Dental adhesive composition with excellent storage stability

Abstract

To provide dental adhesive compositions with excellent storage stability and adhesive strength.SOLUTION: A dental adhesive composition of the present invention is a dental adhesive composition containing (A) a polymerizable monomer, (D) a photopolymerization accelerator, and (F) a volatile organic solvent, (A-1) a polymerizable monomer having an acidic group as (A) a polymerizable monomer is contained, and (D-1) an aliphatic tertiary amine compound represented by the following formula as (D) a photopolymerization accelerator is contained, (where R1 is a substituent consisting of three or more carbons starting from N and having an electron-withdrawing group at the α- and / or β-position carbon of the amine; R2 is a substituent consisting of 3 or more carbons which may have an electron-withdrawing group; R3 is a substituent consisting of one or more carbons which may have an electron withdrawing group.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a dental adhesive composition. [Background technology]

[0002] Dental adhesive compositions are used in the dental field and are applied to dental adhesives, dental composite resins, dental core construction materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicure materials, dental adhesives for fixing loose teeth, dental glass ionomer cements, etc.

[0003] Patent Documents 1 and 2 propose adhesive compositions containing an acidic group-polymerizable monomer and a basic compound containing an aliphatic tertiary amine, and Patent Document 3 proposes an adhesive composition containing an acidic group-polymerizable monomer, an aromatic tertiary amine, and a triazine compound. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-225350 [Patent Document 2] Patent No. 4783151 [Patent Document 3] Japanese Patent Application Laid-Open No. 2006-76973 Summary of the Invention [Problem to be solved by the invention]

[0005] However, conventional dental adhesive compositions have room for improvement in terms of storage stability and adhesive strength.

[0006] An object of the present invention is to provide a dental adhesive composition having excellent storage stability and adhesive strength. [Means for solving the problem]

[0007] The dental adhesive composition of the present invention is a dental adhesive composition comprising (A) a polymerizable monomer, (D) a photopolymerization accelerator, and (F) a volatile organic solvent, wherein the (A) polymerizable monomer comprises (A-1) a polymerizable monomer having an acidic group, and the (D) photopolymerization accelerator comprises (D-1) an aliphatic tertiary amine compound represented by formula (1). [Formula (1)] [ka] (In the formula, R1 is a substituent consisting of three or more carbon atoms which, starting from N, has an electron-withdrawing group at the α-carbon and / or β-carbon of the amine; R2 is a substituent consisting of three or more carbon atoms which may have an electron-withdrawing group; and R3 is a substituent consisting of one or more carbon atoms which may have an electron-withdrawing group. The α-carbon of N in formula (1) is not an electron-withdrawing group.) [Effects of the Invention]

[0008] The dental adhesive composition of the present invention has excellent storage stability and adhesive strength. DETAILED DESCRIPTION OF THE INVENTION

[0009] In the present invention, the electron-withdrawing group in R1 is a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a vinyl group, an aryl group, and a halogen, or an organic group bonded via an ether bond, an ester bond, a urethane bond, or a urea bond, and is a substituent selected from an -OH group, -O- group, -C(O)- group, -S- group, -NH-C(O)-NH- group, -C(O)-O- group, -OC(O)- group, -OC(O)-NH- group, -NH-C(O)-O- group, an aromatic hydrocarbon group, or an organic group that may have a polymerizable functional group capable of radical polymerization.

[0010] In the present invention, the aliphatic tertiary amine compound represented by formula (1) (D-1) can be an aliphatic tertiary amine compound in which R1 and R2 have an aliphatic substituent consisting of three or more carbon atoms and having an electron-withdrawing group at the α-carbon and / or β-carbon.

[0011] In the present invention, the aliphatic tertiary amine compound represented by formula (1) (D-1) can be an aliphatic tertiary amine compound in which R1 and R2 have an aryl group which may have a substituent at the α-position carbon and / or the β-position carbon.

[0012] In the present invention, (G) water may further be contained.

[0013] In the present invention, (B) a photosensitizer may further be contained.

[0014] In the present invention, (C) a photoacid generator may further be contained.

[0015] In the present invention, the photoacid generator (C) contains an aryliodonium salt, and the aryliodonium salt can be a salt of an anion having an organic group and one or more atoms of P, B, Al, S, or Ga, and an aryliodonium cation.

[0016] In the present invention, the composition contains an aryl iodonium salt as a photoacid generator (C), The aryliodonium salt can be a salt of an anion having an organic group in which at least one H is substituted with F and one or more atoms of P, B, Al, S, and Ga, and an aryliodonium cation.

[0017] In the present invention, the dental adhesive composition is a one-component type, and may contain 0.1 to 20 parts by mass of (A-1) a polymerizable monomer having an acidic group, 1 to 99.9 parts by mass of (F) a volatile organic solvent, and 0.01 to 20 parts by mass of (D-1) an aliphatic tertiary amine compound represented by formula (1), relative to 100 parts by mass of the total of (A) the polymerizable monomer and (F) the volatile organic solvent, or, when (G) water is contained, relative to 100 parts by mass of the total of (A) the polymerizable monomer, (F) the volatile organic solvent, and (G) water.

[0018] In the present invention, a dental adhesive composition is provided which comprises a first part and a second part, the mass ratio of the first part to the second part being 0.8-1.2:1.0, the first part containing (A-1) a polymerizable monomer having an acidic group, (F) a volatile organic solvent, and (D-1) an aliphatic tertiary amine compound represented by formula (1), and the first part contains 0.2-20 parts by mass of (A-1) a polymerizable monomer having an acidic group, 1-99.9 parts by mass of (F) a volatile organic solvent, and 0.02-20 parts by mass of (D-1) an aliphatic tertiary amine compound represented by formula (1), relative to a total of 100 parts by mass of the (A) polymerizable monomer and (F) a volatile organic solvent contained in the first part, or relative to a total of 100 parts by mass of the (A) polymerizable monomer, (F) a volatile organic solvent, and (G) water contained in the first part when (G) water is contained.

[0019] The present invention provides a dental adhesive kit comprising a dental photocurable composition and the dental adhesive composition of the present invention, wherein the dental photocurable composition contains 0.001 to 2 parts by mass of (B) a photosensitizer and 0.01 to 10 parts by mass of (C) a photoacid generator relative to 100 parts by mass of (A) a polymerizable monomer contained in the dental photocurable composition.

[0020] Each component of the dental adhesive composition of the present invention will be described in detail below. The dental adhesive composition of the present invention is used as a dental adhesive, a dental composite resin, a dental core construction material, a dental resin cement, a dental coating material, a dental pit and fissure sealant, a dental manicure, a dental adhesive for fixing loose teeth, a dental glass ionomer cement, etc.

[0021] In clinical dentistry, aesthetic and functional restoration of tooth loss caused by caries, fractures, etc. is achieved through direct restoration with dental composite resins or indirect restoration with prosthetic devices made of ceramics or hard resins attached to dental resin cements. Dental adhesives are used to bond these dental composite resins to various dental materials and natural teeth. Dental adhesives are also used to fix loose teeth, as dental coatings to protect sensitive and formed vital teeth from external irritation and secondary caries, as dental pit and fissure sealants to prevent caries by filling complex grooves, particularly those found in primary teeth, as dental nail polish to temporarily restore aesthetics by masking discoloration, and as dental core buildup materials to form abutment teeth when the crown of a tooth has collapsed due to caries.

[0022] In order to achieve both demineralization of enamel and penetration promotion into dentin, dental adhesives have been proposed as self-etching primers containing water and acidic group-containing polymerizable monomers. Such compositions offer the advantage of simplifying the process by eliminating the need for an etching step before applying the primer. However, when the acidic group-containing polymerizable monomer and water are packaged together, the acidic group-containing polymerizable monomer hydrolyzes over long-term storage, resulting in a decrease in adhesive strength to the substrate.

[0023] Therefore, a composition in which an acidic group-containing polymerizable monomer, water, and a basic compound coexist has been proposed. Such a composition improves storage stability by neutralizing the acidity through the formation of a salt between the acidic group-containing polymerizable monomer and the basic compound. However, the commonly used basic inorganic compounds and tertiary aliphatic amine compounds form strong salts with the acidic group-containing polymerizable monomer, resulting in a problem of reduced adhesive strength.

[0024] In order to solve the above problems, the present inventors have found that when an aliphatic tertiary amine having a specific structure is used, the dental adhesive composition of the present invention achieves both excellent storage stability and excellent adhesive strength, and have thus completed the present invention.

[0025] It has also been found that when the dental adhesive composition of the present invention is bonded to a dental photocurable composition containing a photoacid generator, even better adhesive strength is exhibited.

[0026] The dental adhesive composition of the present invention can be used as a dental adhesive, a dental coating material, or a dental manicure material, and can also be used as a kit in combination with dental curable compositions such as a dental adhesive, a dental composite resin, a dental abutment construction material, a dental resin cement, a dental coating material, a dental pit and fissure sealant, a dental manicure material, a dental adhesive for fixing loose teeth, a dental cutting material, or a dental 3D printer material.

[0027] [(A) Polymerizable Monomer] The polymerizable monomer (A) of the present invention can be any known polymerizable monomer. In the polymerizable monomer or compound having a polymerizable group described in the present invention, the polymerizable group preferably exhibits radical polymerizability. Specifically, from the viewpoint of ease of radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. In this specification, "(meth)acrylic" refers to acrylic and / or methacrylic, "(meth)acryloyl" refers to acryloyl and / or methacryloyl, "(meth)acrylate" refers to acrylate and / or methacrylate, and "(meth)acrylamide" refers to acrylamide and / or methacrylamide. Polymerizable monomers having a substituent at the α-position of the acrylic group and / or acrylamide group are also preferably used. Examples of suitable polymerizable monomers include those having one radically polymerizable group, those having two radically polymerizable groups, those having three or more radically polymerizable groups, those having an acidic group, an alkoxysilyl group, and those having a sulfur atom.

[0028] Specific examples of polymerizable monomers having one radically polymerizable group and no acidic 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, 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.

[0029] Specific examples of polymerizable monomers having two radical polymerizable groups and no acidic group 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, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2-(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)propane, 2,2-bis(4-(meth)acryloyloxyphenyl)-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 glycol di(meth)acrylate, 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, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,Examples include 4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA") and 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane.

[0030] Specific examples of polymerizable monomers having three or more radically polymerizable groups and no acidic group include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, and 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane.

[0031] (A-1) The polymerizable monomer having an acidic group can be any polymerizable monomer having one or more polymerizable groups and at least one acidic group such as a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonate group, a sulfonic acid group, or a carboxylic acid group, without any limitations.

[0032] Specific examples of the polymerizable monomer having a phosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyhexyl dihydrogen phosphate, 9-(meth)acryloyloxyheptyl dihydrogen phosphate, 10-(meth)acryloyloxyhexyl dihydrogen phosphate, 11-(meth)acryloyloxyhexyl dihydrogen phosphate, 12-(meth)acryloyloxyhexyl dihydrogen phosphate, 13-(meth)acryloyloxyhexyl dihydrogen phosphate, 14-(meth)acryloyloxyhexyl dihydrogen phosphate, 15-(meth)acryloyloxyhexyl dihydrogen phosphate, 16-(meth)acryloyloxyhexyl dihydrogen phosphate, 17-(meth)acryloyloxyheptyl dihydrogen phosphate, 18-(meth)acryloyloxyhexyl dihydrogen phosphate, 19-(meth)acryloyloxyhexyl dihydrogen phosphate, 20-(meth)acryloyloxyhexyl dihydrogen phosphate, 21-(meth)acryloyloxyhexyl dihydrogen phosphate, 22-(meth)acryloyloxyhexyl dihydrogen phosphate, 23-(meth)acryloyloxyhexyl dihydrogen phosphate, 24-(meth)acryloyloxyhexyl dihydrogen phosphate, 25-(meth)acryloyloxyhexyl dihydrogen phosphate, 26-(meth)acryloyloxyhexyl dihydrogen phosphate, 27- Acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate phosphate, bis[2-(meth)acryloyloxyethyl]hydrogenphosphate, bis[4-(meth)acryloyloxybutyl]hydrogenphosphate, bis[6-(meth)acryloyloxyhexyl]hydrogenphosphate, bis[8-(meth)acryloyloxyoctyl]hydrogenphosphate, bis[9-(meth)acryloyloxynonyl]hydrogenphosphate, bis[10-(meth)acryloyloxydecyl]hydrogenphosphate, 1,3-di( Examples thereof include 2-(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl 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 (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0033] 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; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0034] Specific examples of polymerizable monomers having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogen thiophosphate, 3-(meth)acryloyloxypropyl dihydrogen thiophosphate, 4-(meth)acryloyloxybutyl dihydrogen thiophosphate, 5-(meth)acryloyloxypentyl dihydrogen thiophosphate, 6-(meth)acryloyloxyhexyl dihydrogen thiophosphate, 7-(meth)acryloyloxyheptyl dihydrogen thiophosphate, 8-(meth)acryloyloxyoctyl dihydrogen thiophosphate, and 9-(meth)acryloyloxy. Examples of suitable thiophosphates include 1-(meth)acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, and 20-(meth)acryloyloxyicosyl dihydrogen thiophosphate; their acid chlorides, alkali metal salts, and ammonium salts; and (meth)acrylamide compounds in which the ester bond in these compounds is replaced with an amide bond. Polymerizable monomers having a thiophosphate group are also classified as polymerizable monomers having a sulfur atom.

[0035] Specific examples of the polymerizable monomer having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phosphonoacetate; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0036] Specific examples of polymerizable monomers having a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid and 2-sulfoethyl(meth)acrylate.

[0037] Polymerizable monomers having a carboxylic acid group are classified into (meth)acrylic compounds having one carboxyl group in the molecule and (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, 3-(meth)acryloyloxybenzoic acid, and 4-(meth)acryloyloxybenzoic acid. Examples of the acryloyloxybenzoic acid include 2-(meth)acryloyloxybenzoic acid, 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, and 2-(meth)acryloyloxyethyl hydrogen maleate; acid halides thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.Specific examples of the (meth)acrylic compound 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)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, 4 ...4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth Examples thereof include acryloyloxyethyl trimellitate, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate; acid anhydrides and acid halides thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0038] Specific examples of polymerizable monomers having an alkoxysilyl group include (meth)acrylic compounds having one alkoxysilyl group in the molecule and (meth)acrylic compounds having multiple alkoxysilyl groups in the molecule. Examples of the silane include 2-(meth)acryloxyethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane, 5-(meth)acryloxypentyltrimethoxysilane, 6-(meth)acryloxyhexyltrimethoxysilane, 7-(meth)acryloxyheptyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 9-(meth)acryloxynonyltrimethoxysilane, 10-(meth)acryloxydecyltrimethoxysilane, and 11-(meth)acryloxyundecyltrimethoxysilane.

[0039] The polymerizable monomer having a sulfur atom can be any known compound without any limitation, as long as it is a polymerizable monomer having one or more sulfur atoms and a polymerizable group. Specific examples include compounds having partial structures such as -SH, -SS-, >C=S, >CSC<, and >P=S, or compounds resulting from tautomerization. Specific examples include 10-methacryloxydecyl-6,8-dithiooctanate, 6-methacryloxyhexyl-6,8-dithiooctanate, 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate, 2-(11-methacryloyloxyundecylthio)-5-mercapto-1,3,4-thiadiazole, and 10-(meth)acryloyloxydecyl dihydrogen thiophosphate.

[0040] In addition to these polymerizable monomers, oligomers or prepolymers having at least one polymerizable group in the molecule may be used without any limitation. Furthermore, there is no problem even if the same molecule has a substituent such as a fluoro group. The above-described polymerizable monomers may be used alone or in combination.

[0041] The dental adhesive composition of the present invention contains (A-1) a polymerizable monomer having an acidic group to impart adhesion to tooth structure or prosthetic devices, preferably 10-methacryloyloxydecyl dihydrogen phosphate or 6-methacryloxyhexyl phosphonoacetate, 10-methacryloyloxydecyl dihydrogen thiophosphate, 4-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxyethyl trimellitate anhydride, etc.

[0042] When the dental adhesive composition is a one-component dental adhesive composition, the blending amount of the (A-1) polymerizable monomer having an acidic group is 0.1 to 20 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total of the (A) polymerizable monomer including the (A-1) polymerizable monomer having an acidic group and the (F) volatile organic solvent, or per 100 parts by mass of the total of the (A) polymerizable monomer, the (F) volatile organic solvent, and the (G) water when the dental adhesive composition contains (G) water. If the blending amount is less than 0.1 part by mass, adhesion to tooth structure or prosthetic devices may not be imparted, and if the blending amount exceeds 20 parts by mass, storage stability may be impaired.

[0043] When the dental adhesive composition is a dental adhesive composition consisting of a first agent and a second agent, the blending amount of the (A-1) polymerizable monomer having an acidic group is 0.2 to 20 parts by mass, more preferably 1 to 20 parts by mass, in the first agent relative to 100 parts by mass of the total of the (A) polymerizable monomer and the (F) volatile organic solvent contained in the first agent, or 100 parts by mass of the total of the (A) polymerizable monomer, the (F) volatile organic solvent, and the (G) water contained in the first agent when (G) water is contained. If the blending amount is less than 0.2 parts by mass, adhesion to tooth structure or prosthetic devices may not be imparted, and if the blending amount exceeds 20 parts by mass, storage stability may be impaired.

[0044] The dental adhesive composition of the present invention may contain a silane coupling agent having a polymerizable group as a polymerizable monomer (A) to impart adhesion to glass ceramics or resin materials consisting of a matrix of an inorganic component and a polymerizable monomer. Any known silane coupling agent can be used without limitation, but 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silatricosan-20-yl (meth)acrylate, and 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosan-23-yl (meth)acrylate are preferred. From the viewpoint of imparting adhesiveness, the blending amount is 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the total of (A) polymerizable monomer and (F) volatile organic solvent, or, when (G) water is contained, per 100 parts by mass of the total of (A) polymerizable monomer, (F) volatile organic solvent, and (G) water. The silane coupling agent as a polymerizable monomer is blended separately from the surface treatment agent for the filler, because its purpose is to impart adhesiveness to glass ceramics or resin materials containing a filler made of glass ceramics.

[0045] The dental adhesive composition of the present invention may contain a polymerizable monomer having a sulfur atom as the polymerizable monomer (A) in order to impart adhesiveness to precious metals. From the viewpoint of imparting adhesiveness, the blending amount of the polymerizable monomer having a sulfur atom is 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of the polymerizable monomer (A) and the volatile organic solvent (F), or, when (G) water is contained, per 100 parts by mass of the total of the polymerizable monomer (A), the volatile organic solvent (F), and the water (G).

[0046] <Photopolymerization initiator> The dental adhesive composition of the present invention contains an aliphatic tertiary amine compound represented by formula (1) (D-1). In addition to the aliphatic tertiary amine compound represented by formula (1) (D-1), the dental adhesive composition of the present invention may contain a photosensitizer (B) as a photopolymerization initiator, a photoacid generator (C), and a photopolymerization accelerator (D) other than the aliphatic tertiary amine compound represented by formula (1) (D-1). These may be blended alone, and when contained, they are not particularly limited, and commonly used known compounds can be used without any limitation.

[0047] [(B) Photosensitizer] Specific examples of the photosensitizer (B) that can be used in the present invention include α-diketones such as benzil, camphorquinone, camphorquinonecarboxylic acid, camphorquinonesulfonic acid, α-naphthyl, acetonaphthone, p,p'-dimethoxybenzyl, p,p'-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, and naphthoquinone; benzoins such as benzoin methyl ether and benzoin ethyl ether; Alkyl ethers, thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone, benzophenones such as benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl) Phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl Bis(2,6-diethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis(2,6-dimethoxy 2,6-Dimethoxybenzoylbenzyl phosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropyl phosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethyl phosphine oxide, 2,6-dimethoxybenzoylbenzyl butyl phosphine oxide, 2,6-dimethoxybenzoylbenzyl octyl phosphine oxide, bis(2,4,6-trimethylbenzoyl) isobutyl phosphine oxide and 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl acylphosphine oxides such as n-butylphosphine oxide, acylgermanium compounds such as bisbenzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis(4-methoxybenzoyl)dimethylgermanium, and bis(4-methoxybenzoyl)diethylgermanium, 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-2, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-3, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-4, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-5, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-6, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-7, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-8, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-9, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-1 ...1, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone-2, 2-benzyl α-aminoacetophenones such as α-propanone-1; ketals such as benzil dimethyl ketal, benzil diethyl ketal, and benzil (2-methoxyethyl ketal); and titanocenes such as bis(cyclopentadienyl)-bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]-titanium, bis(cyclopentadienyl)-bis(pentanefluorophenyl)-titanium, and bis(cyclopentadienyl)-bis(2,3,5,6-tetrafluoro-4-disiloxyphenyl)-titanium.

[0048] (B) The photosensitizer can be appropriately selected depending on the wavelength, intensity, and irradiation time of the light used for polymerization, as well as the types and amounts of other components to be combined. The photosensitizers can be used alone or in combination of two or more. Among these, α-diketone compounds having a maximum absorption wavelength in the visible light region are preferably used, and camphorquinone compounds such as camphorquinone, camphorquinonecarboxylic acid, and camphorquinonesulfonic acid are more preferred. Camphorquinone is particularly preferred because of its easy availability.

[0049] When the dental adhesive composition of the present invention contains a (B) photosensitizer, the amount of the (B) photosensitizer is 0.001 to 5 parts by mass, more preferably 0.1 to 1 part by mass, per 100 parts by mass of the total of the (A) polymerizable monomer and the (F) volatile organic solvent, or, when (G) water is contained, per 100 parts by mass of the total of the (A) polymerizable monomer, the (F) volatile organic solvent, and the (G) water. If the amount of the photosensitizer is less than 0.001 part by mass, the polymerization activity in response to irradiated light may be poor, resulting in insufficient curing. If the amount of the photosensitizer is more than 5 parts by mass, sufficient curing is achieved, but the ambient light stability may be shortened and the yellowing may increase.

[0050] [(C) Photoacid generator] The dental adhesive composition of the present invention may contain (C) a photoacid generator. As the (C) photoacid generator, known compounds can be used without limitation. Specific examples include triazine compounds, iodonium salt compounds, sulfonium salt compounds, sulfonate ester compounds, etc. Among these, triazine compounds and iodonium salt compounds are preferred because of their high polymerizability when used in combination with a sensitizer. Iodonium salt compounds are more preferred. Iodonium salt compounds are easily sensitized by photosensitizers that have absorption in the visible light region.

[0051] Specific examples of the triazine compound include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine. 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine s(trichloromethyl)-s-triazine, 2-[2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4, 6-bis(trichloromethyl)-s-triazine, 2-(1-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis(2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,Examples include 6-bis(trichloromethyl)-s-triazine and 2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine. Of these, 2,4,6-tris(trichloromethyl)-s-triazine is preferred.

[0052] Any known iodonium salt compound can be used. To give a specific example, the structural formula of an iodonium salt compound can be represented by the following formula (2): [Formula (2)] [(R1)2I] + [A] - (In the formula [(R1)2I] + is the cationic moiety, [A] - is an anion moiety, and R1 in formula (2) represents an organic group bonded to I, and 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, which 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 halogen.

[0053] Examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl group, and condensed polycyclic aryl groups such as naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, and anthraquinone.

[0054] 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 monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, and pyrazinyl, and fused polycyclic heterocyclic groups such as indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, and dibenzofuranyl.

[0055] Specific examples of the alkyl group having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl, and octadecyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0056] Specific examples of alkenyl groups having 2 to 30 carbon atoms include straight-chain or branched ones such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 1-methyl-1-propenyl.

[0057] Furthermore, specific examples of the alkynyl group having 2 to 30 carbon atoms include straight-chain or branched ones such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl, and 1-methyl-2-propynyl.

[0058] The above-mentioned aryl group having 6 to 30 carbon atoms, heterocyclic group having 4 to 30 carbon atoms, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, or alkynyl group having 2 to 30 carbon atoms may have at least one substituent, and specific examples of the substituent include linear alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, and octadecyl; branched alkyl groups having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, and tert-butyl; cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; hydroxy groups; linear or branched alkoxy groups having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and dodecyloxy; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, and octadecyl. Straight-chain or branched alkylcarbonyl groups having 2 to 18 carbon atoms, such as octanoyl; arylcarbonyl groups having 7 to 11 carbon atoms, such as benzoyl and naphthoyl; straight-chain or branched alkoxycarbonyl groups having 2 to 19 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, and tert-butoxycarbonyl; phenoxycarbonyl aryloxycarbonyl groups having 7 to 11 carbon atoms, such as phenylthiocarbonyl and naphthoxythiocarbonyl; arylthiocarbonyl groups having 7 to 11 carbon atoms, such as phenylthiocarbonyl and naphthoxythiocarbonyl; linear or branched acyloxy groups having 2 to 19 carbon atoms, such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, and octadecylcarbonyloxy;Arylthio groups having 6 to 20 carbon atoms, such as 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-(ptert-butylbenzoyl)phenylthio; straight-chain or branched alkylthio groups having 1 to 18 carbon atoms, such as methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, and dodecylthio; phenylthio aryl groups having 6 to 10 carbon atoms, such as phenyl, tolyl, dimethylphenyl, and naphthyl; heterocyclic groups having 4 to 20 carbon atoms, such as thienyl, furanyl, pyranyl, xanthenyl, chromanyl, isochromanyl, xanthonyl, thioxanthonyl, and dibenzofuranyl; aryloxy groups having 6 to 10 carbon atoms, such as phenoxy and naphthyloxy; linear or branched alkylsulfinyl groups having 1 to 18 carbon atoms, such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, and octylsulfinyl; arylsulfinyl groups having 6 to 10 carbon atoms, such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl; linear or branched alkylsulfonyl groups having 1 to 18 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and octylsulfonyl; Examples include arylsulfonyl groups having 6 to 10 carbon atoms, such as phenylsulfonyl, tolylsulfonyl (tosyl), and naphthylsulfonyl; alkyleneoxy groups; cyano groups; nitro groups; and halogens such as fluorine, chlorine, bromine, and iodine.

[0059] Among iodonium salt compounds, aryliodonium salts are preferred because of their high stability. Furthermore, the aryl group preferably has a substituent to improve liposolubility. Specifically, linear alkyl groups such as methyl, propyl, octyl, decyl, undecyl, dodecyl, and tridecyl, branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, and isohexyl, and functional groups in which one or more H atoms in these groups are replaced with F, perfluoroalkyl groups, and halogens are preferred as the substituent.

[0060] The structure of the anion moiety of the iodonium salt compound is not particularly limited, but examples include those containing atoms such as P, S, B, Al, and Ga. From a safety perspective, anions containing As or Sb can be used, but are not preferred for dental applications. Furthermore, the anion preferably contains an organic group such as an alkyl group and / or an alkoxy group and / or an aryl group, and most preferably 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. Iodonium salt compounds containing such an anion are highly soluble in compositions, which can prevent precipitation during low-temperature or long-term storage and can dissolve in compositions in a short time, thereby shortening production time.

[0061] Furthermore, iodonium salt compounds comprising an anion having an organic group such as an alkyl group, an alkoxy group, and / or an aryl group in which one or more H atoms are substituted with F can be expected to have even higher solubility. Precipitation of the photoacid generator is undesirable because it may cause a decrease in photocolor stability and bending strength. Anions having any atom can be used as anions having an organic group such as an alkyl group, an alkoxy group, and / or an aryl group in which at least one H atom may be substituted with F. However, from the viewpoints of versatility and safety, those having P, S, B, Al, or Ga atoms are preferred.

[0062] Examples of anions having no alkyl group and / or alkoxy group and / or aryl group include halogens such as chloride and bromide, perhalogen acids such as perchloric acid, aromatic sulfonic acids such as p-toluenesulfonate, camphorsulfonic acid, nitrate, acetate, chloroacetate, carboxylate, phenolate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, etc. Among these, p-toluenesulfonate, camphorsulfonic acid, and carboxylate are preferably used.

[0063] [A] of the iodonium salt compound of formula (2) - The anion moiety of [A] is preferably an anion having an alkyl group and / or an alkoxy group and / or an aryl group in which at least one H is substituted with F, because this improves the solubility in the composition. Specifically, [A] of the iodonium salt compound of formula (2) - The alkyl group in the anion moiety preferably has 1 to 8 carbon atoms, and more preferably 1 to 4. Specific examples include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The ratio of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group (F / H) is 4 or more, and preferably the ratio of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group (F / H) is 9 or more. It is more preferable that all hydrogen atoms in the hydrocarbon are substituted with fluorine. The dental adhesive composition may contain an iodonium salt composed of an anion having an alkyl group with a different ratio of hydrogen atoms to fluorine atoms.

[0064] Specific examples of the alkyl group include straight-chain or branched perfluoroalkyl groups such as CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C.

[0065] [A] of the iodonium salt compound of formula (2) - The alkoxy group in the anion moiety preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples include linear alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentoxy, and octoxy, and branched alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy, and tert-butoxy. The ratio of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group (F / H) is 4 or more, and preferably the ratio of the number of hydrogen atoms to the number of fluorine atoms in the alkyl group (F / H) is 9 or more. It is more preferable that all hydrogen atoms in the hydrocarbon are substituted with fluorine. The dental adhesive composition may contain an iodonium salt consisting of an anion having an alkoxy group with a different ratio of hydrogen atoms to fluorine atoms.

[0066] Furthermore, specific examples of the alkoxy group include linear or branched perfluoroalkoxy groups such as CF3O, CF3CF2O, CF3CF2CF2O, (CF3)2CFO, CF3CF2CF2CF2O, (CF3)2CFCF2O, CF3CF2(CF3)CFO, CF3CF2CF2CF2CF2O, CF3CF2CF2CF2CF2CF2CF2CF2CF2CF2O.

[0067] [A] of the iodonium salt compound of formula (2) -The phenyl group in the anion moiety has at least one hydrogen atom substituted with a fluorine atom and / or an alkyl group and / or an alkoxy group substituted with a fluorine atom. The alkyl group and / or alkoxy group substituted with a fluorine atom are preferably those described above. Particularly preferred specific examples of the phenyl group include perfluorophenyl groups such as a pentafluorophenyl group (CF), a trifluorophenyl group (CHF), a tetrafluorophenyl group (CHF), a trifluoromethylphenyl group (CF), a bis(trifluoromethyl)phenyl group ((CF)C), a pentafluoroethylphenyl group (CF), a bis(pentafluoroethyl)phenyl group (CF), a trifluoromethylfluorophenyl group (CF), a bistrifluoromethylfluorophenyl group ((CF)C), a pentafluoroethylfluorophenyl group (CF), a bispentafluoroethylfluorophenyl group (CF)C). The dental adhesive composition may contain an iodonium salt consisting of an anion having a phenyl group with a different ratio of hydrogen atoms to fluorine atoms.

[0068] [A] of the iodonium salt compound of formula (2) - A specific example of the anion portion of the anion having P is [(CF3CF2)3PF3] - , [(CF3CF2CF2)3PF3] - , [((CF3)2CF)2PF4] - , [((CF3)2CF)3PF3] - , [((CF3)2CF)4PF2] - , [((CF3)2CFCF2)2PF4] - , [((CF3)2CFCF2)3PF3] - Anions containing S include [(CF3SO2)3C] - , [(CF3CF2SO2)3C] - , [(CF3CF2CF2SO2)3C] - , [(CF3CF2CF2CF2SO2)3C] -, [CF3CF2CF2CF2SO3] - , [CF3CF2CF2SO3] - , [(CF3CF2SO2)3C] - , [(SO2CF3)3N] - , [(SO2CF2CF3)2N] - , [((CF3)C6H4)SO3] - , [SO3((CF2CF2CF2CF2)SO3] 2- Examples of anions containing B include [B(C6F5)4] - , [(C6H5)B(C6F5)3] - , [(C6H5)B((CF3)2C6H3))3] - Examples of Ga-containing anions include [((CF3)4Ga) - , [Ga(C6F5)4] - Examples of anions containing Al include [((CF3)3CO)4Al] - , [((CF3CF2)3CO)4Al] - Examples include:

[0069] When the dental adhesive composition of the present invention contains a (C) photoacid generator, the amount of the (C) photoacid generator is 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of the (A) polymerizable monomer and the (F) volatile organic solvent, or, when (G) water is contained, per 100 parts by mass of the total of the (A) polymerizable monomer, the (F) volatile organic solvent, and the (G) water. If the amount of the (C) photoacid generator is less than 0.01 part by mass, the polymerization-accelerating ability may be poor, resulting in insufficient curing. If more than 10 parts by mass is added, storage stability may be reduced.

[0070] The photoacid generator that can be used in the dental adhesive composition of the present invention is not limited to the photoacid generators shown as specific examples, and two or more types can be used in combination.

[0071] The dental adhesive composition of the present invention may contain, as the photoacid generator (C), only an aryliodonium salt which is a salt of an aryliodonium cation with an anion having an organic group and one or more atoms of P, B, Al, S, and Ga. The dental adhesive composition of the present invention may contain, as the photoacid generator (C), only a salt of an aryliodonium cation with an organic group in which at least one H is substituted with F and an anion having one or more atoms of P, B, Al, S, and Ga.

[0072] [(D) Photopolymerization accelerator] The dental adhesive composition of the present invention contains, as a photopolymerization accelerator (D), an aliphatic tertiary amine compound represented by formula (1) (D-1). The dental adhesive composition of the present invention may contain a photopolymerization accelerator (D) other than the aliphatic tertiary amine compound represented by formula (1) (D-1). The photopolymerization accelerator (D) other than the aliphatic tertiary amine compound represented by formula (1) (D-1) that can be used in the dental adhesive composition is not particularly limited as long as it has polymerization-accelerating ability, and known photopolymerization accelerators commonly used in the dental field can be used without any restrictions. Examples of photopolymerization accelerators that can be used include aromatic amine compounds, primary to tertiary amine compounds such as aliphatic amine compounds, organometallic compounds, and phosphine compounds. Among these, aromatic amine compounds, tertiary aliphatic amine compounds, and organometallic compounds are preferred due to their excellent curability.

[0073] Aromatic amine compounds are compounds in which one or more H atoms in ammonia (NH3) are substituted with an aromatic ring. They can be classified as aromatic primary amine compounds when one H atom in NH3 is substituted with an aromatic ring, aromatic secondary amine compounds when one H atom in NH3 is substituted with an aromatic ring and another H atom is substituted with an aromatic ring or an alkyl group, and aromatic tertiary amine compounds when one H atom in NH3 is substituted with an aromatic ring and two other H atoms are substituted with aromatic rings or alkyl groups.

[0074] Specific examples of aromatic primary amine compounds include aniline, etc., specific examples of aromatic secondary amine compounds include N-protected amino acids (esters) such as N-phenylbenzylamine, N-benzyl-p-anisidine, N-benzyl-o-phenetidine, N-phenylglycine ethyl, and N-phenylglycine, and specific examples of aromatic tertiary amine compounds include N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline, pN,N-dimethyl-toluidine, mN,N-dimethyl-toluidine, pN,N-diethyl-toluidine, p-bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, and p-dimethylaminobenzoic acid. , p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid 2-butoxyethyl, p-dimethylaminobenzoic acid 2-ethylhexyl, p-dimethylaminobenzoic acid amino ester, N,N-dimethylanthranilic 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, N,N-dimethyl-β-naphthylamine, and the like.

[0075] Specific examples of the organometallic compounds include those containing scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), tin (Sn), zinc (Zn), and zirconium (Zr), and preferably those containing tin (Sn), vanadium (V), and copper (Cu). Specific examples of organometallic compounds containing tin (Sn) include dibutyltin diacetate, dibutyltin dimaleate, dioctyltin dimaleate, dioctyltin dilaurate, dibutyltin dilaurate, dioctyltin diversatate, dioctyltin S,S'-bis-isooctylmercaptoacetate, and tetramethyl-1,3-diacetoxydistannoxane. Specific examples of organometallic compounds containing vanadium (V) include acetylacetone. Examples of organic metal compounds containing copper (Cu) include vanadium tetraoxide, vanadium tetroxide, vanadyl acetylacetonate, vanadium oxide stearate, vanadyl oxalate, vanadyl sulfate, oxobis(1-phenyl-1,3-butanedionate)vanadium, bis(maltolate)oxovanadium, vanadium pentoxide, and sodium metavanadate. Specific examples of organometallic compounds containing copper (Cu) include copper acetylacetonate, copper naphthenate, copper octoate, copper stearate, and copper acetate.

[0076] A phosphine compound refers to a compound in which three organic groups are substituted on the P atom, and an aromatic phosphine compound refers to a compound in which a phenyl group which may have one or more substituents is substituted on the P atom. Specific examples of the phosphine compound include trimethylphosphine, tributylphosphine, trihexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tri(2-thienyl)phosphine, diphenylpropylphosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, methyldiphenylphosphine, triphenylphosphine, 2-(diphenylphosphino)styrene, 3-(diphenylphosphino)styrene, 4-(diphenylphosphino)styrene, allyldiphenylphosphine, 2-(diphenylphosphino)benzaldehyde, 3-(diphenylphosphino)benzaldehyde, 4-(diphenylphosphino)benzaldehyde, and 2-(phenylphosphino)benzoin. Examples of suitable benzoates include benzoic acid, 3-(phenylphosphino)benzoic acid, 4-(phenylphosphino)benzoic acid, tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, 2-(diphenylphosphino)biphenyl, tris(4-fluorophenyl)phosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, 2-(dimethylamino)phenyldiphenylphosphine, 3-(dimethylamino)phenyldiphenylphosphine, 4-(dimethylamino)phenyldiphenylphosphine, 2,2'-bis(diphenylphosphino)biphenyl, and bis[2-(diphenylphosphino)phenyl]ether. Among these, triphenylphosphine, 4-(phenylphosphino)benzoic acid, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, and tri(p-tolyl)phosphine are preferred.

[0077] Aliphatic amine compounds are compounds in which one or more H groups in ammonia (NH3) are substituted with alkyl groups. Alkyl groups are classified as primary alkyl groups (CH3- or -CH2-), secondary alkyl groups (-CH2- with one H substituted), and tertiary alkyl groups (-CH2- with two H groups substituted). Aliphatic amines are classified as primary amines when one H group in NH3 is substituted with an alkyl group, secondary amines when two H groups in NH3 are substituted with alkyl groups, and tertiary amines when three H groups in NH3 are substituted with alkyl groups.

[0078] Specific examples of aliphatic primary amine compounds include benzhydrylamine, triphenylmethylamine, amino acids such as glycine, or amino acid esters. Specific examples of aliphatic secondary amine compounds include dibenzylamine, N-benzyl-1-phenylethylamine, bis(1-phenylethyl)amine, bis(4-cyanobenzyl)amine, N-benzyl-protected amino acids, or N-benzyl-protected amino acid esters. Specific examples of aliphatic tertiary amine compounds include tributylamine, tripropylamine, triethylamine, N,N-Dimethylhexylamine, N,N-Dimethyldodecylamine, N,N-Dimethylstearylamine, N-[3-(dimethylamino)propyl]acrylamide, N,N-Dimethylformamide dimethyl acetal, N,N-Dimethylacetamide dimethyl acetal, N,N-Dimethylformamide diethyl acetal, N,N-Dimethylformamide dipropyl acetal, N,N-Dimethylformamide di-tert-butyl acetal, 1-(2-hydroxyethyl)ethyleneimine, N,N-Dimethylethanolamine, N,N- Dimethylisopropanolamine, N,N-diisopropylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, N-stearyldiethanolamine, triethanolamine, triisopropanolamine, tribenzylamine, dibenzylglycine ethyl ester, N'-(2-hydroxyethyl)-N,N,N'-trimethylethylenediamine, 2-(dimethylamino)-2-methyl-1-propanol, N ,N-Dimethyl-2,3-dihydroxypropylamine, N,N-Diethylethanolamine, 1-Methyl-3-pyrrolidinol, 1-(2-hydroxyethyl)pyrrolidine, 1-Isopropyl-3-pyrrolidinol, 1-Piperidineethanol, 2-[2-(dimethylamino)ethoxy]ethanol, N,N-Dimethylglycine, N,N-Dimethylglycine Methyl, N,N-Diethylglycine Methyl, N,N-Dimethylglycine Ethyl, N,N-Diethylglycine Sodium, 2-(Dimethylamino)ethyl Acetate, N-Methyliminodiacetic Acid, N,Examples include N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diisopropylaminoethyl methacrylate, N,N-dibutylaminoethyl methacrylate, N,N-dibenzylaminoethyl methacrylate, 3-dimethylaminopropionitrile, tris(2-cyanoethyl)amine, N,N-dimethylallylamine, N,N-diethylallylamine, and triallylamine.

[0079] The dental adhesive composition of the present invention contains (D-1) an aliphatic tertiary amine compound represented by formula (1) as a photopolymerization accelerator (D). [Formula (1)] [ka]

[0080] In the formula, R1 is a substituent consisting of three or more carbon atoms having an electron-withdrawing group at the α-carbon and / or β-carbon of the amine, starting from N, R2 is a substituent consisting of three or more carbon atoms which may have an electron-withdrawing group, and R3 is a substituent consisting of one or more carbon atoms which may have an electron-withdrawing group. The α-carbon of N in formula (1) is not an electron-withdrawing group.

[0081] The electron-withdrawing group in R1 can be a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a vinyl group, an aryl group, and a halogen, or a substituent selected from an organic group bonded via an ether bond, an ester bond, a urethane bond, or a urea bond, and which may have a polymerizable functional group capable of radical polymerization, such as an -OH group, -O- group, -C(O)- group, -S- group, -NH-C(O)-NH- group, -C(O)-O- group, -OC(O)- group, -OC(O)-NH- group, -NH-C(O)-O- group, an aromatic hydrocarbon group, or an organic group.

[0082] In the past, dental adhesive compositions have sometimes incorporated aliphatic tertiary amines, such as dimethylaminoethyl methacrylate and triethanolamine, for the purposes of accelerating photopolymerization, improving solubility, and improving storage stability. However, when these amines are incorporated into dental adhesive compositions containing the aforementioned conventional aliphatic tertiary amines and polymerizable monomers (A-1) having acidic groups, it has been confirmed that adhesion to tooth structures and prosthetic appliances decreases after long-term storage. As a result of studies conducted by the inventors, it has been found that by using an aliphatic tertiary amine compound (D-1) represented by formula (1), which has more electron-withdrawing groups and steric hindrance than conventionally used tertiary aliphatic amine compounds, good adhesion to tooth structures and prosthetic appliances can be maintained even during long-term storage. Furthermore, the inventors have found that when the aliphatic tertiary amine compound represented by formula (1) (D-1) is used in a dental adhesive composition containing a photosensitizer (B) and / or a photoacid generator (C), or when the dental adhesive composition is used in combination with a dental curable composition containing a photosensitizer (B) and / or a photoacid generator (C), the aliphatic tertiary amine compound may exhibit curing-accelerating ability, resulting in the development of good adhesive properties and mechanical properties, which led to the invention.

[0083] (D-1) In the aliphatic tertiary amine compound represented by formula (1), R1 is a substituent consisting of three or more carbon atoms, starting from N, that has an electron-withdrawing group at the α- and / or β-position carbon of the amine; R2 is a substituent consisting of three or more carbon atoms that may have an electron-withdrawing group; and R3 is a substituent consisting of one or more carbon atoms that may have an electron-withdrawing group. Here, R2 and R3 may each be a carbon alicyclic compound or heteroalicyclic compound having three or more carbon atoms bonded to a ring. The α- and / or β-position starting from N refers to the carbon bonded to N as the α-position carbon, and the carbon bonded to the α-position carbon as the β-position carbon. The number of substituents consisting of three or more carbon atoms includes the carbon atoms bearing the electron-withdrawing functional group. Furthermore, N in formula (1) does not bond to an electron-withdrawing group without passing through a hydrocarbon group.

[0084] An electron-withdrawing group is a substituent that easily attracts electrons from the atom to which it is bonded. Examples of electron-withdrawing groups include hydroxyl groups, thiol groups, nitro groups, carbonyl groups, carboxyl groups, sulfonyl groups, cyano groups, aryl groups, amino groups, halogens, and organic groups bonded via unsaturated bonds such as vinyl groups and propargyl groups, ether bonds, ester bonds, urethane bonds, or urea bonds.

[0085] Among the electron-withdrawing groups in formula (1), the electron-withdrawing group at the α- and / or β-carbon of R1 can be a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a vinyl group, an aryl group, and a halogen atom, or an organic group having an ether bond, an ester bond, a urethane bond, or a urea bond. This organic group may have an -OH group, an -O- group, an -C(O)- group, an -S- group, an -NH-C(O)-NH- group, an -C(O)-O- group, an -OC(O)- group, an -OC(O)-NH- group, an -NH-C(O)-O- group, an aromatic hydrocarbon group, or a polymerizable functional group capable of radical polymerization. Preferred are organic groups having a hydroxyl group, a carboxyl group, an aryl group, and an ether bond, an ester bond, a urethane bond, or a urea bond, and more preferred are organic groups having an aryl group, a carboxyl group, and an ester bond or a urethane bond, because these are expected to have large steric hindrance or high electron-withdrawing properties, and even more preferred are tertiary aliphatic amine compounds in which the amino group is substituted twice or more with aryl groups which may have substituents.

[0086] When R2 and R3 have an electron-withdrawing group, the electron-withdrawing group can be a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a vinyl group, an aryl group, and a halogen atom, or an organic group having an ether bond, an ester bond, a urethane bond, or a urea bond. The organic group can have an -OH group, an -O- group, an -C(O)- group, an -S- group, an -NH-C(O)-NH- group, an -C(O)-O- group, an -OC(O)- group, an -OC(O)-NH- group, an -NH-C(O)-O- group, an aromatic hydrocarbon group, or a polymerizable functional group capable of radical polymerization. Preferred are organic groups having a hydroxyl group, a carboxyl group, an aryl group, and an ether bond, an ester bond, a urethane bond, or a urea bond, and more preferred are organic groups having an aryl group, a carboxyl group, and an ester bond or a urethane bond, because these are expected to have large steric hindrance or high electron-withdrawing properties, and even more preferred are tertiary aliphatic amine compounds in which the amino group is substituted twice or more with aryl groups which may have substituents.

[0087] In formula (1), R1 and R2 are preferably aliphatic tertiary amine compounds having an aliphatic substituent consisting of three or more carbon atoms and having an electron-withdrawing group at the α- and / or β-carbon. In this case, improved storage stability can be expected. Furthermore, a tertiary aliphatic amine compound in which the amino group is substituted with two or more aryl groups, which may have substituents, i.e., an aliphatic tertiary amine compound having an aryl group, which may have substituents, at the α- and / or β-carbon, is preferred. Specific examples include tribenzylamine, dibenzylglycine ester compounds, and dibenzylaminoalkyl (meth)acrylates. Compounds having such structures are expected to improve interfacial curability and thereby improve adhesive strength when a dental adhesive composition contains a photoacid generator, or when a dental adhesive composition or a dental photocurable composition to be used in combination with the dental adhesive composition contains a photoacid generator.

[0088] (D-1) Specific examples of the aliphatic tertiary amine compound represented by formula (1) include triisopropanolamine, 2-(dibutylamino)-1-phenyl-1-propanol, 1-[(3,3-diphenylpropyl)(methyl)amino]-2-methyl-2-propanol, 3,3',3''-nitrilotripropionic acid, N-benzyl-3,3'-iminodipropionic acid, 1-benzhydrylazetidine-3-carboxylic acid, 1-benzyl-3-pyrrolidone, 1-(2-phenylethyl)-4-piperidone, 1-benzylpiperidine, 1-phenyl-2-(1 -pyrrolidinyl)propan-1-ol, 2-[hydroxy(diphenyl)methyl]-1-methylpyrrolidine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, N,N,N',N'',N''-pentakis(2-hydroxypropyl)diethylenetriamine, 2-piperidino-1,1,2-triphenylethanol, 2-[benzyl(methyl)amino]-1-phenylethanol, 2-(dibenzylamino)-3-phenyl-1-propanol, 2,6-bis[2-(hydroxydiphenylmethyl)-1-pyrrolidinyl- methyl]-4-methylphenol, 2-benzyl-1,2,3,4-tetrahydroisoquinoline-8-carboxylic acid, 2-benzyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid, 2-(dibenzylamino)propionaldehyde, 3-(dibenzylamino)-1-propanol, 2-(dibenzylamino)-1-propanol, 2-(N,N-dibenzylamino)-3-methylbutanol, 1-[(dibenzylamino)methyl]-2-naphthalenol, 2-(dibenzylamino)-4-methyl-1-pentanol, 4-dibenzylamino- Cyclohexanone, N,N-dibenzyl-1,4-dioxaspiro[4.5]decan-8-amine, N,N-dipropyl-L-alanine, N,N-dibenzyl-2-aminoethanol, N,N-dibenzylglycine ethyl ester, tribenzylamine, triallylamine, 1,1'-(methylimino)dipropan-2-ol, 1-(benzyl(2-methylallyl)amino)-2-methylpropan-2-ol, 2-piperidino-1,1,2-triphenylethanol, N,N-dibenzylaminoethanol, N,N-dibenzylaminopropanol, 3-(N,Further examples include N-dibenzylamino)propyltriethoxysilane. Further examples include ester exchange products of tertiary amine compounds having an OH group, such as N,N-dibenzylaminoethanol, N,N-dibenzylaminopropanol, N,N-dibutylethanolamine, N,N-diisopropylaminoethanol, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, and N-tert-butyldiethanolamine, with ester compounds containing (meth)acrylic acid esters, such as methyl methacrylate and butyl methacrylate; urethane compounds synthesized by reacting tertiary amine compounds having an OH group with compounds having an isocyanate, such as 2-isocyanatoethyl (meth)acrylate and 1,1-(bisacryloyloxymethyl)ethyl isocyanate; Examples of the urea compounds include ester exchange products of amine compounds having a carboxyl group or an ester bond, such as ',3''-nitrilotripropionic acid, N-benzyl-3,3'-iminodipropionic acid, N-methyliminodiacetic acid, N-(2-hydroxyethyl)iminodiacetic acid, N-(2-carboxyethyl)iminodiacetic acid, N,N-dipropyl-L-alanine, and N,N-dibenzylglycine, with alcohols or compounds having an OH group, such as 2-hydroxyethyl methacrylate, and urea compounds synthesized by reacting secondary amines, such as diisopropylamine and dibenzylamine, with compounds having an isocyanate, such as 2-isocyanatoethyl (meth)acrylate and 1,1-(bisacryloyloxymethyl)ethyl isocyanate. Among these, preferred are ester exchange products of tertiary amine compounds having an OH group, such as dibenzylaminoethyl methacrylate and dibenzylaminopropyl methacrylate, with ester compounds having a polymerizable group, including a (meth)acrylic acid ester; urethane compounds synthesized by reaction with compounds having an isocyanate, such as 2-isocyanatoethyl (meth)acrylate and 1,1-(bisacryloyloxymethyl)ethyl isocyanate; N,N-dibenzylglycine ester compounds; triisopropanolamine; and tribenzylamine.

[0089] Furthermore, when R2 or R3 in formula (1) is an aliphatic tertiary amine compound having an alkoxysilyl group, it can also be used as a surface treatment agent for fillers. For example, there is 3-(N,N-dibenzylamino)propyltriethoxysilane, which has both a benzylamino group and an alkoxysilyl group. For example, it can be synthesized by benzyl-protecting aminopropylethoxysilane. Similar to dental adhesive compositions containing 3-(N,N-dibenzylamino)propyltriethoxysilane, dental adhesive compositions containing fillers surface-treated with 3-(N,N-dibenzylamino)propyltriethoxysilane are expected to exhibit high cure depths. Even when an aliphatic tertiary amine compound is covalently immobilized on a filler, storage stability is reduced if the structure of formula (1) is not satisfied.

[0090] When the dental adhesive composition is a one-component dental adhesive composition, the aliphatic tertiary amine compound represented by formula (1) (D-1) is blended in an amount of 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total of the polymerizable monomer (A) and the volatile organic solvent (F) contained in the dental adhesive composition, or per 100 parts by mass of the total of the polymerizable monomer (A), the volatile organic solvent (F), and the water (G) contained in the dental adhesive composition when water (G) is contained. If the amount of the aliphatic tertiary amine compound represented by formula (1) (D-1) in the dental adhesive composition is less than 0.01 part by mass, the expected improvement in storage stability may not be achieved, whereas if it exceeds 20 parts by mass, a decrease in adhesive strength may occur.

[0091] When the dental adhesive composition is a dental adhesive composition consisting of a first agent and a second agent, the aliphatic tertiary amine compound represented by formula (D-1) is blended in an amount of 0.02 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, in the first agent relative to a total of 100 parts by mass of the polymerizable monomer (A) and the volatile organic solvent (F) contained in the first agent, or relative to a total of 100 parts by mass of the polymerizable monomer (A), the volatile organic solvent (F), and the water (G) contained in the first agent when water (G) is contained. If the amount is less than 0.02 parts by mass, adhesion to tooth structure or prosthetic devices may not be imparted, and if the amount is more than 20 parts by mass, storage stability may be impaired.

[0092] The type of (D) photopolymerization accelerator can be appropriately selected depending on the types and amounts of other components to be combined. The (D) photopolymerization accelerator can be used alone or in combination of two or more types.

[0093] The dental adhesive composition of the present invention may contain, as the photopolymerization accelerator (D), only an aliphatic tertiary amine compound represented by formula (1) (D-1). The dental adhesive composition of the present invention may contain, as the photopolymerization accelerator (D), only an aliphatic tertiary amine compound represented by formula (1) (D-1), in which R1 and R2 have aliphatic substituents consisting of three or more carbon atoms and having an electron-withdrawing group at the α-carbon and / or β-carbon. The dental adhesive composition of the present invention may contain, as the photopolymerization accelerator (D), only an aliphatic tertiary amine compound represented by formula (1) (D-1), in which R1 and R2 have an aryl group which may have a substituent at the α-carbon and / or β-carbon.

[0094] These polymerization initiators (B) photosensitizer, (C) photoacid generator, and (D) photopolymerization accelerator may be subjected to secondary treatment such as fine pulverization, carrier adsorption, or encapsulation in microcapsules, if necessary. Furthermore, these various types of photopolymerization initiators can be used alone or in combination of two or more types, regardless of the polymerization mode or polymerization method.

[0095] [(E) Filler] The dental adhesive composition of the present invention may contain a filler (E), and any known filler that is commonly used may be used without any limitation.

[0096] The type of (E) filler is not limited as long as it is a known filler, and a filler suitable for the intended use can be blended, and it is preferable to blend fillers such as inorganic fillers, organic fillers, or organic-inorganic composite fillers. These may be used alone or in combination regardless of the type of filler.

[0097] The inorganic filler is not particularly limited in chemical composition, and specific examples include silicon dioxide, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. In particular, barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, fluoroaluminosilicate glass, etc., which are used in dental glass ionomer cements, resin-reinforced glass ionomer cements, resin cements, etc., can also be suitably used. The fluoroaluminosilicate glass referred to here has a basic skeleton of silicon oxide and aluminum oxide, and contains alkali metals for the introduction of non-bridging oxygen. It also contains alkaline earth metals, including strontium, and fluorine as modifying and coordinating ions. Furthermore, it is a composition in which lanthanide series elements are incorporated into the skeleton to impart further radiopacity. Depending on the composition range, these lanthanide series elements are also incorporated into the composition as modifying and coordinating ions.

[0098] Specific examples of the organic filler include polymers such as 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.

[0099] Examples of organic-inorganic composite fillers include, but are not limited to, fillers whose surfaces are polymerized and coated with polymerizable monomers, fillers obtained by mixing and polymerizing a filler and a polymerizable monomer and then pulverizing the mixture to an appropriate particle size, and fillers obtained by dispersing a filler in a polymerizable monomer in advance and then emulsion-polymerizing or suspension-polymerizing the dispersed filler.

[0100] The filler (E) can be treated with a surface treatment agent, typically a silane coupling agent, to improve its affinity with the polymerizable monomer, its dispersibility in the polymerizable monomer, and the mechanical strength and water resistance of the cured product. The surface treatment agent and surface treatment method are not particularly limited, and known methods can be used without limitation. Preferred silane coupling agents used for the surface treatment of the filler 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, and hexamethyldisilazane. In addition to silane coupling agents, the filler can also be surface-treated using a titanate-based coupling agent or an aluminate-based coupling agent. The amount of the surface treatment agent on the filler is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the filler before treatment.

[0101] The shape of the filler is not particularly limited, and any shape such as amorphous, spherical, needle-like, plate-like, crushed, scale-like, etc. The average particle size of the filler is preferably 0.01 μm to 50 μm, more preferably 0.01 μm to 30 μm, still more preferably 0.05 μm to 20 μm, and even more preferably 0.05 μm to 10 μm.

[0102] When the dental adhesive composition contains (E) filler, the amount is preferably 0.1 to 50 parts by mass per 100 parts by mass of the total of (A) polymerizable monomer and (F) volatile organic solvent, or, when (G) water is contained, per 100 parts by mass of the total of (A) polymerizable monomer, (F) volatile organic solvent, and (G) water. If the amount of filler is less than 0.1 part by mass, the effects of adding the filler to improve mechanical strength and to develop thixotropy may be poor, while if more than 50 parts by mass is added, a decrease in adhesive strength may occur.

[0103] The dental adhesive composition of the present invention contains (F) a volatile organic solvent. The volatile organic solvent is used for purposes such as dissolving the (A-1) polymerizable monomer component containing the polymerizable monomer having an acidic group and water in the composition, or for reducing the viscosity of the dental adhesive composition. The volatile organic solvent typically has a boiling point of 150°C or lower at atmospheric pressure and a solubility in water at 25°C of 5% by weight or more, more preferably 30% by weight or more, and most preferably an organic solvent that can be dissolved in water at any ratio. Among these, water-soluble volatile organic solvents with a boiling point of 100°C or lower at atmospheric pressure are preferred, and specific examples include ethanol, methanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane, and tetrahydrofuran. Of the aforementioned volatile organic solvents, ethanol, isopropyl alcohol, acetone, and methyl ethyl ketone are more preferred.

[0104] The (F) volatile organic solvent may be used alone or in combination of two or more. When the dental adhesive composition is a one-component dental adhesive composition, the blending amount of the (F) volatile organic solvent is preferably 1 to 99.9 parts by mass, more preferably 5 to 99.9 parts by mass, and most preferably 10 to 80 parts by mass, relative to 100 parts by mass of the total of the (A) polymerizable monomer and the (F) volatile organic solvent contained in the dental adhesive composition, or, when (G) water is contained, relative to 100 parts by mass of the total of the (A) polymerizable monomer, the (F) volatile organic solvent, and the (G) water.

[0105] When the dental adhesive composition is a dental adhesive composition consisting of a first agent and a second agent, the amount of the (F) volatile organic solvent is preferably 1 to 99.9 parts by mass, more preferably 5 to 99.9 parts by mass, and most preferably 10 to 80 parts by mass, relative to 100 parts by mass of the total of the (A) polymerizable monomer and the (F) volatile organic solvent contained in the first agent, or, when (G) water is contained, relative to 100 parts by mass of the total of the (A) polymerizable monomer, the (F) volatile organic solvent, and the (G) water contained in the first agent.

[0106] The dental adhesive composition of the present invention may contain (G) water to improve wettability to an adherend, specific examples of which include deionized water, distilled water, etc. The amount of water is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, per 100 parts by mass of the total of (A) polymerizable monomer, (F) volatile organic solvent, and (G) water contained in the dental adhesive composition.

[0107] The dental adhesive composition of the present invention may contain a chemical polymerization initiator. Examples of organic peroxides as chemical polymerization initiators include diacyl peroxides, peroxy esters, dialkyl peroxides, peroxyketals, ketone peroxides, peroxydicarbonates, and hydroperoxides. Specific examples of diacyl peroxides include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. Specific examples of peroxyesters include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, and t-butylperoxymaleic acid. Specific examples of dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne. Specific examples of peroxyketals include 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, n-butyl 4,4-(t-butylperoxy)pallate, and 1,1-di(t-amylperoxy)cyclohexane. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.Specific examples of peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate. Specific examples of hydroperoxides include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0108] The organic peroxide may be one of the above organic peroxides, or two or more organic peroxides may be used in combination. Among these organic peroxides, benzoyl peroxide and cumene hydroperoxide are preferred from the viewpoint of curability. To improve curability, the amount of organic peroxide used as a chemical polymerization initiator is preferably set to 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, per 100 parts by mass of the total of (A) polymerizable monomer and (F) volatile organic solvent, or, when (G) water is contained, per 100 parts by mass of the total of (A) polymerizable monomer, (F) volatile organic solvent, and (G) water. If the amount of organic peroxide is more than 5 parts by mass, it may be difficult to ensure sufficient operation time. On the other hand, if the amount of organic peroxide is less than 0.1 part by mass, mechanical strength may be insufficient.

[0109] The dental adhesive composition of the present invention may further contain a chemical polymerization accelerator to further improve curability. Examples of chemical polymerization accelerators include fourth-period transition metal compounds, thiourea derivatives, aliphatic amines, aromatic amines, sulfinic acids and their salts, borate compounds, sulfur-containing reducing inorganic compounds, nitrogen-containing reducing inorganic compounds, barbituric acid derivatives, triazine compounds, and halogen compounds. The amount of the chemical polymerization accelerator is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total of (A) polymerizable monomer and (F) volatile organic solvent. When (G) water is contained, the amount of the chemical polymerization accelerator is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total of (A) polymerizable monomer, (F) volatile organic solvent, and (G) water.

[0110] The fourth period transition metal compound used as a chemical polymerization accelerator refers to a metal compound of Groups 3 to 12 of the fourth period of the periodic table. Specifically, any metal compound of scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), or zinc (Zn) can be used without limitation. Each of the above transition metal elements can have multiple valences, but any valence that allows stable existence can be added to the dental adhesive composition of the present invention. Examples include Sc (trivalent), Ti (tetravalent), V (tri-, tetra-, or pentavalent), Cr (di-, tri-, or hexavalent), Mn (di- to heptavalent), Fe (di- or trivalent), Co (di- or trivalent), Ni (divalent), Cu (mono- or divalent), and Zn (divalent). Specific examples of transition metal compounds include scandium compounds such as scandium iodide (trivalent), titanium compounds such as titanium chloride (tetravalent) and titanium (tetravalent) tetraisopropoxide, and vanadium compounds such as vanadium acetylacetonate (trivalent), divanadium tetroxide (tetravalent), vanadyl acetylacetonate (tetravalent), vanadium stearate oxide (tetravalent), vanadyl oxalate (tetravalent), vanadyl sulfate (tetravalent), oxobis(1-phenyl-1,3-butanedionate)vanadium (tetravalent), and bis(maltolato)oxovanadium (tetravalent). ), vanadium pentoxide (5), sodium metavanadate (5), etc.; manganese compounds include manganese acetate (2), manganese naphthenate (2); iron compounds include iron acetate (2), iron chloride (2), iron acetate (3), iron chloride (3); cobalt compounds include cobalt acetate (2), cobalt naphthenate (2); nickel compounds include nickel chloride (2); copper compounds include copper chloride (1), copper bromide (1), copper chloride (2), copper acetate (2); zinc compounds include zinc chloride (2), zinc acetate (2).

[0111] Among these, trivalent or tetravalent vanadium compounds and divalent copper compounds are preferred, with trivalent or tetravalent vanadium compounds being more preferred due to their higher polymerization-promoting ability, and tetravalent vanadium compounds being most preferred. These fourth-period transition metal compounds may be used in combination as needed. The amount of the transition metal compound is preferably 0.0001 to 1 part by mass per 100 parts by mass of the total of (A) polymerizable monomer and (F) volatile organic solvent, or, when (G) water is included, per 100 parts by mass of the total of (A) polymerizable monomer, (F) volatile organic solvent, and (G) water. Less than 0.0001 part by mass of the transition metal compound may result in insufficient polymerization-promoting effect, while more than 1 part by mass may cause discoloration or gelation of the dental adhesive composition, resulting in reduced storage stability.

[0112] Any known thiourea derivative can be used as a chemical polymerization accelerator without limitation. Specific examples include 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, (2-pyridyl)thiourea, N-acetylthiourea, and N-benzoylthiourea are preferred. If necessary, multiple types of these thiourea derivatives may be used in combination. The amount of the thiourea derivative to be blended is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the total of the (A) polymerizable monomer and the (F) volatile organic solvent, or, when (G) water is contained, 100 parts by mass of the total of the (A) polymerizable monomer, the (F) volatile organic solvent, and the (G) water. If the amount is less than 0.1 part by mass, the polymerization-promoting ability may be insufficient, and if the amount is more than 5 parts by mass, the storage stability may be reduced.

[0113] Examples of sulfinic acids and their salts include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, 2, Examples thereof include sodium 4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, and calcium 2,4,6-triisopropylbenzenesulfinate, with sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate being particularly preferred.

[0114] Specific examples of borate compounds having one aryl group per molecule include trialkylphenylboron, trialkyl(p-chlorophenyl)boron, trialkyl(p-fluorophenyl)boron, trialkyl(3,5-bistrifluoromethyl)phenylboron, trialkyl[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, trialkyl(p-nitrophenyl)boron, trialkyl(m-nitrophenyl)boron, trialkyl(p-butylphenyl)boron, trialkyl(m-butylphenyl)boron, trialkyl(p-butylphenyl)boron, Examples of suitable alkyl groups include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of trialkyl(m-butyloxyphenyl)boron, trialkyl(p-octyloxyphenyl)boron, and trialkyl(m-octyloxyphenyl)boron (wherein the alkyl group is at least one selected from the group consisting of an n-butyl group, an n-octyl group, an n-dodecyl group, and the like).Specific examples of borate compounds having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron, dialkyldi(3,5-bistrifluoromethyl)phenylboron, dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, dialkyldi(p-nitrophenyl)boron, dialkyldi(m-nitrophenyl)boron, dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron, and dialkyldi(p-butyloxyphenyl). )boron, dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p-octyloxyphenyl)boron, and dialkyldi(m-octyloxyphenyl)boron (wherein the alkyl group is at least one selected from the group consisting of an n-butyl group, an n-octyl group, an n-dodecyl group, and the like), sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, and butylquinolinium salt.Specific examples of borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron, monoalkyltri(p-fluorophenyl)boron, monoalkyltri(3,5-bistrifluoromethyl)phenylboron, monoalkyltri[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, monoalkyltri(p-nitrophenyl)boron, monoalkyltri(m-nitrophenyl)boron, monoalkyltri(p-butylphenyl)boron, monoalkyltri(m-butylphenyl)boron, monoalkyltri( Examples of suitable alkyl groups include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(p-octyloxyphenyl)boron, and monoalkyltri(m-octyloxyphenyl)boron (wherein the alkyl group is one selected from an n-butyl group, an n-octyl group, an n-dodecyl group, etc.).Specific examples of borate compounds having four aryl groups in one molecule include tetraphenylboron, tetrakis(p-chlorophenyl)boron, tetrakis(p-fluorophenyl)boron, tetrakis(3,5-bistrifluoromethyl)phenylboron, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, tetrakis(p-nitrophenyl)boron, tetrakis(m-nitrophenyl)boron, tetrakis(p-butylphenyl)boron, tetrakis(m-butylphenyl)boron, tetrakis(p-butyloxyphenyl)boron, tetrakis(m-butyloxyphenyl)boron, tetrakis(p-octyloxyphenyl)boron, and tetrakis(m Examples of the methyl quinolinium salt include sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of (m-octyloxyphenyl)triphenylboron, (p-octyloxyphenyl)triphenylboron, (p-fluorophenyl)triphenylboron, (3,5-bistrifluoromethyl)phenyltriphenylboron, (p-nitrophenyl)triphenylboron, (m-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron, and (p-octyloxyphenyl)triphenylboron.

[0115] Among these aryl borate compounds, it is more preferable to use a borate compound having three or four aryl groups in one molecule from the viewpoint of storage stability. Furthermore, these aryl borate compounds can be used alone or in combination of two or more.

[0116] Examples of sulfur-containing reducing inorganic compounds include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, and dithionites. Specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

[0117] Examples of the nitrogen-containing reducing inorganic compound include nitrites, and specific examples include sodium nitrite, potassium nitrite, calcium nitrite, and ammonium nitrite.

[0118] Barbituric acid derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propyl ... Examples of the salts of barbituric acids include pyrubarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and thiobarbituric acids (preferably salts of alkali metals or alkaline earth metals). Specific examples of the salts of these barbituric acids include sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate.

[0119] Specific examples of the halogen compound include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, and dilauryldimethylammonium bromide.

[0120] The dental adhesive composition of the present invention may be one that does not contain a chemical polymerization initiator or a chemical polymerization accelerator, and may be one that does not contain a polymerization initiator system of a polymerization system other than a photopolymerization system.

[0121] <Other ingredients> The dental adhesive composition of the present invention may contain components other than those described above, provided that the effects of the present invention are not impaired. For example, the dental adhesive composition of the present invention may optionally contain components such as fillers typified by fumed silica, benzophenone-based and benzotriazole-based UV absorbers, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, and 2,5-ditertiarybutyl-4-methylphenol, chain transfer agents such as α-alkylstyrene compounds, mercaptan compounds such as n-butyl mercaptan and n-octyl mercaptan, terpenoid compounds such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, and α-pinene, metal capture agents such as aminocarboxylic acid-based chelating agents and phosphonic acid-based chelating agents, discoloration inhibitors, antibacterial agents, color pigments, and other conventionally known additives, as needed.

[0122] The method for preparing the dental adhesive composition of the present invention is not particularly limited. Typical methods for producing dental adhesive compositions include simultaneously mixing (A) a polymerizable monomer containing (A-1) a polymerizable monomer having an acidic group, (D) a photopolymerization accelerator containing (D-1) an aliphatic tertiary amine compound represented by formula (1), (F) a volatile organic solvent, and (G) water, or mixing (A-1) a polymerizable monomer containing (A) a polymerizable monomer having an acidic group, (D) a photopolymerization accelerator containing (D-1) an aliphatic tertiary amine compound represented by formula (1), and (F) a volatile organic solvent, followed by adding (G) water and mixing. A mixer such as a mix rotor can be used for mixing. The dental adhesive composition of the present invention can also be produced using the above-mentioned production method without any problems.

[0123] The dental adhesive composition of the present invention can be used for dental bonding materials such as one-component dental adhesive compositions and two-component dental adhesive compositions, dental primers, dental coating materials, dental glass ionomer cements, etc. It can also be used as a dental adhesive kit combining the dental adhesive composition of the present invention with a dental hardenable composition. The dental hardenable composition can be used for dental adhesives, dental composite resins, dental core build-up materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicures, dental adhesives for fixing loose teeth, etc.

[0124] <One-component dental adhesive composition> When the present invention is used in a one-component dental adhesive composition, it is preferably used in dental bonding materials, dental primers, and dental coating materials. One-component dental adhesive compositions eliminate the need for complicated steps such as mixing before use, which is expected to reduce technical errors and ease the burden on the surgeon. The one-component dental adhesive composition may contain (A-1) a polymerizable monomer having an acidic group, (D-1) an aliphatic tertiary amine compound represented by formula (1), (F) a volatile organic solvent, (G) water, and / or (A) a polymerizable monomer such as a polymerizable monomer having an alkoxysilyl group or a polymerizable monomer having a sulfur atom, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator. In particular, the inclusion of (B) a photosensitizer and (C) a photoacid generator is preferred because the one-component dental adhesive composition hardens upon exposure to light after use, which is expected to improve adhesion to the next composition applied.

[0125] <Two-component dental adhesive composition> When the present invention is used in a two-component dental adhesive composition, it is preferably used in dental bonding materials, dental primers and coating materials, and dental glass ionomer cements. The two-component dental adhesive composition is prepared by mixing the two components before use. The preferred mixing ratio is 0.8 to 1.2:1.0 by mass. Curing proceeds without light irradiation, such as through glass ionomer reaction or redox reaction. Because the two-component dental adhesive composition cures without light irradiation, it is suitable for use in deep cavities where light is difficult to reach. Furthermore, light irradiation can be expected to develop high adhesive strength. The two-component dental adhesive composition is packaged in a first and second component. The first component contains (A-1) a polymerizable monomer having an acidic group, (D-1) an aliphatic tertiary amine compound represented by formula (1), (F) a volatile organic solvent, and (G) water. The first and second components contain a chemical polymerization accelerator and an organic peroxide, respectively. The first and second agents may contain (A) a polymerizable monomer such as a polymerizable monomer having an alkoxysilyl group or a polymerizable monomer having a sulfur atom, (B) a photosensitizer, (C) a photoacid generator, (D-1) a photopolymerization accelerator other than the aliphatic tertiary amine compound represented by formula (1), and the like.

[0126] <Dental adhesive kit> The dental adhesive composition of the present invention can be used as a dental adhesive kit in combination with a dental hardenable composition. The dental adhesive composition may be the one-component dental adhesive composition or the two-component dental adhesive composition described above. Examples of dental hardenable compositions include dental adhesives, dental composite resins, dental core buildup materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicures, dental adhesives for loose teeth, and glass ionomer cements. Among these, the dental adhesive composition is particularly useful as a two-step dental bonding material in combination with a dental adhesive, or as a dental adhesive kit in combination with a dental composite resin, dental core buildup material, dental resin cement, or glass ionomer cement. The dental hardenable composition contains (A) a polymerizable monomer and a polymerization initiator as essential components, and preferably also contains (E) a filler. The polymerization initiator can be classified as a photopolymerization initiator or a chemical polymerization initiator, and either one or both of these may be included. In particular, when a dental curable composition contains a (B) photosensitizer and a (C) photoacid generator as photopolymerization initiators, high adhesive strength and improved mechanical properties can be expected when combined with a dental adhesive composition containing the (D-1) aliphatic tertiary amine compound of the present invention represented by formula (1). The preferred blending amounts of such a dental curable composition are 0.001 to 2 parts by mass of the (B) photosensitizer and 0.01 to 10 parts by mass of the (C) photoacid generator per 100 parts by mass of the (A) polymerizable monomer contained in the dental photocurable composition, and the dental curable composition is preferably a one-part or two-part type.

[0127] The dental adhesive composition of the present invention may contain only (A) the polymerizable monomer, (D) the photopolymerization accelerator, and (F) the volatile organic solvent, or may contain only one or more of the above-mentioned components as components other than (A), (D), and (F). [Example]

[0128] Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

[0129] The materials used in the examples and comparative examples and their abbreviations are shown below. [(A) Polymerizable Monomer] Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane 2.6E: 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, in which the average number of moles of ethoxy groups added is 2.6 UDMA: N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)ethanol]methacrylate TEGDMA: Triethylene glycol dimethacrylate GDMA: Glycerin dimethacrylate HEMA: 2-hydroxyethyl methacrylate [(A-1) Polymerizable Monomer Having an Acidic Group] MDP: 10-methacryloyloxydecyl dihydrogen phosphate MHPA: 6-methacryloxyhexylphosphonoacetate MET: 4-methacryloxyethyl trimellitate META: 4-Methacryloyloxyethoxycarbonylphthalic anhydride [Polymerizable monomers having an alkoxysilyl group] MPTMS: 3-methacryloxypropyltrimethoxysilane [Polymerizable monomers containing sulfur atoms] MDDT: 10-methacryloxydecyl-6,8-dithioctanate

[0130] [(B) Photosensitizer] CQ: α-camphorquinone BAPO: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[0131] [(C) Photoacid generator] C1: Bis(4-tert-butylphenyl)iodonium nonafluorobutanesulfonate [ka] C2: Bis(4-tert-butylphenyl)iodonium camphorsulfonate [ka] C3: Bis(4-tert-butylphenyl)iodonium tris(pentafluoropropyl)trifluorophosphate [ka] C4: Bis(4-n-dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate [ka] C5: Bis[4-(tert-butyl)phenyl]iodonium tetra(nonafluoro-tert-butoxy)aluminate [ka] C6: Bis[4-(tert-butyl)phenyl]iodonium tetra(pentafluorophenyl)gallate [ka] C7: Diphenyliodonium trifluoromethanesulfonate [ka] C8: Bis(4-tert-butylphenyl)iodonium-p-toluenesulfonate [ka] C9: Bis(4-tert-butylphenyl)iodonium hexafluorophosphate [Chemical formula] C10: Bis(4-n-dodecylphenyl)iodonium hexafluorophosphate [Chemical formula] ·C11: 2,4,6-Tris(trichloromethyl)-1,3,5-triazine [Chemical formula] ·C12: Diphenyliodonium-2-carboxylate monohydrate [Chemical formula]

[0132] [(D) Photoinitiator] [(D-1) Aliphatic tertiary amine represented by formula (1)] [Having one substituent consisting of three or more carbons having an electron-withdrawing group at the α-carbon and / or β-carbon of the amine starting from N] ·D1-1: N,N-Diisopropylaminoethyl methacrylate [Chemical formula] ·D1-2: 3-Isopropyl-2-methyl-7-oxo-6,11-dioxo-3,8-diaza-tridecan-13-yl methacrylate [Chemical formula] ·D1-3: 2-(((2-(Dibutylamino)ethoxy)carbonyl)amino)ethyl methacrylate [Chemical formula] · D1-4: 1-[(3,3-diphenylpropyl)(methyl)amino]-2-methyl-2-propanol

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[0133] [(F) Volatile organic solvent] Ac: Acetone EtOH: Ethanol

[0134] [(G)Water] DW: Ion-exchanged water

[0135] [(E) Filler] The manufacturing method of each filler used in preparing the dental adhesive composition and / or the dental photocurable composition is shown below.

[0136] (Filler E1) To 100.0 g of fluoroaluminosilicate glass (average particle size 0.9 μm), 50.0 g of water, 35.0 g of ethanol, and 3.0 g of 3-methacryloyloxypropyltrimethoxysilane (a silane coupling agent) were stirred at room temperature for 2 hours, and the resulting silane coupling treatment solution was added and stirred for 30 minutes. The mixture was then heat-treated at 100°C for 15 hours to obtain filler E1.

[0137] (filler E2) To 100.0 g of zirconium silicate filler (average particle size 0.8 μm: zirconia 85 wt%, silica 15 wt%), 50.0 g of water, 35.0 g of ethanol, and 5.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours, and the resulting silane coupling treatment liquid was added and stirred for 30 minutes. Then, the mixture was heat-treated at 100 ° C for 15 hours to obtain filler E2.

[0138] (filler E3) To 100.0 g of Aerosil OX-50 (manufactured by Evonik), 5 g of water, 100 g of ethanol, and 10.0 g of silane coupling agent, di-3-(N,N-dibenzylamino)propyltriethoxysilane, were stirred at room temperature for 2 hours to obtain a silane coupling treatment solution, which was then added and mixed with stirring for 24 hours. After that, the mixture was heat-treated at 100°C for 15 hours to obtain filler E3.

[0139] (Filler E4) Aerosil R7200 (manufactured by Evonik)

[0140] (Filler E5) Aerosil OX-50 (manufactured by Evonik)

[0141] [Chemical polymerization initiator] CHP: Cumene hydroperoxide tBHP: tert-butyl hydroperoxide TPE: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate [Chemical polymerization accelerator] PTU: (2-pyridyl)thiourea DMPT: N,N-dimethyl-p-toluidine DEPT: N,N-dihydroxyethyl-p-toluidine GLA: Copper Gluconate VOA: Vanadyl acetylacetonate TMBA: Trimethylbarbituric acid

[0142] [UV absorber] BT: 2-(2-hydroxy-5-methylphenyl)benzotriazole [Polymerization inhibitor] BHT: 2,6-di-t-butyl-4-methylphenol MeHQ: p-Methoxyphenol [Fluorescent agent] FA: Diethyl 2,5-dihydroxyterephthalate

[0143] <Method for producing one-component dental adhesive composition> The components shown in Tables 1 and 2 were placed in a wide-mouth plastic container and mixed for 48 hours at 100 rpm using a VMRC-5 mix rotor under light-shielded conditions to prepare dental adhesive compositions. The resulting mixture was filled into light-shielding bottles to prepare dental adhesive compositions P and CP. In Tables 1 and 2, the abbreviation for each component is followed by the mass part of each component in parentheses.

[0144] [Table 1]

[0145] [Table 2]

[0146] <Method for producing two-component dental adhesive composition> The components of the first part shown in Tables 3 to 5 were placed in a wide-mouth plastic container and mixed for 48 hours at 100 rpm using a VMRC-5 mixer under light-shielded conditions. Similarly, the components of the second part were placed in a wide-mouth plastic container and mixed for 48 hours at 100 rpm using a VMRC-5 mixer under light-shielded conditions. The first and second parts were filled into different light-shielded bottles to prepare dental adhesive compositions Q and CQ. Each of Compositions Q and CQ was mixed in a weight ratio of 0.8 to 1.2:1.0 before use. In Tables 3 to 5, the abbreviation for each component is followed by the mass part of each component in parentheses.

[0147] [Table 3]

[0148] [Table 4]

[0149] [Table 5]

[0150] <Method for producing dental curable composition> All components except for the (E) filler shown in Tables 6 and 7 were mixed for 48 hours using a VMRC-5 mix rotor at 100 rpm to obtain a binder resin. The binder resin and (E) filler were then placed in a planetary centrifugal mixer (ARV-300) and mixed at 1400 rpm for 10 minutes, after which the mixture was degassed under vacuum. The one-component dental hardenable compositions shown in Table 6 were directly collected, and the two-component dental hardenable compositions shown in Table 7 were filled into a double syringe container manufactured by Mixpack, to prepare dental hardenable compositions R1 to R7 and S1 to S7. In Tables 6 and 7, the abbreviation for each component is followed by the part by mass of each component in parentheses.

[0151] [Table 6]

[0152] [Table 7]

[0153] The test method using each composition is as follows: As the two-component dental hardenable compositions S1 to S7, pastes prepared by mixing pastes 1 and 2 using a mixing tip manufactured by Mixpack Co., Ltd. were used.

[0154] <Storage stability of dental adhesive composition (accelerated test)> In a dark room at 23±2°C, 5 mL of each composition was taken with a plastic dropper and filled into a black polypropylene bottle. After attaching a nozzle and a cap, it was confirmed that the composition would not leak even when the bottle was inverted. The bottles filled with the compositions were stored in an incubator at 50°C for 3 months, and it was confirmed that no significant increase in viscosity or gelation had occurred.

[0155] [Adhesion strength to enamel] <Adhesion test 1> A test specimen of a bovine central incisor embedded in epoxy resin was polished with waterproof abrasive paper #600 to remove the enamel surface. Then, a 4 mm diameter perforated tape (20 μm thick) was attached to the adhesion surface to define the adhesive area. The composition was applied to the perforated tape and immediately air-dried. For two-component dental adhesive compositions, the same weight was weighed and thoroughly mixed before application, and then the composition was applied and immediately air-dried. The specimen was irradiated for 5 seconds with a dental polymerization LED light irradiator (Penbrite, Matsufu). A 2mm high, 4mm diameter perforated plastic mold was placed on top of the perforated tape and filled with dental composite resin (BeautyFillFlow Plus A3: Matsukaze) or the dental curable composition listed in Table 3. The mold was then irradiated for 10 seconds using a dental LED light irradiator (Penbrite, Matsukaze) and then immersed in 37°C water for 24 hours. The mold was then subjected to 5,000 cycles using a thermal shock tester (Thomas Scientific Instruments) in a 4°C cold water phase and a 60°C hot water phase, each 60 seconds counted as one cycle. After removal, the shear bond strength was measured using a universal testing machine (Instron) at a crosshead speed of 1 mm / min. Bond strengths of 20 MPa or greater were considered particularly good, 12 MPa to less than 20 MPa were considered good, 5 MPa to less than 12 MPa were considered acceptable, and less than 5 MPa was considered insufficient. In tests using dental curable compositions R1 to R7, the specimens were immersed in a 4°C cold water phase and a 60°C hot water phase for 60 seconds each, and the test was repeated 20,000 times using a thermal shock tester (manufactured by Thomas Scientific Instruments). After removing the specimens, the adhesive strength was measured at a crosshead speed of 1 mm / min using a universal testing machine (manufactured by Instron). Adhesive strengths of 28 MPa or more were judged to be extremely good, 20 MPa to less than 28 MPa to be particularly good, 12 MPa to less than 20 MPa to be good, 5 MPa to less than 12 MPa to be acceptable, and less than 5 MPa to be insufficient. <Adhesion test 2> Bovine central incisor specimens embedded in epoxy resin were polished with #600 waterproof abrasive paper to remove the enamel surface. Subsequently, a 4 mm diameter perforated tape (20 μm thick) was applied to the adhesion surface to define the adhesion area. The composition was applied within the perforated tape and immediately air-dried. For two-component dental adhesive compositions, the same weight was weighed and thoroughly mixed before application, followed by immediate air-drying. The adhesion surface of a stainless steel rod (φ4.5 mm) was sandblasted with alumina (50 μm) (0.2 MPa, 1 second), rinsed with water, dried, and then coated with a metal adhesive primer (Metal Link, Matsukaze). An appropriate amount of resin cement (ResiCem, Matsukaze) or a mixture of the dental curable composition listed in Table 4 was applied to the adhesion surface of the stainless steel rod, and the tooth structure and stainless steel rod were cemented so that they fit within the frame of the perforated double-sided tape. A 200N load was applied perpendicular to the stainless steel rod, and excess cement was wiped off with a cloth. The specimens were then exposed to light for 10 seconds using a dental LED curing light source (Penbrite, Matsufu). After the load was removed, the resulting adhesive specimens were immersed in 37°C water for 24 hours. Then, using a thermal shock tester (Thomas Scientific Instruments), the specimens were immersed in a cold water phase at 4°C and a hot water phase at 60°C for 60 seconds each, counting each as one cycle, and then subjected to 5,000 cycles. After removal, the shear bond strength was measured using a universal testing machine (Instron) at a crosshead speed of 1 mm / min. Bond strengths of 20 MPa or greater were considered excellent, 12 MPa to less than 20 MPa good, 5 MPa to less than 12 MPa acceptable, and less than 5 MPa insufficient. In tests using dental curable compositions S1 to S7 in combination, the specimens were immersed in a 4°C cold water phase and a 60°C hot water phase for 60 seconds each, and the test was repeated 20,000 times using a thermal shock tester (manufactured by Thomas Scientific Instruments). After removing the specimens, the adhesive strength was measured at a crosshead speed of 1 mm / min using a universal testing machine (manufactured by Instron). Adhesion strengths of 28 MPa or more were judged to be extremely good, 20 MPa or more but less than 28 MPa particularly good, 12 MPa or more but less than 20 MPa good, 5 MPa or more but less than 12 MPa acceptable, and less than 5 MPa insufficient.

[0156] A high adhesive strength is preferable because low adhesive strength increases the risk of detachment of the filling material or prosthetic device, marginal leakage, and secondary caries.

[0157] [Bonding strength to dentin] <Adhesion test 1> A bovine central incisor specimen embedded in epoxy resin was polished with #600 waterproof abrasive paper to remove the dentin surface. A 4 mm diameter perforated tape (20 μm thick) was then applied to the surface to define the adhesive area. The composition was applied to the perforated tape and immediately air-dried. The two-component dental adhesive composition was weighed out and thoroughly mixed before application, then immediately air-dried. Irradiation was performed for 5 seconds using a dental LED polymerization light irradiator (Penbrite, Matsufu). A 2 mm high, 4 mm diameter perforated plastic mold was placed on top of the perforated tape and filled with dental composite resin (Beautifil Flow Plus A3: Matsufu) or the dental curable composition listed in Table 3. The mold was then irradiated for 10 seconds using a dental LED polymerization light irradiator (Penbrite, Matsufu). The mold was then immersed in 37°C water for 24 hours. After immersion for 60 seconds each in a 4°C cold water phase and a 60°C hot water phase, the test was repeated 5,000 times using a thermal shock tester (Thomas Scientific Instruments). After removal, the shear bond strength was measured using a universal testing machine (Instron) at a crosshead speed of 1 mm / min. Adhesion strengths of 12 MPa or more were judged to be particularly good, 8 MPa to less than 12 MPa to be good, 3 MPa to less than 8 MPa to be applicable, and less than 3 MPa to be insufficient. In tests using dental curable compositions R1 to R7 in combination, immersion for 60 seconds in a cold water phase at 4°C and a high temperature phase at 60°C was counted as one cycle, and the test specimens were subjected to 20,000 cycles using a thermal shock tester (manufactured by Thomas Scientific Instruments). After removing the specimens, adhesion strengths were measured at a crosshead speed of 1 mm / min using a universal testing machine (manufactured by Instron). Adhesion strengths of 19 MPa or more were judged to be extremely good, 12 MPa to less than 19 MPa to be particularly good, 8 MPa to less than 12 MPa to be good, 3 MPa to less than 8 MPa to be applicable, and less than 3 MPa to be insufficient. <Adhesion test 2> Bovine central incisor specimens embedded in epoxy resin were polished with #600 waterproof abrasive paper to remove the dentin surface. Subsequently, a 4 mm diameter perforated tape (20 μm thick) was applied to the adhesion surface to define the bonding area. The composition was applied within the perforated tape and immediately air-dried. For two-component dental adhesive compositions, the same weight was weighed and thoroughly mixed before application, followed by immediate air-drying. The adhesion surface of a stainless steel rod (φ4.5 mm) was sandblasted with alumina (50 μm) (0.2 MPa, 1 second), rinsed with water, dried, and then coated with a metal adhesive primer (Metal Link, Matsukaze). An appropriate amount of resin cement (ResiCem, Matsukaze) or a mixture of the dental curable composition listed in Table 4 was applied to the adhesion surface of the stainless steel rod, and the tooth and stainless steel rod were cemented so that they fit within the frame of the perforated double-sided tape. A 200 N load was applied perpendicular to the stainless steel rod, and excess cement was wiped off with a cloth. The specimens were then exposed to light for 10 seconds using a dental LED curing light source (Penbrite, Matsufu). After the load was removed, the resulting adhesive specimens were immersed in 37°C water for 24 hours. Then, using a thermal shock tester (Thomas Scientific Instruments), the specimens were immersed in a cold water phase at 4°C and a hot water phase at 60°C for 60 seconds each, counting each as one cycle, and then subjected to 5,000 cycles. After removal, the shear bond strength was measured using a universal testing machine (Instron) at a crosshead speed of 1 mm / min. Bond strengths of 12 MPa or greater were considered excellent, 8 MPa to less than 12 MPa were considered good, 3 MPa to less than 8 MPa were considered acceptable, and less than 3 MPa was considered insufficient. In tests using dental curable compositions S1 to S7 in combination, the specimens were immersed in a 4°C cold water phase and a 60°C hot water phase for 60 seconds each, and the test was repeated 20,000 times using a thermal shock tester (manufactured by Thomas Scientific Instruments). After removing the specimens, the adhesive strength was measured at a crosshead speed of 1 mm / min using a universal testing machine (manufactured by Instron). Adhesion strengths of 19 MPa or more were judged to be extremely good, 12 MPa to less than 19 MPa particularly good, 8 MPa to less than 12 MPa good, 3 MPa to less than 8 MPa acceptable, and less than 3 MPa insufficient.

[0158] [Adhesion strength to zirconia] <Adhesion test 1> Zirconia (Shofu Disk ZR Lucent Supra, manufactured by Shofu) was processed using a specified method to prepare test pieces measuring 3 mm thick and 20 mm long and wide. The adhesion surface was then sandblasted, and a 4 mm diameter perforated tape (20 μm thick) was attached to define the adhesive area. The composition was applied to the perforated tape and immediately air-dried. For two-component dental adhesive compositions, the same weight was weighed out and thoroughly mixed before application, and then the composition was applied and immediately air-dried. The test pieces were irradiated for 5 seconds using a dental polymerization LED light irradiator (Penbrite, Shofu). A 2mm high, 4mm diameter perforated plastic mold was placed on top of the perforated tape and filled with dental composite resin (BeautyFillFlow Plus A3: Matsukaze) or the dental curable composition listed in Table 3. The mold was then irradiated for 10 seconds using a dental LED light irradiator (Penbrite, Matsukaze) and then immersed in 37°C water for 24 hours. The mold was then subjected to 5,000 cycles using a thermal shock tester (Thomas Scientific Instruments) in a 4°C cold water phase and a 60°C hot water phase, each 60 seconds counted as one cycle. After removal, the shear bond strength was measured using a universal testing machine (Instron) at a crosshead speed of 1 mm / min. Bond strengths of 20 MPa or greater were considered particularly good, 12 MPa to less than 20 MPa were considered good, 5 MPa to less than 12 MPa were considered acceptable, and less than 5 MPa was considered insufficient. In tests using dental curable compositions R1 to R7, the specimens were immersed in a 4°C cold water phase and a 60°C hot water phase for 60 seconds each, and the test was repeated 20,000 times using a thermal shock tester (manufactured by Thomas Scientific Instruments). After removing the specimens, the adhesive strength was measured at a crosshead speed of 1 mm / min using a universal testing machine (manufactured by Instron). Adhesive strengths of 28 MPa or more were judged to be extremely good, 20 MPa to less than 28 MPa to be particularly good, 12 MPa to less than 20 MPa to be good, 5 MPa to less than 12 MPa to be acceptable, and less than 5 MPa to be insufficient. <Adhesion test 2> Zirconia (Shofu Disk ZR Lucent Supra, manufactured by Shofu) was processed using a specified method to prepare a test piece measuring 3 mm in thickness and 20 mm in length and width. The adhesion surface was then sandblasted, and a 4 mm diameter perforated tape (20 μm thick) was applied to define the adhesive area. The composition was applied within the perforated tape and immediately air-dried. For two-component dental adhesive compositions, the same weight was weighed and thoroughly mixed before application, followed by immediate air-drying. The adhesion surface of a stainless steel rod (φ4.5 mm) was sandblasted with alumina (50 μm) (0.2 MPa, 1 second), rinsed with water, dried, and then coated with a metal adhesive primer (Metal Link, Matsukaze). An appropriate amount of resin cement (ResiCem, Matsukaze) or a dental curable composition mix listed in Table 4 was applied to the adhesion surface of the stainless steel rod, and the tooth structure and stainless steel rod were bonded so that they fit within the frame of the perforated double-sided tape. A load of 200 N was applied vertically to the stainless steel rod, and excess cement was wiped off with a cloth. The specimens were then irradiated with light for 10 seconds using a dental polymerization LED light irradiator (Penbrite, Matsufu). After the load was removed, the resulting adhesive test specimens were immersed in water at 37°C for 24 hours. Using a thermal shock tester (manufactured by Thomas Scientific Instruments), the specimens were immersed in a cold water phase at 4°C and a high-temperature phase at 60°C for 60 seconds each, counting each as one cycle, and then cycled 5,000 times. After removal, the shear bond strength was measured using a universal testing machine (manufactured by Instron) at a crosshead speed of 1 mm / min. Bond strengths of 20 MPa or more were considered particularly good, 12 MPa to less than 20 MPa good, 5 MPa to less than 12 MPa acceptable, and less than 5 MPa insufficient. In addition, when tested in combination with dental curable compositions S1 to S7, the specimens were cycled 20,000 times using a thermal shock tester (manufactured by Thomas Scientific Instruments), counting each as one cycle, in a cold water phase at 4°C and a high-temperature phase at 60°C. After removing the specimen, the adhesive strength was measured using a universal testing machine (manufactured by Instron) at a crosshead speed of 1 mm / min. Adhesive strength of 28 MPa or more was judged as extremely good, 20 MPa or more but less than 28 MPa as particularly good, 12 MPa or more but less than 20 MPa as good, 5 MPa or more but less than 12 MPa as acceptable, and less than 5 MPa as insufficient.

[0159] [Evaluation of storage stability of accelerated test samples] The storage stability of accelerated test samples was evaluated by measuring the adhesive strength of the same composition on the same adherend before and after the accelerated test, and calculating the adhesive strength retention rate according to Equation 3. A retention rate of 90% or more was determined to be particularly good storage stability, 70% or more but less than 90% was good storage stability, 50% or more but less than 70% was applicable storage stability, and less than 50% was determined to be poor storage stability. [Formula 3] (Adhesion strength after accelerated test [MPa] / Adhesion strength before accelerated test [MPa]) x 100 [%]

[0160] Tables 8 and 9 show the results for each composition P and each composition CP.

[0161] [Table 8]

[0162] [Table 9]

[0163] Compositions P1 to P47 showed good adhesion and retention rate. Among them, Examples P1, P7 to P17, P23, P24, P26, P27, P31 to 40, and P42 to 47 were confirmed to have both high adhesive strength and extremely high retention rate.

[0164] On the other hand, compositions CP1 and CP2 did not contain an amine compound, and therefore exhibited a significant decrease in adhesive strength after storage. Composition CP3 did not contain (A-1) a polymerizable monomer having an acidic group, and therefore exhibited almost no adhesive strength. Compositions CP4 to CP13 contained an amine compound, but because the amine compound had a structure different from that represented by formula (1), their adhesive strength after storage significantly decreased. From the above, it can be inferred that high adhesiveness and performance can be maintained when (A-1) a polymerizable monomer having an acidic group and (D-1) an aliphatic tertiary amine compound represented by formula (1) coexist and are blended in appropriate amounts.

[0165] Tables 10 to 12 show the results for each composition Q and each composition CQ.

[0166] [Table 10]

[0167] [Table 11]

[0168] [Table 12]

[0169] Compositions Q1 to Q40 showed good adhesion and retention rate. Among them, Examples Q7 to 17, Q26, Q27, and Q31 to 40 were confirmed to have both high adhesive strength and extremely high retention rate.

[0170] On the other hand, composition CQ1, lacking an amine compound, exhibited a significant decrease in adhesive strength after storage. Composition CQ42, lacking (A-1) a polymerizable monomer with an acidic group, demonstrated almost no adhesive strength. Composition CQ43 exhibited good adhesive properties, but their retention was low. This is thought to be due to the fact that, although it contained an amine compound, it was an aromatic amine. Composition CQ44, containing a photoacid generator, exhibited good adhesive properties, but its adhesive strength after storage significantly decreased. Furthermore, composition Q was tested in the same manner as in Adhesion Test 1. After each composition was applied, air-dried, and then irradiated for 5 seconds with a dental LED curing light (Penbrite, Matsukaze), good adhesive strength and its retention were confirmed.

[0171] Table 13 shows the test results for Kit R and Kit CR, which consist of combinations of curable compositions R1 to R7 and adhesive compositions P4, P14, P35, CP3, CP5, and CP11.

[0172] [Table 13]

[0173] Examples R1 to R5, R8 to R12, and R15 to R19 exhibited excellent adhesion and retention. Among these, Examples R1 to R5 and R15 to R19 exhibited extremely high adhesion, demonstrating a synergistic effect due to the inclusion of (A-1) a polymerizable monomer having an acidic group and (D-1) an aliphatic tertiary amine compound represented by formula (1) in the adhesive composition and the inclusion of a photoacid generator in the curable composition. Examples R6 and R7 exhibited reduced adhesive strength after storage, presumably due to the absence of (C) a photoacid generator. Comparative Examples CR1 to CR7, which were combined with Composition CP3, demonstrated almost no adhesive strength, due to the absence of (A-1) a polymerizable monomer having an acidic group in Composition CP3. Comparative Examples CR8 to CR21, which contained Composition CP5 or CP11, exhibited low adhesive strength after storage and a reduced retention rate. Like other compositions, the adhesive composition contains only the aliphatic tertiary amine compound (D-1) represented by formula (1), and it is presumed that this is why the adhesive strength decreases after storage.

[0174] Table 14 shows the test results of the kits of Examples S1 to S42, which consisted of combinations of two-component dental curable compositions S1 to S7 and adhesive compositions P1, P15, P36, Q1, Q7, and Q14.

[0175] [Table 14]

[0176] Examples S1 to S42 showed good adhesion and retention. In particular, Kits S1 to S5, S8 to S12, S15 to S19, S22 to S26, S29 to S33, and S36 to S40 showed extremely high adhesion, demonstrating a synergistic effect due to the inclusion of (A-1) a polymerizable monomer having an acidic group and (D-1) an aliphatic tertiary amine compound represented by formula (1) in the adhesive composition, and the inclusion of a photoacid generator in the curable composition.

[0177] The dental adhesive composition of the present invention evaluated in the examples can be applied as any known dental adhesive, dental composite resin, dental abutment construction material, dental resin cement, dental coating material, dental pit and fissure sealant, dental manicure material, dental adhesive for fixing loose teeth, dental glass ionomer cement, etc. [Industrial Applicability]

[0178] According to the present invention, a dental adhesive composition having excellent storage stability and adhesive strength can be provided.

Claims

1. A one-component dental adhesive composition comprising (A) a polymerizable monomer, (D) a photopolymerization accelerator, and (F) a volatile organic solvent, (A) the polymerizable monomer includes (A-1) a polymerizable monomer having an acidic group, (D) a photopolymerization accelerator (D-1) containing an aliphatic tertiary amine compound represented by formula (1), (C) further comprising an aryliodonium salt as a photoacid generator; per 100 parts by mass of the total of the polymerizable monomer (A) and the volatile organic solvent (F), or per 100 parts by mass of the total of the polymerizable monomer (A), the volatile organic solvent (F), and the water (G) when water (G) is contained, (A-1) contains 0.1 to 20 parts by mass of a polymerizable monomer having an acidic group, (F) 1 to 99.9 parts by mass of a volatile organic solvent; and (D-1) A dental adhesive composition containing 0.01 to 20 parts by mass of an aliphatic tertiary amine compound represented by formula (1). [Formula (1)] 【Chemical 1】 (In the formula, R １ is a substituent having a total of 3 or more carbon atoms starting from N and having the α-position carbon and / or β-position carbon of the amine. The α-position carbon and / or β-position carbon of R 1 do not constitute an electron-withdrawing group. An electron-withdrawing group that is electron-withdrawing to the α-position carbon and / or β-position carbon of R 1 is bonded to the α-position carbon and / or β-position carbon of R 1 . R ２ is a substituent having a total of 3 or more carbon atoms starting from N and having the α-position carbon and / or β-position carbon of the amine. The α-position carbon and / or β-position carbon of R 2 do not constitute an electron-withdrawing group. R 2 may have an electron-withdrawing group at the α-position carbon and / or β-position carbon of R 2 that is electron-withdrawing to the α-position carbon and / or β-position carbon of R 2 . R ３ is a substituent having a total carbon number of 1 or more, starting from N and having the α-carbon and / or β-carbon of the amine. The α-carbon and / or β-carbon of R 3 do not constitute an electron-withdrawing group. R 3 may have, at the α-carbon and / or β-carbon of R 3 , an electron-withdrawing group that is electron-withdrawing toward the α-carbon and / or β-carbon of R 3 . The electron-withdrawing group in R 1 , R 2 , and R 3 is a substituent selected from a hydroxyl group, a carboxyl group, a vinyl group, an aryl group, or an organic group bonded via an ether bond, an ester bond, a urethane bond, or a urea bond, and which is an —OH group, —O— group, —C(O)— group, —S— group, —NH—C(O)—NH— group, —C(O)—O— group, —O—C(O)— group, —O—C(O)—NH— group, —NH—C(O)—O— group, an aromatic hydrocarbon group, or an organic group which may have a polymerizable functional group capable of radical polymerization.

2. (D-1) The aliphatic tertiary amine compound represented by formula (1) is R １ and R ２ 2. The dental adhesive composition according to claim 1, wherein is an aliphatic tertiary amine compound having an aliphatic substituent consisting of three or more carbon atoms and having an electron-withdrawing group at the α-carbon and / or β-carbon.

3. (D-1) The aliphatic tertiary amine compound represented by formula (1) is R １ and R ２ 2. The dental adhesive composition according to claim 1, wherein is an aliphatic tertiary amine compound having an aryl group which may have a substituent at the α-position carbon and / or the β-position carbon.

4. The dental adhesive composition according to any one of claims 1 to 3, further comprising (G) water.

5. 5. The dental adhesive composition according to claim 1, further comprising (B) a photosensitizer.

6. The dental adhesive composition according to any one of claims 1 to 5, wherein the aryliodonium salt is a salt of an aryliodonium cation and an anion having an organic group and one or more atoms of P, B, Al, S, and Ga.

7. The dental adhesive composition according to any one of claims 1 to 5, wherein the aryliodonium salt is a salt of an anion having an organic group in which at least one H is substituted with F and one or more atoms of P, B, Al, S, and Ga, and an aryliodonium cation.

8. A dental adhesive kit comprising a dental photocurable composition and the dental adhesive composition according to any one of claims 1 to 7, The dental photocurable composition comprises (A') a polymerizable monomer, (B') a photosensitizer, and (C') a photoacid generator, relative to 100 parts by mass of the polymerizable monomer (A′) contained in the dental photocurable composition, (B') contains 0.001 to 2 parts by mass of a photosensitizer, and (C') A dental adhesive kit containing 0.01 to 10 parts by mass of a photoacid generator.

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