Dental adhesive material kit

Abstract

To provide a dental adhesive material kit having high adhesion to teeth, excellent removability of excess cement when removed in a semi-cured state by preliminary irradiation with a light irradiation unit, and appropriate strength.SOLUTION: The present invention relates to a dental adhesive material kit comprising a dental aqueous adhesive composition (A) and a dental curable composition (B) and satisfying the following formula (I): 0≤t2-t1≤3.0 (I) (where t1 (min) represents the contact polymerization initiation time of the dental aqueous adhesive composition (A) and the dental curable composition (B), and t2 (min) represents the polymerization initiation time of the dental curable composition (B)).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a dental adhesive material kit comprising a dental water-based adhesive composition and a dental hardenable composition, and is particularly suitable as a dental cement kit. [Background technology]

[0002] Dental cements are used as materials for attaching prosthetic devices such as crowns, inlays, and bridges to missing portions of affected teeth.

[0003] Prosthetics are often made of materials such as metals and ceramics, and dental cements often have strong adhesion to these materials but weak adhesion to tooth structure. Furthermore, when hardening only the dental cement, radicals are generated uniformly because the polymerization initiator is uniformly dispersed in the dental cement, generating a contraction force toward the center of the dental cement. This contraction force acts in a direction that peels the dental cement from the tooth structure, which also reduces adhesion.

[0004] For this reason, dental cement kits that combine a primer and dental cement are widely used. The primer used in dental cement kits penetrates into the tooth structure, thereby exhibiting high adhesion to the tooth structure. Furthermore, when the primer and dental cement are cured, many radicals are generated on the tooth surface to which the primer is applied, and polymerization and hardening proceeds more rapidly on the tooth surface. In this case, the contractile force is generated toward the tooth surface of the dental cement, so adhesion is not reduced. Therefore, dental cement kits can achieve high adhesion to both the tooth structure and the prosthesis.

[0005] Patent Document 1 proposes a dental composition containing a hydroperoxide compound having one or more hydroperoxide groups bonded to a tertiary carbon, a thiourea derivative, and a soluble copper compound.

[0006] Patent Document 2 discloses an adhesive kit including a curable composition containing a hydroperoxide compound, a substituted ethylenethiourea compound having a specific structure in which a substituent has been introduced into the cyclic structure portion, a vanadium compound, and / or a copper compound, and a pretreatment material containing an acidic group-containing radically polymerizable monomer, a polymerization accelerator, a solvent, and a hydrophilic radically polymerizable monomer not having an acidic group. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-56020 [Patent Document 2] International Publication No. 2014 / 156077 Summary of the Invention [Problem to be solved by the invention]

[0008] However, according to the inventors' investigations, when the combination of the hydroperoxide compound, thiourea derivative, and soluble copper compound described in Patent Document 1 is applied to a dental composition, the hardening is not sufficiently accelerated in the tooth surface direction when the dental composition comes into contact with the primer, and a strong adhesive layer is not obtained, so high durability of the dental adhesive bond cannot be obtained. Furthermore, the adhesive kit described in Patent Document 2 has different polymerization progress rates in the areas that come into contact with the primer and those that do not, so there is room for improvement in the removal of excess cement by light irradiation.

[0009] Therefore, the object of the present invention is to provide a dental adhesive material kit that has excellent adhesion to tooth tissue and excellent removability when excess cement that protrudes from the margin when bonding a crown restoration to tooth tissue is temporarily irradiated with a light irradiator and removed in a semi-hardened state, and that also has appropriate strength. [Means for solving the problem]

[0010] As a result of intensive research into overcoming the above technical problems, the present inventors have found that the above problems can be solved by setting the relationship between the polymerization initiation time upon contact between the dental aqueous adhesive composition and the dental curable composition and the polymerization initiation time of the dental curable composition within a specific range, and have thus completed the present invention.

[0011] That is, the present invention provides the following inventions. (1) A dental adhesive material kit comprising a dental aqueous adhesive composition (A) and a dental curable composition (B), which satisfies the following formula (I): 0≦t2-t1≦3.0 (I) (In the formula, t1 (minutes) represents the polymerization initiation time upon contact between the dental aqueous adhesive composition (A) and the dental curable composition (B), and t2 (minutes) represents the polymerization initiation time of the dental curable composition (B).) (2) The maximum polymerization rate V upon contact between the dental aqueous adhesive composition (A) and the dental curable composition (B) max The dental adhesive material kit according to (1), wherein the viscosity is 40% / min or more. (3) A dental adhesive material kit according to (1) or (2), wherein the dental curable composition (B) comprises a radical polymerizable monomer (b) not containing an acidic group, a polymerization accelerator (c), a chemical polymerization initiator (f), a photopolymerization initiator (g), and a filler (h). (4) A dental adhesive material kit according to any one of (1) to (3), wherein the dental aqueous adhesive composition (A) comprises a radical polymerizable monomer (a) containing an acidic group, a radical polymerizable monomer (b-1) containing neither an amino group nor an acidic group, a polymerization accelerator (c), and water (d). (5) A dental adhesive material kit according to (3) or (4), wherein the polymerization accelerator (c) of the dental aqueous adhesive composition (A) and / or the dental hardenable composition (B) contains a fourth period transition metal compound (c-3). (6) The dental adhesive material kit according to (5), wherein the polymerization accelerator (c) of the dental curable composition (B) comprises a fourth period transition metal compound (c-3), the fourth period transition metal compound (c-3) comprises a vanadium compound (c-3-1) and a copper compound (c-3-2), and the content of the vanadium compound (c-3-1) is 0.01 to 0.04 parts by mass and the content of the copper compound (c-3-2) is 0.001 to 0.0025 parts by mass relative to 100 parts by mass of the radically polymerizable monomer (b) not containing an acidic group contained in the dental curable composition (B). (7) The dental adhesive material kit according to any one of (1) to (6), wherein t1 (minutes) is more than 0.1 minutes and not more than 3.0 minutes. (8) The dental adhesive material kit according to any one of (1) to (7), wherein t2 (minutes) is 1.0 minutes or more and less than 4.0 minutes. (9) A dental adhesive material kit according to any one of (1) to (8), wherein the dental curable composition (B) contains a chemical polymerization initiator (f), and the chemical polymerization initiator (f) contains a hydroperoxide. (10) A dental adhesive material kit according to (5), wherein the polymerization accelerator (c) of the dental aqueous adhesive composition (A) comprises a fourth period transition metal compound (c-3), and the fourth period transition metal compound (c-3) comprises a vanadium compound (c-3-1) and / or a copper compound (c-3-2). (11) The dental adhesive material kit according to any one of (3) to (10), wherein the polymerization accelerator (c) of the dental curable composition (B) includes a thiourea compound (c-2). (12) The dental adhesive material kit according to any one of (1) to (11), wherein the dental curable composition (B) is a two-component type. (13) A dental adhesive material kit according to any one of (1) to (12), which is a dental cement kit. [Effects of the Invention]

[0012] According to the present invention, a dental adhesive material kit is provided which has excellent adhesion to tooth tissue and excellent removability when excess cement that protrudes from the margin when bonding tooth tissue to a crown restoration is temporarily irradiated with a light irradiator and removed in a semi-hardened state, and which also has appropriate strength. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 2 is a diagram illustrating a method for calculating t1, t2, and Vmax for the dental adhesive material kit of the present invention. [Figure 2A] FIG. 2A is a graph showing the polymerization behavior of only the dental curable composition (B) in relation to the polymerization behavior of the dental adhesive material kit of Example 1. [Figure 2B] FIG. 2B is a graph showing the polymerization behavior of the dental adhesive material kit of Example 1 when the dental water-based adhesive composition (A) and the dental curable composition (B) come into contact with each other. [Figure 3A] FIG. 3A is a graph showing the polymerization behavior of only the dental curable composition (B) in relation to the polymerization behavior of the dental adhesive material kit of Example 2. [Figure 3B] FIG. 3B is a graph showing the polymerization behavior of the dental adhesive material kit of Example 2, showing the polymerization behavior when the dental water-based adhesive composition (A) and the dental curable composition (B) come into contact with each other. [Figure 4A] FIG. 4A is a graph showing the polymerization behavior of only the dental curable composition (B) in relation to the polymerization behavior of the dental adhesive material kit of Comparative Example 1. [Figure 4B] FIG. 4B is a graph showing the polymerization behavior of the dental adhesive material kit of Comparative Example 1 when the dental water-based adhesive composition (A) and the dental curable composition (B) come into contact with each other. [Figure 5A] FIG. 5A is a graph showing the polymerization behavior of only the dental curable composition (B) in relation to the polymerization behavior of the dental adhesive material kit of Comparative Example 2. [Figure 5B] FIG. 5B is a graph showing the polymerization behavior of the dental adhesive material kit of Comparative Example 2 when the dental water-based adhesive composition (A) and the dental curable composition (B) come into contact with each other. DETAILED DESCRIPTION OF THE INVENTION

[0014] First, the dental adhesive material kit of the present invention will be specifically described below.

[0015] It is important that the dental adhesive material kit of the present invention comprises the dental aqueous adhesive composition (A) and the dental curable composition (B) and satisfies the following formula (I). 0≦t2-t1≦3.0 (I) (In the formula, t1 (minutes) represents the polymerization initiation time upon contact between the dental aqueous adhesive composition (A) and the dental curable composition (B), and t2 (minutes) represents the polymerization initiation time of the dental curable composition (B).)

[0016] In the present invention, the dental aqueous adhesive composition (A) refers to a surface treatment agent (primer) for tooth surfaces, and the dental curable composition (B) refers to a resin cement material that bonds tooth structure to a prosthesis when used in a dental cement kit, a composite resin material that fills and repairs tooth structure when used in a dental composite resin kit, and a bonding material that bonds tooth structure to a composite resin when used in a dental adhesive material kit.

[0017] In this specification, the contact polymerization initiation time t1 refers to the time from contacting the dental aqueous adhesive composition (A) with the dental curable composition (B) until the polymerization rate begins to increase significantly. The polymerization initiation time t2 refers to the time from contacting the dental aqueous adhesive composition (A) with the dental curable composition (B) until the polymerization rate of the dental curable composition (B) begins to increase significantly. The contact polymerization initiation time t1 and the polymerization initiation time t2 can be measured by the method described in the Examples below.

[0018] The t2-t1 is not particularly limited, but is preferably 2.99 minutes or less, more preferably 2.95 minutes or less, and even more preferably 2.90 minutes or less, from the viewpoints of small difference in the degree of polymerization progress and excellent removability of excess cement when pre-irradiated with a light irradiator and removed in a semi-cured state. Furthermore, from the viewpoints of strengthening the contact curing effect of the adhesive interface by applying a primer and excellent adhesion and adhesion durability, the t2-t1 is 0 minutes or more, preferably 0.2 minutes or more, more preferably 0.5 minutes or more, and even more preferably 0.85 minutes or more.

[0019] The polymerization initiation time t1 upon contact is preferably 3.0 minutes or less, more preferably 2.7 minutes or less, and even more preferably 2.5 minutes or less, from the viewpoints of high curing at the adhesive interface and excellent adhesiveness and durability. Furthermore, the curing time after contact is relatively slow, making it suitable for positioning after prosthesis attachment and providing excellent operability. Therefore, it is preferably 0.1 minutes or more, more preferably 0.2 minutes or more, and even more preferably 0.3 minutes or more. The polymerization initiation time t2 is preferably less than 6.0 minutes, more preferably 5.0 minutes or less, and even more preferably 4.5 minutes or less, from the viewpoints of excellent curing of the paste, increased crosslink density, and therefore excellent mechanical strength, adhesiveness, and durability of the paste. Furthermore, it is preferably 1.0 minutes or more, more preferably 1.5 minutes or more, and even more preferably 2.0 minutes or more, from the viewpoints of ensuring an appropriate time from mixing into the paste until the prosthesis can be attached and providing excellent operability.

[0020] When the dental adhesive material kit of the present invention is used as a dental cement kit, it is preferable to use a dental aqueous adhesive composition (A) containing a polymerization accelerator (c) to obtain high adhesion to tooth tissue. On the other hand, when the dental aqueous adhesive composition (A) contains a polymerization accelerator (c), polymerization of the dental curable composition (B) proceeds first in the area in contact with the dental aqueous adhesive composition (A), while the area not in contact with the dental aqueous adhesive composition (A) remains unpolymerized. This results in a difference in the degree of polymerization. Therefore, when attempting to remove excess cement (hereinafter referred to as "excess cement") that protrudes from the margin of a dental restoration by provisional irradiation with a light irradiator in a semi-cured state during bonding between tooth tissue and a dental restoration, if irradiation is performed for a short time, the excess cement on the surface remains completely unpolymerized and highly fluid, making removal with a probe difficult. However, if irradiation is performed for a long time, polymerization of the excess cement in the area in contact with the dental aqueous adhesive composition (A) proceeds too quickly, making removal of the excess cement difficult. Therefore, the present inventors have found that when a dental adhesive material kit satisfies the above formula (I), when the dental adhesive material kit is pre-irradiated with a light irradiator and then removed in a semi-cured state, there is little difference in the degree of polymerization of the dental curable composition (B) in the portion that comes into contact with the dental water-based adhesive composition (A) and the dental curable composition (B) in the portion that does not come into contact with the dental water-based adhesive composition (A), and the excess cement can be easily removed in one lump.

[0021] For example, the dental adhesive kit of the present invention can satisfy the above formula (I) by combining specific catalysts in a specific ratio. This allows the dental curable composition (B) of the present invention to have an appropriate strength and improve the removability of excess cement when pre-irradiated with a light irradiator and removed in a semi-cured state, by extending the polymerization initiation time t1 of the dental curable composition (B) upon contact with the dental aqueous adhesive composition (A) and shortening the polymerization initiation time t2 of the dental curable composition (B) itself, without significantly affecting the final polymerization rate. While the reason for this is unclear, a specific example of a catalyst system is shown below, and a presumed mechanism is explained.

[0022] The polymerization initiation mechanism of the ternary catalyst system consisting of a fourth-period transition metal compound, a hydroperoxide, and a thiourea compound is that an oxidized low-valent transition metal ion coordinates with the hydroperoxide, cleaving the hydroperoxide group to generate a hydroxy anion, a high-valent transition metal ion, and a radical. The thiourea compound then reduces the high-valent transition metal ion, regenerating the oxidized low-valent transition metal ion, thereby maintaining a constant polymerization rate. The reaction rate for the formation of the hydroperoxide-fourth-period transition metal coordination complex varies depending on the type of fourth-period transition metal used.

[0023] When a dental curable composition (B) uses a catalyst system consisting of a vanadium compound, a hydroperoxide, and a thiourea compound, the activation energy required to form a coordination complex between the vanadium compound and the hydroperoxide is high, resulting in a long time until polymerization begins. However, when the dental curable composition (B) comes into contact with a dental aqueous adhesive composition (A) containing a fourth-period transition metal compound, the polymerization initiation time is accelerated. Furthermore, once the coordination complex between the vanadium compound and the hydroperoxide is formed, a hydrogen abstraction reaction readily occurs, actively generating radicals and initiating polymerization with high activity. Therefore, when a dental curable composition (B) using only a vanadium compound as the fourth-period transition metal compound comes into contact with a dental aqueous adhesive composition (A), the polymerization initiation time is shortened, and once polymerization begins, the composition rapidly hardens completely. This makes it difficult to remove excess cement.

[0024] On the other hand, catalyst systems containing copper compounds, hydroperoxides, and thiourea compounds are characterized by low activation energy, a short time until polymerization begins, and a gradual hydrogen abstraction reaction. Therefore, compared with catalyst systems containing vanadium compounds, hydroperoxides, and thiourea compounds, these systems are superior in the ability to remove excess cement from dental curable composition (B) after contact with dental aqueous adhesive composition (A). However, the slow polymerization rate of this catalyst system and the slow polymerization rate upon contact with dental aqueous adhesive composition (A) can sometimes result in reduced crosslink density and adhesion to tooth structure in the resulting cured product.

[0025] In response to this, the present inventors conducted extensive research focusing on reducing the difference in the degree of polymerization of excess cement after contact with the dental aqueous adhesive composition (A). As a result, they discovered that by blending a vanadium compound and a copper compound in a specific ratio, the difference between the polymerization initiation time t2 of the dental curable composition (B) and the polymerization initiation time t1 upon contact between the dental aqueous adhesive composition (A) and the dental curable composition (B) can be controlled to 3 minutes or less. The specific mechanism is presumed to be as follows: First, in the dental curable composition (B) in contact with the dental aqueous adhesive composition (A), the hydroperoxide preferentially coordinates with the copper compound, causing the initial polymerization rate to proceed slowly. Subsequently, the coordination complex between the vanadium compound and the hydroperoxide initiates polymerization, driving the polymerization forward. This allows the polymerization initiation time of the chemical polymerization of the dental curable composition (B) upon contact with the dental aqueous adhesive composition (A) to be extended without significantly affecting the final polymerization rate. Similarly, in the portion of the dental curable composition (B) that is not in contact with the dental aqueous adhesive composition (A), polymerization can be initiated by a catalyst system of a copper compound, a hydroperoxide, or a thiourea compound, which has a low activation energy, thereby shortening the polymerization initiation time of the dental curable composition (B).

[0026] The dental adhesive material kit of the present invention is characterized in that the maximum polymerization rate V max The maximum polymerization rate upon contact V is preferably 40% / min or more. max By setting the polymerization rate at 40% / min or more, a strong adhesive layer with a high crosslink density can be obtained, resulting in excellent adhesion to tooth structure and durability of adhesion. max The maximum polymerization rate upon contact V is preferably 300% / min or less, more preferably 200% / min or less, and even more preferably 100% / min or less. max can be measured by the method described in the Examples below.

[0027] Next, each component constituting the dental adhesive kit of the present invention will be described in detail. In the dental adhesive kit of the present invention, the dental aqueous adhesive composition (A) preferably contains an acidic group-containing radical polymerizable monomer (a), an amino group- and acidic group-free radical polymerizable monomer (b-1), a polymerization accelerator (c), and water (d). Also, the dental curable composition (B) preferably contains an acidic group-free radical polymerizable monomer (b), a polymerization accelerator (c), a chemical polymerization initiator (f), a photopolymerization initiator (g), and a filler (h).

[0028] First, the dental aqueous adhesive composition (A) will be described in detail.

[0029] The dental aqueous adhesive composition (A) of the present invention preferably contains a radically polymerizable monomer (a) containing an acidic group. The radically polymerizable monomer (a) containing an acidic group not only promotes demineralization of tooth tissue and improves adhesion to tooth tissue, but also promotes chemical polymerization at the adhesive interface. In this specification, "(meth)acrylic" means methacrylic or acrylic, and "(meth)acryloyl" means methacryloyl or acryloyl.

[0030] Examples of the radical polymerizable monomer (a) containing an acidic group include (meth)acrylic polymerizable monomers having at least one acidic group such as a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonate group, a carboxylic acid group, or a sulfonic acid group, and at least one acryloyl group or methacryloyl group. The radical polymerizable monomer (a) containing an acidic group can be used alone or in appropriate combination of two or more. Specific examples of the radical polymerizable monomer (a) containing an acidic group are shown below.

[0031] Examples of the (meth)acrylic polymerizable monomer containing a phosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, and 8-(meth)acryloyloxyoctyl Dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl hydrogen monofunctional phosphate group-containing (meth)acrylic acid esters such as 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2-methacryloyloxyethyl-(4-methoxyphenyl) hydrogen phosphate, 2-methacryloyloxypropyl-(4-methoxyphenyl) hydrogen phosphate, and their acid chlorides, alkali metal salts, and amine salts; bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, Examples of suitable (meth)acrylic acid esters include difunctional phosphate group-containing (meth)acrylic acid esters such as benzophenone phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, and 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, as well as acid chlorides, alkali metal salts, and amine salts thereof.

[0032] Examples of the (meth)acrylic polymerizable monomer 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, and acid chlorides, alkali metal salts, and amine salts thereof.

[0033] Examples of the (meth)acrylic polymerizable monomer 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, and 8-(meth)acryloyloxyoctyl dihydrogenthiophosphate. acryloyloxyhexadecyldihydrogenthiophosphate, 20-(meth)acryloyloxyeicosyldihydrogenthiophosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

[0034] Examples of the (meth)acrylic polymerizable monomer containing a phosphonic acid group include 2-(meth)acryloyloxyethyl phenyl phosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl phosphonoacetate, 10-(meth)acryloyloxydecyl phosphonoacetate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

[0035] Examples of the (meth)acrylic polymerizable monomer containing a carboxylic acid group include a monofunctional polymerizable monomer having one carboxyl group or an acid anhydride group thereof in the molecule; and a monofunctional polymerizable monomer having multiple carboxyl groups or acid anhydride groups thereof in the molecule.

[0036] Examples of monofunctional polymerizable monomers having one carboxyl group or an acid anhydride group thereof in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen maleate, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine Examples of the acryloyloxybenzoic acid include N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, and N-(meth)acryloyl-4-aminosalicylic acid, as well as compounds in which the carboxyl group of these compounds has been converted to an acid anhydride group.

[0037] Examples of monofunctional polymerizable monomers having a plurality of carboxyl groups or acid anhydride groups thereof in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxyethyl trimellitate anhydride ... Examples of the acryloyloxyethyl methyl acrylate include 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate, 6-(meth)acryloyloxyethylnaphthalene-1,2,6-tricarboxylic anhydride, 6-(meth)acryloyloxyethylnaphthalene-2,3,6-tricarboxylic anhydride, 4-(meth)acryloyloxyethylcarbonylpropionoyl-1,8-naphthalic anhydride, and 4-(meth)acryloyloxyethylnaphthalene-1,8-tricarboxylic anhydride.

[0038] Examples of the (meth)acrylic polymerizable monomer containing a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid and 2-sulfoethyl (meth)acrylate.

[0039] Among the above-mentioned radically polymerizable monomers (a) containing an acidic group, from the viewpoint of providing good adhesive strength when used in a dental aqueous adhesive composition, one or more selected from the group consisting of 10-(meth)acryloyloxydecyl dihydrogen phosphate, 4-(meth)acryloyloxyethyl trimellitate anhydride, 4-(meth)acryloyloxyethyl trimellitate, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, and a mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis(2-methacryloyloxyethyl)hydrogen phosphate are preferred.

[0040] The content of the acidic group-containing radical polymerizable monomer (a) in the dental aqueous adhesive composition (A) is preferably 1 to 45 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 38 parts by mass, per 100 parts by mass of the total amount of the radical polymerizable monomer and solvent contained in the dental aqueous adhesive composition (A). The total amount of the radical polymerizable monomer and solvent refers to the total amount of the acidic group-containing radical polymerizable monomer (a), water (d), organic solvent, and other polymerizable monomers (e.g., radical polymerizable monomer (b-1) that does not contain an amino group or an acidic group).

[0041] The dental aqueous adhesive composition (A) of the present invention preferably contains a radical polymerizable monomer (b-1) that does not contain an amino group or an acidic group. The radical polymerizable monomer (b-1) that does not contain an amino group or an acidic group means a radical polymerizable monomer that does not contain an amino group and does not contain an acidic group (such as a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonate group, a carboxylic acid group, or a sulfonic acid group), and examples thereof include (meth)acrylic acid, (meth)acrylic acid esters, (meth)acrylamide, and (meth)acrylamide derivatives.

[0042] The radical polymerizable monomer (b-1) not containing an amino group or an acidic group is roughly classified into aliphatic radical polymerizable monomers and aromatic radical polymerizable monomers. It may be monofunctional, bifunctional, or trifunctional or higher functional. In this specification, "monofunctional," "bifunctional," and "trifunctional or higher functional" mean having one, two, and three or more radical polymerizable groups, respectively. Furthermore, hereinafter, methacryloyl and acryloyl are collectively referred to as (meth)acryloyl.

[0043] Specific examples include monofunctional aliphatic radical polymerizable monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, (meth)acryloylmorpholine, and diethyl (meth)acrylamide.Examples of bifunctional aliphatic radical polymerizable monomers include erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, glycerol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1, Examples of the acrylic acid copolymer include 5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA"), tricyclodecane dimethanol di(meth)acrylate, ethylene bis(meth)acrylamide, propylene bis(meth)acrylamide, butylene bis(meth)acrylamide, N,N'-(dimethyl)ethylene bis(meth)acrylamide, N,N'-diethyl-1,3-propylene bis(meth)acrylamide, bis[2-(2-methyl-(meth)acrylamino)ethoxycarbonyl]hexamethylenediamine, and 2,2,4-trimethylhexamethylene-1,6-bis(meth)acrylamide.Examples of the trifunctional or higher aliphatic radical polymerizable monomer include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, and 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane.

[0044] Examples of monofunctional aromatic radical polymerizable monomers include benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalate, and neopentyl glycol-(meth)acrylic acid-benzoate. Examples of bifunctional aromatic radical polymerizable monomers include 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane, 2,2-bis[4-(4-(meth)acryloyloxy-3-hydroxybutoxy)phenyl]propane, 2,2-bis[4-(4-(meth)acryloyloxy-2-hydroxybutoxy)phenyl]propane, and 2,2-bis[4-(5-(meth)acryloyloxy-4- hydroxypentoxyphenyl)propane, 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl) Propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, and the like.Examples of trifunctional or higher aromatic radical polymerizable monomers include pentaerythritol tri(meth)acrylate, etc. As the radical polymerizable monomer (b-1) containing no amino group or no acidic group in the present invention, these may be used alone or in combination of two or more.

[0045] The radical polymerizable monomer (b-1) of the present invention that does not contain an amino group or an acidic group is preferably a hydrophilic radical polymerizable monomer (b-1-1) that does not contain an amino group or an acidic group, because it penetrates into the tooth structure, improves the degree of polymerization of the cured product, and improves adhesive strength. As the hydrophilic radical polymerizable monomer (b-1-1) that does not contain an amino group or an acidic group, a monofunctional hydrophilic radical polymerizable monomer that does not contain an amino group or an acidic group is preferred. Among these, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, erythritol mono(meth)acrylate, methoxypolyethylene glycol (meth)acrylate, (meth)acryloylmorpholine, and diethyl(meth)acrylamide are preferred, with 2-hydroxyethyl methacrylate being particularly preferred, from the viewpoint of improving the permeability into the collagen layer of dentin.

[0046] The content of the radical polymerizable monomer (b-1) not containing an amino group or an acidic group in the dental aqueous adhesive composition (A) is preferably 25 to 70 parts by mass, more preferably 28 to 60 parts by mass, and even more preferably 30 to 50 parts by mass, per 100 parts by mass of the total amount of the radical polymerizable monomer and solvent contained in the dental aqueous adhesive composition (A). When the content of the radical polymerizable monomer (b-1) not containing an amino group or an acidic group is 25 parts by mass or more, the effect of adding the radical polymerizable monomer (b-1) not containing an amino group or an acidic group, i.e., improved adhesion, can be more significantly achieved. On the other hand, when the content is 70 parts by mass or less, the dental aqueous adhesive composition (A) can exhibit a high level of tooth demineralization ability without impairing the effect of the radical polymerizable monomer (b-1) not containing an amino group or an acidic group.

[0047] The dental aqueous adhesive composition (A) of the present invention may contain a radically polymerizable monomer (b-2) containing an amino group but not an acidic group. Specific examples include 2-(dimethylamino)ethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, 2-(dipropylamino)ethyl (meth)acrylate, 6-(diethylamino)hexyl (meth)acrylate, 6-(dimethylamino)hexyl (meth)acrylate, N-methyldiethanolamine di(meth)acrylate, and triethanolamine di(meth)acrylate. These may be used alone or in combination of two or more. Among these, 2-(dimethylamino)ethyl methacrylate is most preferably used due to its excellent curing properties. The radical polymerizable monomer (b-2) containing an amino group but not an acidic group is a component that adjusts the pH of the dental aqueous adhesive composition (A), preventing excessive demineralization when applied to dentin, ensuring appropriate demineralization for penetration and curing, and improving the storage stability of the dental aqueous adhesive composition (A). The pH of the dental aqueous adhesive composition (A) is preferably less than 4.0, more preferably 1.2 to 3.5, and even more preferably 1.5 to 3.0. The content of the radical polymerizable monomer (b-2) containing an amino group but not an acidic group is preferably set so as to fall within these ranges. The pH can be measured using a known measuring device. An example of such a measuring device is the "LAQUAtwin" manufactured by HORIBA Corporation.

[0048] The dental aqueous adhesive composition (A) of the present invention preferably contains a polymerization accelerator (c). The polymerization accelerator (c) is a component that functions as a reducing agent for redox polymerization. Examples of the polymerization accelerator (c) in the dental aqueous adhesive composition (A) include aromatic amines (c-1) that do not have an electron-withdrawing group in the aromatic ring, thiourea compounds (c-2), and fourth-period transition metal compounds (c-3). The polymerization accelerator (c) contained in the dental aqueous adhesive composition (A) may be used alone or in combination of two or more. A preferred embodiment is a dental adhesive kit comprising a dental aqueous adhesive composition (A) and a dental curable composition (B), wherein the dental aqueous adhesive composition (A) contains a polymerization accelerator (c), which is at least one selected from the group consisting of aromatic amines (c-1) having no electron-withdrawing group in the aromatic ring, thiourea compounds (c-2), and fourth-period transition metal compounds (c-3). Examples of the polymerization accelerator (c) contained in the dental aqueous adhesive composition (A) include borate compounds such as aryl borate compounds; and transition metal compounds other than those of the fourth period (c-4). However, these may not be included. In terms of a high polymerization-promoting effect, it is preferable that the polymerization accelerator (c) contains a fourth-period transition metal compound (c-3).

[0049] Examples of the aromatic amine (c-1) having no electron-withdrawing group in the aromatic ring include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, and N,N-bis(2-hydroxyethyl)-3,5-diisopropylaniline. Examples of aromatic amines (c-1) that do not have an electron-withdrawing group on the aromatic ring include propylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline, N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline, N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4-t-butylaniline, and N,N-dimethyl-3,5-di-t-butylaniline. The aromatic amines (c-1) that do not have an electron-withdrawing group on the aromatic ring may be used alone or in combination of two or more.

[0050] Examples of the thiourea compound (c-2) include thiourea, methylthiourea, ethylthiourea, ethylenethiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, N,N'-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, tetracyclohexylthiourea, 1-(2-pyridyl)-2-thiourea, and 4,4-dimethylethylenethiourea.

[0051] The fourth period transition metal compound (c-3) may be any of a vanadium compound (c-3-1), a copper compound (c-3-2), and a fourth period transition metal compound (c-3-3) other than vanadium and copper. The polymerization accelerator (c) in the present invention preferably contains a vanadium compound (c-3-1) and / or a copper compound (c-3-2) from the viewpoint of a high polymerization-accelerating effect. Examples of the vanadium compound (c-3-1) include vanadium acetylacetonate, vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, vanadyl oxalate, bis(maltolato)oxovanadium(IV), oxobis(1-phenyl-1,3-butanedionato)vanadium(IV), vanadium(V) oxytriisopropoxide, ammonium metavanadate(V), sodium metavanadate(V), vanadium pentoxide(V), divanadium(IV) tetroxide, and vanadyl(IV) sulfate. Among these, vanadium acetylacetonate, vanadyl acetylacetonate, and bis(maltolato)oxovanadium(IV) are preferred from the viewpoint of solubility in solvents, and vanadyl acetylacetonate and bis(maltolato)oxovanadium(IV) are more preferred. The vanadium compounds (c-3-1) can be used singly or in combination of two or more. Preferred examples of the copper compounds (c-3-2) are compounds soluble in radical polymerizable monomers. Specific examples thereof include copper carboxylates such as copper acetate, copper isobutyrate, copper gluconate, copper citrate, copper phthalate, copper tartrate, copper oleate, copper octoate, copper octenoate, copper naphthenate, copper methacrylate, and copper 4-cyclohexylbutyrate; β-diketone coppers such as copper acetylacetonate, copper trifluoroacetylacetonate, copper hexafluoroacetylacetonate, copper 2,2,6,6-tetramethyl-3,5-heptanedionato, and copper benzoylacetone; β-ketoester coppers such as copper acetoacetate; copper alkoxides such as copper methoxide, copper ethoxide, copper isopropoxide, copper 2-(2-butoxyethoxy)ethoxide, and copper 2-(2-methoxyethoxy)ethoxide; copper dithiocarbamates such as copper dimethyldithiocarbamate; and salts of copper with inorganic acids such as copper nitrate and copper chloride.These can be used alone or in appropriate combination of two or more. Among these, from the viewpoint of solubility and reactivity with radical polymerizable monomers, copper carboxylate, copper β-diketone, and copper β-ketoester are preferred, and copper acetate and copper acetylacetonate are particularly preferred. Examples of other fourth period transition metal compounds (c-3-3) include scandium isopropoxide, iron(III) ethoxide, titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium butoxide, titanium hydroxide, and titanium fluoride. The polymerization accelerator (c) may contain a transition metal compound (c-4) other than a fourth period transition metal. Examples of the other transition metal compounds (c-4) include strontium carbonate, strontium hydroxide, strontium ethoxide, tin(II) methoxide, indium ethoxide, actinium ethoxide, yttrium isopropoxide, lanthanum methoxide, lanthanum ethoxide, lanthanum isopropoxide, lanthanum butoxide, lanthanum hydroxide, lanthanum carbonate, lanthanum fluoride, cerium isopropoxide, praseodymium isopropoxide, promethium isopropoxide, neodymium isopropoxide, and samium fluoride. Examples of the tungsten (IV) isopropoxide include tungsten (IV) methoxide, tungsten (IV) isopropoxide, tungsten (IV) butoxide, and the like. Suitable examples of the fourth period transition metal compound (c-3) include divanadium(IV) tetroxide, vanadyl acetylacetonate(IV), vanadyl oxalate(IV), vanadyl sulfate(IV), oxobis(1-phenyl-1,3-butanedionato)vanadium(IV), bis(maltolato)oxovanadium(IV), vanadium(V) pentoxide, sodium metavanadate(V), and ammonium metavanadate(V).Among these, vanadyl acetylacetonate(IV) and bis(maltolato)oxovanadium(IV) are preferred, with vanadyl acetylacetonate(IV) being most preferred, from the viewpoint of their high polymerization-promoting effect. The polymerization accelerator (c) may be used singly or in combination of two or more.

[0052] The content of the polymerization accelerator (c) in the dental aqueous adhesive composition (A) is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and even more preferably 0.001 parts by mass or more, relative to 100 parts by mass of the radically polymerizable monomer contained in the dental aqueous adhesive composition (A), in order to prevent a delay in the curing rate. From the viewpoint of storage stability, the content is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 2.0 parts by mass or less.

[0053] The dental aqueous adhesive composition (A) of the present invention preferably contains water (d). Water (d) contributes to promoting penetration of the composition into tooth structure. Water (d) also dissolves the acidic group-containing radical polymerizable monomer (a) and polymerization accelerator (c), and functions as a dissolution and reaction field for substances that contribute to polymerization initiation.

[0054] The content of water (d) in the dental aqueous adhesive composition (A) is preferably 5 to 75 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 15 to 45 parts by mass, per 100 parts by mass of the total amount of the radical polymerizable monomer and solvent contained in the dental aqueous adhesive composition (A).

[0055] The dental aqueous adhesive composition (A) of the present invention may contain a polymerization inhibitor to impart storage stability. The polymerization inhibitor in the dental aqueous adhesive composition (A) inhibits discoloration and loss of adhesiveness of the dental aqueous adhesive composition (A), improving storage stability. Examples of polymerization inhibitors include phenolic compounds, phosphorus compounds, sulfur compounds, and amine compounds. Phenol compounds are preferred, and specific examples include hydroquinone, hydroquinone monomethyl ether, 3,5-di-t-butyl-4-hydroxytoluene, 3,5-di-t-butyl-4-hydroxyanisole, and 4-t-butylpyrocatechol. Among these, hydroquinone monomethyl ether and 3,5-di-t-butyl-4-hydroxytoluene are preferred because they do not inhibit adhesiveness and have a strong effect of inhibiting discoloration and gelation.

[0056] The dental aqueous adhesive composition (A) of the present invention may contain a photopolymerization initiator to impart photocurability.

[0057] The dental aqueous adhesive composition (A) of the present invention may contain a filler (h) to improve application properties and fluidity. From the viewpoint of application properties and fluidity, the filler (h) is preferably a fine particle filler having an average primary particle diameter of 1 nm to 0.1 μm. Specific examples include "Aerosil (registered trademark) OX50," "Aerosil (registered trademark) 50," "Aerosil (registered trademark) 200," "Aerosil (registered trademark) 380," "Aerosil (registered trademark) R972," and "Aerosil (registered trademark) 130" (all of which are trade names manufactured by Nippon Aerosil Co., Ltd.). The average primary particle diameter can be measured by the same method as for the filler (h) in the dental curable composition (B).

[0058] The dental aqueous adhesive composition (A) of the present invention may contain a water-soluble organic solvent to improve adhesive strength, application properties, penetration into tooth tissue, and the solubility of the radically polymerizable monomer (a) containing an acidic group and the radically polymerizable monomer (b-1) containing neither an amino group nor an acidic group in water (d). The water-soluble organic solvent typically has a boiling point of 150°C or lower at atmospheric pressure and a solubility in water at 25°C of 5% by mass or higher, more preferably 30% by mass or higher, and most preferably is soluble in water at any desired ratio. Among these, water-soluble organic solvents with a boiling point of 100°C or lower at atmospheric pressure are preferred, including ethanol, methanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane, and tetrahydrofuran.

[0059] In the dental adhesive material kit of the present invention, the dental aqueous adhesive composition (A) is preferably a one-component type, since mixing is not required and the operation is simple.

[0060] Next, the dental curable composition (B) will be described.

[0061] The dental curable composition (B) of the present invention preferably contains a radical polymerizable monomer (b) that does not contain an acidic group. Specific examples of the radical polymerizable monomer (b) that does not contain an acidic group include the radical polymerizable monomer (b-1) that does not contain an amino group and an acidic group, and the radical polymerizable monomer (b-2) that contains an amino group but does not contain an acidic group, which are used in the dental aqueous adhesive composition (A).

[0062] Among these, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane is preferred from the viewpoint of good wettability with the dental aqueous adhesive composition (A) and high adhesion to tooth tissue. Furthermore, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane and 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethoxy groups added: 2.6) are preferred from the viewpoint of high mechanical strength of the cured product.

[0063] The content of the radically polymerizable monomer (b) not containing an acidic group in the dental curable composition (B) is preferably 15 to 99.5 parts by mass per 100 parts by mass of the total amount of the radically polymerizable monomer and filler in the dental curable composition (B). If the amount of the radically polymerizable monomer is less than 15 parts by mass, the viscosity of the dental curable composition (B) may become too high, resulting in reduced operability. The effects of adding the filler, such as viscosity adjustment and improved mechanical strength of the dental curable composition (B) after hardening, may not be achieved. On the other hand, if the amount exceeds 99.5 parts by mass, the effects of adding the filler, such as viscosity adjustment and improved mechanical strength of the dental curable composition (B) after hardening, may not be achieved. The dental curable composition (B) of the present invention is preferably used in dental bonding materials, dental composite resins, dental resin cements, etc. When the dental curable composition (B) is used as a dental composite resin or a dental resin cement, from the viewpoint of the viscosity of the dental curable composition (B) and the mechanical strength after curing, the amount of the acidic group-free radical polymerizable monomer (b) and the filler in the dental curable composition (B) is preferably 15 to 60 parts by mass, more preferably 19 to 50 parts by mass, and even more preferably 24 to 48 parts by mass, per 100 parts by mass of the total amount of the acidic group-free radical polymerizable monomer (b) and the filler in the dental curable composition (B).

[0064] The dental curable composition (B) of the present invention preferably contains a polymerization accelerator (c). Specific examples of the polymerization accelerator (c) include those used in the dental aqueous adhesive composition (A). A preferred embodiment includes a dental adhesive kit comprising a dental aqueous adhesive composition (A) and a dental curable composition (B), wherein the dental curable composition (B) contains a polymerization accelerator (c), and the polymerization accelerator (c) is at least one selected from the group consisting of aromatic amines (c-1) having no electron-withdrawing group in the aromatic ring, thiourea compounds (c-2), and fourth-period transition metal compounds (c-3). Examples of the polymerization accelerator (c) contained in the dental curable composition (B) include borate compounds such as aryl borate compounds; and transition metal compounds other than those of the fourth-period transition metal compounds (c-4). However, these may not be included.

[0065] In the dental adhesive kit of the present invention, the redox polymerization accelerator (c) in the dental curable composition (B) preferably contains a thiourea compound (c-2) and a fourth-period transition metal compound (c-3). In one embodiment, the dental curable composition (B) preferably contains 0.01 to 0.04 parts by mass of the vanadium compound (c-3-1) and 0.001 to 0.0025 parts by mass of the copper compound (c-3-2) relative to 100 parts by mass of the radically polymerizable monomer contained in the dental curable composition (B), and more preferably contains 0.02 to 0.035 parts by mass of the vanadium compound (c-3-1) and 0.0015 to 0.0025 parts by mass of the copper compound (c-3-2). If the content of the vanadium compound (c-3-1) is too low, the effect of adding the vanadium compound (c-3-1) cannot be obtained, and the maximum polymerization rate V maxThe rate of polymerization is less than 40% / min, which may reduce the adhesiveness and mechanical strength of the dental adhesive kit to tooth tissue. On the other hand, if the content is too high, the polymerization initiation time t1 between the dental aqueous adhesive composition (A) and the dental curable composition (B) upon contact tends to be short, which may result in excessive hardening of the dental curable composition (B) in the area in contact with the dental aqueous adhesive composition (A) when used as a dental curable composition (B) kit. Furthermore, if the content of the copper compound (c-3-2) is too low, the polymerization initiation time t2 of the dental curable composition (B) tends to be long, which may result in insufficient curing of the dental curable composition (B) in the area not in contact with the dental aqueous adhesive composition (A) during pre-irradiation when used as a dental curable composition (B) kit. On the other hand, if the content is too high, the radically polymerizable monomer in the dental curable composition (B) tends to polymerize easily, which may result in reduced storage stability of the dental curable composition (B).

[0066] Specific examples of the polymerization accelerator (c) include those used in the dental aqueous adhesive composition (A). In particular, the content of the vanadium compound (c-3-1) in the dental curable composition (B) is preferably in the range of 0.01 to 0.04 parts by mass, more preferably 0.015 to 0.038 parts by mass, and even more preferably 0.02 to 0.035 parts by mass, per 100 parts by mass of the radically polymerizable monomer contained in the dental curable composition (B). The content of the copper compound (c-3-2) in the dental curable composition (B) is preferably in the range of 0.001 to 0.0030 parts by mass, more preferably 0.0012 to 0.0028 parts by mass, and even more preferably 0.0015 to 0.0025 parts by mass, per 100 parts by mass of the radically polymerizable monomer contained in the dental curable composition (B).

[0067] The dental curable composition (B) of the present invention preferably contains a chemical polymerization initiator (f), which is an oxidizing agent component of a redox polymerization initiator.

[0068] Examples of the chemical polymerization initiator (f) include organic peroxides, azo compounds, and inorganic peroxides. Examples of organic peroxides include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, and hydroperoxides. Specific examples of diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluoyl peroxide. Specific examples of peroxyesters include t-butyl peroxybenzoate, bis(t-butylperoxy)isophthalate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxy-2-ethylhexanoate, and t-butylperoxyisopropyl carbonate. Specific examples of dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, and lauroyl peroxide. Specific examples of peroxyketals include 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 1,1-bis(t-hexylperoxy)cyclohexane. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl acetoacetate peroxide. Specific examples of hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, p-diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide. Specific examples of azo compounds include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). Examples of inorganic peroxides include sodium persulfate, potassium persulfate, aluminum persulfate, and ammonium persulfate.

[0069] Among these chemical polymerization initiators (f), hydroperoxides are preferred from the viewpoint of storage stability. Furthermore, 1,1,3,3-tetramethylbutyl hydroperoxide is particularly preferred because of its excellent polymerizability at the tooth interface.

[0070] The content of the chemical polymerization initiator (f) in the dental curable composition (B) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the radical polymerizable monomer contained in the dental curable composition (B). If it is less than 0.1 part by mass, curing may be delayed, so it is more preferably 0.2 parts by mass or more, and even more preferably 0.3 parts by mass or more. If it exceeds 10 parts by mass, curing may be too rapid and high adhesion may not be achieved, so it is more preferably 7.5 parts by mass or less, and even more preferably 5.0 parts by mass or less. That is, from the above viewpoints, the content of the chemical polymerization initiator (f) is more preferably 0.2 to 7.5 parts by mass, and even more preferably 0.3 to 5.0 parts by mass relative to 100 parts by mass of the radical polymerizable monomer contained in the dental curable composition (B).

[0071] Examples of the photopolymerization initiator (g) in the dental curable composition (B) include (bis)acylphosphine oxides and their salts, α-diketones, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, coumarins, anthraquinones, benzoin alkyl ether compounds, α-aminoketone compounds, etc. Specific examples of these include those described in WO 2008 / 087977. Among the (bis)acylphosphine oxides, examples of the acylphosphine oxide include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi(2,6-dimethylphenyl)phosphonate, and salts thereof (sodium salt, potassium salt, ammonium salt), and the like, with 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt being preferred. Examples of bisacylphosphine oxides include bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, and salts thereof (sodium salts, potassium salts, ammonium salts), and the like.Examples of α-diketones include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, acenaphthenequinone, etc. Among these, camphorquinone is particularly preferred because it has a maximum absorption wavelength in the visible light region.

[0072] Among these photopolymerization initiators (g), it is preferable to use at least one selected from the group consisting of (bis)acylphosphine oxides and their salts, and α-diketones, which provides a composition that is excellent in photocurability in the visible and near-ultraviolet regions and exhibits sufficient photocurability using any light source, such as a halogen lamp, a light-emitting diode (LED), or a xenon lamp.

[0073] The content of the photopolymerization initiator (g) in the dental curable composition (B) is not particularly limited, but from the viewpoint of photocurability, it is preferably 0.01 to 10 parts by mass, more preferably 0.10 to 3.0 parts by mass, per 100 parts by mass of the radical polymerizable monomer contained in the dental curable composition (B).

[0074] When the photopolymerization initiator (g) is used, it may be used in combination with a known photopolymerization accelerator for the purpose of accelerating photopolymerization. Therefore, the dental curable composition (B) may contain a photopolymerization accelerator.

[0075] Examples of photopolymerization accelerators contained in the dental curable composition (B) include amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, tin compounds, copper compounds, halogen compounds, aldehydes, thiol compounds, sulfites, and bisulfites. One or more photopolymerization accelerators may be used alone or in combination. In some embodiments, the dental curable composition (B) does not need to contain a borate compound. In other embodiments, the dental curable composition (B) includes a photopolymerization accelerator, and the photopolymerization accelerator is at least one selected from the group consisting of amines, sulfinic acid and its salts, barbituric acid derivatives, triazine compounds, tin compounds, copper compounds, halogen compounds, aldehydes, thiol compounds, sulfites, and bisulfites.

[0076] Examples of amines used as the photopolymerization accelerator include aliphatic amines and aromatic amines. However, in this specification, the radical polymerizable monomers containing an amino group but not an acidic group are not included in the amines of the polymerization accelerator (c).

[0077] Examples of the aliphatic amine photopolymerization accelerator include primary aliphatic amines such as n-butylamine, n-hexylamine, and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine, and N-methylethanolamine; and tertiary aliphatic amines such as N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, trimethylamine, triethylamine, and tributylamine. Among these, from the viewpoints of the curability and storage stability of the dental curable composition (B), tertiary aliphatic amines are preferred, and N-methyldiethanolamine and triethanolamine are more preferably used.

[0078] Examples of aromatic amines for the photopolymerization accelerator include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4-isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-isopropylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine, and N,N-diethyl-p-toluidine. Examples of the benzophenone include 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, ethyl 4-(N,N-dimethylamino)benzoate, methyl 4-(N,N-dimethylamino)benzoate, propyl 4-(N,N-dimethylamino)benzoate, n-butoxyethyl 4-(N,N-dimethylamino)benzoate, 2-[(meth)acryloyloxy]ethyl 4-(N,N-dimethylamino)benzoate, 4-(N,N-dimethylamino)benzophenone, butyl 4-dimethylaminobenzoate, and 4-(dimethylamino)benzonitrile. Among these, at least one selected from the group consisting of N,N-bis(2-hydroxyethyl)-p-toluidine, ethyl 4-(N,N-dimethylamino)benzoate, n-butoxyethyl 4-(N,N-dimethylamino)benzoate, and 4-(N,N-dimethylamino)benzophenone is preferably used, from the viewpoint of imparting excellent curability to the composition.

[0079] The content of the photopolymerization accelerator in the dental curable composition (B) is not particularly limited, but from the viewpoint of photocurability, it is preferably 0.01 to 5.0 parts by mass, and more preferably 0.10 to 3.0 parts by mass, per 100 parts by mass of the radical polymerizable monomer contained in the dental curable composition (B).

[0080] The filler (h) in the dental curable composition (B) of the present invention is roughly classified into inorganic fillers, organic fillers, and organic-inorganic composite fillers.

[0081] Examples of inorganic filler materials include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. These inorganic fillers can be used alone or in combination of two or more. The shape of the inorganic filler is not particularly limited, and the particle size of the filler can be appropriately selected. The average particle size of the inorganic filler is preferably 0.001 to 50 μm, more preferably 0.001 to 10 μm. The inorganic filler may be a combination of ultrafine particles having an average particle size of 0.001 to 0.1 μm and macroparticles having an average particle size of 1 to 50 μm (preferably 1 to 10 μm). The shape of the inorganic filler may be irregular or spherical, and may be appropriately selected for use.

[0082] The inorganic filler may be surface-treated in advance with a known surface treatment agent such as a silane coupling agent, if necessary, before use. Examples of such surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-aminopropyltriethoxysilane.

[0083] Examples of organic filler materials include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, and acrylonitrile-styrene-butadiene copolymer. These may be used alone or in combination of two or more. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. The average particle size of the organic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm. The organic filler may be a combination of ultrafine particles with an average particle size of 0.001 to 0.1 μm and macroparticles with an average particle size of 1 to 50 μm (preferably 1 to 10 μm).

[0084] The organic-inorganic composite filler is obtained by adding a monomer compound to the inorganic filler described above in advance, forming a paste, polymerizing it, and pulverizing it. Examples of the organic-inorganic composite filler that can be used include TMPT filler (trimethylolpropane methacrylate and silica filler mixed, polymerized, and then pulverized). The shape of the organic-inorganic composite filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. The average particle size of the organic-inorganic composite filler is preferably 0.001 to 50 μm, more preferably 0.001 to 10 μm. The organic-inorganic composite filler may be a combination of ultrafine particles with an average particle size of 0.001 to 0.1 μm and macroparticles with an average particle size of 1 to 50 μm (preferably 1 to 10 μm).

[0085] In this specification, the average particle size of the filler (h) refers to the average particle size of the primary particles of the filler (average primary particle size), and can be determined by laser diffraction scattering or electron microscope observation of the particles. Specifically, laser diffraction scattering is convenient for measuring the average particle size of particles of 0.1 μm or more, while electron microscope observation is convenient for measuring the average particle size of ultrafine particles of less than 0.1 μm. 0.1 μm is a value measured by laser diffraction scattering.

[0086] The laser diffraction scattering method can be performed, for example, by a laser diffraction particle size distribution analyzer (SALD-2300, manufactured by Shimadzu Corporation) using a 0.2% aqueous solution of sodium hexametaphosphate as a dispersion medium.

[0087] Electron microscope observation can be performed, for example, by taking a photograph of the particles with a scanning electron microscope (S-4000 model, manufactured by Hitachi, Ltd.) and measuring the particle diameters of the particles (200 or more) observed within a unit field of view of the photograph using image analysis particle size distribution measurement software (Macview (Mountec Co., Ltd.)). In this case, the particle diameter of the particles is determined as the arithmetic mean value of the longest and shortest lengths of the particles, and the average primary particle diameter is calculated from the number of particles and their particle diameters.

[0088] When it is desired to impart fluoride sustained-release properties to the dental hardenable composition (B), it is preferable to use at least one selected from the group consisting of fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass as the filler (h), and it is more preferable to use fluoroaluminosilicate glass and / or barium fluoroaluminosilicate glass.On the other hand, when it is desired to impart X-ray contrast properties to the dental hardenable composition (B), it is preferable to use at least one selected from the group consisting of barium glass, strontium glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, strontium fluoroaluminosilicate glass, and barium fluoroaluminosilicate glass as the filler (h), and it is more preferable to use barium glass and / or barium fluoroaluminosilicate glass.

[0089] The content of the filler (h) in the dental curable composition (B) is preferably 0.5 to 85 parts by mass, based on 100 parts by mass of the total amount of the radically polymerizable monomer and filler contained in the dental curable composition (B). If the content of the filler (h) is less than 0.5 parts by mass, the effects of adding the filler, such as adjusting the viscosity of the dental curable composition (B) and improving the mechanical strength of the dental curable composition (B) after hardening, may not be achieved. On the other hand, if the content exceeds 85 parts by mass, the viscosity of the dental curable composition (B) may become too high, resulting in reduced operability. The dental curable composition (B) of the present invention is preferably used in dental bonding materials, dental composite resins, dental curable compositions (B), etc., as described below. When the dental curable composition (B) is used as a dental composite resin or dental curable composition (B), from the viewpoints of the viscosity of the dental curable composition (B) and the mechanical strength after curing, the content of the filler is preferably 40 to 85 parts by mass, more preferably 50 to 81 parts by mass, and even more preferably 52 to 76 parts by mass, relative to 100 parts by mass of the total amount of the radical polymerizable monomer and filler contained in the dental curable composition (B).

[0090] The dental curable composition (B) of the present invention may contain, but is not limited to, a radical polymerizable monomer (a) containing an acidic group in order to improve adhesion to teeth and prostheses. Specific examples of the radical polymerizable monomer (a) containing an acidic group include those used in the dental aqueous adhesive composition (A).

[0091] Furthermore, the dental curable composition (B) of the present invention may contain a polymerization inhibitor, an ultraviolet absorber, a thickener, a colorant, an antibacterial agent, a fragrance, etc., within the range that does not impair the effects of the present invention.

[0092] In the dental adhesive kit of the present invention, from the viewpoint of storage stability, the dental curable composition (B) is preferably a two-component (two-paste) type. Specifically, it is preferable that a first part (e.g., a first paste) containing a hydroperoxide as the chemical polymerization initiator (f) and a second part (e.g., a second paste) containing a thiourea compound (c-2) as the polymerization accelerator (c) are packaged separately. A preferred embodiment (X-1) of the present invention is a dental adhesive kit comprising a dental aqueous adhesive composition (A) and a dental curable composition (B), wherein the dental curable composition (B) contains a first part and a second part, the first part containing a radical polymerizable monomer (b) not containing an acidic group, a chemical polymerization initiator (f), and a filler (h), and the second part containing a radical polymerizable monomer (b) not containing an acidic group, a polymerization accelerator (c), a photopolymerization initiator (g), and a filler (h). Another preferred embodiment (X-2) is the aforementioned embodiment (X-1) in which the first agent contains a photopolymerization accelerator. Another preferred embodiment (X-3) is the aforementioned embodiment (X-1) or (X-2) in which the first agent contains an ultraviolet absorber. Another preferred embodiment (X-4) is any of the aforementioned embodiments (X-1) to (X-3) in which the first agent and / or the second agent contains a polymerization inhibitor. Another preferred embodiment (X-5) is any of the aforementioned preferred embodiments (X-1) to (X-4) in which the dental aqueous adhesive composition (A) contains a radical polymerizable monomer (a) containing an acidic group, a radical polymerizable monomer (b-1) containing neither an amino group nor an acidic group, a polymerization accelerator (c), and water (d). Another preferred embodiment (X-6) is the dental aqueous adhesive composition (A) of the embodiment (X-5), in which the aqueous dental adhesive composition (A) contains a radical polymerizable monomer (b-2) containing an amino group but not an acidic group. In any of the above embodiments (X-1) to (X-6), the amount of each component can be appropriately changed based on the above explanation, and any component can be added, deleted, or otherwise modified.In any of the above-described embodiments, the composition and properties (tensile bond strength, bending strength, etc.) of each dental adhesive material kit can be appropriately changed and combined.

[0093] The dental adhesive kit of the present invention has excellent adhesion to tooth tissue, excellent removability when excess cement protruding from the margins of a dental restoration is removed in a semi-cured state by provisional irradiation with a light irradiator when bonding the tooth tissue to the dental restoration, and appropriate strength. Therefore, it is suitable for dental applications. When the dental adhesive kit of the present invention is used for dental applications, the dental aqueous adhesive composition (A) can be used as a dental primer, and the dental curable composition (B) can be used as a dental bonding material, dental composite resin, dental resin cement, etc. It is preferred that the dental adhesive kit of the present invention is a dental cement kit, and a more preferred embodiment is a dental cement kit in which the dental aqueous adhesive composition (A) is used as a dental primer and the dental curable composition (B) is used as a dental resin cement. [Example]

[0094] The present invention will be described below based on examples and comparative examples, but the present invention is not limited to these examples, etc. The abbreviations used below are as follows.

[0095] [Radical polymerizable monomer (a) containing an acidic group] MDP: 10-methacryloyloxydecyl dihydrogen phosphate [Radical polymerizable monomer (b-1) containing neither an amino group nor an acidic group] HEMA: 2-hydroxyethyl methacrylate #801: 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane BisGMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane D2.6E: 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethoxy groups added: 2.6) 3G: Triethylene glycol dimethacrylate [Radical polymerizable monomer (b-2) containing an amino group but not an acidic group] DMAEMA: Dimethylaminoethyl methacrylate (pH adjuster) [Thiourea compound (c-2)] DMETU: 4,4-dimethylethylenethiourea [Vanadium compounds (c-3-1)] VOAA: Vanadyl acetylacetonate BMOV: Bis(maltolato)oxovanadium(IV) [Copper compound (c-3-2)] Cu(OAc)2: Copper(II) acetate CuAA2: Copper(II) acetylacetonate [Chemical polymerization initiator (f)] THP: 1,1,3,3-tetramethylbutyl hydroperoxide [Polymerization inhibitor] BHT: 3,5-di-t-butyl-4-hydroxytoluene [UV absorber] TN326: Tinuvin 326 (BASF Japan Ltd.) [Photopolymerization initiator (g)] CQ: Camphorquinone [Photopolymerization accelerator] JJA: Ethyl 4-(N,N-dimethylamino)benzoate Filler (h) 8235: Silane-treated barium glass powder manufactured by Schott, average particle size: 2 μm, silane treatment concentration: 1.4% G018-117: Silane-treated barium fluoroaluminosilicate glass powder manufactured by Schott, average particle size: 2 μm, silane treatment concentration: 1.4% Ar380: AEROSIL® 380 fine particle silica manufactured by Nippon Aerosil Co., Ltd. Average particle size: 7 nm

[0096] <Examples 1 to 6 and Comparative Examples 1 to 3> The dental aqueous adhesive compositions (A) and dental curable compositions (B) of the respective Examples and Comparative Examples were prepared as follows, and their properties were evaluated. The results are shown in Table 2.

[0097] [Preparation of Dental Water-Based Adhesive Composition (A)] The raw materials were mixed at room temperature (25°C) in the mass ratios shown in Table 2 to prepare a primer as a dental aqueous adhesive composition (A), and the properties were examined according to the evaluation methods described below. [Preparation of dental curable composition (B)] The raw materials were mixed at room temperature (25°C) in the mass ratios shown in Table 1 to prepare a first monomer composition and a second monomer composition, respectively. Then, the resulting monomer compositions and various fillers were mixed at room temperature in the mass ratios shown in Table 2 to prepare a first paste and a second paste. Subsequently, 15 g of the second paste alone was transferred to a resin container of "Clearfil (registered trademark) FII" (manufactured by Kuraray Noritake Dental Co., Ltd.), the container was capped, and the container was left standing in a 60°C incubator for 24 hours, after which it was returned to room temperature (25°C). The first paste and second paste obtained as described above were filled into a paste container of "Clearfil (registered trademark) Aesthetic Cement" (manufactured by Kuraray Noritake Dental Co., Ltd.), which is an automix syringe. In each evaluation method described below, when using a dental curable composition (B) obtained by mixing the first paste and the second paste, a mixing tip ("Clearfil (registered trademark) Aesthetic Cement Mixing Tip", manufactured by Kuraray Noritake Dental Co., Ltd.) was attached to the tip of the paste container, and the first paste and the second paste were mixed at a volume ratio of 1:1 using the mixing tip to obtain the dental curable composition (B).

[0098] [Method for evaluating tensile bond strength to bovine dentin] The labial surfaces of bovine mandibular anterior teeth were polished under running water with (#80) silicon carbide paper (Nihon Kenshi Co., Ltd.) to obtain samples with exposed smooth dentin surfaces. Each sample was further polished under running water with #1000 silicon carbide paper (Nihon Kenshi Co., Ltd.). After polishing, the surface was dried by air blowing. After drying, adhesive tape approximately 150 μm thick with a 3 mm diameter circular hole was attached to the smooth surface to determine the adhesive area.

[0099] The dental aqueous adhesive composition (A) prepared above was applied to the circular hole using a brush, left for 20 seconds, and then air-dried until the applied dental aqueous adhesive composition (A) lost its fluidity. A dental curable composition (B) obtained by kneading the first and second pastes at a volume ratio of 1:1 using a mixing tip as described above was placed on the surface coated with the dental aqueous adhesive composition (A). A release film (manufactured by Kuraray Co., Ltd., product name "EVAL®") was then applied, and the composition was allowed to harden at room temperature for 1 hour. Next, one end (circular cross-section) of a stainless steel cylindrical rod (7 mm diameter, 2.5 cm length) was bonded to the cured surface using dental resin cement (manufactured by Kuraray Noritake Dental Co., Ltd., product name "Panavia® 21") and allowed to stand for 30 minutes. After that, excess dental resin cement that had protruded from the periphery of the stainless steel cylindrical rod was removed, and the rod was then immersed in distilled water. The test sample immersed in distilled water was left to stand in an incubator maintained at 37°C for 24 hours to prepare a test sample for the adhesion test. A total of 10 test samples for the adhesion test were prepared.

[0100] The tensile bond strength of the above five adhesion test samples was measured using a universal testing machine (manufactured by Shimadzu Corporation) with a crosshead speed set to 2 mm / min, and the average value was taken as the initial tensile bond strength.

[0101] The remaining five adhesion test samples were subjected to a thermal cycle (TC) load by alternately immersing them in a 4°C water bath and a 60°C water bath for one minute each 10,000 times, and then the tensile bond strength was measured. The tensile bond strength after this thermal cycle load was used to evaluate the adhesion durability.

[0102] [Method for evaluating bending strength and elastic modulus of cured paste] A polyester film was laid on a glass slide, and a stainless steel mold measuring 2 mm long, 25 mm wide, and 2 mm deep was placed on top of it. The dental curable composition (B), obtained by kneading the first and second pastes at a volume ratio of 1:1 using a mixing tip, was then filled into the mold. A polyester film was also laid on top of the filled composition, and a glass slide was placed on top of that. The surface of the composition filled into the mold was pressed against a glass slide via the polyester film, and the two glass slides were fixed using a 25 mm wide double clip. The sample fixed with the double clip was left in an incubator at 37°C for 1 hour to polymerize and harden, after which the sample was removed from the incubator, and the cured dental curable composition (B) was removed from the mold. The cured product was immersed in distilled water at 37°C for 24 hours and then used as a test specimen for a bending test. The bending strength and bending modulus were measured by a three-point bending test using a universal testing machine (Shimadzu Corporation) with a support distance of 20 mm and a crosshead speed of 1 mm / min. The average values ​​of the bending strength and bending modulus for five test pieces were taken as the bending strength and bending modulus of the cured paste.

[0103] [Method for evaluating excess cement removal during pre-irradiation] The labial surfaces of bovine mandibular anterior teeth were polished with (#80) silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water to obtain bovine tooth samples with exposed smooth dentin surfaces. The obtained bovine tooth samples were further polished with #1000 silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water. The bovine tooth samples were left to stand in an open chamber set at 35°C for 2 hours before use in the test.

[0104] After placing the bovine tooth sample in the open chamber, the water on the surface was dried by air blowing, and then the sample was fixed onto a glass slide with utility wax (manufactured by GC Corporation) with the smooth side facing up. The slide with the bovine tooth sample was placed on the work surface of the open chamber, and the position of the bovine tooth sample was adjusted so that the work surface and the smooth side of the bovine tooth sample were parallel. Next, the dental aqueous adhesive composition (A) prepared above was applied to the smooth surface with a brush, left for 20 seconds, and then the surface was dried by air blowing until the applied dental aqueous adhesive composition (A) lost its fluidity.

[0105] A dental curable composition (B) obtained by kneading the first paste and the second paste in a volume ratio of 1:1 using a mixing tip as described above was placed on one end face (circular cross section) of a stainless steel cylindrical rod (7 mm diameter, 2.5 cm length, hereinafter referred to as "SUS tip"), and the SUS tip was then gently placed on the bovine tooth sample so that the surface coated with the composition was in contact with the smooth surface of the bovine tooth sample.A test sample was prepared in which the dental curable composition (B) protruded around the SUS tip (the protruding dental curable composition (B) corresponded to excess cement).

[0106] The test samples obtained as described above were returned to an incubator maintained at 37°C and used to conduct an excess cement removability test (n=3). The excess cement was irradiated in standard mode using a dental LED light irradiator "PenCure 2000" (Morita Corporation) approximately 1 cm away from the test sample. The light irradiation was initiated 1 minute after the SUS tip was pressed against the applied dental hardenable composition (B) and the excess cement had squeezed out, followed by a 10-second rotation. For each test sample irradiated for the above time periods, the excess cement was immediately removed from the boundary between the SUS tip and the excess cement using a dental probe. The removability of excess cement after temporary irradiation was evaluated according to the following criteria. If all three samples met the "A" grade, they were rated "A." If even one sample met the "C" grade, they were rated "C." (Evaluation criteria for removability of excess cement) A: Excess cement can be easily removed in one go. B: Excess cement is hard and adheres to the tooth structure, but can be removed in multiple chunks. C: The hardness of the excess cement is very high, making it difficult to remove, or there is a lot of unpolymerized material in the excess cement, making it difficult to remove.

[0107] [Method for measuring contact polymerization initiation time t1 and polymerization initiation time t2] A diamond micro ATR instrument (single-reflection horizontal type ATRSmartOrbit) was installed in an FT-IR measurement instrument (Fourier transform infrared spectrometer "Nicolet 6700", manufactured by ThermoFisherScientific). The measurement conditions were a measurement range of 4000 cm -1 ~650cm -1 The number of scans was set to one.

[0108] (measurement for t2) The dental curable composition (B) obtained by kneading the first paste and the second paste at a volume ratio of 1:1 using a mixing tip as described above was placed on the sample stage of a diamond micro ATR machine set at 32°C. Real-time IR measurement was performed to measure the spectrum of the dental curable composition (B) at each time point. The real-time IR measurement was started from the time when the first paste and the second paste were kneaded, as can be seen from Figures 2A and 3A.

[0109] (t1, V max Measurements related to On the other hand, the dental aqueous adhesive composition (A) prepared above was applied with a brush to the sample stage of a diamond micro ATR machine set at 32°C, and the surface was dried by air blowing until the applied dental aqueous adhesive composition (A) lost its fluidity. Next, dental curable composition (B), obtained by kneading the first paste and the second paste at a volume ratio of 1:1 using a mixing tip as described above, was placed on the sample. Real-time IR measurement was performed to measure the spectra of the dental curable composition (B) used in combination with the dental aqueous adhesive composition (A) at various time intervals. The real-time IR measurement was started from the time the dental curable composition (B) came into contact with the dental aqueous adhesive composition (A).

[0110] The spectral analysis conditions were 1659 cm -1 From 1550cm -1 The baseline was set between 1700 and 1700 cm. The peak of the carbonyl bond (C=O, 1700 cm) before and after polymerization was measured, which was not affected by polymerization from the baseline. -1 ) a1 and a2 are used as the standard, and the double bond peak (C=C, 1600 cm ) before and after polymerization for each standard is -1 ) Using the area ratios of b1 and b2 (b1 / a1, b2 / a2), the residual double bond amount and polymerization rate c (%) were calculated, and t1, t2, and V were calculated as follows: max was calculated (see Figure 1). Relative ratio of double bonds before polymerization: b1 / a1 Relative ratio of double bonds after polymerization: b2 / a2 Residual double bond amount = (b2 × a1 / b1 × a2) × 100 Polymerization rate c(%)={1-(b2×a1) / (b1×a2)}×100 Polymerization average speed V(% / min)=(cy-cx) / (ty-tx) cx, cy: polymerization rate when time is tx, ty (minutes) (ty>tx) cx ={1-(bx×a1) / (b1×ax)}×100 cy ={1-(by×a1) / (b1×ay)}×100 ax, ay: Area of ​​the carbonyl bond peak when times are tx and ty (ty>tx) bx, by: Area of ​​double bond peak when time is tx, ty (ty>tx) Maximum polymerization rate V when dental water-based adhesive composition (A) and dental hardenable composition (B) come into contact max (% / min) is the maximum value of the average polymerization velocity V. The polymerization initiation time t2 (minutes) of the dental curable composition (B) was set to the minimum value of tx that satisfied the average polymerization rate V≧5 (% / minute) when the first paste and second paste of the dental curable composition (B) were kneaded. The polymerization initiation time t1 (minutes) upon contact between the dental water-based adhesive composition (A) and the dental curable composition (B) was set to the minimum value of tx that satisfied the average polymerization rate V≧5 (% / minute) when the dental curable composition (B) obtained by kneading the first paste and the second paste was brought into contact with the dental water-based adhesive composition (A).

[0111] [Table 1]

[0112] [Table 2]

[0113] The results in Table 2 show that the dental adhesive kit of the present invention exhibits superior initial adhesion and durability to dentin compared with the comparative example, and also exhibits superior removability of excess cement by light irradiation. [Industrial Applicability]

[0114] The dental adhesive material kit of the present invention is particularly ideal for dental cement kits because it has excellent adhesion to tooth structure, excellent removability when excess cement is temporarily irradiated with a light irradiator and removed in a semi-hardened state, and appropriate strength.

Claims

1. A dental adhesive material kit comprising a dental aqueous adhesive composition (A) and a dental curable composition (B), which satisfies the following formula (I): 0≦t2-t1≦3.0 (I) (In the formula, t1 (minutes) represents the polymerization initiation time upon contact between the dental aqueous adhesive composition (A) and the dental curable composition (B), and t2 (minutes) represents the polymerization initiation time of the dental curable composition (B).)

2. The maximum polymerization rate V when the dental water-based adhesive composition (A) and the dental curable composition (B) come into contact with each other max The dental adhesive material kit according to claim 1 , wherein the viscosity is 40% / min or more.

3. 3. The dental adhesive material kit according to claim 1, wherein the dental curable composition (B) comprises a radical polymerizable monomer (b) not containing an acidic group, a polymerization accelerator (c), a chemical polymerization initiator (f), a photopolymerization initiator (g), and a filler (h).

4. 4. The dental adhesive material kit according to claim 1, wherein the dental aqueous adhesive composition (A) comprises a radical polymerizable monomer (a) containing an acidic group, a radical polymerizable monomer (b-1) containing neither an amino group nor an acidic group, a polymerization accelerator (c), and water (d).

5. 5. The dental adhesive material kit according to claim 3, wherein the polymerization accelerator (c) of the dental aqueous adhesive composition (A) and / or the dental hardenable composition (B) comprises a fourth period transition metal compound (c-3).

6. 6. The dental adhesive material kit according to claim 5, wherein the polymerization accelerator (c) of the dental curable composition (B) comprises a fourth period transition metal compound (c-3), the fourth period transition metal compound (c-3) comprises a vanadium compound (c-3-1) and a copper compound (c-3-2), and the content of the vanadium compound (c-3-1) is 0.01 to 0.04 parts by mass and the content of the copper compound (c-3-2) is 0.001 to 0.0025 parts by mass relative to 100 parts by mass of the radically polymerizable monomer (b) containing no acidic group contained in the dental curable composition (B).

7. The dental adhesive material kit according to any one of claims 1 to 6, wherein t1 (minutes) is more than 0.1 minutes and not more than 3.0 minutes.

8. The dental adhesive material kit according to any one of claims 1 to 7, wherein t2 (minutes) is 1.0 minute or more and less than 4.0 minutes.

9. The dental adhesive material kit according to any one of claims 1 to 8, wherein the dental curable composition (B) contains a chemical polymerization initiator (f), and the chemical polymerization initiator (f) contains a hydroperoxide.

10. 6. The dental adhesive material kit according to claim 5, wherein the polymerization accelerator (c) of the dental aqueous adhesive composition (A) comprises a fourth period transition metal compound (c-3), and the fourth period transition metal compound (c-3) comprises a vanadium compound (c-3-1) and / or a copper compound (c-3-2).

11. The dental adhesive material kit according to any one of claims 3 to 10, wherein the polymerization accelerator (c) of the dental curable composition (B) includes a thiourea compound (c-2).

12. The dental adhesive material kit according to any one of claims 1 to 11, wherein the dental curable composition (B) is a two-component type.

13. The dental adhesive material kit according to any one of claims 1 to 12, which is a dental cement kit.

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