Individually packaged dental curing composition

Abstract

The present invention provides a divided dental curing composition which has favorable chemical polymerization curing properties, and exhibits excellent adhesion durability to a CAD / CAM resin. The present invention pertains to a divided dental curing composition which contains: a polymerizable monomer (A) which has an acidic group; a polymerizable monomer (B) which does not have an acidic group; an ascorbic acid compound (C); an organic peroxide compound (D); a transition metal compound (E); and a silane coupling agent (F) which is represented by general formula (f-1) (explanation of symbols in formula is omitted).

Description

Technical Field

[0001] The present invention relates to a sub-packaged dental curable composition used for adhesion between dental prostheses such as crowns, inlays, and bridges and tooth substance, and for abutment construction, etc. in dental treatment. More specifically, it relates to a sub-packaged dental curable composition having good chemical polymerization curability and excellent adhesion durability to CAD / CAM resins.

Background Art

[0002] In the restoration of teeth damaged by caries or the like, when the damaged part is relatively large, a prosthetic device adapted to the shape of the restoration part such as an inlay, onlay or crown is prefabricated outside the oral cavity, and this is adhered using a dental adhesive. This prosthetic restoration method is common. In particular, from the viewpoints of aesthetics and metal allergy, prosthetic devices made of CAD / CAM resins obtained by thermally and / or photopolymerizing composite materials composed of (meth)acrylate-based polymerizable monomers and inorganic fillers or hard resins for dental crowns have become the mainstream instead of the conventionally used metal prosthetic devices.

[0003] Some resin cured bodies have a material strength similar to that of teeth by being polymerized by heat and / or light. In particular, the material strength of resin cured bodies highly polymerized by heating, typified by CAD / CAM resins, is very high and can be applied even to the molar region where occlusal pressure is applied. When using these resin cured bodies for dental prostheses and adhering them to abutment teeth, dental resin cement is usually used.

[0004] However, since the CAD / CAM resin undergoes thermal polymerization by heating as described above, it has fewer unreacted polymerizable groups on the surface compared to photopolymerizable resin materials, has low reactivity with dental adhesives, and its adhesiveness has been a problem.

[0005] Patent Document 1 proposes a two-paste type dental curable composition that has clinically acceptable adhesive durability to dental substrates, including dental glass-ceramic restorations (particularly glass-ceramic restorations containing lithium disilicate), without the need for conventionally used primers.

[0006] Patent Document 2 discloses a polymerization initiator system for a sachet-type dental curable composition that provides good mechanical properties, aesthetic properties, and good adhesion, comprising an organic peroxide selected from hydroperoxides and diperoxides, a transition metal compound, and an ascorbic acid derivative.

[0007] Patent Document 3 proposes a polymerization initiator system for a sachet-type dental curable composition that exhibits excellent curability under wet conditions and flexural strength of the cured product, comprising an organic peroxide, a thiourea derivative, an ascorbate, and a vanadium compound.

[0008] [Patent Document 1] International Publication No. 2019 / 004391 [Patent Document 2] International Publication No. 2016 / 007453 [Patent Document 3] International Publication No. 2017 / 038218 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] As a result of the inventors' investigation, it was found that while the composition described in Patent Document 1 shows high adhesive durability to glass ceramic restorations containing lithium disilicate, there is room for improvement in adhesive durability to CAD / CAM resins that undergo thermal polymerization by heating, due to the small number of unreacted polymerizable groups on the surface. Furthermore, while the dental curable compositions containing polymerization initiator systems disclosed in Patent Documents 2 and 3 have high polymerization curability, there is room for improvement in adhesive durability to CAD / CAM resins.

[0010] Therefore, the present invention aims to provide a sachet-type dental curable composition that has good chemical polymerization curability and excellent adhesive durability to CAD / CAM resins. [Means for solving the problem]

[0011] As a result of diligent research, the inventors discovered that a sachet-type dental curing composition with a specific composition can solve the above problems, and through further research, completed the present invention.

[0012] In other words, the present invention encompasses the following inventions. [1] Polymerizable monomers having acidic groups (A), polymerizable monomers without acidic groups (B), ascorbic acid compounds (C), organic peroxides (D), transition metal compounds (E), and the following general formula (f-1) [ka] A sachet-type dental curable composition containing a silane coupling agent (F) represented by the formula (wherein A1 represents a polymerizable functional group selected from the group consisting of (meth)acryloyloxy groups, vinyl groups, and epoxy groups; M represents a divalent aliphatic group having a straight chain with a carbon chain length of 5 or more, or a divalent aromatic group having 6 or more carbon atoms; A2, A3, and A4 are each independently a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and at least one of A2, A3, and A4 is an alkoxy group having 1 to 5 carbon atoms). [2] The sachet-type dental curing composition according to [1], wherein the ascorbic acid compound (C) is at least one compound selected from the group consisting of salts and esters of ascorbic acid. [3] The sachet-type dental curable composition according to [1] or [2], wherein the transition metal compound (E) is a copper compound or a vanadium compound. [4] A dental curable composition in individual packets according to any one of [1] to [3], comprising a first agent containing the polymerizable monomer (A) having the acidic group and a second agent containing the silane coupling agent (F). [5] A sachet-type dental curable composition according to any one of [1] to [4], wherein M is a divalent aliphatic group having a straight chain with a carbon chain length of 7 or more, or a divalent aromatic group having 7 or more carbon atoms. [6] A sachet-type dental curable composition according to any one of [1] to [5], wherein A2, A3, and A4 are each independently a hydroxyl group, a C1-C3 alkyl group, or a C1-C3 alkoxy group, and at least one of A2, A3, and A4 is a C1-C3 alkoxy group. [7] A sachet-type dental curable composition according to any one of [1] to [6], wherein A2, A3, and A4 are each independently a hydroxyl group, a methyl group, or a methoxy group, and at least one of A2, A3, and A4 is a methoxy group. [8] A sachet-type dental curable composition according to any one of [1] to [7], wherein A2, A3, and A4 are methoxy groups. [9] A sachet-type dental curable composition according to any one of [1] to [8], wherein M is an alkylene group having a straight chain with a carbon chain length of 8 or more.

[10] The sachet-type dental curable composition according to any one of [1] to [9], wherein the silane coupling agent (F) is at least one selected from the group consisting of 5-(meth)acryloyloxypentyltrimethoxysilane, 6-(meth)acryloyloxyhexyltrimethoxysilane, 7-(meth)acryloyloxyheptyltrimethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 9-(meth)acryloyloxynonyltrimethoxysilane, 10-(meth)acryloyloxydecyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, 8-(meth)acryloyloxyoctylmethyldimethoxysilane, 10-(meth)acryloyloxydecylmethyldimethoxysilane, 11-(meth)acryloyloxyundecylmethyldimethoxysilane, and (meth)acryloyloxymethylphenethyltrimethoxysilane.

[11] A sachet-type dental curable composition according to any one of [1] to

[10] , wherein the silane coupling agent (F) is at least one selected from the group consisting of 8-(meth)acryloyloxyoctyltrimethoxysilane, 9-(meth)acryloyloxynonyltrimethoxysilane, 10-(meth)acryloyloxydecyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, and (meth)acryloyloxymethylphenethyltrimethoxysilane.

[12] A sachet-type dental curable composition according to any one of [1] to

[11] , wherein the mass ratio of the content of the ascorbic acid compound (C) to the content of the silane coupling agent (F) is ascorbic acid compound (C):silane coupling agent (F) = 1:1 to 1:200.

[13] A sachet-type dental curing composition according to any one of [1] to

[12] , further containing filler (G).

[14] A sachet-type dental curable composition according to any one of [1] to

[13] , further containing a ligand compound.

[15] A dental resin cement, a sachet-type dental curing composition as described in any of [1] to

[14] . [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a pre-packaged dental curable composition that has good chemical polymerization curability and excellent adhesive durability to CAD / CAM resins. [Modes for carrying out the invention]

[0014] The following describes preferred embodiments of the sachet-type dental curing composition according to the present invention. However, the present invention is not limited in any way to the embodiments described below.

[0015] The present invention provides a packaged dental curable composition comprising: a polymerizable monomer having an acidic group (A), a polymerizable monomer not having an acidic group (B), an ascorbic acid compound (C), an organic peroxide (D), a transition metal compound (E), and the following general formula (f-1) [ka] (In the formula, A1 represents a polymerizable functional group selected from the group consisting of (meth)acryloyloxy groups, vinyl groups, and epoxy groups; M represents a divalent aliphatic group having a straight chain with a carbon chain length of 5 or more, or a divalent aromatic group having 6 or more carbon atoms; and A2, A3, and A4 are each independently a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, with at least one of A2, A3, and A4 being an alkoxy group having 1 to 5 carbon atoms.) It comprises a silane coupling agent (F) represented by [formula].

[0016] The mechanism by which the individually packaged dental curable composition of the present invention achieves the effects of the present invention is not clear, but it is presumed to be as follows. CAD / CAM resins are manufactured by thermal polymerization through heating, resulting in a small number of unreacted polymerizable groups on the resin surface. The polymerization initiator system of the present invention, which contains a polymerizable monomer having an acidic group (A), a polymerizable monomer without an acidic group (B), an ascorbic acid compound (C), an organic peroxide (D), and a transition metal compound (E), exhibits high polymerization initiation efficiency even under acidic conditions. This significantly improves the polymerization rate, allowing for efficient crosslinking reactions with the few polymerizable groups on the surface of the CAD / CAM resin. The CAD / CAM resin contains a filler (such as silica) and a polymerizable monomer (such as (meth)acrylic acid ester), and its form is not particularly limited; it may be in the form of a block, a disc, or the like. Furthermore, regarding the hydrolysis reaction of the chemical bond between silica in the CAD / CAM resin and the silane coupling agent in the curable composition, which causes a decrease in adhesive durability, the silane coupling agent (F) represented by the general formula (f-1) of the present invention exhibits high hydrophobicity because it has a long spacer portion with a carbon chain length of 5 or more, thereby suppressing the aforementioned hydrolysis reaction. It is presumed that the two effects described above work synergistically without interfering with each other, resulting in improved adhesive durability to CAD / CAM resins in the pre-packaged dental curing composition of the present invention. The components contained in the pre-packaged dental curing composition of the present invention will be described below.

[0017] The polymerizable monomer (A) having an acidic group in the present invention is an essential component for the dental curable composition of the present invention to exhibit adhesive properties. The polymerizable monomer (A) having an acidic group has the effect of demineralizing tooth structure. The polymerizable monomer (A) having an acidic group is a polymerizable monomer having at least one acidic group such as a phosphate group, phosphonic acid group, pyrophosphate group, thiophosphate group, carboxylic acid group, or sulfonic acid group, and at least one polymerizable group such as an acryloyl group, methacryloyl group, acrylamide group, or methacrylamide group. From the viewpoint of adhesion to tooth structure and CAD / CAM resin (polymerized and cured products of thermally polymerizable resin materials containing a thermal polymerization initiator), and especially adhesive durability, it is preferable that the polymerizable monomer (A) having an acidic group is monofunctional, having one of the following polymerizable groups: acryloyl group, methacryloyl group, acrylamide group, or methacrylamide group. Specific examples of polymerizable monomers (A) having an acidic group are listed below.

[0018] Examples of polymerizable monomers having a phosphate group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, and 11-(meth)acryloyloxyundecyl dihydrogen phosphate. Monofunctional (meth)acrylate compounds having a phosphate group, such as hydrogen phosphates, 12-(meth)acryloyloxide decyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-(4-methoxyphenyl) hydrogen phosphate, and 2-(meth)acryloyloxypropyl-(4-methoxyphenyl) hydrogen phosphate; acid chlorides, alkali metal salts, ammonium salts, and amine salts thereof;Examples include difunctional (meth)acrylate compounds having a phosphate group, such as bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, and 1,3-di(meth)acryloyloxypropyldihydrogen phosphate, as well as their acid chlorides, alkali metal salts, ammonium salts, and amine salts.

[0019] Examples of polymerizable monomers having a phosphonic acid group include 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexylphosphonoacetate, 10-(meth)acryloyloxydecylphosphonoacetate, their acid chlorides, alkali metal salts, ammonium salts, and amine salts.

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

[0021] 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, and 8-(meth)acryloyloxyoctyl dihydrogen Examples include thiophosphates, 9-(meth)acryloyloxynonyldihydrogenthiophosphate, 10-(meth)acryloyloxydecyldihydrogenthiophosphate, 11-(meth)acryloyloxyundecyldihydrogenthiophosphate, 12-(meth)acryloyloxidedecyldihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyldihydrogenthiophosphate, 20-(meth)acryloyloxyeicosyldihydrogenthiophosphate, and their acid chlorides, alkali metal salts, ammonium salts, etc.

[0022] Examples of polymerizable monomers having a carboxylic acid group include (meth)acrylic acid, 4-[2-[(meth)acryloyloxy]ethoxycarbonyl]phthalic acid, 4-(meth)acryloyloxyethyl trimellitic acid, 4-(meth)acryloyloxybutyloxycarbonylphthalic acid, 4-(meth)acryloyloxyhexyloxycarbonylphthalic acid, 4-(meth)acryloyloxyoctyloxycarbonylphthalic acid, and 4-(meth)acryloyloxydecyloxy Examples include cyclonitrate and acid anhydrides thereof; 5-(meth)acryloylaminopentylcarboxylic acid, 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 8-(meth)acryloyloxyoctane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, acid chlorides thereof, alkali metal salts, ammonium salts, and amine salts.

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

[0024] Among the polymerizable monomers (A) having acidic groups, polymerizable monomers having phosphate groups, polymerizable monomers having pyrophosphate groups, and polymerizable monomers having carboxylic acid groups are preferred because they exhibit better adhesion to tooth structure, better adhesion to CAD / CAM resins, and especially better adhesive durability. Polymerizable monomers having phosphate groups and polymerizable monomers having carboxylic acid groups are more preferred. Among these, (meth)acrylate monofunctional polymerizable monomers having a phosphate group with 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 polymerizable monomers having a carboxylic acid group are more preferred, and (meth)acrylate monofunctional polymerizable monomers having a phosphate group with an alkylene group having 8 to 12 carbon atoms as the main chain in the molecule are even more preferred. Furthermore, 10-methacryloyloxydecyl dihydrogen phosphate, 4-(meth)acryloyloxyethyl trimellitic acid, and 4-(meth)acryloyloxyethyl trimellitic anhydride are particularly preferred, with 10-methacryloyloxydecyl dihydrogen phosphate being the most preferred.

[0025] The polymerizable monomer (A) having an acidic group may be blended alone or in combination of two or more types. The content of the polymerizable monomer (A) having an acidic group is not particularly limited as long as the effects of the present invention are achieved, but in terms of adhesion to CAD / CAM resin, particularly adhesive durability, it 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 polymerizable monomer component of the packaged dental curable composition of the present invention. In this specification, "100 parts by mass of the total polymerizable monomer components of the dental curable composition" means the sum of the polymerizable monomers contained in the first component and the polymerizable monomers contained in the second component, converted to 100 parts by mass. Furthermore, in this specification, "total amount of dental hardening composition" means the sum of the components contained in the first component and the components contained in the second component.

[0026] The individually packaged dental curable composition of the present invention contains a polymerizable monomer (B) that does not have an acidic group. The polymerizable monomer (B) that does not have an acidic group is a polymerizable monomer that undergoes a radical polymerization reaction by 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. As polymerizable monomers (B) that do not have acidic groups, the following hydrophilic polymerizable monomers (B-1) and hydrophobic polymerizable monomers (B-2) are preferred.

[0027] A hydrophilic polymerizable monomer (B-1) refers to a polymerizable monomer having a solubility in water of 10% by mass or more at 25°C. A solubility of 30% by mass or more is preferred, and a monomer that can dissolve in water in any proportion at 25°C is more preferred. The hydrophilic polymerizable monomer (B-1) promotes the penetration of components of dental hardening compositions into tooth structure, and also penetrates the tooth structure itself and adheres to organic components (collagen) within the tooth structure. Examples of hydrophilic polymerizable monomers (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 difunctional (meth)acrylic acid ester polymerizable monomers such as polyethylene glycol di(meth)acrylate (average number of added moles of oxyethylene groups: 9 or more). 2-hydroxyethyl (meth)acrylate is preferred because it exhibits superior adhesion to tooth structure, superior adhesion to CAD / CAM resins, and especially superior adhesive durability. In this specification, "(meth)acrylic" means acrylic and methacrylic, and the same applies to expressions such as "(meth)acryloyl" and "(meth)acrylate."

[0028] A hydrophobic polymerizable monomer (B-2) refers to a crosslinkable polymerizable monomer whose solubility in water at 25°C is less than 10% by mass. Examples of hydrophobic polymerizable monomers (B-2) include monofunctional and difunctional polymerizable monomers based on aromatic compounds, monofunctional and difunctional polymerizable monomers based on aliphatic compounds, and polymerizable monomers with three or more functions. Hydrophobic polymerizable monomers (B-2) improve the mechanical strength and handling properties of cured products of dental curable compositions.

[0029] Examples of monofunctional polymerizable monomers based on aromatic compounds 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.

[0030] Examples of bifunctional polymerizable monomers based on aromatic compounds include aromatic di(meth)acrylates. Specific examples of bifunctional polymerizable monomers of aromatic compounds include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]propane, 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (hereinafter sometimes abbreviated as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, and 2,2-bis(4-(meth) Examples include 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, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, and 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitate. 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.

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

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

[0033] Examples of polymerizable monomers with three or more functionalities include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, and 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxaheptane.

[0034] Among the polymerizable monomers (B) that do not have an acidic group, HEMA, Bis-GMA, D-2.6E, and TEGDMA are more preferred from the viewpoint of adhesive strength and polymerization curability of the dental curable composition of the present invention.

[0035] The above polymerizable monomers (B) that do not have acidic groups (hydrophilic polymerizable monomer (B-1) and hydrophobic polymerizable monomer (B-2)) may be included individually or in combination of two or more. The content of the polymerizable monomer (B) that does not contain acidic groups is not particularly limited as long as the effects of the present invention are achieved. However, in order to obtain the composition's high penetration into tooth structure and excellent adhesion, and for the cured product to have sufficient mechanical strength, the content of the polymerizable monomer component in the pre-packaged dental curable composition of the present invention 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 polymerizable monomer component.

[0036] Next, we will discuss polymerization initiator systems. The present invention provides a pre-packaged dental curable composition comprising an ascorbic acid compound (C), an organic peroxide (D), and a transition metal compound (E) as polymerization initiators. By combining these polymerization initiators and using them together with other components, the pre-packaged dental curable composition of the present invention exhibits excellent chemical polymerization curability and superior adhesive durability to CAD / CAM resins. Furthermore, by combining these polymerization initiators and using them together with other components, the operating time when using the pre-packaged dental curable composition can be set within an appropriate range.

[0037] Examples of ascorbic acid compounds (C) include salts, esters, and ethers of ascorbic acid. Among these, salts and esters of ascorbic acid are preferred because they exhibit superior effects. By including a polymerization initiator system containing ascorbic acid compound (C), polymerization initiation efficiency is high even under acidic conditions, the polymerization rate can be sufficiently improved, and good chemical polymerization curability can be obtained. Despite the limited number of polymerizable groups on the surface of the CAD / CAM resin, a crosslinking reaction occurs efficiently between these polymerizable groups and the components contained in the pre-packaged dental curable composition of the present invention. This effect, along with the hydrolysis reaction suppression effect by using a silane coupling agent (F), acts synergistically without interfering with each other, resulting in excellent adhesion to the CAD / CAM resin, particularly in terms of adhesive durability.

[0038] Examples of ascorbic acid salts include sodium L-ascorbate, calcium L-ascorbate, potassium ascorbate, and their stereoisomers (e.g., sodium isoascorbate). Among these, sodium L-ascorbate is preferred.

[0039] Esters of ascorbic acid include those formed by reacting one or more hydroxyl 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, including 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, linole-elaidic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid. The number of carbon atoms in 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 preferred.

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

[0041] Ascorbic acid compound (C) may be included alone or in combination of two or more types. From the viewpoint of curability, mechanical strength of the cured product, and adhesion to tooth structure and CAD / CAM resin, particularly adhesive durability, the content of ascorbic acid compound (C) in the pre-packaged dental curable composition of the present invention 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, even more preferably in the range of 0.5 to 2 parts by mass, particularly preferably in the range of 0.8 to 2 parts by mass, and most preferably in the range of 1.2 to 2 parts by mass, with particularly excellent effects. Furthermore, the content of ascorbic acid compound (C) is preferably 0.001 to 7.0% by mass, more preferably 0.01 to 5.0% by mass, even more preferably 0.1 to 2.0% by mass, and particularly preferably 0.2 to 1.5% by mass, in the total amount of the packaged dental curable composition of the present invention, from the viewpoint of curability, mechanical strength of the cured product, and adhesion to tooth structure and CAD / CAM resin, especially adhesive durability.

[0042] The ascorbic acid compound (C) may be dissolved in the composition or dispersed in the composition in the form of a powder.

[0043] When dispersing ascorbic acid compound (C) in powder form, if the average particle size is too large, the handling properties or curing properties tend to decrease. Therefore, a particle size of 20 μm or less is preferred, 10 μm or less is more preferred, and 5 μm or less is even more preferred.

[0044] The average particle size of ascorbic acid compound (C) powder can be calculated as the volume-average particle size after performing image analysis using image analysis-based particle size distribution measurement software (Mac-View; manufactured by Mountec Co., Ltd.) based on electron microscope images of 100 or more particles.

[0045] When dispersing ascorbic acid compound (C) in powder form, the particle shape can be spherical, needle-shaped, plate-shaped, crushed, or various other shapes, but is not particularly limited. Ascorbic acid compound (C) can be prepared by conventionally known methods such as grinding, freeze-drying, and reprecipitation, and grinding and freeze-drying are preferred in terms of the average particle size of the resulting powder.

[0046] Examples of organic peroxides (D) include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, and hydroperoxides. Specific examples of diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluyl peroxide. Specific examples of peroxyesters include t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxy-2-ethylhexanoate, and t-butylperoxyisopropyl carbonate. Specific examples of dialkylperoxides 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, and 1,1-bis(t-hexylperoxy)cyclohexane. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl acetacetate peroxide. Specific examples of hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, p-diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0047] Among organic peroxides (D), hydroperoxides and peroxyesters are particularly preferred. Among hydroperoxides, t-butyl hydroperoxide, cumene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide are preferably used. Among peroxyesters, t-butyl peroxybenzoate is preferably used.

[0048] Organic peroxide (D), when combined with other components, exhibits excellent chemical polymerization curability, adhesion to CAD / CAM resins, and especially adhesive durability. Organic peroxide (D) may be formulated alone or in combination of two or more types. From the viewpoint of chemical polymerization curability, adhesion to CAD / CAM resins, and especially adhesive durability, the content of organic peroxide (D) in the packaged dental curable composition of the present invention 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, based on 100 parts by mass of the total amount of polymerizable monomer components. Furthermore, by having the content of organic peroxide (D) within the above range, the desired operating time can be adjusted.

[0049] Copper compounds and vanadium compounds are preferably used as the transition metal compound (E).

[0050] Examples of copper compounds include copper(II) carboxylate, copper(II) β-diketone, copper(II) β-ketoester, copper alkoxide, 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) octoate, copper(II) octate, copper(II) naphthenate, copper(II) methacrylate, and copper(II) 4-cyclohexyl butyrate. Examples of β-diketone copper(II) include acetylacetone copper(II), trifluoroacetylacetone copper(II), hexafluoroacetylacetone copper(II), 2,2,6,6-tetramethyl-3,5-heptanedionatocopper(II), and benzoylacetone copper(II). Examples of β-ketoester copper(II) include copper(II) acetate. 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 copper-inorganic acid salts include copper(II) nitrate, copper(II) bromide, and copper(II) chloride. These may be used individually or in appropriate combinations of two or more. Among these, copper(II) carboxylate, β-diketone copper(II), and β-ketoester copper(II) are preferred from the viewpoint of solubility and reactivity with polymerizable monomers, and copper(II) acetate and acetylacetone copper(II) are more preferred.

[0051] The vanadium compounds are preferably IV-valent and / or V-valent vanadium compounds. Examples of IV-valent and / or V-valent vanadium compounds include divanadium(IV) tetroxide, vanadylacetylacetonate(IV), vanadium(IV) stearate oxide, oxovanadium(IV) oxo-vanadium oxalate, vanadyl(IV) sulfate, vanadium naphthenate, vanadium benzoylacetonate, bis(maltrate)oxovanadium(IV), oxobis(1-phenyl-1,3-butanedione)vanadium(IV), vanadium(V) pentoxide, vanadium(V) oxytriisopropoxide, sodium metavanadate(V), and ammonium metavanadate(V). In particular, from the viewpoint of adhesion and other factors, divanadium(IV) tetroxide, vanadyl(IV) sulfate, vanadylacetylacetonate(IV), and bis(maltrate)oxovanadium(IV) are preferred, with vanadylacetylacetonate(IV) and bis(maltrate)oxovanadium(IV) being more preferred. The vanadium compounds can be used individually or in combination of two or more.

[0052] Transition metal compounds (E), when combined with other components, exhibit excellent chemical polymerization curability, adhesion to CAD / CAM resins, and especially adhesive durability. 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, based on 100 parts by mass of the total amount of polymerizable monomer components in the pre-packaged dental curable composition of the present invention, from the viewpoint of chemical polymerization curability, adhesion to CAD / CAM resin, and especially adhesive durability. Furthermore, by having the content of the transition metal compound (E) within the above range, the desired operating time can be adjusted.

[0053] In the general formula (f-1) of the silane coupling agent (F), A1 represents a polymerizable functional group selected from the group consisting of (meth)acryloyloxy groups, vinyl groups, and epoxy groups; M represents a divalent aliphatic group having a straight chain with a carbon chain length of 5 or more, or a divalent aromatic group having 6 or more carbon atoms; and A2, A3, and A4 are each independently a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, with at least one of A2, A3, and A4 being an alkoxy group having 1 to 5 carbon atoms.

[0054] As for A1, from the viewpoint of polymerizability such as copolymerization between a silane coupling agent (F) and a polymerizable monomer (a polymerizable monomer having an acidic group (A) and a polymerizable monomer without an acidic group (B)), a (meth)acryloyloxy group is preferred, and a methacryloyloxy group is more preferred.

[0055] The divalent aliphatic group of M can be any divalent aliphatic group having a straight chain with a carbon chain length of 5 or more, and may also have branched chains. It is thought that having a straight chain with a carbon chain length of 5 or more makes it easier for the molecules to align when bonded to CAD / CAM resin, thereby increasing the hydrophobicity of the adhesive interface. Furthermore, as the aliphatic group, a linear aliphatic group with a carbon chain length of 5 or more is preferred from the viewpoint of further enhancing the hydrophobicity of the adhesive interface. The aliphatic group may consist only of carbon atoms and hydrogen atoms, or it may contain heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms.

[0056] The length of the straight carbon chain of the aliphatic group of M is preferably 6 or more, more preferably 7 or more, and even more preferably 8 or more, as this can further enhance the hydrophobicity of the adhesive interface. Furthermore, the length of the straight carbon chain of the aliphatic group of M is preferably 20 or less, more preferably 15 or less, and even more preferably 12 or less. Examples of aliphatic groups include alkylene groups, alkenylene groups, and alkynylene groups, with alkylene groups being preferred. Examples of alkylene groups include pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, and dodecamethylene. One preferred embodiment is a sachet-type dental curable composition containing a silane coupling agent (F) in which M is a linear alkylene group having a carbon chain length of 8 or more in general formula (f-1).

[0057] Furthermore, the aliphatic or aromatic group of M may contain any divalent group. Examples of any divalent group include non-carbon bonds such as ether groups, ester groups, amide groups, sulfonyl groups, urethane groups, and thioether groups. The number of carbon atoms in the alkylene group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 8, and particularly preferably 1 to 6.

[0058] Furthermore, the divalent aliphatic group and the divalent aromatic group of M may have substituents. Examples of substituents include halogen atoms; carbon-free functional groups such as hydroxyl groups, oxo groups, amino groups, cyano groups, and nitro groups; C1-C6 alkyl groups; C1-C6 alkoxy groups; and C2-C6 alkenyl groups. The number of substituents is preferably 1-10, more preferably 1-8, and even more preferably 1-4.

[0059] The divalent aromatic group M may be a monocyclic group containing only carbon atoms, or a heterocyclic group. Examples of heteroatoms in the heterocyclic group include nitrogen, sulfur, and oxygen atoms. The number of heteroatoms in the heterocyclic group is preferably 1 to 3. The aromatic group has 6 or more carbon atoms, preferably 7 or more, more preferably 8 or more, and even more preferably 9 or more. Furthermore, the aromatic group has 35 or fewer carbon atoms, more preferably 20 or fewer, and even more preferably 16 or fewer. Examples of divalent aromatic groups include arylene groups and arylene groups having an alkylene group. Examples of the aforementioned arylene group include polycyclic aromatic groups such as phenylene group, naphthylene group, anthracenylene group, phenanthrylene group, biphenylene group, and fluorenylene group. Examples of alkylene groups in an arylene group containing an alkylene group include methylene, ethylene, n-propylene, isopropylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, and dodecylene groups. Furthermore, the aromatic group M may have two bonds both connected to an alkylene group. Examples of arylene groups having an alkylene group include ethylenephenylene group, diethylenephenylene group, triethylenephenylene group, propylenephenylene group, and butylenephenylene group. When the aromatic group is an arylene group having an alkylene group with a substituent, the substituent may be on the aromatic ring or on the alkylene group. As the aromatic group of M, an arylene group having an alkylene group is preferred. Furthermore, from the viewpoint of further enhancing the hydrophobicity of the adhesive interface, it is preferable that the bond of the divalent aromatic group be located at the para position of the aromatic ring.

[0060] The alkyl groups of A2, A3, and A4 preferably have 1 to 3 carbon atoms, with 1 carbon atom being more preferable. The number of carbon atoms in the alkoxy groups of A2, A3, and A4 is preferably 1 to 3, and from the viewpoint of adhesive durability to CAD / CAM resin, a carbon number of 1 is more preferable. Examples of alkoxy groups for A2, A3, and A4 include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and tert-butoxy groups. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups. From the viewpoint of adhesive durability to CAD / CAM resins, methoxy groups are more preferred for the alkoxy groups of A2, A3, and A4.

[0061] By incorporating a silane coupling agent (F) into the dental curing composition, separate from the filler surface treatment agent, good adhesive durability to CAD / CAM resin can be obtained even without using a primer. This is because the hydrolysis reaction of the chemical bond between silica in the CAD / CAM resin and the silane coupling agent in the dental curing composition, which causes a decrease in adhesive durability, can be suppressed by using a silane coupling agent (F) containing a compound with a long spacer portion having a carbon chain length of 5 or more. Due to the high hydrophobicity of the silane coupling agent (F), the adhesive interface is sufficiently hydrophobic, thereby suppressing the hydrolysis reaction. Furthermore, in addition to the effect of suppressing hydrolysis reactions, the polymerization initiator system exhibits high polymerization initiation efficiency even under acidic conditions, and the polymerization rate is sufficiently improved. As a result, even though there are few polymerizable groups on the surface of the CAD / CAM resin, a cross-linking reaction occurs efficiently between these polymerizable groups and the components contained in the pre-packaged dental curable composition of the present invention. These components work synergistically without interfering with each other's effects, resulting in excellent adhesive durability to the CAD / CAM resin.

[0062] The silane coupling agent (F) may be used alone or in combination of two or more types. Any known silane coupling agent (F) that satisfies general formula (f-1) can be used without limitation. Specific examples of silane coupling agents (F) include vinyl group-containing silane coupling agents such as vinylhexyltrimethoxysilane, vinylheptyltrimethoxysilane, and vinyloctyltrimethoxysilane; 5-(meth)acryloyloxypentyltrimethoxysilane, 6-(meth)acryloyloxyhexyltrimethoxysilane, 7-(meth)acryloyloxyheptyltrimethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, and 9-(meth)acryloyloxynonyltrimethoxysilane. Examples of silane coupling agents containing a (meth)acryloyloxy group include toxysilane, 10-(meth)acryloyloxydecyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, 8-(meth)acryloyloxyoctylmethyldimethoxysilane, 10-(meth)acryloyloxydecylmethyldimethoxysilane, 11-(meth)acryloyloxyundecylmethyldimethoxysilane, and (meth)acryloyloxymethylphenethyltrimethoxysilane.

[0063] Among these silane coupling agents (F), 8-(meth)acryloyloxyoctyltrimethoxysilane, 9-(meth)acryloyloxynonyltrimethoxysilane, 10-(meth)acryloyloxydecyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, and (meth)acryloyloxymethylphenethyltrimethoxysilane are particularly preferred from the viewpoint of adhesive durability to CAD / CAM resins and ease of handling.

[0064] The silane coupling agent (F) content is preferably 0.1 to 10.0% by mass in the total amount of the packaged dental curable composition of the present invention, from the viewpoint of having excellent adhesive strength, more preferably 0.5 to 9.0% by mass, even more preferably 1.0 to 8.0% by mass, and particularly preferably 1.2 to 7.0% by mass, from the viewpoint of adhesive durability to CAD / CAM resin. Furthermore, in a preferred embodiment, in the packaged dental curable composition of the present invention, the mass ratio of the ascorbic acid compound (C) content to the silane coupling agent (F) content is preferably 1:1 to 1:200, more preferably 1:1.5 to 1:150, even more preferably 1:2 to 1:80, particularly preferably 1:3 to 1:70, and most preferably 1:4 to 1:50, from the viewpoint of curability, mechanical strength of the cured product, and adhesion to tooth structure and CAD / CAM resin, especially adhesive durability.

[0065] One preferred embodiment is a sachet-type dental curable composition in which a first agent containing a polymerizable monomer (A) having an acidic group and a second agent containing a silane coupling agent (F) are sachet-type dental curable compositions. To suppress hydrolysis of the silane coupling agent (F) during storage of the sachet-type dental curable composition and improve storage stability, it is preferable to sachet the polymerizable monomer (A) having an acidic group and the silane coupling agent (F) separately.

[0066] In order to obtain sufficient handling properties of the composition, as well as sufficient radiopaqueness and mechanical strength of the cured product, at least one of the first and second components of the present invention may contain a filler (G).

[0067] Any filler can be used as filler (G) as long as it does not impair the effects of the present invention, and examples include inorganic fillers, organic fillers, and composite fillers of inorganic and organic fillers. Filler (G) may be blended alone or in combination of two or more types. The average particle size of filler (G) is preferably 0.001 to 10 μm, and more preferably 0.001 to 5 μm.

[0068] Inorganic fillers include silica; minerals based on silica such as kaolin, clay, mica, and other silica-based materials; and ceramics and glasses based on silica and containing Al2O3, B2O3, TiO2, ZrO2, BaO, La2O3, SrO, ZnO, CaO, P2O5, Li2O, Na2O, etc. Examples of glasses include lithium borosilicate glass, borosilicate glass, bioglass, lanthanum glass, barium glass, strontium glass, soda glass, zinc glass, and fluoroaluminosilicate glass. Other suitable inorganic fillers include crystalline quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride. In terms of adhesion and handling properties, fine silica particles with an average particle size of 0.001 to 0.1 μm are preferably used. One preferred embodiment is a sachet-type dental curable composition further comprising filler (G), wherein filler (G) comprises an inorganic filler having an average particle size of 0.001 μm or more and 0.1 μm or less, and an inorganic filler having an average particle size of more than 0.1 μm and 10 μm or less. Commercially available inorganic fillers may be used. Examples of commercially available products include "Aerosil® OX50", "Aerosil® 50", "Aerosil® 200", "Aerosil® 380", "Aerosil® R972", "Aerosil® 130", and "AEROXIDE® Alu C" (all manufactured by Nippon Aerosil Co., Ltd., product names). In this invention, if the inorganic filler is surface-treated as described below, the average particle size of the inorganic filler refers to the average particle size before surface treatment.

[0069] Examples of organic fillers include polymethyl methacrylate, polyethyl methacrylate, polymers of polyfunctional methacrylates, polyamides, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.

[0070] Examples of composite fillers combining 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.

[0071] To improve curability, mechanical strength, and handling properties, the filler (G) may be pre-treated with a known surface treatment agent such as a silane coupling agent before use. Examples of surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane.

[0072] The average particle diameter (average primary particle diameter) can be determined by laser diffraction scattering or electron microscopy observation of particles. Specifically, laser diffraction scattering is convenient for measuring particle diameters of 0.1 μm or larger, while electron microscopy observation is convenient for measuring the particle diameter of ultrafine particles smaller than 0.1 μm. The reference value of 0.1 μm is the value measured by laser diffraction scattering. Laser diffraction scattering can be used, for example, to measure particle size distribution by volume using a laser diffraction particle size analyzer (SALD-2300, manufactured by Shimadzu Corporation) with a 0.2% sodium hexametaphosphate aqueous solution as the dispersion medium. For electron microscopy observation, scanning electron microscopes (such as the SU3800 and S-4000 manufactured by Hitachi High-Technologies Corporation) can be used. Electron microscopy observation involves taking electron microscope images of particles and measuring the particle diameter of the particles (200 or more) observed within a unit field of view of the image using image analysis-based particle size distribution measurement software (Mac-View, manufactured by Mountec Co., Ltd.). In this case, the particle diameter is determined as the arithmetic mean of the longest and shortest lengths of the particles, and the average primary particle diameter is calculated from the number of particles and their respective particle diameters.

[0073] The content of filler (G) is not particularly limited as long as the effects of the present invention are achieved, but it is preferably in the range of 20 to 500 parts by mass, more preferably in the range of 50 to 300 parts by mass, and even more preferably in the range of 100 to 250 parts by mass, based on 100 parts by mass of the total amount of polymerizable monomer components in the packaged dental curable composition of the present invention. Within these ranges, sufficient radiopaqueness or sufficient mechanical strength of the cured product can be obtained, as well as sufficient paste workability. Furthermore, the content of filler (G) is not particularly limited as long as it achieves the effects of the present invention, but it is preferably 50 to 97% by mass, more preferably 55 to 95% by mass, and even more preferably 60 to 90% by mass in the total amount of the packaged dental curable composition of the present invention.

[0074] The sachet-type dental curing composition of the present invention may contain a ligand compound. In one preferred embodiment, the ligand compound is at least one compound selected from the group consisting of ligands containing a phosphorus atom and ligands containing a nitrogen atom. Ligands containing a phosphorus atom contain a phosphorus atom as a coordinating atom. Ligands containing a nitrogen atom contain a nitrogen atom as a coordinating atom.

[0075] One embodiment is a sachet-type dental curable composition that further contains a ligand compound. The sachet-type dental curable composition containing the ligand compound also has good chemical polymerization curability and excellent adhesive durability to CAD / CAM resins.

[0076] One preferred embodiment is a sachet-type dental curing composition in which the ligand compound contains a ligand containing a nitrogen atom.

[0077] Other preferred embodiments include a sachet-type dental curing composition in which the ligand compound contains a ligand containing a phosphorus atom.

[0078] Examples of ligands containing a phosphorus atom include phosphine ligands and phosphite ligands. Specifically, examples of ligands containing a phosphorus atom include compounds represented by the following general formula (1), compounds represented by general formula (2), compounds represented by general formula (3), and compounds represented by general formula (4). Ligands containing a phosphorus atom may be used individually or in combination of two or more.

[0079] [ka] (R1~R 15 Each of these independently represents a hydrogen atom, a halogen atom, a polar group, an optionally substituted alkyl group, or an optionally substituted alkoxy group.

[0080] [ka] (R 16 ~R 35 Each of the following independently represents a hydrogen atom, a halogen atom, a polar group, an optionally substituted alkyl group, or an optionally substituted alkoxy group, and X1 represents an optionally substituted divalent aliphatic group.

[0081] [ka] (Each Ar independently represents a group expressed by the following general formula (3-a).) [ka] (Each of Z1 to Z3 is independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or an optionally substituted alkoxy group, and at least one of Z1 to Z3 is a hydrogen atom.) P(OY1)3(4) (Each Y1 independently represents an optionally substituted alkyl group or an optionally substituted aryl group.)

[0082] Among the ligands containing a phosphorus atom, from the viewpoints of curability, mechanical strength of the cured product, and adhesiveness to dentin and resins for CAD / CAM, particularly adhesive durability, the compound represented by the above general formula (1) and the compound represented by general formula (2) are preferable.

[0083] R1~R 15 is preferably a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.

[0084] R 16 ~R 35 is preferably a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.

[0085] Z1~Z3 are preferably a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent.

[0086] R1~R 15 The alkyl group which may have a substituent of R1~R may be either linear or branched. The carbon number of the alkyl group of R1~R 15 is not particularly limited, preferably 1~12, more preferably 1~6, still more preferably 1~4, and particularly preferably 1~3. R1~R 15 Examples of the alkyl group of R1~R include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. The alkyl group of R1~R 15 may be unsubstituted. R1~R 15 Examples of the substituent of the alkyl group of R1~R include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxy group, alkoxy groups having 1~6 carbon atoms, dialkylamino groups each having an alkyl group having 1~6 carbon atoms, amino group, etc.

[0087] R1~R 15 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0088] R1~R 15 Examples of polar groups include acid anhydride groups, carboxylic acid groups, carboxylic acid ester groups, carboxylic acid chloride groups, carboxylic acid amide groups, carboxylic acid bases, sulfonic acid groups, sulfonic acid ester groups, sulfonate chloride groups, sulfonic acid amide groups, sulfonic acid bases, aldehyde groups, epoxy groups, cyano groups, amino groups, monoalkyl-substituted amino groups, dialkyl-substituted amino groups, imide groups, oxazoline groups, etc. From the viewpoint of curability and the mechanical strength of the cured product, carboxylic acid groups, carboxylic acid ester groups, carboxylic acid chloride groups, carboxylic acid amide groups, Preferred are carboxylic acid bases, sulfonic acid groups, sulfonic acid ester groups, sulfonate chloride groups, sulfonic acid amide groups, sulfonic acid bases, and aldehyde groups; more preferably carboxylic acid groups, carboxylic acid ester groups, carboxylic acid chloride groups, carboxylic acid bases, sulfonic acid groups, sulfonic acid ester groups, sulfonate chloride groups, sulfonic acid bases, and aldehyde groups; and even more preferably carboxylic acid groups, carboxylic acid ester groups, carboxylic acid chloride groups, carboxylic acid bases, sulfonic acid groups, sulfonate chloride groups, and sulfonic acid bases. Examples of salts of carboxylic acid bases and sulfonic acid bases include alkali metal salts such as lithium, sodium, and potassium; and alkaline earth metal salts such as magnesium, calcium, strontium, barium, and radium. R1~R 15 If it is a polar group, the number of polar groups is preferably 1 to 9, more preferably 1 to 5, and even more preferably 1 to 3. R1~R 15 When it is an alkyl group having a substituent, specific examples include a trifluoromethyl group.

[0089] R1~R 15 The alkoxy group, which may have substituents, may be linear or branched. R1~R 15The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 12, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 to 3. R1~R 15 Examples of alkoxy groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, neopentyloxy group, n-hexyloxy group, isohexyloxy group, sec-hexyloxy group, tert-hexyloxy group, and neohexyloxy group. R1~R 15 The substituents on the alkoxy group are R1 to R 15 Examples include substituents similar to those on the alkyl group.

[0090] R1~R 15 They may be the same or they may be different. R1~R 15 These may, for example, consist of some of the same hydrogen atoms, alkyl groups, or alkoxy groups.

[0091] R 16 ~R 35 The alkyl group which may have substituents is R1~R 15 This is similar to alkyl groups which may have substituents. 16 ~R 35 The alkoxy group which may have substituents is R1~R 15 This is similar to an alkoxy group which may have substituents. 16 ~R 35 The halogen atoms are R1~R 15 It is similar to the halogen atom. 16 ~R 35 The polar groups are R1~R 15 It is similar to a polar group.

[0092] The divalent aliphatic group X1, which may have substituents, may be linear or branched. The number of carbon atoms in the divalent aliphatic group is preferably 1 to 20, more preferably 1 to 16, even more preferably 1 to 12, and particularly preferably 1 to 8. Examples of divalent aliphatic groups of X1 include alkylene groups, alkenylene groups, and alkylylene groups, with alkylene groups being preferred. Examples of alkylene groups include methylene, ethylene, propylene, butylene, methylpropylene, dimethylpropylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, and dodecamethylene. The substituents on the divalent aliphatic group of X1 are R1~R 15 Examples include substituents similar to those on the alkyl group.

[0093] In formula (3), the multiple Ars may be the same or different. In the group represented by general formula (3-a), Z1 to Z3 may be the same or different. The alkyl group which may have substituents on Z1 to Z3 is R1 to R 15 This is similar to alkyl groups which may have substituents. At least one of Z1 to Z3 is a hydrogen atom, and Z1 to Z3 may all be hydrogen atoms. Specific examples of Ar include the following groups: [ka]

[0094] In one embodiment, one or two of Z1 to Z3 are hydrogen atoms, and the other one or two of Z1 to Z3 may be linear or branched C1-C6 alkyl groups substituted with halogen atoms, linear or branched C1-C4 alkyl groups substituted with fluorine atoms, or trifluoromethyl groups. The alkoxy groups that may have substituents on Z1 to Z3 are R1 to R 15This is similar to an alkoxy group which may have substituents. One preferred embodiment is a phosphine compound in which all Ar groups are 3,5-dimethylphenyl groups in the compound represented by general formula (3). Another preferred embodiment is a phosphine compound in which all Ar groups are 4-methylphenyl groups in the compound represented by general formula (3).

[0095] For the phosphite ligand represented by general formula (4), the three Y1s may be the same or different. The alkyl groups that may have substituents on Y1 are R1 to R1. 15 This is similar to an alkyl group which may have substituents. The carbon number of the aryl group which may have substituents Y1 is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10. The substituents of the aryl group Y1 are R1 to R 15 Examples of substituents similar to those for the alkyl group include: aryl groups that may have substituents on Y1 include phenyl, biphenyl, indenyl, naphthyl, anthryl, phenanthryl, fluorenyl, pyrenyl; and phenyl groups substituted with alkyl groups such as tolyl, xylyl, trimethylphenyl, ethylphenyl, isopropylphenyl, and tetramethylphenyl. One preferred embodiment is a phosphite compound in which three Y1 groups are 1,1,1,3,3,3-hexafluoro-2-propyl groups. Another preferred embodiment is a phosphite compound in which three Y1 groups are 2,4,-di-tert-butylphenyl groups.

[0096] The monodentate phosphine compounds represented by the above general formula (1) include phosphine compounds having electron-donating groups such as triphenylphosphine, diphenyl(o-tolyl)phosphine, tri(o-tolyl)phosphine, tri(p-tolyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(2-methoxyphenylphosphine), tris(4-methoxyphenylphosphine), tris(2,6-dimethoxyphenyl)phosphine (hereinafter sometimes abbreviated as "DMPP"), diphenyl(2-methoxyphenyl)phosphine, 4-(dimethylamino)triphenylphosphine; (2-fluorophenyl)diphenylphosphine, (2-chlorophenyl)diphenylphosphine, (2-bromophenyl Examples of phosphine compounds having electron-withdrawing groups include diphenylphosphine, (pentafluorophenyl)diphenylphosphine, bis(pentafluorophenyl)phenylphosphine (hereinafter sometimes abbreviated as "BPFPP"), tris(pentafluorophenyl)phosphine (hereinafter sometimes abbreviated as "TPFPP"), tris(4-fluorophenyl)phosphine (hereinafter sometimes abbreviated as "TFPP"), tris(4-chlorophenyl)phosphine, tris(4-bromophenyl)phosphine, tris(4-trifluoromethylphenyl)phosphine, tris(4-carboxyphenyl)phosphine, sodium diphenylphosphinobenzene-3-sulfonate, and triphenylphosphine-3,3',3”-trisulfonate trisodium.

[0097] 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.

[0098] 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, and (±)-2,2'-bis[di(3,5-xylyl)phosphino]-1,1'-binaphthyl.

[0099] Examples of phosphite compounds of the above general formula (4) include trimethyl phosphite, triethyl phosphite, tris(1,1,1,3,3,3-hexafluoro-2-propyl) phosphite, triphenyl phosphite, and tris(2,4-di-t-butylphenyl) phosphite.

[0100] Examples of ligands containing nitrogen atoms include compounds represented by general formula (5), compounds represented by general formula (6), and polydentate ligands (7) containing nitrogen-containing heterocycles. Ligands containing nitrogen atoms may be used individually or in combination of two or more.

[0101] R 36 R 37 N-X2-NR 38 R 39 (5) (R 36 ~R 39 Each of the following independently represents an alkyl group which may have substituents, and X2 represents a divalent aliphatic group which may have substituents.

[0102] [ka] (R 40 , R 41 , and R 42Each independently represents an optionally substituted alkyl group, X3 and X4 independently represent an optionally substituted divalent aliphatic group which may contain an oxygen atom and / or a nitrogen atom, m and n independently represent an integer of 1 or more, Y2 represents an optionally substituted monoalkylamino group or dialkylamino group, R 40 , R 41 , R 42 And any two or more of Y2 may come together to form a ring. 41 , R 42 If there are multiple X3 and X4 values, they may be the same or different.

[0103] R 36 ~R 39 The alkyl group which may have substituents is R1~R 15 This is similar to alkyl groups which may have substituents.

[0104] A divalent aliphatic group which may have substituent X2 is the same as a divalent aliphatic group which may have substituent X1.

[0105] R 40 , R 41 , and R 42 The alkyl group which may have substituents is R1~R 15 This is similar to alkyl groups which may have substituents. The monoalkylamino group of Y2 (‐NHR a (R a (represents an alkyl group)) and a dialkylamino group (-NR b R c (R b and R c The number of carbon atoms in (where represents an alkyl group) is not particularly limited, but is preferably 1 to 12, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 to 3. The alkyl groups of the monoalkylamino group and dialkylamino group of Y2 are R1 to R 15Examples of alkyl groups that may have substituents and satisfy the above number of carbon atoms include those that satisfy the above number of carbon atoms. As for the dialkylamino group, each alkyl group may have the above number of carbon atoms. Examples of monoalkylamino groups that may have substituents on Y2 include methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, t-butylamino group, pentylamino group, hexylamino group, etc. Examples of dialkylamino groups that may have substituents on Y2 include dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, dipentylamino group, dihexylamino group, ethylmethylamino group. The alkyl groups of the monoalkylamino group and dialkylamino group of Y2 may be substituted with substituents. Examples of such substituents include R1 to R 15 Examples include substituents similar to those on the alkyl group.

[0106] The divalent aliphatic groups of X3 and X4 may be linear or branched. The number of carbon atoms in the divalent aliphatic group is preferably 1 to 20, more preferably 1 to 16, even more preferably 1 to 12, and particularly preferably 1 to 8. Examples of divalent aliphatic groups include alkylene groups, alkenylene groups, and alkylylene groups, with alkylene groups being preferred. Examples of alkylene groups include methylene groups, ethylene groups, propylene groups, butylene groups, methylpropylene groups, dimethylpropylene groups, pentamethylene groups, hexamethylene groups, heptamethylene groups, octamethylene groups, nonamethylene groups, decamethylene groups, undecamethylene groups, and dodecamethylene groups. Substituents for the divalent aliphatic groups of X3 and X4 are the same as those for 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.

[0107] m and n each independently represent an integer greater than or equal to 1, preferably an integer between 1 and 8, more preferably an integer between 1 and 6, even more preferably an integer between 1 and 5, and particularly preferably an integer between 1 and 3. m and n may be the same or different.

[0108] R 40 , R 41 , R 42 Any two or more of Y2 may come together to form a ring. For example, R 40 , R 41 , or R 42 And Y2 may come together to form a ring. Also, R 40 and Y2, R 41 and R 42 These elements combine to form a ring, and the compound may have two rings. Furthermore, the nitrogen atom of the amino group of Y2 and R 40 The two may come together to form a ring. The ring may contain an oxygen atom and / or a nitrogen atom. Furthermore, in some embodiments, the compound represented by general formula (6) may be a compound having a bicyclo ring. For example, in other embodiments, in the compound represented by general formula (6), Y2 and R 40 The ring formed together with R 41 or R 42 The compound may have a bicyclo ring, having a ring formed by the combination of Y2 and the compound itself.

[0109] In one preferred embodiment, R 40 , R 41 and R 42 This is a linear or branched alkyl group which may have substituents having 1 to 6 carbon atoms.

[0110] Another preferred embodiment is a sachet-type dental curable composition in which at least one of the first and second components contains a ligand compound, and the ligand compound is at least one selected from the group consisting of compounds represented by general formula (1) and compounds represented by general formula (5).

[0111] Also, in another preferred embodiment, at least one of the first agent and the second agent contains a ligand compound, the ligand compound is a compound represented by the general formula (6), and in the compound represented by the general formula (6), R 40 , R 41 and R 42 represent a linear or branched alkyl group which may have a substituent having 1 to 6 carbon atoms, the divalent aliphatic group of X3 and X4 represents an alkylene group not containing an oxygen atom and a nitrogen atom, m and n each independently represent an integer of 1 or more, Y2 represents a monoalkylamino group or a dialkylamino group which may have a substituent, R 40 , R 41 , or R 42 and Y2 together form a ring, and an encapsulated dental curable composition is exemplified.

[0112] Also, in another preferred embodiment, at least one of the first agent and the second agent contains a ligand compound, the ligand compound is a compound represented by the general formula (6), and in the general formula, m is 1 and n is 2, and an encapsulated dental curable composition which is a compound containing 4 nitrogen atoms as a whole compound is exemplified.

[0113] The polydentate ligand (7) containing a nitrogen-containing heterocycle contains a heterocycle containing a 5-membered ring or a 6-membered ring containing a nitrogen atom, has two or more nitrogen atoms in its molecule, and represents a ligand compound with two or more dentates. The polydentate ligand (7) has two or more nitrogen atoms in its molecule, and may have three or more. The number of heterocycles contained in the polydentate ligand (7) may be one or two or more. Examples of the nitrogen-containing heterocycle include nitrogen-containing 5-membered rings such as pyrrole rings, pyrazole rings, and imidazole rings; and nitrogen-containing 6-membered rings such as pyridine rings, pyrazine rings, pyridazine rings, piperazine rings, pyrimidine rings, and triazine rings. The nitrogen-containing heterocycle may be a fused ring of the nitrogen-containing 5-membered ring or 6-membered ring with another ring (e.g., an aromatic ring), or it may be a fused ring of two nitrogen-containing 5-membered rings or 6-membered rings. Examples of fused rings formed by a five-membered or six-membered ring containing a nitrogen atom and an aromatic ring include quinoline rings, isoquinoline rings, indole rings, benzimidazole rings, and benzotriazole rings. The polydentate ligand (7) only needs to contain a heterocycle containing a five-membered or six-membered ring containing a nitrogen atom. Examples include ligand compounds containing a fused ring such as an indole ring, benzimidazole ring, or benzotriazole ring, and a heterocycle containing a five-membered or six-membered ring containing a nitrogen atom. The polydentate nature of the polydentate ligand (7) only needs to be two or more dentates, and may also be three-dentate, four-dentate, etc.

[0114] Examples of polydentate amine compounds of the above general formula (5) include 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 bidentate polydentate amine compounds such as N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine.

[0115] Compounds represented by the above general formula (6) include cyclocyclic compounds such as 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane; bicyclocyclic compounds such as 4,11-dimethyl-1,4,8,11-tetraazabicyclohexadecane; 2,5,9,12-tetramethyl-2,5,9,12-tetraazatetradecane, 2,6,9,13-tetramethyl-2,6,9,13-tetraazatetradecane, and 2,5,8,12-tetramethyl-2,5,8,12-tetra Examples of polydentate amine compounds include azatetradecane, N,N,N,N',N'',N''-pentamethyldiethylenetriamine (hereinafter sometimes abbreviated as "PMDETA"), hexamethyltris(2-aminoethyl)amine, N,N-bis(2-dimethylaminoethyl)-N,N'-dimethylethylenediamine (hereinafter sometimes abbreviated as "HMTETA"), tris[2-(dimethylamino)ethyl]amine (hereinafter sometimes abbreviated as "Me6TREN"), and other ring-less compounds.

[0116] The above-mentioned polydentate ligands (7) containing nitrogen-containing heterocycles include 2,2-bipyridine, 4,4'-di-(5-nonyl)-2,2'-bipyridine, N-(n-propyl)pyridylmethanymine, N-(n-octyl)pyridylmethanymine, 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, and 2,4,6-tri(2-pyridyl)-1,3,5-triazine.

[0117] Among these, tri(o-tolyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, triphenyl phosphite, TMEDA, TMPDA, TEEDA, PMDETA, and Me6TREN are preferably used. Ligand compounds may be formulated individually or in combination of two or more. Ligand compounds are used to enhance the catalytic activity of transition metal compounds in the pre-packaged dental curable composition of the present invention. From the viewpoint of curability, mechanical strength of the cured product, and adhesion to tooth structure and CAD / CAM resin, particularly adhesive durability, the ligand compound content 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, based on 100 parts by mass of the total amount of polymerizable monomer components in the pre-packaged dental curable composition of the present invention.

[0118] The individually packaged dental curable composition of the present invention contains a redox-type polymerization initiator. The individually packaged dental curable composition of the present invention may, if necessary, be a dual-cure composition that also polymerizes by light irradiation, and in order to achieve this, at least one of the first and second components may further contain a conventionally known photopolymerization initiator as a component separate from the polymerization initiator system described above.

[0119] Examples of photopolymerization initiators include α-diketones, ketals, thioxanthones, (bis)acylphosphine oxides, and α-aminoacetophenones.

[0120] Examples of α-diketones include dl-camphorquinone (commonly known as "CQ"), benzyl, and 2,3-pentanedione.

[0121] Examples of ketals include benzyldimethyl ketal and benzyldiethyl ketal.

[0122] Examples of thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

[0123] Among the (bis)acylphosphine oxides mentioned above, examples of acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, benzoylbis(2,6-dimethylphenyl)phosphine oxide, water-soluble acylphosphine oxide compounds disclosed in Japanese Patent Publication No. 3-57916, and salts thereof (e.g., sodium salts, potassium salts, ammonium salts). Examples of bisacylphosphine oxides include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, dibenzoylphenylphosphine oxide, tris(2,4-dimethylbenzoyl)phosphine oxide, tris(2-methoxybenzoyl)phosphine oxide, and their salts (e.g., sodium salts, potassium salts, ammonium salts). 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.

[0124] 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.

[0125] The photopolymerization initiator may be used alone or in combination of two or more. The content of the photopolymerization initiator is not particularly limited, but from the viewpoint of the curability of the resulting 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, based on 100 parts by mass of the total amount of polymerizable monomer components.

[0126] Furthermore, the individually packaged dental curable composition of the present invention may also contain a photopolymerization initiator and a polymerization accelerator for the photopolymerization initiator in combination to enhance its photocurability. Furthermore, organic peroxide (D) may be used in combination with a polymerization accelerator. Polymerization accelerators used with organic peroxides (D) and / or photoinitiators include tertiary amines, aldehydes, thiol compounds, triazine compounds substituted with trihalomethyl groups, thiourea compounds, sulfinic acids, benzotriazole compounds, benzimidazole compounds, sulfites, bisulfites, borate compounds, barbituric acids and their derivatives. A single polymerization accelerator may be used, or two or more may be used in combination.

[0127] 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-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-diisopropylaniline Examples include N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, 4-(N,N-dimethylamino)benzoate n-butoxyethyl, 4-(N,N-dimethylamino)benzoate 2-(methacryloyloxy)ethyl, 4-(N,N-dimethylamino)benzoate ethyl, 4-(N,N-dimethylamino)benzoate butyl, N-methyldiethanolamine, 4-(N,N-dimethylamino)benzophenone, trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2-(dimethylamino)ethyl(meth)acrylate, N-methyldiethanolamine di(meth)acrylate, N-ethyldiethanolamine di(meth)acrylate, triethanolamine mono(meth)acrylate, triethanolamine di(meth)acrylate, and triethanolamine tri(meth)acrylate.

[0128] Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, and pn-octyloxybenzaldehyde. Examples of thiol compounds include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, decanethiol, and thiobenzoic acid. As for triazine compounds substituted with trihalomethyl groups, any known s-triazine compounds having at least one trihalomethyl group, such as a trichloromethyl group or a tribromomethyl group, can be used without any limitations.

[0129] 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 individually or in combination of two or more.

[0130] Examples of the aforementioned sulfinic acids include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, 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 include calcium sulfinate, 2,4,6-triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, 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 may be used individually or in combination of two or more.

[0131] Examples of benzotriazole compounds include 1H-benzotriazole (hereinafter sometimes abbreviated as "BTA"), 5-methyl-1H-benzotriazole, and 5,6-dimethyl-1H-benzotriazole. Examples of benzimidazole compounds include benzimidazole, 5-methylbenzimidazole, and 5,6-dimethylbenzimidazole. Examples of sulfites include sodium sulfite, potassium sulfite, calcium sulfite, and ammonium sulfite. Examples of bisulfites include sodium bisulfite and potassium bisulfite. 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 acids and their 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.

[0132] The polymerization accelerator for the photopolymerization initiator may be used alone or in combination of two or more. The content of the polymerization accelerator for the photopolymerization initiator is not particularly limited, but from the viewpoint of the curability of the resulting dental curable composition, 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, based on 100 parts by mass of the total amount of polymerizable monomer components in the packaged dental curable composition of the present invention.

[0133] The dental curing composition of the present invention may further contain a fluoride ion-releasing substance in at least one of the first and second components. By incorporating a fluoride ion-releasing substance, a dental resin cement that can impart acid resistance to tooth structure can be obtained. Examples of fluoride-releasing substances include fluoride-releasing polymers such as copolymers of methyl methacrylate and methacrylate fluoride; hydrofluoric acid salts 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-releasing substances may be used individually or in combination of two or more.

[0134] The individually packaged dental curable composition of the present invention may contain a pH adjusting agent in at least one of its first and second components. The pH adjusting agent is used for the purpose of adjusting and stabilizing the pH of the individually packaged dental curable composition of the present invention. The pH adjusting agent is not particularly limited 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, as well as their salts, are preferably used. The pH adjusting agent may be used alone or in combination of two or more types.

[0135] Examples of phosphates include alkali metal phosphates such as trisodium phosphate and tripotassium phosphate; alkali metal phosphates such as disodium hydrogen phosphate and dipotassium hydrogen phosphate; alkali metal phosphates such as sodium dihydrogen phosphate and potassium dihydrogen phosphate; alkyl alkali metal phosphates such as sodium dodecyl phosphate; sodium glycerophosphate and disodium glycerophosphate; alkaline earth metal phosphates such as tricalcium phosphate and trimagnesium phosphate; alkaline earth metal phosphates such as calcium hydrogen phosphate and magnesium hydrogen phosphate; and alkaline earth metal phosphates such as calcium dihydrogen phosphate. Among these, disodium hydrogen phosphate, sodium dodecyl phosphate, sodium glycerophosphate, and disodium glycerophosphate are preferably used.

[0136] In addition, the pre-packaged dental curable composition of the present invention may contain additives such as polymerization inhibitors, ultraviolet absorbers, thickeners, solvents (e.g., water, organic solvents), colorants, antibacterial agents, and fragrances in at least one of the first and second components, to the extent that they do not impair the effects of the present invention. These may be included individually or in combination of two or more components. Examples of polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, and 2,6-di-t-butyl-4-methylphenol. In one embodiment, the solvent content (e.g., water, organic solvent) in the individually packaged dental curable composition is preferably less than 1% by mass, more preferably less than 0.1% by mass, and even more preferably less than 0.01% by mass, based on the total amount of the individually packaged dental curable composition.

[0137] The individually packaged dental curable composition of the present invention may be prepared according to conventional methods depending on the type and amount of the above-mentioned components. The individually packaged dental curable composition of the present invention is used in a two-part form. The two-part form can be appropriately selected from powder and liquid forms, paste and liquid forms, two-paste forms, etc., but in a more preferred embodiment from the viewpoint of operability, it is used in a two-paste form. It is preferable to store each paste in a state where the pastes are separated from each other, and to knead the two pastes immediately before use to allow chemical polymerization to proceed and harden them. The paste is usually prepared by kneading a liquid component prepared by mixing components other than filler (G) with powdered filler (G).

[0138] The individually packaged dental curing composition of the present invention is used for bonding dental prostheses such as crowns, inlays, and bridges to tooth structure in the affected area of ​​a tooth, and for core buildup, etc. The individually packaged, hardening dental composition of the present invention can be used as a dental cement, such as a dental resin cement. Among dental resin cements, it is particularly suitable for use as a self-adhesive dental resin cement.

[0139] The present invention includes embodiments that combine the above configuration in various ways, within the scope of the technical idea of ​​the present invention, as long as they achieve the effects of the present invention. [Examples]

[0140] 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. Unless otherwise specified regarding the manufacturing method, the compounds and fillers used in the following examples and comparative examples were commercially available products.

[0141] [Polymerizable monomer having an acidic group (A)] MDP:10-Methacryloyloxydecyldihydrogenphosphate

[0142] [Polymerizable monomer (B) without acidic groups] HEMA: 2-hydroxyethyl methacrylate Bis-GMA: 2,2-Bis[4-(2-hydroxy-3-methacryloyloxypropoxy)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

[0143] [Ascorbic acid compounds (C)] PA: Ascorbyl palmitate ANa: Sodium L-ascorbate

[0144] [Organic peroxide (D)] THP: 1,1,3,3-Tetramethylbutylhydroperoxide BPB: t-butylperoxybenzoate

[0145] [Transition metal compound (E)] CuA: Copper(II) acetate VOAA: Vanadylacetylacetonate (IV)

[0146] [Silane coupling agent (F)] 8-MOS:8-Methacryloyloxyoctyltrimethoxysilane 11-MUS:11-Methacryloyloxyundecyltrimethoxysilane 11-MUES:11-Methacryloyloxyundecyltriethoxysilane

[0147] [Silane coupling agents other than silane coupling agent (F)] γ-MPS: γ-methacryloyloxypropyltrimethoxysilane

[0148] [Filler (G)] Surface-treated barium glass: Barium glass (manufactured by ESTEC Co., Ltd., product code "E-3000") was crushed in a ball mill to obtain barium glass powder. The average particle size of the obtained barium glass powder was measured by volume using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model "SALD-2300") and was found to be 2.4 μm. 100 parts by mass of this barium glass powder was surface-treated with 3 parts by mass of γ-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain surface-treated barium glass. R972: Microparticle silica manufactured by Nippon Aerosil Co., Ltd., product name "Aerosil (registered trademark) R972", average particle size: 16nm Alumina: Aluminum oxide manufactured by Nippon Aerosil Co., Ltd., product name "AEROXIDE(registered trademark) Alu C", average particle size: 13nm

[0149] [Ligand compound] P(OPh)3: Triphenylphosphite

[0150] [Polymerization accelerator] TPBSS: Sodium triisopropylbenzenesulfinate (2,4,6-triisopropylbenzenesulfinate) DEPT: N,N-bis(2-hydroxyethyl)-p-toluidine BTA: 1H-benzotriazole DMETU: 4,4-dimethylethylenethiourea

[0151] [Polymerization inhibitors] BHT: 2,6-di-t-butyl-4-methylphenol

[0152] (Examples 1-9 and Comparative Examples 1-4) From the components listed in Tables 1 and 2, all components except the filler and the ascorbic acid compound were mixed at room temperature to obtain a homogeneous liquid component. Then, the obtained liquid component was kneaded with the ascorbic acid compound and the filler to prepare the individually packaged dental curable compositions of Examples 1-9 and Comparative Examples 1-4. Next, using these individually packaged dental curing compositions, the polymerization rate at 32°C and the adhesive strength to CAD / CAM resin were measured immediately after manufacturing according to the method described below. Tables 1 and 2 show the mixing ratio (parts by mass) and test results of these dental curing compositions.

[0153] [Polymerization rate of individually packaged dental curing compositions at 32°C] An ATR (Automatic Transistor Radiography) measuring device (Diamond Micro ATR, Single Reflection Horizontal ATR SmartOrbit®, ThermoFisher Scientific) was installed on an FT-IR (Fourier Transform Infrared Spectrometer "Nicolet 6700") measuring instrument. Measurement conditions: Measurement range: 4000 cm² -1 ~650cm -1 The incident angle was 45°, the number of scans was 1, and the prism was a diamond.

[0154] The dental curable compositions obtained by mixing the first and second components in each example and comparative example were placed on the sample stage of a diamond micro-ATR machine set to 32°C. Real-time IR measurements were performed to measure the spectra of the dental curable compositions at each time point. Real-time IR measurements were started from the moment the dental curable composition was placed immediately after mixing.

[0155] The spectral analysis conditions were such that the peaks of the carbonyl bond before and after polymerization were unaffected by polymerization (C=O, 1710 cm⁻¹). -1 Using a1 and a2 as references, the peaks of double bonds before and after polymerization for each reference (C=C, 1640 cm) -1 The polymerization rate c (%) was calculated using the area ratios of b1 and b2 (b1 / a1, b2 / a2). The polymerization rates in the table are the maximum values ​​measured over 40 minutes (n=3). Polymerization rate c(%)={1-(b2 / a2) / (b1 / a1)}×100

[0156] The polymerization rate at 32°C is preferably 45% or higher, more preferably 47.5% or higher, and even more preferably 50% or higher, from the viewpoint of adhesion to CAD / CAM resins with few unreacted polymerizable groups on the resin surface, and especially adhesive durability.

[0157] [Tensile adhesion strength of individually packaged dental curing compositions to CAD / CAM resins] A CAD / CAM resin (manufactured by Kuraray Noritake Dental Co., Ltd., product name "Katana Avencia Block") was polished under running water with #1000 silicon carbide paper. After polishing, the surface was dried by air blowing off the water. After drying, the dried surface was further sandblasted with alumina abrasive 50 microns (manufactured by Morita Corporation) to create the substrate treatment surface. An adhesive tape with a diameter of 5 mm and a thickness of approximately 150 μm was attached to the substrate treatment surface to control the adhesion area. In each example and comparative example, the dental hardening composition obtained by mixing the first and second components was built up on one end face (circular cross-section) of a stainless steel cylindrical rod (7 mm in diameter, 2.5 cm in length). Next, the end face on the side where the dental hardening composition was built up was placed on the smooth surface (adhesion surface) inside 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 bond it and prepare a test sample. Ten test samples were prepared. After removing the excess dental hardening composition that had seeped out from around the stainless steel cylindrical rod when pressed, the test samples were left to stand at room temperature for 30 minutes and then immersed in distilled water. The test samples immersed in distilled water were left to stand in a constant temperature incubator maintained at 37°C for 24 hours. After being left to stand in a constant temperature incubator maintained at 70°C for 10 days, the tensile adhesive strength was measured and evaluated as adhesive durability. Tensile adhesive strength was measured using a universal testing machine (manufactured by Shimadzu Corporation) with a crosshead speed set to 2 mm / min. The tensile adhesive strength values ​​in the table are the average values ​​of measurements taken from 10 test samples.

[0158] [Table 1]

[0159] [Table 2]

[0160] As shown in Table 1, the individually packaged dental curing compositions of the present invention (Examples 1-9) have a polymerization rate of 48-54% and exhibit excellent tensile adhesive strength to CAD / CAM resins of 12.9 MPa or higher.

[0161] On the other hand, as shown in Table 2, in the individually packaged dental curable compositions that did not contain a silane coupling agent (F) (Comparative Examples 1 and 2), the polymerization rate was 49% to 51% when using a polymerization initiator system containing an ascorbic acid compound (C), but it was confirmed that the tensile adhesive strength to CAD / CAM resin was low, at 6.7 MPa or less. Furthermore, in the individually packaged dental curing compositions that did not contain ascorbic acid compound (C) (Comparative Examples 3 and 4), the polymerization rate was 39% or less, and even with the inclusion of a silane coupling agent (F), the tensile adhesive strength to CAD / CAM resin was low at 8.3 MPa or less. In Comparative Examples 3 and 4, although a polymerization accelerator was used instead of ascorbic acid compound (C), it was not possible to increase the polymerization rate or the tensile adhesive strength to CAD / CAM resin. [Industrial applicability]

[0162] The individually packaged dental curing 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 core buildup, etc.

Claims

1. Polymerizable monomers having acidic groups (A), polymerizable monomers without acidic groups (B), ascorbic acid compounds (C), organic peroxides (D), transition metal compounds (E), and the following general formula (f-1) 【Chemistry 1】 (In the formula, A 1 A represents a polymerizable functional group selected from the group consisting of (meth)acryloyloxy groups, vinyl groups, and epoxy groups, M represents a divalent aliphatic group having a straight chain with a carbon chain length of 5 or more, or a divalent aromatic group having 6 or more carbon atoms, A 2 A 3 , and A 4 Each of these is independently a hydroxyl group, a C1-C5 alkyl group, or a C1-C5 alkoxy group, and A 2 A 3 , and A 4 At least one of the groups is an alkoxy group having 1 to 5 carbon atoms. The mixture contains a silane coupling agent (F) represented by ), A sachet-type dental curable composition wherein the mass ratio of the ascorbic acid compound (C) content to the silane coupling agent (F) content is ascorbic acid compound (C):silane coupling agent (F) = 1:1 to 1:

200.

2. The sachet-type dental curable composition according to claim 1, wherein the ascorbic acid compound (C) is at least one compound selected from the group consisting of salts and esters of ascorbic acid.

3. The sachet-type dental curable composition according to claim 1 or 2, wherein the transition metal compound (E) is a copper compound or a vanadium compound.

4. The dental hardening agent in a sachet type according to claim 1 or 2 is sachet-packaged in a first agent containing the polymerizable monomer (A) having the acidic group and a second agent containing the silane coupling agent (F). chemical composition.

5. The sachet-type dental curable composition according to claim 1 or 2, wherein M is a divalent aliphatic group having a straight chain with a carbon chain length of 7 or more, or a divalent aromatic group having 7 or more carbon atoms.

6. A 2 、 A 3 、 and A 4 are each independently a hydroxyl group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and at least one of A 2 、 A 3 、 and A 4 is an alkoxy group having 1 to 3 carbon atoms. The sub-packaged dental curable composition according to claim 1 or 2.

7. A 2 A 3 , and A 4 However, each is independently a hydroxyl group, a methyl group, or a methoxy group, A 2 A 3 , and A 4 The sachet-type dental curable composition according to claim 1 or 2, wherein at least one of the members is a methoxy group.

8. A 2 A 3 , and A 4 A sachet-type dental curable composition according to claim 1 or 2, wherein the group is a methoxy group.

9. The sachet-type dental curable composition according to claim 1 or 2, wherein M is an alkylene group having a straight chain with a carbon chain length of 8 or more.

10. The sachet-type dental curable composition according to claim 1 or 2, wherein the silane coupling agent (F) is at least one selected from the group consisting of 5-(meth)acryloyloxypentyltrimethoxysilane, 6-(meth)acryloyloxyhexyltrimethoxysilane, 7-(meth)acryloyloxyheptyltrimethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 9-(meth)acryloyloxynonyltrimethoxysilane, 10-(meth)acryloyloxydecyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, 8-(meth)acryloyloxyoctylmethyldimethoxysilane, 10-(meth)acryloyloxydecylmethyldimethoxysilane, 11-(meth)acryloyloxyundecylmethyldimethoxysilane, and (meth)acryloyloxymethylphenethyltrimethoxysilane.

11. The sachet-type dental curable composition according to claim 1 or 2, wherein the silane coupling agent (F) is at least one selected from the group consisting of 8-(meth)acryloyloxyoctyltrimethoxysilane, 9-(meth)acryloyloxynonyltrimethoxysilane, 10-(meth)acryloyloxydecyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, and (meth)acryloyloxymethylphenethyltrimethoxysilane.

12. A sachet-type dental curable composition according to claim 1 or 2, further containing filler (G).

13. A sachet-type dental curable composition according to claim 1 or 2, further containing a ligand compound.

14. A dental resin cement, a sachet-type dental curing composition according to claim 1 or 2.

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