container filled state. Dental hardenable compositions are required to maintain a certain level of performance within their expiration date.

(Meth)acrylates are generally used as the polymerizable monomer contained in dental resin cements or composite resins for dental core construction. To impart adhesive properties to teeth or prostheses, dental resin cements contain polymerizable monomers with acidic groups such as phosphate groups or carboxyl groups. Dental resin cements that contain polymerizable monomers with acidic groups and have adhesive properties are called self-adhesive dental resin cements.

In order to polymerize and harden these dental hardenable compositions, a redox-type polymerization initiator system consisting of an oxidizing agent, a reducing agent, etc. may be used. In this case, the oxidizing agent and the reducing agent of the polymerization initiator system are packaged, for example, in a first agent containing an oxidizing agent and a second agent containing a reducing agent, and the dental hardenable composition is provided to the user, the dentist, in the form of a packaged dental hardenable composition. Just before the dentist uses this packaged dental hardenable composition, the first agent containing an oxidizing agent and the second agent containing a reducing agent are mixed together, whereby radicals are generated by a redox reaction, and the polymerization and hardening of the dental hardenable composition proceeds.

Conventionally, a polymerization initiator system consisting of benzoyl peroxide and an aromatic amine compound has been widely used as a redox-type polymerization initiator system for dental hardenable compositions. However, when this initiator system is used, there is a problem that the storage stability of the composition is low due to the low thermal stability of benzoyl peroxide. Specifically, when a composition containing benzoyl peroxide is stored for a long period of time in a temperature environment above room temperature, problems such as a decrease in hardening due to decomposition of benzoyl peroxide and solidification of the composition before use may occur. Therefore, when providing a composition containing benzoyl peroxide to users such as dentists, measures such as specifying the storage temperature to be lower than room temperature and setting a short expiration date are necessary, and there is room for improvement in terms of usability and quality stability.

In recent years, therefore, polymerization initiator systems have been proposed that use various organic peroxides, which are more stable than benzoyl peroxide, as oxidizing agents. For example, Patent Document 1 discloses a polymerization initiator system that consists of an organic peroxide selected from hydroperoxides and diperoxides, a transition metal compound, and ascorbic acid or a derivative thereof. It is described that a two-component self-adhesive dental composition containing this polymerization initiator system has good mechanical properties, aesthetic properties, and good adhesion.

Patent Document 2 discloses a two-component self-adhesive dental composition that further contains a stabilizer selected from phosphites or sulfites that contributes to stabilizing ascorbic acid or its derivatives in a polymerization initiator system consisting of an organic peroxide, a transition metal compound, and ascorbic acid or its derivatives. Ascorbic acid or its derivatives are prone to decomposition over time, it has been necessary to incorporate an excessive amount of ascorbic acid or its derivatives in the polymerization initiator system of dental hardenable compositions, which has traditionally caused the problem of discoloration. However, Patent Document 2 discloses that by incorporating the stabilizer described therein, the decomposition of ascorbic acid or its derivatives is suppressed, making it possible to reduce the content, resulting in improved aesthetics of the composition.

International Publication No. 2016/007453 International Publication No. 2017/100231

As a result of the study by the present inventors, it was confirmed that among the dental hardenable compositions disclosed in Patent Documents 1 and 2, there are compositions that have a suitable operating time, excellent adhesion to tooth tissue, and excellent mechanical strength of the hardened product, and that do not significantly decrease in these properties even after storage for a certain period of time, and that also suppress discoloration of the composition. However, when the storage was continued for a longer period of time, it was found that all of the above compositions solidified and became essentially unusable. Therefore, it was found that there is room for further improvement in terms of storage stability in the dental hardenable compositions disclosed in Patent Documents 1 and 2, since there is a risk of the paste solidifying if the storage period is extended for a long period of time, it is necessary to set the period during which the compositions can be used from the time of manufacture to be short when provided to users such as dentists.

The present invention therefore aims to provide a dental hardenable composition in a packaged form that has an appropriate operating time, excellent adhesion to tooth structure and mechanical strength of the hardened product, and exhibits little deterioration in performance during long-term storage, as well as little discoloration of the composition and a low risk of hardening.

The inventors conducted extensive research into a individually packaged dental hardenable composition that has an appropriate operating time, excellent adhesion to tooth structure and mechanical strength of the cured product, and exhibits little deterioration in performance during long-term storage, as well as little discoloration of the composition and a low risk of hardening. As a result, they found that the above problems can be solved by packaging a polymerizable monomer having an acidic group and a polymerization initiator system in a specific individually packaged state, and further research led to the completion of the present invention.

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 dental hardenable composition in a separate package type, comprising: a second agent that contains a polymerizable monomer (B) having no acidic group, an organic peroxide (D), and a transition metal compound (E), and does not contain a polymerizable monomer (A) having an acidic group.
[2] The dental hardenable composition of the individual package type described in [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 dental curable composition of the individual package type described in [2], wherein 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 the general formula (2), a compound represented by the general formula (3), and a compound represented by the general formula (4).
(R ₁ to R ₁₅ each independently represent a hydrogen atom, a halogen atom, a polar group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.)
(R ₁₆ to R ₃₅ each independently represent a hydrogen atom, a halogen atom, a polar group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and X ₁ represents a divalent aliphatic group which may have a substituent.)
(Each Ar independently represents a group represented by the following general formula (3-a).)
(Z ₁ to Z ₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and at least one of Z ₁ to Z ₃ is a hydrogen atom.)
P(OY ₁ ) ₃ (4)
(Each _Y1 is independently an alkyl group which may have a substituent, or an aryl group which may have a substituent).
[4] The dental curable composition of the individual package type described in [3], wherein the ligand containing a phosphorus atom is at least one compound selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (2).
[5] The ligand compound (F) is a ligand containing a nitrogen atom,
the nitrogen atom-containing ligand is at least one compound selected from the group consisting of a compound represented by general formula (5), a compound represented by general formula (6), and a multidentate ligand containing a nitrogen-containing heterocycle (7),
The dental curable composition of the divided type according to [2], wherein the polydentate ligand (7) is a bidentate or higher ligand compound that contains a heterocycle containing a nitrogen atom and a 5- or 6-membered ring, has two or more nitrogen atoms in the molecule, and is a bidentate or higher ligand compound.
R ₃₆ R ₃₇ N-X ₂ -NR ₃₈ R ₃₉ (5)
(R ₃₆ to R ₃₉ each independently represent an alkyl group which may have a substituent, and X ₂ represents a divalent aliphatic group which may have a substituent.)
(R ₄₀ , R ₄₁ , and R ₄₂ each independently represent an alkyl group which may have a substituent, X ₃ and X ₄ each independently represent a divalent aliphatic group which may have a substituent and which may contain an oxygen atom and/or a nitrogen atom, m and n each independently represent an integer of 1 or more, Y ₂ represents a monoalkylamino group or a dialkylamino group which may have a substituent, and any two or more of R ₄₀ , R ₄₁ , R ₄₂ , and Y ₂ may be bonded together to form a ring. When there are a plurality of R ₄₁ , R ₄₂ , X ₃ , and X ₄ , they may be the same or different.)
[6] The dental hardenable composition of any one of [1] to [5], wherein the ascorbic acid compound (C) is at least one compound selected from the group consisting of salts and esters of ascorbic acid.
[7] The dental hardenable composition of any one of [1] to [6], wherein the transition metal compound (E) is a copper compound or a vanadium compound.
[8] The individually packaged dental hardenable composition according to any one of [1] to [7], wherein at least one of the first agent and the second agent further contains a filler (G).
[9] The packaged dental hardenable composition according to any one of [1] to [8], wherein at least one of the first agent and the second agent further contains a pH adjuster.
[10] The individually packaged dental hardenable composition according to [9], wherein the pH adjuster is a phosphate.
[11] The individually packaged dental hardenable composition according to any one of [1] to [10], which is a dental resin cement.
[12] The individually packaged dental hardenable composition according to [11], wherein the dental resin cement is a self-adhesive dental resin cement.

The present invention provides a dental hardenable composition in a packaged form that has an appropriate operating time, excellent adhesion to tooth structure, and mechanical strength of the hardened product, and exhibits little deterioration in performance during long-term storage, as well as little discoloration of the composition and a low risk of solidification.

The dental hardenable composition of the present invention in a separate package type comprises 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), and a second agent containing a polymerizable monomer (B) not having an acidic group, an organic peroxide (D), and a transition metal compound (E), but not containing a polymerizable monomer (A) having an acidic group.

The mechanism by which the individually packaged dental hardenable composition of the present invention exerts its effects is unclear, but it is presumed that the stability of the organic peroxide is improved by blending the organic peroxide (D) with the second agent that does not contain the polymerizable monomer (A) having an acidic group, thereby reducing the risk of solidification due to decomposition of the organic peroxide. Below, each of the components contained in the individually packaged dental hardenable composition of the present invention will be described.

The dental hardenable composition of the present invention contains the polymerizable monomer (A) having an acidic group in the first agent, but not in the second agent. The polymerizable monomer (A) having an acidic group is an essential component for the dental hardenable composition of the present invention to exhibit adhesiveness. On the other hand, if the second agent contains the polymerizable monomer (A) having an acidic group, problems such as a decrease in hardening property 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 the effect of demineralizing tooth tissue. The polymerizable monomer (A) having an acidic group is a polymerizable monomer having at least one acidic group such as a phosphoric acid group, a phosphonic acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a carboxylic acid group, or a sulfonic acid group, and at least one polymerizable group such as an acryloyl group, a methacryloyl group, an acrylamide group, or a methacrylamide group. From the viewpoint of adhesion to tooth structure, it is preferable that the polymerizable monomer (A) having an acidic group is monofunctional and has one of an acryloyl group, a methacryloyl group, an acrylamide group, or a methacrylamide group as a polymerizable group. Specific examples include the following.

Examples of polymerizable monomers having a phosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, and 8-(meth)acryloyloxyoctyl dihydrogen phosphate. 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 phenyl hydrogen phosphate, Monofunctional (meth)acrylate compounds having a phosphoric acid group, such as 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-(4-methoxyphenyl)hydrogen phosphate, and 2-(meth)acryloyloxypropyl-(4-methoxyphenyl)hydrogen phosphate, their acid chlorides, alkali metal salts, ammonium salts, and amine salts; bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, and the like. Examples of such difunctional (meth)acrylate compounds having a phosphoric acid group include 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, and 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, as well as their acid chlorides, alkali metal salts, ammonium salts, and amine salts.

Examples of polymerizable monomers having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenyl phosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl phosphonoacetate, 10-(meth)acryloyloxydecyl phosphonoacetate, acid chlorides, alkali metal salts, ammonium salts, and amine salts of these.

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

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

Examples of polymerizable monomers having a carboxylic acid group include (meth)acrylic acid, 4-[2-[(meth)acryloyloxy]ethoxycarbonyl]phthalic acid, 4-(meth)acryloyloxyethyltrimellitic acid, 4-(meth)acryloyloxybutyloxycarbonylphthalic acid, 4-(meth)acryloyloxyhexyloxycarbonylphthalic acid, 4-(meth)acryloyloxyoctyloxycarbonylphthalic acid, 4-(meth)acryloyloxydecyloxy dicarbonylphthalic acid and their acid anhydrides; 5-(meth)acryloylaminopentylcarboxylic acid, 6-(meth)acryloyloxy-1,1-hexanedicarboxylic acid, 8-(meth)acryloyloxy-1,1-octanedicarboxylic acid, 10-(meth)acryloyloxy-1,1-decanedicarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, their acid chlorides, alkali metal salts, ammonium salts, and amine salts.

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

Among the polymerizable monomers (A) having an acidic group, polymerizable monomers having a phosphate group, polymerizable monomers having a pyrophosphate group, and polymerizable monomers having a carboxylic acid group are preferred because they exhibit better adhesion to tooth structure, and polymerizable monomers having a phosphate group and a carboxylic acid group are particularly preferred. Among them, (meth)acrylate-based monofunctional polymerizable monomers having a phosphate group and an alkyl group having 6 to 20 carbon atoms or an alkylene group having 6 to 20 carbon atoms as the main chain in the molecule, or (meth)acrylate-based monofunctional polymerizable monomers having a carboxylic acid group are more preferred, and (meth)acrylate-based monofunctional polymerizable monomers having a phosphate group and an alkylene group having 8 to 12 carbon atoms as the main chain in the molecule are even more preferred. Additionally, 10-methacryloyloxydecyl dihydrogen phosphate, 4-(meth)acryloyloxyethyl trimellitic acid, and 4-(meth)acryloyloxyethyl trimellitic anhydride are preferred, with 10-methacryloyloxydecyl dihydrogen phosphate being the most preferred.

The polymerizable monomer (A) having an acidic group may be blended alone or in combination of two or more kinds. The content of the polymerizable monomer (A) having an acidic group is not particularly limited as long as the effect of the present invention is exhibited, but from the viewpoint of superior adhesion, the content is preferably in the range of 1 to 50 parts by mass, more preferably in the range of 2 to 25 parts by mass, and even more preferably in the range of 2 to 10 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer components of the individually packaged dental hardenable composition of the present invention. In this specification, "100 parts by mass of the total amount of the polymerizable monomer components of the dental hardenable composition" means the case where the total amount 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.

The individually packaged dental hardenable composition of the present invention contains a polymerizable monomer (B) that does not have an acidic group in both the first and second agents. The polymerizable monomer (B) that does not have an acidic group is a polymerizable monomer that undergoes a radical polymerization reaction in the presence of a polymerization initiator system to become a polymer. The polymerizable monomer (B) that does not have an acidic group may be used alone or in combination of two or more types. Suitable examples of the polymerizable monomer (B) that does not have an acidic group include the following hydrophilic polymerizable monomer (B-1) and hydrophobic polymerizable monomer (B-2).

Hydrophilic polymerizable monomer (B-1) refers to a polymerizable monomer having a solubility in water of 10% by mass or more at 25°C. Preferably, the solubility is 30% by mass or more, and more preferably, the monomer is soluble in water at any ratio at 25°C. The hydrophilic polymerizable monomer (B-1) promotes the penetration of the components of the dental hardenable composition into the tooth structure, and also penetrates into the tooth structure itself and adheres to the organic components (collagen) in the tooth structure. Examples of the hydrophilic polymerizable monomer (B-1) include monofunctional (meth)acrylic acid ester polymerizable monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter sometimes abbreviated as "HEMA"), 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and 2-((meth)acryloyloxy)ethyltrimethylammonium chloride; and bifunctional (meth)acrylic acid ester polymerizable monomers such as polyethylene glycol di(meth)acrylate (having 9 or more oxyethylene groups), with 2-hydroxyethyl (meth)acrylate being preferred. In this specification, "(meth)acrylic" means acrylic and methacrylic, and the same applies to expressions such as "(meth)acryloyl" and "(meth)acrylate".

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

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

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

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

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

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

Among the polymerizable monomers (B) not having an acidic group, HEMA, Bis-GMA, D-2.6E, and TEGDMA are more preferred from the viewpoint of the adhesive strength and polymerization curing properties of the dental curable composition of the present invention.

The above-mentioned polymerizable monomer (B) not having an acidic group (hydrophilic polymerizable monomer (B-1) and hydrophobic polymerizable monomer (B-2)) may be used alone or in combination of two or more. The content of the polymerizable monomer (B) not having an acidic group is not particularly limited as long as the effects of the present invention are achieved. However, in terms of the high permeability of the composition into the tooth structure and excellent adhesion, and the cured product having sufficient mechanical strength, the content is preferably in the range of 50 to 99 parts by mass, more preferably in the range of 60 to 98 parts by mass, and even more preferably in the range of 70 to 95 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer components in the individually packaged dental curable composition of the present invention.

Next, the polymerization initiator system will be described. The individually packaged dental hardenable composition of the present invention contains, as a polymerization initiator system, an ascorbic acid compound (C) in the first agent, and an organic peroxide (D) and a transition metal compound (E) in the second agent. By combining such polymerization initiator systems and using them together with other components, the individually packaged dental hardenable composition of the present invention can set the operation time within an appropriate range, has excellent adhesion to tooth structure and mechanical strength of the hardened product, and has excellent storage stability, can suppress deterioration of performance during long-term storage, has little discoloration of the composition, and can suppress the risk of solidification.

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

Salts of ascorbic acid include sodium L-ascorbate, calcium L-ascorbate, potassium ascorbate, and stereoisomers thereof (e.g., sodium isoascorbate, etc.). Of these, sodium L-ascorbate is preferred.

Esters 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 carboxylic acids include fatty acids such as saturated or unsaturated fatty acids having 6 to 30 carbon atoms, 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, linoleelaidic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid. The number of carbon atoms of the fatty acid is preferably 10 to 28, more preferably 12 to 26, and even more preferably 14 to 24. Among these, esters of stearic acid and ascorbic acid, and esters of palmitic acid and ascorbic acid (ascorbyl palmitate) are particularly suitable.

Examples of ethers of ascorbic acid include ethyl ether ascorbate and cetyl ether ascorbate.

Ascorbic acid compounds (C) may be used alone or in combination of two or more. From the viewpoints of hardening property, mechanical strength of the hardened product, and adhesion to tooth structure, the content of ascorbic acid compounds (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 even more preferably in the range of 0.5 to 2 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer components in the individually packaged dental hardenable composition of the present invention.

In the individually packaged dental hardenable 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. The ascorbic acid compound (C) undergoes oxidative decomposition under neutral or higher conditions, which can result in the problem of yellowing of the composition. However, blending it in a first agent containing the polymerizable monomer (A) having an acidic group can suppress discoloration (yellowing) of the composition. The pH of the first agent containing the ascorbic acid compound (C) (pH when the paste is brought into contact with water) is optimally in the range of 3 to 7.

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 may be dispersed in the form of a powder in the composition of the first agent.

When the ascorbic acid compound (C) is dispersed as a powder, if the average particle size is too large, the operability or curability is likely to decrease, so the average particle size is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less.

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

When the ascorbic acid compound (C) is dispersed in powder form, the particle shape may be, but is not limited to, various shapes such as spherical, needle-like, plate-like, and crushed. The ascorbic acid compound (C) can be prepared by a conventional method such as a pulverization method, a freeze-drying method, or a reprecipitation method, and the pulverization method and the freeze-drying method are preferred from the viewpoint of the average particle size of the resulting powder.

Examples of organic peroxides (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, and m-toluoyl peroxide. Specific examples of peroxy esters include t-butyl peroxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxy-2-ethylhexanoate, and t-butylperoxyisopropyl carbonate. Specific examples of dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, and lauroyl peroxide. Specific examples of peroxyketals include 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 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.

Among the organic peroxides (D), hydroperoxides and peroxyesters are particularly preferred. Among the hydroperoxides, t-butyl hydroperoxide, cumene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide are preferably used. Also, among the peroxyesters, t-butyl peroxybenzoate is preferably used.

By incorporating the organic peroxide (D) in the second agent and combining it with other components, the decomposition of the organic peroxide (D) is suppressed while the desired curing properties are obtained, so that the operation time is within a reasonable range, adhesion to tooth tissue and mechanical strength of the cured product are excellent, and the performance degradation during long-term storage is small, and the risk of solidification can be reduced. The organic peroxide (D) may be incorporated alone or in combination of two or more types. From the viewpoints of curing properties, mechanical strength of the cured product, adhesion to tooth tissue, 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, relative to 100 parts by mass of the total amount of the polymerizable monomer components in the individually packaged dental curable composition of the present invention.

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

Examples of copper compounds include copper(II) carboxylates, β-diketone copper(II), β-ketoester copper(II), copper alkoxides, copper dithiocarbamate, and salts of copper and inorganic acids. Examples of copper(II) carboxylates include copper(II) citrate, copper(II) acetate, copper(II) phthalate, copper(II) tartrate, copper(II) oleate, copper(II) octylate, copper(II) octenate, copper(II) naphthenate, copper(II) methacrylate, and copper(II) 4-cyclohexylbutyrate. Examples of copper(II) diketones include copper(II) acetylacetone, copper(II) trifluoroacetylacetone, copper(II) hexafluoroacetylacetone, copper(II) 2,2,6,6-tetramethyl-3,5-heptanedionato, and copper(II) benzoylacetone. Examples of copper(II) β-ketoesters include copper(II) ethyl acetoacetate. Examples of copper alkoxides include copper(II) methoxide, copper(II) ethoxide, copper(II) isopropoxide, copper(II) 2-(2-butoxyethoxy)ethoxide, and copper(II) 2-(2-methoxyethoxy)ethoxide. Examples of copper dithiocarbamate include copper(II) dimethyldithiocarbamate. Examples of salts of copper and inorganic acids include copper(II) nitrate, copper(II) bromide, and copper(II) chloride. These may be used alone or in combination of two or more. Among these, from the viewpoint of solubility and reactivity with polymerizable monomers, 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.

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

By blending the transition metal compound (E) in the second agent and combining it with other components, the operation time is within a reasonable range, and the adhesiveness to tooth tissue and the mechanical strength of the cured product are excellent, as well as the storage stability during long-term storage. From the viewpoints of curability, mechanical strength, and adhesiveness to tooth tissue, 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 parts by mass, and even more preferably in the range of 0.001 to 0.2 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer components in the individually packaged dental curable composition of the present invention.

At least one of the first and second agents of the dental hardenable composition of the present invention may contain a ligand compound (F). In a 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.

One embodiment is a dental hardenable composition in a separate package, in which the first agent contains a ligand compound (F).

One preferred embodiment is a dental hardenable composition in a separate package, in which the ligand compound (F) contains a ligand that includes a nitrogen atom.

Another preferred embodiment is a dental hardenable composition in a separate package, in which the ligand compound (F) contains a ligand that contains a phosphorus atom.

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

(R ₁ to R ₁₅ each independently represent a hydrogen atom, a halogen atom, a polar group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.)

(R ₁₆ to R ₃₅ each independently represent a hydrogen atom, a halogen atom, a polar group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and X ₁ represents a divalent aliphatic group which may have a substituent.)

(Each Ar independently represents a group represented by the following general formula (3-a).)
(Z ₁ to Z ₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and at least one of Z ₁ to Z ₃ is a hydrogen atom.)
P(OY ₁ ) ₃ (4)
(Each _Y1 is independently an alkyl group which may have a substituent, or an aryl group which may have a substituent).

Among the ligands containing phosphorus atoms, compounds represented by the above general formula (1) and compounds represented by the general formula (2) are more preferred from the viewpoints of hardening property, mechanical strength of the hardened product, and adhesion to tooth structure.

It is more preferable that R ₁ to R ₁₅ each represent a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.

It is more preferable that R ₁₆ to R ₃₅ each represent a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.

Z ₁ to Z ₃ each more preferably represent a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.

The alkyl groups of R ₁ to R ₁₅ , which may have a substituent, may be either linear or branched. The number of carbon atoms of the alkyl groups of R ₁ to R ₁₅ is not particularly limited, and is preferably 1 to 12, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 to 3. Examples of the alkyl groups of _{R 1} to R ₁₅ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl. The alkyl groups of _{R 1} to R ₁₅ may be unsubstituted. Examples of the substituent of the alkyl group of R ₁ to R ₁₅ include a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, a dialkylamino group each having an alkyl group having 1 to 6 carbon atoms, and an amino group.

Examples of the halogen atom for R ₁ to R ₁₅ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the polar group of R ₁ to R ₁₅ 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 carboxylate group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid amide group, a sulfonate 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, and an oxazoline group. From the viewpoints of curability and the mechanical strength of the cured product, the carboxylic acid group, the carboxylic acid ester group, the carboxylic acid chloride group, and the carboxylic acid amide group are preferable. , carboxylate group, sulfonic acid group, sulfonate group, sulfonyl chloride group, sulfonamide group, sulfonate group, and aldehyde group are preferred, carboxylate group, carboxylate group, carboxylate chloride group, carboxylate group, sulfonate group, sulfonate ester group, sulfonyl chloride group, sulfonate group, and aldehyde group are more preferred, and carboxylate group, carboxylate group, carboxylate group, carboxylate chloride group, carboxylate group, sulfonate group, sulfonate ester group, sulfonyl chloride group, and sulfonate group are even more preferred. Examples of the salts of carboxylate group and sulfonate group include alkali metal salts such as lithium, sodium, and potassium; and alkaline earth metal salts such as magnesium, calcium, strontium, barium, and radium. When R ₁ to R ₁₅ are polar groups, the number of polar groups is preferably 1 to 9, more preferably 1 to 5, and even more preferably 1 to 3. When R ₁ to R ₁₅ are alkyl groups having a substituent, specific examples include trifluoromethyl group.

The alkoxy group of R ₁ to R ₁₅ , which may have a substituent, may be either linear or branched. The number of carbon atoms of the alkoxy group of R ₁ to R ₁₅ is not particularly limited, and is preferably 1 to 12, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 1 to 3. Examples of the alkoxy group of _{R 1} to R ₁₅ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a tert-pentyloxy group, a neopentyloxy group, an n-hexyloxy group, an isohexyloxy group, a sec-hexyloxy group, a tert-hexyloxy group, and a neohexyloxy group. Examples of the substituent of the alkoxy group of R ₁ to R ₁₅ include the same as the substituent of the alkyl group of R ₁ to R ₁₅ .

R ₁ to R ₁₅ may be the same or different, and may be, for example, a portion of R ₁ to R ₁₅ that is the same hydrogen atom, alkyl group, or alkoxy group.

The alkyl groups which may have a substituent of R ₁₆ to R ₃₅ are the same as the alkyl groups which may have a substituent of R ₁ to R _15. The alkoxy groups which may have a substituent of R ₁₆ to R ₃₅ are the same as the alkoxy groups which may have a substituent of R ₁ to R _15. The halogen atoms of R ₁₆ to R ₃₅ are the same as the halogen atoms of R ₁ to R _15. The polar groups of R ₁₆ to R ₃₅ are the same as the polar groups of R ₁ to R ₁₅ .

The divalent aliphatic group of X ₁ , which may have a substituent, 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, and an alkylene group is preferred. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a methylpropylene group, a dimethylpropylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, and a dodecamethylene group. Examples of the substituent of the divalent aliphatic group of X ₁ include the same as the substituent of the alkyl group of R ₁ to R ₁₅ .

In formula (3), multiple Ar may be the same or different. In the group represented by general formula (3-a), Z ₁ to Z ₃ may be the same or different. The alkyl groups which may have a substituent of _{Z 1} to Z ₃ are the same as the alkyl groups which may have a substituent of R ₁ to R _15. At least one of Z ₁ to Z ₃ may be a hydrogen atom, and all of Z ₁ to Z ₃ may be hydrogen atoms. Specific examples of Ar include the following groups.

In one embodiment, one or two of Z ₁ to Z ₃ are hydrogen atoms, and the other one or two of Z ₁ to Z ₃ may be a linear or branched alkyl group having 1 to 6 carbon atoms substituted with a halogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms substituted with a fluorine atom, or a trifluoromethyl group. The alkoxy groups which may have a substituent of Z ₁ to Z ₃ are the same as the alkoxy groups which may have a substituent of R ₁ to R _15. One preferred embodiment is a phosphine compound in which all Ar in the compound represented by the general formula (3) are 3,5-dimethylphenyl groups. Another preferred embodiment is a phosphine compound in which all Ar in the compound represented by the general formula (3) are 4-methylphenyl groups.

In the phosphite ligand represented by the general formula (4), the three Y ₁ may be the same or different. The alkyl group which may have a substituent of _{Y 1} is the same as the alkyl group which may have a substituent of R ₁ to R _15. The number of carbon atoms of the aryl group which may have a substituent of Y ₁ is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10. The substituent of the aryl group of Y ₁ may be the same as the substituent of the alkyl group of R ₁ to R _15. The aryl group which may have a substituent of Y ₁ may be a phenyl group, a biphenyl group, an indenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a pyrenyl group; a phenyl group substituted with an alkyl group such as a tolyl group, a xylyl group, a trimethylphenyl group, an ethylphenyl group, an isopropylphenyl group, or a tetramethylphenyl group. A preferred embodiment is a phosphite compound in which the three Y ₁ are 1,1,1,3,3,3-hexafluoro-2-propyl group. Other preferred embodiments include phosphite compounds in which three Y ₁ are 2,4-di-tert-butylphenyl groups.

Examples of monodentate phosphine compounds represented by the above 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, and 4-(dimethylamino)triphenylphosphine; (2-fluorophenyl)diphenylphosphine, (2-chlorophenyl)diphenylphosphine, (2-bromophenyl)diphenylphosphine, and the like. )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, triphenylphosphine-3,3',3"-trisulfonate trisodium, and other phosphine compounds having an electron-withdrawing group.

Examples of bidentate phosphine compounds of the above 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, and 1,6-bis(diphenylphosphino)hexane.

Examples of bidentate phosphine compounds of the above 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.

Examples of the phosphite compound of the above 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, etc.

Examples of the nitrogen atom-containing ligand include a compound represented by general formula (5), a compound represented by general formula (6), and a multidentate ligand containing a nitrogen-containing heterocycle (7). The nitrogen atom-containing ligand may be used alone or in combination of two or more kinds.

R ₃₆ R ₃₇ N-X ₂ -NR ₃₈ R ₃₉ (5)
(R ₃₆ to R ₃₉ each independently represent an alkyl group which may have a substituent, and X ₂ represents a divalent aliphatic group which may have a substituent.)

(R ₄₀ , R ₄₁ , and R ₄₂ each independently represent an alkyl group which may have a substituent, X ₃ and X ₄ each independently represent a divalent aliphatic group which may have a substituent and which may contain an oxygen atom and/or a nitrogen atom, m and n each independently represent an integer of 1 or more, Y ₂ represents a monoalkylamino group or a dialkylamino group which may have a substituent, and any two or more of R ₄₀ , R ₄₁ , R ₄₂ , and Y ₂ may be bonded together to form a ring. When there are a plurality of R ₄₁ , R ₄₂ , X ₃ , and X ₄ , they may be the same or different.)

The alkyl groups R ₃₆ to R ₃₉ which may have a substituent are the same as the alkyl groups R ₁ to R ₁₅ which may have a substituent.

The optionally substituted divalent aliphatic group of _X2 is the same as the optionally substituted divalent aliphatic group of _X1 .

The alkyl groups which may have a substituent of R ₄₀ , R ₄₁ , and R ₄₂ are the same as the alkyl groups which may have a substituent of R ₁ to R _15. The number of carbon atoms of the monoalkylamino group (-NHR _a ⁽ R ^a represents an alkyl group)) and dialkylamino group (-NR ^b R ^c (R ^b and R ^c represent an alkyl group)) of Y 2 is not particularly limited, and is preferably 1 to 12, more preferably 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 3. The alkyl groups of the monoalkylamino group and dialkylamino group of Y ₂ include those which satisfy the above number of carbon atoms among the alkyl groups which may have a substituent of R ₁ to R _15. As the dialkylamino group, each alkyl group may have the above number of carbon atoms. The monoalkylamino group which may have a substituent of _{Y 2} includes a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, an isobutylamino group, a t-butylamino group, a pentylamino group, a hexylamino group, and the like. The dialkylamino group of _Y2 which may have a substituent includes a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group, a dibutylamino group, a diisobutylamino group, a dipentylamino group, a dihexylamino group, and an ethylmethylamino group. The alkyl group of the monoalkylamino group and the dialkylamino group of _Y2 may be substituted with a substituent. Examples of the substituent include the same as the substituent of the alkyl group of _R1 to _R15 .

The divalent aliphatic groups of _X3 and _X4 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, and an alkylene group is preferred. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a methylpropylene group, a dimethylpropylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, and a dodecamethylene group. Examples of the substituent of the divalent aliphatic group of _X3 and _X4 include the same as the substituent of the divalent aliphatic group of _X1 . 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.

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, even more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3. m and n may be the same or different.

Any two or more of R ₄₀ , R ₄₁ , R ₄₂ and Y ₂ may be joined together to form a ring. For example, R ₄₀ , R ₄₁ or R ₄₂ may be joined together with Y ₂ to form a ring. In addition, R ₄₀ and Y ₂ , and R ₄₁ and R ₄₂ may be joined together to form a ring, and the compound may have two rings. Furthermore, the nitrogen atom of the amino group of Y ₂ and R ₄₀ may be joined together to form a ring. The ring may contain an oxygen atom and/or a nitrogen atom. Furthermore, in one embodiment, the compound represented by general formula (6) may be a compound having a bicyclo ring. For example, in another embodiment, the compound represented by general formula (6) may be a compound having a bicyclo ring, which has a ring formed by Y ₂ and R ₄₀ together, and a ring formed by R ₄₁ or R ₄₂ together with Y ₂ .

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

Another preferred embodiment is a dental hardenable composition in a separate package, in which at least one of the first and second agents 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).

Another preferred embodiment is a packaged dental curable composition in which at least one of the first agent and the second agent contains a ligand compound (F), and the ligand compound (F) is a compound represented by general formula (6), and in the compound represented by general formula (6), R ₄₀ , R ₄₁ and R ₄₂ represent a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, the divalent aliphatic groups of X ₃ and X ₄ represent an alkylene group not containing an oxygen atom 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, and R ₄₀ , R ₄₁ or R ₄₂ and Y ₂ together form a ring.

Another preferred embodiment is a dental hardenable composition in a separate package, in which at least one of the first agent and the second agent contains a ligand compound (F), and the ligand compound (F) is a compound represented by general formula (6), in which m is 1, n is 2, and the compound as a whole contains four nitrogen atoms.

The multidentate ligand (7) containing a nitrogen-containing heterocycle contains a heterocycle containing a 5- or 6-membered ring containing a nitrogen atom, has two or more nitrogen atoms in the molecule, and represents a bidentate or more ligand compound. The number of nitrogen atoms contained in the molecule of the multidentate ligand (7) is two or more, and may be three or more. The number of heterocycles contained in the multidentate ligand (7) may be one or more. Examples of the nitrogen-containing heterocycle include nitrogen-containing 5-membered rings such as pyrrole ring, pyrazole ring, and imidazole ring; nitrogen-containing 6-membered rings such as pyridine ring, pyrazine ring, pyridazine ring, piperazine ring, pyrimidine ring, and triazine ring. The nitrogen-containing heterocycle may be a condensed ring of the 5- or 6-membered ring containing the nitrogen atom and another ring (e.g., an aromatic ring), or a condensed ring of 5- or 6-membered rings containing nitrogen atoms. Examples of the condensed ring of the 5- or 6-membered ring containing a nitrogen atom and an aromatic ring include a quinoline ring, an isoquinoline ring, an indole ring, a benzimidazole ring, and a benzotriazole ring. The multidentate ligand (7) may contain a heterocyclic ring containing a 5- or 6-membered ring containing a nitrogen atom, and examples of the multidentate ligand (7) include a ligand compound containing a condensed ring such as an indole ring, a benzimidazole ring, or a benzotriazole ring, and a heterocyclic ring containing a 5- or 6-membered ring containing a nitrogen atom. The multidentate nature of the multidentate ligand (7) may be two or more dentates, and may be three or four dentates, etc.

Examples of the polydentate amine compound of the above general formula (5) include bidentate polydentate amine compounds such as N,N,N',N'-tetramethylethylenediamine (hereinafter sometimes abbreviated as "TMEDA"), N,N,N',N'-tetramethylpropylenediamine (hereinafter sometimes abbreviated as "TMPDA"), N,N,N',N'-tetramethyl-1,4-diaminobutane, N,N,N',N'-tetraethylethylenediamine (hereinafter sometimes abbreviated as "TEEDA"), and N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine.

Examples of the compound represented by the above 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; compounds having a 2,5,9,12-tetramethyl-2,5,9,12-tetraazatetradecane, 2,6,9,13-tetramethyl-2,6,9,13-tetraazatetradecane, 2,5,8 Examples of polydentate amine compounds include compounds having no ring, such as N,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"), and tris[2-(dimethylamino)ethyl]amine (hereinafter sometimes abbreviated as "Me ₆ TREN").

Examples of the polydentate ligand (7) containing a nitrogen-containing heterocycle 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, Examples include 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, etc.

Among these, tri(o-tolyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, TMEDA, TMPDA, TEEDA, PMDETA, and Me ₆ TREN 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 individually packaged dental hardenable composition of the present invention. From the viewpoints of hardening property, mechanical strength of the cured product, and adhesion to tooth structure, the content of the ligand compound (F) is preferably in the range of 0.005 to 10 parts by mass, more preferably in the range of 0.01 to 5 parts by mass, and even more preferably in the range of 0.05 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer components in the individually packaged dental hardenable composition of the present invention.

In the individually packaged dental hardenable composition of the present invention, at least one of the first and second agents may contain a filler (G) in order to obtain sufficient workability of the composition and sufficient X-ray opacity and mechanical strength of the cured product.

As the filler (G), any filler can be used as long as it does not impair the effects of the present invention, and examples of such fillers 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 types. The average particle diameter of the filler (G) is preferably 0.001 to 10 μm, and more preferably 0.001 to 5 μm.

Examples of inorganic fillers include silica; minerals based on silica, such as kaolin, clay, mica, and mica; _{ceramics and glasses} based on silica and containing _Al2O3 , _B2O3 , _TiO2 , _ZrO2 , _{BaO, La2O3 ,} SrO, ZnO, CaO, _P2O5 , _Li2O , and _Na2O . Examples of glasses include lithium borosilicate glass, borosilicate glass, bioglass, lanthanum glass, barium glass, strontium glass, soda glass, zinc glass, and fluoroaluminosilicate glass. Examples of inorganic fillers that can be used include crystalline quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride. In terms of adhesion and handling, fine particle silica having an average particle size 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 which are trade names manufactured by Nippon Aerosil Co., Ltd.). In the present invention, when the inorganic filler is surface-treated as described below, the average particle size of the inorganic filler means the average particle size before the surface treatment.

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

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

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

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

The content of the filler (G) is not particularly limited as long as the effects of the present invention are achieved, but is preferably in the range of 50 to 300 parts by mass, and more preferably in the range of 100 to 250 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomer components in the individually packaged dental hardenable composition of the present invention. Within these ranges, sufficient X-ray opacity or sufficient mechanical strength of the cured product can be obtained, and sufficient paste operability can be obtained.

The first agent of the individually packaged dental hardenable composition of the present invention may further contain a thiourea compound, a sulfinic acid and its salt, a sulfite, a hydrogen sulfite, a borate compound, or a barbituric acid and its derivative.

Examples of thiourea compounds include thiourea, methylthiourea, ethylthiourea, ethylenethiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, N,N'-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, tetracyclohexylthiourea, 1-(2-pyridyl)-2-thiourea, and 4,4-dimethylethylenethiourea. The thiourea compounds may be used alone or in combination of two or more.

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, and 2,4,6-trimethylbenzenesulfinate. Examples of the sulfinic acid include calcium benzenesulfinate, 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, and calcium 2,4,6-triisopropylbenzenesulfinate. Among these, sodium benzenesulfinate, sodium p-toluenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, and sodium 2,4,6-triisopropylbenzenesulfinate are preferred. The sulfinic acids and their salts may be used alone or in combination of two or more.

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

The individually packaged dental hardenable composition of the present invention contains a redox type polymerization initiator. In order to make the individually packaged dental hardenable composition of the present invention a dual cure type composition that also initiates polymerization by light irradiation, at least one of the first and second agents may further contain a conventionally known photopolymerization initiator as a component separate from the above-mentioned polymerization initiator system.

Photopolymerization initiators include α-diketones, ketals, thioxanthones, (bis)acylphosphine oxides, and α-aminoacetophenones.

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

Examples of ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

Examples of thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

Among the (bis)acylphosphine oxides, examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, benzoylbis(2,6-dimethylphenyl)phosphine oxide, water-soluble acylphosphine oxide compounds disclosed in JP-B-3-57916, and salts thereof (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 salts, potassium salts, ammonium salts), and the like. Among these (bis)acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are preferred.

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.

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

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

Examples of tertiary amines include N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, 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, Examples of the amines include 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-lauryldiethanolamine, triethanolamine, 2-(dimethylamino)ethyl(meth)acrylate, N-methyldiethanolamine di(meth)acrylate, N-ethyldiethanolamine di(meth)acrylate, triethanolamine mono(meth)acrylate, triethanolamine di(meth)acrylate, and triethanolamine tri(meth)acrylate. Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, and p-n-octyloxybenzaldehyde. Examples of thiol compounds include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid. As triazine compounds substituted with trihalomethyl groups, any known s-triazine compound having at least one trihalomethyl group such as a trichloromethyl group or a tribromomethyl group can be used without any restrictions.

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

In the dental hardenable 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 tooth structure can be obtained. Examples of such fluoride ion releasing substances include fluoride ion releasing polymers such as copolymers of methyl methacrylate and methacrylic acid fluoride; hydrofluorides of aliphatic or alicyclic primary, secondary or tertiary amines such as cetylamine hydrofluoride, cyclohexylamine hydrofluoride, diisobutylamine hydrofluoride, and triethylamine trihydrofluoride; and metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride. The fluoride ion releasing substances may be used alone or in combination of two or more.

In the individually packaged dental hardenable 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 and stabilizing the pH of the individually packaged dental hardenable composition of the present invention. There are no particular limitations on the pH adjuster as long as it achieves the effects of the present invention, but acids such as lactic acid, succinic acid, gluconic acid, citric acid, phosphoric acid, and carbonic acid, and salts thereof are preferably used. The pH adjusters may be used alone or in combination of two or more types.

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; alkali metal alkyl 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.

In addition, in the individually packaged dental hardenable composition of the present invention, additives such as polymerization inhibitors, ultraviolet absorbers, thickeners, solvents (e.g., water, organic solvents), colorants, antibacterial agents, and fragrances may be blended in at least one of the first and second agents, as long as they do not inhibit the effects of the present invention. These may be blended alone or in combination of two or more. Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, dibutyl hydroquinone, dibutyl hydroquinone monomethyl ether, t-butyl catechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, and 2,6-di-t-butyl-4-methylphenol. In one embodiment, the content of the solvent (e.g., water, organic solvent) in the individually packaged dental hardenable 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 individually packaged dental hardenable composition.

The individually packaged dental hardenable composition of the present invention may be prepared according to a conventional method depending on the type and amount of the components. The individually packaged dental hardenable composition of the present invention is used in a two-component form. The two-component form may be appropriately selected from a powder and liquid form, a paste and liquid form, a two-paste form, etc., but in a more preferred embodiment from the viewpoint of operability, the composition is used in a two-paste form. It is preferable to store each paste in a state where the pastes are isolated from each other, and to knead the two pastes just before use and allow chemical polymerization to proceed to harden them. The paste is usually prepared by kneading a liquid component prepared by mixing components other than the filler (G) with the filler (G) (powder).

The individually packaged dental hardenable composition of the present invention is used for bonding dental prostheses such as crowns, inlays, and bridges to tooth structure in damaged areas of teeth, and for building abutments. It is particularly suitable for use as a self-adhesive dental resin cement.

The present invention includes embodiments that combine the above configurations in various ways within the scope of the technical concept of the present invention, as long as the effects of the present invention are achieved.

The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The abbreviations and symbols used below are as follows. The compounds and fillers used in the following examples and comparative examples were commercially available products, except where the manufacturing method is specifically described.

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

[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 moles of ethoxy groups added: 2.6)
TEGDMA: Triethylene glycol dimethacrylate

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

[Organic peroxide (D)]
THP: 1,1,3,3-tetramethylbutyl hydroperoxide BPB: t-butyl peroxybenzoate

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

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

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

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

[pH adjuster]
Disodium hydrogen phosphate Sodium dodecyl phosphate

(Examples 1 to 10 and Comparative Examples 1 to 3)
Among the components shown in Table 1, the components other than the filler and the ascorbic acid compound were mixed at room temperature to obtain a uniform liquid component, and the obtained liquid component was kneaded with the ascorbic acid compound and the filler to prepare the individually packaged dental hardenable compositions of Examples 1 to 10 and Comparative Examples 1 to 3. Next, using these individually packaged dental hardenable compositions, the operation time at 23°C, the adhesive strength to bovine dentin, and the bending strength were measured immediately after production according to the methods described below. In addition, after storage at 60°C for 3 weeks, the operation 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 compounding ratio (parts by mass) of the dental hardenable composition and the test results.

[Working time of individually packaged dental hardenable composition at 23° C.]
The first and second agents were mixed in a mass ratio of 1:1 in a thermostatic chamber at 23°C, and thoroughly mixed with a spatula to obtain one agent. The time (operation time) from the time of mixing to the time when the temperature started to rise due to the start of hardening of the paste was measured using a thermocouple (manufactured by Okazaki Manufacturing Co., Ltd.) connected to a recorder (manufactured by Yokogawa Electric Corporation). The operation time was the average value of the measured values for five test samples. From the viewpoint of the operation margin time that allows the composition to be operated with ease and allows hardening after operation, the operation time suitable for practical use is 2 to 10 minutes. In addition, 4 g each of the first and second agents of the individually packaged dental hardenable composition of the present invention was filled into a product container of "SA Louting (registered trademark) Multi" (manufactured by Kuraray Noritake Dental Co., Ltd.), and stored at 60°C for 3 weeks in a dry atmosphere, and then the operation time was measured using this in the same manner.

[Adhesive strength of individually packaged dental hardenable composition to bovine dentin]
The labial surface of the bovine mandibular anterior tooth was polished with #80 silicon carbide paper (manufactured by Nihon Kenshi 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 Nihon Kenshi Co., Ltd.) under running water. After polishing, the water on the surface was dried by air blowing. An adhesive tape with a thickness of about 150 μm having a round hole with a diameter of 3 mm was attached to the smooth surface after drying to determine the adhesive area. The first and second agents of each dental hardenable composition of the Examples and Comparative Examples were taken in equal amounts and mixed for 10 seconds, and the resulting mixture was piled up on one end surface (circular cross section) of a stainless steel cylindrical rod (diameter 7 mm, length 2.5 cm). Next, the end face on the side where the dental curable composition was built up was placed on the smooth surface (adhering surface) in the round hole so that the center of the round hole and the center of the stainless steel cylindrical rod were approximately aligned, and the stainless steel cylindrical rod was pressed perpendicularly against the smooth surface to adhere to the smooth surface, thereby preparing a test sample. Five test samples were prepared. The test samples were left at 25°C for 30 minutes and then immersed in distilled water. The test samples immersed in distilled water were left at 37°C for 24 hours in an incubator maintained at 37°C. The tensile bond strength of the test samples to bovine dentin after leaving them at 37°C for 24 hours was measured. The tensile bond strength was measured using a universal testing machine (Shimadzu Corporation, Autograph "AG-I 100kN") with a crosshead speed set to 2mm/min. The tensile bond strength to dentin in the table is the average value of the measured tensile bond strength to bovine dentin for five test samples after standing at 37° C. for 24 hours.
In addition, 4 g of each of the first and second agents of the individually packaged dental hardenable composition of the present invention was filled into a product container of "SA Rooting (registered trademark) Multi" (manufactured by Kuraray Noritake Dental Co., Ltd.) and stored at 60°C in a dry atmosphere for 3 weeks, and then the adhesive strength was measured using this in the same manner as when it was stored at 37°C for 24 hours.

[Flexural strength of cured product of individually packaged dental curable composition]
A polyester film was laid on a glass slide plate, and a stainless steel mold of 2 mm length x 25 mm width x 2 mm depth was placed on the polyester film. Next, the mold was filled with a mixture of the first and second agents of the dental hardenable composition of the present invention in a packaged form, and the surface of the composition in the mold was pressed with a glass slide via the polyester film, and the two glass slides were fixed using a double clip with a width of 25 mm. The sample fixed with the double clip was left to stand in a 37°C incubator for 1 hour to polymerize and harden, and then the sample was removed from the incubator and the polymerized and hardened product of the composition was removed from the mold. The polymerized and hardened product was immersed in distilled water at 37°C for 24 hours and stored, and then a bending test was performed using this as a test piece. The bending strength was measured by a three-point bending test using a universal testing machine (Shimadzu Corporation, Autograph "AG-I 100kN") with a span of 20 mm and a crosshead speed of 1 mm/min. The average bending strength of the five test pieces was taken as the bending strength of the sample.

[Solidification of individually packaged dental hardenable composition]
The first and second agents of the individually packaged dental hardenable composition of the present invention were filled into product containers of "SA Louting (registered trademark) Multi" (manufactured by Kuraray Noritake Dental Co., Ltd.) at 4 g each and stored for 3 weeks in a dry atmosphere at 60°C, and the presence or absence of hardened matter was confirmed for each of the first and second agents. If a hardened matter was present, it was judged as "solidified", and if no hardened matter was present, it was judged as "not solidified". The confirmation of the presence or absence of solidification was carried out for five samples, and if the presence of a hardened matter was confirmed in even one sample, it was noted as "present".

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

As shown in Table 1, the individually packaged dental hardenable compositions of the present invention (Examples 1 to 10) had an appropriate handling time at 23°C immediately after preparation (in the table, "23°C handling time" for the refrigerated product) and showed excellent results in terms of adhesive strength to bovine dentin and bending strength. In addition, no solidification was observed in the paste after storage at 60°C for three weeks, and discoloration of the paste was below the level observed with the naked eye (ΔE ^* ≦5). In addition, the adhesive strength to bovine dentin after storage at 60°C for three weeks for the handling time at 23°C (in the table, "23°C handling time" for the temperature accelerated product) showed little change compared to immediately after production.

On the other hand, the first agent of the dental hardenable composition of Comparative Examples 1 and 2, in which the polymerizable monomer having an acidic group (A), the organic peroxide (D), and the transition metal compound (E) were blended in the same agent, solidified after storage at 60°C for three weeks. In Comparative Example 1, when an ascorbic acid compound was blended in the second agent that did not contain the polymerizable monomer having an acidic group (A), the second agent discolored significantly. Furthermore, in Comparative Example 3, in which the polymerizable monomer having an acidic group (A) was included in both the first and second agents, solidification occurred in the second agent in which the polymerizable monomer having an acidic group (A) and the organic peroxide (D) coexisted after storage at 60°C for three weeks.

The individually packaged dental hardenable composition of the present invention can be suitably used in dental treatment for bonding dental prostheses such as crowns, inlays, and bridges to tooth structure, and for constructing abutments.

Claims (12)

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 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 ;
The ascorbic acid compound (C) is a photolabile reducing agent represented by the following formula:
wherein each of R ¹ and R ² is H, alkyl, aryl, or R ^Photo , provided that at least one of R ¹ and R ² is R ^Photo ;
R ^Photo is a photolabile group;
Each of R3 and R4 ^is independently H, alkyl, aryl including ester, ether, ^urethane or carbonate functional groups;
A packaged dental hardenable composition , wherein the transition metal compound (E) is a copper compound or a vanadium compound . The individually packaged dental hardenable 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 ligands containing a phosphorus atom and ligands containing a nitrogen atom. The ligand compound (F) is a ligand containing a phosphorus atom,
3. The dental hardenable composition of claim 2, wherein 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 the general formula (2), a compound represented by the general formula (3), and a compound represented by the general formula (4).
(R ₁ to R ₁₅ each independently represent a hydrogen atom, a halogen atom, a polar group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.)
(R ₁₆ to R ₃₅ each independently represent a hydrogen atom, a halogen atom, a polar group, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and X ₁ represents a divalent aliphatic group which may have a substituent.)
(Each Ar independently represents a group represented by the following general formula (3-a).)
(Z ₁ to Z ₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent, and at least one of Z ₁ to Z ₃ is a hydrogen atom.)
P(OY ₁ ) ₃ (4)
(Each _Y1 is independently an alkyl group which may have a substituent, or an aryl group which may have a substituent). The individually packaged dental hardenable composition according to claim 3, wherein the ligand containing a phosphorus atom is at least one compound selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (2). The ligand compound (F) is a ligand containing a nitrogen atom,
the nitrogen atom-containing ligand is at least one compound selected from the group consisting of a compound represented by general formula (5), a compound represented by general formula (6), and a multidentate ligand containing a nitrogen-containing heterocycle (7),
The packaged dental hardenable composition according to claim 2, wherein the polydentate ligand (7) is a bidentate or higher ligand compound that contains a heterocycle containing a nitrogen atom and a 5- or 6-membered ring, has two or more nitrogen atoms in the molecule, and is a bidentate or higher ligand compound.
R ₃₆ R ₃₇ N-X ₂ -NR ₃₈ R ₃₉ (5)
(R ₃₆ to R ₃₉ each independently represent an alkyl group which may have a substituent, and X ₂ represents a divalent aliphatic group which may have a substituent.)
(R ₄₀ , R ₄₁ , and R ₄₂ each independently represent an alkyl group which may have a substituent, X ₃ and X ₄ each independently represent a divalent aliphatic group which may have a substituent and which may contain an oxygen atom and/or a nitrogen atom, m and n each independently represent an integer of 1 or more, Y ₂ represents a monoalkylamino group or a dialkylamino group which may have a substituent, and any two or more of R ₄₀ , R ₄₁ , R ₄₂ , and Y ₂ may be bonded together to form a ring. When there are a plurality of R ₄₁ , R ₄₂ , X ₃ , and X ₄ , they may be the same or different.) The dental hardenable composition of any one of claims 1 to 5, wherein the ascorbic acid compound (C) is at least one compound selected from the group consisting of salts and esters of ascorbic acid. the copper compound is at least one selected from the group consisting of copper(II) carboxylate, copper(II) β-diketone, copper(II) β-ketoester, copper alkoxide, copper dithiocarbamate, and a salt of copper and an inorganic acid;
7. The dental hardenable composition according to claim 1 , wherein the vanadium compound is a IV and/or V vanadium compound . The individually packaged dental hardenable composition according to any one of claims 1 to 7, further comprising at least one of the first and second agents containing a filler (G). The individually packaged dental hardenable composition according to any one of claims 1 to 8, further comprising at least one of the first and second agents containing a pH adjuster. The dental hardenable composition of claim 9, wherein the pH adjuster is a phosphate. The individually packaged dental hardenable composition according to any one of claims 1 to 10, which is a dental resin cement. The individually packaged dental hardenable composition according to claim 11, wherein the dental resin cement is a self-adhesive dental resin cement.