Dental bonding kit

Abstract

We provide dental bonding kits. [Solution] (I) a dental adhesive composition comprising (A) a polymerizable monomer having an acidic group (A1), (B) water, (C) a volatile organic solvent, and (D) an aromatic tertiary amine compound which is a photopolymerization initiator, (II) A dental adhesive kit comprising a dental photocurable composition containing (A) a polymerizable monomer, (D) a photopolymerization initiator, and (E) a filler. (II) The (D) photopolymerization initiator contained in the dental photocurable composition comprises (D2) an α-diketone compound, (D3) an iodonium salt compound, and (D4) an aliphatic tertiary amine compound having an aromatic ring, and substantially does not contain (D1) an aromatic tertiary amine compound. Dental bonding kit.

Description

[Technical Field]

[0001] This invention relates to a dental adhesive kit. [Background technology]

[0002] Dental treatment uses dental adhesive kits consisting of dental adhesive compositions and dental light-curing compositions. Examples of dental light-curing compositions used in combination with dental adhesive compositions include dental composite resins, dental resin cements, dental core buildup materials, orthodontic materials, dental pit and fissure sealing materials, and dental tooth stabilization materials. Among these, orthodontic materials, dental pit and fissure sealing materials, and dental tooth stabilization materials generally require high durability and adhesive strength to enamel, and therefore pretreatment materials are commonly used in combination.

[0003] Patent Document 1 discloses a dental filling and restoration kit, and Patent Document 2 discloses a composition suitable for aligner attachments. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2009-215254 [Patent Document 2] WO2022 / 030642 [Overview of the initiative] [Problems that the invention aims to solve]

[0005] However, these compositions still had room for improvement in achieving both high durability and color stability when used with tooth stabilization materials or orthodontic adhesive kits.

[0006] The present invention aims to provide a dental adhesive kit that achieves both high durability and color stability. [Means for solving the problem]

[0007] As a result of intensive studies, the present inventors have found that the above problem can be solved by providing a predetermined dental adhesive kit.

[0008] The following items are provided according to the present disclosure. (Item 1) (I) a dental adhesive composition comprising: (A) a polymerizable monomer, which is (A1) a polymerizable monomer having an acidic group; (B) water; (C) a volatile organic solvent; and (D) a photopolymerization initiator, which is (D1) an aromatic tertiary amine compound; a dental adhesive kit comprising: (II) a dental photocurable composition comprising (A) a polymerizable monomer, (D) a photopolymerization initiator, and (E) a filler, wherein the (D) photopolymerization initiator contained in the (II) dental photocurable composition comprises (D2) an α-diketone compound, (D3) an iodonium salt compound, and (D4) an aliphatic tertiary amine compound having an aromatic ring, and is substantially free of (D1) an aromatic tertiary amine compound, a dental adhesive kit. (Item 2) The dental adhesive kit according to Item 1, wherein the (I) dental adhesive composition comprises (F) a compound containing a disulfide group. (Item 3) The dental adhesive kit according to Item 2, wherein the (F) compound containing a disulfide group contained in the (I) dental adhesive composition is thioctic acid. (Item 4) The dental adhesive kit according to Item 1, wherein the (I) dental adhesive composition is substantially free of an aliphatic tertiary amine compound. (Item 5) The dental adhesive kit according to Item 3, wherein the (I) dental adhesive composition is substantially free of an aliphatic tertiary amine compound. (Item 6) The (I) dental adhesive composition comprises, relative to 100 parts by mass of the (I) dental adhesive composition, 3 to 20 parts by mass of (A1) the polymerizable monomer having an acidic group, 10 to 50 parts by mass of (B) water 10 to 50 parts by mass of (B) water (C) 10 to 60 parts by mass of a volatile organic solvent, and (D1) Contains 0.05 to 2 parts by mass of an aromatic tertiary amine compound. (II) Dental photocurable composition (II) For every 100 parts by mass of (A) polymerizable monomer contained in the dental photocurable composition, (D2) 0.05 to 0.6 parts by mass of α-diketone compound (D3) 0.3 to 5 parts by mass of iodonium salt compound (D4) 0.5 to 5 parts by mass of an aliphatic tertiary amine compound having an aromatic ring, and (E) A dental adhesive kit as described in item 1, comprising 10 to 400 parts by mass of a filler. (Item 7) (I) Dental adhesive compositions (I) Per 100 parts by mass of dental adhesive composition, (A1) 3 to 20 parts by mass of polymerizable monomer having an acidic group (B) 10 to 50 parts by mass of water (C) 10 to 60 parts by mass of a volatile organic solvent, and (D1) Contains 0.05 to 2 parts by mass of an aromatic tertiary amine compound. (II) Dental photocurable composition (II) For every 100 parts by mass of (A) polymerizable monomer contained in the dental photocurable composition, (D2) 0.05 to 0.6 parts by mass of α-diketone compound (D3) 0.3 to 5 parts by mass of iodonium salt compound (D4) 0.5 to 5 parts by mass of an aliphatic tertiary amine compound having an aromatic ring, and (E) A dental adhesive kit as described in item 3, comprising 10 to 400 parts by mass of a filler. (Item 8) (I) Dental adhesive compositions (I) Per 100 parts by mass of dental adhesive composition, (A1) 3 to 20 parts by mass of polymerizable monomer having an acidic group (B) 10 to 50 parts by mass of water (C) 10 to 60 parts by mass of a volatile organic solvent, and (D1) Contains 0.05 to 2 parts by mass of an aromatic tertiary amine compound. (II) Dental photocurable composition (II) For every 100 parts by mass of (A) polymerizable monomer contained in the dental photocurable composition, (D2) 0.05 to 0.6 parts by mass of α-diketone compound (D3) 0.3 to 5 parts by mass of iodonium salt compound (D4) 0.5 to 5 parts by mass of an aliphatic tertiary amine compound having an aromatic ring, and (E) A dental adhesive kit as described in item 4, comprising 10 to 400 parts by mass of a filler. (Item 9) (I) Dental adhesive compositions (I) Per 100 parts by mass of dental adhesive composition, (A1) 3 to 20 parts by mass of polymerizable monomer having an acidic group (B) 10 to 50 parts by mass of water (C) 10 to 60 parts by mass of a volatile organic solvent, and (D1) Contains 0.05 to 2 parts by mass of an aromatic tertiary amine compound. (II) Dental photocurable composition (II) For every 100 parts by mass of (A) polymerizable monomer contained in the dental photocurable composition, (D2) 0.05 to 0.6 parts by mass of α-diketone compound (D3) 0.3 to 5 parts by mass of iodonium salt compound (D4) 0.5 to 5 parts by mass of an aliphatic tertiary amine compound having an aromatic ring, and (E) A dental adhesive kit as described in item 5, comprising 10 to 400 parts by mass of a filler. (Item 10) Dental adhesive kits for fixing mobile teeth and / or for use in orthodontic treatment, used for bonding to enamel as described in items 1-9. (Item 11) Furthermore, dental adhesive kits as described in items 1-9, including dental etching materials. (Item 12) Furthermore, a dental adhesive kit as described in item 10, including dental etching materials. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a dental adhesive kit that achieves both durable adhesive strength and color stability. [Modes for carrying out the invention]

[0010] Dental bonding kits are used, for example, in orthodontic treatment and to stabilize mobile teeth. Orthodontic bonding kits are materials that can be used to bond devices used in orthodontic treatment to improve malocclusion and bite, and to create attachments in aligner-based orthodontic treatment. Because fixed devices such as brackets and bands used in orthodontic treatment are subjected to heavy loads, materials with high durability and bonding strength are required. Typically, fixed devices are bonded to unground enamel, so the enamel surface is roughened using a phosphate etching agent before the bonding procedure. However, phosphate etching agents carry the risk of roughening the enamel more than necessary, and in some cases, can result in excessively strong bonding. Therefore, it is preferable to use dental adhesive compositions such as self-etching primers to reduce the risk of over-demineralization and simplify the procedure. Furthermore, in recent years, in addition to the traditional fixed devices, aligner-based orthodontic treatment has also become popular. In aligner-based orthodontic treatment, attachments, which are protrusions, are created on the tooth surface to help ensure a secure fit of the aligner and to control tooth movement. Attachments, like fixed appliances, preferably have high durability and adhesive strength to enamel. Furthermore, in cases where high durability and adhesive strength to enamel is required, such as in orthodontic treatment, dental adhesive materials for fixing mobile teeth are known.

[0011] Aromatic amine compounds are used as photopolymerization initiators in dental adhesive compositions and dental photocurable compositions. Due to their high activity, aromatic amine compounds contribute to the development of good durable adhesive strength when used in dental adhesive compositions, and may contribute to the development of good mechanical properties when used in dental photocurable compositions. However, compositions containing aromatic amine compounds tend to discolor easily and have poor color stability, making it difficult to incorporate large amounts of aromatic amine compounds to achieve sufficient properties in compositions where aesthetics are required. In particular, when orthodontic adhesive kits are used to prepare attachments for aligner orthodontic treatment, it is desirable that the attachments do not discolor over the long term.

[0012] On the other hand, aliphatic amine compounds are also used as photopolymerization initiators in dental adhesive compositions and dental photocurable compositions. When aliphatic amine compounds are used, the polymerization activity is lower than that of aromatic amine compounds, but depending on the type of compound, discoloration of the composition may be less likely to occur. However, the aliphatic amine compounds sometimes react with polymerizable monomers containing acidic groups in dental adhesive compositions, resulting in a decrease in durable adhesive strength.

[0013] As a result of their investigations, the inventors discovered that in a dental adhesive kit comprising a dental adhesive composition and a dental photocurable composition, the dental adhesive composition should be formulated with an aromatic tertiary amine compound with high photopolymerization activity, and the dental photocurable composition should be formulated with a photoacid generator and an aliphatic tertiary amine compound containing an aromatic ring, thus completing the present invention.

[0014] [(A) Polymerizable monomers] The polymerizable monomer (A) contained in the dental adhesive composition (I) and the dental photocurable composition (II) included in the dental adhesive kit of the present invention (A) can be used without limitation as long as it is known. The polymerizable monomer (A) includes (A1) a polymerizable monomer having an acidic group and / or (A2) a polymerizable monomer not having an acidic group. In the polymerizable monomer described in the present invention, the polymerizable group is preferably one that exhibits radical polymerizability, and specifically, from the viewpoint of easy radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. In this specification, "(meth)acrylic" means acrylic and / or methacrylic, "(meth)acryloyl" means acryloyl and / or methacryloyl, "(meth)acrylate" means acrylate and / or methacrylate, and "(meth)acrylamide" means acrylamide and / or methacrylamide. Polymerizable monomers having substituents at the α-position of a (meth)acrylic group and / or a (meth)acrylamide group can also be preferably used. In this specification, silane coupling agents having polymerizable groups, particles surface-treated with silane coupling agents having polymerizable groups, and components (B) to (F) containing polymerizable groups are not classified as (A) polymerizable monomers.

[0015] [(A1) Polymerizable monomers having acidic groups] (I) The dental adhesive composition included in the dental adhesive kit of the present invention contains (A1) a polymerizable monomer having an acidic group (also referred to as "component (A1)" in the present invention). The polymerizable monomer having an acidic group (A1) can be used without limitation as long as it has one or more polymerizable groups and at least one or more acidic groups such as a phosphate group, pyrophosphate group, thiophosphate group, phosphonic acid group, sulfonic acid group, or carboxylic acid group. By including a polymerizable monomer having an acidic group, adhesion to tooth structure and prosthetic devices can be imparted.

[0016] Specific examples of polymerizable monomers having a phosphate group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, and 8-(meth)acryloyl Royloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxidedecyl 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 phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di(meth)acryloy Examples include hydroxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl] hydrogen phosphate; acid chlorides, alkali metal salts, and ammonium salts thereof; and one or more (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond.

[0017] Specific examples of polymerizable monomers having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate; their acid chlorides, alkali metal salts, ammonium salts; and one or more selected from (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond.

[0018] Specific examples of polymerizable monomers 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, 8-(meth)acryloyloxyoctyl dihydrogenthiophosphate, and 9-(meth)acryloyloxypropyl Examples include nyl dihydrogenthiophosphate, 10-(meth)acryloyloxydecyl dihydrogenthiophosphate, 11-(meth)acryloyloxyundecyl dihydrogenthiophosphate, 12-(meth)acryloyloxidedecyl dihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogenthiophosphate, 20-(meth)acryloyloxyicosyl dihydrogenthiophosphate; acid chlorides, alkali metal salts, and ammonium salts thereof; and one or more selected from (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond.

[0019] Specific examples of polymerizable monomers having a phosphonic acid group include 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phosphonoacetate; acid chlorides, alkali metal salts, and ammonium salts of these compounds; and one or more (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond.

[0020] Specific examples of polymerizable monomers having a sulfonic acid group include one or more selected from 2-(meth)acrylamide-2-methylpropanesulfonic acid and 2-sulfoethyl (meth)acrylate.

[0021] Polymerizable monomers containing a carboxylic acid group are classified into (meth)acrylic compounds having one carboxyl group in the molecule, or (meth)acrylic compounds having multiple carboxyl groups in the molecule. Specific examples of (meth)acrylic compounds having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid, and 3-(meth)acryloyloxybenzoic acid. One or more selected from acids, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen malate; halides of these acids; and (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond.Specific examples of (meth)acrylic compounds having multiple carboxyl groups 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)acryloyloxidedodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, and 4-(meth)acrylo Examples include yloxyethyl trimetate, 4-(meth)acryloyloxybutyl trimetate, 4-(meth)acryloyloxyhexyl trimetate, 4-(meth)acryloyloxydecyl trimetate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate; their acid anhydrides and acid halides; and one or more (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond.

[0022] [(A2) Polymerizable monomers that do not have acidic groups] (A2) A polymerizable monomer that does not have an acidic group (also referred to as "component (A2)" in the present invention) can be used without limitation as long as it has one or more polymerizable groups and does not have an acidic group. (A2) A polymerizable monomer that does not have an acidic group includes one or more selected from polymerizable monomers having one radical polymerizable group, polymerizable monomers having two radical polymerizable groups, and polymerizable monomers having three or more radical polymerizable groups.

[0023] (A2) Among polymerizable monomers that do not have acidic groups, specific examples of polymerizable monomers that have one radical polymerizable group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, propylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, erythritol mono(meth)acrylate, N-methylol (meth)acrylamide, Examples include one or more selected from N-hydroxyethyl (meth)acrylamide, N,N-(dihydroxyethyl)(meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, 3-(meth)acryloyloxypropyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, and (meth)acrylamide.

[0024] (A2) Among polymerizable monomers that do not have acidic groups, specific examples of polymerizable monomers that have two radical polymerizable groups include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, and 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl )propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxydiethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyditriethoxyphenyl) Propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitate, glycerol di(meth)acrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, ethylene glyco Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,Examples include one or more selected from 2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA"), and 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane.

[0025] (A2) Among polymerizable monomers that do not have acidic groups, specific examples of polymerizable monomers that have three radical polymerizable groups include one or more selected from 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]tetramethacrylate, and 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane.

[0026] There are no restrictions on using oligomers or prepolymers having at least one polymerizable group in the molecule other than these polymerizable monomers. Furthermore, there is no problem with having substituents such as fluorogroups within the same molecule. The polymerizable monomers described above can be used individually or in combination.

[0027] (I) The dental adhesive composition contained in the dental adhesive kit of the present invention contains (A1) a polymerizable monomer having an acidic group. Examples of preferred polymerizable monomers having an acidic group include one or more selected from 10-methacryloyloxydecyl dihydrogen phosphate, 6-methacryloxyhexyl phosphonoacetate, 4-methacryloxyethyl trimellitic acid, and 4-methacryloxyethyl trimellitic anhydride. A preferred amount of polymerizable monomer having an acidic group (A1) is 3 to 20 parts by mass per 100 parts by mass of the dental adhesive composition (I). When it contains 3 parts by mass or more, good durable adhesive strength to enamel is exhibited, and when it contains 20 parts by mass or less, good storage stability is obtained. Furthermore, a preferred amount of polymerizable monomer (A) contained in the dental adhesive composition (I) is 60 parts by mass or less per 100 parts by mass of the dental adhesive composition (I), and more preferably 50 parts by mass or less. In such cases, (I) the film thickness of the dental adhesive composition tends to be thinner, and aesthetically pleasing treatment can be expected.

[0028] [(B)Water] The dental adhesive composition (I) contained in the dental adhesive kit contains (B) water (also referred to as "component (B)" in this invention). Specific examples of water (B) include one or more selected from deionized water and distilled water. The amount of water (B) is preferably 10 to 50 parts by mass per 100 parts by mass of the dental adhesive composition (I). When the amount is 10 parts by mass or more, the durable adhesive strength to enamel tends to be good, and when the amount is 50 parts by mass or less, the solubility of the polymerizable monomer (A) contained in the dental adhesive composition (I) may be good.

[0029] [(C) Volatile organic solvent] The (I) dental adhesive composition contained in the dental adhesive kit may contain (C) a volatile organic solvent (also referred to as "component (C)" in the present invention). Component (C) is typically an organic solvent 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 most preferably soluble in water in any proportion. Among these, water-soluble volatile organic solvents with a boiling point of 100°C or less under normal pressure are preferred. Specific examples include one or more selected from ethanol, methanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane, and tetrahydrofuran. Furthermore, one or more selected from ethanol, isopropyl alcohol, acetone, and methyl ethyl ketone are even more preferred among the aforementioned volatile organic solvents. The amount of component (C) is preferably 10 to 60 parts by mass per 100 parts by mass of the (I) dental adhesive composition. When the amount of (I) dental adhesive composition is 10 parts by mass or more, the film thickness when applied to the bonded surface tends to be thinner, which can be expected to result in aesthetically pleasing treatment, and the solubility of the polymerizable monomer (A) contained in (I) dental adhesive composition can be expected to be good. When the amount is 60 parts by mass or less, the balance of the mixture with other components is often good.

[0030] [(D) Photopolymerization initiator] The dental adhesive kit of the present invention contains (I) a dental adhesive composition and (II) a dental photocurable composition, which contain (D) a photopolymerization initiator (also referred to as "component (D)" in the present invention). A photopolymerization initiator is a polymerization initiator that can initiate polymerization by irradiation with light. One or more photopolymerization initiators that can be used in the dental adhesive composition of the present invention are selected from photosensitizers, photoacid generators, and photopolymerization accelerators. These can be any commonly used known compounds without any limitations. The dental adhesive kit of the present invention contains (I) a dental adhesive composition and (II) a dental photocurable composition, which may use the exemplified photopolymerization initiators alone or in combination of two or more types.

[0031] [(D1) Aromatic tertiary amine compounds] (I) The dental adhesive composition included in the dental adhesive kit of the present invention contains (D1) an aromatic tertiary amine compound (also referred to as "component (D1)" in the present invention), and (II) the dental photocurable composition is substantially free of the aromatic tertiary amine compound (D1). Aromatic amine compounds refer to compounds in which one or more hydrogen atoms of ammonia (NH3) are substituted with aromatic rings. They can be classified as follows: aromatic primary amines are those in which one hydrogen atom of NH3 is substituted with an aromatic ring; aromatic secondary amines are those in which one hydrogen atom of NH3 is substituted with an aromatic ring and one other hydrogen atom is substituted with an aromatic ring or an alkyl group; and aromatic tertiary amines are those in which one hydrogen atom of NH3 is substituted with an aromatic ring and two other hydrogen atoms are substituted with aromatic rings or alkyl groups.

[0032] Specific examples of aromatic tertiary amine compounds include N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline, pN,N-dimethyltoluidine, mN,N-dimethyltoluidine, pN,N-diethyltoluidine, p-bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and p-dimethylaminobenzoic acid 2. -One or more selected from butoxyethyl, p-dimethylaminobenzoic acid 2-ethylhexyl, p-dimethylaminobenzoic acid amino ester, N,N-dimethylanthranic acid methyl ester, N,N-dihydroxyethylaniline, N,N-diisopropanolaniline, pN,N-dihydroxyethyl-toluidine, pN,N-diisopropanol-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N,N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine, and N,N-dimethyl-β-naphthylamine, etc.

[0033] The dental adhesive composition (I) contained in the dental adhesive kit of the present invention contains 0.05 to 2 parts by mass of component (D1) per 100 parts by mass of the dental adhesive composition (I). A good durable adhesive strength tends to be exhibited when component (D1) is present in an amount of 0.05 parts by mass or more, and good storage stability tends to be exhibited when it is present in an amount of 2 parts by mass or less. The reason why good durable adhesive strength is exhibited is that component (D1) has high radical polymerization activity when combined with the (D2) α-diketone compound, so that at the interface where the dental adhesive composition (I) and the dental photocurable composition (II) come into contact, high curability can be exhibited by light when the dental photocurable composition (II) is cured by light irradiation, and as a result, good durable adhesive strength can be exhibited. Specific examples of preferred (D1) components include one or more selected from p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, 1-cyano-4-(dimethylamino)benzene, pN,N-dihydroxyethyl-toluidine, and pN,N-diisopropanol-toluidine, among which one or more selected from (D1) components having a dialkylamino group and electron-withdrawing groups such as an ester group or cyano group at positions 1 and 4, such as p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and 1-cyano-4-(dimethylamino)benzene.

[0034] The (II) dental photocurable composition included in the dental adhesive kit of the present invention substantially does not contain component (D1). "Substantially absent" means intentionally omitted; it does not apply if it is present as an impurity or trace component in the raw materials. Compositions containing component (D1) tend to discolor when exposed to light for extended periods. Therefore, methods to suppress this discoloration by incorporating UV absorbers are known. However, UV absorbers generally do not sufficiently improve the mechanical properties of the composition; therefore, it is preferable not to incorporate UV absorbers in large quantities, such as 2 parts by mass or more per 100 parts by mass of the composition. The (I) dental adhesive composition of the dental adhesive kit of the present invention, when applied to a substrate and air-dried, has a thin film thickness of 50 μm or less, preferably 20 μm or less, and more preferably 5 μm or less. Therefore, even if discoloration occurs due to the presence of component (D1), it is not easily noticeable. On the other hand, the (II) dental photocurable composition is usually used with a thickness of 1 mm or more. Therefore, changes in the color tone of the cured material are easily noticeable. The dental adhesive kit of the present invention (I) achieves good durable adhesive strength by incorporating component (D1) into the dental adhesive composition, and (II) is less prone to discoloration and has excellent aesthetics because the dental photocurable composition substantially does not contain component (D1).

[0035] [(D2)α-diketone compounds] The (II) dental photocurable composition included in the dental adhesive kit of the present invention contains (D2) an α-diketone compound (also referred to as "component (D2)" in the present invention). The (D2) α-diketone compound refers to a diketone compound having a structure in which two ketone groups are adjacent to each other. Examples of such compounds include benzyl, camphorquinone, camphorquinone carboxylic acid, and camphorquinone sulfonic acid. Component (D2) can be appropriately selected depending on the wavelength, intensity, and duration of light used for polymerization, as well as the type and amount of other components combined with it. The photosensitizer can be used alone or in combination of two or more types. Among the (D2) components, an α-diketone compound having a maximum absorption wavelength in the visible light region is preferably used, and more preferably, one or more camphorquinone compounds selected from camphorquinone, camphorquinone carboxylic acid, and camphorquinone sulfonic acid are preferred, with camphorquinone being particularly preferred due to its easy availability.

[0036] The preferred amount of component (D2) of the (II) dental photocurable composition contained in the dental adhesive kit of the present invention is preferably 0.05 to 0.6 parts by mass per 100 parts by mass of the total amount of polymerizable monomer (A) contained in the (II) dental photocurable composition. If the amount of photosensitizer is less than 0.05 parts by mass, the polymerization activity to irradiated light is poor and curing is insufficient. If it is 0.6 parts by mass or less, ambient light stability is good and the yellowing is less, so the aesthetics tend to be good.

[0037] [(D3) Iodonium salt compounds] The dental adhesive kit of the present invention contains (II) a dental photocurable composition (D3) iodonium salt compound (also referred to as "component (D3)" in the present invention). Any known component (D3) can be used. For example, the structural formula of component (D3) can be represented by the following formula (1). [Formula (1)] [(R1)2I] + [A] - ([(R1)2I] in the formula) + [A] is the cation part. - R1 is the anionic part, and in formula (1), R1 represents the organic group bonded to I. R1 may be the same or different. R1 represents, for example, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms. These may be substituted with at least one selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogens. Note that the I in the formula and (I) in this book are different; the I in the formula is the element symbol for iodine.

[0038] In the above, the aryl group having 6 to 30 carbon atoms can be a monocyclic aryl group such as a phenyl group, or one or more condensed polycyclic aryl groups selected from naphthyl, anthracenyl, phenanthrenyl, pyrenyl, crisenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, and anthraquinone.

[0039] Examples of heterocyclic groups having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 heteroatoms such as oxygen, nitrogen, and sulfur, which may be the same or different. Specific examples include one or more monocyclic heterocyclic groups selected from thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, and pyrazinyl, as well as one or more condensed polycyclic heterocyclic groups selected from indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl.

[0040] Specific examples of alkyl groups having 1 to 30 carbon atoms include one or more linear alkyl groups selected from methyl, ethyl, propyl, butyl, hexadecyl, and octadecyl; one or more branched alkyl groups selected from isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl; and one or more cycloalkyl groups selected from cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0041] Furthermore, specific examples of alkenyl groups having 2 to 30 carbon atoms include one or more linear or branched groups selected from vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 1-methyl-1-propenyl.

[0042] Furthermore, specific examples of alkynyl groups having 2 to 30 carbon atoms include one or more linear or branched groups selected from ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl, and 1-methyl-2-propynyl.

[0043] The above-mentioned aryl groups having 6 to 30 carbon atoms, heterocyclic groups having 4 to 30 carbon atoms, alkyl groups having 1 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, or alkynyl groups having 2 to 30 carbon atoms may have at least one substituent. Specific examples of substituents include one or more linear alkyl groups having 1 to 18 carbon atoms selected from methyl, ethyl, propyl, butyl, and octadecyl; one or more branched alkyl groups having 1 to 18 carbon atoms selected from isopropyl, isobutyl, sec-butyl, and tert-butyl; and cyclopropyl, cyclopropyl One or more C3-C18 cycloalkyl groups selected from butyl, cyclopentyl, and cyclohexyl; hydroxyl groups; one or more C1-C18 linear or branched alkoxy groups selected from methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and dodecyloxy; selected from acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanol, 2-methylbutanoyl, 3-methylbutanoyl, and octanoyl. One or more linear or branched alkylcarbonyl groups having 2 to 18 carbon atoms; one or more arylcarbonyl groups having 7 to 11 carbon atoms selected from benzoyl and naphthoyl, etc.; one or more linear or branched alkoxycarbonyl groups having 2 to 19 carbon atoms selected from methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, and tert-butoxycarbonyl, etc.; phenoxycarbonyl and naphthoyl One or more aryloxycarbonyl groups having 7 to 11 carbon atoms selected from oxycarbonyl, etc.; one or more arylthiocarbonyl groups having 7 to 11 carbon atoms selected from phenylthiocarbonyl and naphthoxythiocarbonyl, etc.; one or more linear or branched acyloxy groups having 2 to 19 carbon atoms selected from acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, and octadecylcarbonyloxy, etc.;One or more C6-C20 arylthio groups selected from phenylthio, biphenylylthio, methylphenylthio, chlorophenylthio, bromophenylthio, fluorophenylthio, hydroxyphenylthio, methoxyphenylthio, naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4-[4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl-chlorophenylthio, 4-benzoyl-methylthiophenylthio, 4-(methylthiobenzoyl)phenylthio, and 4-(tert-butylbenzoyl)phenylthio, etc.; One or more C1-C20 linear or branched alkylthio groups selected from methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, and dodecylthio, etc.; Selected from phenyl, tolyl, dimethylphenyl, and naphthyl, etc. One or more aryl groups having 6 to 10 carbon atoms; one or more heterocyclic groups having 4 to 20 carbon atoms selected from thienyl, furanyl, pyranyl, xanthenyl, chromanyl, isochromanyl, xanthonyl, thioxanthonyl, and dibenzofuranyl, etc.; one or more aryloxy groups having 6 to 10 carbon atoms selected from phenoxy and naphthyloxy, etc.; one or more linear or branched alkylsulfinyl groups having 1 to 18 carbon atoms selected from methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, and octylsulfinyl, etc.; one or more arylsulfinyl groups having 6 to 10 carbon atoms selected from phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl, etc.; one or more linear or branched alkylsulfonyl groups having 1 to 18 carbon atoms selected from methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and octylsulfonyl, etc. Examples include one or more arylsulfonyl groups having 6 to 10 carbon atoms selected from phenylsulfonyl, tolylsulfonyl (tosyl group), and naphthylsulfonyl; alkylene oxy groups; cyano groups; nitro groups; and one or more halogens selected from fluorine, chlorine, bromine, and iodine.

[0044] Among iodonium salt compounds, aryliodonium salts are preferred due to their high stability. Furthermore, it is preferable that the aryl group has substituents to improve lipophilicity. Specifically, suitable substituents include one or more linear alkyl groups selected from methyl, propyl, octyl, decyl, undecyl, dodecyl, and tridecyl; one or more branched alkyl groups selected from isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl; functional groups obtained by substituting one or more H of these hydrocarbon groups with F; perfluoroalkyl groups; and one or more halogens.

[0045] The structure of the anionic portion of the iodonium salt compound is not particularly limited, but examples include those having atoms such as halogens, P, S, B, Al, and Ga. Furthermore, it is preferable that the anion composed of these atoms has an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group. In this case, if the organic group has an alkyl group and / or an alkoxy group and / or an aryl group in which one or more H atoms are substituted with F, the solubility in the dental photocurable composition is increased, which can be expected to prevent precipitation during low-temperature storage and long-term storage, and shorten the manufacturing time because it dissolves in the composition in a short time. Low solubility of the iodonium salt compound and the occurrence of precipitation are undesirable because they may cause a decrease in the color stability and flexural strength of the dental photocurable composition.

[0046] [A] of the iodonium salt compound of formula (1) - The anionic portion of [A] of the iodonium salt compound of formula (1) is preferable because it improves solubility in dental photocurable compositions, and therefore preferably has an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group in which at least one H is substituted with F. Specifically, [A] of the iodonium salt compound of formula (1) -The preferred number of carbon atoms in the alkyl group of the anionic portion is 1 to 8, more preferably 1 to 4. Specific examples include one or more linear alkyl groups selected from methyl, ethyl, propyl, butyl, pentyl, and octyl; one or more branched alkyl groups selected from isopropyl, isobutylsec-butyl, and tert-butyl; and one or more cycloalkyl groups selected from cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The ratio of hydrogen atoms to fluorine atoms in the alkyl group (F / H) is 4 or more, preferably 9 or more. More preferably, all hydrogen atoms of the hydrocarbon are substituted with fluorine. The dental photocurable composition may also contain an iodonium salt comprising an anion having alkyl groups with different ratios of hydrogen atoms to fluorine atoms.

[0047] Furthermore, specific examples of alkyl groups include one or more linear or branched perfluoroalkyl groups selected from CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C.

[0048] [A] of the iodonium salt compound of formula (1) -The alkoxy group in the anion moiety preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples include one or more linear alkoxy groups selected from methoxy, ethoxy, propoxy, butoxy, pentoxy, octoxy and the like, and one or more branched alkoxy groups selected from isopropoxy, isobutoxy, sec-butoxy, tert-butoxy and the like. The ratio of the number of fluorine atoms to the number of hydrogen atoms in the alkyl group (F / H) is 4 or more, and the ratio of the number of fluorine atoms to the number of hydrogen atoms in the alkyl group (F / H) is preferably 9 or more. More preferably, all hydrogen atoms of the hydrocarbon are substituted with fluorine atoms. The photocurable composition for dental use may be blended with an iodonium salt composed of an anion having an alkoxy group with a different ratio of hydrogen atoms to fluorine atoms.

[0049] Further, specific examples of the alkoxy group include one or more linear or branched perfluoroalkoxy groups selected from CF3O, CF3CF2O, CF3CF2CF2O, (CF3)2CFO, CF3CF2CF2CF2O, (CF3)2CFCF2O, CF3CF2(CF3)CFO, CF3CF2CF2CF2CF2O, CF3CF2CF2CF2CF2CF2CF2CF2CF2O and the like.

[0050] [A] of the iodonium salt compound of formula (1) -The phenyl group in the anionic portion contains at least one hydrogen atom that is a fluorine atom, and / or a phenyl group that is substituted with an alkyl group and / or alkoxy group substituted with a fluorine atom. The alkyl group and / or alkoxy group substituted with a fluorine atom is preferably one of those described above. Particularly preferred phenyl groups include one or more perfluorophenyl groups selected from pentafluorophenyl group (C6F5), trifluorophenyl group (C6H2F3), tetrafluorophenyl group (C6HF4), trifluoromethylphenyl group (CF3C6H4), bis(trifluoromethyl)phenyl group ((CF3)2C6H3), pentafluoroethylphenyl group (CF3CF2C6H4), bis(pentafluoroethyl)phenyl group ((CF3CF2)2C6H3), trifluoromethylfluorophenyl group (CF3C6H3F), bistrifluoromethylfluorophenyl group ((CF3)2C6H2F), pentafluoroethylfluorophenyl group (CF3CF2C6H3F), and bispentafluoroethylfluorophenyl group ((CF3CF2)2C6H2F). The dental photocurable composition may also contain iodonium salts consisting of anions having phenyl groups with different ratios of hydrogen atoms to fluorine atoms.

[0051] [A] of the iodonium salt compound of formula (1) - As a specific example of the anion part, an anion containing P is [(CF3CF2)3PF3] - [(CF3CF2CF2)3PF3] - [((CF3)2CF)2PF4] - [((CF3)2CF)3PF3] - [((CF3)2CF)4PF2] - [((CF3)2CFCF2)2PF4] - , and [((CF3)2CFCF2)3PF3] - One or more can be selected from the following. An anion containing S is [(CF3SO2)3C] - [(CF3CF2SO2)3C] - [(CF3CF2CF2SO2)3C] -[(CF3CF2CF2CF2SO2)3C] - [CF3CF2CF2CF2SO3] - [CF3CF2CF2SO3] - [(CF3CF2SO2)3C] - [(SO2CF3)3N] - [(SO2CF2CF3]2N] - [((CF3)C6H4)SO3] - , and [SO3((CF2CF2CF2CF2)SO3] 2- One or more of the following can be selected. An anion containing B is [B(C6F5)4]. - [(C6H5)B((CF3)2C6H3)3] - , and [(C6H5)B(C6F5)3] - One or more can be selected from the following. An anion containing Ga is [((C6F5)3(C6H5)Ga)] - [((C6F5)3(C4F9)Ga)] - , [((C6H2F3)4Ga)] - [((CF3)2C6H3)4Ga)] - [[((CF3)4Ga)] - , and [Ga(C6F5)4] - One or more can be selected from the following. An example of an anion containing Al is [((CF3)3CO)4Al] - , and [((CF3CF2)3CO)4Al] - One or more of the following can be selected.

[0052] Other anions include one or more halogens selected from chlorides and bromides, perhalates such as perchloric acid, aromatic sulfonic acids such as p-toluenesulfonate, camphorsulfonic acid, nitrates, acetates, chloroacetates, carboxylates, phenolates, tetrafluoroborates, hexafluorophosphates, hexafluoroantimonates, and hexafluoroarsenates. Among these, one or more selected from p-toluenesulfonate, camphorsulfonic acid, and carboxylates are preferably used.

[0053] The preferred amount of component (D3) of the (II) dental photocurable composition contained in the dental adhesive kit of the present invention is 0.3 to 5 parts by mass per 100 parts by mass of the (A) polymerizable monomer contained in the (II) dental photocurable composition. When the amount is 0.3 parts by mass or more, good polymerization promoting ability is exhibited, and when it is 5 parts by mass or less, good ambient light stability is exhibited, and aesthetics are good because the yellowish or brownish tint in the initial stages of curing is small.

[0054] [(D4) Aliphatic tertiary amine compounds having an aromatic ring] (II) The dental photocurable composition included in the dental adhesive kit of the present invention contains (D4) an aliphatic tertiary amine compound having an aromatic ring (also referred to as "component (D4)" in the present invention). Aliphatic tertiary amine compounds having an aromatic ring (D4) are distinguished from (D1) aromatic tertiary amine compounds. If an aromatic ring is bonded to the N contained in the amine compound, it corresponds to component (D1). Aliphatic tertiary amine compounds refer to those in which the N contained in the amine compound is bonded to a carbon that does not form an aromatic ring, such as a methine group or a methylene group. Furthermore, aliphatic tertiary amine compounds having an aromatic ring (D4) refer to aliphatic tertiary amine compounds that have an aromatic ring in their compound structure, and which do not have an aromatic ring bonded to the N. In component (D4), the aromatic ring is preferably a benzyl group bonded to the carbon at the α position relative to the N atom derived from the amine.

[0055] The (II) dental photocurable composition included in the dental adhesive kit of the present invention can exhibit good curability by containing a (D) photopolymerization initiator containing components (D2), (D3), and (D4). In the dental field, N-methylethanolamine and dimethylaminoethyl methacrylate are commonly used as aliphatic tertiary amine compounds. However, when such aliphatic tertiary amine compounds are used in dental adhesive kits, the durable adhesive strength may decrease. This was particularly noticeable when the (II) dental photocurable composition was applied on top of the (I) dental adhesive composition, which had not been photocured, after the (I) dental adhesive composition included in the dental adhesive kit had been applied to the bonded surface. In the present invention, it has been found that using component (D4) as the aliphatic tertiary amine compound results in good durable adhesive strength. It is speculated that this effect is due to steric hindrance by the aromatic ring contained in component (D4), which makes neutralization with the polymerizable monomer having an acidic group (A1) contained in the (I) dental adhesive composition less likely to occur, resulting in good durable adhesive strength.

[0056] Specific examples of component (D4) include N,N-dimethylbenzylamine, N-ethyl-N-methylbenzylamine, N,N-dimethyl-1-phenylethylamine, N,N-dimethylaminomethylphenol, N-methyl-N-(2-propyne-1-yl)benzylamine, 3-benzyloxazolidine, N,N-diethylbenzylamine, 3-[1-(dimethylamino)ethyl]phenol, 1-benzyl-3-pyrrolidone, 1-benzylpiperidine, N-benzyldiethanolamine, N-cyanodibenzylamine, N-benzyliminodiacetic acid, N-benzyl-3,3'-iminodipropionic acid, 1-benzhydryl-3-azetidinone, 1-(diphenylmethyl)-3-azetidinol, N,N-dibe Dibenzylaminoethanol, N,N-dibenzylaminopropanol, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4,6-tris(dimethylaminomethyl)phenol, dibenzylaminopropionaldehyde, tribenzylamine, dibenzylaminoethyl (meth)acrylate, dibenzylaminopropyl (meth)acrylate, benzylaminodiethyl (meth)acrylate, tris(2-picolyl)amine, N-(4-tert-butylbenzyl)-N-methyl-1-naphthalenemethaneamine, 3-dibenzylamino-2-fluoropronaphthalenemethylaminepionic acid benzyl ester, 9-[2-(dibenzylamino)ethyl]-6-methyl-2,3,4,9-Tetrahydro-1H-carbazole-1-one, (S)-(-)-2-(dibenzylamino)propionaldehyde, (S)-(+)-2-(dibenzylamino)-1-propanol, (S)-2-(dibenzylamino)-3-methylbutanol, 1-[(dibenzylamino)methyl]-2-naphthalene, (2S)-2-(dibenzylamino)-4-methyl-1-pentanol, and (S)-(+)-2-(dibenzylamino)- One or more selected from 3-phenyl-1-propanol, etc., and one or more selected from N-benzoylmeroquinene tert-butyl, 1-benzyl-4-piperidinecarboxylate ethyl, N-benzylnortropinone, 1-benzyl-3-methyl-4-piperidone, 1-benzyl-4-piperidinecarboxyaldehyde, 1-benzyl-4-piperidone, and 1-benzylpiperidine, etc., that have a heterocyclic structure. Furthermore, one or more benzyl-protected amino acids and benzyl-protected amino acid esters can be selected from, for example, N,N-dibenzylglycine ethyl, N-benzoyl-L-tyrosine ethyl, benzoyl-DL-phenylalanine, benzoyl-DL-alanine, benzoyl-DL-methionine, benzoyl-DL-leucine, benzoyl-DL-valine, N-benzoyl-L-glutamic acid, N-benzoyl-DL-phenylalanine 2-naphthyl, and N-benzoyl-L-tyrosine.

[0057] Among the compounds listed above, those having a benzyl group are preferred, and those having a dibenzyl group are even more preferred. Specifically, one or more selected from dibenzylaminoethyl (meth)acrylate, dibenzylaminopropyl (meth)acrylate, dibenzylaminoethanol, dibenzylaminopropanol, dibenzylmethylamine, N,N-dibenzylglycine ethyl, and tripenzylamine are examples.

[0058] The dental photocurable composition (II) included in the dental adhesive kit of the present invention preferably contains 0.5 to 5 parts by mass of component (D4) per 100 parts by mass of the total amount of polymerizable monomer (A). When it contains 0.5 parts by mass or more, good curing properties tend to be exhibited, and when it contains 5 parts by mass or less, ambient light stability tends to be good.

[0059] It is preferable that the dental adhesive composition (I) included in the dental adhesive kit of the present invention is substantially free of aliphatic tertiary amine compounds. The inclusion of aliphatic tertiary amine compounds may reduce the durable adhesive strength to enamel. "Substantially free" means intentionally not included, and it does not apply if they are included as impurities or trace components in the raw materials. More specifically, it is preferable that the amount of aliphatic tertiary amine compound is 0.1 parts by mass or less per 100 parts by mass of the dental adhesive composition (I). Specific examples of aliphatic tertiary amine compounds that are preferably substantially free include N-methylethanolamine and dimethylaminoethyl methacrylate.

[0060] (D) Compounds included in the photopolymerization initiator can be used in combination of multiple compounds.

[0061] <(E) Filler> The dental photocurable composition (II) included in the dental adhesive kit of the present invention contains (E) a filler (also referred to as "component (E)" in the present invention). Examples of (E) fillers include inorganic fillers, organic fillers, organic-inorganic composite fillers, and ion-releasing glass. The dental photocurable composition (II) of the present invention may use the exemplified fillers individually or in combination of two or more types.

[0062] While the chemical composition of inorganic fillers is not particularly limited, specific examples include one or more selected from silicon dioxide, alumina, titania, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramics, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. In particular, one or more selected from barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, and fluoroaluminosilicate glass, which are used in dental glass ionomer cement, resin-reinforced glass ionomer cement, and resin cement, can also be suitably used. The fluoroaluminosilicate glass referred to here has a basic framework of silicon oxide and aluminum oxide, and contains alkali metals for non-crosslinking oxygen introduction. Furthermore, it contains alkaline earth metals, including strontium, and fluorine as modifying and coordinating ions. In addition, it is a composition that incorporates elements from the lanthanide series into the framework to impart further X-ray opacity. These lanthanide series elements are also incorporated into the composition as modifying and coordinating ions depending on the composition range.

[0063] The inorganic filler may contain hydrophobic inorganic fine particles. The hydrophobic inorganic fine particles preferably have an average particle size of 0.1 to 50 nm, and the hydrophobicity is preferably achieved by treatment with a silane coupling agent and / or modified silicone oil. In addition to improving flexural strength, the inclusion of hydrophobic inorganic fine particles can also be expected to suppress sedimentation of the inorganic filler and impart rheological properties.

[0064] Specific examples of organic fillers include one or more polymers selected from polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, and polycarbonate.

[0065] Examples of organic-inorganic composite fillers include, but are not limited to, one or more selected from the following: an inorganic filler whose surface is polymerized and coated with a polymerizable monomer; an inorganic filler and a polymerizable monomer mixed and polymerized and then pulverized to an appropriate particle size; an inorganic filler dispersed in a polymerizable monomer beforehand and subjected to emulsion polymerization or suspension polymerization; an inorganic filler dispersed in a polymerizable monomer and a solvent beforehand, spray-dried and then polymerized; and an inorganic filler dispersed in a solvent beforehand, spray-dried, impregnated with a polymerizable monomer and then polymerized.

[0066] The ion-releasing glass is characterized by its ability to release at least one of the following ions: fluoride ions, strontium ions, borate ions, and aluminum ions. It is preferable that multiple of these ions are released simultaneously.

[0067] The ion-releasing glass used in this invention is not limited in any way, as long as it contains one or more glass skeleton-forming elements that form a glass skeleton and one or more glass-modifying elements that modify the glass skeleton. These ion-releasing glasses can be used individually or in combination with other ion-releasing glasses. Furthermore, in this invention, glass amphoteric elements that have the role of either a glass skeleton-forming element or a glass-modifying element depending on the glass composition are included in the category of glass skeleton-forming elements. Specific examples of glass skeleton-forming elements included in ion-releasing glass include one or more selected from silica, aluminum, boron, and phosphorus. Specific examples of glass-modifying elements include one or more halogen elements selected from fluorine, bromine, and iodine; one or more alkali metal elements selected from sodium and lithium; and one or more alkaline earth metal elements selected from calcium and strontium. Among these, it is preferable that the glass contains one or more elements selected from silica, aluminum, and boron as glass skeleton forming elements, and one or more elements selected from fluorine, sodium, and strontium as glass modifying elements. Specifically, examples include one or more elements selected from silica glass, fluoroaluminosilicate glass, fluoroborosilicate glass, and fluoroaluminoborosilicate glass, which contain one or more elements selected from strontium and sodium. Furthermore, from the viewpoint of gradually releasing one or more elements selected from fluoride ions, strontium ions, borate ions, and aluminum ions, fluoroaluminoborosilicate glass containing strontium is more preferable. A more preferred glass composition range is specifically SiO2: 10-40% by mass, Al2O3: 10-35% by mass, B2O3: 2.5-30% by mass, SrO: 15-50% by mass, F: 2.5-20% by mass, and Na2O: 0-15% by mass. This glass composition can be confirmed using instrumental analysis methods such as elemental analysis, Raman spectroscopy, and X-ray fluorescence analysis. However, there is no problem as long as the measured values ​​from any of these analytical methods fall within the specified compositional range.

[0068] There are no particular restrictions on the manufacturing method of these ion-releasing glasses, and they can be manufactured by methods such as melting or sol-gel processes. Among these, the melting method using a melting furnace is preferred in terms of the ease of designing the glass composition, including the selection of raw materials. The ion-releasing glasses used in the present invention have an amorphous structure, but there is no problem if they contain some crystalline structure, and there is no problem even if they are mixtures of glasses with amorphous structures and glasses with crystalline structures. Whether or not the glass structure is amorphous can be confirmed using analytical instruments such as X-ray diffraction analysis or transmission electron microscopes. Among these, the ion-releasing glasses used in the present invention are preferably amorphous in structure, as they release various ions in equilibrium with the ion concentration in the external environment.

[0069] Furthermore, in order to enhance the ion-releasing properties from ion-releasing glass, it is preferable to functionalize the glass surface by surface treatment to improve the ion-releasing properties. Specific examples of surface treatment materials used include one or more selected from surfactants, fatty acids, organic acids, inorganic acids, monomers, polymers, various coupling materials, silane compounds, metal alkoxide compounds and their partial condensates. Among these surface treatment materials, it is preferable to perform composite surface treatment using acidic polymers and silane compounds.

[0070] This composite surface treatment is a method in which the surface of an ion-releasing glass is coated with a silane compound, and then the surface is treated with an acidic polymer, which will be explained in detail below. A silane compound is mixed into an aqueous dispersion containing ion-releasing glass that has been finely ground to a desired average particle size by grinding or the like, and this is hydrolyzed or partially hydrolyzed in system to obtain a silanol compound, which is then condensed to obtain a polysiloxane, and the surface of the ion-releasing glass is coated with it to obtain a polysiloxane-coated ion-releasing glass.

[0071] Specific examples of silane compounds that can be used for polysiloxane coating include one or more selected from tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraalyloxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, trimethoxychlorosilane, triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane, diethoxydichlorosilane, tetraphenoxysilane, tetrachlorosilane, and silicon hydroxide (silicon oxide hydrate), with tetramethoxysilane and / or tetraethoxysilane being more preferred.

[0072] Furthermore, it is more preferable that the silane compounds used for polysiloxane coating are low-condensation compounds. For example, low-condensation silane compounds obtained by partially hydrolyzing and condensing tetramethoxysilane and / or tetraethoxysilane. These compounds can be used alone or in combination.

[0073] The polysiloxane-coated ion-sustaining glass obtained in the previous step can be subjected to an acidic polymer treatment, in which an acidic polymer is reacted to produce ion-sustaining glass. The acidic polymer treatment can be carried out using any dry-flow type agitator commonly used in the industry, such as a Hensil mixer, super mixer, or high-speed mixer. The reaction of the acidic polymer with the polysiloxane-coated ion-sustaining glass can be carried out by contacting it with the acidic polymer solution through impregnation or spraying. For example, the polysiloxane-coated ion-sustaining glass can be dry-flowed, and the acidic polymer solution can be dispersed from above while it is flowing, followed by thorough stirring. While there are no particular restrictions on the dispersion method of the acidic polymer solution, a dropping or spraying method that allows for uniform dispersion is more preferable. Furthermore, the reaction is preferably carried out at around room temperature, as higher temperatures accelerate the reaction between the acid-reactive elements and the acidic polymer, resulting in uneven formation of the cement phase.

[0074] It is preferable to remove moisture from the cement reaction phase by performing heat treatment after the reaction. If moisture remains in the cement reaction phase, it will be disadvantageous in terms of strength, but the filler of the present invention has its reduction in mechanical strength suppressed by the polysiloxane coating. The heat treatment method after acid polymer treatment is not particularly limited and can be carried out by known general methods. Preferred equipment for heat treatment is a box-type hot air dryer or a rotary heat treatment device that can heat uniformly. The heat treatment temperature is in the range of room temperature to 200°C, more preferably in the range of 40 to 150°C. If the temperature is lower than this range, the removal of the aqueous medium will be insufficient, and if it is higher than this range, the organic layer of the acid polymer may decompose or discolor. The heat treatment time depends on the capacity of the dryer, etc., so there is no problem as long as it is long enough to sufficiently remove the aqueous medium. After heat treatment, the heat-treated material can be easily crushed by applying shear force or impact force, and the crushing method can be carried out using the equipment used in the above reaction.

[0075] The solvent used to prepare the acidic polymer solution for the reaction can be any solvent that dissolves the acidic polymer, and can be selected from one or more options such as water, ethanol, isopropanol, and acetone. Of these, water is particularly preferred because it allows the acidic groups of the acidic polymer to dissociate and react uniformly with the surface of the basic filler core.

[0076] The weight-average molecular weight of the acidic polymer is in the range of 2,000 to 50,000, preferably in the range of 5,000 to 40,000. When treated with an acidic polymer having a weight-average molecular weight of less than 2,000, the acidic polymer reaction phase does not form in the polysiloxane-coated ion-sustaining glass, resulting in a tendency for low ion-sustaining performance. On the other hand, when treated with an acidic polymer having a weight-average molecular weight exceeding 50,000, the viscosity of the acidic polymer solution increases, making it difficult to treat the polysiloxane-coated ion-sustaining glass homogeneously. Furthermore, the concentration of the acidic polymer in the acidic polymer solution is preferably in the range of 3 to 25 parts by mass, more preferably in the range of 8 to 20 parts by mass. If the acidic polymer concentration is less than 3 parts by mass, the acidic polymer reaction phase described above becomes fragile, and the effect of improving ion-sustaining performance cannot be obtained. Furthermore, if the acidic polymer concentration exceeds 25 parts by mass, it becomes difficult to diffuse uniformly through the polysiloxane layer (porous), resulting in a non-homogeneous acidic polymer reaction phase. Additionally, the reaction occurs immediately upon contact with the polysiloxane-coated ion-releasing glass, leading to problems such as the formation of strongly reacted aggregates. The amount of acidic polymer solution added to the polysiloxane-coated ion-releasing glass is preferably in the range of 6 to 40 parts by mass, and more preferably 10 to 30 parts by mass. Based on this addition amount, the optimal amount of acidic polymer relative to the polysiloxane-coated ion-releasing glass is 1 to 7 parts by mass, and the optimal amount of water is in the range of 10 to 25 parts by mass.

[0077] The acidic polymer that can be used to form an acidic polymer reaction phase on the surface of polysiloxane-coated ion-releasing glass by the above method can be any copolymer or homopolymer of polymerizable monomers having acidic groups such as phosphate residues, pyrophosphate residues, thiophosphate residues, carboxylic acid residues, or sulfonic acid residues, without any problems. Specific examples of these polymerizable monomers include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic anhydride, 5-(meth)acryloylaminopentylcarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 2-(meth)acryloyloxyethyl dihydrogen phosphate, and 10-(meth)acryloyloxydecyl dihydrogen phosphate. One or more selected from the following: 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, 1,3-di(meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl phosphate, 2-(meth)acryloyloxyethyl-2'-bromoethyl phosphate, (meth)acryloyloxyethylphenyl phosphonate, di(2-(meth)acryloyloxyethyl) pyrophosphate, 2-(meth)acryloyloxyethyl dihydrogen dithiophosphophosphate, and 10-(meth)acryloyloxydecyl dihydrogen thiophosphate. Among the polymers (co)polymerized using these polymerizable monomers, it is preferable to use homopolymers or copolymers of α-β unsaturated carboxylic acids that undergo relatively slow acid-base reactions with acid-reactive elements contained in polysiloxane-coated ion-sustaining glass. Specifically, one or more selected from acrylic acid polymers, acrylic acid-maleic acid copolymers, and acrylic acid-itaconic acid copolymers are used.

[0078] The above-mentioned (E) filler can be treated with a surface treatment material, such as a silane coupling agent, for the purpose of improving its affinity with polymerizable monomers, dispersibility in polymerizable monomers, mechanical strength of the cured product, and water resistance. Such surface treatment materials and surface treatment methods are not particularly limited, and known methods can be used without limitation, such as spraying the surface treatment material while stirring the powdered filler, dispersing and mixing the filler and surface treatment material in a solvent, or supplying a silane coupling agent in vapor or gaseous form to the surface of the filler. Preferred silane coupling agents used for surface treatment of fillers include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, or hexamethyldisilazane. In addition to silane coupling agents, surface treatment of fillers can also be performed by using one or more selected from titanate-based coupling agents and aluminate-based coupling agents. The amount of surface treatment material applied to the filler is preferably 0.01 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the filler before treatment.

[0079] (E) The shape of the filler is not particularly limited, and fillers of any shape such as spherical, needle-shaped, plate-shaped, crushed, or flaky can be used. The average particle size of the filler is preferably in the range of 0.01 μm to 50 μm, more preferably 0.01 μm to 30 μm, even more preferably 0.05 μm to 20 μm, and particularly preferably 0.05 μm to 10 μm.

[0080] [(E1) Hydrophobic silica fine particles with a primary particle size of less than 0.1 μm] The (II) dental photocurable composition of the present invention contains (E1) hydrophobic silica fine particles having a primary particle diameter of less than 0.1 μm (also referred to as "component (E1)" in the present invention). Component (E1) is used as a viscosity modifier in the present invention. By using component (E1), rheological properties are exhibited, resulting in good operability where the dental photocurable composition does not drip appropriately. Furthermore, because the dental photocurable composition can be positioned appropriately, good durable adhesive strength can also be expected. The use of hydrophobic silica fine particles having a primary particle diameter of less than 0.1 μm as a viscosity modifier in the present invention is preferable because it is an inorganic filler, which is important as it can be expected to improve mechanical strength, and it is less likely to cause a decrease in curability when reacting with polymerization initiators and the like contained in the (I) dental adhesive composition and (II) dental photocurable composition of the present invention.

[0081] Specific methods for hydrophobizing hydrophobic silica nanoparticles include surface treatment with a modified silicone oil such as dimethyl silicone oil, and / or surface treatment with a silane coupling agent having one or more functional groups selected from a trimethylsilyl group, a dimethylsilyl group, a methylsilyl group, and an alkylsilyl group which may have an alkyl chain having 3 to 18 carbon atoms and a (meth)acryloyl group. It is preferable that the silane coupling agent hydrophobizes the silica nanoparticles via covalent bonds.

[0082] Specific examples of modified silicone oils and silane coupling agents include polydimethylsiloxane, hexamethyldisilazane, dimethylpolysiloxane, methylchlorosilane, alkyltrialkoxysilane, dialkyldialkoxysilane, alkylalkoxysilanes such as octadecylalkoxysilane and octylalkoxysilane, and one or more (meth)acryloylalkylalkoxysilanes selected from 3-methacryloylpropyltrimethoxysilane and 8-methacryloyloctyltrimethoxysilane, etc.

[0083] To further improve the rheological properties, silica nanoparticles may be hydrophobized in several ways. For example, they may be treated with a silane coupling agent and / or a modified silicone oil, or simultaneously with a surface treatment agent.

[0084] (E1) Examples of hydrophobic silica fine particles with a primary particle diameter of less than 0.1 μm include dry silica, silica aerogel, and wet silica, but dry silica is more preferred.

[0085] Among the hydrophobic silica nanoparticles listed above, dry silica is manufactured and sold commercially under the trade name Aerosil by, for example, Nippon Aerosil Co., Ltd. For example, Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, and also silica fine powders with a hydrophobic surface treatment, such as Aerosil R972, Aerosil R974, Aerosil R976, Aerosil R976S, Aerosil R202, Aerosil R812, Aerosil R812S, Aerosil R805, Aerosil R104, Aerosil R106, RY200, RX200, R711, RY200S, RA200H, R8200, and RA200HS, may be used.

[0086] (E1) The amount of hydrophobic silica fine particles with a primary particle diameter of less than 0.1 μm is 0.5 to 20 parts by mass per 100 parts by mass of polymerizable monomer (A) contained in (II) dental photocurable composition. When the amount is 0.5 parts by mass or more per 100 parts by mass of polymerizable monomer (A), rheological properties tend to be exhibited in (II) dental photocurable composition, and when it is 20 parts by mass or less, the operability of (II) dental photocurable composition tends to be good.

[0087] In this invention, the primary particle diameter refers to the average primary particle diameter. (E) The primary particle diameter of the filler can be the average calculated based on the particle size distribution measured by, for example, a laser diffraction particle size distribution analyzer. For example, it can be measured by a laser diffraction particle size analyzer (Microtrac MT3300EXII: manufactured by Nikkiso Co., Ltd.). When measuring using a laser diffraction particle size analyzer, the measurement is performed after dispersing the filler with ultrasound or the like to ensure uniformity. In addition, the primary particle diameter can be measured by dynamic light scattering particle size measurement, or, in the case of primary particles that have strongly aggregated to form secondary particles, by using electron microscope images. For fillers with a primary particle diameter of less than 0.1 μm, it is preferable to calculate the primary particle diameter from electron microscope images, and for those with a primary particle diameter of 0.1 μm or more, it is preferable to calculate the primary particle diameter using a laser diffraction particle size distribution analyzer.

[0088] The (II) dental photocurable composition of the present invention contains (E) a filler, preferably in an amount of 10 to 400 parts by mass per 100 parts by mass of the polymerizable monomer (A) contained in the (II) dental photocurable composition. Containing 10 parts by mass or more tends to result in good operability and durable adhesive strength, while containing 400 parts by mass or less tends to result in particularly good paste properties and ease of use.

[0089] The (I) dental adhesive composition of the present invention preferably does not contain (E) fillers. The (I) dental adhesive composition contains (D1) aromatic tertiary amine compounds, and therefore has poor color stability when it is sufficiently thick. However, in actual use, the film thickness is thin, so even if discoloration occurs, it will not be visible. The thinness of the film thickness is important as it also affects the durable adhesive strength, and in the present invention, the film thickness of the (I) dental adhesive composition is preferably 50 μm or less, preferably 20 μm or less, and more preferably 5 μm or less.

[0090] [Chemical polymerization initiator] The dental adhesive kit of the present invention may contain a chemical polymerization initiator. Chemical polymerization is a polymerization method that hardens without requiring special equipment such as a light curing unit, and a chemical polymerization initiator is a polymerization initiator that can start chemical polymerization. Commonly used, known compounds can be used without any limitations.

[0091] Specific examples of transition metal compounds that can be used in the dental adhesive kit of the present invention include copper (Cu) compounds or vanadium (V) compounds, which can be preferably used. As copper (Cu) compounds, one or more can be selected from copper chloride (monovalent), copper bromide (monovalent), copper chloride (divalent), copper acetate (divalent), copper gluconate (divalent), copper acetylacetone (divalent), and copper methacrylate (divalent). As vanadium compounds, one or more can be selected from acetylacetone vanadium (trivalent), divanadium tetroxide (tetravalent), vanadylacetylacetonate (tetravalent), vanadium stearate oxide (tetravalent), vanadyl oxalate (tetravalent), vanadyl sulfate (tetravalent), oxobis(1-phenyl-1,3-butanedione)vanadium (tetravalent), bis(maltrate)oxovanadium (tetravalent), vanadium pentoxide (pentavalent), and sodium metavanadate (pentavalent).

[0092] Specific examples of thiourea compounds that can be used in the dental adhesive kit of the present invention include one or more selected from dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl)thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, N-benzylthiourea, 1,3-dicyclohexylthiourea, N,N'-diphenylthiourea, 1,3-di(p-tolyl)thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea, and dicyclohexylthiourea. Among these, one or more selected from (2-pyridyl)thiourea, N-acetylthiourea, N-benzoylthiourea, and N-benzylthiourea can be used.

[0093] Organic peroxides that can be used in the dental adhesive kit of the present invention include one or more selected from diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, peroxyesters, peroxydicarbonates, and hydroperoxides. Among these, one or more selected from t-butyl peroxy-2-ethylhexanoate, t-butyl peroxybenzoate, t-amyl peroxy-2-ethylhexanoate, t-amyl peroxyacetate, t-amyl peroxybenzoate, 1,1-di(t-butyl peroxy)cyclohexane, 1,1-di(t-amyl peroxy)cyclohexane, dibenzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0094] Other chemical polymerization initiators include one or more selected from phosphine compounds, sulfinic acid compounds, borate compounds, barbituric acid derivatives, and ascorbic acid compounds. Specific examples of phosphine compounds include one or more phosphine compounds selected from triphenylphosphine and 4-(phenylphosphino)benzoic acid. Specific examples of sulfinic acid compounds include one or more sulfinic acid compounds selected from sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate. Borate compounds include one or more borate compounds selected from sodium salts, lithium salts, potassium salts, and tetrabutylammonium salts of tetraarylborate compounds. Barbituric acid derivatives include one or more barbituric acid derivatives selected from 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, and sodium or calcium salts of the aforementioned barbituric acid derivatives. Specific examples of ascorbic acid compounds include one or more ascorbic acid compounds selected from ascorbic acid, ascorbyl 6-palmitate, and salt compounds of the aforementioned ascorbic acid compounds.

[0095] The polymerization initiators included in the dental adhesive kit of the present invention can be subjected to secondary treatments such as fine grinding, carrier adsorption, or encapsulation in microcapsules as needed, without any problems. Furthermore, these various types of polymerization initiators can be used individually or in combination of two or more, regardless of the polymerization mode or method.

[0096] [(F) Compounds containing a disulfide group] The dental adhesive composition (I) contained in the dental adhesive kit of the present invention contains (F) a compound containing a disulfide group (also referred to as "component (F)" in the present invention). If the compound containing a disulfide group (F) has a polymerizable group and corresponds to component (A), it is treated as component (F) in the present invention. This is because although component (F) has copolymerizability due to the presence of a polymerizable group, the amount included is less than that of component (A).

[0097] (I) The dental adhesive composition exhibits good durable adhesive strength to enamel due to the presence of (A1) a polymerizable monomer having an acidic group and (D1) an aromatic tertiary amine compound. However, when (A1) a polymerizable monomer having an acidic group and (D1) an aromatic tertiary amine compound are present together, discoloration and gelation of (I) the dental adhesive composition may occur. It has been confirmed that the above-mentioned discoloration and gelation can be suppressed when component (F) is added to (I) the dental adhesive composition. Furthermore, it has been confirmed that the suppression of discoloration and gelation by component (F) tends to be effective even in small amounts, and that its effect on durable adhesive strength is less than that of known stabilizing agents. The upper limit of the amount of component (F) to be added is preferably 0.001 parts by mass or more, and more preferably 0.01 parts by mass or more, per 100 parts by mass of (I) the dental adhesive composition. Furthermore, the amount of component (F) is preferably 0.001 to 2 parts by mass, and more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the dental adhesive composition (I). When the amount is 0.001 parts by mass or more, discoloration and gelation tend to be suppressed, and when it is 2 parts by mass or less, good durable adhesive strength can be maintained.

[0098] Examples of compounds containing a (F) disulfide group include one or more selected from 10-methacryloxydecyl-6,8-dithiocanate, 6-methacryloxyhexyl-6,8-dithiocanate, 2-methacryloyloxyethyl thioctic acid, thioctic acid (lipoic acid), N,N'-bis(acryloyl)cystamine, bis(2-hydroxyethyl) disulfide, diflufuryl disulfide, and bis(3-carboxypropyl) disulfide. In addition to the compounds containing the (F) disulfide group described, any known compound having a disulfide group (-SS-) can be used. Examples of (F) components that can be preferably used include compounds having a structure derived from a thioctic group. Specifically, one or more compounds selected from 10-methacryloxydecyl-6,8-dithiocanate, 6-methacryloxyhexyl-6,8-dithiocanate, 2-methacryloyloxyethyl thioctic acid, and thioctic acid (lipoic acid) are examples. When such compounds are used, discoloration and gelation can be suppressed with smaller amounts. Among these, thioctic acid is even more preferred. When a large amount of highly hydrophobic compounds such as 10-methacryloxydecyl-6,8-dithiocanate is included, the (I) dental adhesive composition containing water may become cloudy or precipitates may form in the composition. On the other hand, thioctic acid (lipoic acid) has a low molecular weight and is less hydrophobic than 10-methacryloxydecyl-6,8-dithiocanate, so the possibility of precipitation occurring in the (I) dental adhesive composition is greatly reduced. Although thioctic acid (lipoic acid) is an optical isomer, either the R-form or the L-form is acceptable when used in the present invention. It is not a problem if thioctic acid (lipoic acid) contains some oxidized beta-lipoic acid or reduced dihydrolipoic acid.

[0099] <Other ingredients> Furthermore, the dental photocurable composition of the present invention may contain components other than those listed in (A) to (F) above, as long as they do not hinder the effects of the present invention. For example, components such as benzophenone-based and benzotriazole-based ultraviolet absorbers, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and 2,5-diter-butyl-4-methylphenol, mercaptan compounds such as α-alkylstyrene compounds, n-butyl mercaptan, and n-octyl mercaptan, chain transfer agents such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, and α-pinene terpenoid compounds, metal scavenging agents such as aminocarboxylic acid-based chelating agents and phosphonic acid-based chelating agents, discoloration inhibitors, antibacterial agents, coloring pigments, and other conventionally known additives can be added as needed.

[0100] The dental adhesive composition of the dental adhesive kit of the present invention may contain only components (A), (B), (C), and (D). Alternatively, it may contain only one or more of the above-mentioned components as components other than (A) to (D).

[0101] The (II) dental photocurable composition of the dental adhesive kit of the present invention may contain only components (A), (D), and (E). Alternatively, it may contain only one or more of the above-mentioned components as components other than (A), (D), and (E).

[0102] The method of using the dental adhesive kit of the present invention involves (I) applying the dental adhesive composition to the substrate, followed by appropriate air drying. Subsequently, the surface of the applied (I) dental adhesive composition may or may not be irradiated with light. With regard to the dental adhesive kit of the present invention, it is preferable not to irradiate the surface of the applied (I) dental adhesive composition with light. This is because irradiating with light increases the number of operating steps, and when light irradiation is not performed, the durable adhesive strength is better. In general combinations consisting of dental bonding material and dental composite resin, the surface of the applied dental bonding material is irradiated with light, so the dental adhesive kit of the present invention differs in this respect. The dental adhesive kit of the present invention is used in a procedure in which the (II) dental photocurable composition is laminated onto the surface of the applied (I) dental adhesive composition, and the (II) dental photocurable composition is irradiated with light to cure the (II) dental photocurable composition.

[0103] When using the dental bonding kit of the present invention, a dental etching material can also be used in combination. A dental etching material is a material containing an acidic compound and water, and those containing phosphoric acid as the acidic compound are called phosphoric acid etching materials. In particular, when bonding to unground enamel, using a dental etching material in combination may result in even higher adhesive strength. A dental etching material is a composition containing an acidic component such as phosphoric acid, water, and an appropriate rheological modifier, and is used to create surface irregularities by demineralizing the enamel surface. When used in combination with the dental bonding kit of the present invention, the process can be carried out in the following order: (I) treatment with a dental etching material, (II) application of a dental adhesive composition, and (II) lamination of a dental photocurable composition. On the other hand, the use of a dental etching material increases the number of operating steps.

[0104] The dental adhesive kit of the present invention can also be used by following only the procedure of (I) applying a dental adhesive composition to a surface without irradiating it with light, (II) laminating a dental photocurable composition, and (II) irradiating the dental photocurable composition with light. [Examples]

[0105] The materials used in the examples and comparative examples, along with their abbreviations, are shown below. [(A) Polymerizable monomers] <(A1) Polymerizable monomer having an acidic group> MDP: 10-Methacryloyloxydecyldihydrogen phosphate • MET:4-methacryloxyethyl trimellitic acid • META:4-Methacryloyloxyethoxycarbonylphthalic anhydride <(A2) Polymerizable monomers that do not have acidic groups> • BisGMA: 2,2-Bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane UDMA: N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)ethanol]methacrylate TEGDMA: Triethylene glycol dimethacrylate GDMA: Glycerol dimethacrylate • HEMA: Hydroxyethyl methacrylate MPTMS: (3-methacryloyloxypropyl)trimethoxysilane

[0106] [(B)Water] DW: Distilled water

[0107] [(C) Volatile organic solvent] • EtOH: Ethanol • Ac: Acetone

[0108] [(D) Photopolymerization initiator] <(D1) Aromatic tertiary amine compound> • DMBE: Ethyl dimethylaminobenzoate DMBN: 4-(dimethylamino)benzonitrile DEPT: N,N-di(2-hydroxyethyl)-p-toluidine <(D2)α-diketone compound> • CQ: Camphorquinone <(D3) Iodonium salt compounds> • TBIB: Bis(p-tert-butylphenyl)iodonium tetraquispentafluorophenyl borate • CTIP: p-Cumenyl(p-Tolyl)iodonium tris(pentafluoroethyl)trifluorophosphate • TBIG: Bis(p-tert-butylphenyl)iodonium tetraquispentafluorophenyl gallate <(D4) Aliphatic tertiary amine compounds having an aromatic ring> TBA: Tribenzylamine DBMA: N-benzyl-N-methylbenzylamine • DBAE: N,N-Dibenzylglycine ethyl <Other photopolymerization initiators> • DMAEMA: Dimethylaminoethyl methacrylate • MDEA: N-methyldiethanolamine

[0109] [(E) Fillers] (Filler E-1) To 100g of zirconium silicate filler (average particle size 1.5 μm: 20 wt% zirconia, 80 wt% silica), a silane coupling treatment solution containing 20g of water, 35g of ethanol, and 3g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent was added and stirred for 2 hours. Subsequently, the mixture was heat-treated at 90°C for 15 hours, followed by a sieving process to obtain filler E-1.

[0110] (Filler E-2) To 100g of barium silicate filler (average particle size 1 μm, Al2O3: 10 wt%, B2O3: 10 wt%, BaO: 25 wt%, SiO2: 55 wt%), 20g of water, 35g of ethanol, and a silane coupling treatment solution containing 6g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were added and stirred for 2 hours. After that, the mixture was heat-treated at 90°C for 15 hours, followed by a sieving process to obtain packing material E-2.

[0111] (Filler E-3) To 100g of fluoroaluminoborosilicate glass (average particle size 1 μm, SiO2: 22.5 wt%, Al2O3: 20.0 wt%, B2O3: 12.3 wt%, SrO: 35.7 wt%, Na2O: 2.5 wt%, F: 7.0 wt%), a silane coupling treatment solution containing 20g of water, 35g of ethanol, and 6g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent was added and stirred for 2 hours. After that, the mixture was heat-treated at 90°C for 15 hours, followed by a sieving process to obtain packing material E-3.

[0112] (Filler E-4) To 100g of fluoroaluminoborosilicate glass (average particle size 1 μm, SiO2: 22.5 wt%, Al2O3: 20.0 wt%, B2O3: 12.3 wt%, SrO: 35.7 wt%, Na2O: 2.5 wt%, F: 7.0 wt%), 4.5 g of the low-condensate silane compound "MKC Silicate MS56S" (SiO2 content 56.0 mass%, degree of polymerization 2-100, manufactured by Mitsubishi Chemical Corporation) was added and stirred for approximately 90 minutes. After mixing for the specified time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours, and then cooled to obtain a heat-treated product. The obtained heat-treated product was placed in a Henschel mixer and crushed at 1800 rpm for 5 minutes. Next, 16.0 g of an aqueous polyacrylic acid solution (polymer concentration 13% by mass, weight-average molecular weight 10,000: manufactured by Nacalai Tesque Co., Ltd.) was sprayed from above. After spraying, the powder removed from the mixer was heated in a hot air dryer at 100°C for 3 hours. To 100 g of the prepared filler, 100 g of water, 80 g of ethanol, and 9 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours to obtain a silane coupling solution, which was then stirred and mixed for 30 minutes. After that, heat treatment was performed at 90°C for 15 hours to obtain filler E-4.

[0113] (Filler E-5) A uniform matrix was prepared by mixing 60 parts by mass of BisGMA, 40 parts by mass of TEGDMA, and 0.2 parts by mass of BPO. A cured product was obtained by mixing and polymerizing the matrix with 300 parts by mass of fluoroboroaluminosilicate glass (average primary particle size 0.5 μm), 15 parts by mass of Aerosil R711, and 15 parts by mass of γ-methacryloxypropyltrimethoxysilane using a kneader under a nitrogen atmosphere. The cured product was obtained by coarse grinding of the cured product using a roll crusher and fine grinding using a vibratory mill to obtain a finely ground product with an average particle size of 20 μm. 100 parts by mass of the sieved finely ground product was mixed with 1 part by mass of water, 1 part by mass of ethanol, and 6 parts by mass of γ-methacryloxypropyltrimethoxysilane, and dried at 90°C for 10 hours to obtain filler E-5, an organic-inorganic composite filler.

[0114] (Filler E-6) • Titanium dioxide (average particle size 0.25 μm)

[0115] <(E1) Hydrophobic silica fine particles with a primary particle size of less than 0.1 μm> (Filler E1-1) • Aerosil R-8200 (manufactured by Evonik) (Filler E1-2) • Aerosil R-711 (manufactured by Evonik)

[0116] <(F) Compounds containing a disulfide group> MDDT:10-Methacryloxydecyl-6,8-dithiocanate MEDT: 2-methacryloyloxyethyl thioctic acid THAC: Thioctic acid

[0117] [others] [Polymerization inhibitor] • MeHQ: p-methoxyphenol BHT: Dibutylhydroxytoluene [UV absorber] OB: 2-Hydroxy-4-(octyloxy)benzophenone [Fluorescent dye] • FA: 2.5-Diethyl dihydroxyterephthalate

[0118] <Manufacturing Example 1-1: (I) Method for Manufacturing Dental Adhesive Composition (1-1)> All the ingredients listed in Table 1 were placed in a wide-mouthed plastic container and mixed using a VMRC-5 mix rotor at 100 rpm for 48 hours to obtain (I) dental adhesive composition (1-1). In Table 1, the parts by mass of each component are indicated in parentheses after the abbreviation of each component.

[0119] <Manufacturing Examples 1-2 to 1-11 and Comparative Manufacturing Examples 1-1 to 1-4> Manufacturing Examples 1-2 to 1-11 and Comparative Manufacturing Examples 1-1 to 1-4 were obtained using the same method as Manufacturing Example 1-1, except that the composition was changed as described in Tables 1 to 2. Note that the manufacturing example numbers correspond to the numbers of (I) dental adhesive compositions.

[0120] <Production Example 2-1: (II) Method for producing dental photocurable composition (2-1)> All of the materials except for the (E) filler shown in Table 3 were placed in a wide-mouthed plastic container and mixed for 48 hours at 100 rpm using a VMRC-5 mix rotor to obtain the matrix. Then, the matrix and the (E) filler were placed in a kneader, mixed uniformly, and degassed under vacuum to obtain (II) dental photocurable composition (2-1). In Table 3, the mass of each component is indicated in parentheses after the abbreviation of each component.

[0121] <Manufacturing Examples 2-2 to 2-15 and Comparative Manufacturing Examples 2-1 to 2-4> Manufacturing Examples 2-2 to 2-15 and Comparative Manufacturing Examples 2-1 to 2-4 were obtained using the same method as Manufacturing Example 2-1, except that the composition was changed as described in Tables 3 to 4. Note that the manufacturing example numbers correspond to the dental curable composition numbers.

[0122] <Evaluation 1: Durable adhesive strength> Test specimens of bovine central incisors embedded in epoxy resin were polished with #500 grit waterproof abrasive paper, then with #1000 grit waterproof abrasive paper to remove the enamel surface. Subsequently, the (I) dental adhesive composition described in the examples was applied to the bonding surface and air-dried. Only in Example 21, after air-drying the surface coated with (I) dental adhesive composition, light irradiation was performed. In Example 23, a dental etching material (Opal Etch, manufactured by ULTRADENT) was applied to the enamel surface, washed with water, and air-dried, after which the (I) dental adhesive composition was applied, air-dried, and then light irradiation was performed. Light irradiation was performed for 5 seconds using a dental polymerization LED light curing unit (Penbright, manufactured by Matsukaze Co., Ltd.). Next, a φ2.38 mm perforated mold (manufactured by Ultradent Co., Ltd.) was placed on top of the surface coated with (I) dental adhesive composition. After laminating the (II) dental photocurable composition described in the example, the surface was irradiated with a dental polymerization LED light curing unit (Penbright, manufactured by Matsukaze Co., Ltd.) for 10 seconds. After removing the mold, the prepared adhesive test specimen was immersed in 37°C water for 24 hours, and then immersed in a 4°C cold water phase and a 60°C high-temperature phase for 30 seconds each, 5,000 times using a thermal shock tester (manufactured by Thomas Scientific Instruments Co., Ltd.). Subsequently, the prepared test specimen was subjected to a shear test using a universal testing machine (manufactured by Instron Co., Ltd.) at a crosshead speed of 1 mm / min. A test result of 20 MPa or more was considered to be an extremely good durable adhesive strength. A result of 15 MPa or more but less than 20 MPa was considered to be an average durable adhesive strength, and a result of less than 15 MPa was considered to be an insufficient durable adhesive strength.

[0123] <Evaluation 2: Color Stability> (II) After filling a stainless steel mold (15φ × 1 mm: disc-shaped) with the dental photocurable composition, a cover glass was placed on top and pressed down with a glass plate. The cover glass was then cured by irradiating it with a dental polymerization LED light curing unit (Penbright, manufactured by Matsukaze Co., Ltd.) for 1 minute. After removing the cured product from the mold, the cover glass was removed. After polishing one side of the cured body of (II) dental photocurable composition with waterproof abrasive paper #500, (I) dental adhesive composition was applied to the surface of the cured body of (II) dental photocurable composition and air-dried. In Example 21 only, the surface coated with (I) dental adhesive composition was air-dried before light irradiation. Light irradiation was performed for 5 seconds using a dental polymerization LED light curing unit (Penbright, manufactured by Matsukaze Co., Ltd.). Color measurement was performed on the side of the cured body of (II) dental photocurable composition that was not coated with (I) dental adhesive composition. Colorimetric measurements were performed using a spectrophotometer (manufactured by Vic Chemie) with the test specimen placed on a standard white plate (D65 / 10° X=81.07, Y=86.15, Z=93.38) background, under predetermined conditions (light source: C, field of view: 2°, measurement area: 11 mm). Subsequently, the specimen was exposed to light for 24 hours using a xenon lamp light exposure tester (Suntest CPS+) with the uncoated side of the (I) dental adhesive composition of the cured (II) dental photocurable composition as the exposure side. The color tone of the test specimen was then measured again, and the difference in discoloration was expressed as ΔE calculated using the following formula. ΔE = {(ΔL*)} 2 +(Δa*) 2 +(Δb*) 2} 1 / 2 ΔL* = L1* - L2* Δa* = a1* - a2* Δb* = b1* - b2* Here, L1* is the lightness index before light exposure, L2* is the lightness index after light exposure, a1* and b1* are the color quality indices before light exposure, and a2* and b2* are the color quality indices after light exposure. A was assigned to those with a ΔE of less than 9, which was considered the best, and C was assigned to those with a ΔE of 9 or more, which was considered undesirable. Good color stability means that there is less discoloration when used and high aesthetic appeal can be maintained.

[0124] <Evaluation 3: (I) Confirmation of the stability of the dental adhesive composition> 5 mL of the prepared (I) dental adhesive composition was filled into a polypropylene bottle and sealed with a cap. After visually checking the color of the (I) dental adhesive composition before storing it in an incubator, it was stored in an incubator set to 50°C for 2 months. After storage, the (I) dental adhesive composition was discharged from the bottle and visually checked the color before and after storage in an incubator set to 50°C. If there was no change in color or only a slight change in color, it was considered acceptable (A), and if there was a significant change in color, it was considered undesirable (B). A significant change in the color of the (I) dental adhesive composition is undesirable because it may cause discomfort to the practitioner.

[0125] The results of each test, shown in Tables 5-6, are described below.

[0126] [Table 1]

[0127] [Table 2]

[0128] [Table 3]

[0129] [Table 4]

[0130] [Table 5]

[0131] [Table 6]

[0132] The compositions described in the examples were confirmed to possess both good durable adhesion to enamel and color stability.

[0133] Examples 4 and 5 tended to have slightly inferior durable adhesive strength. This is thought to be due to the low amount of component (D2) in manufacturing example 2-4 and the low amount of component (D3) in manufacturing example 2-5.

[0134] Examples 18, 19, and 20 tended to exhibit slightly inferior durable adhesive strength. This is thought to be due to the inclusion of component (E) in production examples 1-9, the low amount of component (A1) (less than 3 parts by mass) in production example 1-10, and the inclusion of an aliphatic tertiary amine compound having an aromatic ring (D4) in production example 1-11.

[0135] In Examples 10, 19, and 20, (I) the color stability of the dental adhesive composition was poor. This is thought to be due to the absence of component (F) in Production Examples 1-8, 1-10, and 1-11.

[0136] In Example 21, (I) a dental adhesive composition was applied, followed by light irradiation, and then (II) a dental photocurable composition was applied. Compared to Example 1, in which (I) the dental adhesive composition was not applied and then light irradiation was not performed, the durable adhesive strength tended to be lower.

[0137] Example 22 tended to have low durable adhesive strength. This is thought to be due to the cloudy appearance of Manufacturing Examples 1-12, and the cause of the cloudiness is thought to be the high amount of MDDT added. (I) Among the components, THAC is preferable due to its high solubility in dental adhesive compositions.

[0138] Example 23 showed the best durable adhesive strength among the examples conducted, but the procedure was more complicated compared to the other examples because it involved treating the enamel with a dental etching material.

[0139] Comparative Examples 1-3 tended to have poor color stability. This is thought to be due to the inclusion of component (D1) in Comparative Production Examples 2-1-2-3. Next, Comparative Examples 4-7 tended to have poor durable adhesive strength. In Comparative Example 4, this is thought to be due to the fact that Comparative Production Example 2-4 did not contain components (D1) and (D4), and when combined with a dental adhesive composition (I) with a low amount of component (A1), such as Production Example 1-10, sufficient adhesive strength may not be achieved. In Comparative Examples 5 and 6, this is thought to be due to the fact that Comparative Production Example 1-1 and Comparative Production Example 1-2 did not contain component (D1). In Comparative Example 7, this is thought to be due to the fact that Comparative Production Example 1-3 did not contain component (B).

[0140] The dental adhesive kit evaluated in the examples can be used for composite resin, resin cement, dental core buildup materials, orthodontic materials, dental pit and fissure sealing materials, and dental mobility fixation materials. Among these, the dental orthodontic materials, dental pit and fissure sealing materials, and dental mobility fixation materials are particularly suitable for use because they require high durability and adhesive strength to enamel. [Industrial applicability]

[0141] According to the present invention, it is possible to achieve both good durable adhesive strength to enamel and color stability.

Claims

1. (I) a dental adhesive composition comprising (A) a polymerizable monomer having an acidic group (A1), (B) water, (C) a volatile organic solvent, and (D) an aromatic tertiary amine compound which is a photopolymerization initiator, (II) A dental adhesive kit comprising a dental photocurable composition including (A) a polymerizable monomer, (D) a photopolymerization initiator, and (E) a filler. (II) The (D) photopolymerization initiator contained in the dental photocurable composition comprises (D2) an α-diketone compound, (D3) an iodonium salt compound, and (D4) an aliphatic tertiary amine compound having an aromatic ring, and substantially does not contain (D1) an aromatic tertiary amine compound. Dental bonding kit.

2. (I) The dental adhesive kit according to claim 1, characterized in that the dental adhesive composition comprises (F) a compound containing a disulfide group.

3. (I) The dental adhesive kit according to claim 2, characterized in that (F) the compound containing a disulfide group in the dental adhesive composition is thioctic acid.

4. (I) The dental adhesive kit according to claim 1, characterized in that the dental adhesive composition substantially does not contain an aliphatic tertiary amine compound.

5. (I) The dental adhesive kit according to claim 3, characterized in that the dental adhesive composition substantially does not contain an aliphatic tertiary amine compound.

6. (I) Dental adhesive compositions (I) Per 100 parts by mass of dental adhesive composition, (A1) 3 to 20 parts by mass of polymerizable monomer having an acidic group (B) 10 to 50 parts by mass of water (C) 10 to 60 parts by mass of a volatile organic solvent, and (D1) Contains 0.05 to 2 parts by mass of an aromatic tertiary amine compound, (II) Dental photocurable composition (II) For every 100 parts by mass of (A) polymerizable monomer contained in the dental photocurable composition, (D2) 0.05 to 0.6 parts by mass of an α-diketone compound (D3) 0.3 to 5 parts by mass of an iodonium salt compound (D4) 0.5 to 5 parts by mass of an aliphatic tertiary amine compound having an aromatic ring, and (E) The dental adhesive kit according to claim 1, comprising 10 to 400 parts by mass of a filler.

7. (I) Dental adhesive compositions (I) Per 100 parts by mass of dental adhesive composition, (A1) 3 to 20 parts by mass of polymerizable monomer having an acidic group (B) 10 to 50 parts by mass of water (C) 10 to 60 parts by mass of a volatile organic solvent, and (D1) Contains 0.05 to 2 parts by mass of an aromatic tertiary amine compound, (II) Dental photocurable composition (II) For every 100 parts by mass of (A) polymerizable monomer contained in the dental photocurable composition, (D2) 0.05 to 0.6 parts by mass of an α-diketone compound (D3) 0.3 to 5 parts by mass of an iodonium salt compound (D4) 0.5 to 5 parts by mass of an aliphatic tertiary amine compound having an aromatic ring, and (E) The dental adhesive kit according to claim 3, comprising 10 to 400 parts by mass of a filler.

8. (I) Dental adhesive compositions (I) Per 100 parts by mass of dental adhesive composition, (A1) 3 to 20 parts by mass of polymerizable monomer having an acidic group (B) 10 to 50 parts by mass of water (C) 10 to 60 parts by mass of a volatile organic solvent, and (D1) Contains 0.05 to 2 parts by mass of an aromatic tertiary amine compound, (II) Dental photocurable composition (II) For every 100 parts by mass of (A) polymerizable monomer contained in the dental photocurable composition, (D2) 0.05 to 0.6 parts by mass of an α-diketone compound (D3) 0.3 to 5 parts by mass of an iodonium salt compound (D4) 0.5 to 5 parts by mass of an aliphatic tertiary amine compound having an aromatic ring, and (E) The dental adhesive kit according to claim 4, comprising 10 to 400 parts by mass of a filler.

9. (I) Dental adhesive compositions (I) Per 100 parts by mass of dental adhesive composition, (A1) 3 to 20 parts by mass of polymerizable monomer having an acidic group (B) 10 to 50 parts by mass of water (C) 10 to 60 parts by mass of a volatile organic solvent, and (D1) Contains 0.05 to 2 parts by mass of an aromatic tertiary amine compound, (II) Dental photocurable composition (II) For every 100 parts by mass of (A) polymerizable monomer contained in the dental photocurable composition, (D2) 0.05 to 0.6 parts by mass of an α-diketone compound (D3) 0.3 to 5 parts by mass of an iodine salt compound (D4) 0.5 to 5 parts by mass of an aliphatic tertiary amine compound having an aromatic ring, and (E) The dental adhesive kit according to claim 5, comprising 10 to 400 parts by mass of a filler.

10. A dental adhesive kit for fixing a mobile tooth for use in bonding to enamel, as described in claims 1 to 9, and / or a dental adhesive kit for use in orthodontic treatment.

11. The dental adhesive kit according to claims 1 to 9, further comprising a dental etching material.

12. The dental adhesive kit according to claim 10, further comprising a dental etching material.

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