Dental adhesive compositions characterized by specific silane coupling agent formulation ratios.

Abstract

To provide a dental adhesive composition, while realizing excellent durability adhesiveness with respect to lithium disilicate glass, resin for dental cutting work, and dentin, having excellent storage stability.SOLUTION: A dental adhesive composition comprises silane coupling materials including a silane coupling material (A1) having a specified structural formula, a polymerizable monomer having acidic groups, a polymerizable monomer having no acidic group, and a volatile organic solvent, and water, and further comprises a polymerization initiator, a polymerization promoter, either thereof, or both thereof. The total sum of silane coupling material blending amount indexes in the composition for each kind of the silane coupling materials including the silane coupling material (A1) satisfies the following formula (1). The formula (1) is: 0.001≤the total sum of the silane coupling material blending amount indexes in the matrix ((S×W) / M)≤0.015 (M represents a molecular mass of the silane coupling materials, S represents the number of alkoxysilyl groups in the molecules of the silane coupling materials, and W represents blending amounts (%) of the silane coupling materials).SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In the dental field, dental adhesive compositions are widely used as dental adhesives, dentin primers, metal primers, and ceramic primers.

[0003] In dental treatment, adherents for adhesion include various materials such as dentin, noble metal alloys, non-noble metal alloys, oxide-based ceramics, glass-based ceramics, and composite resins containing inorganic fillers. Therefore, it is common to use dedicated dental adhesive compositions suitable for various adherent objects. For example, when the adherent is dentin (dentin, enamel), a dental adhesive composition containing an acidic group-containing polymerizable monomer is used. When the treated surface is a noble metal alloy mainly composed of gold, platinum, palladium, silver, etc., a dental adhesive composition containing a sulfur atom-containing polymerizable monomer is used. When the adherent is a non-noble metal alloy such as iron, nickel, chromium, cobalt, tin, aluminum, copper, titanium, etc. or an oxide-based ceramic such as zirconia or alumina, a dental adhesive composition containing an acidic group-containing polymerizable monomer is used. Furthermore, when the adherent is a glass-based ceramic or a composite resin containing inorganic fillers, a dental adhesive composition containing a silane coupling agent is used. The silane coupling agent has an alkoxysilyl group (-Si-OR group) in its molecular structure, and it is considered that the alkoxysilyl group reacts and bonds with the glass ceramic surface or inorganic filler by mixing or heating with an acidic or basic aqueous solution to exhibit adhesiveness.

[0004] Patent Document 1 describes a one-component dental adhesive composition, characterized by being one-component, one-step, and exhibiting excellent adhesive strength to various dental restorative materials. Patent Document 2 describes a dental adhesive composition that can exhibit adhesion to precious metal alloys, non-precious metal alloys, oxide ceramics, glass ceramics, composite resins, and even tooth structure. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2016-124811 [Patent Document 2] Japanese Patent Publication No. 2018-177677 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a dental adhesive composition that exhibits excellent durability and adhesion to lithium disilicate glass, dental cutting resin, and tooth structure, particularly to dental cutting resin made of glass fiber reinforced resin, while also providing excellent storage stability. [Means for solving the problem]

[0007] The present invention relates to (A) a silane coupling material, (B) Polymerizable monomer having an acidic group, (C) Polymerizable monomers that do not have acidic groups, (F)Volatile organic solvent and (G)Water, (A) The silane coupling material includes the silane coupling material shown in (A1) structural formula [Chemical Formula 1], [C1] [ka] (In the formula, R 3C2~C may have -O-, -S-, -NH-, -C(O)-O-, -O-C(O)-, -O-C(O)-NH- and / or -NH-C(O)-O- groups. 15 R represents a (meth)acryloyl group having an alkyl group, 1 and R 2 (where n represents an alkyl group from C1 to C4, and these groups may be the same or different. n is between 1 and 3.) Furthermore, it includes either or both of (D) polymerization initiators and (E) polymerization accelerators, (A1) A dental adhesive composition is provided in which the sum of the silane coupling material content index in the composition calculated in formula (1) for each type of silane coupling material, which is represented by the structural formula [Chemical Formula 1], satisfies formula (1). [Formula (1)] 0.001 ≤ Total of the silane coupling agent content index in the composition ((S × W) / M) ≤ 0.015) (In formula (1), M is the molecular weight of each silane coupling agent contained in the composition, S is the number of alkoxysilyl groups in the molecule of each silane coupling agent contained in the composition, and W is the amount of each silane coupling agent blended in 100 parts by mass of the composition.)

[0008] The dental adhesive composition of the present invention comprises (C) a polymerizable monomer having no acidic groups, and (C1) a polymerizable monomer having one or more hydroxyl groups but no acidic groups, and the amount of (C1) a polymerizable monomer having one or more hydroxyl groups but no acidic groups can be 20 to 70 parts by mass per 100 parts by mass of the total of (A) a silane coupling material containing (A1) a silane coupling material shown in structural formula [Chemical Formula 1], (B) a polymerizable monomer having acidic groups, and (C) a polymerizable monomer having no acidic groups.

[0009] The dental adhesive composition of the present invention may be a silane coupling material having an acryloyl group, as shown in (A1) structural formula [Chemical Formula 1].

[0010] The dental adhesive composition of the present invention may be one in which (A) a silane coupling material represented by structural formula [Chemical Formula 1] is included, and (A) the sum of the silane coupling material content index in the composition calculated in formula (2) for each type of silane coupling material satisfies formula (2). [Formula (2)] 0.002 ≤ Total silane coupling agent content index ((S × W) / M) in the composition ≤ 0.008 (In formula (2), M is the molecular weight of each silane coupling agent contained in the composition, S is the number of alkoxysilyl groups in the molecule of each silane coupling agent contained in the composition, and W is the amount of each silane coupling agent blended in 100 parts by mass of the composition.)

[0011] The dental adhesive composition of the present invention can be used as a dental adhesive composition for bonding to dental cutting resins.

[0012] The dental adhesive composition of the present invention can be a dental adhesive composition for bonding to dental cutting resins made of glass fiber-reinforced materials containing glass fibers and epoxy resin.

[0013] The dental adhesive composition of the present invention is (A1) For each type of silane coupling material represented by the structural formula [Chemical Formula 1], the sum of the silane coupling material content index in the composition calculated using formula (3) satisfies formula (3). [Formula (3)] 0.001 ≤ Total of the silane coupling agent content index ((S × W) / M) in the composition ≤ 0.015 (In formula (3), M is the molecular weight of each silane coupling material represented by the (A1) structural formula [Chemical Formula 1] contained in the composition, S is the number of alkoxysilyl groups in the molecule of each silane coupling material represented by the (A1) structural formula [Chemical Formula 1] contained in the composition, and W is the amount of each silane coupling material represented by the (A1) structural formula [Chemical Formula 1] blended in 100 parts by mass of the composition.) (C) A polymerizable monomer that does not have an acidic group contains (C1) a polymerizable monomer that does not have an acidic group but has one or more hydroxyl groups, The (B) polymerizable monomer having an acidic group contained in 100 parts by mass of the dental adhesive composition is 1 to 40 parts by mass, The (C) polymerizable monomer having no acidic group contained in 100 parts by mass of the dental adhesive composition is 5 to 60 parts by mass, (D) The polymerization initiator is contained in 0.01 to 5 parts by mass per 100 parts by mass of the dental adhesive composition, and / or (E) the polymerization accelerator is contained in 0.01 to 5 parts by mass per 100 parts by mass of the dental adhesive composition, The (F) volatile organic solvent contained in 100 parts by mass of the dental adhesive composition is 5 to 90 parts by mass, The (G) water contained in 100 parts by mass of the dental adhesive composition is 1 to 50 parts by mass, The polymerizable monomer having no acidic group and having two or more polymerizable groups is 40 to 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer having no acidic group contained in the dental adhesive composition, Among the total 100 parts by weight of the (A) silane coupling agent containing the silane coupling agent represented by the structural formula [Chemical Formula 1] (A1), the (B) polymerizable monomer having an acidic group, and the (C) polymerizable monomer having no acidic group contained in the dental adhesive composition, 20 to 70 parts by mass is the (C1) polymerizable monomer having no acidic group and having one or more hydroxyl groups, Among the total 100 parts by mass of the (A) silane coupling agent containing the silane coupling agent represented by the structural formula [Chemical Formula 1] (A1), the (B) polymerizable monomer having an acidic group, and the (C) polymerizable monomer having no acidic group contained in the dental adhesive composition, the blending amount of the compound having a methacryloyl group and / or a methacrylamide group can be 60 to 99.9 parts by mass.

[0014] The dental adhesive composition of the present invention can be used in the adhesion to dental cutting resins.

[0015] The dental adhesive composition of the present invention can be used in the adhesion to a dental cutting resin made of a glass fiber reinforced type material containing glass fiber, glass fiber, and an epoxy resin.

Effects of the Invention

[0016] The present invention provides a dental adhesive composition that achieves excellent durable adhesion to lithium disilicate, dental cutting resin, and tooth structure, particularly to dental cutting resin made of glass fiber reinforced resin, while also providing excellent storage stability. [Modes for carrying out the invention]

[0017] The dental adhesive composition of the present invention comprises (A) a silane coupling agent, (B) a polymerizable monomer having an acidic group, (C) a polymerizable monomer not having an acidic group, (F) a volatile organic solvent, (G) water, and (D) a polymerization initiator and (E) a polymerization accelerator, wherein (A) the silane coupling agent includes (A1) the silane coupling agent shown in structural formula [Chemical Formula 1].

[0018] The components of the dental adhesive composition of the present invention will be described in detail below.

[0019] The silane coupling material and polymerizable monomer contained in the composition described in the present invention preferably contain polymerizable groups that exhibit radical polymerizability, and more specifically, from the viewpoint of facilitating radical polymerization, it is preferable that the polymerizable groups include (meth)acrylic groups and / or (meth)acrylamide groups. In this specification, "(meth)acrylic" means acrylic and / or methacrylic, "(meth)acryloyl" means acryloyl and / or methacryloyl, and "(meth)acrylate" means acrylate and / or methacrylate.

[0020] The dental adhesive composition of the present invention comprises (A) a silane coupling material represented by the structural formula [Chemical Formula 1]. [C1] [ka] (In the formula, R 3C2~C may have -O-, -S-, -NH-, -C(O)-O-, -O-C(O)-, -O-C(O)-NH- and / or -NH-C(O)-O- groups. 15 R represents a (meth)acryloyl group having an alkyl group, 1 and R 2 (where n represents an alkyl group from C1 to C4, and these groups may be the same or different. n is between 1 and 3.)

[0021] Specific examples include 2-(meth)acryloxyethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltriproposisilane, 3-(meth)acryloxypropylmethyldiproposisilane, 3-(meth)acryloxypropyltributoxysilane, 3-(meth)acryloxypropylmethyldibutoxysilane Examples include lan, 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. Furthermore, those having urethane or ether groups include 3,3-dimethoxy-8,37-dioxo-2,9,36-trioxa-7,38-diaza-3-silatetracontane-40-yl(meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,18-trioxa-7-aza-3-cyranonadecane-19-oil)amino)-2-methylpropane-1,3-diyldi(meth)acrylate, and 3,3-dimethoxy-8,19-dioxo-2,9,18-trioxa-7,20-diaza-3-siladocosane-22-yl(meth)acrylate. Relate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21-hexaoxa-7,23-diaza-3-silapentacosan-25-yl(meth)acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21,26-heptaoxa-7,23-diaza-3-silaoctacosan-28-yl(meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18-pentaoxa-7,20-diaza-3-siladocosan-22-yl(meth)acrylate, 3,3-dimeth Xy-8,19-dioxo-2,9,12,15,18,23-hexaoxa-7,20-diaza-3-silapentacosan-25-yl(meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,12,15,18-pentaoxa-7-aza-3-cyranonadecane-19-oil)amino)-2-methylpropane-1,3-diyldi(meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosane-23-yl(meth)acrylate, 4,4-diethoxy-17-ox Examples include so-3,16,21,24-tetraoxa-18-aza-4-silahexacosan-26-yl(meth)acrylate, 4,4-diethoxy-13-oxo-3,12,17-trioxa-14-aza-4-cyranonadecane-19-yl(meth)acrylate, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silaikosane-20-yl(meth)acrylate, and 2-methyl-2-((11-(triethoxysilyl)undecyloxy)carbonylamino)propane-1,3-diyldi(meth)acrylate.These can be used individually or in appropriate combinations of two or more. Among these, 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silatricosane-20-yl(meth)acrylate, and 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosane-23-yl(meth)acrylate are preferred. 3-(meth)acryloxypropyltrimethoxysilane is preferred because it exhibits excellent adhesive strength to dental cutting resins even in small amounts. 8-(meth)acryloxyoctyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silatricosane-20-yl(meth)acrylate, and 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosane-23-yl(meth)acrylate are preferred because they have excellent durable adhesion to dental cutting resins. Furthermore, long-chain aliphatic alkoxysilanes such as 3-(meth)acryloxypropyltriproposisilane, 3-(meth)acryloxypropylmethyldiproposisilane, 3-(meth)acryloxypropyltributoxysilane, and 3-(meth)acryloxypropylmethyldibutoxysilane are preferred because they have excellent storage stability. From the viewpoint of versatility and adhesiveness, compounds having three alkoxysilyl groups, as in the above structural formula where n=3, are preferred.

[0022] The dental adhesive composition of the present invention may contain a silane coupling material other than the silane coupling material represented by structural formula [Chemical Formula 1] (A1). The silane coupling material other than the silane coupling material represented by structural formula [Chemical Formula 1] (A1) may be a conventionally known silane coupling material. The dental adhesive composition of the present invention may also be made free of the silane coupling material other than the silane coupling material represented by structural formula [Chemical Formula 1] (A1).

[0023] The dental adhesive composition of the present invention includes a silane coupling material represented by the structural formula [Chemical Formula 1] (A1). With respect to silane coupling materials having alkoxysilyl groups, the amount to be added to the composition is calculated such that the sum of the silane coupling material content index in the composition shown in formula (1) satisfies formula (1). [Formula (1)] 0.001 ≤ Index of silane coupling agent content in composition ((S × W) / M) ≤ 0.015 (In formula (1), M is the molecular weight of each silane coupling agent contained in the composition, S is the number of alkoxysilyl groups in the molecule of each silane coupling agent contained in the composition, and W is the amount of each silane coupling agent blended in 100 parts by mass of the composition.) Silane coupling agents are added to dental adhesive compositions to provide a function that contributes to adhesion to the adherend. In particular, a certain amount is desirable to provide excellent adhesive strength to glass ceramics containing lithium disilicate and dental cutting resins. On the other hand, if the amount of silane coupling agent is too high, storage stability and durable adhesive strength to tooth structure will decrease. As a result of diligent research by the inventors, it was found that the amount of alkoxysilyl groups in the silane coupling agent added to the dental adhesive composition affects adhesive strength, storage stability, and stain resistance. For this reason, it is preferable to consider the amount of alkoxysilyl groups when adding silane coupling agent to the composition, and a silane coupling agent amount index was found. In the silane coupling agent amount index, the molecular weight can be calculated from the structural formula of the silane coupling agent, and if the molecular weight cannot be determined from the structural formula, the average molecular weight measured by gel permission chromatography (GPC) can be used. Next, the number of alkoxysilyl groups in the molecule of the silane coupling agent can be counted from the structural formula of the silane coupling agent. For example, in the structural formula of the silane coupling material shown in (A1) [Chemical Formula 1], the number of alkoxysilyl groups is counted as 3 when n=3, and as 1 when n=1. An alkoxysilyl group is represented as (-Si-OR). R represents a carbon chain, and at least one oxygen atom is bonded to Si and C. The number of alkoxysilyl groups in the silane coupling material is counted by distinguishing them by the number of -OR groups, even if multiple -OR groups are bonded to the same Si atom. If the number of alkoxysilyl groups cannot be determined from the structural formula, the number of alkoxysilyl groups can be identified by adding an excess of an alcohol with a carbon chain length different from that of the alkoxysilyl group in the silane coupling material to the silane coupling material and then performing quantitative analysis by gas chromatography. The molecular weight of the silane coupling material relative to the number of alkoxysilyl groups can be derived from the molecular weight of the silane coupling material and the number of alkoxysilyl groups, which can be rephrased as the molar mass of the silane coupling material relative to the alkoxysilyl groups.By dividing 100 parts by mass of the dental adhesive composition by this value, the amount of substance (moles) of alkoxysilyl groups contained in 100 parts by mass of the dental adhesive composition can be expressed.

[0024] If the amount of silane coupling agent incorporated into the dental adhesive composition of the present invention exceeds 0.015 in the silane coupling agent content index calculated based on formula (1), the durable adhesive strength to tooth structure decreases, and storage stability also decreases. On the other hand, if the silane coupling agent content index is less than 0.001, the adhesion to glass ceramics containing lithium disilicate and dental cutting resins decreases. The silane coupling agent content index calculated based on formula (1) considers only the components that contribute to adhesion. Commonly used silane coupling agents bond to the adherend via alkoxysilyl groups. For example, silane coupling agents used as surface treatment agents for filling materials are generally subjected to hydrolysis and dehydration condensation by mixing with an aqueous solution with a low pH of 5 or less or a high pH of 9 or more, or by a heating process. Since the alkoxysilyl groups of silane coupling agents used as surface treatment agents for filling materials condense and bond to the surface of the filling material or to each other, they do not contribute to chemical adhesion to the adherend. Therefore, it is not included when calculating the index for the amount of silane coupling agent in the composition.

[0025] The amount of the silane coupling material (A) having an alkoxysilyl group, including the silane coupling material represented by structural formula [Chemical Formula 1], to be incorporated into the dental adhesive composition of the present invention is preferably such that the following formula (2) is satisfied. [Formula (2)] 0.002 ≤ Total silane coupling agent content index ((S × W) / M) in the composition ≤ 0.008 (In formula (2), M is the molecular weight of each silane coupling agent contained in the composition, S is the number of alkoxysilyl groups in the molecule of each silane coupling agent contained in the composition, and W is the amount of each silane coupling agent blended in 100 parts by mass of the composition.)

[0026] The total index of silane coupling agent content in a composition is the sum of the silane coupling agent content indices calculated using the formula for each type of silane coupling agent when multiple silane coupling agents are included in a dental adhesive composition. When only one type of silane coupling agent is included in a dental adhesive composition, the index is the value of the dental adhesive composition silane coupling agent content indices calculated using the formula for that silane coupling agent.

[0027] (A1) The silane coupling material represented by structural formula [Chemical Formula 1] may be used individually or in combination of two or more types. The amount of silane coupling material represented by structural formula [Chemical Formula 1] in the dental adhesive composition is preferably such that the sum of the (A1) silane coupling material content index in the composition calculated in formula (3) for each type of silane coupling material represented by structural formula [Chemical Formula 1] is 0.001 or more, more preferably 0.015 or less, and particularly preferably satisfies formula (3). [Formula (3)] 0.001 ≤ Total of the silane coupling agent content index ((S × W) / M) in the composition ≤ 0.015 (In formula (3), M is the molecular weight of each silane coupling material represented by the (A1) structural formula [Chemical Formula 1] contained in the composition, S is the number of alkoxysilyl groups in the molecule of each silane coupling material represented by the (A1) structural formula [Chemical Formula 1] contained in the composition, and W is the amount of each silane coupling material represented by the (A1) structural formula [Chemical Formula 1] blended in 100 parts by mass of the composition.) More preferably, the total index of the amount of (A1) silane coupling agent in the composition is 0.002 or more, and more preferably 0.008 or less.

[0028] The silane coupling material represented by structural formula [Chemical Formula 1] (A1) incorporated into the dental adhesive composition of the present invention preferably has an acryloyl group. Incorporating the silane coupling material represented by structural formula [Chemical Formula 1] (A1) having an acryloyl group improves the adhesive strength to glass ceramics containing lithium disilicate. When incorporating the silane coupling material represented by structural formula [Chemical Formula 1] (A1) having an acryloyl group, the (A) silane coupling material containing the silane coupling material represented by structural formula [Chemical Formula 1], the (B) polymerizable monomer having an acidic group, the (C) polymerizable monomer without an acidic group, and the optionally included (H) polymerizable monomer having one or more sulfur atoms preferably have a methacryloyl group and / or a methacrylamide group, in which case further improvement in adhesive strength to glass ceramics containing lithium disilicate can be expected. Specifically, when the total amount of (A) a silane coupling material containing (A1) a silane coupling material shown in structural formula [Chemical Formula 1], (B) a polymerizable monomer having an acidic group, and (C) a polymerizable monomer without an acidic group (including polymerizable monomers having one or more (H) sulfur atoms, which are optionally included) is 100 parts by mass, the amount of the compound having a methacryloyl group and / or a methacrylamide group is preferably 60 to 99.9 parts by mass, and more preferably 80 to 99.9 parts by mass.

[0029] (B) Polymerizable monomers having acidic groups can be used without restriction as long as they have one or more polymerizable groups and at least one acidic group such as a phosphoric acid group, pyrophosphate group, thiophosphate group, phosphonic acid group, sulfonic acid group, or carboxylic acid group.

[0030] Polymerizable monomers having acidic groups with phosphate groups include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, and 8-(meth) (Meth)Acryloyloxyoctyldihydrogenphosphate, 9-(meth)acryloyloxynonyldihydrogenphosphate, 10-(meth)acryloyloxydecyldihydrogenphosphate, 11-(meth)acryloyloxyundecyldihydrogenphosphate, 12-(meth)acryloyloxidedecyldihydrogenphosphate, 16-(meth)acryloyloxyhexadecyldihydrogenphosphate, 20-(meth)acryloyloxyicosyldihydrogen Hydrogen phosphate, bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di Examples include (meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl]hydrogen phosphate; acid chlorides, alkali metal salts, and ammonium salts of these compounds; and (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond.

[0031] Examples of polymerizable monomers having an acidic group containing a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate; their acid chlorides, alkali metal salts, and ammonium salts; and (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond.

[0032] Polymerizable monomers having an acidic group containing a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, 4-(meth)acryloyloxybutyl dihydrogenthiophosphate, 5-(meth)acryloyloxypentyl dihydrogenthiophosphate, 6-(meth)acryloyloxyhexyl dihydrogenthiophosphate, 7-(meth)acryloyloxyheptyl dihydrogenthiophosphate, 8-(meth)acryloyloxyoctyl dihydrogenthiophosphate, and 9-(meth)acryloyl Examples include acryloyloxynonyl dihydrogenthiophosphate, 10-(meth)acryloyloxydecyl dihydrogenthiophosphate, 11-(meth)acryloyloxyundecyl dihydrogenthiophosphate, 12-(meth)acryloyloxidedecyl dihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogenthiophosphate, 20-(meth)acryloyloxyicosyl dihydrogenthiophosphate; acid chlorides, alkali metal salts, and ammonium salts of these compounds; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0033] Polymerizable monomers having acidic groups containing phosphonic acid groups include 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phosphonoacetate; acid chlorides, alkali metal salts, and ammonium salts of these compounds; and (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond.

[0034] Examples of polymerizable monomers having an acidic group containing a sulfonic acid group include 2-(meth)acrylamido-2-methylpropanesulfonic acid and 2-sulfoethyl (meth)acrylate.

[0035] Polymerizable monomers having acidic groups containing carboxylic acid groups include (meth)acrylic compounds having one carboxyl group in the molecule and (meth)acrylic compounds having multiple carboxyl groups in the molecule. Examples of (meth)acrylic compounds having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid, and 3-(meth)acryloyloxy Examples include benzoic 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, 2-(meth)acryloyloxyethyl hydrogen malate; halides of these acids; and (meth)acrylamide compounds obtained by replacing the ester bonds of these compounds with amide bonds.Examples of (meth)acrylic compounds having multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxidedodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, and 4-(meth)acryloyloxy Examples include liloyloxyethyl 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; their acid anhydrides and acid halides; and (meth)acrylamide compounds in which the ester bonds of these compounds are replaced with amide bonds.

[0036] Among the polymerizable monomers having the above-mentioned (B) acidic group, it is preferable that they have a phosphate group or a phosphonic acid group from the viewpoint of adhesion of dental adhesive compositions. In particular, it is preferable that they have an alkyl group or alkylene group with 4 or more carbon atoms in the main chain within the molecule, and 10-(meth)acryloyloxydecyldihydrogen phosphate or (6-methacryloyloxy)hexylphosphonoacetate, 4-methacryloxyethyl trimellitic acid, and 4-methacryloyloxyethoxycarbonylphthalic anhydride are more preferable. Multiple types of these polymerizable monomers having the (B) acidic group may be used in combination as needed. The amount of polymerizable monomer having the (B) acidic group is preferably 1 to 40 parts by mass per 100 parts by mass of the dental adhesive composition. If it is less than 1 part by mass, the expected adhesive strength may not be achieved, and if it exceeds 40 parts by mass, the storage stability may decrease.

[0037] (B) Among polymerizable monomers having acidic groups, polymerizable monomers having highly acidic functional groups such as phosphate esters and phosphonic acid esters, such as 10-(meth)acryloyloxydecyldihydrogen phosphate or (6-methacryloyloxy)hexylphosphonoacetate, are preferably present in amounts of 0.1 to 20 parts by mass. If the amount is less than 0.1 parts by mass, the expected adhesive strength may not be achieved, and if it exceeds 20 parts by mass, the storage stability may decrease.

[0038] The polymerizable monomers of the present invention that do not have an acidic group (C) can be used without limitation as long as they are known monomers that have one or more polymerizable groups and do not have an acidic group. Polymerizable monomers that do not have an acidic group (C) include those that have one radical polymerizable group, those that have two radical polymerizable groups, and those that have three radical polymerizable groups.

[0039] Polymerizable monomers having one radical 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-H Examples include droxyethyl (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. Among these, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, or erythritol mono(meth)acrylate are preferred because the resulting dental adhesive composition has high affinity with tooth structure.

[0040] Polymerizable monomers having two radical polymerizable groups and no acidic groups include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acrylo Iloxytetraethoxyphenyl)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)acryloyloxydipropoxy Phenyl)-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. Among these, 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate and 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane are preferred from the viewpoint of mechanical strength, while triethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate and glycerol di(meth)acrylate are preferred from the viewpoint of ease of handling. Furthermore, among 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane compounds, those with an average number of added ethoxy groups of 2.6 (commonly known as "D2.6E") are preferred.

[0041] Examples of polymerizable monomers having three or more radical polymerizable groups and no acidic groups 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. Among these, trimethylolpropane tri(meth)acrylate is preferred because it yields a dental adhesive composition with high mechanical strength.

[0042] These polymerizable monomers without (C) acidic groups may be used in combination of multiple types as needed. It is preferable to include 5 to 60 parts by mass of polymerizable monomers without (C) acidic groups in 100 parts by mass of the dental adhesive composition. If the amount is less than 5 parts by mass, the mechanical properties when used as a dental adhesive may be low, and if it exceeds 60 parts by mass, the film thickness when applied to the bonded surface will be thick, and a good handling feel may not be obtained. Furthermore, among the polymerizable monomers without (C) acidic groups, it is preferable to set the amount of polymerizable monomers without acidic groups that have two or more radical polymerizable groups to 40 to 100 parts by mass in 100 parts by mass of polymerizable monomers without (C) acidic groups. Also, if the amount of polymerizable monomers without acidic groups that have two radical polymerizable groups is less than 40 parts by mass, the mechanical properties may be low.

[0043] More preferably, among the polymerizable monomers that do not contain the above-mentioned acidic groups, it is preferable to include polymerizable monomers that do not have a (C1) acidic group but have one or more hydroxyl groups. For example, 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, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane, glycerol di(meth)acrylate, 1-(acryloyl Examples include oxy)-3-(methacryloyloxy)-2-propanol, pentaerythritol triacrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 1,4-cyclohexanedimethanol monoacrylate. Preferably, 2-hydroxyethyl (meth)acrylate, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane, glycerol di(meth)acrylate, and 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol are preferred, and more preferably, 2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane, glycerol di(meth)acrylate, and 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol having two polymerizable groups are preferred.

[0044] (C1) A polymerizable monomer having one or more hydroxyl groups but lacking an acidic group may be of multiple types in combination as needed. The amount of polymerizable monomer having one or more hydroxyl groups but lacking an acidic group (C1) should be 20 to 70 parts by mass per 100 parts by mass of the total of (A) silane coupling agent, (B) polymerizable monomer having an acidic group, and (C) polymerizable monomer lacking an acidic group. This is expected to improve the adhesive strength to dental cutting resin and further improve the storage stability of the silane coupling agent contained in the composition. More preferably, the amount of polymerizable monomer having one or more hydroxyl groups but lacking an acidic group (C1) should be 30 to 60 parts by mass. If it exceeds 70 parts by mass, storage stability may decrease, and if it is less than 20 parts by mass, the expected adhesive strength to dental cutting resin may not be achieved.

[0045] The dental adhesive composition of the present invention may contain a polymerizable monomer having one or more (H) sulfur atoms to impart adhesion to noble metals. The polymerizable monomer having one or more (H) sulfur atoms in the present invention can be any known compound without limitation, as long as it is a polymerizable monomer having a functional group having at least one sulfur group and one or more polymerizable groups in its molecule. Among the functional groups having sulfur groups, those that do not form coordinate bonds with noble metals, such as sulfo groups, are not included. Functional groups having sulfur groups are formed from substructures such as >P=S, >C=S, >CSC<, etc. Examples of sulfur atom-containing polymerizable monomers include compounds that can generate mercapto groups by tautomerism, disulfide compounds, thiophosphates, and linear or cyclic thioether compounds. Specific examples include 10-methacryloxydecyl-6,8-dithiocanate, 6-methacryloxyhexyl-6,8-dithiocanate, 6-methacryloyloxyhexyl-2-thiouracil-5-carboxylate, 2-(11-methacryloyloxyundecylthio)-5-mercapto-1,3,4-thiadiazole, 8-(meth)acryloyloxyoctyldihydrogenthiophosphate, and 10-(meth)acryloyloxydecyldihydrogenthiophosphate. (H) It is preferable to include 0.01 to 10 parts by mass of a polymerizable monomer having one or more sulfur atoms per 100 parts by mass of the dental adhesive composition. If the amount is less than 0.01 parts by mass, good adhesion to noble metals may not be achieved, and even if it exceeds 10 parts by mass, an improvement in adhesion proportional to the amount added may not be achieved.

[0046] The dental adhesive composition of the present invention can contain any known filler without limitation, and it is preferable to include fillers such as inorganic fillers, organic fillers, or organic-inorganic composite fillers.

[0047] The inorganic fillers mentioned above are not particularly limited in their chemical composition, but 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 ceramics, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. In particular, barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, and fluoroaluminosilicate glass, which are used in dental glass ionomer cement, resin-reinforced glass ionomer cement, and resin cement, can also be suitably used. The fluoroaluminosilicate glass referred to here has a basic framework of silicon oxide and aluminum oxide, and contains alkali metals for non-crosslinking oxygen introduction. Furthermore, it contains alkaline earth metals, including strontium, and fluorine as modifying and coordinating ions. In addition, it is a composition that incorporates elements from the lanthanide series into the framework to impart further X-ray opacity. These lanthanide series elements also participate in the composition as modifying and coordinating ions depending on the composition range.

[0048] Examples of organic fillers 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.

[0049] Examples of organic-inorganic composite fillers include those obtained by pulverizing a composite of the aforementioned inorganic oxide (inorganic filler) and polymer (organic filler).

[0050] The dental adhesive composition of the present invention comprises either or both of (D) a polymerization initiator and (E) a polymerization accelerator. Preferably, (D) the polymerization initiator is present in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the dental adhesive composition, and (E) the polymerization accelerator is present in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the dental adhesive composition.

[0051] The dental adhesive composition of the present invention may also contain (D) a photopolymerization initiator and / or a chemical polymerization initiator as a polymerization initiator. The dental adhesive composition of the present invention may contain a photopolymerization initiator for the purpose of imparting photopolymerizability. Examples of photopolymerization initiators include α-diketones, mono-, bis- or trisacylphosphine oxide compounds, and mono-, di-acylgermanium compounds. The amount of photopolymerization initiator to be added is not particularly limited, but from the viewpoint of photocurability, 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the dental adhesive composition is preferred.

[0052] Examples of α-diketones include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4'-oxybenzyl, and acenaphthenequinone. Among these, camphorquinone is preferred because it exhibits excellent photocurability in the visible and near-ultraviolet regions and shows sufficient photocurability regardless of whether a halogen lamp, light-emitting diode (LED), or xenon lamp is used as the light source.

[0053] Examples of mono-, bis-, or trisacylphosphine oxide compounds include bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropyl-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylpropyl-1-yl)phosphine oxide, and bis(2,6-dimethoxyben Zoyl-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylpropyl-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylpropyl-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylpropyl-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylpropyl-1-yl)phosphine oxide Phenoxide, bis(2,6-dibutoxybenzoyl)(2-methylpropyl-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylpropyl-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-dimeth Xybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,Examples include 6-trimethylbenzoyl)isobutylphosphine oxide and 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide. Among these, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferred from the viewpoint of photocurability.

[0054] Examples of mono- and diacylgermanium compounds include bisbenzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis(4-methoxybenzoyl)dimethylgermanium, and bis(4-methoxybenzoyl)diethylgermanium, with bis(4-methoxybenzoyl)diethylgermanium being one example.

[0055] The dental adhesive composition of the present invention may contain a chemical polymerization initiator as (D) polymerization initiator. Examples of organic peroxides as chemical polymerization initiators include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, peroxyesters, 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-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 2,2,4-trimethylpentyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxyisophthalate, di-t-butyl peroxyhexahydroterephthalate, t-butyl peroxy-3,3,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butyl peroxymalelic acid. Specific examples of dialkylperoxides include di-t-butylperoxide, dicumylperoxide, t-butylcumylperoxide, 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-hexine. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.Specific examples of peroxyesters include α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 2,2,4-trimethylpentyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxyisophthalate, di-t-butyl peroxyhexahydroterephthalate, t-butyl peroxy-3,3,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butyl peroxymalelic acid. 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.

[0056] The organic peroxide may be one of the above-mentioned organic peroxides used alone, 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 curing properties. From the viewpoint of improving curing properties, the amount of organic peroxide is preferably set to 0.1 to 5 parts by mass per 100 parts by mass of the dental adhesive composition, and more preferably to 0.3 to 3 parts by mass. If the amount of organic peroxide is greater than 5 parts by mass, it may be difficult to ensure sufficient working time, while if the amount of organic peroxide is less than 0.1 parts by mass, the mechanical strength may be insufficient.

[0057] The dental adhesive composition of the present invention may further contain (E) a polymerization accelerator to further improve curability. Examples of (E) polymerization accelerators include fourth-period transition metal compounds, thiourea derivatives, aliphatic amines, aromatic amines, sulfinic acid and its salts, borate compounds, sulfur-containing reducing inorganic compounds, nitrogen-containing reducing inorganic compounds, borate compounds, barbituric acid derivatives, triazine compounds, halogen compounds, and the like. The amount of (E) polymerization accelerator added is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3.0 parts by mass, per 100 parts by mass of the total amount of the dental adhesive composition.

[0058] The transition metal compounds of the fourth period refer to the metal compounds 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 restriction. Each of the above transition metal elements can exist in multiple valencies, but as long as it is in a valency that allows it to exist stably, it can be added to the dental adhesive composition of the present invention. For example, Sc (trivalent), Ti (tetravalent), V (trivalent, quadrivalent, or pentavalent), Cr (divalent, trivalent, or hexavalent), Mn (divalent to hepatic), Fe (divalent or trivalent), Co (divalent or trivalent), Ni (divalent), Cu (one or divalent), and Zn (divalent). Specific examples of transition metal compounds include scandium iodide (trivalent) as a scandium compound, titanium chloride (tetravalent), titanium (tetravalent) tetraisopropoxide as a titanium compound, and acetylacetone vanadium (trivalent), divanadium tetroxide (tetravalent), vanadylacetylacetonate (tetravalent), vanadium stearate oxide (tetravalent), vanadyl oxalate (tetravalent), vanadyl sulfate (tetravalent), oxobis(1-phenyl-1,3-butanedione)vanadium (tetravalent), and bis(maltolate)oxovanadium (tetravalent) as vanadium compounds. Examples of iron compounds include vanadium pentoxide (pentavalent), sodium metavanadate (pentavalent), manganese compounds such as manganese acetate (divalent), manganese naphthenate (divalent), iron compounds such as iron acetate (divalent), iron chloride (divalent), iron acetate (trivalent), iron chloride (trivalent), cobalt compounds such as cobalt acetate (divalent), cobalt naphthenate (divalent), nickel compounds such as nickel chloride (divalent), copper compounds such as copper chloride (monovalent), copper bromide (monovalent), copper chloride (divalent), copper acetate (divalent), and zinc compounds such as zinc chloride (divalent) and zinc acetate (divalent).

[0059] Among these, trivalent or tetravalent vanadium compounds and divalent copper compounds are preferred, with trivalent or tetravalent vanadium compounds having higher polymerization promoting ability being more preferred, and most preferably tetravalent vanadium compounds. Multiple types of these fourth-period transition metal compounds may be used in combination as needed. The amount of transition metal compound is preferably 0.001 to 1 part by mass per 100 parts by mass of the dental adhesive composition. If it is less than 0.001 parts by mass, the polymerization promoting effect is insufficient, and if it exceeds 1 part by mass, it can cause discoloration or gelation of the dental adhesive composition, reducing storage stability.

[0060] Any known thiourea derivative can be used without restriction. 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. Multiple types of these thiourea derivatives may be used in combination as needed. The amount of thiourea derivative added is preferably 0.1 to 4 parts by mass per 100 parts by mass of the dental adhesive composition. Below 0.1 parts by mass, the polymerization promoting ability is insufficient, and above 4 parts by mass, storage stability may decrease.

[0061] Examples of aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine, and n-octylamine; secondary aliphatic amines such as diisopropylamine and dibutylamine; and tertiary aliphatic amines such as N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl (meth)acrylate, N-methyldiethanolamine di(meth)acrylate, N-ethyldiethanolamine di(meth)acrylate, triethanolamine mono(meth)acrylate, triethanolamine di(meth)acrylate, triethanolamine tri(meth)acrylate, triethanolamine, trimethylamine, triethylamine, and tributylamine. Among these, tertiary aliphatic amines are preferred in terms of the curability and storage stability of the composition, and among them, 2-(dimethylamino)ethyl (meth)acrylate, N-methyldiethanolamine di(meth)acrylate, and triethanolamine are preferred.

[0062] Aromatic amine compounds include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-di(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-isopropylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-dimethyl-m-toluidine. Examples include N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, 4-N,N-dimethylaminobenzoate ethyl ester, 4-N,N-dimethylaminobenzoate methyl ester, N,N-dimethylaminobenzoate-n-butoxyethyl ester, 4-N,N-dimethylaminobenzoate-2-(methacryloyloxy)ethyl ester, 4-N,N-dimethylaminobenzophenone, and 4-dimethylaminobenzoate butyl. Among these, N,N-di(2-hydroxyethyl)-p-toluidine, 4-N,N-dimethylaminobenzoate ethyl ester, and N,N-dimethylaminobenzoate-n-butoxyethyl ester are preferred from the viewpoint of excellent solubility in polymerizable monomers, storage stability, and the ability to impart excellent curability to the composition.

[0063] Sulfinic acid and its salts include p-toluenesulfinic acid, p-toluenesulfinate sodium, p-toluenesulfinate potassium, p-toluenesulfinate lithium, p-toluenesulfinate calcium, benzenesulfinic acid, benzenesulfinate sodium, benzenesulfinate potassium, benzenesulfinate lithium, benzenesulfinate calcium, 2,4,6-trimethylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinate sodium, 2,4,6-trimethylbenzenesulfinate potassium, 2,4,6-trimethylbenzenesulfinate lithium, 2,4,6-trimethylbenzenesulfinate calcium, 2,4,6-triethylbenzenesulfinic acid, 2, Examples include sodium 4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, etc., with sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate being particularly preferred.

[0064] As examples of borate compounds, those having one aryl group in one molecule include, for example, 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, and trialkyl(p-butylphenyl)boron. Examples 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-octyloxyphenyl)boron, trialkyl(m-butyloxyphenyl)boron, trialkyl(p-octyloxyphenyl)boron, and trialkyl(m-octyloxyphenyl)boron (where the alkyl group is selected from the group consisting of n-butyl, n-octyl, and n-dodecyl groups).Specific examples of borate compounds having two aryl groups in one molecule include, for example, 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) Examples 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 phenyl)boron, dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p-octyloxyphenyl)boron, and dialkyldi(m-octyloxyphenyl)boron (where the alkyl group is selected from the group consisting of n-butyl, n-octyl, and n-dodecyl groups).Specific examples of borate compounds having three aryl groups in one molecule include, for example, 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, monoalkyl Examples 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 tri(p-butyloxyphenyl)boron, monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(p-octyloxyphenyl)boron, and monoalkyltri(m-octyloxyphenyl)boron (where the alkyl group is selected from an n-butyl group, an n-octyl group, or an n-dodecyl group, etc.).Specific examples of borate compounds having four aryl groups in one molecule include, for example, 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 include (-octyloxyphenyl)boron, (p-fluorophenyl)triphenylboron, (3,5-bistrifluoromethyl)phenyltriphenylboron, (p-nitrophenyl)triphenylboron, (m-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron, and 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 (p-octyloxyphenyl)triphenylboron.

[0065] Among these arylborate compounds, it is more preferable to use borate compounds having three or four aryl groups in one molecule, from the viewpoint of storage stability. Furthermore, these arylborate compounds can be used individually or in combination of two or more types.

[0066] Examples of reducing inorganic compounds containing sulfur include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, and dithionites. Specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

[0067] Examples of nitrogen-containing reducing inorganic compounds include nitrites, specifically sodium nitrite, potassium nitrite, calcium nitrite, and ammonium nitrite.

[0068] Examples of 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, and 5-propyl Examples include barbituric 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 salts of thiobarbituric acids (alkali metals or alkaline earth metals are preferred). Specific examples of these barbituric acid salts include sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate.

[0069] Examples of triazine compounds include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(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, 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,Examples include 6-bis(trichloromethyl)-s-triazine and 2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine.

[0070] Examples of halogen compounds include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, and dilauryldimethylammonium bromide.

[0071] In the present invention, the (F) volatile organic solvent is typically an organic solvent that has a boiling point of 150°C or less under normal pressure and a solubility in water at 25°C of 5% by mass or more, more preferably 30% by mass or more, and most preferably any ratio of solubility in water. Among these, water-soluble volatile organic solvents with a boiling point of 100°C or less under normal 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. Furthermore, among the above-mentioned volatile organic solvents, ethanol, isopropyl alcohol, acetone, and methyl ethyl ketone are even more preferred.

[0072] (F) One or more volatile organic solvents may be used in combination. (F) The amount of volatile organic solvent is preferably 5 to 90 parts by mass, more preferably 10 to 90 parts by mass, and even more preferably 30 to 60 parts by mass, per 100 parts by mass of the total amount of the dental adhesive composition.

[0073] Specific examples of (G) water incorporated in the present invention include deionized water and distilled water. The amount of (G) water incorporated is preferably 1 to 50 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 25 to 35 parts by mass, per 100 parts by mass of the total amount of the dental adhesive composition.

[0074] Furthermore, the dental adhesive composition of the present invention may contain known additives, provided that they do not impair its performance. Examples of such additives include polymerization inhibitors, antioxidants, pigments, dyes, ultraviolet absorbers, organic solvents, and thickeners. Examples include hydroxydecylammonium chloride and triclosan.

[0075] Preferred embodiments of the dental adhesive composition of the present invention include dental adhesives, tooth structure primers, metal primers, and ceramic primers. Furthermore, for each application, the components of the dental adhesive composition of the present invention may be divided into two parts to form a two-part formulation. Specific embodiments of the application of the dental adhesive composition are shown below.

[0076] <Dental adhesive> When the present invention is used as a dental adhesive, there are three types: a two-liquid, one-step type in which two components, separated into a first liquid and a second liquid, are mixed immediately before use; a two-liquid, two-step type in which the second liquid is applied after the first liquid; and a one-liquid, one-step type in which one component can be used as is. Among these, the one-liquid, one-step type is more preferable because the work during use is simple and less prone to technical errors. In the case of the one-liquid, one-step type, the composition contains (A) a silane coupling material, which is represented by the structural formula [Chemical Formula 1], (B) a polymerizable monomer having an acidic group, (C) a polymerizable monomer without an acidic group, (D) a polymerization initiator and / or (E) a polymerization accelerator, (F) a volatile organic solvent, and (G) water. When a one-liquid, one-step type dental adhesive composition is prepared according to the silane coupling material content index in the composition of the present invention, good storage stability can be expected. Furthermore, by using a silane coupling material having an acryloyl group in the structural formula [Chemical Formula 1] (A1), better adhesive strength to glass ceramics such as lithium disilicate and composite resins containing inorganic components can be expected compared to when using conventional silane coupling materials having a methacryloyl group.

[0077] <Primer for tooth structure> A tooth primer is used to enhance the adhesive strength when cement and prosthetic devices are bonded to tooth structure by modifying the tooth surface. When the present invention is used as a tooth primer, there are two types: a two-liquid, one-step type in which two components, a first liquid and a second liquid, are mixed immediately before use; a two-liquid, two-step type in which the second liquid is applied after the first liquid; and a one-liquid, one-step type in which one component can be used as is. Among these, the one-liquid, one-step type is more preferable because the work during use is simple and less prone to technical errors. In the case of the one-liquid, one-step type, the composition includes (A) a silane coupling material containing the structural formula [Chemical Formula 1], (B) a polymerizable monomer having an acidic group, (C) a polymerizable monomer not having an acidic group, (D) a polymerization initiator and / or (E) a polymerization accelerator, (F) a volatile organic solvent, and (G) water. It is more preferable to include (D) a polymerization initiator and / or (E) a polymerization accelerator that promotes interfacial polymerization of the material applied on top of the tooth structure primer (e.g., resin cement).

[0078] <Primer for metals> Metal primers are used to modify the surfaces of precious and non-precious metals when bonding them to each other, thereby increasing the bonding strength when cementing prosthetic devices made of metal or non-precious metals to an abutment tooth. When the present invention is used as a tooth structure primer, there are three types: a two-liquid mixing one-step type in which the two components, separated into a first liquid and a second liquid, are mixed immediately before use; a two-liquid two-step type in which the second liquid is applied after the first liquid; and a one-liquid one-step type in which the single component can be used as is. Among these, the one-liquid one-step type is more preferable because the work during use is simple and less prone to technical errors. In the case of the one-liquid one-step type, the composition includes (A) a silane coupling material containing the structural formula [Chemical Formula 1], (B) a polymerizable monomer having an acidic group, (C) a polymerizable monomer not having an acidic group, (D) a polymerization initiator and / or (E) a polymerization accelerator, (F) a volatile organic solvent, and (G) water.

[0079] <Primer for ceramics> A ceramic primer is used to modify the surface of ceramics such as zirconia and alumina, and glass ceramics made of feldspar and lithium disilicate, when bonding them to a prosthetic device made of ceramics and glass ceramics with cement, thereby increasing the adhesive strength when cementing the abutment tooth to the prosthetic device made of ceramics and glass ceramics. When the present invention is used as a ceramic primer, there are two types: a two-component, one-step type in which two components, a first liquid and a second liquid, are mixed just before use, and a one-component, one-step type in which one component can be used as is. Among these, the one-component, one-step type is more preferable because the work during use is simpler and less prone to technical errors. In the case of the one-component, one-step type, the composition includes (A) a silane coupling material containing the structural formula [Chemical Formula 1], (B) a polymerizable monomer having an acidic group, (C) a polymerizable monomer without an acidic group, (D) a polymerization initiator and / or (E) a polymerization accelerator, (F) a volatile organic solvent, and (G) water. When a one-component, one-step dental adhesive composition is prepared according to the silane coupling agent content index in the composition of the present invention, good storage stability can be expected. Furthermore, by using a silane coupling agent having an acryloyl group in the silane coupling agent shown in structural formula (A1) [Chemical Formula 1], better adhesive strength to glass ceramics such as lithium disilicate and composite resins containing inorganic components can be expected compared to when using conventional silane coupling agents having a methacryloyl group.

[0080] There are no particular limitations on the method for producing the dental adhesive composition of the present invention, and it can be produced by blending each component. Preferably, the composition can be produced by mixing (B) a polymerizable monomer having an acidic group, (C) a polymerizable monomer not having an acidic group, and (F) a volatile organic solvent to obtain a homogeneous solution, and then adding (A1) a silane coupling material containing the silane coupling material shown in structural formula [Chemical Formula 1], (D) a polymerization initiator and / or (E) a polymerization accelerator, and (G) water. If (B) the polymerizable monomer having an acidic group and (A1) the silane coupling material containing the silane coupling material shown in structural formula [Chemical Formula 1] and (D) the polymerization initiator come into contact during weighing, it may induce decomposition of (A1) the silane coupling material containing the silane coupling material shown in structural formula [Chemical Formula 1] and (D) the polymerization initiator, and by mixing (G) water later, the production time can be shortened. [Examples]

[0081] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The abbreviations used in the examples are as follows. The proportions of the components in each example and comparative example are shown in parts by mass in the table.

[0082] [(A) Silane coupling material] OTES:n-octyltriethoxysilane MTTSP: 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate AAPTMS:3-Acrylamidopropyltrimethoxysilane [(A1) Silane coupling material shown by structural formula [Chemical Formula 1]] (Silane coupling material containing methacrylic groups) MPTMS: Methacryloylpropyltrimethoxysilane MOTMS: Methacryloyloctyltrimethoxysilane MPTBS: Methacryloylpropyltri-n-butoxylan C11EG:4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosan-23-ylmethacrylate [ka] (Silane coupling material containing acrylic groups) APTMS: Acryloylpropyltrimethoxysilane C11A: 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silicosan-20-ylacrylate [ka] C11DA:2-methyl-2-((((11-(triethoxysilyl)undecyl)oxy)carbonyl)amino)propane-1,3-diyldiaacrylate [ka]

[0083] [(B) Polymerizable monomers having acidic groups] MDP:10-Methacryloyloxydecyldihydrogenphosphate MHPA: (6-methacryloyloxy)hexylphosphonoacetate MET:4-Methacryloxyethyl trimellitic acid META:4-[2-(methacryloyloxy)ethoxycarbonyl]phthalic anhydride

[0084] [(C) Polymerizable monomers that do not have acidic groups] (Polymerizable monomers that do not have methacryl groups and / or methacrylamide groups) A3.0E: Bisphenol A EO adduct diacrylate with an average number of ethoxy groups added (number of polymerizable groups per molecule: 2) EBAA: N,N'-Ethylenebisacrylamide (Number of polymerizable groups per molecule: 2) TMPTA: Trimethylolpropane triacrylate (Number of polymerizable groups per molecule: 3) (Polymerizable monomer having a methacryl group and / or a methacrylamide group) BisGMA: 2,2-Bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane (Number of polymerizable groups per molecule: 2) UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (Number of polymerizable groups per molecule: 2) 3G: Triethylene glycol dimethacrylate (Number of polymerizable groups per molecule: 2) GDMA: Glycerin dimethacrylate (Number of polymerizable groups per molecule: 2) HEMA: 2-Hydroxyethyl methacrylate (Number of polymerizable groups per molecule: 1) MBMA: N,N'-Methylenebismethacrylamide (Number of polymerizable groups per molecule: 2)

[0085] [(D) Polymerization initiator] CQ: Camphorquinone

[0086] [(E) Polymerization accelerator] DMBE: 4-(dimethylamino)benzoate ethyl PTU:N-pyridylthiourea GLC: Copper gluconate VOA: Vanadylacetylacetonate

[0087] [(F) Volatile organic solvent] Acetone: Acetone EtOH: Ethanol

[0088] [(G)Water] DW: Distilled water

[0089] [polymerizable monomers containing sulfur atoms] MDDT:10-Methacryloxydecyl-6,8-dithiocanate (Polymerization inhibitor) BHT: 2,6-di-t-butyl-4-methylphenol

[0090] (Method for producing the compositions described in the examples and comparative examples) The polymerizable monomers, polymerization inhibitors, and volatile organic solvents shown in the Examples and Comparative Examples were placed in a light-shielding plastic container and mixed for 48 hours at 100 rpm using a VMRC-5 mix rotor. Subsequently, all components listed in the table, excluding the pre-mixed components, were added and mixed again for 48 hours at 100 rpm using a VMRC-5 mix rotor to obtain the compositions.

[0091] (Storage stability of dental adhesive compositions) In a darkroom at a room temperature of 23±2℃, 5 mL of the composition described in the example or comparative example was taken using a plastic dropper, filled into a polypropylene bottle, and the nozzle and cap were attached in order. It was confirmed that the composition did not leak out even when the bottle was inverted. The bottles filled with the composition were stored in a 50℃ incubator for 3 months, and it was confirmed that no significant increase in viscosity or gelation had occurred.

[0092] (Adhesion strength to glass ceramics containing lithium disilicate (hereinafter referred to as lithium disilicate)) A substrate (15 mm in diameter, 3 mm thick) was prepared by firing a glass ceramic containing lithium disilicate (Vintage PRIME Press, color E-1, manufactured by Shofu) under the conditions specified by the manufacturer, and the surface of the substrate was polished with waterproof abrasive paper #600. Then, the substrate surface of the substrate was sandblasted with alumina (50 μm) (0.2 MPa, 1 second) → washed with water and dried. After that, a 4 mm diameter perforated double-sided tape was applied to the substrate surface to define the bonding area. The one-component composition described in the Examples and Comparative Examples was applied to the perforated tape, immediately air-dried, and then irradiated with a dental polymerization LED light curing unit (Penbright, manufactured by Shofu) for 5 seconds. Meanwhile, the substrate surface of a stainless steel rod (φ4.5 mm) was sandblasted with alumina (50 μm) (0.2 MPa, 1 second) → washed with water and dried, and a metal-adhesive primer (Metal Link, manufactured by Shofu) was applied. An appropriate amount of mixed resin cement (Resicem, manufactured by Shofu) was applied to the bonding surface of the stainless steel rod, and the resin block and stainless steel rod were bonded together so that they fit within the frame of the perforated double-sided tape. A load of 200N was applied perpendicular to the stainless steel rod, and excess cement was wiped off with a cloth. After that, the test specimens were irradiated with dental polymerization LED light curing unit (Penbright, manufactured by Shofu) for 10 seconds, and after removing the load, the prepared bond test specimens were immersed in 37°C water for 24 hours. Then, using a thermal shock tester (manufactured by Thomas Scientific Instruments), each immersion in a 4°C cold water phase and a 60°C high-temperature phase for 60 seconds each was counted as one cycle, and this was repeated 5000 times. After removing the test specimens, the tensile adhesive strength was measured using a universal testing machine (manufactured by Instron) at a crosshead speed of 1 mm / min. A specimen exhibiting an adhesive strength of 15 MPa or higher was considered to have excellent adhesive strength. Conversely, a specimen exhibiting a strength of less than 10 MPa was considered to have low adhesive strength.

[0093] (Adhesion strength to dental cutting resin (hereinafter referred to as resin block)) A resin block (Shofu Block HC Super Hard, manufactured by Shofu) was processed into a 3mm thick plate using Isomet (manufactured by JEOL) and polished with #600 grit waterproof abrasive paper. The bonding surface of the workpiece was sandblasted with alumina (50μm) (0.2MPa, 1 second) → rinsed with water and dried. Then, a 4mm diameter perforated tape (200μm thick) was applied to the bonding surface to define the bonding area. The one-component composition described in the Examples and Comparative Examples was applied to the perforated tape, immediately air-dried, and then irradiated with a dental polymerization LED light curing unit (Penbright, manufactured by Shofu) for 5 seconds. Meanwhile, the bonding surface of a stainless steel rod (φ4.5mm) was sandblasted with alumina (50μm) (0.2MPa, 1 second) → rinsed with water and dried, and a metal-adhesive primer (Metal Link, manufactured by Shofu) was applied. An appropriate amount of mixed resin cement (Resicem, manufactured by Shofu) was applied to the bonding surface of the stainless steel rod, and the resin block and stainless steel rod were bonded together so that they fit within the frame of the perforated double-sided tape. A load of 200N was applied from the vertical direction of the stainless steel rod, and excess cement was wiped off with a cloth. After that, the test specimen was irradiated with a dental polymerization LED light curing unit (Penbright, manufactured by Shofu) for 10 seconds, and after removing the load, the prepared adhesive test specimen was immersed in 37°C water for 24 hours. Then, using a thermal shock tester (manufactured by Thomas Scientific Instruments), each immersion in a 4°C cold water phase and a 60°C high-temperature phase for 60 seconds was counted as one cycle, and this was repeated 5000 times. After removing the test specimen, the tensile adhesive strength was measured using a universal testing machine (manufactured by Instron) at a crosshead speed of 1 mm / min. An adhesive strength of 15 MPa or higher was judged to be excellent. On the other hand, an adhesive strength of less than 10 MPa was judged to be low.

[0094] (Adhesion strength to dental cutting resin made of glass fiber reinforced resin (hereinafter referred to as GF reinforced resin)) GF reinforced resin (Trinia, manufactured by Bicon) was processed into a 3mm thick plate using Isomet (manufactured by JEOL) and polished with #600 grit waterproof abrasive paper. During this process, the direction in which the glass fiber mesh was visible on the bonded surface (mesh bonded surface) and the direction in which the laminated surface of the glass fiber was visible (laminated bonded surface) were distinguished during processing. Next, a 4mm diameter perforated tape (200μm thick) was applied to the bonded surface to define the bonding area. The one-component composition described in the Examples and Comparative Examples was applied to the perforated tape, immediately air-dried, and then irradiated with a dental polymerization LED light curing unit (Penbright, manufactured by Shofu) for 5 seconds. Meanwhile, the bonded surface of a stainless steel rod (φ4.5mm) was sandblasted with alumina (50μm) (0.2MPa, 1 second) → washed with water and dried, and then a metal-adhesive primer (Metallink, manufactured by Shofu) was applied. An appropriate amount of resin cement (Resicem, Matsukaze) was applied to the bonding surface of the stainless steel rod, and the GF reinforced resin and stainless steel rod were bonded together so that they fit within the frame of the perforated double-sided tape. A load of 200N was applied from the vertical direction of the stainless steel rod, and excess cement was wiped off with a cloth. After that, the test specimen was irradiated with a dental polymerization LED light curing unit (Penbright, Matsukaze) for 10 seconds, and after removing the load, the prepared bond test specimen was immersed in 37°C water for 24 hours. Then, using a thermal shock tester (Thomas Scientific Instruments), each immersion in a 4°C cold water phase and a 60°C high-temperature phase for 60 seconds was counted as one cycle, and this was repeated 5000 times. After removing the test specimen, the tensile bond strength was measured using a universal testing machine (Instron) at a crosshead speed of 1 mm / min. A bond strength of 15 MPa or higher was judged to be excellent. On the other hand, a bond strength of less than 10 MPa was judged to be low.

[0095] (Adhesion strength to tooth structure) Test specimens of bovine central incisors embedded in epoxy resin were polished with #600 grit waterproof abrasive paper to remove the dentin surface. Subsequently, a 4mm diameter perforated tape (200μm thick) was applied to the bonding surface to define the bonding area. The one-component compositions described in the Examples and Comparative Examples were applied to the perforated tape, immediately air-dried, and then irradiated with a dental polymerization LED light curing unit (Penbright, manufactured by Shofu) for 5 seconds. Meanwhile, the bonding surface of a stainless steel rod (φ4.5mm) was sandblasted with alumina (50μm) (0.2MPa, 1 second) → washed with water and dried, and a metal-adhesive primer (Metallink, manufactured by Shofu) was applied. An appropriate amount of mixed resin cement (Resicem, manufactured by Shofu) was applied to the bonding surface of the stainless steel rod, and the resin block and stainless steel rod were bonded together so that they fit within the frame of the perforated double-sided tape. A 200N load was applied vertically to a stainless steel rod, and excess cement was wiped off with a cloth. Then, the test specimens were irradiated with a dental polymerization LED light curing unit (Penbright, manufactured by Shofu) for 10 seconds. After removing the load, the prepared adhesive test specimens were immersed in 37°C water for 24 hours. Following this, a thermal shock tester (manufactured by Thomas Scientific Instruments) was used, counting each 60-second immersion in a 4°C cold water phase and a 60°C high-temperature phase as one cycle, and this was repeated 5000 times. After removing the test specimens, the tensile adhesive strength was measured using a universal testing machine (manufactured by Instron) at a crosshead speed of 1 mm / min. A bonding strength of 10 MPa or higher was considered excellent. Conversely, a bonding strength of less than 5 MPa was considered low.

[0096] [Table 1]

[0097] [Table 2]

[0098] The adhesive compositions described in Examples 1 to 32 showed good adhesive strength of 10 MPa or more to lithium disilicate, resin block, GF-reinforced resin, and tooth structure.

[0099] Examples 4, 6, 7, 8, 9, 10, 15, and 27, because they contained a silane coupling material having an acryloyl group, tended to show good adhesive strength of 20 MPa or more to lithium disilicate in their initial preparation stage.

[0100] The compositions of Examples 5, 11, 12, and 13, whose total silane coupling material content index in the composition was around 0.001, the lower limit of formula (1), tended to have slightly lower adhesive strength to lithium disilicate. The compositions of Examples 10, 14, 15, 16, 18, 19, 20, 25, and 27, whose total silane coupling material content index in the composition was around 0.015, the upper limit of formula (1), tended to have decreased durable adhesive strength after accelerated testing compared to the initial adjusted product.

[0101] In Examples 22, 25, 26, 28, and 29, the amount of polymerizable monomer having one or more hydroxyl groups but no acidic groups was less than 30 parts by mass per 100 parts by mass of polymerizable monomers contained in the composition. These compositions exhibited low adhesive strength to resin blocks and GF-reinforced resins, and tended to have particularly low adhesive strength to GF-reinforced resins. Examples 26, 28, and 29, with less than 20 parts by mass of polymerizable monomers, showed a particularly large decrease in adhesive strength. On the other hand, in Examples 10, 11, 20, and 27, the amount of polymerizable monomer having one or more hydroxyl groups but no acidic groups exceeded 60 parts by mass per 100 parts by mass of polymerizable monomers. These compositions tended to show a decrease in adhesive strength in accelerated testing compared to the initial preparation samples. Examples 10, 11, and 20, with more than 70 parts by mass of polymerizable monomers, showed a particularly pronounced decrease in adhesive strength.

[0102] Examples 18, 19, 20, and 21, in which the content of compounds having methacryloyl groups and / or methacrylamide groups in the composition was less than 80 parts by mass, did not show an adhesive strength of 20 MPa or more to lithium disilicate, even when they contained a silane coupling material having acryloyl groups.

[0103] Comparative Examples 1 to 4, in which the sum of the silane coupling agent content index in the composition was below the lower limit of formula (1), tended to have low adhesive strengths of 10 MPa or less to lithium disilicate, resin block, and GF-reinforced resin.

[0104] Comparative Examples 5 to 8, in which the sum of the silane coupling agent content index in the composition exceeded the upper limit of formula (1), showed a tendency for poor storage stability, with adhesive strengths of 10 MPa or less to lithium disilicate, resin block, and GF-reinforced resin after accelerated testing.

[0105] Comparative Example 9, which did not contain polymerizable monomers with acidic groups, had a low adhesive strength to tooth structure of 5 MPa or less.

[0106] Comparative example 10, which did not contain water, showed a low adhesive strength to tooth structure of 5 MPa or less.

[0107] Comparative Example 11, which did not contain a volatile organic solvent, could not be prepared because the components of the composition did not become a homogeneous solution.

[0108] (A1) Comparative examples 12, 13, and 14, which do not contain the silane coupling material shown in structural formula [Chemical Formula 1], had an adhesive strength of 10 MPa or less to lithium disilicate, resin block, and GF-reinforced resin. [Industrial applicability]

[0109] Because this invention is widely used in the dental field as a dental adhesive, a primer for tooth structure, a primer for metals, a primer for ceramics, etc., it has industrial applications.

Claims

1. (A) Silane coupling material, (B) Polymerizable monomer having an acidic group, (C) Polymerizable monomers that do not have acidic groups, (F) Contains a volatile organic solvent and (G) water. (A) The silane coupling material includes the silane coupling material shown in (A1) structural formula [Chemical Formula 1], [Chemical formula 1] 【Chemistry 1】 (In the formula, R ３ C may have -O-, -S-, -NH-, -C(O)-O-, -O-C(O)-, -O-C(O)-NH- and / or -NH-C(O)-O- groups. ２ ~C １５ R represents a (meth)acryloyl group having an alkyl group, １ and R ２ is C １ ~C ４ These represent alkyl groups, which may be the same or different. Note that n is between 1 and 3. Furthermore, it includes either or both of (D) a polymerization initiator and (E) a polymerization accelerator, (A1) The sum of the silane coupling material content index in the composition calculated in formula (1) for each type of silane coupling material, including the silane coupling material shown in structural formula [Chemical Formula 1], satisfies formula (1). (C) A polymerizable monomer that does not have an acidic group contains (C1) a polymerizable monomer that does not have an acidic group but has one or more hydroxyl groups, (C1) The amount of polymerizable monomer having one or more hydroxyl groups but no acidic groups is 20 to 70 parts by mass per 100 parts by mass of the total of (A) silane coupling material containing the silane coupling material shown in structural formula [Chemical Formula 1], (B) polymerizable monomer having acidic groups, and (C) polymerizable monomer not having acidic groups. (A1) A dental adhesive composition in which the silane coupling material shown by the structural formula [Chemical Formula 1] is one or more selected from the group consisting of methacryloylpropyltrimethoxysilane, methacryloyloctyltrimethoxysilane, methacryloylpropyltri-n-butoxylane, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosan-23-ylmethacrylate, acryloylpropyltrimethoxysilane, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silatricosan-20-ylacrylate, and 2-methyl-2-((((11-(triethoxysilyl)undecyl)oxy)carbonyl)amino)propane-1,3-diyldiaacrylate. [Formula (1)] 0.001 ≤ Total index of silane coupling agent content in the composition ((S × W) / M) ≤ 0.015) (In formula (1), M is the molecular weight of each silane coupling material contained in the composition, S is the number of alkoxysilyl groups in the molecule of each silane coupling material contained in the composition, and W is the amount of each silane coupling material in parts by mass per 100 parts by mass of the composition.)

2. (A1) The dental adhesive composition according to claim 1, wherein the silane coupling material shown by the structural formula [Chemical Formula 1] is a silane coupling material having an acryloyl group.

3. (A1) A dental adhesive composition according to claim 1 or 2, wherein (A) a silane coupling material represented by the structural formula [Chemical Formula 1] is included, and the sum of the silane coupling material content index in the composition calculated in formula (2) for each type of silane coupling material satisfies formula (2). [Formula (2)] 0.002 ≤ Total silane coupling agent content index in composition ((S × W) / M) ≤ 0.008 (In formula (2), M is the molecular weight of each silane coupling material contained in the composition, S is the number of alkoxysilyl groups in the molecule of each silane coupling material contained in the composition, and W is the amount of each silane coupling material in parts by mass per 100 parts by mass of the composition.)

4. A dental adhesive composition according to any one of claims 1 to 3 for bonding to dental cutting resin.

5. A dental adhesive composition according to any one of claims 1 to 4 for bonding to dental cutting resin made of a glass fiber reinforced material containing glass fibers and epoxy resin.

6. (A1) For each type of silane coupling material shown in structural formula [Chemical Formula 1], the sum of the silane coupling material content index in the composition calculated using formula (3) satisfies formula (3). [Formula (3)] 0.001 ≤ Total of the silane coupling agent content index ((S × W) / M) in the composition ≤ 0.015 (In formula (3), M is the molecular weight of each silane coupling material represented by the (A1) structural formula [Chemical Formula 1] contained in the composition, S is the number of alkoxysilyl groups in the molecule of each silane coupling material represented by the (A1) structural formula [Chemical Formula 1] contained in the composition, and W is the amount of each silane coupling material represented by the (A1) structural formula [Chemical Formula 1] in parts by mass per 100 parts by mass of the composition.) (C) A polymerizable monomer that does not have an acidic group contains (C1) a polymerizable monomer that does not have an acidic group but has one or more hydroxyl groups, The (B) polymerizable monomer having an acidic group is contained in 100 parts by mass of the dental adhesive composition in an amount of 1 to 40 parts by mass. The amount of polymerizable monomers without acidic groups contained in 100 parts by mass of the dental adhesive composition is 5 to 60 parts by mass. (D) The polymerization initiator is contained in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the dental adhesive composition, and / or (E) The polymerization accelerator is contained in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the dental adhesive composition. The volatile organic solvent (F) contained in 100 parts by mass of the dental adhesive composition is 5 to 90 parts by mass. The amount of (G) water contained in 100 parts by mass of the dental adhesive composition is 1 to 50 parts by mass. (C) The dental adhesive composition contains 100 parts by mass of polymerizable monomers that do not have acidic groups, and 40 to 100 parts by mass of polymerizable monomers that do not have acidic groups and have two or more polymerizable groups. The dental adhesive composition contains (A1) a silane coupling material represented by structural formula [Chemical Formula 1], (A) a silane coupling material, (B) a polymerizable monomer having an acidic group, and (C) a polymerizable monomer without an acidic group. For every 100 parts by weight of these, 20 to 70 parts by mass is (C1) a polymerizable monomer having one or more hydroxyl groups but without an acidic group, which is included in (C) the polymerizable monomer without an acidic group. The dental adhesive composition according to claim 1, wherein of the total of 100 parts by mass of (A) a silane coupling material containing (A1) a silane coupling material represented by structural formula [Chemical Formula 1], (B) a polymerizable monomer having an acidic group, and (C) a polymerizable monomer not having an acidic group, the amount of a compound having a methacryloyl group and / or a methacrylamide group is 60 to 99.9 parts by mass.

7. Use of the dental adhesive composition according to any one of claims 1 to 3 in bonding to dental cutting resin (excluding methods for treating humans).

8. Use of the dental adhesive composition according to any one of claims 1 to 3 for bonding to dental cutting resin made of a glass fiber reinforced material containing glass fibers and epoxy resin (excluding methods for treating humans).

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