Dental Filling Kit

Abstract

To provide a dental filling kit that has excellent adhesion to dentin and cavity sealability and comprises a two-component dental bonding material and a self-adhesive dental composite resin.SOLUTION: Provided is a dental filling kit comprising: a self-adhesive dental composite resin (X) containing a monomer (a) having an acidic group, a monomer (b) having no acidic group, and a photoinitiator (c); and a two-component dental bonding material (Y) containing a first agent and a second agent, the first agent containing a monomer (f) having an acidic group, at least one of the first agent and the second agent containing a chemical polymerization accelerator (h), and at least one of the first agent and the second agent containing water (i).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a dental filling kit. [Background technology]

[0002] Currently, when relatively small cavities are formed due to damage to tooth structure (enamel, dentin, and cementum) caused by dental caries or other factors, the mainstream method of restorative filling treatment is to use an adhesive system that combines a one-component dental bonding material and a one-material dental composite resin. The general procedure for such restorative filling treatment involves first applying a one-component dental bonding material to the entire cavity, removing volatile components such as water or organic solvents with an air blower if necessary, and then curing the dental bonding material with light irradiation. The cavity is then filled with a one-component dental composite resin, which is then cured by light irradiation or other means. The surface of the cured dental composite resin is then reshaped or polished as necessary to complete the restorative filling treatment.

[0003] One-component dental bonding materials used in such filling and restorative treatments are compositions containing a monomer having an acidic group, a monomer not having an acidic group, a polymerization initiator, and water, while one-component dental composite resins are generally compositions containing a monomer not having an acidic group, a polymerization initiator, and a filler, but not containing a monomer having an acidic group. The majority of dental bonding materials are one-component, photocurable materials containing a photopolymerization initiator as a polymerization initiator. Meanwhile, Patent Document 1 discloses a two-component dental bonding material in which a monomer having an acidic group and a specific compound are individually packaged from the standpoint of storage stability, and also describes an embodiment in which the material is used in combination with a dental composite resin.

[0004] In such filling and restorative treatments, the operational steps are being simplified. For example, Patent Document 2 discloses a dental filling kit that comprises a specific dental bonding material containing a monomer with an acidic group and a dental composite resin containing a monomer with an acidic group, and describes that sufficient adhesive strength and marginal sealing can be obtained without irradiating the bonding material with light. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-121869 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-131621 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the inventors' investigations revealed that the two-component dental bonding material of Patent Document 1, not only when it is a composition that does not contain a photopolymerization initiator, but also when it is a composition that contains a photopolymerization initiator and is irradiated with light, leaves room for improvement in adhesion to tooth structure and sealing ability at the cavity margin when used in combination with a dental composite resin. More specifically, even when the dental composite resin of Patent Document 1 is used in combination with a two-component dental bonding material, when a cavity is filled with the dental composite resin and polymerized and cured, sealing ability at the cavity margin (hereinafter also referred to as "cavity sealing ability") is poor. The shrinkage stress during polymerization of the dental composite resin causes the composite resin, which is the cured product after polymerization, to peel off from the cavity wall, creating a gap between the composite resin and the tooth structure, and marginal leakage, a phenomenon in which oral bacteria and the like invade through this gap, was not sufficiently suppressed.

[0007] Furthermore, the commercially available light-curing dental composite resin (product name "Palfique Esthelite", Tokuyama Dental Co., Ltd.) disclosed in Patent Document 1 does not contain a monomer having an acidic group.

[0008] Furthermore, the dental filling kit of Patent Document 2 is said to have excellent adhesive strength to tooth tissue and excellent marginal sealing ability, but marginal sealing ability was not evaluated in the examples. The inventors of the present invention have studied Patent Document 2 and found that when a dental composite resin is filled into a cavity and polymerized and cured, the shrinkage stress during polymerization of the dental composite resin causes gaps between the dental composite resin and the tooth tissue, and marginal leakage cannot be sufficiently suppressed, as in Patent Document 1. Furthermore, the dental filling kit of Patent Document 2 has been found to reduce the curing depth when a shade with low transparency is used, such as when filling a composite resin whose color matches the discolored tooth tissue due to various reasons such as aging, resulting in a decrease in the curing depth of the bonding material and a decrease in cavity sealing ability.

[0009] Therefore, the present invention aims to provide a dental filling kit that includes a two-component dental bonding material that has excellent adhesion to tooth structure and cavity sealing properties, and a self-adhesive dental composite resin. [Means for solving the problem]

[0010] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a dental filling kit comprising a two-component dental bonding material having a specific composition containing a monomer having an acidic group and a chemical polymerization accelerator, and a dental composite resin having a specific composition containing a monomer having an acidic group, and after further research, have completed the present invention. That is, the present invention encompasses the following inventions.

[0011] [1] A self-adhesive dental composite resin (X) containing a monomer (a) having an acidic group, a monomer (b) not having an acidic group, and a photopolymerization initiator (c); Contains a first agent and a second agent, the first agent contains a monomer (f) having an acidic group, At least one of the first agent and the second agent contains a chemical polymerization accelerator (h), and a two-component dental bonding material (Y) in which at least one of the first and second components contains water (i); A dental filling kit comprising: [2] The dental filling kit according to [1], wherein the self-adhesive dental composite resin (X) further contains a filler (d). [3] A dental filling kit according to [1] or [2], wherein at least one of the first and second agents further contains a monomer (g) that does not have an acidic group. [4] A dental filling kit according to any one of [1] to [3], wherein the chemical polymerization accelerator (h) comprises at least one selected from the group consisting of amines, borate compounds, sulfinic acids and their salts, thiourea compounds, copper compounds, thiol compounds, and vanadium compounds. [5] The dental filling kit according to any one of [1] to [4], wherein the chemical polymerization accelerator (h) contains a borate compound. [6] A dental filling kit according to any one of [1] to [5], wherein the second agent further contains at least one chemical polymerization initiator (j) selected from the group consisting of organic peroxides and inorganic peroxides. [7] The dental filling kit according to [6], wherein the chemical polymerization initiator (j) is an organic peroxide, and the organic peroxide includes at least one selected from the group consisting of hydroperoxides, ketone peroxides, peroxyesters, and diacyl peroxides. [8] The dental filling kit according to any one of [1] to [7], wherein the second agent contains water. [9] The dental filling kit according to any one of [1] to [8], wherein the first and second agents are substantially free of a photopolymerization initiator.

[10] The dental filling kit according to any one of [1] to [8], wherein at least one of the first and second agents further contains a photopolymerization initiator (k).

[11] The dental filling kit according to any one of [1] to

[10] , wherein at least one of the first agent and the second agent further contains an organic solvent.

[12] The dental filling kit according to any one of [1] to

[11] , wherein the photopolymerization initiator (c) contains a water-soluble photopolymerization initiator (c-1).

[13] The dental filling kit according to any one of [1] to

[12] , wherein the monomer (a) having an acidic group includes a monomer having a phosphate group.

[14] The dental filling kit according to

[13] , wherein the monomer having a phosphate group includes a monomer having a divalent phosphate group and an alkylene group having 6 to 20 carbon atoms.

[15] The dental filling kit according to any one of [1] to

[14] , wherein the monomer (a) having an acidic group and the monomer (f) having an acidic group contain the same monomer. [Effects of the Invention]

[0012] According to the present invention, a dental filling kit can be provided that includes a two-component dental bonding material and a self-adhesive dental composite resin, which have excellent adhesion to tooth structure and cavity sealing properties. Furthermore, by using a combination of the self-adhesive dental composite resin and the two-component dental bonding material, the dental filling kit of the present invention has excellent cavity sealing properties, even for deep cavities, such as those 2 mm or deeper, compared to a combination of a one-component dental bonding material and a self-adhesive dental composite resin. Furthermore, by using a combination of the self-adhesive dental composite resin and the two-component dental bonding material, the dental filling kit of the present invention also has excellent durability of adhesion to tooth structure and cavity sealing properties compared to a combination of a one-component dental bonding material and a self-adhesive dental composite resin. DETAILED DESCRIPTION OF THE INVENTION

[0013] The dental filling kit of the present invention comprises a self-adhesive dental composite resin (X) and a two-component dental bonding material (Y) (hereinafter, simply referred to as "dental bonding material (Y)"). The self-adhesive dental composite resin (X) contains a monomer (a) having an acidic group, a monomer (b) not having an acidic group, and a photopolymerization initiator (c). The two-component dental bonding material (Y) contains a first part and a second part, the first part containing a monomer (f) having an acidic group, at least one of the first part and the second part containing a chemical polymerization accelerator (h), and at least one of the first part and the second part containing water (i). The two-component dental bonding material (Y) can be mixed immediately before use.

[0014] Known chemical polymerization initiator systems that exhibit high polymerization activity in the presence of acid include an oxidizing agent consisting of a thermally stable organic peroxide and a reducing agent (reducing agents may function as a single reducing agent or as a combination of two or more types, collectively referred to as "polymerization accelerators"). Such chemical polymerization initiator systems are formulated taking into consideration the properties of the oxidizing agent, the reducing agent, and reactions with other components. For example, it is known that the oxidizing agent and the reducing agent are packaged separately and used as a two-component dental hardenable composition (e.g., bonding material).

[0015] Although the reasons why the dental filling kit of the present invention has excellent adhesion to tooth structure, sealing ability at the cavity margin, and durability thereof are unclear, the inventors presume as follows: In the two-component dental bonding material (Y) of the present invention, at least one of the first and second components contains a chemical polymerization accelerator (h). By combining the two-component dental bonding material (Y) using such a chemical polymerization system with the self-adhesive dental composite resin (X), This is presumably because hardening is accelerated at the interface between the dental bonding material (Y) and the self-adhesive dental composite resin (X), strengthening the bond between the two. While achieving the demineralization effect required for adhesion to tooth structure (especially dentin), the strong bond at the interface between the dental bonding material (Y) and the self-adhesive dental composite resin (X) prevents the self-adhesive dental composite resin (X), which is the cured product after polymerization and filled into the cavity, from peeling from the cavity wall and cavity floor due to contraction stress during polymerization of the self-adhesive dental composite resin (X), and because no gaps are created between the self-adhesive dental composite resin (X) and the tooth structure, the cavity margins (cavity margins) are also well sealed. Furthermore, as mentioned above, it has excellent initial adhesion and sealing properties at the edges of the cavity, and both the interface between the tooth substance and the dental bonding material (Y) and the interface between the dental bonding material (Y) and the self-adhesive dental composite resin (X) are strong, so it also has excellent durability (durability of adhesion to the tooth substance and durability of cavity sealing properties) over the entire range of the dental bonding material (Y) and the self-adhesive dental composite resin (X).

[0016] Hereinafter, each component used in the dental filling kit of the present invention will be described. In this specification, "(meth)acrylic" is a general term for methacrylic and acrylic, and the same applies to similar expressions (such as "(meth)acrylic acid" and "(meth)acrylonitrile"). In this specification, the upper and lower limits of the numerical ranges (contents of each component, values ​​calculated from each component, and physical properties) can be appropriately combined.

[0017] First, the self-adhesive dental composite resin (X) will be described.

[0018] <Monomer (a) Having an Acidic Group> The self-adhesive dental composite resin (X) of the present invention requires a monomer (a) having an acidic group from the viewpoints of adhesion to tooth structure, cavity sealing ability, and durability thereof. A radical monomer is preferably used for the self-adhesive dental composite resin (X). Specific examples of the radical monomer in the monomer (a) having an acidic group include (meth)acrylate monomers, (meth)acrylamide monomers, esters of α-cyanoacrylic acid, (meth)acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, itaconic acid, etc., vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives, etc. Among these, (meth)acrylate monomers and (meth)acrylamide monomers are preferred from the viewpoint of curability.

[0019] Examples of the monomer (a) having an acidic group used in the present invention include monomers having at least one acidic group such as a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonate group, a carboxylic acid group, or a sulfonic acid group. Examples of the monomer (a) having an acidic group include a monomer having an acidic group represented by general formula (6) and a monomer having an acidic group represented by general formula (7), which are examples of the monomer (f) having an acidic group used in the dental bonding material (Y) described below. The monomer (a) having an acidic group can be used alone or in appropriate combination of two or more. Specific examples of the monomer (a) having an acidic group are listed below.

[0020] Examples of the monomer 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, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-( (Meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate, 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 Examples of the acryloyloxypropyl methyl acrylate include 2-(meth)acryloyloxyethylphenyl phosphate, 2-(meth)acryloyloxyethyl-(2-bromoethyl)hydrogenphosphate, 2-methacryloyloxyethyl-(4-methoxyphenyl)hydrogenphosphate, 2-methacryloyloxypropyl-(4-methoxyphenyl)hydrogenphosphate, and acid chlorides, alkali metal salts, and amine salts thereof. Among the monomers having a phosphate group, preferred are monomers having a divalent phosphate group with an alkylene group having 6 to 20 carbon atoms, and from the viewpoint of superior adhesion to tooth structure, cavity sealing ability, and durability thereof, more preferred are monomers having a divalent phosphate group with an alkylene group having 6 to 12 carbon atoms, and even more preferred are monomers having a divalent phosphate group with an alkylene group having 8 to 12 carbon atoms.

[0021] Examples of monomers having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, and acid chlorides, alkali metal salts, and amine salts thereof.

[0022] Examples of the monomer having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, 4-(meth)acryloyloxybutyl dihydrogenthiophosphate, 5-(meth)acryloyloxypentyl dihydrogenthiophosphate, 6-(meth)acryloyloxyhexyl dihydrogenthiophosphate, 7-(meth)acryloyloxyheptyl dihydrogenthiophosphate, and 8-(meth)acryloyloxyoctyl dihydrogenthiophosphate. Examples of the acryloyloxypropyl methyl phosphate include acryloyloxypropyl methyl phosphate, 9-(meth)acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, 20-(meth)acryloyloxyicosyl dihydrogen thiophosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

[0023] Examples of the monomer having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phosphonoacetate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

[0024] The monomer having a carboxylic acid group is a monomer having one carboxyl group or its acid anhydride in the molecule. Examples of the acrylic acid ester include a monofunctional (meth)acrylic acid ester having a carboxylic acid group, and a monofunctional (meth)acrylic acid ester having a plurality of carboxyl groups or acid anhydride groups thereof in the molecule.

[0025] Examples of monofunctional monomers having one carboxyl group or an acid anhydride group thereof in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen maleate, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine Examples of the acryloyloxybenzoic acid include N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, and N-(meth)acryloyl-4-aminosalicylic acid, as well as compounds in which the carboxyl group of these compounds has been converted to an acid anhydride group.

[0026] Examples of monofunctional monomers having a plurality of carboxyl groups or acid anhydride groups thereof in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxyethyl trimellitate anhydride ... Examples of suitable acrylic anhydrides include 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate, 6-(meth)acryloyloxyethyl naphthalene-1,2,6-tricarboxylic anhydride, 6-(meth)acryloyloxyethyl naphthalene-2,3,6-tricarboxylic anhydride, 4-(meth)acryloyloxyethyl carbonylpropionoyl-1,8-naphthalic anhydride, and 4-(meth)acryloyloxyethyl naphthalene-1,8-tricarboxylic anhydride.

[0027] Examples of the monomer having a sulfonic acid group include 2-sulfoethyl (meth)acrylate.

[0028] Furthermore, among the above-mentioned monomers (a) having an acidic group, from the viewpoint of achieving good adhesion to tooth structure, cavity sealing ability, and durability thereof when used as a self-adhesive dental composite resin (X), it is preferable to contain a monomer having a phosphate group or a monomer having a carboxylic acid group, and examples thereof 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)acryloyloxyethyl dihydrogen phosphate, 8-(meth)acryloyloxypropyl dihydrogen phosphate, 9-(meth)acryloyloxybutyl dihydrogen phosphate, 10-(meth)acryloyloxypentyl dihydrogen phosphate, 11-(meth)acryloyloxyhexyl dihydrogen phosphate, 12-(meth)acryloyloxyhexyl dihydrogen phosphate, 13-(meth)acryloyloxyhexyl dihydrogen phosphate, 14-(meth)acryloyloxyhexyl dihydrogen phosphate, 15-(meth)acryloyloxyhexyl dihydrogen phosphate, 16-(meth)acryloyloxyhexyl dihydrogen phosphate, 17-(meth)acryloyloxyhexyl dihydrogen phosphate, 18-(meth)acryloyloxyhexyl dihydrogen phosphate, 19-(meth)acryloyloxyhexyl dihydrogen phosphate, 20-(meth)acryloyloxyethyl dihydrogen phosphate, 21-(meth)acryloyloxypropyl dihydrogen phosphate, 22-(meth)acryloyloxypropyl dihydrogen phosphate, 23-(meth)acryloyloxypropyl dihydrogen phosphate, 24-(meth)acryloyloxy ) Acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate, 4-(meth)acryloyloxyethyl trimellitate hydride, 4-(meth)acryloyloxyethyl trimellitate, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, and a mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis(2-methacryloyloxyethyl)hydrogen phosphate are more preferred, and 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxyoctyl dihydrogen phosphate, 11-(meth)acryloyloxyethyl trimethylol phosphate, 4-(meth)acryloyloxyethyl trimellitate, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, and a mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis(2-methacryloyloxyethyl)hydrogen phosphate are more preferred, Cidodecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, and 20-(meth)acryloyloxyicosyl dihydrogen phosphate are more preferred, and from the viewpoint of a balance of curability, 10-(meth)acryloyloxydecyl dihydrogen phosphate is particularly preferred.

[0029] From the viewpoints of adhesion to tooth structure, cavity sealing ability, and the durability thereof, the content of the monomer (a) having an acidic group in the self-adhesive dental composite resin (X) of the present invention is preferably 1 to 40 parts by mass, more preferably 2.5 to 35 parts by mass, and even more preferably 5 to 30 parts by mass, per 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X) of the present invention.

[0030] <Monomer (b) having no acidic group> Examples of the monomer (b) having no acidic group in the present invention include an asymmetric acrylamide-methacrylate compound (b-1); a hydrophobic monomer (b-2) having no acidic group and having a solubility in water at 25°C of less than 10% by mass (hereinafter simply referred to as "hydrophobic monomer (b-2)"); and a hydrophilic monomer (b-3) having no acidic group and having a solubility in water at 25°C of 10% by mass or more (hereinafter simply referred to as "hydrophilic monomer (b-3)"). The monomer (b) having no acidic group may be used alone or in combination of two or more. In the present invention, compounds that do not have an acidic group and contain an acrylamide group and a methacryloyloxy group are defined as asymmetric acrylamide-methacrylate compounds (b-1), and compounds that do not have an acidic group and are not included in the asymmetric acrylamide-methacrylate compounds (b-1) are classified into hydrophobic monomers (b-2) and hydrophilic monomers (b-3) according to the degree of hydrophilicity.

[0031] Asymmetric acrylamide-methacrylate compound (b-1) A preferred embodiment of the present invention is a self-adhesive dental composite resin (X) containing an asymmetric acrylamide-methacrylate compound (b-1). The asymmetric acrylamide-methacrylate compound (b-1) is preferably a compound represented by the following general formula (1), because it improves adhesion to tooth structure, cavity sealing properties, and the durability of these properties.

[0032] [ka] In the formula, Z represents a C1 to C8 linear or branched aliphatic or aromatic group which may have a substituent, and the aliphatic group is -O-, -S-, -CO-, -CO-O-, -O-CO-, -NR 1 -, -CO-NR 1 -, -NR 1 -CO-, -CO-O-NR 1 -, -O-CO-NR 1 - and -NR 1 -CO-NR 1at least one bond selected from the group consisting of may be interrupted by R groups. 1 is a hydrogen atom or a C1- It represents a C8 linear or branched aliphatic group.

[0033] Z is a moiety that adjusts the hydrophilicity of the asymmetric acrylamide-methacrylate compound (b-1). The optionally substituted C1-C8 aliphatic group represented by Z may be either a saturated aliphatic group (an alkylene group or a cycloalkylene group (e.g., a 1,4-cyclohexylene group)) or an unsaturated aliphatic group (an alkenylene group or an alkynylene group). From the viewpoints of availability or ease of production and chemical stability, a saturated aliphatic group (an alkylene group) is preferred. From the viewpoints of adhesion to tooth substrate, polymerization curing property, etc., Z is preferably a linear or branched C1-C4 aliphatic group that may have a substituent, and more preferably a linear or branched C2-C4 aliphatic group that may have a substituent. The aliphatic group is preferably an alkylene group. Examples of the C1-C8 alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and an n-butylene group.

[0034] Examples of the aromatic group represented by Z, which may have a substituent, include an arylene group and an aromatic heterocyclic group. As the aromatic group, an arylene group is more preferable than an aromatic heterocyclic group. The heterocycle of the aromatic heterocyclic group is generally unsaturated. The aromatic heterocycle is preferably a 5- or 6-membered ring. As the arylene group, a phenylene group is preferable. As the heterocycle of the aromatic heterocyclic group, for example, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, a triazole ring, a pyran ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a 1,3,5-triazine ring are preferable. Among the aromatic groups, a phenylene group is particularly preferable.

[0035] R1 The aliphatic group in the R may be either a saturated aliphatic group (an alkyl group or an alkynyl group), but from the viewpoint of ease of availability or production and chemical stability, a saturated aliphatic group (an alkyl group) is preferred. 1 The direct contact of C1 to C8 in Examples of the branched or unbranched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an ethyl ... pentyl, isopentyl, sec-pentyl, neopentyl, tert-pentyl, 1 Examples of the alkyl group include an 1,1-ethylpropyl group, a hexyl group, an isohexyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a 3,3-dimethylbutyl group, and a 2-ethylbutyl group, and preferred are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0036] R 1 As the alkyl group, a hydrogen atom or a linear or branched C1 to C4 alkyl group which may have a substituent is more preferred, and a hydrogen atom or a linear or branched C1 to C4 alkyl group which may have a substituent is particularly preferred. A branched C1 to C3 alkyl group is more preferred.

[0037] When the aliphatic group of Z is interrupted by the linking group, the number of linking groups is not particularly limited, but may be about 1 to 10, preferably 1, 2, or 3, and more preferably 1 or 2. Furthermore, in the formula (1), the aliphatic group of Z is preferably not interrupted by consecutive linking groups. That is, it is preferable that the linking groups are not adjacent to each other. The linking group is more preferably at least one linking group selected from the group consisting of -O-, -S-, -CO-, -CO-O-, -O-CO-, -NH-, -CO-NH-, -NH-CO-, -CO-O-NH-, -O-CO-NH-, and -NH-CO-NH-, and particularly preferably at least one linking group selected from the group consisting of -O-, -S-, -CO-, -NH-, -CO-NH-, and -NH-CO-.

[0038] The substituents in Z include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.). atom), a carboxyl group, a C2 to C6 linear or branched acyl group, a C1 to C6 linear or branched alkyl group, a C1 to C6 linear or branched alkoxy group, and the like.

[0039] Specific examples of the asymmetric acrylamide-methacrylate compound (b-1) include, but are not limited to, the following:

[0040] [ka]

[0041] Among these, from the viewpoints of adhesion to tooth structure, cavity sealing ability, and their durability and polymerization curing property, asymmetric acrylamide-methacrylate compounds in which Z is a C2-C4 linear or branched aliphatic group which may have a substituent are preferred, and N-methacryloyloxyethyl acrylamide (commonly known as "MAEA"), N-methacryloyloxypropyl acrylamide, N-methacryloyloxybutyl acrylamide, N-(1-ethyl-(2-methacryloyloxy)ethyl)acrylamide, and N-(2-(2-methacryloyloxyethoxy)ethyl)acrylamide are more preferred, and from the viewpoint of high hydrophilicity which is involved in penetration into the collagen layer of dentin, MAEA and N-methacryloyloxypropyl acrylamide are more preferred. More preferred is arylamide.

[0042] The asymmetric acrylamide-methacrylate ester compound (b-1) may be used alone or in combination of two or more. The content of the asymmetric acrylamide-methacrylate ester compound (b-1) is not particularly limited as long as the effects of the present invention are achieved, but is preferably 1 to 60 parts by mass, more preferably 2 to 45 parts by mass, even more preferably 3 to 30 parts by mass, and particularly preferably 5 to 25 parts by mass, per 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X) of the present invention.

[0043] Hydrophobic monomers without acidic groups (b-2) The hydrophobic monomer (b-2) without an acidic group improves the handleability of the self-adhesive dental composite resin (X) and the mechanical strength of the cured product. The hydrophobic monomer (b-2) is preferably a radical monomer without an acidic group and with a polymerizable group. From the viewpoint of ease of radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. The hydrophobic monomer (b-2) refers to a monomer that does not have an acidic group, does not correspond to the asymmetric acrylamide-methacrylate ester compound (b-1), and has a solubility in water at 25°C of less than 10% by mass. Examples of the hydrophobic monomer (b-2) include crosslinkable monomers such as aromatic bifunctional monomers, aliphatic bifunctional monomers, and trifunctional or higher functional monomers.

[0044] Examples of aromatic compound-based bifunctional monomers include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, phenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, and the like. Among these, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethoxy groups added: 2.6, commonly known as "D-2.6E"), 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)acryloyloxypentaethoxyphenyl)propane are preferred.

[0045] Examples of the aliphatic compound-based bifunctional monomer include glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, and neopentyl glycol. Examples of the di(meth)acrylate include cholestrol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, and 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)di(meth)acrylate. Among these, triethylene glycol diacrylate, triethylene glycol dimethacrylate (commonly known as "3G"), neopentyl glycol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA"), 1,10-decanediol dimethacrylate (commonly known as "DD"), and 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate are preferred.

[0046] Examples of trifunctional or higher functional monomers include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetra(meth)acrylate, and 1,7-diacryloyloxy-2,2,6,6-tetra(meth)acryloyloxymethyl-4-oxaheptane. Among these, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate is preferred.

[0047] Among the hydrophobic monomers (b-2), aromatic bifunctional monomers and aliphatic bifunctional monomers are preferred in terms of mechanical strength and handling. Bis-GMA and D-2.6E are preferred aromatic bifunctional monomers. Glycerol di(meth)acrylate, 3G, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, DD, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, and UDMA are preferred aliphatic bifunctional monomers.

[0048] Among the above hydrophobic monomers (b-2), Bis-GMA, D-2.6E, 3G, UDMA, and DD are more preferred, and D-2.6E, 3G, and Bis-GMA are even more preferred, from the viewpoint of good adhesion to tooth tissue, cavity sealing properties, and durability thereof when used as a self-adhesive dental composite resin (X).

[0049] The hydrophobic monomer (b-2) may be used alone or in combination of two or more. When the content of the hydrophobic monomer (b-2) is equal to or less than the upper limit described below, it is easy to prevent the wettability of the self-adhesive dental composite resin (X) to tooth structure from decreasing, resulting in a decrease in adhesion. When the content is equal to or greater than the lower limit described above, it is easy to obtain the desired mechanical strength of the cured product. The content of the hydrophobic monomer (b-2) in the self-adhesive dental composite resin (X) of the present invention is preferably 20 to 98 parts by mass, more preferably 40 to 95 parts by mass, and even more preferably 60 to 92 parts by mass, per 100 parts by mass of the total amount of the monomers in the self-adhesive dental composite resin (X) of the present invention.

[0050] Hydrophilic monomers without acidic groups (b-3) The hydrophilic monomer (b-3) improves the wettability of the self-adhesive dental composite resin (X) to tooth structure. As the hydrophilic monomer (b-3), a radical monomer having a polymerizable group but no acidic group is preferred, and from the viewpoint of facilitating radical polymerization, the polymerizable group is preferably a (meth)acidic monomer. Acryl groups and / or (meth)acrylamide groups are preferred. The hydrophilic monomer (b-3) means a monomer that does not have an acidic group, does not correspond to the asymmetric acrylamide-methacrylate ester compound (b-1), and has a solubility in water at 25°C of 10% by mass or more, preferably 30% by mass or more, and more preferably is soluble in water at 25°C in any proportion. As the hydrophilic monomer, those having a hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxypropylene group, or an amide group are preferred. Examples of the hydrophilic monomer (b-3) include hydrophilic monofunctional (meth)acrylate monomers such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-((meth)acryloyloxy)ethyltrimethylammonium chloride, and polyethylene glycol di(meth)acrylate (having 9 or more oxyethylene groups); Examples thereof include hydrophilic monofunctional (meth)acrylamide monomers such as tyrol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N,N-bis(2-hydroxyethyl) (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, diacetone (meth)acrylamide, 4-(meth)acryloylmorpholine, N-trihydroxymethyl-N-methyl (meth)acrylamide, N,N-dimethylacrylamide, and N,N-diethylacrylamide.

[0051] Among these hydrophilic monomers (b-3), from the viewpoints of adhesion to tooth substance, cavity sealing ability, and durability thereof, 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and hydrophilic monofunctional (meth)acrylamide monomers are preferred, and 2-hydroxyethyl (meth)acrylate, N,N-dimethylacrylamide, and N,N-diethylacrylamide are more preferred. One type of hydrophilic monomer (b-3) may be blended alone, or two or more types may be blended in combination.

[0052] The content of the hydrophilic monomer (b-3) in the self-adhesive dental composite resin (X) of the present invention is preferably in the range of 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, and even more preferably 0 to 30 parts by mass, per 100 parts by mass of the total amount of monomers. The content of the hydrophilic monomer (b-3) may be 0 part by mass, per 100 parts by mass of the total amount of monomers. When the content of the hydrophilic monomer (b-3) in the self-adhesive dental composite resin (X) of the present invention is equal to or greater than the lower limit, a sufficient improvement in adhesion is likely to be obtained, and when the content is equal to or less than the upper limit, the desired mechanical strength of the cured product is likely to be obtained.

[0053] The content of the monomer (b) having no acidic group in the self-adhesive dental composite resin (X) is preferably 60 to 99 parts by mass, more preferably 65 to 97.5 parts by mass, and even more preferably 70 to 95 parts by mass, per 100 parts by mass of the total amount of monomers. From the viewpoints of adhesion to tooth structure, cavity sealing ability, and durability thereof, the mass ratio of the hydrophobic monomer (b-2) to the hydrophilic monomer (b-3) is preferably hydrophobic monomer (b-2):hydrophilic monomer (b-3) = 10:0 to 1:2, more preferably 10:0 to 1:1, and even more preferably 10:0 to 2:1.

[0054] A preferred embodiment includes a self-adhesive dental composite resin (X) that is substantially free of difunctional or higher functional (meth)acrylamide monomers. Another preferred embodiment includes a self-adhesive dental composite resin (X) that is substantially free of a hydrogen phosphate diester group-containing monomer. The hydrogen phosphate diester group-containing monomer preferably has a (meth)acryloyloxy group and / or a (meth)acrylamide group. In the present invention, "substantially free of a certain monomer" means that the content of the monomer is less than 0.5 parts by mass, preferably less than 0.1 parts by mass, per 100 parts by mass of the total amount of monomers contained in the composition of the self-adhesive dental composite resin (X). The content of the monomer that is substantially absent may be less than 0.5% by mass or less than 0.1% by mass in the entire composition of the self-adhesive dental composite resin (X).

[0055] <Photopolymerization initiator (c)> The photopolymerization initiator (c) is classified into a water-soluble photopolymerization initiator (c-1) and a water-insoluble photopolymerization initiator (c-2). As the photopolymerization initiator (c), only the water-soluble photopolymerization initiator (c-1) may be used, only the water-insoluble photopolymerization initiator (c-2) may be used, or the water-soluble photopolymerization initiator (c-1) and the water-insoluble photopolymerization initiator (c-2) may be used in combination, but it is preferable to use them in combination.

[0056] Water-soluble photopolymerization initiator (c-1) The water-soluble photopolymerization initiator (c-1) improves polymerization curing at the hydrophilic tooth surface interface, achieving high adhesive strength. The water-soluble photopolymerization initiator (c-1) has a solubility in water at 25°C of 10 g / L or more, preferably 15 g / L or more, more preferably 20 g / L or more, and even more preferably 25 g / L or more. A solubility of 10 g / L or more allows the water-soluble photopolymerization initiator (c-1) to dissolve sufficiently in the water in the tooth at the adhesive interface, making it easier to achieve a polymerization-promoting effect.

[0057] Examples of the water-soluble photopolymerization initiator (c-1) include water-soluble thioxanthones, water-soluble acylphosphine oxides, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one in which a (poly)ethylene glycol chain is introduced to the hydroxyl group, 1-hydroxycyclohexyl phenyl ketone in which a (poly)ethylene glycol chain is introduced to the hydroxyl group and / or phenyl group, and 1-hydroxycyclohexyl phenyl ketone in which -OCHCOO is introduced to the phenyl group. - Na + Incorporating 2-hydroxybenzoates (Poly)ethylene glycol chains introduced into the hydroxyl and / or phenyl groups of 2-hydroxy-2-methyl-1-phenylpropan-1-one, and -OCH2COO - Na + α- Hydroxyalkylacetophenones; α-aminoalkylphenones such as 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2-(dimethylamino)-1-[(4-morpholino)phenyl]-1-butanone in which the amino group is converted into a quaternary ammonium salt;

[0058] Examples of the water-soluble thioxanthones include 2-hydroxy-3-(9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(1-methyl-9-oxo-9H-thioxanthen-4-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2- Hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(3,4-dimethyl-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(1,3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanaminium chloride, and the like can be used.

[0059] Examples of the water-soluble acylphosphine oxides include acylphosphine oxides represented by the following general formula (2) or (3).

[0060] [ka]

[0061] [ka]

[0062] In formulas (2) and (3), R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 are independent of each other, C1~ C4 linear or branched alkyl group or halogen atom, M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, a magnesium ion, a pyridinium ion (the pyridine ring may have a substituent), or HN + R 9 R 10 R 11 (In the formula, R 9 , R 10 , and R 11 are each independently an organic group or a hydrogen atom) is an ammonium ion. n is 1 or 2, X is a C1 to C4 linear or branched alkylene group, and R 8 -CH(CH3)COO(C2H4O) p It is represented by CH3, and p represents an integer of 1 to 1000.

[0063] R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 The alkyl group of R is not particularly limited as long as it is a C1 to C4 linear or branched chain group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a 2-methylpropyl group, and a tert-butyl group. 2 , R 3 , R 4 , R 5 , R 6 , and R 7The alkyl group is preferably a C1 to C3 linear alkyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. Examples of X include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and an n-butylene group. X is preferably a C1 to C3 linear alkylene group, more preferably a methylene group or an ethylene group, and even more preferably a methylene group.

[0064] When M is a pyridinium ion, examples of the substituent on the pyridine ring include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a carboxyl group, a C2-C6 linear or branched acyl group, a C1-C6 linear or branched alkyl group, a C1-C6 linear or branched alkoxy group, etc. M is an alkali metal ion, an alkaline earth metal ion, a magnesium ion, a pyridinium ion (the pyridine ring may have a substituent), or HN + R 9 R 10 R 11 (wherein the symbols have the same meanings as above) is preferred. Examples of alkali metal ions include lithium ion, sodium ion, potassium ion, rubidium ion, and cesium ion. Examples of alkaline earth metal ions include calcium ion, strontium ion, barium ion, and radium ion. R 9 , R 10 , and R 11 The organic group may be the above-mentioned pyridine. The substituents are the same as those on the lysine ring (excluding halogen atoms).

[0065] Among these, R 2 , R 3 , R 4 , R 5 , R 6 , and R 7In terms of storage stability and color stability in the composition of the self-adhesive dental composite resin (X), compounds in which all of the groups are methyl groups are particularly preferred. Furthermore, examples of the ammonium ion include ammonium ions derived from various amines. Examples of amines include ammonia, trimethylamine, diethylamine, dimethylaniline, ethylenediamine, triethanolamine, N,N-dimethylamino methacrylate, 4-(N,N-dimethylamino)benzoic acid and its alkyl esters, 4-(N,N-diethylamino)benzoic acid and its alkyl esters, and N,N-bis(2-hydroxyethyl)-p-toluidine.

[0066] R 8 From the viewpoint of adhesion to tooth structure, p is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and particularly preferably 4 or more. p is preferably 1000 or less, more preferably 100 or less, even more preferably 75 or less, and particularly preferably 50 or less.

[0067] Among these water-soluble acylphosphine oxides, M n+ A compound represented by general formula (2) in which R is a lithium ion, and 8 Particularly preferred is a compound represented by general formula (3) synthesized from polyethylene glycol methyl ether methacrylate, the molecular weight of which is 950, in which the moiety corresponding to the group represented by R 2 , R 3 , and R 4 and R in general formula (3) 2 , R 3 , R 4 , R 5 , R 6 , and R 7 is as described above.

[0068] Water-soluble acylphosphine oxides having such a structure can be synthesized according to known methods, and some are commercially available. For example, they can be synthesized by the methods disclosed in JP-A-57-197289 and WO 2014 / 095724. The water-soluble photopolymerization initiator (c-1) may be used alone or in combination of two or more.

[0069] The water-soluble photopolymerization initiator (c-1) may be dissolved in the self-adhesive dental composite resin (X) or dispersed in the composition of the self-adhesive dental composite resin (X) in the form of a powder.

[0070] When the water-soluble photopolymerization initiator (c-1) is dispersed in the composition in powder form, an excessively large average particle size tends to cause sedimentation, so it is preferably 500 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less. On the other hand, an excessively small average particle size results in an excessively large specific surface area of ​​the powder, reducing the amount of self-adhesive dental composite resin (X) that can be dispersed in the composition. Therefore, an average particle size of 0.01 μm or more is preferred. That is, the average particle size of the water-soluble photopolymerization initiator (c-1) is preferably in the range of 0.01 to 500 μm, more preferably 0.01 to 100 μm, and even more preferably 0.01 to 50 μm.

[0071] The average particle size of each water-soluble photopolymerization initiator (c-1) powder can be calculated as the volume average particle size after performing image analysis using image analysis particle size distribution measurement software (Mac-View; manufactured by Mountec Co., Ltd.) based on electron microscope photographs of 100 or more particles.

[0072] When the water-soluble photopolymerization initiator (c-1) is dispersed in the composition in the form of a powder, the shape of the initiator is not particularly limited, and various shapes such as spherical, needle-like, plate-like, crushed, etc. can be mentioned. The water-soluble photopolymerization initiator (c-1) can be prepared by a conventionally known method such as a pulverization method, a freeze-drying method, or a reprecipitation method. From the viewpoint of the average particle size of the obtained powder, the freeze-drying method and the reprecipitation method are preferred, and the freeze-drying method is more preferred.

[0073] From the viewpoint of the curing property of the self-adhesive dental composite resin (X) to be obtained, the content of the water-soluble photopolymerization initiator (c-1) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total amount of the monomers in the self-adhesive dental composite resin (X) of the present invention. From the viewpoint of adhesion to substrates, the content is more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass. When the content of the water-soluble photopolymerization initiator (c-1) is equal to or greater than the lower limit, polymerization at the adhesion interface proceeds sufficiently, and sufficient adhesive strength is likely to be obtained. On the other hand, when the content of the water-soluble photopolymerization initiator (c-1) is equal to or less than the upper limit, sufficient adhesive strength is likely to be obtained.

[0074] Non-water-soluble photopolymerization initiator (c-2) From the viewpoint of curing property, the self-adhesive dental composite resin (X) of the present invention preferably contains, in addition to the water-soluble photopolymerization initiator (c-1), a water-insoluble photopolymerization initiator (c-2) having a solubility in water at 25°C of less than 10 g / L (hereinafter, sometimes referred to as the water-insoluble photopolymerization initiator (c-2)). The water-insoluble photopolymerization initiator (c-2) used in the present invention can be a known photopolymerization initiator. The water-insoluble photopolymerization initiator (c-2) may be used alone or in combination of two or more.

[0075] Examples of the water-insoluble photopolymerization initiator (c-2) include (bis)acylphosphine oxides, thioxanthones, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, and α-aminoketone compounds other than the water-soluble photopolymerization initiator (c-1).

[0076] Among the (bis)acylphosphine oxides, examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, and benzoyldi(2,6-dimethylphenyl)phosphonate. Examples of bisacylphosphine oxides include bis(2,6-dichlorobenzoyl)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, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide.

[0077] Examples of the thioxanthones include thioxanthone and 2-chlorothioxanthen-9-one.

[0078] Examples of the ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

[0079] Examples of the α-diketones include diacetyl, benzyl, dl-camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, acenaphthenequinone, etc. Among these, dl-camphorquinone is particularly preferred because it has a maximum absorption wavelength in the visible light region.

[0080] Examples of the coumarins include 3,3'-carbonylbis(7-diethylaminocoumarin), 3-(4-methoxybenzoyl)coumarin, 3-thienoylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-7-methoxycoumarin, 3- Benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3-(p-nitrobenzoyl)coumarin, 3-(p-nitrobenzoyl)coumarin, 3,5-carbonylbis(7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3'-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo[f]coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl hydroxycarbonyl-8-methoxycoumarin, 3-acetylbenzo[f]coumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin, 7-dimethylamino-3-(4-methoxybenzoyl)coumarin, 7-diethylamino-3-(4-methoxybenzoyl)coumarin, 7-diethylamino-3-(4-diethylamino)coumarin, 7-methoxy-3-(4-methoxybenzoyl)coumarin, 3-(4-nitrobenzoyl)benzo[f]coumarin, 3-(4-ethoxycinnamoyl)-7-methoxycoumarin, 3-(4- dimethylaminocinnamoyl)coumarin, 3-(4-diphenylaminocinnamoyl)coumarin, 3-[(3-dimethylbenzothiazol-2-ylidene)acetyl]coumarin, 3-[(1-methylnaphtho[1,2-d]thiazol-2-ylidene)acetyl]coumarin, 3,3'-carbonylbis(6-methoxycoumarin), 3,3'-carbonylbis(7-acetoxycoumarin), 3,3'-carbonylbis(7-dimethylaminocoumarin), 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-( (dibutylamino)coumarin, 3-(2-benzimidazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dioctylamino)coumarin, 3-acetyl-7-(dimethylamino)coumarin, 3,3'-carbonylbis(7-dibutylaminocoumarin), 3,3'-carbonyl-7-diethylaminocoumarin-7'-bis(butoxyethyl)aminocoumarin, 10-[3-[4-(dimethylamino)phenyl]-1-oxo-2-propenyl]-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,Examples of the compounds include those described in JP-A-9-3109 and JP-A-10-245525, such as 11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one and 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one.

[0081] Among the above-mentioned coumarins, 3,3'-carbonylbis(7-diethylaminocoumarin) and 3,3'-carbonylbis(7-dibutylaminocoumarin) are particularly preferred.

[0082] Examples of the anthraquinones include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, and 1-hydroxyanthraquinone.

[0083] Examples of the benzoin alkyl ether compounds include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0084] Examples of the α-aminoketone compounds include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one.

[0085] Among these non-water-soluble photopolymerization initiators (c-2), it is preferable to use at least one selected from the group consisting of (bis)acylphosphine oxides, α-diketones, and coumarins. This allows for excellent photocuring properties in the visible and near-ultraviolet regions, and sufficient photocuring properties whether using a halogen lamp, a light-emitting diode (LED), or a xenon lamp. Thus, a self-adhesive dental composite resin (X) exhibiting good adhesion properties is obtained.

[0086] The content of the water-insoluble photopolymerization initiator (c-2) is not particularly limited, but from the viewpoint of the curing property of the resulting self-adhesive dental composite resin (X), it is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total amount of monomers in the self-adhesive dental composite resin (X) of the present invention. By keeping the content of the water-insoluble photopolymerization initiator (c-2) at or below the upper limit, sufficient bond strength can be easily obtained even when the polymerization performance of the water-insoluble photopolymerization initiator (c-2) itself is low, and further, precipitation of the polymerization initiator (c-1b) itself from the self-adhesive dental composite resin (X) can be suppressed.

[0087] When the water-soluble photopolymerization initiator (c-1) and the water-insoluble photopolymerization initiator (c-2) are used in combination, the mass ratio of the water-soluble photopolymerization initiator (c-1) to the water-insoluble photopolymerization initiator (c-2) [(c-1):(c-2)] in the present invention is preferably 10:1 to 1:10, more preferably 7:1 to 1:7, even more preferably 5:1 to 1:5, and particularly preferably 3:1 to 1:3. If the water-soluble photopolymerization initiator (c-1) is contained in a mass ratio of more than 10:1, the curing ability of the self-adhesive dental composite resin (X) itself may be reduced, and when used in combination with the two-component dental bonding material (Y), it may be difficult to achieve the effects of the present invention, such as adhesion to tooth structure, cavity sealing ability, and the durability thereof. On the other hand, if the non-water-soluble photopolymerization initiator (c-2) is contained in a mass ratio of more than 1:10, the hardening property of the self-adhesive dental composite resin (X) itself is increased, but the promotion of polymerization at the adhesive interface is insufficient, and it may be difficult to achieve high adhesiveness.

[0088] Chemical polymerization initiator The self-adhesive dental composite resin (X) of the present invention may further contain a chemical polymerization initiator. Examples of chemical polymerization initiators include organic peroxides and inorganic peroxides, with organic peroxides being preferred. The organic peroxide used as the chemical polymerization initiator is not particularly limited, and known peroxides can be used. Representative organic peroxides include, for example, ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxydicarbonates. Specific examples of these organic peroxides include those described in International Publication No. 2008 / 087977. One type of chemical polymerization initiator may be used alone, or two or more types may be used in combination. Examples of inorganic peroxides include peroxodisulfates and peroxodiphosphates, with peroxodisulfates being preferred in terms of curability.

[0089] <Filler (d)> The self-adhesive dental composite resin (X) of the present invention contains a filler (d) to adjust handling properties and to increase the mechanical strength (e.g., flexural modulus) of the cured product. Examples of the filler (d) include inorganic fillers, organic-inorganic composite fillers, and organic fillers. One type of filler (d) may be used alone, or two or more types may be used in combination.

[0090] Inorganic filler materials include quartz, silica; silica-based minerals such as kaolin, clay, mica, and mica; alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, zinc glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate. Examples of inorganic fillers include quartz glass, ytterbium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide, and silica-coated ytterbium fluoride. These may also be used alone or in combination of two or more. Among these, quartz, silica, silica-zirconia, barium glass, ytterbium oxide, and silica-coated ytterbium fluoride are preferred because they provide excellent mechanical strength and transparency to the resulting self-adhesive dental composite resin (X), and more preferably quartz, silica, silica-zirconia, barium glass, and silica-coated ytterbium fluoride. From the viewpoints of the handleability and mechanical strength of the resulting self-adhesive dental composite resin (X), the average particle size of the inorganic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm. In the present invention, when the inorganic filler has been surface-treated as described below, the average particle size of the inorganic filler refers to the average particle size before the surface treatment. A preferred embodiment includes a dental filling kit in which the filler (d) of the self-adhesive dental composite resin (X) contains an inorganic filler. Commercially available products include "Aerosil (registered trademark) OX50," "Aerosil (registered trademark) 50," "Aerosil (registered trademark) 200," "Aerosil (registered trademark) 380," "Aerosil (registered trademark) R972," and "Aerosil (registered trademark) 130" (all of which are trade names manufactured by Nippon Aerosil Co., Ltd.).

[0091] The shape of the inorganic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. Examples include amorphous fillers and spherical fillers. From the viewpoint of improving the mechanical strength of the cured product of the self-adhesive dental composite resin (X), it is preferable to use a spherical filler as the inorganic filler. The spherical filler used in the present invention is a filler in which, when a photograph of the filler is taken with an electron microscope, the particles observed within a unit field of view are rounded and the average uniformity, calculated by dividing the particle diameter in a direction perpendicular to the maximum diameter by the maximum diameter, is 0.6 or more. The average particle diameter of the spherical filler is preferably 0.05 to 5 μm. If the average particle diameter is less than 0.05 μm, the filling rate of the spherical filler in the self-adhesive dental composite resin (X) may decrease, resulting in a decrease in mechanical strength. On the other hand, if the average particle size exceeds 5 μm, the surface area of ​​the spherical filler decreases, and it may not be possible to obtain a cured product of the self-adhesive dental composite resin (X) having high mechanical strength.

[0092] The inorganic filler may be surface-treated with a known surface treatment agent such as a silane coupling agent before use, if necessary, in order to adjust the fluidity of the self-adhesive dental composite resin (X). The silane coupling agents may be used singly or in combination of two or more. Any known silane coupling agent may be used without limitation. Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, vinyltrippropoxysilane, vinyltributoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltris(β-methoxyethoxy)silane, 6-(meth)acryloyloxyhexyltrimethoxysilane, 6-(meth)acryloyloxypropyltris(β-methoxyethoxy) ... Examples thereof include oxyhexyltriethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, 8-(meth)acryloyloxyoctyltriethoxysilane, κ-methacryloyloxydecyltrimethoxysilane, κ-methacryloyloxydecyltriethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, 11-(meth)acryloyloxyundecyltriethoxysilane, γ-aminopropyltriethoxysilane, and (γ-mercaptopropyl)trimethoxysilane.

[0093] The surface treatment method is not particularly limited and may be any known method, such as a method of spraying the surface treatment agent onto the inorganic filler while vigorously stirring the inorganic filler, a method of dispersing or dissolving the inorganic filler and the surface treatment agent in a suitable solvent and then removing the solvent, or or a method in which the alkoxy groups of the surface treatment agent are hydrolyzed in an aqueous solution with an acid catalyst to convert them to silanol groups, and the silanol groups are then attached to the surface of the inorganic filler in the aqueous solution, after which the water is removed. In either method, the reaction between the inorganic filler surface and the surface treatment agent is completed by heating the resulting mixture, usually within a range of 50 to 150° C., thereby completing the surface treatment. The amount of the surface treatment is not particularly limited, and for example, 1 to 10 parts by mass of the surface treatment agent can be used per 100 parts by mass of the inorganic filler before treatment.

[0094] The organic-inorganic composite filler used in the present invention is obtained by adding a monomer to the inorganic filler described above in advance, forming a paste, polymerizing the mixture, and pulverizing it. Examples of the organic-inorganic composite filler that can be used include TMPT filler (trimethylolpropane methacrylate and silica filler mixed, polymerized, and then pulverized). The shape of the organic-inorganic composite filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. From the viewpoints of the handleability and mechanical strength of the resulting composition, the average particle size of the organic-inorganic composite filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

[0095] Examples of organic filler materials include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, and acrylonitrile-styrene-butadiene copolymer. These may be used alone or in combination. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected. From the viewpoint of the handleability and mechanical strength of the resulting self-adhesive dental composite resin (X), the average particle size of the organic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

[0096] In this specification, the average particle size of the filler can be determined by laser diffraction scattering or electron microscope observation of the particles. Specifically, laser diffraction scattering is convenient for measuring the particle size of particles 0.1 μm or larger, while electron microscope observation is convenient for measuring the particle size of ultrafine particles less than 0.1 μm. 0.1 μm is the value measured by laser diffraction scattering. In this specification, the average particle size of the filler refers to the average particle size of the primary particles of the filler (average primary particle size).

[0097] Specifically, the laser diffraction scattering method can be performed by, for example, measuring on a volume basis using a laser diffraction particle size distribution analyzer (SALD-2300, manufactured by Shimadzu Corporation) and a 0.2% aqueous solution of sodium hexametaphosphate as a dispersion medium.

[0098] Specifically, electron microscope observation can be performed by taking a photograph of the particles using an electron microscope (S-4000 model, manufactured by Hitachi, Ltd.) and measuring the particle diameters of the particles (200 or more) observed within a unit field of view of the photograph using image analysis particle size distribution measurement software (Mac-View, manufactured by Mountec Co., Ltd.). In this case, the particle diameter is determined as the arithmetic mean value of the longest and shortest lengths of the particles, and the average primary particle diameter is calculated from the number of particles and their particle diameters.

[0099] The self-adhesive dental composite resin (X) of the present invention preferably uses a mixture or combination of two or more fillers with different materials, particle size distributions, and shapes. By combining two or more fillers, the fillers are densely packed and the number of interaction points between the filler and the monomer or between the fillers themselves increases. In addition, depending on the type of filler, the shearing From the viewpoint of the handling property and paste properties of the self-adhesive dental composite resin (X) of the present invention, the filler (d) is preferably a combination (I) of a filler (d-1) having an average particle size of 1 nm or more and less than 0.1 μm and a filler (d-2) having an average particle size of 0.1 μm or more and 1 μm or less, or a combination (I) of a filler (d-3) having an average particle size of 1 nm or more and less than 0.1 μm. A combination (II) of a filler (d-1) having a diameter of 1 nm or more and less than 0.1 μm and a filler (d-3) having an average particle diameter of more than 1 μm and 10 μm or less, a combination (d-1) of a filler having an average particle diameter of 1 nm or more and less than 0.1 μm and a filler (d-2) having an average particle diameter of 0.1 μm or more and 1 μm or less, and a combination (d-3) of a filler having an average particle diameter of more than 1 μm and 10 μm or less, and a combination (III) of a filler having an average particle diameter of more than 1 μm and 10 μm or less, A combination (IV) of fillers (d-2) having a particle diameter of 0.1 μm or more and 1 μm or less is preferred. Among these combinations, (I), (II), and (III) are more preferred, and (I) and (II) are even more preferred, from the viewpoint of the paste properties of the self-adhesive dental composite resin (X). It is preferable. The combination (IV) of fillers (d-2) having an average particle size of 0.1 μm or more and 1 μm or less means an embodiment including two fillers (d-2) having different average particle sizes of 0.1 μm or more and 1 μm or less. Note that, as long as the combination is as described above, different types of fillers may be included in the fillers (d) having each particle size. Furthermore, particles other than fillers may be unintentionally included as impurities within a range that does not impair the effects of the present invention.

[0100] The content of the filler (d) is not particularly limited, but from the viewpoint of the mechanical strength of the cured product and adhesion to tooth structure, it is preferably 50 parts by mass or more, more preferably 50 to 90 parts by mass, even more preferably 55 to 85 parts by mass, and particularly preferably 60 to 80 parts by mass, per 100 parts by mass of the total amount of the self-adhesive dental composite resin (X).

[0101] The method for producing the self-adhesive dental composite resin (X) of the present invention is not particularly limited, as long as it contains a monomer (a) having an acidic group, a monomer (b) not having an acidic group, a photopolymerization initiator (c), and, if necessary, a filler (d), and the self-adhesive dental composite resin (X) can be easily produced by a method known to those skilled in the art.

[0102] <Chemical polymerization accelerator (e)> The self-adhesive dental composite resin (X) of the present invention can use a chemical polymerization accelerator (e) together with the water-insoluble photopolymerization initiator (c-2) and / or the chemical polymerization initiator described below. Examples of the chemical polymerization accelerator (e) used in the self-adhesive dental composite resin (X) include amines, sulfinic acid and its salts, benzotriazole compounds, benzimidazole compounds, sulfur-containing reducing inorganic compounds, thiourea compounds, aldehydes, thiol compounds, borate compounds, barbituric acid compounds, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, fourth period transition metal compounds (excluding copper compounds), and transition metal compounds other than fourth period transition metal compounds. Preferred are amines, sulfinic acid and its salts, sulfur-containing reducing inorganic compounds, thiourea compounds, aldehydes, thiol compounds, borate compounds, barbituric acid compounds, triazine compounds, copper compounds, tin compounds, vanadium compounds, and halogen compounds. The chemical polymerization accelerator (e) may be used alone or in combination of two or more.

[0103] Amines used as the chemical polymerization accelerator (e) are divided into aliphatic amines and aromatic amines. Examples of aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine, and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine, and N-methylethanolamine; N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine di ... and tertiary aliphatic amines such as diethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine, etc. Among these, from the viewpoint of the curing property and storage stability of the self-adhesive dental composite resin (X), tertiary aliphatic amines are preferred, and among them, N-methyldiethanolamine and triethanolamine are more preferably used.

[0104] Examples of aromatic amines include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-diisopropylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, and 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, 4-(N,N-dimethylamino)ethyl benzoate, 4-(N,N-dimethylamino)methyl benzoate, 4-(N,N-dimethylamino)propyl benzoate, 4-(N,N-dimethylamino)n-butoxyethyl benzoate, 4-(N,N-dimethylamino)2-(methacryloyloxy)ethyl benzoate, 4-(N,N-dimethylamino)benzophenone, 4-(N,N-dimethylamino)butyl benzoate, and the like. Among these, at least one selected from the group consisting of N,N-bis(2-hydroxyethyl)-p-toluidine, ethyl 4-(N,N-dimethylamino)benzoate, n-butoxyethyl 4-(N,N-dimethylamino)benzoate, and 4-(N,N-dimethylamino)benzophenone is preferably used, from the viewpoint of being able to impart excellent curing properties to the self-adhesive dental composite resin (X).

[0105] Examples of sulfinic acids and salts thereof include lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, calcium salts, strontium salts, iron salts, zinc salts, ammonium salts, tetramethylammonium salts, and tetraethylammonium salts of aromatic sulfinic acids such as benzenesulfinic acid, p-toluenesulfinic acid, o-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, 2,4,6-triisopropylbenzenesulfinic acid (the sodium salt may be abbreviated as "TPBSS" hereinafter), chlorobenzenesulfinic acid, and naphthalenesulfinic acid. Among these, in terms of the curability and storage stability of the composition, the lithium salts, sodium salts, potassium salts, magnesium salts, and calcium salts of p-toluenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, and 2,4,6-triisopropylbenzenesulfinic acid are preferred, and the lithium salts, sodium salts, potassium salts, magnesium salts, and calcium salts of p-toluenesulfinic acid and 2,4,6-triisopropylbenzenesulfinic acid are more preferred.

[0106] The benzotriazole compound and / or benzimidazole compound may be a compound represented by the following general formula (4) or a compound represented by the following general formula (5), respectively.

[0107] [ka]

[0108] [ka]

[0109] In the above general formulas (4) and (5), A1 to A8 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an alkenyl group, an aralkyl group, or a halogen atom.

[0110] The alkyl groups represented by A1 to A8 may be linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, cycloheptanyl, n-octyl, 2-ethylhexyl, cyclooctyl, n-nonyl, cyclononyl, and n-decyl. Of these, methyl and ethyl groups are particularly preferred.

[0111] The aryl group represented by A1 to A8 preferably has 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

[0112] The alkoxy groups represented by A1 to A8 may be linear, branched, or cyclic, and preferably have a carbon number of 1 to 8. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an n-hexyloxy group, a cyclohexyloxy group, an n-octyloxy group, and a 2-ethylhexyloxy group.

[0113] The alkenyl groups represented by A1 to A8 may be linear, branched, or cyclic, and preferably have a carbon number of 1 to 6. Specific examples include a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.

[0114] Examples of the aralkyl group represented by A1 to A8 include an alkyl group (particularly, an alkyl group having 1 to 10 carbon atoms) substituted with an aryl group (particularly, an aryl group having 6 to 10 carbon atoms), and specific examples include a benzyl group.

[0115] Examples of halogen atoms represented by A1 to A8 include chlorine atoms, bromine atoms, and iodine atoms. Examples include:

[0116] A1 to A8 are preferably a hydrogen atom or a methyl group.

[0117] The benzotriazole compound and the benzimidazole compound may be used alone or in combination of two or more. Specific examples of the benzotriazole compound and the benzimidazole compound include 1H-benzotriazole (hereinafter sometimes abbreviated as "BTA"), 5-methyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazole, benzimidazole, 5-methylbenzimidazole, and 5,6-dimethylbenzimidazole. Among these, 1H-benzotriazole and 5-methyl-1H-benzotriazole are preferred in terms of the color tone and storage stability of the composition.

[0118] Examples of reducing inorganic compounds containing sulfur include sulfites, bisulfites (hydrogen sulfites), pyrosulfites, thiosulfates, thionates, and dithionites. Among these, sulfites and bisulfites are preferred, and specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, and potassium hydrogen sulfite. One type of reducing inorganic compound containing sulfur may be used alone, or two or more types may be used in combination.

[0119] Examples of the thiourea compound include 1-(2-pyridyl)-2-thiourea, thiourea, methylthiourea, ethylthiourea, ethylenethiourea, 4,4-dimethylethylenethiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-N-propylthiourea, dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, dicyclohexylthiourea, tetracyclohexylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea, and pyridylthiourea. Of these, 4,4-dimethylethylenethiourea, pyridylthiourea, and N-benzoylthiourea are preferred.

[0120] Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, and pn-octyloxybenzaldehyde. Among these, pn-octyloxybenzaldehyde is preferred from the viewpoint of adhesion to tooth structure.

[0121] Examples of the thiol compound include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, decanethiol, and thiobenzoic acid.

[0122] Specific examples of borate compounds, barbituric acid compounds, triazine compounds, copper compounds, tin compounds, vanadium compounds, and halogen compounds include those described in WO 2008 / 087977.

[0123] The borate compound is preferably an aryl borate compound, such as a borate compound having 1 to 4 aryl groups in one molecule.

[0124] Examples of borate compounds having one aryl group in one molecule include trialkyl borate compounds. Phenylboron, trialkyl(p-chlorophenyl)boron, trialkyl(p-fluorophenyl)boron, trialkyl[3,5-bis(trifluoromethyl)phenyl]boron, trialkyl[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, trialkyl(p-nitrophenyl)boron, trialkyl(m-nitrophenyl)boron, trialkyl(p-butylphenyl)boron, trialkyl(m-butylphenyl)boron, trialkyl(p-butyloxyphenyl)boron, trialkyl(m- Examples thereof include alkyl(p-butyloxyphenyl)boron, trialkyl(p-octyloxyphenyl)boron, trialkyl(m-octyloxyphenyl)boron (the alkyl group in each of the above examples is an n-butyl group, an n-octyl group, an n-dodecyl group, or the like), and salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, and the like).

[0125] Examples of borate compounds having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron, dialkyldi[3,5-bis(trifluoromethyl)phenyl]boron, dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, dialkyldi(p-nitrophenyl)boron, dialkyldi(m-nitrophenyl)boron, dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron, and dialkyldi(p-butyloxophenyl). dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p-octyloxyphenyl)boron, dialkyldi(m-octyloxyphenyl)boron (the alkyl group in each of the above examples is an n-butyl group, an n-octyl group, an n-dodecyl group, or the like), and salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, or the like).

[0126] Examples of borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron, monoalkyltri(p-fluorophenyl)boron, monoalkyltri[3,5-bis(trifluoromethyl)phenyl]boron, monoalkyltri[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, monoalkyltri(p-nitrophenyl)boron, monoalkyltri(m-nitrophenyl)boron, monoalkyltri(p-butylphenyl)boron, monoalkyltri(m-butylphenyl)boron, monoalkyltri( Examples of the alkyl group include monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(p-octyloxyphenyl)boron, monoalkyltri(m-octyloxyphenyl)boron (the alkyl group in each of the above examples is an n-butyl group, an n-octyl group, an n-dodecyl group, etc.), and salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc.).

[0127] Examples of borate compounds having four aryl groups in one molecule include tetraphenylboron, tetrakis(p-chlorophenyl)boron, tetrakis(p-fluorophenyl)boron, tetrakis[3,5-bis(trifluoromethyl)phenyl]boron, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, tetrakis(p-nitrophenyl)boron, tetrakis( (m-nitrophenyl)boron, tetrakis(p-butylphenyl)boron, tetrakis(m-butylphenyl)boron, tetrakis(p-butyloxyphenyl)boron, tetrakis(m-butyloxyphenyl)boron, tetrakis(p-octyloxyphenyl)boron, tetrakis(m-octyloxyphenyl)boron, (p-fluorophenyl)triphenylboron, [3,5-bis(trifluoromethyl)phenyl]triphenylboron, (p-nitrophenyl)triphenylboron, (m-butyloxyphenyl) (m-octyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron, (p-octyloxyphenyl)triphenylboron, and salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc.).

[0128] Among the aryl borate compounds, borate compounds having three or four aryl groups in one molecule are preferred from the viewpoint of storage stability. The aryl borate compounds may be used alone or in combination of two or more.

[0129] Examples of the barbituric acid compounds include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-5-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclo Examples thereof include hexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, thiobarbituric acids, and salts thereof. Salts of these barbituric acid compounds include, for example, alkali metal salts and alkaline earth metal salts (including magnesium salts), and more specific examples include sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate.

[0130] Particularly preferred barbituric acid compounds are 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and sodium salts thereof.

[0131] Examples of the triazine compound include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl) -s-triazine, 2-[2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(1-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis(2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, and 2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine.

[0132] Among these triazine compounds, 2,4,6-tris(trichloromethyl)-s-triazine is preferred in terms of polymerization activity, and 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine are preferred in terms of storage stability. The triazine compounds may be used alone or in combination of two or more.

[0133] The copper compound is preferably, for example, a compound soluble in the radical polymerizable monomer. Monovalent or divalent copper compounds are used as the copper compound, with divalent copper compounds being more preferred. Examples of monovalent copper compounds include copper(I) acetate, copper(I) isobutyrate, copper(I) citrate, copper(I) phthalate, copper(I) octoate, copper(I) octenoate, copper(I) naphthenate, and copper(I) methacrylate. Examples of divalent copper compounds include copper(II) carboxylate, copper(II) β-diketone, copper(II) β-ketoester, copper(II) 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) octenoate, copper(II) naphthenate, copper(II) methacrylate, and copper(II) 4-cyclohexylbutyrate. Examples of β-diketone copper(II) include acetylacetonate copper(II), trifluoroacetylacetonate copper(II), hexafluoroacetylacetonate copper(II), 2,2,6,6-tetramethyl-3,5-heptanedionato copper(II), and benzoylacetone copper(II). Examples of β-ketoester copper(II) include ethyl acetoacetate copper(II). 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 dithiocarbamates include copper(II) dimethyldithiocarbamate. Examples of copper salts with inorganic acids include copper(II) nitrate, copper(II) bromide, and copper(II) chloride. Copper compounds can be used singly or in combination of two or more. Among these, copper(II) carboxylate, β-diketone copper(II), and β-ketoester copper(II) are more preferred, with copper(II) acetate and copper(II) acetylacetonate being particularly preferred, from the viewpoints of solubility and reactivity with radically polymerizable monomers.

[0134] Examples of the tin compound include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, di-n-butyltin dilaurate, etc. Among these, di-n-octyltin dilaurate and di-n-butyltin dilaurate are preferred.

[0135] As the vanadium compound, a trivalent, tetravalent or pentavalent vanadium compound is used, and a tetravalent or pentavalent vanadium compound is preferred. Specific examples of the vanadium compound include vanadium (IV) acetylacetonate, vanadium (V) acetylacetonate, ... Vanadium(IV) oxyacetylacetonate, vanadyl(IV) stearate, vanadium(III) naphthenate, vanadium(III) benzoylacetonate, vanadyl(IV) benzoylacetonate, oxovanadium(IV) oxalate, bis(maltolate)oxovanadium(IV), oxobis(1-phenyl-1,3-butanedionato)vanadium(IV), vanadium(V) oxytriisopropoxide, ammonium(V) metavanadate, sodium(V) metavanadate, vanadium(V) pentoxide, divanadium(IV) tetroxide, and vanadyl(IV) sulfate. Among these, from the viewpoint of solubility in the solvent (C), vanadium(IV) acetylacetonate, vanadium(V) acetylacetonate, vanadyl acetylacetonate, and bis(maltolato)oxovanadium(IV) are preferred, with vanadyl acetylacetonate and bis(maltolato)oxovanadium(IV) being more preferred.

[0136] Examples of the halogen compounds include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, and dilauryldimethylammonium bromide.

[0137] Examples of the fourth period transition metal compounds include scandium isopropoxide, iron (III) ethoxide, titanium methoxide, titanium ethoxide, and titanium isopropoxide. Examples of suitable titanium compounds include titanium oxide, titanium butoxide, and titanium hydroxide.

[0138] Examples of transition metal compounds other than the fourth period transition metal compounds include strontium carbonate, strontium hydroxide, strontium ethoxide, tin(II) methoxide, indium ethoxide, yttrium isopropoxide, lanthanum methoxide, lanthanum ethoxide, lanthanum isopropoxide, lanthanum butoxide, lanthanum hydroxide, lanthanum carbonate, lanthanum fluoride, cerium isopropoxide, praseodymium isopropoxide, promethium isopropoxide, neodymium isopropoxide, and samarium isopropoxide. tungsten(IV) methoxide, tungsten(IV) butoxide, tungsten(IV) methoxide, tungsten(IV) butoxide, and the like.

[0139] The content of the chemical polymerization accelerator (e) used in the present invention is not particularly limited, but from the viewpoint of the curing property of the obtained dental filling kit, it is preferably 0.001 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total amount of the monomers in the self-adhesive dental composite resin (X). When the content of the chemical polymerization accelerator (e) is equal to or greater than the lower limit, polymerization proceeds sufficiently and sufficient adhesiveness is easily obtained, and the content is more preferably 0.05 parts by mass or more. On the other hand, when the content of the chemical polymerization accelerator (e) is equal to or less than the upper limit, sufficient adhesiveness is easily obtained and precipitation of the chemical polymerization accelerator (e) itself from the self-adhesive dental composite resin (X) can be suppressed, and therefore the content is more preferably 20 parts by mass or less.

[0140] <Fluoride ion-releasing substances> The self-adhesive dental composite resin (X) of the present invention may further contain a fluoride ion-releasing substance. By containing a fluoride ion-releasing substance, a self-adhesive dental composite resin (X) can be obtained that can impart acid resistance to tooth structure. Examples of the fluoride ion-releasing substance include fluoride ion-releasing polymers such as copolymers of methyl methacrylate and methacrylic acid fluoride; metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride; and fluoroaluminosilicate glass. One type of fluoride ion-releasing substance may be contained alone, or two or more types may be contained in combination.

[0141] The self-adhesive dental composite resin (X) of the present invention may contain known additives within the range that does not impair performance. Examples of such additives include polymerization inhibitors, antioxidants, colorants (pigments, dyes), UV absorbers, solvents such as organic solvents, and thickeners. One type of additive may be used alone, or two or more types may be used in combination. In some embodiments, the content of solvents (e.g., water, organic solvents) in the self-adhesive dental composite resin (X) 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 self-adhesive dental composite resin (X).

[0142] Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t-butylphenol, 3,5-di-t-butyl-4-hydroxytoluene, etc. The content of the polymerization inhibitor is preferably 0.001 to 1.0 part by mass per 100 parts by mass of the total amount of the monomers of the self-adhesive dental composite resin (X).

[0143] The following shows an example of the composition ratio of a self-adhesive dental composite resin (X): When the total amount of monomers in the self-adhesive dental composite resin (X) is taken as 100 parts by mass, it preferably contains 1 to 40 parts by mass of a monomer (a) having an acidic group and 60 to 99 parts by mass of a monomer (b) not having an acidic group, and 0.05 to 10 parts by mass of a photopolymerization initiator (c), 100 to 900 parts by mass of a filler (d), and 0.001 to 30 parts by mass of a chemical polymerization accelerator (e), and when the total amount of monomers is 100 parts by mass, it preferably contains 2.5 to 35 parts by mass of the monomer (a) having an acidic group and 65 to 97.5 parts by mass of the monomer (b) not having an acidic group. It is more preferable that the total amount of monomers is 100 parts by mass, and ... In addition, in the self-adhesive dental composite resin (X), the total amount of the monomers is preferably 10 to 50 mass%, more preferably 15 to 45 mass%, and even more preferably 20 to 40 mass%. The content of the filler (d) in the self-adhesive dental composite resin (X) is preferably 50 to 90 mass%, more preferably 55 to 85 mass%, and even more preferably 60 to 80 mass%. More preferable.

[0144] From the viewpoint of ease of use, the self-adhesive dental composite resin (X) of the present invention is preferably a one-component type (one-paste type) in which all components are premixed. When a two-component self-adhesive dental composite resin is used, the two components must be mixed immediately before use, which may result in the introduction of air bubbles and affect the properties of the cured self-adhesive dental composite resin. Therefore, in the present invention, the self-adhesive dental composite resin (X) is a one-component type, which eliminates the need to mix the two components and allows it to be used as is, resulting in excellent operability, no risk of air bubbles being introduced, and reduced waste of the composition paste. The one-component self-adhesive dental composite resin (X) of the present invention is more preferably used by filling it into a cylindrical syringe container. The size of the cylindrical portion of the syringe container is preferably 10 cm in length and 15 mm or less in inner diameter, more preferably 7.5 cm in length and 10 mm or less in inner diameter. Alternatively, to improve handling, a nozzle can be attached to the tip of the syringe. The nozzle size is preferably 25 mm in length and 1.5 mm or less in inner diameter at the opening, more preferably 20 mm in length and 0.75 mm or less in inner diameter at the opening.

[0145] [Two-component dental bonding material (Y)] The two-component dental bonding material (Y) of the present invention comprises a first part and a second part, the first part containing a monomer (f) having an acidic group. At least one of the first part and the second part contains a chemical polymerization accelerator (h). Furthermore, at least one of the first part and the second part contains water (i).

[0146] Dental bonding materials (Y) may undergo a redox reaction between a chemical polymerization initiator and a reducing agent (chemical polymerization accelerator (h)), or the chemical polymerization accelerator (h) may cure under acidic conditions. For example, when the chemical polymerization accelerator (h) is an arylborate compound, the arylborate compound first decomposes under the action of an acidic compound to form an arylborane compound, which is then oxidized by oxygen present in the atmosphere to generate radicals, a polymerization-active species. Furthermore, if peroxide is added to this radical generation mechanism, the arylborane compound is also actively oxidized by the peroxide, which is presumably further activating the radical generation. From the perspective of adhesion to tooth structure, a redox reaction between a chemical polymerization initiator and a reducing agent (chemical polymerization accelerator (h)) is preferred.

[0147] Since the dental bonding material (Y) contains water (i), it is preferable to volatilize the water (i) with an air blower after use.

[0148] <Monomer> The monomer used in the two-component dental bonding material (Y) of the present invention is preferably a radically polymerizable monomer. Specific examples of radically polymerizable monomers include (meth)acrylate-based polymerizable monomers, (meth)acrylamide-based polymerizable monomers, esters of α-cyanoacrylic acid, (meth)acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, itaconic acid, etc., vinyl esters, vinyl ethers, mono-N-vinyl derivatives, and styrene derivatives. Among these, (meth)acrylate-based polymerizable monomers and (meth)acrylamide-based polymerizable monomers are preferred from the viewpoint of curability. Furthermore, from the viewpoints of adhesion to tooth structure, cavity sealing ability, and the durability thereof, the monomer in the two-component dental bonding material (Y) of the present invention must contain a monomer (f) having an acidic group. Preferably, the two-component dental bonding material (Y) further contains a monomer (g) not having an acidic group.

[0149] <Monomer (f) having an acidic group> Monomers (f) with acidic groups mainly have adhesive properties to tooth structures (dentin, enamel). The monomer (f) having an acidic group used in the present invention can be, for example, the same as the monomer (a) having an acidic group, and can also include a monomer having an acidic group represented by the following general formula (6) and a monomer having an acidic group represented by the following general formula (7), which will be described later. The monomer (f) having an acidic group can be used alone or in combination of two or more. Among the monomers (f) having an acidic group, from the viewpoint of achieving good adhesion to tooth structure, cavity sealing ability, and durability thereof when used as a two-component dental bonding material (Y), it is preferable to contain a monomer having a phosphate group or a monomer having a carboxylic acid group, and examples thereof 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)acryloyloxyhexyl dihydrogen phosphate, 9-(meth)acryloyloxyheptyl dihydrogen phosphate, 10-(meth)acryloyloxyhexyl dihydrogen phosphate, 11-(meth)acryloyloxyhexyl dihydrogen phosphate, 12-(meth)acryloyloxyhexyl dihydrogen phosphate, 13-(meth)acryloyloxyhexyl dihydrogen phosphate, 14-(meth)acryloyloxyheptyl dihydrogen phosphate, 15-(meth)acryloyloxyhexyl dihydrogen phosphate, 16-(meth)acryloyloxyhexyl dihydrogen phosphate, 17-(meth)acryloyloxyheptyl dihydrogen phosphate, 18-(meth)acryloyloxyhexyl dihydrogen phosphate, 19-(meth)acryloyloxyhexyl dihydrogen phosphate, 20-(meth)acryloyloxyhexyl dihydrogen phosphate, 21-(meth)acryloyloxyhexyl dihydrogen phosphate, 22-(meth)acryloyloxyhexyl dihydrogen phosphate, 23-(meth)acryloyloxyhexyl dihydrogen phosphate, 24-(meth ) Acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate, 4-(meth)acryloyloxyethyl trimellitate anhydride, 4-(meth)acryloyloxyethyl trimellitate, 11-(meth)acryloyloxyundecane-1,1-Dicarboxylic acid and a mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis(2-methacryloyloxyethyl)hydrogen phosphate are more preferred, and 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, and 20-(meth)acryloyloxyicosyl dihydrogen phosphate are even more preferred, with 10-(meth)acryloyloxydecyl dihydrogen phosphate being particularly preferred from the viewpoint of a balance of curability.

[0150] The content of the monomer (f) having an acidic group in the two-component dental bonding material (Y) of the present invention is preferably 1 to 30 parts by mass, more preferably 2.5 to 27.5 parts by mass, and even more preferably 5 to 25 parts by mass, per 100 parts by mass of the total amount of monomers, from the viewpoints of adhesion to tooth structure, cavity sealing ability, and their durability. The "total amount of monomers" in the two-component dental bonding material (Y) means the total amount of monomers contained in the first and second parts.

[0151] Other embodiments of the two-component dental bonding material (Y) of the present invention include those in which the monomer (f) having an acidic group includes a monomer having an acidic group represented by the following general formula (6) and a monomer having an acidic group represented by the following general formula (7).

[0152] The blending ratio of the monomer having an acidic group represented by general formula (7) to the total amount of the monomer having an acidic group represented by general formula (6) and the monomer having an acidic group represented by general formula (7) is preferably 3% by mass to 40% by mass.

[0153] [ka]

[0154] [In general formula (6), R A11 represents a hydrogen atom or a methyl group, W 1 represents an oxycarbonyl group (-COO-), an iminocarbonyl group (-CONH-), or a phenylene group (-C6H4-), and R A21 (i) bond, (ii) divalent to hexavalent hydrocarbons with 1 to 30 carbon atoms or (iii) a divalent to hexavalent organic group having 1 to 30 carbon atoms and containing at least one bond selected from an ether bond and an ester bond, 1 represents a monovalent acidic group. Furthermore, m1 represents an integer of 1 to 4, and n1 represents an integer of 1 to 6-m1, where m1+n1 is R A21 represents the valence of

[0155] [ka] [In general formula (7), R A11 and R A12 each independently represents a hydrogen atom or a methyl group; W 1 and W 2 each independently represents an oxycarbonyl group (-COO-), an iminocarbonyl group (-CONH-), or a phenylene group (-CH-), and R A21 and R A22 each independently represents (i) a bond, (ii) a divalent to hexavalent hydrocarbon group having 1 to 30 carbon atoms, or (iii) a divalent to hexavalent organic group having 1 to 30 carbon atoms and containing at least one bond selected from an ether bond and an ester bond, and X 1 represents a monovalent acidic group, and X 2 represents a divalent acidic group. Furthermore, m1 and m2 each independently represent an integer of 1 to 4, n1 represents an integer of 1 to 6-m1, and n2 represents an integer of 1 to 6-m2. Here, m1+n1 is R A21 represents the valence of R A22 represents the valence of

[0156] Examples of the monovalent acidic group include those exemplified as the acidic group of the monomer (a) having an acidic group. Examples of the divalent acidic group include a dihydrogen phosphate monoester group {-OP(=O)(OH)2} and a dihydrogen phosphate diester group {-OP(=O)(OH)-O-}. In a preferred embodiment, in general formula (7), R A11 and R A12 each independently represents a hydrogen atom or a methyl group; W 1 and W 2 each independently represents an oxycarbonyl group (-COO-) or an iminocarbonyl group (-CONH-), and R A21 and R A22 each independently represents (ii) a divalent hydrocarbon group having 1 to 10 carbon atoms, or (iii) a divalent organic group having 1 to 10 carbon atoms and containing at least one bond selected from an ether bond and an ester bond; X 2 is a dihydrogen phosphate monoester group {-OP(=O )(OH)2} or a hydrogen phosphate diester group {-OP(=O)(OH)-O-} and m1, m2, n1, and n2 are each 1. Examples of compounds of the monomer having an acidic group represented by general formula (6) and the monomer having an acidic group represented by general formula (7) include the compounds disclosed in WO2018 / 034212. Specific examples of the monomer having an acidic group represented by general formula (6) and the monomer having an acidic group represented by general formula (7) include bis(2-methacryloyloxyethyl) acid phosphate.

[0157] Monomers without acidic groups (g) The monomer (g) having no acidic group in the present invention may be a monomer (b ) are listed. Examples of the monomer (g) that does not have an acidic group include an asymmetric acrylamide-methacrylate ester compound (g-1); a hydrophobic monomer (g-2) that does not have an acidic group and has a solubility in water at 25°C of less than 10% by mass (hereinafter simply referred to as "hydrophobic monomer (g-2)"); and a hydrophilic monomer (g-3) that does not have an acidic group and has a solubility in water at 25°C of 10% by mass or more (hereinafter simply referred to as "hydrophilic monomer (g-3)"). The monomer (g) that does not have an acidic group may be used alone or in combination of two or more. In the present invention, compounds that do not have an acidic group and contain an acrylamide group and a methacryloyloxy group are referred to as asymmetric acrylamide-methacrylate compounds (g-1), and compounds that do not have an acidic group and are not included in asymmetric acrylamide-methacrylate compounds (g-2) are classified into hydrophobic monomers (g-2) and hydrophilic monomers (g-3) according to the degree of hydrophilicity.

[0158] Asymmetric acrylamide-methacrylate compound (g-1) Examples of the asymmetric acrylamide-methacrylate ester compound (g-1) include those similar to the asymmetric acrylamide-methacrylate ester compound (b-1). The asymmetric acrylamide-methacrylate ester compound (g-1) is preferably a compound represented by general formula (1), as it improves the adhesive properties of the two-component dental bonding material (Y) to tooth structure. The asymmetric acrylamide-methacrylate ester compound (g-1) may be used alone or in combination with two or more types.

[0159] The content of the asymmetric acrylamide-methacrylate compound (g-1) is not particularly limited as long as the effects of the present invention are achieved, but is preferably 1 to 60 parts by mass, more preferably 2 to 45 parts by mass, even more preferably 3 to 30 parts by mass, and particularly preferably 5 to 25 parts by mass, per 100 parts by mass of the total amount of monomers in the two-component dental bonding material (Y) of the present invention.

[0160] Hydrophobic monomer without acidic group (g-2) The hydrophobic monomer (g-2) without an acidic group improves the handleability of the two-component dental bonding material (Y) and the mechanical strength of the cured product. The hydrophobic monomer (g-2) is preferably a radical monomer without an acidic group and a polymerizable group. From the viewpoint of ease of radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. The hydrophobic monomer (g-2) refers to a monomer that does not have an acidic group, does not correspond to the asymmetric acrylamide-methacrylic acid ester compound (g-1), and has a solubility in water at 25°C of less than 10% by mass. Examples of the hydrophobic monomer (g-2) include those similar to the hydrophobic monomer (b-2) without an acidic group.

[0161] Among the hydrophobic monomers (g-2), Bis-GMA, D-2.6E, 3G, UDMA, and DD are more preferred, and D-2.6E, 3G, and Bis-GMA are even more preferred, from the viewpoint of good adhesion to tooth structure, cavity sealing properties, and durability thereof when used as a two-component dental bonding material (Y) (composition). One type of hydrophobic monomer (g-2) may be blended alone, or two or more types may be blended in combination.

[0162] If the content of the hydrophobic monomer (g-2) is too high, the wettability of the two-component dental bonding material (Y) to the tooth structure may decrease, resulting in decreased adhesiveness, while if the content is too low, the strength of the cured product may be insufficient. Therefore, the content of the hydrophobic monomer (g-2) in the two-component dental bonding material (Y) of the present invention is preferably 20 to 99 parts by mass, more preferably 40 to 95 parts by mass, and even more preferably 60 to 95 parts by mass, per 100 parts by mass of the total amount of the monomers.

[0163] Hydrophilic monomers without acidic groups (g-3) The two-component dental bonding material (Y) of the present invention is a hydrophilic bonding material in which the monomer does not have an acidic group. The hydrophilic monomer (g-3) preferably contains a hydrophilic monomer (g-3). The hydrophilic monomer (g-3) improves the wettability of the two-component dental bonding material (Y) to tooth structure. The hydrophilic monomer (g-3) is preferably a radical monomer having a polymerizable group but no acidic group. From the viewpoint of ease of radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. The hydrophilic monomer (g-3) is a monomer that does not have an acidic group, does not correspond to the asymmetric acrylamide-methacrylate ester compound (g-1), and has a solubility in water at 25°C of 10% by mass or more, preferably 30% by mass or more, and more preferably is soluble in water at any ratio at 25°C. Examples of the hydrophilic monomer (g-3) include those similar to the hydrophilic monomer (b-3) that does not have an acidic group.

[0164] Among these hydrophilic monomers (g-3), from the viewpoints of adhesion to tooth structure, cavity sealing ability, and durability thereof, 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and hydrophilic monofunctional (meth)acrylamide monomers are preferred, and 2-hydroxyethyl (meth)acrylate, N,N-dimethylacrylamide, and N,N-diethylacrylamide are more preferred. One type of hydrophilic monomer (g-3) may be blended alone, or two or more types may be blended in combination.

[0165] If the content of the hydrophilic monomer (g-3) in the two-component dental bonding material (Y) of the present invention is too low, the adhesive strength may not be sufficiently improved, and if it is too high, the mechanical strength of the cured product may decrease. Therefore, the content of the hydrophilic monomer (g-3) in the two-component dental bonding material (Y) of the present invention is preferably in the range of 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, and even more preferably 0 to 30 parts by mass, per 100 parts by mass of the total amount of monomers. The content of the hydrophilic monomer (g-3) may be 0 part by mass per 100 parts by mass of the total amount of monomers.

[0166] The content of the monomer (g) not having an acidic group is preferably 50 to 99 parts by mass, more preferably 60 to 97 parts by mass, and even more preferably 70 to 95 parts by mass, per 100 parts by mass of the total amount of monomers. From the viewpoints of adhesion to tooth structure, cavity sealing ability, and durability thereof, the mass ratio of the hydrophilic monomer to the hydrophobic monomer is preferably 0:10 to 2:1, more preferably 0:10 to 1:1, and even more preferably 0:10 to 1:2.

[0167] One preferred embodiment is a two-component dental bonding material (Y) that is substantially free of di- or higher-functional (meth)acrylamide-based monomers.

[0168] <Water(i)> The two-component dental bonding material (Y) of the present invention contains water (i). Water demineralizes the surface of tooth tissue to improve adhesion to the tooth tissue. When a silane coupling agent is present, water also improves adhesion to prostheses containing inorganic fillers (e.g., CAD / CAM resin blocks, composite resins, ceramic materials such as zirconia, alumina, lithium disilicate glass, and porcelain, as well as dental ceramics) in the presence of the silane coupling agent. Furthermore, in the two-component dental bonding material (Y) of this embodiment, by mixing the first and second components and applying the mixture to the surface of the adherend, interactions between the components described above and the adherend, as well as chemical polymerization caused by interactions between the components described above, are promoted, resulting in adhesion. The water used must be substantially free of impurities that adversely affect adhesion; distilled water or ion-exchanged water is preferred. If the water content is too low, the demineralization-promoting effect may be insufficient, while if the water content is too high, adhesion may be reduced. Furthermore, the storage stability of the silane coupling agent may decrease, and in particular the adhesive strength of silica-based oxides may decrease. Therefore, the content of water (i) is preferably in the range of 1 to 50 mass %, more preferably in the range of 2 to 50 mass %, and even more preferably in the range of 3 to 20 mass %, based on the total mass of the dental bonding material (Y). "Amount" means the total mass of the first agent and the second agent.

[0169] <Chemical polymerization accelerator (h)> The two-component dental bonding material (Y) of the present invention contains a chemical polymerization accelerator (h) from the viewpoints of adhesion to tooth structure, cavity sealing ability, and the durability thereof. Known chemical polymerization accelerators can be used as the chemical polymerization accelerator (h). Examples of the chemical polymerization accelerator (h) include those similar to the chemical polymerization accelerator (e). The chemical polymerization accelerator (h) may be used alone or in combination of two or more.

[0170] In one preferred embodiment, the chemical polymerization accelerator (h) includes at least one selected from the group consisting of amines, borate compounds, sulfinic acids and their salts, thiourea compounds, copper compounds, thiol compounds, and vanadium compounds. In another preferred embodiment, the chemical polymerization accelerator (h) includes a borate compound.

[0171] The content of the chemical polymerization accelerator (h) in the two-component dental bonding material (Y) of the present invention is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, per 100 parts by mass of the total amount of monomers, from the viewpoint of the adhesiveness of the resulting two-component dental bonding material (Y) to tooth structure, etc. Furthermore, the content of the chemical polymerization accelerator (h) is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 5 parts by mass or less, per 100 parts by mass of the total amount of polymerizable monomer components, from the viewpoint of the adhesiveness of the resulting two-component dental bonding material (Y) to tooth structure, etc.

[0172] Organic solvents In the two-component dental bonding material (Y), at least one of the first and second parts may further contain an organic solvent. When the dental bonding material (Y) of the present invention contains an organic solvent, adhesion, application properties, and penetration into tooth tissue can be further improved, and separation of the components of the composition (bonding material) can be more effectively prevented. As the organic solvent, an organic solvent is usually used that has a boiling point of 150°C or less under normal pressure and a solubility in water at 25°C of 5% by mass or more, more preferably 30% by mass or more, and even more preferably is soluble in water in any proportion.

[0173] Examples of organic solvents include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-methyl-2-propanol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, diethyl ether, and diisopropyl ether; hydrocarbons such as hexane, toluene, and chloroform; and esters such as ethyl acetate and butyl acetate. Among these, taking into consideration both safety to living organisms and ease of removal based on volatility, it is preferable that the organic solvent is a water-soluble organic solvent. Specifically, ethanol, 2-propanol, 2-methyl-2-propanol, acetone, and tetrahydrofuran are preferred, and ethanol, 2-propanol, acetone, 2-methyl-2-propanol, and tetrahydrofuran are more preferred. The content of the organic solvent is not particularly limited, and in some embodiments, the incorporation of the organic solvent is not necessary. In the embodiment in which the organic solvent is used, the content of the organic solvent is preferably in the range of 1 to 85 mass %, more preferably in the range of 10 to 80 mass %, and even more preferably in the range of 15 to 75 mass %, based on the total mass of the dental bonding material (Y).

[0174] [Chemical polymerization initiator (j)] Since the two-component dental bonding material (Y) of the present invention can be cured by the dental bonding material (Y) alone, it is preferable that at least one of the first and second parts further contains a chemical polymerization initiator (j) in some embodiments. As the chemical polymerization initiator (j), an organic peroxide Examples of the chemical polymerization initiator (j) include inorganic peroxides. One type of the chemical polymerization initiator (j) may be used alone, or two or more types may be used in combination. The chemical polymerization initiator (j) may be contained in either the first agent or the second agent.

[0175] In one embodiment, a two-component dental bonding material (Y) is used in which the first component contains a chemical polymerization initiator (j). In another embodiment, a two-component dental bonding material (Y) is used in which the second component contains a chemical polymerization initiator (j).

[0176] The chemical polymerization initiator (j) may be an oxidizing agent for a redox polymerization initiator, which will be explained below.

[0177] As described above, in a preferred embodiment, the two-component dental bonding material (Y) contains a redox polymerization initiator that undergoes a redox reaction between a chemical polymerization initiator (j) and a chemical polymerization accelerator (h) as a reducing agent. Examples of the chemical polymerization initiator (j) used as an oxidizing agent for the redox polymerization initiator include organic peroxides.

[0178] When the two-component dental bonding material (Y) contains a redox polymerization initiator, the oxidizing agent and reducing agent are packaged separately and must be mixed immediately before use. Examples of the chemical polymerization initiator (j) used as the oxidizing agent for the redox polymerization initiator include organic peroxides. One type of organic peroxide may be used alone, or two or more types may be used in combination.

[0179] In the two-component dental bonding material (Y) containing the redox polymerization initiator, examples of the redox polymerization initiator include a combination of an organic peroxide as an oxidizing agent (chemical polymerization initiator (j)) and an amine compound as a reducing agent (chemical polymerization accelerator (h)); a combination of an organic peroxide as an oxidizing agent, an amine compound as a reducing agent, and a sulfinate salt; or a combination of an organic peroxide as an oxidizing agent, and an amine compound as a reducing agent and a borate compound.

[0180] The organic peroxide used as the oxidizing agent for the redox polymerization initiator can be any known compound. Examples of organic peroxides include those similar to the chemical polymerization initiators used in the self-adhesive dental composite resin (X). Examples of organic peroxides include ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxydicarbonates. Specific examples of these organic peroxides include those described in International Publication No. 2008 / 087977.

[0181] Examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide.

[0182] Examples of hydroperoxides include p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide.

[0183] Examples of diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, and benzoyl peroxide. It can be obtained.

[0184] Examples of dialkyl peroxides include α,α-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3.

[0185] Peroxyketals include 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclododecane, 2,2-bis(t-butylperoxy)butane, n-butyl-4,4-bis(t-butylperoxy)valerate, and 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane.

[0186] Peroxyesters include α,α-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, and t-butyl peroxy-2-ethylhexanoate. t-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, and the like.

[0187] Examples of peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, di(2-methoxybutyl)peroxydicarbonate, and di(3-methyl-3-methoxybutyl)peroxydicarbonate.

[0188] In addition to these, t-butyltrimethylsilyl peroxide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, etc. can also be suitably used. These organic peroxides may be used alone or in combination of two or more, but from the viewpoint of polymerization activity, hydroperoxides are particularly preferred.

[0189] Examples of inorganic peroxides include peroxodisulfates and peroxodiphosphates, and among these, peroxodisulfates are preferred in terms of curability. Specific examples of peroxodisulfates include sodium peroxodisulfate, potassium peroxodisulfate, aluminum peroxodisulfate, and ammonium peroxodisulfate.

[0190] From the viewpoint of curability, the content of the chemical polymerization initiator (j) is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 8 parts by mass, and even more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the total amount of monomers in the two-component dental bonding material (Y).

[0191] <Photopolymerization initiator (k)> At least one of the first and second parts of the two-component dental bonding material (Y) may further contain a photopolymerization initiator (k).

[0192] The photopolymerization initiator (k) is classified into a water-soluble photopolymerization initiator (k-1) and a water-insoluble photopolymerization initiator (k-2). As the photopolymerization initiator (k), only the water-soluble photopolymerization initiator (k-1) may be used, only the water-insoluble photopolymerization initiator (k-2) may be used, or the water-soluble photopolymerization initiator (k-1) and the water-insoluble photopolymerization initiator (k-2) may be used in combination, but it is preferable to use them in combination.

[0193] Water-soluble photopolymerization initiator (k-1) The water-soluble photopolymerization initiator (k-1) improves polymerization curing at the hydrophilic tooth surface interface, enabling high adhesion to tooth structure. The water-soluble photopolymerization initiator (k-1) has a solubility in water at 25°C of 10 g / L or more, preferably 15 g / L or more, more preferably 20 g / L or more, and even more preferably 25 g / L or more. A solubility of 10 g / L or more allows the water-soluble photopolymerization initiator (k-1) to dissolve sufficiently in the water in the tooth structure at the adhesive interface, making it easier to achieve a polymerization-promoting effect.

[0194] Examples of the water-soluble photopolymerization initiator (k-1) include the same as the water-soluble photopolymerization initiator (c-1). One type of water-soluble photopolymerization initiator (k-1) may be used alone, or two or more types may be used in combination.

[0195] The water-soluble photopolymerization initiator (k-1) may be dissolved in the two-component dental bonding material (Y) or dispersed in the composition in the form of a powder.

[0196] When the water-soluble photopolymerization initiator (k-1) is dispersed as a powder, if its average particle size is too large, it tends to settle, so it is preferably 500 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less. On the other hand, if the average particle size is too small, the specific surface area of ​​the powder becomes too large, reducing the amount dispersible in the composition, so it is preferably 0.01 μm or more. That is, the average particle size of the water-soluble photopolymerization initiator (k-1) is preferably in the range of 0.01 to 500 μm, more preferably 0.01 to 100 μm, and even more preferably 0.01 to 50 μm.

[0197] The average particle size of each water-soluble photopolymerization initiator (k-1) powder can be calculated in the same manner as for the water-soluble photopolymerization initiator (c-1) powder.

[0198] When the water-soluble photopolymerization initiator (k-1) is dispersed in the two-component dental bonding material (Y) as a powder, the shape of the initiator is not particularly limited, and various shapes such as spherical, needle-like, plate-like, crushed, etc. can be mentioned. The water-soluble photopolymerization initiator (k-1) can be prepared by a conventionally known method such as a pulverization method, a freeze-drying method, or a reprecipitation method. From the viewpoint of the average particle size of the obtained powder, the freeze-drying method and the reprecipitation method are preferred, and the freeze-drying method is more preferred.

[0199] The content of the water-soluble photopolymerization initiator (k-1) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total amount of the monomers in the two-component dental bonding material (Y) of the present invention from the viewpoint of the curing property of the obtained two-component dental bonding material (Y), and the ... From this viewpoint, the content is more preferably 0.05 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass. If the content of the water-soluble photopolymerization initiator (k-1) is less than 0.01 part by mass, polymerization at the adhesive interface may not proceed sufficiently, which may result in a decrease in adhesiveness. On the other hand, if the content of the water-soluble photopolymerization initiator (k-1) exceeds 20 parts by mass, sufficient adhesiveness may not be obtained, and furthermore, dissolution, dispersion, and diffusion in the two-component dental bonding material (Y) may be insufficient.

[0200] Non-water-soluble photopolymerization initiator (k-2) From the viewpoint of curing property, the two-component dental bonding material (Y) of the present invention preferably contains, in addition to the water-soluble photopolymerization initiator (k-1), a water-insoluble photopolymerization initiator (k-2) having a solubility in water at 25°C of less than 10 g / L (hereinafter, sometimes referred to as the water-insoluble photopolymerization initiator (k-2)). The water-insoluble photopolymerization initiator (k-2) used in the present invention can be a known photopolymerization initiator. The water-insoluble photopolymerization initiator (k-2) may be blended singly or in combination of two or more.

[0201] Examples of the water-insoluble photopolymerization initiator (k-2) include the same as the water-insoluble photopolymerization initiator (c-2).

[0202] Among the water-insoluble photopolymerization initiators (k-2), it is preferable to use at least one selected from the group consisting of (bis)acylphosphine oxides, α-diketones, and coumarins. This allows for the production of a two-component dental bonding material (Y) that has excellent photocurability in the visible and near-ultraviolet regions and exhibits sufficient photocurability whether using a halogen lamp, a light-emitting diode (LED), or a xenon lamp.

[0203] The content of the water-insoluble photopolymerization initiator (k-2) is not particularly limited, but from the viewpoint of the curability of the resulting composition, it is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, and even more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total amount of monomers in the two-component dental bonding material (Y) of the present invention. Note that if the content of the water-insoluble photopolymerization initiator (k-2) exceeds 10 parts by mass, sufficient adhesive strength may not be obtained if the polymerization performance of the polymerization initiator itself is low, and further, precipitation from the two-component dental bonding material (Y) may occur.

[0204] When a water-soluble photopolymerization initiator (k-1) and a water-insoluble photopolymerization initiator (k-2) are used in combination, the mass ratio of the water-soluble photopolymerization initiator (k-1) to the water-insoluble photopolymerization initiator (k-2) [(k-1):(k-2)] in the present invention is preferably 10:1 to 1:10, more preferably 7:1 to 1:7, even more preferably 5:1 to 1:5, and most preferably 3:1 to 1:3. If the water-soluble photopolymerization initiator (k-1) is contained in a mass ratio of more than 10:1, the curing property of the two-component dental bonding material (Y) itself may be reduced, making it difficult to achieve high adhesiveness. On the other hand, if the water-insoluble photopolymerization initiator (k-2) is contained in a mass ratio of more than 1:10, although the curing property of the two-component dental bonding material (Y) itself is enhanced, the polymerization promotion at the adhesive interface may be insufficient, making it difficult to achieve high adhesiveness.

[0205] Another embodiment is a dental filling kit including a two-component dental bonding material (Y) further containing a filler. Examples of fillers used in the two-component dental bonding material (Y) include those similar to the filler (d) in the self-adhesive dental composite resin (X). One type of filler may be used alone, or two or more types may be used in combination. The method for measuring the average particle size of the filler is the same as that described for the filler (d) in the self-adhesive dental composite resin (X).

[0206] Examples of the shape of the inorganic filler include amorphous fillers and spherical fillers. From the viewpoint of improving the mechanical strength of the two-component dental bonding material (Y), it is preferable to use a spherical filler as the inorganic filler. Here, the spherical filler is as explained in the filler (d) of the self-adhesive dental composite resin (X). The average particle size of the filler is preferably 0.01 μm or more in order to maintain the mechanical strength without reducing the filler filling rate in the dental bonding material (Y), and is preferably 1 μm or less in order to maintain the dispersion stability of the filler.

[0207] In the two-component dental bonding material (Y), two or more fillers having different materials, particle size distributions, and shapes may be mixed or combined, and particles other than the filler may be unintentionally contained as impurities within a range that does not impair the effects of the present invention. Commercially available fillers may be used as the filler in the present invention.

[0208] The content of the filler used in the two-component dental bonding material (Y) is not particularly limited, and is preferably in the range of 0.1 to 30 mass %, more preferably in the range of 0.5 to 20 mass %, and even more preferably in the range of 1.0 to 10 mass %, based on the total mass of the two-component dental bonding material (Y).

[0209] In addition, the two-component dental bonding material (Y) may contain fluoride ion-releasing substances, pH adjusters, polymerization inhibitors (e.g., dibutylhydroxytoluene (BHT), hydroquinone monomethyl ether (MEHQ)), colorants, fluorescent agents, fragrances, functional monomers, and the like, as long as the effects of the present invention are not impaired. These may be used alone or in combination of two or more. Antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxydodecylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydecylammonium chloride, and triclosan may also be contained. Examples of functional monomers that impart adhesion to metals include 10-mercaptodecyl (meth)acrylate, 6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4-dithione, 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate, and monomers containing sulfur, such as the thiouracil derivatives described in JP-A-10-1473 and the disulfide compounds described in JP-A-11-92461, with 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate being preferred due to its excellent adhesion to precious metals.

[0210] In one embodiment, from the viewpoint of storage stability of the dental bonding material (Y), it is preferable that the dental bonding material (Y) is substantially free of a photopolymerization initiator. Substantially free of a photopolymerization initiator means that the content of the photopolymerization initiator is less than 0.1 mass %, preferably less than 0.05 mass %, more preferably less than 0.01 mass %, and may be 0 mass %, relative to the total amount of monomers contained in the two-component dental bonding material (Y).

[0211] Based on the total mass of the two-component dental bonding material (Y), the content of the monomer (f) having an acidic group is preferably 0.1 to 20 mass%, more preferably 0.5 to 15 mass%, and even more preferably 1 to 10 mass%, from the viewpoints of adhesion to tooth structure, cavity sealing ability, and durability thereof. Based on the total mass of the two-component dental bonding material (Y), the content of the chemical polymerization accelerator (h) is preferably 0.01 to 10 mass%, more preferably 0.05 to 8 mass%, and even more preferably 0.1 to 6 mass%, from the viewpoints of adhesion to tooth structure, cavity sealing ability, and durability thereof. The total amount of the monomers is preferably 5 to 97 mass %, more preferably 10 to 95 mass %, and even more preferably 15 to 90 mass %, based on the total mass of the two-component dental bonding material (Y). The content of the filler is preferably 0 to 50 mass %, more preferably 0 to 40 mass %, and even more preferably 0 to 30 mass %, based on the total mass of the two-component dental bonding material (Y).

[0212] The two-component dental bonding material (Y) is stored in a state where it is packaged separately into a first agent and a second agent. Here, the form of packaging is not particularly limited as long as the composition constituting the first agent and the composition constituting the second agent do not come into contact with or mix with each other during storage, but typically the first agent and the second agent are stored separately in various containers such as syringes, bags, and bottles. Meanwhile, when using the bonding material, the first agent and the second agent are typically mixed to prepare a mixed composition, and then this mixed composition is applied to the surface of an adherend such as a tooth. However, it is also possible to mix the first agent and the second agent on the surface of the adherend by applying the first agent and the second agent simultaneously or separately and sequentially to the surface of the adherend.

[0213] The first agent contains a monomer (f) having an acidic group. Preferably, the first agent further contains a monomer (g) not having an acidic group and an organic solvent. Preferably, the first agent further contains a chemical polymerization accelerator (h) or a polymerization inhibitor. In some embodiments, the first agent further contains water (j), a photopolymerization initiator (k), a chemical polymerization accelerator (h), and a chemical polymerization initiator (j).

[0214] The content of each component in the first agent is preferably 1 to 50 parts by mass of a monomer (f) having an acidic group and 50 to 99 parts by mass of a monomer (g) not having an acidic group, based on a total of 100 parts by mass of the monomer components of the first agent; more preferably 3 to 30 parts by mass of a monomer (f) having an acidic group and 70 to 97 parts by mass of a monomer (g) not having an acidic group; and even more preferably 3 to 25 parts by mass of a monomer (f) having an acidic group and 75 to 92.5 parts by mass of a monomer (g) not having an acidic group.

[0215] Furthermore, the first agent preferably contains, relative to 100 parts by mass of the total amount of the monomer components, 0.001 to 10 parts by mass of a chemical polymerization accelerator (h), 0.001 to 10 parts by mass of a chemical polymerization initiator (j), 0 to 30 parts by mass of a filler, 0 to 50 parts by mass of water (i), and 0 to 500 parts by mass of an organic solvent, and more preferably contains 0.01 to 5 parts by mass of a polymerization accelerator (h), 0.01 to 5 parts by mass of a chemical polymerization initiator (j), 0 to 20 parts by mass of a filler, 0 to 30 parts by mass of water (i), and 0 to 200 parts by mass of an organic solvent.

[0216] The total content of the monomers in the first agent is preferably 20 to 90 mass %, more preferably 30 to 80 mass %, and even more preferably 35 to 70 mass %, based on the total mass of the first agent. The content of water (i) in the first agent is preferably 0 to 40 mass %, more preferably 0 to 30 mass %, and even more preferably 0 to 20 mass %, based on the total mass of the first agent. The content of the organic solvent in the first agent is preferably 5 to 90 mass %, more preferably 15 to 80 mass %, and even more preferably 25 to 70 mass %, based on the total mass of the first agent. The content of the filler in the first agent is preferably 0 to 20 mass %, more preferably 0 to 10 mass %, and even more preferably 0 to 7.5 mass %, based on the total mass of the first agent.

[0217] The second part contains the essential materials constituting the two-component dental bonding material (Y) that are not contained in the first part. The second part may contain materials contained in the first part. The second part may contain, but preferably does not contain, a monomer (f) having an acidic group or a monomer (g) not having an acidic group. The second part preferably contains an organic solvent and water (j). The second part may contain a chemical polymerization accelerator (h) and a chemical polymerization initiator (j).

[0218] Regarding the content of each component in the second agent, the total content of the chemical polymerization accelerator (h) is preferably 0.01 to 15 mass%, more preferably 0.1 to 10 mass%, and even more preferably 0.5 to 7.5 mass%, based on the total mass of the second agent. The content of water (i) in the second part is preferably 1 to 40 mass %, more preferably 3 to 30 mass %, and even more preferably 5 to 25 mass %, based on the total mass of the second part. The content of the organic solvent in the second part is preferably 50 to 97 mass %, more preferably 60 to 92 mass %, and even more preferably 65 to 89 mass %, based on the total mass of the second part. The content of water (i) in the second part is preferably 1 to 40 mass %, more preferably 3 to 30 mass %, and even more preferably 5 to 25 mass %, based on the total mass of the second part. The total amount of the chemical polymerization initiator (j) in the second agent is preferably from 0 to 15% by mass, more preferably from 0.01 to 10% by mass, and even more preferably from 0.1 to 7.5% by mass.

[0219] The chemical polymerization initiator (j) may be contained in both the first and second parts, but is preferably contained in only one of them. Furthermore, since it is preferable that the three components of the monomer, chemical polymerization accelerator (h), and chemical polymerization initiator (j) do not come into contact during storage, it is preferable that at least one of the chemical polymerization accelerator (h) and chemical polymerization initiator (j) is not contained in the first part. A preferred embodiment is a two-component dental bonding material (Y) in which the first component contains a monomer (f) having an acidic group, a monomer (g) not having an acidic group, an organic solvent, a chemical polymerization accelerator (h), and a polymerization inhibitor, and the second component contains the chemical polymerization accelerator (h), water (j), an organic solvent, and a chemical polymerization initiator (j).

[0220] The mixing ratio (first part / second part) of the first and second parts of the two-component dental bonding material (Y) can be appropriately selected as long as the adhesive properties and operability are not significantly impaired. However, from the practical viewpoint of ease of handling and product packaging, the mixing ratio (first part / second part) is preferably in the range of 1 / 5 to 5 / 1 by volume, more preferably 1 / 3 to 3 / 1. Alternatively, the mixing ratio (first part / second part) is preferably in the range of 1 / 5 to 5 / 1 by mass, more preferably 1 / 3 to 3 / 1. Furthermore, users of the two-component dental bonding material (Y) of this embodiment typically mix the first and second parts according to the mixing ratio (hereinafter referred to as the "designated mixing ratio") specified by the developer, manufacturer, or seller of the two-component dental bonding material (Y) of this embodiment. The actual mixing ratio during use is permissible to deviate from the specified mixing ratio as long as the adhesiveness and operability are not significantly impaired. For example, when the specified mixing ratio is taken as the standard (100%), the actual mixing ratio during use may be in the range of 33% to 300%, and preferably in the range of 50% to 200%.

[0221] The specified mixing ratio can be displayed on a mixing ratio information display medium. Examples of this mixing ratio information display medium include: i) product packaging such as a paper box; ii) product instructions provided as paper and / or electronic data; iii) containers (bottles, syringes, packaging bags, etc.) in which the first and second parts are sealed; iv) product catalogs provided as paper and / or electronic data; and v) correspondence sent to product users by email, mail, etc. separately from the product. The specified mixing ratio may also be provided to product users in a manner that allows the product user to recognize it, other than the above i) to v).

[0222] <Configuration of the dental filling kit of the present invention> The dental filling kit of the present invention comprises a self-adhesive dental composite resin (X) and a two-component dental bonding material (Y). The self-adhesive dental composite resin (X) and the two-component dental bonding material (Y) are usually filled in independent containers.

[0223] The dental filling kit of the present invention may further contain an etching material, a dental primer, etc. in combination. From the viewpoint of cavity sealing ability, it is preferable to apply the etching material only to the enamel. From the viewpoint of adhesive strength to the tooth structure and cavity sealing ability, it is preferable to combine it with a dental primer. The dental primer may or may not be polymerized alone, but from the viewpoint of cavity sealing ability, it is preferable to polymerize it by photo- or chemical polymerization. The etching material and The dental primer and the etching agent may be used alone or in combination. From the viewpoint of cavity sealing, the procedure of applying the dental primer after using the etching agent is preferred.

[0224] <Specific application methods and procedures> Dental bonding material (Y) processing The tooth surface to which the self-adhesive dental composite resin (X) is applied is treated with a dental bonding material (Y). Treatment methods include applying the dental bonding material (Y) and leaving it to stand for a predetermined treatment time, or applying the dental bonding material (Y) and rubbing it with an instrument such as a microbrush for a predetermined treatment time. However, from the viewpoint of cavity sealing, rubbing it with an instrument such as a microbrush for a predetermined treatment time is preferred. The solvent is then removed by air blowing. If the dental bonding material contains a photopolymerization initiator, the solvent is removed and the resulting material is then irradiated with light using a dental light irradiator.

[0225] ·Application of self-adhesive dental composite resin (X) After treating the tooth surface (cavity) with dental bonding material (Y), a self-adhesive dental composite resin (X) is applied. After filling with the self-adhesive dental composite resin (X) and smoothing the surface, if the self-adhesive dental composite resin (X) contains a photopolymerization initiator, it is irradiated with light using a dental light curing device to harden. If the self-adhesive dental composite resin (X) contains a chemical polymerization initiator, it is left to stand until hardening is complete. After that, the surface shape is corrected and polished as needed.

[0226] When combining an etching agent and a dental primer, if an etching agent is used, it should be used before applying the dental bonding material (Y), and if a dental primer is used, it should be used before applying the dental bonding material (Y). [Example]

[0227] 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. In the examples, parts are by mass unless otherwise specified.

[0228] Next, the components of the dental filling kits of the Examples and Comparative Examples are listed below together with their abbreviations.

[0229] Self-adhesive dental composite resin (X) [Monomer (a) having an acidic group] MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[0230] [Monomer (b) having no acidic group] Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane D-2.6E: 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethoxy groups added: 2.6) 3G: Triethylene glycol dimethacrylate DD: 1,10-decanediol dimethacrylate MAEA: N-methacryloyloxyethyl acrylamide DEAA: N,N-diethylacrylamide HEMA: 2-hydroxyethyl methacrylate

[0231] [Photopolymerization initiator (c)] Water-soluble photopolymerization initiator (c-1) Li-TPO: Lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate, a water-insoluble photoinitiator (c-2) CQ: Camphorquinone BAPO: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide

[0232] Filler (d) Filler 1: Nippon Aerosil Co., Ltd., ultrafine silica particle "Aerosil (registered trademark) R972", average particle size: 16 nm Filler 2: Silane-treated silica 100 g of OX50 (Nippon Aerosil Co., Ltd., ultrafine silica particle "Aerosil (registered trademark) OX50", average particle size: 0.04 μm), 7 g of γ-methacryloyloxypropyltrimethoxysilane, and 200 mL of 0.3 mass% acetic acid aqueous solution were placed in a three-necked flask and stirred at room temperature for 2 hours. After removing water by freeze-drying, the mixture was heated at 80°C for 5 hours to obtain Filler 2. Filler 3: Silane-treated silica powder Silica powder (quartz, manufactured by Nichitsu Corporation, product name: Hi-Silica) was pulverized in a ball mill to obtain pulverized silica powder. The average particle size of the obtained pulverized silica powder was measured on a volume basis using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model "SALD-2300") and found to be 2.2 μm. 100 parts by mass of this pulverized silica powder was surface-treated with 4 parts by mass of γ-methacryloyloxypropyltrimethoxysilane by a standard method to obtain silane-treated silica powder. Filler 4: Silane-treated barium glass powder Barium glass (manufactured by Estec Co., Ltd., product code "E-3000") was pulverized in a ball mill to obtain barium glass powder. The average particle size of the obtained barium glass powder was measured on a volume basis using a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model "SALD-2300") and found to be 2.4 μm. 100 parts by mass of this barium glass powder was surface-treated with 3 parts by mass of γ-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain silane-treated barium glass powder. Filler 5: Silane-treated barium glass powder 100 g of GM27884 NF180 grade (barium glass manufactured by SCHOTT, average particle size: 0.18 μm), 13 g of γ-methacryloyloxypropyltrimethoxysilane, and 200 mL of 0.3 mass% acetic acid aqueous solution were placed in a three-necked flask and stirred at room temperature for 2 hours. After removing water by freeze-drying, the mixture was heated at 80°C for 5 hours to obtain Filler 5. Filler 6: Silane-treated barium glass powder 100 g of 8235 UF0.7 grade (barium glass manufactured by SCHOTT, average particle size: 0.7 μm), 6 g of γ-methacryloyloxypropyltrimethoxysilane, and 200 mL of 0.3 mass% acetic acid aqueous solution were placed in a three-necked flask and stirred at room temperature for 2 hours. After removing water by freeze-drying, the mixture was heated at 80°C for 5 hours to obtain Filler 6. Filler 7: Silane-treated spherical silica-zirconia composite oxide powder 100 g of spherical silica-zirconia composite oxide (average particle size: 0.3 μm), 10 g of γ-methacryloyloxypropyltrimethoxysilane, and 200 mL of 0.3 mass% acetic acid aqueous solution were placed in a three-necked flask and stirred at room temperature for 2 hours. After removing water by freeze-drying, the mixture was heated at 80°C for 5 hours to obtain Filler 7.

[0233] [Chemical polymerization accelerator (e)] DABE: Ethyl 4-(N,N-dimethylamino)benzoate

[0234] [Polymerization inhibitor] BHT: 3,5-di-t-butyl-4-hydroxytoluene

[0235] Dental bonding material (Y) [Monomer having an acidic group (f)] MDP: 10-methacryloyloxydecyl dihydrogen phosphate P-2M: Bis(2-methacryloyloxyethyl) acid phosphate 4-META: 4-methacryloyloxyethyl trimellitic anhydride

[0236] [Monomer (g) having no acidic group] Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane 3G: Triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate MMA: Methyl methacrylate

[0237] Filler (d) AEROSIL R972: AEROSIL® R972 fine particle silica manufactured by Nippon Aerosil Co., Ltd. (hydrophobic fumed silica, average particle size: 16 nm)

[0238] [Chemical polymerization accelerator (h)] BMOV: Bis(maltolato)oxovanadium(IV) PhB-TEOA: Triethanolamine salt of tetraphenylboron PhB-Na: sodium salt of tetraphenylboron Cu-AcAc: copper acetylacetonate MBI: 2-mercaptobenzimidazole p-TSA: p-toluenesulfonic acid PTS-Na: sodium p-toluenesulfinate DEPT: N,N-dimethyl-p-toluidine DABE: Ethyl 4-(N,N-dimethylamino)benzoate

[0239] [Water (i)] purified water [Organic solvents] acetone ethanol IPA: Isopropanol

[0240] [Chemical polymerization initiator (j)] BPO: Benzoyl peroxide Perocta® H: 1,1,3,3-tetramethylbutyl hydroperoxide

[0241] [Photopolymerization initiator (k)] CQ: Camphorquinone TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

[0242] [others] MTU-6: 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate (formula (8) below) [ka] MPS: γ-methacryloyloxypropyltrimethoxysilane

[0243] [Polymerization inhibitor] BHT: 3,5-di-t-butyl-4-hydroxytoluene

[0244] [Examples 1 to 32 and Comparative Examples 1 to 5] [Preparation of self-adhesive dental composite resin (X)] The raw materials (excluding bonding materials) shown in Tables 3 to 5 below were mixed and kneaded in a dark place at room temperature (23°C) to prepare paste-like self-adhesive dental composite resins, and their properties were investigated according to the methods of the following Test Examples 1 and 2. The results are shown in Tables 3 to 5.

[0245] [Preparation of dental bonding material (Y)] The components shown in Tables 1 and 2 below were divided into a first part and a second part, which were mixed at room temperature (23°C) to prepare the first and second parts. The combination of the first and second parts corresponds to dental bonding material (Y). The first and second parts obtained were each filled into a container of "Clearfil (registered trademark) Tri-S Bond ND Quick" (manufactured by Kuraray Noritake Dental Co., Ltd.) and used.

[0246] Test Example 1: Bond strength to dentin [Shear adhesion test to dentin] The labial surfaces of bovine mandibular anterior teeth were polished under running water with #80 silicon carbide paper (Nihon Kenshi Co., Ltd.) to expose the flat surface of the dentin. The sample teeth were fixed onto tape attached to the bottom of a 15-hole mold (Ultradent, φ35 mm x H25 mm). Plaster was filled into the mold and allowed to stand for approximately 30 minutes to harden. The samples were removed from the mold and polished under running water with #600 silicon carbide paper (Nihon Kenshi Co., Ltd.) to a size sufficient for adhesion (φ2.38 mm or larger). The adhesion surface was then ultrasonically rinsed for 5 minutes to prepare the samples.

[0247] One drop each of the first and second parts of dental bonding material (Y) was placed in the same mixing dish, mixed with a microbrush, and then applied to the surface of the sample and left for 10 seconds. The solvent was then removed by air blowing. For dental bonding materials containing a photopolymerization initiator, the dental bonding material (Y) was then cured by irradiating it with light for 10 seconds using a dental LED light irradiator (Ultradent, product name "VALO").

[0248] Next, a separately prepared φ2.38 mm CR filling mold (Bonding Mold Insert, manufactured by Ultradent) was attached to a dedicated tool (Bonding Clamp, manufactured by Ultradent). Next, the CR filling mold attached to the dedicated tool was lowered to fix the sample so that it was in close contact with the surface of the sample where the dental bonding material (Y) had hardened. Next, the dental composite resin (X) prepared in each example and comparative example was thinly filled into the hole in the CR filling mold to a thickness of 1 mm or less. After that, it was filled into the mold again (up to about 2 / 3 of the mold, about 2 mm thick), left for 10 seconds, and then the dental LED light irradiator (Ultradent) was used. The self-adhesive dental composite resin (X) was cured by 10 seconds of light irradiation using a VALO (manufactured by VALO Co., Ltd.). The sample was removed from the mold and used as a test sample for the adhesion test. 20 samples were prepared for each adhesion test. For 10 of the 20 samples, the shear bond strength was measured immediately after leaving them in water at 37°C for 24 hours to evaluate the initial bond strength. For the remaining 10 samples, the shear bond strength was measured after leaving them in water at 37°C for 24 hours and then undergoing 4,000 thermal cycles, each cycle consisting of alternating immersion in cold water at 4°C and hot water at 60°C for 1 minute. The shear bond strength after the thermal cycles, which relates to bond durability, is shown in the table as "Durability." The adhesive strength (shear adhesive strength) was measured by attaching the adhesive test sample to a dedicated holder (Test Base Clamp, manufactured by Ultradent), and using a dedicated jig (Crosshead Assembly, manufactured by Ultradent) and a universal testing machine (manufactured by Shimadzu Corporation) with a crosshead speed set to 1 mm / min. The average values ​​are shown in the table (n=10).

[0249] Test Example 2: Cavity sealing The occlusal surfaces of human molars were brushed with a toothbrush to remove surface deposits. A cylindrical cavity measuring 4 mm in diameter and 4 mm in depth was created using an air turbine under water using a Mani® Diabur® SF-21 (Mani Corporation). After cavity creation, the root was removed and the tooth tissue was polished from the root side so that a thickness of approximately 2 mm remained from the cavity bottom. The cavity was rinsed with running water and then dried with an air blower. One drop each of the first and second parts of the dental bonding material (Y) was placed in the same mixing dish, mixed with a microbrush, and then applied to the cavity with the microbrush and left for 10 seconds. The solvent was then removed with an air blower. If the dental bonding material (Y) contained a photopolymerization initiator, the dental bonding material was then cured by irradiating it with light for 10 seconds using a dental LED light irradiator (Ultradent, product name "VALO"). Next, a self-adhesive dental composite resin (X) was filled in, left for 10 seconds, and then irradiated with light for 10 seconds using a dental LED light irradiator (manufactured by Ultradent, product name "VALO").

[0250] Eight test samples were prepared for each test. Four of the eight samples were immersed in water at 37°C for 24 hours, and then immediately measured for initial cavity sealing property to evaluate the initial cavity sealing property. The remaining four samples were immersed in water at 37°C for 24 hours, and then subjected to 4,000 thermal cycles, each cycle consisting of alternating immersion in cold water at 4°C and hot water at 60°C for 1 minute, to evaluate the durability of cavity sealing property. The cavity sealing property after the thermal cycles regarding the durability of cavity sealing property is shown in the table as "durability". The measurement method was to measure the cavity sealing property by optical coherence tomography (OCT, IVS-2000, The cavity was observed using a dental hygienist (Santec Co., Ltd.) and the cavity compatibility was evaluated (n=4). The upper half of the cavity was observed from the crown side, and the lower (cavity floor) part was observed from the root side. Samples with no visible cavity delamination were given a score of 0, samples with visible cavity side delamination were given a score of 1, samples with visible cavity floor delamination were given a score of 2, and samples with visible cavity side and floor delamination were given a score of 3. The score with the most samples out of n=4 was used as the evaluation result.

[0251]

Table 1

[0252]

Table 2

[0253]

Table 3

[0254]

Table 4

[0255]

Table 5

[0256]

Table 6

[0257] The results in Tables 3 to 5 show that the dental filling kits of the examples had initial bond strengths to dentin of 22 MPa or more and bond durability of 20 MPa or more. The scores for both initial and durability cavity sealing were 1 or less. The dental filling kits of the present invention were excellent not only in initial adhesion and cavity sealing properties to tooth tissue, but also in long-term adhesion and cavity sealing properties to tooth tissue. On the other hand, as shown in Table 6, among the comparative examples, Comparative Example 1, in which the self-adhesive dental composite resin (X) did not contain the monomer (a) having an acidic group, did not exhibit good adhesion and cavity sealing properties to dentin. Comparative Examples 2 to 4, which did not satisfy the constituent requirements of the dental bonding material (Y), did not exhibit good adhesion and cavity sealing properties to dentin. Testing of Comparative Example 5 was not possible because bonding material 22 gelled after preparation. Patent Document 2 discloses a one-component bonding material composition containing a photopolymerization initiator, which corresponds to Comparative Example 5. [Industrial Applicability]

[0258] The dental filling kit of the present invention can be suitably used for filling treatment in dental treatment. The dental filling kit of the present invention has excellent cavity sealing ability even in deep cavities, and can be particularly suitably used for dental filling treatment of deep cavities, such as cavities of 4 mm or more.

Claims

1. A self-adhesive dental composite resin (X) containing a monomer (a) having an acidic group, a monomer (b) not having an acidic group, and a photopolymerization initiator (c); Contains a first agent and a second agent, the first agent contains a monomer (f) having an acidic group, At least one of the first agent and the second agent contains a chemical polymerization accelerator (h) and a chemical polymerization initiator (j), and the chemical polymerization initiator (j) is an organic peroxide; and a two-component dental bonding material (Y) in which at least one of the first and second components contains water (i); Equipped with A dental filling kit in which the self-adhesive dental composite resin (X) is a one-material type.

2. The dental filling kit according to claim 1 , wherein the self-adhesive dental composite resin (X) further comprises a filler (d).

3. The dental filling kit according to claim 1 or 2, wherein at least one of the first and second agents further comprises a monomer (g) having no acidic group.

4. The dental filling kit according to any one of claims 1 to 3, wherein the chemical polymerization accelerator (h) comprises at least one selected from the group consisting of amines, borate compounds, sulfinic acids and their salts, thiourea compounds, copper compounds, thiol compounds, and vanadium compounds.

5. The dental filling kit according to any one of claims 1 to 4, wherein the chemical polymerization accelerator (h) comprises a borate compound.

6. The dental filling kit according to any one of claims 1 to 5, wherein the second part contains a chemical polymerization initiator (j).

7. A dental filling kit described in any one of claims 1 to 6, wherein the organic peroxide includes at least one selected from the group consisting of hydroperoxides, ketone peroxides, peroxyesters, and diacyl peroxides.

8. The dental filling kit according to any one of claims 1 to 7, wherein the second agent comprises water.

9. 9. The dental filling kit according to claim 1, wherein the first and second parts are substantially free of a photopolymerization initiator.

10. The dental filling kit according to any one of claims 1 to 8, wherein at least one of the first and second parts further comprises a photopolymerization initiator (k).

11. The dental filling kit according to any one of claims 1 to 10, wherein at least one of the first and second agents further comprises an organic solvent.

12. The dental filling kit according to any one of claims 1 to 11, wherein the photopolymerization initiator (c) comprises a water-soluble photopolymerization initiator (c-1).

13. The dental filling kit according to any one of claims 1 to 12, wherein the monomer (a) having an acidic group includes a monomer having a phosphate group.

14. The dental filling kit according to claim 13, wherein the monomer having a phosphate group includes a monomer having a divalent phosphate group and an alkylene group having 6 to 20 carbon atoms.

15. The dental filling kit according to any one of claims 1 to 14, wherein the monomer (a) having an acidic group and the monomer (f) having an acidic group comprise the same monomer.

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