JP7356338B2 - Dental curable composition - Google Patents

Description

The present invention relates to dental curable compositions.

Dental curable compositions used as dental cement, dental adhesives, dental composite resins, self-adhesive dental composite resins, dental sealants, dental room temperature polymerization resins, etc. contain polymerizable monomers and Curable compositions containing radical polymerization initiators are widely used.

Radical polymerization initiators are broadly classified into photopolymerization initiators and chemical polymerization initiators, and in recent years, dual-cure products containing both have been widely used clinically. Among these radical polymerization initiators, a combination of an oxidizing agent and a reducing agent is generally used as a chemical polymerization initiator. By mixing these, a so-called redox reaction occurs and radicals are generated, and the polymerization reaction is accelerated. Curing begins and progresses. A dental composition containing a redox polymerization initiator is usually stored separately into a composition containing an oxidizing agent and a composition containing a reducing agent, and the two compositions are mixed immediately before use.

Dental curable compositions are commonly used when their application requires adhesion to adherends, such as dental cement, dental adhesives, self-adhesive dental composite resins, and dental sealants. Generally, compositions containing acidic components are used, but in recent years, radical polymerization initiators containing copper compounds have been proposed as redox polymerization initiators for use in dental curable compositions containing such acidic components. ing.

For example, Patent Document 1 discloses a redox polymerization initiator containing barbituric acid or thiobarbituric acid, peroxodisulfate and/or peroxodiphosphoric acid compound, sulfinic acid compound, and copper compound. Further, Patent Document 2 discloses a two-component initiator system having a hydroperoxide of a specific structure, a thiourea derivative, and a copper compound as a polymerization accelerator. Patent Document 3 discloses an initiator system containing a specific benzotriazole compound and/or a specific benzimidazole compound and a copper compound, each of which has an unsubstituted nitrogen atom at the 1st position.

It is generally known that the introduction of a copper compound improves the curability of the curable composition, and that the higher the content, the more excellent the mechanical strength can be obtained. On the other hand, it is also known that, especially in dental applications, when the content of copper compounds increases, a problem arises in that the operational margin time is shortened due to improved hardenability. That is, in a dental curable composition, it has been difficult to achieve both excellent mechanical strength and sufficient operating time by adjusting the content of the copper compound.

Specifically, the present inventors investigated and found that the redox polymerization initiator described in Patent Document 1 improves the hardenability of dental compositions by containing a sulfinic acid compound and a high concentration of copper compound. However, it was found that there was a problem in that the operational margin time was shortened at the same time. Furthermore, in the two-component initiator system described in Patent Document 2, it is necessary to contain a certain amount or more of a copper compound in order to ensure the hardenability of the dental composition, and the operational margin time is similarly shortened. I understand. On the other hand, in Patent Document 3, the catalytic activity of the copper compound is improved by using a specific benzotriazole compound and/or a specific benzimidazole compound, both of which have an unsubstituted nitrogen atom at position 1, with a copper compound. Therefore, it is possible to reduce the content of copper compounds. However, by incorporating the above-mentioned benzotriazole compound and/or specific benzimidazole compound, the operating margin time is shortened, so the cured product still has excellent mechanical strength and an operating margin of more than a certain time can be ensured. However, it has not yet been possible to achieve a high level of balance between the contradictory characteristics of being able to be used, and there is still room for further improvement.

Special Publication No. 2004-529947 Japanese Patent Application Publication No. 2007-56020 International Publication No. 2012/086189

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a dental curable composition that has excellent mechanical strength as a cured product and has a certain operating time or more.

As a result of intensive research aimed at solving the above problems, the present inventors have discovered that, in addition to a copper compound and an acidic group-containing polymerizable monomer, the present invention contains a specific benzotriazole compound and/or a specific benzimidazole compound. The present inventors discovered that a dental curable composition has excellent mechanical strength as a cured product and also ensures a certain operating margin time, and after further study, the present invention was completed.

（式中、Ｒ¹～Ｒ⁴はそれぞれ独立して、水素原子、水酸基、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアラルキル基、又はハロゲン原子を表し、Ｘは窒素原子又は－ＣＨを表し、Ｙは、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアラルキル基、又はハロゲン原子を表す。）
［２］前記ベンゾアゾール系化合物（ｃ）が、下記一般式〔１－１〕で表されるベンゾトリアゾール化合物（ｃ１）及び／又は下記一般式〔１－２〕で表されるベンゾイミダゾール化合物（ｃ２）を含む、［１］に記載の歯科用硬化性組成物。

（式中、Ｒ⁵～Ｒ¹²はそれぞれ独立して、水素原子、水酸基、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアラルキル基、又はハロゲン原子を表し、Ｙ¹及びＹ²はそれぞれ独立して、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアラルキル基、又はハロゲン原子を表す。）
［３］前記ベンゾトリアゾール化合物（ｃ１）及び／又はベンゾイミダゾール化合物（ｃ２）のＹ¹及びＹ²がそれぞれ独立して、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルケニル基、又は置換基を有していてもよいアラルキル基であり、前記置換基が電子吸引基である、［２］に記載の歯科用硬化性組成物。
［４］前記電子吸引基が、アセチル基、エステル基、エーテル基、カルボキシル基、シアノ基、スルホン酸基、スルホニル基、及びホスフェート基からなる群より選ばれる少なくとも１種である、［３］に記載の歯科用硬化性組成物。
［５］前記電子吸引基が、カルボキシル基である、［４］に記載の歯科用硬化性組成物。
［６］前記ベンゾアゾール系化合物（ｃ）が、２－（１Ｈ－ベンゾトリアゾール－１－イル）ブタン二酸、及び／又は２－（１Ｈ－ベンゾトリアゾール－１－イルメチル）ブタン二酸である、［１］～［５］のいずれかに記載の歯科用硬化性組成物。
［７］前記銅化合物（ｂ）の含有量が前記重合性単量体成分の総量１００質量部に対して、０．００００１～０．００５質量部である、［１］～［６］のいずれかに記載の歯科用硬化性組成物。
［８］さらに芳香族スルフィン酸塩（ｄ）を含む、［１］～［７］のいずれかに記載の歯科用硬化性組成物。
［９］さらに酸性基を含まない重合性単量体を含む、［１］～［８］のいずれかに記載の歯科用硬化性組成物。
［１０］第１剤と、第２剤とに分包され、
前記第１剤が、前記酸性基含有重合性単量体（ａ）、及び前記銅化合物（ｂ）を含み、
前記第２剤が、前記ベンゾアゾール系化合物（ｃ）、及び前記芳香族スルフィン酸塩（ｄ）を含む、［８］又は［９］に記載の歯科用硬化性組成物。
［１１］さらに第１剤に有機過酸化物（ｅ）を含む、［１０］に記載の歯科用硬化性組成物。
［１２］前記有機過酸化物（ｅ）が、ペルオキシエステルである、［１１］に記載の歯科用硬化性組成物。
［１３］前記重合性単量体成分が、前記酸性基含有重合性単量体（ａ）、及びさらに酸性基を有しない重合性単量体を含み、
前記重合開始剤系成分が、前記銅化合物（ｂ）、前記ベンゾアゾール系化合物（ｃ）、さらに芳香族スルフィン酸塩（ｄ）、無機過酸化物（ｆ）、及びアミン系還元剤（ｇ）を含み、
前記銅化合物（ｂ）の含有量が前記重合性単量体成分の総量１００質量部に対し、０．００００１～０．００５質量部である、［１］～［７］のいずれかに記載の歯科用硬化性組成物。
［１４］第１剤と、第２剤とに分包され、
前記第１剤が、前記酸性基含有重合性単量体（ａ）、前記銅化合物（ｂ）、前記ベンゾアゾール系化合物（ｃ）、及び前記無機過酸化物（ｆ）を含み、
前記第２剤が、前記酸性基を有しない重合性単量体、前記芳香族スルフィン酸塩（ｄ）、及び前記アミン系還元剤（ｇ）を含む、［１３］に記載の歯科用硬化性組成物。
［１５］さらに、重合開始剤系成分が、第２剤に硫黄を含有する還元性無機化合物（ｈ）を含む、［１３］に記載の歯科用硬化性組成物。
［１６］さらに、重合開始剤系成分が、第１剤に有機過酸化物（ｅ）を含む、［１４］又は［１５］に記載の歯科用硬化性組成物。
［１７］前記有機過酸化物（ｅ）が、ペルオキシエステルである、［１６］に記載の歯科用硬化性組成物。
［１８］前記無機過酸化物（ｆ）が、平均粒子径０．０１～５０μｍの粉末状である、［１３］～［１７］のいずれかに記載の歯科用硬化性組成物。
［１９］前記酸性基含有重合性単量体（ａ）の含有量が、重合性単量体成分の総量１００質量部中において１～５０質量部である、［１３］～［１８］のいずれかに記載の歯科用硬化性組成物。
［２０］前記無機過酸化物（ｆ）の含有量が、重合性単量体成分の総量１００質量部に対して０．０１～１０質量部である、［１３］～［１９］のいずれかに記載の歯科用硬化性組成物。
［２１］前記アミン系還元剤（ｇ）の含有量が、重合性単量体成分の総量１００質量部に対して０．０１～１０質量部である、［１３］～［２０］のいずれかに記載の歯科用硬化性組成物。
［２２］前記芳香族スルフィン酸塩（ｄ）の含有量が、重合性単量体成分の総量１００質量部に対して０．１～２０質量部である、［１３］～［２１］のいずれかに記載の歯科用硬化性組成物。
［２３］前記銅化合物（ｂ）と前記芳香族スルフィン酸塩（ｄ）とのモル比が、０．０００００３：１～０．０１：１である、［１３］～［２２］のいずれかに記載の歯科用硬化性組成物。
［２４］前記ベンゾアゾール系化合物（ｃ）と前記銅化合物（ｂ）とのモル比が、１：０．００００１～１：０．０１である、［１３］～［２３］のいずれかに記載の歯科用硬化性組成物。
［２５］前記銅化合物（ｂ）の含有量が、重合開始剤系成分の総量において０．０００００１～１質量％である、［１３］～［２４］のいずれかに記載の歯科用硬化性組成物。 That is, the present invention includes the following inventions.
[1] Contains a polymerizable monomer component and a polymerization initiator component,
The polymerizable monomer component includes an acidic group-containing polymerizable monomer (a),
A dental curable composition, wherein the polymerization initiator component includes a copper compound (b) and a benzazole compound (c) represented by the following general formula [1].

(In the formula, R ¹ to R ⁴ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. represents an optionally substituted alkoxy group, optionally substituted alkenyl group, optionally substituted aralkyl group, or halogen atom, X represents a nitrogen atom or -CH, and Y represents a substituted Alkyl group that may have a group, aryl group that may have a substituent, alkenyl group that may have a substituent, aralkyl group that may have a substituent, or halogen atom )
[2] The benzazole compound (c) is a benzotriazole compound (c1) represented by the following general formula [1-1] and/or a benzimidazole compound (c1) represented by the following general formula [1-2] ( c2) The dental curable composition according to [1].

(In the formula, R ⁵ to R ¹² each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent) represents an alkoxy group which may have a substituent, an alkenyl group which may have a substituent, an aralkyl group which may have a substituent, or a halogen atom, and Y ¹ and Y ² each independently represent a substituent. Represents an alkyl group that may have an optional substituent, an aryl group that may have a substituent, an alkenyl group that may have an optional substituent, an aralkyl group that may have an optional substituent, or a halogen atom .)
[3] Y ¹ and Y ² of the benzotriazole compound (c1) and/or benzimidazole compound (c2) each independently have an optionally substituted alkyl group or a substituent; The dental product according to [2], which is an optionally substituted aryl group, an optionally substituted alkenyl group, or an optionally substituted aralkyl group, and the substituent is an electron-withdrawing group. Curable composition.
[4] In [3], the electron-withdrawing group is at least one selected from the group consisting of an acetyl group, an ester group, an ether group, a carboxyl group, a cyano group, a sulfonic acid group, a sulfonyl group, and a phosphate group. The dental curable composition described.
[5] The dental curable composition according to [4], wherein the electron-withdrawing group is a carboxyl group.
[6] The benzazole compound (c) is 2-(1H-benzotriazol-1-yl)butanedioic acid and/or 2-(1H-benzotriazol-1-ylmethyl)butanedioic acid, The dental curable composition according to any one of [1] to [5].
[7] Any one of [1] to [6], wherein the content of the copper compound (b) is 0.00001 to 0.005 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer components. A dental curable composition according to claim 1.
[8] The dental curable composition according to any one of [1] to [7], further comprising an aromatic sulfinate (d).
[9] The dental curable composition according to any one of [1] to [8], further comprising a polymerizable monomer that does not contain an acidic group.
[10] Separately packaged into a first agent and a second agent,
The first agent contains the acidic group-containing polymerizable monomer (a) and the copper compound (b),
The dental curable composition according to [8] or [9], wherein the second agent contains the benzazole compound (c) and the aromatic sulfinate (d).
[11] The dental curable composition according to [10], further comprising an organic peroxide (e) in the first agent.
[12] The dental curable composition according to [11], wherein the organic peroxide (e) is a peroxyester.
[13] The polymerizable monomer component includes the acidic group-containing polymerizable monomer (a) and a polymerizable monomer that does not have an acidic group,
The polymerization initiator components include the copper compound (b), the benzazole compound (c), an aromatic sulfinate (d), an inorganic peroxide (f), and an amine reducing agent (g). including;
According to any one of [1] to [7], the content of the copper compound (b) is 0.00001 to 0.005 parts by mass based on 100 parts by mass of the total amount of the polymerizable monomer components. Dental curable composition.
[14] Separately packaged into a first agent and a second agent,
The first agent contains the acidic group-containing polymerizable monomer (a), the copper compound (b), the benzazole compound (c), and the inorganic peroxide (f),
The dental curable material according to [13], wherein the second agent contains the polymerizable monomer having no acidic group, the aromatic sulfinate (d), and the amine reducing agent (g). Composition.
[15] The dental curable composition according to [13], wherein the polymerization initiator component further includes a reducing inorganic compound (h) containing sulfur as a second agent.
[16] The dental curable composition according to [14] or [15], wherein the polymerization initiator component further contains an organic peroxide (e) as a first agent.
[17] The dental curable composition according to [16], wherein the organic peroxide (e) is a peroxyester.
[18] The dental curable composition according to any one of [13] to [17], wherein the inorganic peroxide (f) is in powder form with an average particle size of 0.01 to 50 μm.
[19] Any of [13] to [18], wherein the content of the acidic group-containing polymerizable monomer (a) is 1 to 50 parts by mass in 100 parts by mass of the total amount of polymerizable monomer components. A dental curable composition according to claim 1.
[20] Any one of [13] to [19], wherein the content of the inorganic peroxide (f) is 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of polymerizable monomer components. The dental curable composition described in .
[21] Any one of [13] to [20], wherein the content of the amine-based reducing agent (g) is 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of polymerizable monomer components. The dental curable composition described in .
[22] Any of [13] to [21], wherein the content of the aromatic sulfinate (d) is 0.1 to 20 parts by mass based on 100 parts by mass of the total amount of polymerizable monomer components. A dental curable composition according to claim 1.
[23] Any one of [13] to [22], wherein the molar ratio of the copper compound (b) and the aromatic sulfinate (d) is 0.000003:1 to 0.01:1. The dental curable composition described.
[24] Any one of [13] to [23], wherein the molar ratio of the benzazole compound (c) and the copper compound (b) is 1:0.00001 to 1:0.01. dental curable composition.
[25] The dental curable composition according to any one of [13] to [24], wherein the content of the copper compound (b) is 0.000001 to 1% by mass based on the total amount of polymerization initiator components. thing.

The dental curable composition of the present invention has excellent mechanical strength of the cured product, and can secure an operational margin of a certain amount of time or more.

The dental curable composition of the present invention includes a polymerizable monomer component and a polymerization initiator component, and the polymerizable monomer component includes an acidic group-containing polymerizable monomer (a). , the polymerization initiator component contains a copper compound (b) and a specific benzazole compound (c). First, these essential components will be explained.

The acidic group-containing polymerizable monomer (a) has at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, a carboxylic acid group, and an acryloyl Examples include polymerizable monomers having at least one polymerizable group such as a methacryloyl group, a vinyl group, a styrene group, and the like. The acidic group-containing polymerizable monomer (a) has an affinity with the adherend and has a demineralizing effect on tooth substance. The acidic group-containing polymerizable monomer (a) preferably has an acryloyl group or a methacryloyl group as a polymerizable group from the viewpoint of polymerizability, and more preferably has a methacryloyl group from the viewpoint of safety for living organisms. preferable. Specific examples of the acidic group-containing polymerizable monomer (a) are shown below. In the following, the description "(meth)acrylic" is a general term for methacrylic and acrylic. The same applies to expressions such as "(meth)acryloyl".

Examples of the phosphoric acid group-containing polymerizable monomer include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, and 4-(meth)acryloyloxybutyl dihydrogen phosphate. , 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyoctyl dihydro Genphosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxy Dodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate, bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis [4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxyoctyl]hydrogen phosphate, ) acryloyloxynonyl] hydrogen phosphate, bis[10-(meth)acryloyloxydecyl] hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethylphenylhydro Genphosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl] hydrogen phosphate, 2-methacryloyloxyethyl (4- methoxyphenyl) hydrogen phosphate, 2-methacryloyloxypropyl (4-methoxyphenyl) hydrogen phosphate, JP-A-52-113089, JP-A-53-67740, JP-A-53-69494, PT. Phosphate group-containing polymerizable monomers and their acid chlorides, alkali metal salts, as exemplified in JP-A-53-144939, JP-A-58-128393, and JP-A-58-192891; Examples include ammonium salts.

Examples of the pyrophosphate group-containing polymerizable monomer include bis[2-(meth)acryloyloxyethyl pyrophosphate], bis[4-(meth)acryloyloxybutyl pyrophosphate], and bis[6-(meth)acryloyl pyrophosphate]. oxyhexyl], bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, and their acid chlorides, alkali metal salts, and ammonium salts.

Examples of the thiophosphoric acid group-containing polymerizable monomer include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyldihydrogenthiophosphate, and 4-(meth)acryloyloxybutyldihydro. gentiophosphate, 5-(meth)acryloyloxypentyldihydrogenthiophosphate, 6-(meth)acryloyloxyhexyldihydrogenthiophosphate, 7-(meth)acryloyloxyheptyldihydrogenthiophosphate, 8-(meth)acryloyloxyheptyldihydrogenthiophosphate, ) Acryloyloxyoctyldihydrogenthiophosphate, 9-(meth)acryloyloxynonyldihydrogenthiophosphate, 10-(meth)acryloyloxydecyldihydrogenthiophosphate, 11-(meth)acryloyloxyundecyldihydrogen Thiophosphate, 12-(meth)acryloyloxydodecyldihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyldihydrogenthiophosphate, 20-(meth)acryloyloxyicosyldihydrogenthiophosphate and these acids Examples include chlorides, alkali metal salts, and ammonium salts.

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

Examples of the sulfonic acid group-containing polymerizable monomer include 2-(meth)acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl (meth)acrylate.

Examples of the carboxylic acid group-containing polymerizable monomer include a polymerizable monomer having one carboxyl group in the molecule and a polymerizable monomer having multiple carboxyl groups in the molecule.

Examples of polymerizable monomers having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloyl aspartic acid, O-(meth)acryloyltyrosine, N- (meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyl-p-aminobenzoic acid, ) Acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, Examples include 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen malate, and acid halides thereof.

Examples of polymerizable monomers having multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, and 10-dicarboxylic acid. -(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, 4-(meth)acryloyloxybutyl trimellitate tate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3, Examples include 4-dicarboxybenzoyloxy)propyl succinate and acid anhydrides or acid halides thereof.

The above acidic group-containing polymerizable monomers (a) may be used alone or in combination of two or more. Among these acidic group-containing polymerizable monomers, 10-(meth)acryloyloxydecyl dihydrogen phosphate and 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate have a high adhesive strength to adherends. Hydrogen phosphate, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 4-(meth)acryloyloxyethyl trimellitate anhydride, 4-(meth)acryloyloxyethyl trimellitate, 2-(meth)acrylamide 2-methylpropanesulfonic acid and 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid are preferred.

The content of the acidic group-containing polymerizable monomer (a) is preferably 1 to 50 parts by mass in 100 parts by mass of the total amount of polymerizable monomer components in the dental curable composition of the present invention. , more preferably 2 to 40 parts by weight, and even more preferably 5 to 30 parts by weight. When the content of the acidic group-containing polymerizable monomer (a) is 1 part by mass or more, it is easy to obtain high adhesiveness to various adherends. When the content of a) is 50 parts by mass or less, it is easy to maintain a balance between polymerizability and adhesiveness. Note that the total amount of polymerizable monomer components refers to the total amount of the acidic group-containing polymerizable monomer (a) and the below-mentioned polymerizable monomer not having an acidic group.

The copper compound (b) is preferably a compound soluble in the polymerizable monomer component. Specific examples include copper acetate, copper isobutyrate, copper gluconate, copper citrate, copper phthalate, copper tartrate, copper oleate, copper octylate, copper octenoate, copper naphthenate, and methacrylate. Acid copper, copper 4-cyclohexylbutyrate; β-diketone copper, copper acetylacetone, copper trifluoroacetylacetone, copper hexafluoroacetylacetone, copper 2,2,6,6-tetramethyl-3,5-heptanedionato, copper benzoylacetone; β-ketoester copper as ethyl copper acetoacetate; copper alkoxide as copper methoxide, copper ethoxide, copper isopropoxide, copper 2-(2-butoxyethoxy) ethoxide, copper 2-(2-methoxyethoxy) ethoxide; dithiocarbamic acid Examples of copper include copper dimethyldithiocarbamate; examples of salts of copper and inorganic acids include copper nitrate; and copper chloride. These may be used alone or in combination of two or more. Among these, from the viewpoint of solubility and reactivity with the polymerizable monomer, copper carboxylate, copper β-diketone, and copper β-ketoester are preferred, and copper acetate and copper acetylacetone are particularly preferred.

In the present invention, since the catalytic activity of the copper compound (b) is improved by the benzazole compound (c) represented by the general formula [1] described below, the content of the copper compound (b) is lower than that of the conventional one. can also be made smaller. The content of the copper compound (b) is determined based on the total amount of polymerizable monomer components in the dental curable composition 100 mass from the viewpoint of mechanical strength of the cured product, adhesive strength with the adherend, and operation time. The amount is preferably 0.00001 to 0.005 parts by mass. Regarding the lower limit, the content of the copper compound (b) is more preferably 0.0001 parts by mass or more, even more preferably 0.00025 parts by mass or more, particularly 0.0005 parts by mass or more. preferable. Regarding the upper limit, it is more preferably 0.003 parts by mass or less.

（式中、Ｒ¹～Ｒ⁴はそれぞれ独立して、水素原子、水酸基、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアラルキル基、又はハロゲン原子を表し、Ｘは窒素原子又は－ＣＨを表し、Ｙは、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアラルキル基、又はハロゲン原子を表す。） The dental curable composition of the present invention contains a benzazole compound (c) represented by the following general formula [1] (hereinafter also referred to as "benzazole compound (c)").

(In the formula, R ¹ to R ⁴ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. represents an optionally substituted alkoxy group, optionally substituted alkenyl group, optionally substituted aralkyl group, or halogen atom, X represents a nitrogen atom or -CH, and Y represents a substituted Alkyl group that may have a group, aryl group that may have a substituent, alkenyl group that may have a substituent, aralkyl group that may have a substituent, or halogen atom )

Examples of the benzazole compound (c) include a benzotriazole compound (c1) and a benzimidazole compound (c2). The benzotriazole compound (c1) and the benzimidazole compound (c2) are represented by the following general formulas [1-1] and [1-2], respectively.

In the above general formula [1-1] and formula [1-2], R ⁵ to R ¹² each independently have a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, or a substituent. Y ¹ and Y ² each independently represent an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, or an alkenyl group that may have a substituent. Indicates an optional aralkyl group or a halogen atom.

Although the reason why the dental curable composition of the present invention has excellent mechanical strength of the cured product and ensures a certain operating time or more is not clear, the present inventors speculate as follows. ing. Coordination of the benzazole compound (c) of the present invention to the copper compound (b) improves the catalytic activity of the copper compound (b), resulting in a cured product with high mechanical strength. On the other hand, the substituents (Y, Y ¹ and Y ² ) bonded to the nitrogen atom at the 1-position of the benzazole compound (c) of the present invention pose a steric hindrance to the coordination to the copper compound, and the coordination is slightly impaired. It is estimated that a certain amount of operating time was secured because of the restrictions. In other words, the coordination of the benzazole compound (c) to the copper compound (b) itself occurs without any problem, and a cured product with high mechanical strength is finally obtained after curing, but due to coordination limitations due to steric hindrance. Since the speed until coordination, that is, the reaction speed, is delayed, we believe that as a result, we were able to achieve both high mechanical strength of the cured product and a certain amount of operational margin time.

The alkyl group represented by R ¹ to R ¹² may be linear, branched, or cyclic, and preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. , 1 to 4 are more preferred. Examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl. , neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptanyl group, n-octyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, Examples include cyclononyl group and n-decyl group. Among these, methyl group and ethyl group are particularly preferred.

The aryl group represented by R ¹ to R ¹² preferably has 6 to 10 carbon atoms, and examples thereof include phenyl group, naphthyl group, and anthryl group.

The alkoxy group represented by R ¹ to R ¹² may be linear, branched, or cyclic, and preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. , 1 to 4 are more preferred. Examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-hexyloxy, cyclohexyloxy, n-octyloxy, 2-ethylhexyloxy. etc.

The alkenyl group represented by R ¹ to R ¹² may be linear, branched, or cyclic, and preferably has 2 to 6 carbon atoms, more preferably 2 to 5 carbon atoms. , 2 to 4 are more preferred. Examples include vinyl, allyl, methylvinyl, propenyl, butenyl, pentenyl, hexenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.

Examples of the aralkyl group represented by R ¹ to R ¹² include alkyl groups (especially alkyl groups having 1 to 10 carbon atoms) substituted with aryl groups (especially aryl groups having 6 to 10 carbon atoms). A specific example is a benzyl group.

Examples of the halogen atom represented by R ¹ to R ¹² include a chlorine atom, a bromine atom, an iodine atom, and the like.

R ¹ to R ¹² are preferably hydrogen atoms or methyl groups. Examples of substituents for each of R ¹ to R ¹² include halogen atom, hydroxyl group, cyano group, nitro group, lower alkyl group, alkyl group having 1 to 6 carbon atoms substituted with halogen atom, and 1 to 6 carbon atoms. Examples include a hydroxyalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms substituted with a halogen atom, and the like. The groups R ¹ to R ¹² may be unsubstituted.

The alkyl group represented by Y, Y ¹ and Y ² may be linear, branched, or cyclic, and preferably has 1 to 10 carbon atoms, and preferably 1 to 6 carbon atoms. More preferably, 1 to 4 are even more preferable. Examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl. , neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptanyl group, n-octyl group, 2-ethylhexyl group, cyclooctyl group, n-nonyl group, Examples include cyclononyl group and n-decyl group.

The aryl group represented by Y, Y ¹ and Y ² preferably has 6 to 10 carbon atoms, and examples thereof include phenyl group, naphthyl group, and anthryl group.

The alkenyl group represented by Y, Y ¹ and Y ² may be linear, branched, or cyclic, and preferably has 2 to 6 carbon atoms, and preferably 2 to 5 carbon atoms. More preferably, 2 to 4 are even more preferable. Examples include vinyl, allyl, methylvinyl, propenyl, butenyl, pentenyl, hexenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.

Examples of aralkyl groups represented by Y, Y ¹ and Y ² include alkyl groups (especially alkyl groups having 1 to 10 carbon atoms) substituted with aryl groups (especially aryl groups having 6 to 10 carbon atoms); Specific examples include benzyl group and the like.

Examples of the halogen atom represented by Y, Y ¹ and Y ² include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

In addition, from the viewpoint of ensuring operational margin time, Y, Y ¹ and Y ² are each independently an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. It is preferably an alkenyl group which may have a group or an aralkyl group which may have a substituent, and it is more preferable that the substituent of these groups is an electron-withdrawing group. Electron-withdrawing groups are not particularly limited as long as they are substituents that exhibit electron-withdrawing properties, but include acetyl groups, ketone groups in esters, ether groups, carboxyl groups, cyano groups, sulfonic acid groups, sulfonyl groups, and phosphate groups. At least one selected from the group is preferable, and among these, carboxyl It is more preferable that it is a group. Further, the number of substituted electron-withdrawing groups is preferably one or more, more preferably two or more. Because Y, Y ¹ and Y ² have an electron-withdrawing group, the electron density on the nitrogen atom coordinating to the copper compound (b) decreases, and the benzazole compound (c) is transferred to the copper compound (b). It is presumed that because the coordination is restricted, the reduction in operating margin time is further suppressed.

The benzazole compound (c) may be used alone or in combination of two or more. Specific examples of the benzotriazole compound (c1) and benzimidazole compound (c2) include 2-(1H-benzotriazol-1-yl)butanedioic acid and 2-(1H-benzotriazol-1-ylmethyl)butanedioic acid. , 2-(1H-benzotriazol-1-yl)-dimethylester-2-(E)-butenedioic acid, 2-(1H-benzotriazol-1-yl)-dimethylester-2-(Z)-butene diacid, 2-(1H-benzotriazol-1-yl)-1,4-dimethylester-2-butenedioic acid, 2-(1H-benzotriazol-1-yl)-3-(1-piperidinyl) methyl)-dimethylester-2-(E)-butenedioic acid, 2-(1H-benzotriazol-1-yl)-3-(1-piperidinylmethyl)-1,4-dimethylester-2-butene diacid, 2-(1H-benzotriazol-1-yl)-3-(4-morpholinylmethyl)-dimethyl ester-2-(E)-butenedioic acid, 2-(1H-benzotriazol-1-yl) yl)-di-9-(Z)-octadecenyl ester-2-(Z)-butenedioic acid and the like. Among these, 2-(1H-benzotriazol-1-yl)butanedioic acid, 2-(1H-benzotriazol-1-yl)butanedioic acid, -(1H-benzotriazol-1-ylmethyl)butanedioic acid is preferred.

The content of the benzazole compound (c) is determined based on the total amount of polymerizable monomer components in the dental curable composition from the viewpoints of mechanical strength of the cured product, adhesive strength with the adherend, and operation time. When the amount is 100 parts by weight, it is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and even more preferably 0.5 to 3 parts by weight.

The content ratio (molar ratio) of the benzazole compound (c) and the copper compound (b) is preferably 1:0.00001 to 1:0.01, and preferably 1:0.0001 to 1:0. 005 is more preferable. When the molar ratio of the benzazole compound (c) and the copper compound (b) is within this range, better mechanical strength can be obtained while further suppressing discoloration due to hydrogen sulfide.

By further containing specific optional components in the dental curable composition of the present invention, properties useful for dental applications can be improved. Such optional components include, as a polymerizable monomer component, a polymerizable monomer that does not contain an acidic group; as a polymerization initiator component, an aromatic sulfinate (d), an organic peroxide (e) , an inorganic peroxide (f), an amine reducing agent (g), a reducing inorganic compound containing sulfur (h); and a filler (i) as other components. These may be used alone or in combination of two or more.

Aromatic sulfinate salts (d) include benzenesulfinic acid, p-toluenesulfinic acid, o-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid. Lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, calcium salts, strontium salts, iron salts of acids, 2,4,6-triisopropylbenzenesulfinic acid, chlorobenzenesulfinic acid, naphthalenesulfinic acid, etc. , zinc salt, ammonium salt, tetramethylammonium salt, and tetraethylammonium salt. Among these, lithium salts, sodium salts of 2,4,6-trimethylbenzenesulfinic acid and 2,4,6-triisopropylbenzenesulfinic acid, Potassium salts, magnesium salts, and calcium salts are preferred, and lithium salts, sodium salts, potassium salts, magnesium salts, and calcium salts of 2,4,6-triisopropylbenzenesulfinic acid are more preferred.

At least a portion of the aromatic sulfinate (d) is preferably dispersed in powder form in the dental curable composition. By dispersing the dental curable composition in the form of a powder, the dental curable composition of the present invention can secure a longer operating time, and when applied to the tooth structure, the aromatic sulfinate (d) is absorbed into the tooth structure. Since it dissolves in water on the surface, it is possible to further enhance the polymerization curability at the adhesive interface and inside the resin-impregnated layer. When the aromatic sulfinate (d) is dispersed in powder form, the aromatic sulfinate (d) preferably has a solubility in water of 1 mg/100 mL or more at room temperature (25° C.). If the solubility is less than 1 mg/100 mL, when the dental curable composition of the present invention is applied to the tooth, the aromatic sulfinate (d) will be sufficiently dissolved in the water of the tooth at the adhesive interface. As a result, the effect of dispersing with powder becomes difficult to express. Moreover, since the aromatic sulfinate salt (d) tends to settle if the particle size is too large, the average particle size is preferably 500 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less. However, if the average particle diameter is too small, the specific surface area of the powder may become too large and the handleability of the curable composition may deteriorate, so the average particle diameter is preferably 0.01 μm or more. That is, when dispersing as a powder, the average particle diameter is preferably in the range of 0.01 to 500 μm, more preferably in the range of 0.01 to 100 μm.

The average particle size of the aromatic sulfinate (d) refers to the volume average particle size, and the volume average particle size is calculated using image analysis software (based on electron micrographs of 100 or more particles). For example, it can be calculated by performing image analysis using Mac-View (manufactured by Mountec Co., Ltd.).

When the aromatic sulfinate salt (d) is dispersed as a powder, the shape thereof may be various shapes such as spherical, acicular, plate-like, and crushed shapes, but is not particularly limited. The aromatic sulfinate (d) can be made into a fine powder by a conventionally known method such as a pulverization method or a freeze-drying method.

The content of aromatic sulfinate (d) is determined based on the total amount of polymerizable monomer components in the dental curable composition from the viewpoint of mechanical strength of the cured product, adhesive strength with the adherend, and operation time. When 100 parts by mass, 0.01 to 20 parts by mass is preferable. If the content is less than 0.01 parts by mass, the adhesive strength of the resulting dental curable composition to the adherend may decrease, and more preferably 0.05 parts by mass or more, even more preferably The amount is 0.1 parts by weight or more, even more preferably 0.2 parts by weight or more, particularly preferably 0.25 parts by weight or more, and most preferably 0.3 parts by weight or more. On the other hand, if the content exceeds 20 parts by mass, there is a risk that the handleability of the resulting dental curable composition and the mechanical strength of the resulting cured product may decrease, and more preferably 15 parts by mass or less, More preferably it is 10 parts by mass or less, most preferably 5 parts by mass or less.

When the dental curable composition of the present invention contains the organic peroxide (e), the mechanical strength of the resulting cured product can be further improved.

The organic peroxide (e) is not particularly limited and any known organic peroxide can be used. Typical organic peroxides include hydroperoxides, peroxyesters, ketone peroxides, peroxyketals, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and the like. Among these, hydroperoxides and peroxy esters are particularly preferred, and from the viewpoint of storage stability of the resulting dental curable composition, peroxy esters are most preferred. The organic peroxide (e) may be used alone or in combination of two or more.

More specifically, the hydroperoxides include cumene hydroperoxide, t-butyl hydroperoxide, t-hexyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide. Examples include peroxide.

As the peroxy ester, any known peroxy ester can be used without any restriction as long as it has an acyl group on one side of the peroxy group (-OO- group) and a hydrocarbon group (or a group similar thereto) on the other side. Specific examples include α,α-bis(neodecanoylperoxy)diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1- Methyl ethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, 1,1,3,3-tetramethyl Butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t- Hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxysobutyrate, t-hexylperoxysopropyl monocarbonate, t-butylperoxymaleic acid, t-butyl Peroxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis(m-toluoylperoxy)hexane, t-butylperoxysopropyl monocarbonate, t -Butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-butylperoxym-toluoylbenzoate, t -butylperoxybenzoate, bis(t-butylperoxy)isophthalate and the like. These can be used alone or in an appropriate combination of two or more. Among these, from the viewpoint of storage stability and reactivity, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxybenzoate, t-butylperoxyso Propyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, and t-butylperoxyacetate are preferred, and t-butylperoxybenzoate is more preferred.

Examples of the ketone peroxide include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide.

Peroxyketals include 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)3, , 3,5-trimethylcyclohexanone, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)cyclodecane, 2,2-bis(t-butylperoxy)butane, n-butyl Examples include 4,4-bis(t-butylperoxy)valerate and 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane.

Examples of dialkyl peroxides include α,α-bis(t-butylperoxy)diisopropylbenzene, dicumylperoxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylcumylperoxide, and dicumylperoxide. -t-butylperoxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)3-hexyne, and the like.

Examples of diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide. , benzoyl peroxides.

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

The content of organic peroxide (e) is determined based on the total amount of polymerizable monomer components in the dental curable composition from the viewpoint of mechanical strength of the cured product, adhesive strength with the adherend, and operation time. The amount is preferably 0.001 to 10 parts by weight, more preferably 0.005 to 3 parts by weight, and even more preferably 0.025 to 1 part by weight, per 100 parts by weight.

Examples of the inorganic peroxide (f) include peroxodisulfate and peroxodiphosphate, and among these, peroxodisulfate is preferred in terms of redox reactivity. Specific examples of peroxodisulfate include sodium peroxodisulfate, potassium peroxodisulfate, aluminum peroxodisulfate, and ammonium peroxodisulfate.

The above peroxodisulfates may be used alone or in combination of two or more. Among the above peroxodisulfates, sodium peroxodisulfate, potassium peroxodisulfate, and ammonium peroxodisulfate are preferred.

It is preferable that at least a part of the inorganic peroxide (f) is dispersed in powder form in the dental curable composition, since this provides high storage stability of the dental curable composition. At this time, the average particle diameter of the powdered inorganic peroxide (f) is preferably in the range of 0.01 to 50 μm, more preferably in the range of 0.1 to 20 μm. When the powdered inorganic peroxide (f) has such an average particle size, the powdered inorganic peroxide (f) is efficiently dissolved in the water on the tooth surface at the bonding interface, and the bonding is improved. It is possible to selectively increase the polymerization curability at the adhesive interface and inside the resin-impregnated layer formed on the tooth substance, which is important for the properties of the tooth. In addition, the said average particle diameter can be measured similarly to the said average particle diameter of aromatic sulfinate (d).

The shape of the powdered inorganic peroxide (f) includes various shapes such as spherical, acicular, plate-like, and crushed shapes, but is not particularly limited. Powdered inorganic peroxide (f) can be produced by conventionally known methods such as a pulverization method, a freeze-drying method, and a reprecipitation method. Among these methods for producing the powdered inorganic peroxide (f), the pulverization method and freeze-drying method are preferred, and the pulverization method is more preferred, from the viewpoint of the average particle size of the resulting powder.

The content of the inorganic peroxide (f) is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of polymerizable monomer components in the dental curable composition of the present invention. If the content is less than 0.01 parts by mass, the adhesive strength may decrease. On the other hand, if the content exceeds 10 parts by mass, the adhesive strength and the mechanical strength of the cured product may decrease.

The amine reducing agent (g) is broadly classified into aromatic amines and aliphatic amines, and in the present invention, either aromatic amines or aliphatic amines may be used. The amine reducing agent (g) may be used alone or in combination of two or more.

As the aromatic amine, known aromatic secondary amines, aromatic tertiary amines, etc. may be used. As the aromatic secondary amine or aromatic tertiary amine, N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-di(2-hydroxyethyl)-p-toluidine , N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethylaniline, N,N-bis(2-hydroxyethyl)-4 -isopropylaniline, N,N-bis(2-hydroxyethyl)-4-t-butylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-isopropylaniline, N,N-bis( 2-Hydroxyethyl)-3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, 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-isopropyl Examples include aniline, N,N-dimethyl-4-t-butylaniline, and N,N-dimethyl-3,5-di-t-butylaniline. Among these, N,N-di(2-hydroxyethyl)-p-toluidine is preferred in terms of redox reactivity.

Examples of aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine, and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine, and N-methylethanolamine; Methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl (meth)acrylate, N-methyldiethanolamine di(meth)acrylate, N-ethyldiethanolamine di(meth) Examples include tertiary aliphatic amines such as acrylate, triethanolamine tri(meth)acrylate, triethanolamine, trimethylamine, triethylamine, and tributylamine. Among these, tertiary aliphatic amines are preferred in terms of redox reactivity, and among these, N-methyldiethanolamine, triethanolamine, and 2-(dimethylamino)ethyl methacrylate are particularly preferred.

The preferred content of the amine reducing agent (g) is preferably 0.01 to 10 parts by mass, and 0.01 to 10 parts by mass, based on 100 parts by mass of the total amount of polymerizable monomer components in the dental curable composition of the present invention. More preferably 0.02 to 5 parts by weight, most preferably 0.05 to 2 parts by weight. If the content is less than 0.01 part by mass, the adhesive strength of the resulting dental curable composition to tooth structure may be reduced. On the other hand, if the content exceeds 10 parts by mass, the color stability of the resulting dental curable composition may decrease.

Sulfur-containing reducing inorganic compounds (h) (hereinafter also referred to as "reducing inorganic compounds (h)") include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, and Examples include dithionates, and among these, sulfites and bisulfites are preferred, and specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, and the like. One type of reducing inorganic compound (h) may be used alone, or two or more types may be used in combination.

It is preferable that at least a part of the reducing inorganic compound (h) is dispersed in powder form in the dental curable composition. By dispersing the dental curable composition in the form of a powder, the dental curable composition of the present invention can secure a longer operating time, and when applied to the tooth structure, the reducing inorganic compound (h) can be applied to the tooth surface. Since it is soluble in water, it is possible to further enhance the polymerization curability at the adhesive interface and inside the resin-impregnated layer. When the reducing inorganic compound (h) is dispersed as a powder, the reducing inorganic compound (h) preferably has a solubility in water of 1 mg/100 mL or more at room temperature (25° C.). If the solubility is less than 1 mg/100 mL, when the dental curable composition of the present invention is applied to the tooth, the reducing inorganic compound (h) may not be sufficiently dissolved in the water of the tooth at the adhesive interface. As a result, it becomes difficult to achieve the effect of dispersing the powder. Moreover, since the reducing inorganic compound (h) tends to settle if the particle size is too large, the average particle size is preferably 500 μm or less, more preferably 100 μm or less, and even more preferably 50 μm or less. However, if the average particle diameter is too small, the specific surface area of the powder may become excessive and the handling of the dental curable composition may deteriorate, so the average particle diameter is preferably 0.01 μm or more. That is, when dispersing as a powder, the average particle diameter is preferably in the range of 0.01 to 500 μm, more preferably in the range of 0.01 to 100 μm. In addition, the said average particle diameter can be measured similarly to the said average particle diameter of aromatic sulfinate (d).

When the reducing inorganic compound (h) is dispersed as a powder, the shape thereof may be various shapes such as spherical, acicular, plate-like, and crushed shapes, but is not particularly limited. The reducing inorganic compound (h) can be made into a fine powder by a conventionally known method such as a pulverization method or a freeze-drying method.

When the polymerization initiator component of the dental curable composition of the present invention contains components (b), (c), (d), (e), (f), and (h), the dental The adhesion strength of the curable composition for dental use to tooth structure is particularly high.

The content of the reducing inorganic compound (h) is preferably 0.01 to 15 parts by mass, and 0.01 to 15 parts by mass, based on 100 parts by mass of the total amount of polymerizable monomer components in the dental curable composition of the present invention. More preferably 0.5 to 10 parts by weight, and even more preferably 0.1 to 5 parts by weight. If the content is less than 0.01 part by mass, the adhesive strength of the resulting dental curable composition to tooth structure may be reduced. On the other hand, if the content exceeds 15 parts by mass, the mechanical strength of the resulting cured dental curable composition may decrease.

As the polymerizable monomer that does not have an acidic group, a radically polymerizable monomer that has a polymerizable group is preferable, and from the viewpoint of easy radical polymerization, the polymerizable group is a (meth)acrylic group and/or a (meth)acrylic group. ) Preferably it is an acrylamide group. The dental curable composition of the present invention is used in the oral cavity, but the oral cavity is a humid environment, and there is a risk that the polymerizable groups may be removed due to hydrolysis or the like. Considering the irritation to the skin, the polymerizable group is preferably a methacryl group and/or a methacrylamide group. The polymerizable monomer having no acidic group contributes to improving the coating properties, adhesion properties, and mechanical strength of the composition after curing.

Examples of the polymerizable monomer having no acidic group include the following water-soluble polymerizable monomers and hydrophobic polymerizable monomers.

The water-soluble polymerizable monomer means one having a solubility in water of 10% by mass or more at 25°C. It is preferable that the solubility is 30% by mass or more, and more preferably that it can be dissolved in water at an arbitrary ratio at 25°C. The water-soluble polymerizable monomer not only promotes the penetration of components into the tooth structure, but also penetrates into the tooth structure and adheres to the organic component (collagen) in the tooth structure. The water-soluble polymerizable monomer has at least one hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxyproprene group, or an amide group. Examples of water-soluble polymerizable monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2, Hydrophilic monofunctional (meth)acrylate polymerizable monomers such as 3-dihydroxypropyl (meth)acrylate, 2-((meth)acryloyloxy)ethyltrimethylammonium chloride; N-methylol (meth)acrylamide, N -Hydroxyethyl (meth)acrylamide, N,N-bis(2-hydroxyethyl)(meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, diacetone (meth)acrylamide, N- Hydrophilic monofunctional (meth)acrylamide polymerizable monomers such as trihydroxymethyl-N-methyl(meth)acrylamide and N,N-diethylacrylamide; 4-(meth)acryloylmorpholine, polyethylene glycol di(meth) ) acrylate (having 9 or more oxyethylene groups), N,N',N'',N'''-tetraacryloyltriethylenetetramine.

Examples of the hydrophobic polymerizable monomer include crosslinkable polymerizable monomers having a solubility in water at 25°C of less than 10% by mass, aromatic compound-based difunctional polymerizable monomers, aliphatic Examples include compound-based bifunctional polymerizable monomers, trifunctional or higher functional polymerizable monomers, and the like. The hydrophobic polymerizable monomer improves the handleability of the resulting dental curable composition, the mechanical strength after curing, and the like.

Examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-acryloyloxy-2-hydroxy) propoxy)phenyl]propane, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxy) ethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane2,2-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 , 2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2- (4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-( meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 1,4 -bis(2-(meth)acryloyloxyethyl)pyromellitate and the like. Among these, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane, 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of added moles of ethoxy group) 2.6) (hereinafter sometimes abbreviated as "D2.6E") is preferable.

Examples of aliphatic compound-based bifunctional polymerizable monomers include glycerol di(meth)acrylate, erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, and pentaerythritol di(meth)acrylate. meth)acrylate, dipentaerythritol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate ) acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA"), 1,2-bis( Examples include 3-methacryloyloxy-2-hydroxypropyloxy)ethane, N-methacryloxethyl acrylamide, and the like. Among these, glycerol di(meth)acrylate, triethylene glycol di(meth)acrylate, neopentyl glycol dimethacrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate and 1,2- Bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane is preferred.

Examples of trifunctional or higher polymerizable monomers 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) Examples include bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like.

The above polymerizable monomers without acidic groups (water-soluble polymerizable monomers and hydrophobic polymerizable monomers) may be used alone or in combination of two or more. It's okay.

When the dental curable composition of the present invention is used as a dental adhesive, the above-mentioned hydrophobic polymerizable monomer and water-soluble polymerizable monomer are used as the polymerizable monomer that does not have an acidic group. It is preferable to use them together. In that case, the content of the water-soluble polymerizable monomer is preferably in the range of 10 to 90 parts by mass, and 20 parts by mass, when the total amount of polymerizable monomer components in the dental curable composition is 100 parts by mass. The range of 70 parts by weight is more preferable, and the range of 30 to 60 parts by weight is even more preferable. Further, the content of the hydrophobic polymerizable monomer is preferably 9 to 60 parts by mass, and 15 parts by mass, when the total amount of polymerizable monomer components in the dental curable composition is 100 parts by mass. The amount is more preferably 55 parts by weight, and even more preferably 20 to 50 parts by weight.

Furthermore, when the dental curable composition of the present invention is used as a dental cement or a dental self-adhesive composite resin, the hydrophobic polymerizable monomers described above may be used as polymerizable monomers that do not have acidic groups. It is preferable to use a polymerizable monomer and a water-soluble polymerizable monomer together. In that case, the content of the water-soluble polymerizable monomer is preferably in the range of 1 to 50 parts by mass, when the total amount of polymerizable monomer components in the dental curable composition is 100 parts by mass. The range of 40 parts by weight is more preferable, and the range of 5 to 30 parts by weight is even more preferable. Further, the content of the hydrophobic polymerizable monomer is preferably 10 to 95 parts by mass, and preferably 30 to 90 parts by mass in 100 parts by mass of the total amount of polymerizable monomer components in the dental curable composition. The amount is more preferably 50 to 80 parts by mass, and even more preferably 50 to 80 parts by mass. Furthermore, the above-mentioned polymerizable monomers having no acidic groups are preferable for aromatic compound-based bifunctional monomers, from the viewpoint of handling properties, transparency, and mechanical strength after curing of the resulting dental curable composition. It is preferable to use a difunctional polymerizable monomer, a water-soluble polymerizable monomer, and/or an aliphatic compound-based bifunctional polymerizable monomer in combination. The ratio when they are used together is not particularly limited, but when the total amount of polymerizable monomer components in the dental curable composition is 100 parts by mass, the aromatic compound-based bifunctional polymerizable monomer The content is preferably 30 to 80 parts by weight, more preferably 40 to 75 parts by weight, and even more preferably 50 to 70 parts by weight. The content of the water-soluble polymerizable monomer is preferably 0 to 30 parts by weight, more preferably 2 to 25 parts by weight, and even more preferably 5 to 20 parts by weight. The content of the aliphatic compound-based bifunctional polymerizable monomer is preferably 5 to 65 parts by weight, more preferably 7 to 50 parts by weight, and preferably 10 to 35 parts by weight. More preferred.

When the dental curable composition of the present invention contains the filler (i), operability, X-ray opacity, mechanical strength after curing, adhesiveness, etc. can be improved. Examples of the filler (i) include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers. Filler (i) may be used alone or in combination of two or more.

Inorganic fillers include silica; silica-based minerals such as kaolin, clay, mica, and mica; silica-based minerals such as Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , BaO, La2O ₃ , SrO, ZnO, CaO, P ₂ O ₅ , Li ₂ O, Na ₂ O, etc., including ceramics and glasses. As the glasses, lanthanum glass, barium glass, strontium glass, soda glass, lithium borosilicate glass, zinc glass, fluoroaluminosilicate glass, borosilicate glass, and bioglass are preferably used. Crystalline quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride are also preferably used. It will be done. Further, from the viewpoint of adhesive strength and ease of handling, fine particle silica having a primary particle diameter of 0.001 to 0.1 μm is preferably used. Commercial products of the fine particle silica include "Aerosil (registered trademark) OX50", "Aerosil (registered trademark) 50", "Aerosil (registered trademark) 200", "Aerosil (registered trademark) 380", and "Aerosil (registered trademark)". ) R972" and "Aerosil (registered trademark) 130" (both trade names, manufactured by Nippon Aerosil Co., Ltd.).

Examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, polyfunctional methacrylate polymers, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.

Composite fillers of inorganic fillers and organic fillers include those in which inorganic fillers are dispersed in organic fillers, and organic/inorganic composite fillers in which inorganic fillers are coated with various polymers.

In order to improve curability, mechanical strength, and applicability, the filler (i) may be used after being previously surface-treated with a known surface treatment agent such as a silane coupling agent. Surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Examples include mercaptopropyltrimethoxysilane and γ-aminopropyltriethoxysilane.

When the dental curable composition of the present invention is used as a dental adhesive, among the above fillers (i), those having a primary particle size of 0.001 to 0.1 μm are preferred in terms of adhesive strength and applicability. Particulate silica is preferably used. When the dental curable composition of the present invention is used as a dental adhesive, the content of filler (i) is preferably in the range of 0 to 20% by mass based on the total mass of the dental curable composition, The range of 1 to 10% by mass is more preferable.

On the other hand, when the dental curable composition of the present invention is used as dental cement or dental self-adhesive composite resin, the above-mentioned filler ( The content of i) is preferably in the range of 10 to 90% by mass, based on the total mass of the dental curable composition. Regarding the lower limit, the content of filler (i) is more preferably 30% by mass or more, further preferably 40% by mass or more, most preferably 50% by mass or more, and the upper limit is more preferably 85% by mass or less.

The dental curable composition of the present invention contains the above-mentioned chemical polymerization type polymerization initiator component, but in order to make it a dual-cure type dental curable composition in which polymerization is initiated even by light irradiation, The dental curable composition of the present invention may further contain a conventionally known photopolymerization initiator as a component other than the above-mentioned polymerization initiator component. Conventionally known photopolymerization initiators include α-diketones, ketals, thioxanthones, acylphosphine oxides, and α-aminoacetophenones.

Specific examples of α-diketones include camphorquinone, benzyl, and 2,3-pentanedione.

Specific examples of ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

Specific examples of thioxanthone include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

Specific examples of acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, dibenzoylphenylphosphine oxide, bis(2,6-dimethoxy benzoyl)phenylphosphine oxide, tris(2,4-dimethylbenzoyl)phosphine oxide, tris(2-methoxybenzoyl)phosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2, 3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyl-bis(2,6-dimethylphenyl)phosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide and those disclosed in Japanese Patent Publication No. 3-57916 Examples include water-soluble acylphosphine oxide compounds.

Specific examples of α-aminoacetophenones include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)- 1-Butanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-propanone, 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)-1-propanone, 2-benzyl Examples thereof include -2-dimethylamino-1-(4-morpholinophenyl)-1-pentanone and 2-benzyl-2-diethylamino-1-(4-morpholinophenyl)-1-pentanone.

One type of photopolymerization initiator may be used alone, or two or more types may be used in combination. The content of the photopolymerization initiator is preferably in the range of 0.005 to 10 parts by mass, when the total amount of polymerizable monomer components in the dental curable composition is 100 parts by mass. Regarding the lower limit, the content of the photopolymerization initiator is more preferably 0.01 parts by mass or more, even more preferably 0.1 parts by mass or more, and the upper limit is more preferably 5 parts by mass or less.

Moreover, in order to improve photocurability, a photopolymerization initiator and a polymerization accelerator such as aldehydes, thiol compounds, and aminobenzoic acid ester compounds may be used in combination.

Specific examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, pn-octyloxybenzaldehyde, and the like.

Specific examples of thiol compounds include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid.

Specific examples of aminobenzoic acid ester compounds include ethyl 4-(N,N-dimethylamino)benzoate, methyl 4-(N,N-dimethylamino)benzoate, and 4-N,N-(dimethylamino)benzoate. n-butoxyethyl acid, 2-[(meth)acryloyloxy]ethyl 4-(N,N-dimethylamino)benzoate, 4-(N,N-dimethylamino)benzophenone, 4-(N,N-dimethylamino) ) n-butyl benzoate and the like.

Note that the above-mentioned amine-based reducing agent (g) also functions as a polymerization accelerator for the photopolymerization initiator.

One type of polymerization accelerator may be used alone, or two or more types may be used in combination. The content of the polymerization accelerator is preferably in the range of 0.01 to 10 parts by mass, and 0.1 to 5 parts by mass, when the total amount of polymerizable monomer components in the dental curable composition is 100 parts by mass. A range of 100% is more preferable.

The dental curable composition of the present invention may contain a silane coupling agent (j) for the purpose of obtaining good adhesive durability to ceramic materials without using a primer.

The silane coupling agent (j) may be used alone or in combination of two or more. As the silane coupling agent (j), vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(β-methoxyethoxy)silane, γ-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 5-(meth)acryloxypentyltrimethoxysilane, 6-(meth)acryloxyhexyltrimethoxy Silane, 7-(meth)acryloxyheptyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 9-(meth)acryloxynonyltrimethoxysilane, 10-(meth)acryloxydecyltrimethoxysilane, Examples include 8-(meth)acryloxyoctylmethyldimethoxysilane, 10-(meth)acryloxydecylmethyldimethoxysilane, 11-(meth)acryloxyundecylmethyldimethoxysilane, and (meth)acryloxymethylphenethyltrimethoxysilane. It will be done.

Among these silane coupling agents (j), 8-(meth)acryloxyoctyltrimethoxysilane and 9-(meth)acryloxy Nonyltrimethoxysilane, 10-(meth)acryloxydecyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, and (meth)acryloxymethylphenethyltrimethoxysilane are preferably used.

The content of the silane coupling agent (j) is preferably 0.1 to 10.0% by mass based on the total mass of the dental curable composition of the present invention, since it has excellent adhesive strength. More preferably 0.5 to 9.0% by weight, even more preferably 1.0 to 8.0% by weight, particularly preferably 1.2 to 7.0% by weight.

The dental curable composition of the present invention may further contain a fluoride ion-releasing substance for the purpose of imparting acid resistance to tooth structure. Examples of fluoride ion-releasing substances include fluoride ion-releasing polymers such as copolymers of methyl methacrylate and methacrylic acid fluoride, fluoride ion-releasing substances such as cetylamine hydrofluoride, and fluorine ion-releasing substances as described above as inorganic fillers. Examples include aluminosilicate glass, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride.

Further, the dental curable composition of the present invention may further contain additives such as a stabilizer (polymerization inhibitor), a colorant, a fluorescent agent, and an ultraviolet absorber. It may also contain antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxydodecylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydecyl ammonium chloride, and triclosan. good. Further, it may contain known dyes and pigments.

The dental curable composition of the present invention can be configured not only as a single-pack type, but also as a divided package type divided into two or more parts. From the viewpoint of storage stability and operability, the dental curable composition of the present invention is a two-component composition in which the first part and the second part consist of a liquid component and a paste component (a liquid component and a liquid component). It is preferable to use it as a two-paste type composition consisting of a paste component (including a filler) and a paste component.

When the dental curable composition of the present invention is constituted as a packaged dental curable composition containing a first part and a second part, the first part is an acidic group-containing polymerizable monomer. (a) and a copper compound (b), and the second agent preferably contains a benzazole compound (c) and an aromatic sulfinate (d). At this time, it is preferable that the first agent further contains an organic peroxide (e). At this time, when the organic peroxide (e) is a peroxyester, it is preferable because excellent storage stability and high adhesion to enamel and crown restorative materials can be obtained. In some embodiments, the polymerizable monomer that does not have an acidic group may be contained in both the first agent and the second agent, or may be contained in either one (e.g., the second agent). It's okay.

The mixing mass ratio of the first agent and the second agent is preferably 1:10 to 10:1 in terms of the curability of the resulting dental curable composition and the operating time.

As described above, when a benzazole compound (c) is contained in a dental curable composition containing an acidic group-containing polymerizable monomer (a) and a copper compound (b), the copper compound (b) Catalytic activity is significantly improved, and the reaction of copper compounds with hydrogen sulfide is suppressed. As a result, the dental curable composition obtained has excellent curability, little discoloration of the cured product due to hydrogen sulfide in the oral cavity environment, and excellent mechanical strength of the cured product. Since the catalytic activity of the copper compound (b) has been improved, the content of the copper compound (b) can be lower than before, and while obtaining good curability, it is possible to cure the product by hydrogen sulfide in the oral environment. It is also possible to obtain a dental curable composition with extremely small discoloration.

The reason why copper compound (b) and benzazole compound (c) coexist increases the catalytic activity of copper compound (b) and reduces its reactivity to hydrogen sulfide. This is because the benzazole compound (c) coordinates or interacts with Cu.

Therefore, from another aspect, another embodiment of the present invention includes a polymerizable monomer component and a polymerization initiator component, and the polymerizable monomer component is an acidic group-containing polymerizable monomer. Examples include dental curable compositions in which the polymerization initiator component contains a copper salt of a benzazole compound (c) represented by the above general formula [1].

The acidic group-containing polymerizable monomer (a), the benzazole compound that forms a salt with copper (c), and other optional components contained in the dental curable composition are the same as above. . Regarding other optional components, the dental curable composition contains at least one selected from the group consisting of an aromatic sulfinate (d), an organic peroxide (e), and a polymerizable monomer that does not contain an acidic group. It is preferable to contain one type of sulfinate, and it is particularly preferable to contain aromatic sulfinate (d).

The content of the copper salt of the benzazole compound (c) is preferably 0.00001 to 1 part by mass based on 100 parts by mass of the total amount of polymerizable monomer components in the dental curable composition. . Regarding the lower limit, it is more preferably 0.0001 parts by mass or more, even more preferably 0.00025 parts by mass or more, and particularly preferably 0.0005 parts by mass or more. Regarding the upper limit, it is more preferably 0.1 part by mass or less, and even more preferably 0.05 part by mass or less.

Further, another preferred embodiment of the present invention includes a polymerizable monomer component and a polymerization initiator system component, wherein the polymerizable monomer component is an acidic group-containing polymerizable monomer (a). , and a polymerizable monomer having no acidic group, wherein the polymerization initiator component is a copper compound (b), a benzazole compound (c) (a benzo compound represented by the above general formula [1-1]), and a polymerizable monomer having no acidic group. Triazole compound (c1) and/or benzimidazole compound (c2) represented by the above general formula [1-2]), aromatic sulfinate (d), inorganic peroxide (f), and amine reducing agent (g) (hereinafter also simply referred to as "suitable dental curable composition"). The preferred dental curable composition not only has excellent curability and the effect of suppressing discoloration of the cured product due to hydrogen sulfide produced by cariogenic bacteria, but also has particularly excellent adhesion to dentin and enamel, and The cured product has particularly excellent mechanical strength. The preferred dental curable compositions are particularly suitable for dental cements.

Even in the preferred dental curable composition, if the product form (particularly dental cement) is made into a single-component type, the amine reducing agent (g) will be converted into the inorganic peroxide (f) during storage. It may react with and decompose. Further, the aromatic sulfinate (d) may react with the copper compound (b) and decompose. Therefore, in this case, the amount of generated radicals decreases. Therefore, the product form using the suitable dental curable composition is preferably a two-dose type containing a first part and a second part. The suitable dental curable composition also has a good operating time when made into a sachet type.

In the preferred dental curable composition, the content ratio (molar ratio) of the copper compound (b) and the aromatic sulfinate (d) is 0.000003:1 to 0.01:1. The ratio is preferably 0.00003:1 to 0.005:1, and more preferably 0.00003:1 to 0.005:1. When the molar ratio of the copper compound (b) and the aromatic sulfinate (d) is within this range, excellent mechanical strength can be obtained while maintaining a practically preferable operating margin time.

In the preferred dental curable composition, the content of the copper compound (b) is preferably 0.000001 to 0.01% by mass based on the total amount of polymerization initiator components. In the present invention, the polymerization initiator component refers to components (b) to (h), including optional components.

When the suitable dental curable composition is divided into a first part and a second part, for example, the first part contains the inorganic peroxide (f), and the second part contains the amine reducing agent. In a form containing (g), the inorganic peroxide (f) and the amine reducing agent (g) are contained in different agents. The acidic group-containing polymerizable monomer (a) and the polymerizable monomer that does not have an acidic group may be contained in either or both of the first part and the second part, but the storage stability From this point of view, it is preferable that the acidic group-containing polymerizable monomer (a) and the aromatic sulfinate (d) are contained in different agents. Because it is easy to handle, one agent (especially the first agent) contains an acidic group-containing polymerizable monomer (a) (and optionally a polymerizable monomer that does not have an acidic group), It is preferable that the other agent contains a polymerizable monomer having no acidic group. The benzazole compound (c) may be contained in either or both of the first agent and the second agent, but from the viewpoint of storage stability, it may be contained in a different agent from the aromatic sulfinate (d). It is preferable to do so. From the viewpoint of storage stability, the copper compound (b) is preferably contained in a different agent from the aromatic sulfinate (d). In a preferred embodiment, the first agent contains an acidic group-containing polymerizable monomer (a), a copper compound (b), a benzazole compound (c), and an inorganic peroxide (f); An example is a form in which the two agents contain a polymerizable monomer having no acidic group, an amine reducing agent (g), and an aromatic sulfinate (d). At this time, when the dental curable composition contains a sulfur-containing reducing inorganic compound (h), the sulfur-containing reducing inorganic compound (h) may be contained in the second agent. preferable. Moreover, when the dental curable composition contains an organic peroxide (e), the organic peroxide (e) is preferably contained in the first agent.

The mixing mass ratio of the first agent and the second agent is preferably 1:10 to 5:1 in terms of the curability of the resulting dental curable composition and the operating time.

When the product is a dental cement, from the viewpoint of mechanical strength of the cured product, it is preferable that the first part and/or the second part contain filler (i).

The above-mentioned preferred dental curable composition can exhibit high adhesive strength by utilizing only the moisture contained in the tooth substance, even if it does not contain water. Moreover, when the above-mentioned suitable dental curable composition contains water, there is a possibility that the storage stability of the composition is reduced. For this reason, it is preferred that the preferred dental curable compositions described above contain substantially no water. Containing substantially no water means that water is not actively added to each component of the dental curable composition other than the water originally contained in each component, and the water content includes, for example, 1% by weight or less, based on the total weight of the dental curable composition.

The dental curable composition of the present invention can be used as dental cement, dental adhesive, self-adhesive dental composite resin, etc., by applying the composition alone to the adhesive surface, or by applying a primer to the adhesive surface. It is also possible to apply the dental curable composition of the present invention after applying another composition such as .

A specific example of how to use the dental curable composition of the present invention will be explained using a two-dose product as an example. Immediately before use, the first agent and the second agent are mixed to form one agent (dental curable composition of the present invention), which is then applied to the tooth structure. As the mixed dental curable composition permeates into the tooth structure, the curing reaction also progresses inside the moist body near the interface between the tooth structure and the dental curable composition. When the curing reaction is completed, the dental curable composition of the present invention and tooth substance are bonded together. The following is a detailed explanation of the application to teeth as an example. That is, when filling and restoring a tooth cavity, the tooth cavity is cleaned by a conventional method, and then the dental curable composition of the present invention as a single agent is filled into the tooth cavity. When bonding a prosthesis such as a crown or inlay, after cleaning the attachment surface of the abutment tooth or tooth cavity and the attachment surface of the prosthesis, apply the dental curable composition of the present invention as a single agent. is applied to at least one of the tooth cavity, the abutment surface of the abutment tooth, or the prosthesis surface and bonded. Before applying the dental curable composition of the present invention to the tooth surface, the tooth surface is subjected to conventionally known etching treatments such as etching treatment with an acidic aqueous solution, modification treatment with a primer, and simultaneous etching and modification treatment with a primer having etching ability. Pretreatment may be performed.

The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The abbreviations used below are as follows.

[Acidic group-containing polymerizable monomer (a)]
MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[Copper compound (b)]
CA: Copper(II) acetate

[Benzotriazole compound other than benzazole compound (c)]
BTA: 1H-benzotriazole [benzazole compound (c)]
BT-250: 2-(1H-benzotriazol-1-ylmethyl)butanedioic acid BT-M: 2-(1H-benzotriazol-1-yl)butanedioic acid

[Aromatic sulfinate (d)]
TPBSS: Sodium 2,4,6-triisopropylbenzenesulfinate

[Organic peroxide (e)]
<Peroxyester>
BPB: t-butyl peroxybenzoate

[Inorganic peroxide (f)]
KPS: Potassium peroxodisulfate: The average particle size was adjusted to 2.5 μm by grinding with a jet mill. In addition, in this example, the average particle diameter was calculated as the volume average particle diameter after performing image analysis using image analysis software (Mac-View; manufactured by Mountec Co., Ltd.) based on electron micrographs of 100 or more particles. Calculated.

[Amine reducing agent (g)]
DEPT: N,N-di(2-hydroxyethyl)-p-toluidine

[Reducing inorganic compound containing sulfur (h)]
Sodium sulfite: The average particle size was adjusted to 6.1 μm by pulverizing with a vibrating ball mill.

[Polymerizable monomer that does not contain acidic groups]
<Hydrophobic polymerizable monomer>
Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane D2.6E: 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average of ethoxy groups) Number of moles added: 2.6)
NPG: Neopentyl glycol dimethacrylate

<Water-soluble polymerizable monomer>
HEMA: 2-hydroxyethyl methacrylate

[Photopolymerization initiator]
CQ: Camphorquinone PDE: N,N-dimethylaminobenzoic acid ethyl ester (polymerization accelerator for photopolymerization initiator)

[Polymerization inhibitor]
BHT: 2,6-di-t-butyl-4-methylphenol

[Silane coupling agent (j)]
11-MUS: 11-methacryloyloxyundecyltrimethoxysilane

[Filler (i)]
i-1 (R972): Silica (manufactured by Nippon Aerosil Co., Ltd., product name "Aerosil (registered trademark) R972")
i-2: Silanized barium glass powder i-3: Silanized quartz powder i-4 (alumina): Manufactured by Nippon Aerosil Co., Ltd., product name "AEROXIDE (registered trademark) Alu C"

Silanized quartz powder (i-3) and silanized barium glass powder (i-2) are obtained according to the following manufacturing method.

Silanized barium glass powder (i-2):
Barium glass (manufactured by Estech, trade name: "V-117-1190 E-3000 BariumSilicate Glass") was ground in a ball mill to obtain barium glass powder with an average particle size of about 2.4 μm. 100 parts by mass of this barium glass powder was surface-treated with 3 parts by mass of 3-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain silane-treated barium glass powder.

Silanized quartz powder (i-3):
Quartz (manufactured by MARUWA QUARTZ Co., Ltd.) was ground with a ball mill to obtain quartz powder with an average particle size of about 4.5 μm. 100 parts by mass of this quartz powder was surface-treated with 3 parts by mass of 3-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain a silanized quartz powder.

(Examples 1-2)
Prepare a first part and a second part whose compositions are shown in Table 1 (each value in the table is in parts by mass), and add the dental curable composition to the two parts so that the mass ratio of these two parts is 1:1. It was divided into packages. The first agent was prepared by mixing the components other than the filler, stirring to obtain a uniform solution, and then kneading the powdered components and defoaming. In addition, the second agent was prepared by mixing components other than TPBSS and the filler, stirring to obtain a uniform solution, and then kneading and defoaming the TPBSS and filler. These packaged dental curable compositions were examined for operating time and bending strength of the cured product by the method shown below. The results are shown in Table 1.

(Examples 3 to 6 )
Prepare a first part and a second part whose compositions are shown in Table 1 (each value in the table is in parts by mass), and add the dental curable composition to the two parts so that the mass ratio of these two parts is 1:1. It was divided into packages. The first agent was prepared by mixing the components other than the powder components (filler and KPS), stirring to obtain a uniform solution, and then kneading the powder components and defoaming. In addition, the second agent was prepared by mixing components other than TPBSS, sodium sulfite, and filler, stirring to obtain a uniform solution, and then kneading TPBSS and filler and defoaming. These packaged dental curable compositions were examined for operating time and bending strength of the cured product by the method shown below. The results are shown in Table 1.

(Comparative Examples 1-2)
A first part and a second part whose compositions are shown in Table 1 were prepared, and the dental curable composition was divided into two parts so that the mass ratio of these two parts was 1:1. The first agent was prepared by mixing the components other than the filler, stirring to obtain a uniform solution, and then kneading the powdered components and defoaming. In addition, the second agent was prepared by mixing components other than TPBSS and the filler, stirring to obtain a uniform solution, and then kneading and defoaming the TPBSS and filler. Regarding these dental curable compositions, the operating time and bending strength of the cured products were examined in the same manner as in Examples 1 to 6. The results are shown in Table 1.

(Comparative Examples 3 to 4 )
A first part and a second part whose compositions are shown in Table 1 were prepared, and the dental curable composition was divided into two parts so that the mass ratio of these two parts was 1:1. The first agent was prepared by mixing the components other than the powder components (filler and KPS), stirring to obtain a uniform solution, and then kneading the powder components and defoaming. In addition, the second agent was prepared by mixing components other than TPBSS, sodium sulfite, and filler, stirring to obtain a uniform solution, and then kneading TPBSS and filler and defoaming. Regarding these dental curable compositions, the operating time and bending strength of the cured products were examined in the same manner as in Examples 1 to 6. The results are shown in Table 1.

[Operating margin time]
In each Example and Comparative Example, the first agent and the second agent were mixed at a mass ratio of 1:1 in a constant temperature room at 25° C., and mixed well with a spatula to form one agent. The time from the time of mixing until the time when the temperature begins to rise due to the start of hardening of the paste (operation margin time) was measured with a thermocouple (manufactured by Okazaki Seisakusho Co., Ltd.) connected to a recorder (manufactured by Yokogawa Electric Corporation) ( N=5). Table 1 shows the average values of the measured values. Note that when the dental curable composition is used clinically, taking into account the influence of the procedure during use, the longer the operating margin time is, the more preferable it is, and specifically, it is required to be 4 to 8 minutes.

[Bending strength of cured product]
Regarding the dental curable compositions of each Example and Comparative Example, the bending strength was measured according to the following procedure as an index of the mechanical strength of the cured product. A polyester film was laid on a slide glass plate, and a stainless steel molding frame measuring 2 mm in length x 25 mm in width x 2 mm in depth was placed thereon. Next, a dental curable composition obtained by kneading the first part and the second part at a mass ratio of 1:1 is filled into a mold, and the surface of the dental curable composition in the mold is covered with a polyester film. The two glass slides were fixed using a double clip with a width of 25 mm. After the sample fixed with the double clip was allowed to stand still in a 37° C. thermostat for 1 hour to polymerize and harden, the sample was taken out of the thermostat, and the polymerized and cured composition of the composition was removed from the mold. After the polymerized cured product was immersed in distilled water at 37° C. for 24 hours and stored, a bending test was conducted using this as a test piece. The bending strength was measured by performing a three-point bending test using a universal testing machine (Autograph AG-I 100 kN, manufactured by Shimadzu Corporation) at a span (distance between fulcrums) of 20 mm and a crosshead speed of 1 mm/min. The average value of the bending strengths of the five test pieces was taken as the bending strength of that test piece. It is preferable that the bending strength is 100 MPa or more.

As shown in Table 1, the dental curable compositions of Examples 1 to 6 have excellent mechanical strength, with a bending strength of 100 MPa or more even though the operating time exceeds 4 minutes. It showed the strength of the objective. On the other hand, the dental curable compositions of Comparative Examples 1 to 3 had excellent mechanical strength of the cured products, but had a short operating time of less than 4 minutes. In addition, although the dental curable composition of Comparative Example 4 had an operation margin of 4 minutes or more, the bending strength of the cured product was less than 100 MPa, and the mechanical strength was low.

The dental curable composition of the present invention can be suitably used as dental cement, dental adhesive, dental composite resin (preferably self-adhesive dental composite resin), and the like.

Claims (25)

Contains a polymerizable monomer component and a polymerization initiator component,
The polymerizable monomer component includes an acidic group-containing polymerizable monomer (a),
A benzotriazole compound in which the polymerization initiator component includes a copper compound (b) and a benzazole compound (c) represented by the following general formula [1], and the nitrogen atom at the 1st position is unsubstituted; and a dental curable composition that does not contain a benzimidazole compound in which the nitrogen atom at position 1 is unsubstituted .

(In the formula, R ¹ to R ⁴ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. represents an optionally substituted alkoxy group, optionally substituted alkenyl group, optionally substituted aralkyl group, or halogen atom, X represents a nitrogen atom or -CH, and Y represents a substituted Alkyl group that may have a group, aryl group that may have a substituent, alkenyl group that may have a substituent, aralkyl group that may have a substituent, or halogen atom ) The benzazole compound (c) is a benzotriazole compound (c1) represented by the following general formula [1-1] and/or a benzimidazole compound (c2) represented by the following general formula [1-2]. The dental curable composition according to claim 1, comprising:

(In the formula, R ⁵ to R ¹² each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent) represents an alkoxy group which may have a substituent, an alkenyl group which may have a substituent, an aralkyl group which may have a substituent, or a halogen atom, and Y ¹ and Y ² each independently represent a substituent. Represents an alkyl group that may have an optional substituent, an aryl group that may have a substituent, an alkenyl group that may have an optional substituent, an aralkyl group that may have an optional substituent, or a halogen atom .) Y ¹ and Y ² of the benzotriazole compound (c1) and/or benzimidazole compound (c2) are each independently an alkyl group that may have a substituent, or an aryl group that may have a substituent. 3. The dental curable composition according to claim 2, wherein the dental curable composition is an alkenyl group that may have a substituent, or an aralkyl group that may have a substituent, and the substituent is an electron-withdrawing group. thing. 4. The dental implant according to claim 3, wherein the electron-withdrawing group is at least one selected from the group consisting of an acetyl group, an ester group, an ether group, a carboxyl group, a cyano group, a sulfonic acid group, a sulfonyl group, and a phosphate group. curable composition for use. The dental curable composition according to claim 4, wherein the electron-withdrawing group is a carboxyl group. Claim 1, wherein the benzazole compound (c) is 2-(1H-benzotriazol-1-yl)butanedioic acid and/or 2-(1H-benzotriazol-1-ylmethyl)butanedioic acid. 5. The dental curable composition according to any one of items 5 to 5. According to any one of claims 1 to 6, the content of the copper compound (b) is 0.00001 to 0.005 parts by mass based on 100 parts by mass of the total amount of the polymerizable monomer components. dental curable composition. The dental curable composition according to any one of claims 1 to 7, further comprising an aromatic sulfinate (d). The dental curable composition according to any one of claims 1 to 8, further comprising a polymerizable monomer containing no acidic group. It is divided into a first agent and a second agent,
The first agent contains the acidic group-containing polymerizable monomer (a) and the copper compound (b),
The dental curable composition according to claim 8 or 9, wherein the second agent contains the benzazole compound (c) and the aromatic sulfinate (d). The dental curable composition according to claim 10, further comprising an organic peroxide (e) in the first agent. The dental curable composition according to claim 11, wherein the organic peroxide (e) is a peroxyester. The polymerizable monomer component includes the acidic group-containing polymerizable monomer (a) and a polymerizable monomer that does not have an acidic group,
The polymerization initiator components include the copper compound (b), the benzazole compound (c), an aromatic sulfinate (d), an inorganic peroxide (f), and an amine reducing agent (g). including;
According to any one of claims 1 to 7, the content of the copper compound (b) is 0.00001 to 0.005 parts by mass based on 100 parts by mass of the total amount of the polymerizable monomer components. Dental curable composition. It is divided into a first agent and a second agent,
The first agent contains the acidic group-containing polymerizable monomer (a), the copper compound (b), the benzazole compound (c), and the inorganic peroxide (f),
The dental curable material according to claim 13, wherein the second agent contains the polymerizable monomer having no acidic group, the aromatic sulfinate (d), and the amine reducing agent (g). Composition. The dental curable composition according to claim 13, wherein the polymerization initiator component further includes a reducing inorganic compound (h) containing sulfur as a second agent. The dental curable composition according to claim 14 or 15, wherein the polymerization initiator component further contains an organic peroxide (e) as a first agent. The dental curable composition according to claim 16, wherein the organic peroxide (e) is a peroxyester. The dental curable composition according to any one of claims 13 to 17, wherein the inorganic peroxide (f) is in powder form with an average particle size of 0.01 to 50 μm. According to any one of claims 13 to 18, the content of the acidic group-containing polymerizable monomer (a) is 1 to 50 parts by mass in 100 parts by mass of the total amount of polymerizable monomer components. dental curable composition. The content of the inorganic peroxide (f) is 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of polymerizable monomer components, according to any one of claims 13 to 19. Dental curable composition. The content of the amine reducing agent (g) is 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of polymerizable monomer components, according to any one of claims 13 to 20. Dental curable composition. According to any one of claims 13 to 21, the content of the aromatic sulfinate (d) is 0.1 to 20 parts by mass based on 100 parts by mass of the total amount of polymerizable monomer components. dental curable composition. The dental treatment according to any one of claims 13 to 22, wherein the molar ratio of the copper compound (b) and the aromatic sulfinate (d) is 0.000003:1 to 0.01:1. curable composition for use. Dental use according to any one of claims 13 to 23, wherein the molar ratio of the benzazole compound (c) and the copper compound (b) is 1:0.00001 to 1:0.01. Curable composition. The dental curable composition according to any one of claims 13 to 24, wherein the content of the copper compound (b) is 0.000001 to 1% by mass based on the total amount of polymerization initiator components.