JP2022187437A - Two paste type dental curable composition - Google Patents

Abstract

To provide a two paste type dental curable composition which is excellent in dentin adhesive properties, handling properties in paste collecting, and fluidity after blending and mixing, and has less variation in characteristics of a cured object which are evaluated by dentin adhesive properties and the like.SOLUTION: There is provided a two paste dental curable composition which is formed of: a first paste including, a polymerizable monomer (a) having an acidic group, a polymerizable monomer (b) having no acidic group, and a filler (c); and a second paste including, a polymerizable monomer (d) having no acidic group, an isocyanurate compound (e) expressed by a general formula (1) and a filler (f), in which one of these pastes includes a chemical polymerization initiator (g), and the other of these pastes includes, a chemical polymerization promoter (h). (R1-R3 are an organic group respectively and independently, and may have a substituent group, and at least one of the R1-R3 is a hydrocarbon group whose carbon number is 3 or less, and a total carbon number of the R1-R3 is 15 or less.)SELECTED DRAWING: None

Description

The present invention relates to a two-paste dental hardenable composition.

A resin-based dental curable composition comprising a polymerizable monomer, a polymerization initiator, and the like is widely used for restorative treatment of teeth, which is one of living hard tissues.

The polymerization initiator contained in the dental curable composition is a packaging form in which a photopolymerization initiator that polymerizes and cures mainly by irradiation with visible light, a chemical polymerization initiator, and a chemical polymerization accelerator are packaged separately. It is broadly divided into chemical polymerization initiator systems that are mixed and polymerized and cured just before use. Recently, a product called a dual cure type containing both initiators has also been widely used in clinical dentistry. In addition, among dental curable compositions containing a chemical polymerization initiator system, a two-paste type dental curable composition, in which both of the two components are pastes, is generally used because of its excellent ease of operation. there is

Applications of the two-paste type dental curable composition include, for example, dental cements for fixing metal or ceramic crown restorative materials called inlays and crowns to teeth. Among these dental cements, two-paste type dental cements containing a polymerizable monomer having an acidic group such as a phosphate group or a carboxyl group have recently been used to impart self-adhesiveness to tooth substance and prostheses. However, it is widely used due to the simplicity of the operation that pretreatment such as primer is not required.

Compounds having an isocyanurate skeleton are known as constituents of dental curable compositions, and are used as cross-linking agents or the like depending on the properties resulting from their structures.

For example, Patent Document 1 discloses a two-paste type dental curable composition having clinically acceptable adhesion durability to a dental adherend such as a dental glass-ceramic restoration without using a primer. Although disclosed, a specific compound having an isocyanurate skeleton is described as one of its crosslinker components. Patent Document 2 discloses a composition of a polymerizable dental material, and describes a specific compound having an isocyanurate skeleton as one of its reactive paste-forming agents.

WO2019/004391 Japanese Patent Publication No. 2013-538837

As a required property of a two-paste type dental cement having self-adhesive properties, it is a matter of course that it has excellent adhesion to adherends such as tooth substance and prostheses, and in addition, it has excellent handling properties. is also important. That is, a two-paste type curable dental composition such as a dental cement is generally prepared by collecting two pastes on kneading paper in an appropriate ratio, and then mixing and kneading them by hand using a spatula or the like. However, when the desired amount of each paste is accurately collected from a container such as a syringe, the paste has a relatively low fluidity. be done. In addition, in order to mix and knead the paste more easily, an auto-mix type that automatically mixes the two agents by attaching a mixing tip to the tip of the syringe is also widely used recently, but it provides a uniform paste after mixing. In order to do so, it is required that the paste viscosities of the two agents are approximately the same, and that the paste properties have appropriate fluidity for easy mixing.

However, as a result of investigation by the present inventors, the two-paste type dental curable composition of Patent Document 1 is excellent in handleability when extracting the paste, and is excellent in prosthetics such as lithium disilicate glass. Although it has self-adhesiveness, it has been found that there is room for further improvement in terms of adhesiveness to tooth substance (hereinafter also referred to as "tooth substance adhesiveness").

In addition, the dental material of Patent Document 2 has been examined by the present inventors, and the first paste containing triallyl isocyanurate and a reactive paste-forming agent having an acidic group has a problem in handleability when collecting the paste. It turns out there is. Furthermore, since two pastes with different paste properties are mixed and kneaded, the paste after mixing and kneading is uneven, resulting in variations in the properties of the cured product, including the adhesiveness to the tooth substance. I found out.

Therefore, the present invention provides a 2-paste type, which is excellent in adhesiveness to tooth substance, handling property when extracting the paste, and fluidity after mixing and kneading, and which has little variation in properties of the cured product evaluated in terms of adhesiveness to tooth substance and the like. An object of the present invention is to provide a dental curable composition.

The present inventors have made intensive studies to solve the above problems, and as a result, have found a two-paste type dental curable composition in which a polymerizable monomer having an acidic group and an isocyanurate compound having a specific structure are separately packaged. The present inventors have found that the above problems can be solved by using , and have completed the present invention through further studies based on the findings.

（式中、Ｒ¹～Ｒ³はそれぞれ独立して置換基を有していてもよい有機基であり、Ｒ¹～Ｒ³の少なくとも一つが、炭素数３以下の炭化水素基であり、かつＲ¹～Ｒ³の合計の炭素数が１５以下である。）
［２］第２ペーストの粘度（３０℃）が１０００～３５０００ｍＰａ・ｓである、［１］に記載の２ペースト型歯科用硬化性組成物。
［３］第１ペースト及び第２ペーストの粘度（３０℃）がいずれも１０００～３５０００ｍＰａ・ｓである、［１］又は［２］に記載の２ペースト型歯科用硬化性組成物。
［４］第１ペーストと第２ペーストの粘度（３０℃）の比（第１ペーストの粘度／第２ペーストの粘度）が０．８～１．２である、［１］～［３］のいずれかに記載の２ペースト型歯科用硬化性組成物。
［５］前記イソシアヌレート化合物（ｅ）の含有量が、２ペースト型歯科用硬化性組成物の総量１００質量部において、０．５～７．０質量部である、［１］～［４］のいずれかに記載の２ペースト型歯科用硬化性組成物。
［６］Ｒ¹～Ｒ³がいずれも炭素数３以下の直鎖状炭化水素基である、［１］～［５］のいずれかに記載の２ペースト型歯科用硬化性組成物。
［７］さらに第１ペーストと第２ペーストの少なくとも一方に光重合開始剤（ｉ）を含む、［１］～［６］のいずれかに記載の２ペースト型歯科用硬化性組成物。
［８］前記イソシアヌレート化合物（ｅ）が、トリアリルイソシアヌレートである、［１］～［７］のいずれかに記載の２ペースト型歯科用硬化性組成物。
［９］［１］～［８］のいずれかに記載の２ペースト型歯科用硬化性組成物からなる、歯科用セメント。 That is, the present invention includes the following.
[1] A first paste containing a polymerizable monomer (a) having an acidic group, a polymerizable monomer (b) having no acidic group, and a filler (c);
Consists of a second paste containing a polymerizable monomer (d) having no acidic group, an isocyanurate compound (e) represented by the following general formula (1), and a filler (f),
A two-paste dental curable composition, wherein one paste contains a chemical polymerization initiator (g) and the other paste contains a chemical polymerization accelerator (h).

(wherein R ¹ to R ³ are each independently an optionally substituted organic group, at least one of R ¹ to R ³ is a hydrocarbon group having 3 or less carbon atoms, and The total carbon number of R ¹ to R ³ is 15 or less.)
[2] The two-paste type dental curable composition according to [1], wherein the second paste has a viscosity (30°C) of 1000 to 35000 mPa·s.
[3] The two-paste type dental curable composition according to [1] or [2], wherein the viscosity (30° C.) of the first paste and the second paste is 1000 to 35000 mPa·s.
[4] The ratio of the viscosities (30 ° C.) of the first paste and the second paste (viscosity of the first paste/viscosity of the second paste) of [1] to [3] is 0.8 to 1.2 A two-paste dental curable composition according to any one of the above.
[5] The content of the isocyanurate compound (e) is 0.5 to 7.0 parts by mass with respect to the total amount of 100 parts by mass of the two-paste type dental curable composition [1] to [4] 2. A two-paste type dental curable composition according to any one of .
[6] The two-paste type curable dental composition according to any one of [1] to [5], wherein R ¹ to R ³ are all linear hydrocarbon groups having 3 or less carbon atoms.
[7] The two-paste dental curable composition according to any one of [1] to [6], wherein at least one of the first paste and the second paste further contains a photopolymerization initiator (i).
[8] The two-paste type dental curable composition according to any one of [1] to [7], wherein the isocyanurate compound (e) is triallyl isocyanurate.
[9] A dental cement comprising the two-paste type dental curable composition according to any one of [1] to [8].

According to the present invention, a 2-paste that is excellent in adhesiveness to tooth substance, handling property when extracting the paste, fluidity after mixing and kneading, and little variation in properties of the cured product evaluated in terms of adhesiveness to tooth substance and the like. A mold dental curable composition can be provided.

The two-paste type dental curable composition of the present invention comprises a first polymerizable monomer (a) having an acidic group, a polymerizable monomer (b) having no acidic group, and a filler (c). a second paste comprising a paste, a polymerizable monomer (d) having no acidic group, an isocyanurate compound (e) represented by the following general formula (1), and a filler (f); One paste contains a chemical polymerization initiator (g), and the other paste contains a chemical polymerization accelerator (h).

（式中、Ｒ¹～Ｒ³はそれぞれ独立して置換基を有していてもよい有機基であり、Ｒ¹～Ｒ³の少なくとも一つが、炭素数３以下の炭化水素基であり、かつＲ¹～Ｒ³の合計の炭素数が１５以下である。）

(wherein R ¹ to R ³ are each independently an optionally substituted organic group, at least one of R ¹ to R ³ is a hydrocarbon group having 3 or less carbon atoms, and The total carbon number of R ¹ to R ³ is 15 or less.)

The reason why the two-paste type dental curable composition of the present invention is excellent in adhesiveness to tooth substance and handling property when extracting the paste, and that there is little variation in properties of the cured product evaluated in terms of adhesiveness to tooth substance, etc. Although not necessarily certain, the present inventors presume as follows. The conventional two-paste type curable dental composition does not have high fluidity of the paste at the time of collecting the paste, mixing and kneading the paste, and applying the paste to the prosthesis. On the other hand, the two-paste type dental curable composition of the present invention does not have high paste fluidity when the paste is collected, but has high paste fluidity when the paste is mixed and kneaded, making it a moderate paste that is easy to mix and knead. properties. In this way, if the paste has high fluidity, it can be mixed and kneaded uniformly, so there is little variation in the properties of the cured product. doing. In addition, the mechanism of exhibiting high fluidity after mixing and kneading with the configuration of the present invention is presumed as follows. That is, by mixing and kneading a first paste containing a polymerizable monomer (a) having an acidic group and a second paste containing a specific isocyanurate compound (e), H ⁺ is added to the isocyanurate skeleton. coordinates. It is thought that the positively charged isocyanurate compound adsorbs to the surface of the filler, causing repulsion between the fillers, which weakens the ionic interaction, resulting in a paste with moderate fluidity.

The first paste of the two-paste type curable dental composition of the present invention contains a polymerizable monomer (a) having an acidic group. By blending the polymerizable monomer (a) having an acidic group, it is possible to impart excellent adhesiveness to tooth substance and other dental prosthetic materials.

The polymerizable monomer (a) having an acidic group 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, and a carboxylic acid group, and Polymerizable monomers having at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group, and a styrene group can be mentioned. The polymerizable monomer (a) having an acidic group has an affinity for adherends and a demineralizing effect on tooth substance. Specific examples of the polymerizable monomer (a) having an acidic group are given below. In the present specification, "(meth)acrylic" means acrylic and methacrylic, and "(meth)acryloyl" means acryloyl and methacryloyl.

Polymerizable monomers having a phosphoric acid group include, for example, 2-(meth)acryloyloxyethyl dihydrogenphosphate, 3-(meth)acryloyloxypropyl dihydrogenphosphate, 4-(meth)acryloyloxybutyldihydrogenphosphate, hydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth) acryloyloxyhexyl dihydrogen phosphate, 7-(meth) acryloyloxyheptyl dihydrogen phosphate, 8-(meth) acryloyloxy Octyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-acryloyloxydecyl dihydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate (hereinafter sometimes abbreviated as "MDP") ), 11-(meth)acryloyloxy undecyl dihydrogen phosphate, 12-(meth) acryloyl oxidodecyl dihydrogen phosphate, 16-(meth) acryloyloxy hexadecyl dihydrogen phosphate, 20-(meth) acryloyloxy Eicosyl dihydrogen phosphate, bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogenphosphate, bis[10-(meth)acryloyloxydecyl]hydrogenphosphate, 1,3 - Di(meth) acryloyloxypropyl dihydrogen phosphate, 2-(meth) acryloyloxyethylphenyl hydrogen phosphate, 2-(meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth) acryloyloxy-(1-hydroxymethyl)ethyl]hydrogen phosphates and their acid chlorides, alkali metal salts and ammonium salts;

Examples of the polymerizable monomer having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-( meth)acryloyloxyhexyl], bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, and acid chlorides, alkali metal salts, and ammonium salts thereof. be done.

Examples of polymerizable monomers having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, 4-(meth)acryloyloxy butyl dihydrogenthiophosphate, 5-(meth)acryloyloxypentyl dihydrogenthiophosphate, 6-(meth)acryloyloxyhexyl dihydrogenthiophosphate, 7-(meth)acryloyloxyheptyl dihydrogenthiophosphate, 8 -(meth)acryloyloxyoctyl dihydrogenthiophosphate, 9-(meth)acryloyloxynonyl dihydrogenthiophosphate, 10-(meth)acryloyloxydecyl dihydrogenthiophosphate, 11-(meth)acryloyloxyundecyl dihydrogenthiophosphate, 12-(meth)acryloyl oxide decyl dihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogenthiophosphate, 20-(meth)acryloyloxyeicosyl dihydrogenthiophosphate and These acid chlorides, alkali metal salts, ammonium salts and the like are included.

Polymerizable monomers having a phosphonic acid group include, for example, 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxy Hexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexylphosphonoacetate, 10-(meth)acryloyloxydecylphosphonoacetate and acid chlorides, alkali metal salts and ammonium salts thereof.

Polymerizable monomers having a sulfonic acid group include, for example, 2-(meth)acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl (meth)acrylate.

Polymerizable monomers having a carboxylic acid group include polymerizable monomers having one carboxy group in the molecule and polymerizable monomers having a plurality of carboxy groups in the molecule.

Polymerizable monomers having one carboxy group in the molecule include, for example, (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2- (Meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-amino salicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogenmalate and acid halides thereof;

Examples of polymerizable monomers having multiple carboxy groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid and 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid. , 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 13 -(meth)acryloyloxytridecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxyethyl trimellitate anhydride, 4-(meth)acryloyloxybutyl Trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3′-(meth)acryloyloxy-2′-( 3,4-dicarboxybenzoyloxy)propyl succinate and their acid anhydrides or acid halides.

The above polymerizable monomer (a) having an acidic group may be used alone or in combination of two or more. Among these acidic group-containing polymerizable monomers (a), the phosphoric acid group-containing polymerizable monomers and the carboxylic acid group-containing polymerizable monomers have high adhesive strength to dental adherends. One or more selected from the group consisting of a monomer and a polymerizable monomer having a sulfonic acid group is preferable, and a polymerizable monomer having a phosphoric acid group having two or more hydroxyl groups bonded to a phosphorus atom, intramolecular more preferably one or more selected from the group consisting of polymerizable monomers having a plurality of carboxyl groups in and polymerizable monomers having a sulfonic acid group, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogenphosphate, 2-(meth)acryloyloxyethyl dihydrogenphosphate, 4-(meth)acryloyloxyethyl trimellitate anhydride, 4-(meth)acryloyloxy More preferably, one or more selected from the group consisting of ethyl trimellitate, 2-(meth)acrylamido-2-methylpropanesulfonic acid and 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid.

The content of the polymerizable monomer (a) having an acidic group is 1 to 50 parts by mass with respect to 100 parts by mass as the total amount of polymerizable monomer components in the two-paste type dental curable composition of the present invention. preferably 2 to 30 parts by mass, even more preferably 2 to 15 parts by mass. When the content of the polymerizable monomer having an acidic group is 1 part by mass or more, it is easy to obtain excellent adhesiveness to various dental adherends. When the content of (a) is 50 parts by mass or less, it is easy to maintain a balance between polymerizability and adhesion. In particular, by using 2 to 15 parts by mass, a paste having more appropriate fluidity after being mixed and kneaded with the second paste can be obtained. In the present invention, the total amount of polymerizable monomer components in the two-paste type curable dental composition means the polymerizable monomer (a) having an acidic group contained in the first paste and the first paste and It refers to the total amount of polymerizable monomers (b) and (d) having no acidic group contained in the second paste.

In the two-paste type dental curable composition of the present invention, both the first paste and the second paste contain a polymerizable monomer that does not have an acidic group (the one contained in the first paste is defined as "having no acidic group polymerizable monomer (b)", and those contained in the second paste are referred to as "polymerizable monomer (d) having no acidic group"). A polymerizable monomer having no acidic group is a polymerizable monomer that undergoes a radical polymerization reaction with a polymerization initiator to polymerize. The polymerizable monomers (b) and (d) having no acidic group in the present invention may be the same or different. As the polymerizable monomers (b) and (d) having no acidic group, the following water-soluble polymerizable monomers and hydrophobic polymerizable monomers are preferably used.

A water-soluble polymerizable monomer means a polymerizable monomer having a solubility in water of 10% by mass or more at 25°C. Those having a solubility of 30% by mass or more are preferable, and those capable of dissolving in water at an arbitrary ratio at 25°C are more preferable. The water-soluble polymerizable monomer promotes the penetration of the components of the two-paste type curable dental composition into the tooth structure, and also penetrates the tooth structure itself and adheres to the organic component (collagen) in the tooth structure. do. Examples of water-soluble polymerizable monomers include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (hereinafter sometimes abbreviated as "HEMA"), 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-((meth)acryloyloxy)ethyltrimethylammonium chloride, polyethylene glycol di(meth)acrylate (oxy ethylene groups of 9 or more), N-methacryloyloxyethyl acrylamide, etc., and 2-hydroxyethyl (meth)acrylate is preferred.

A hydrophobic polymerizable monomer means a polymerizable monomer having a solubility in water at 25° C. of less than 10% by mass, and is preferably crosslinkable. Examples of crosslinkable polymerizable monomers include aromatic compound-based bifunctional polymerizable monomers, aliphatic compound-based bifunctional polymerizable monomers, and trifunctional or higher polymerizable monomers. body, etc. The hydrophobic polymerizable monomer improves the mechanical strength, handleability, etc. of the two-paste type dental curable composition.

（式中、Ｒ⁴及びＲ⁵は水素原子又はメチル基であり、Ｒ⁶及びＲ⁷はそれぞれ独立して、水素原子、水酸基又は炭素数１～３のアルキル基であり、ｗ、ｘ、ｙ、及びｚは０～６の整数であり、同じであっても、それぞれ互いに異なっていてもよく、また、ｎ及びｍは０～８の整数であって、同じであってもよく、それぞれ互いに異なっていてもよい。）
で表される芳香族ジ（メタ）アクリレートなどが挙げられる。芳香族化合物系の二官能性重合性単量体としては、例えば、２，２－ビス（（メタ）アクリロイルオキシフェニル）プロパン、２，２－ビス〔４－（３－アクリロイルオキシ－２－ヒドロキシプロポキシ）フェニル〕プロパン、２，２－ビス〔４－（３－メタクリロイルオキシ－２－ヒドロキシプロポキシ）フェニル〕プロパン（以下、「Ｂｉｓ－ＧＭＡ」と略称することがある）、２，２－ビス（４－（メタ）アクリロイルオキシエトキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロイルオキシポリエトキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロイルオキシジエトキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロイルオキシトリエトキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロイルオキシテトラエトキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロイルオキシペンタエトキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロイルオキシジプロポキシフェニル）プロパン、２－（４－（メタ）アクリロイルオキシジエトキシフェニル）－２－（４－（メタ）アクリロイルオキシエトキシフェニル）プロパン、２－（４－（メタ）アクリロイルオキシジエトキシフェニル）－２－（４－（メタ）アクリロイルオキシトリエトキシフェニル）プロパン、２－（４－（メタ）アクリロイルオキシジプロポキシフェニル）－２－（４－（メタ）アクリロイルオキシトリエトキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロイルオキシプロポキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロイルオキシイソプロポキシフェニル）プロパン、１，４－ビス（２－（メタ）アクリロイルオキシエチル）ピロメリテートなどが挙げられる。これらの中でも、２，２－ビス〔４－（３－メタクリロイルオキシ－２－ヒドロキシプロポキシ）フェニル〕プロパン、２，２－ビス（４－メタクリロイルオキシポリエトキシフェニル）プロパン（以下、「Ｄ２．６Ｅ」と略称することがある）（エトキシ基の平均付加モル数：２．６）が好ましい。 Examples of the aromatic compound-based bifunctional polymerizable monomer include the following general formula (2)

(Wherein, R ⁴ and R ⁵ are a hydrogen atom or a methyl group, R ⁶ and R ⁷ are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and w, x, y , and z are integers of 0 to 6 and may be the same or different, and n and m are integers of 0 to 8 and may be the same, respectively may be different.)
Aromatic di(meth)acrylates represented by 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 (hereinafter sometimes abbreviated as “Bis-GMA”), 2,2-bis( 4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyl) Oxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyl oxyethoxyphenyl)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)acryloyloxyiso propoxyphenyl)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 (hereinafter, “D2.6E” may be abbreviated) (average number of added moles of ethoxy group: 2.6) is preferable.

Examples of aliphatic compound-based bifunctional polymerizable monomers include erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, pentaerythritol di(meth)acrylate, and dipentaerythritol. Di(meth)acrylate, glycerol 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, 1,2-bis(3-methacryloyloxy-2) -hydroxypropyloxy)ethane and the like. Among these, glycerol dimethacrylate, 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) bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxaheptane and the like.

The above polymerizable monomers (b) and (d) having no acidic group may be blended singly or in combination of two or more. The total amount of the polymerizable monomers (b) and (d) having no acidic group is based on 100 parts by mass of the total amount of the polymerizable monomer components in the two-paste type dental curable composition of the present invention. , preferably 50 to 99 parts by mass, more preferably 70 to 98 parts by mass, even more preferably 85 to 98 parts by mass. The content of the water-soluble polymerizable monomer in the polymerizable monomers (b) and (d) having no acidic group is the ratio of the polymerizable monomers (b) and (d) having no acidic group. It is preferably 1 to 50 parts by mass, more preferably 2 to 25 parts by mass, and even more preferably 3 to 20 parts by mass with respect to the total amount of 100 parts by mass. Further, the content of the hydrophobic polymerizable monomer in the polymerizable monomers (b) and (d) having no acidic group is It is preferably 50 to 99 parts by mass, more preferably 75 to 98 parts by mass, and even more preferably 80 to 97 parts by mass with respect to the total amount of 100 parts by mass.

The two-paste type dental curable composition of the present invention contains a filler in both the first paste and the second paste (the filler contained in the first paste is "filler (c)" and the filler contained in the second paste is is referred to as "filler (f)"). As fillers (c) and (f), any fillers can be used as long as they do not impair the effects of the present invention, and inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers can be used. mentioned. Fillers (c) and (f) may be the same or different. The fillers (c) and (f) may be blended singly or in combination of two or more.

Examples of inorganic fillers include silica; silica _- based minerals such as _{kaolin , clay} , _{mica ,} and mica; Ceramics, glasses and the like containing ₂ O ₃ , SrO, ZnO, CaO, P ₂ O ₅ , Li ₂ O, Na ₂ O and the like. Glasses include lithium borosilicate glass, borosilicate glass, bioglass, lanthanum glass, barium glass, strontium glass, soda glass, zinc glass, and fluoroaluminosilicate glass. Crystalline quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, ytterbium fluoride are also suitable. used for Fine particle silica having an average particle size of 0.001 to 10 μm is preferably used from the viewpoints of adhesive strength and handleability. Commercially available products include "Aerosil (registered trademark) OX50", "Aerosil (registered trademark) 50", "Aerosil (registered trademark) 200", "Aerosil (registered trademark) 380", "Aerosil (registered trademark) R972", "Aerosil (registered trademark) 130" (all trade names, manufactured by Nippon Aerosil Co., Ltd.).

Examples of organic fillers 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 inorganic/organic composite fillers in which inorganic fillers are coated with various polymers.

In addition, in this specification, the average particle size of the fillers (c) and (f) can be determined by a laser diffraction scattering method or electron microscope observation of particles. Specifically, the laser diffraction scattering method is convenient for measuring the particle size of particles of 0.1 μm or more, and the electron microscope observation is convenient for measuring the particle size of ultrafine particles of less than 0.1 μm. 0.1 μm means a value measured by a laser diffraction scattering method.

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

For electron microscopic observation, for example, a scanning electron microscope (manufactured by Hitachi, Ltd., S-4000 type) photograph of the filler particles is taken, and the particle diameter of the particles (200 or more) observed in the unit field of view of the photograph is It can be obtained by measurement using image analysis type particle size distribution measurement software (Mac-View (manufactured by Mountec Co., Ltd.)). At this time, the particle diameter of the particles is obtained as an arithmetic mean value of the longest length and the shortest length of the particles, and the average particle diameter is calculated from the number of particles and their particle diameters.

In order to improve curability, mechanical strength and handleability, the fillers (c) and (f) may be surface-treated in advance with a known surface treatment agent such as a silane coupling agent before use. Examples of surface treatment agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 8-methallyloyloxyoctyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane and the like.

The content of the filler (c) in the first paste is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, and 50 to 80 parts by mass with respect to 100 parts by mass of the first paste. Part is more preferred. When the amount is 10 parts by mass or more, the strength of the cured composition can be improved, and when the amount is 90 parts by mass or less, a paste with good handleability can be obtained.
The content of the filler (f) in the second paste is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, with respect to 100 parts by mass of the second paste. It is more preferably 80 parts by mass. When the amount is 10 parts by mass or more, the strength of the cured composition can be improved, and when the amount is 90 parts by mass or less, a paste with good handleability can be obtained.

The two-paste dental curable composition of the present invention contains an isocyanurate compound (e) in the second paste. In order to exhibit the effects of the present invention, it is important that the polymerizable monomer (a) having an acidic group and the isocyanurate compound (e) are contained in different pastes. In the two-paste type dental curable composition of the present invention, the first paste contains the polymerizable monomer (a) having an acidic group and does not contain the isocyanurate compound (e). Also, the second paste contains the isocyanurate compound (e) and does not substantially contain a polymerizable monomer having an acidic group. In the present specification, substantially free means that the content is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and 0 0.5% by mass or less is more preferable, and 0% by mass is particularly preferable.

（式中、Ｒ¹～Ｒ³はそれぞれ独立して置換基を有していてもよい有機基であり、Ｒ¹～Ｒ³の少なくとも一つが、炭素数３以下の炭化水素基であり、かつＲ¹～Ｒ³の合計の炭素数が１５以下である。） The isocyanurate compound (e) used in the present invention is a compound represented by the following general formula (1).

(wherein R ¹ to R ³ are each independently an optionally substituted organic group, at least one of R ¹ to R ³ is a hydrocarbon group having 3 or less carbon atoms, and The total carbon number of R ¹ to R ³ is 15 or less.)

R ¹ to R ³ may be the same or different. The organic group represented by R ¹ to R ³ may be an organic group having a polymerizable group or an organic group having no polymerizable group. Examples of polymerizable groups include vinyl groups, (meth)acryloyl groups, and epoxy groups. As the organic group, a linear or branched hydrocarbon group is preferred. An allyl group, a glycidyl group, etc. are mentioned as a linear or branched hydrocarbon group which has a polymerizable group. ^The number of ^carbon atoms in ^{each organic group of R 1 to R 3 is particularly} It is not limited, and may be 6 or less, for example. Examples of substituents for R ¹ to R ³ include halogen atoms, cyano groups, alkoxysilyl groups (methoxysilyl groups, ethoxysilyl groups, etc.), alkoxy groups (methoxy groups, ethoxy groups, etc.), amino groups and the like. R ¹ to R ³ may be unsubstituted organic groups. The total number of carbon atoms in R ¹ to R ³ is preferably 14 or less, more preferably 12 or less. At least one of R ¹ to R ³ is a linear hydrocarbon group having 3 or less carbon atoms, and the total number of carbon atoms of R ¹ to R ³ is preferably 15 or less. More preferably, it is a straight-chain hydrocarbon group having a functional group and the total number of carbon atoms of R ¹ to R ³ is 15 or less. On the other hand, all of R ¹ to R ³ are organic groups other than hydrocarbon groups, such as tris(2-(meth)acryloxyethyl)isocyanurate, or all of R ¹ to R ³ have In the case of a compound having a linear hydrocarbon group of 4 or more, or a compound having a total carbon number of R ¹ to R ³ exceeding 15, the viscosity of the paste becomes high and the fluidity becomes low after mixing and kneading. No clear improvement in fluidity is observed, and the effects of the present invention cannot be obtained. At least one of R ¹ to R ³ must be a hydrocarbon group that does not easily interact with the filler. If any of ¹ to R ³ contains a substituent such as a methoxysilyl group that easily interacts with the filler, repulsion between the fillers will not occur and the fluidity will not increase, so that the effect of the present invention cannot be obtained.

Examples of the isocyanurate compound (e) used in the present invention include triallyl isocyanurate, tripropyl isocyanurate, mono(trimethoxysilylpropyl) diallyl isocyanurate, 1,3-bis(2-allyloxyethyl)-5-methyl Isocyanurate, 1-(2-allyloxyethyl)-3,5-dimethylisocyanurate, 1-methyl-3,5-bis(2-oxiranylmethoxyethyl)isocyanurate, 1,3-dimethyl-5- (2-oxiranylmethoxyethyl) isocyanurate, 1-methyl-3-(2-hydroxyethyl)-5-(2-vinylcarbonyloxyethyl) isocyanurate, 1-methyl-3-(2-hydroxyethyl) -5-[2-(2-propenyl)carbonyloxyethyl]isocyanurate, 1-methyl-3,5-bis(2-vinylcarbonyloxyethyl)isocyanurate, 1-methacryloyl-3,5-dimethylisocyanurate, 1,3-diacryloyl-5-methylisocyanurate, 1,3-dimethacryloyl-5-methylisocyanurate, and 1,3-bis(2-allyloxyethyl)-5-methylisocyanurate. Among these, ^{two or more of R 1 to} R ³ are preferably linear hydrocarbon groups having ³ or less carbon atoms from the viewpoint of the fluidity of the paste after mixing and kneading. are more preferably linear hydrocarbon groups having 3 or less carbon atoms. Examples of such compounds include triallyl isocyanurate and tripropyl isocyanurate, and among these, triallyl isocyanurate is more preferred. The isocyanurate compound (e) may be blended alone or in combination of two or more. The isocyanurate compound (e) can be produced by a known method, for example, by the production method described in JP-A-2015-051972.

The isocyanurate compound (e) is added in an amount of 0.5 parts per 100 parts by mass in total of the two-paste type dental curable composition of the present invention, from the viewpoint of reducing variations in paste properties, tooth adhesiveness, and properties of the cured product. It is preferably 7.0 parts by mass, more preferably 1.5 to 3.0 parts by mass. Further, in order to increase the fluidity after mixing and kneading with the first paste, the mass ratio of the polymerizable monomer (a) having an acidic group and the isocyanurate compound (e) [(a):(e)] is preferably in the range of 1.0:0.2 to 1.0:5.0, more preferably in the range of 1.0:0.5 to 1.0:2.0. More preferably, the range is from 0:0.8 to 1.0:1.2.

The two-paste type dental curable composition of the present invention contains a chemical polymerization initiator (g) in at least one of the first paste and the second paste. Examples of the chemical polymerization initiator (g) include organic peroxides, inorganic peroxides and transition metal complexes, and known ones can be used without particular limitation. The chemical polymerization initiator (g) may be blended alone or in combination of two or more.

Representative organic peroxides include hydroperoxides, peroxyesters, ketone peroxides, peroxyketals, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and the like. Among these, hydroperoxides and peroxyesters are preferred, and peroxyesters are particularly preferred because the change in operable time is small even when the two-paste type curable dental composition of the present invention is stored for a long period of time. An organic peroxide may be used individually by 1 type, and may use 2 or more types together.

Examples of hydroperoxides include cumene hydroperoxide, t-butyl hydroperoxide, t-hexyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide (hereinafter referred to as may be abbreviated as “THP”) and the like.

As the peroxyester, known peroxyesters having an acyl group on one side of the peroxy group (-OO- group) and a hydrocarbon group (or a similar group) on the other side can be used without any limitation. For example, α,α-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxy Neodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy- 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-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3, 5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2 -ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate (hereinafter sometimes abbreviated as “BPB”), bis(t-butylperoxy)isophthalate, and the like. These can be used individually by 1 type or in combination of 2 or more types as appropriate. Among these, from the viewpoint of storage stability and reactivity, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxybenzoate, t-butylperoxyisopropyl Monocarbonate, t-butylperoxy-2-ethylhexylmonocarbonate, t-butylperoxyacetate are preferred, and t-butylperoxybenzoate is more preferred.

Ketone peroxides include, for example, methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide and the like.

Examples of 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 4,4-bis(t-butylperoxy)valerate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane and the like.

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

Diacyl peroxides include, for example, isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide, m-toluoyl peroxide. benzoyl peroxide, benzoyl peroxide and the like.

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

Examples of inorganic peroxides include peroxodisulfates and peroxodiphosphates. Among these, peroxodisulfates are preferred from the viewpoint of curability. Specific examples of peroxodisulfates include sodium peroxodisulfate, potassium peroxodisulfate (hereinafter sometimes abbreviated as KPS), aluminum peroxodisulfate, and ammonium peroxodisulfate.

From the viewpoint of curability, the amount of organic peroxide and inorganic peroxide is 0.01 to 5 parts per 100 parts by mass of the total amount of polymerizable monomer components in the two-paste type dental curable composition of the present invention. It is preferably 0.05 to 2 parts by mass, more preferably 0.05 to 2 parts by mass.

Examples of transition metal complexes include copper compounds and vanadium compounds.

As the copper compound, a compound soluble in the polymerizable monomer component is preferred. Specific examples thereof include copper carboxylates such as copper (II) acetate, copper (II) isobutyrate, copper (II) gluconate, copper (II) citrate, copper (II) phthalate, and copper (II) tartrate. , copper (II) oleate, copper (II) octoate, copper (II) octenoate, copper (II) naphthenate, copper (II) methacrylate, copper (II) 4-cyclohexylbutyrate; as copper β-diketone , acetylacetone copper (II), trifluoroacetylacetone copper (II), hexafluoroacetylacetone copper (II), 2,2,6,6-tetramethyl-3,5-heptanedionato copper (II), benzoylacetone copper (II) as β-ketoester copper, ethyl copper(II) acetoacetate; as copper alkoxide, copper(II) methoxide, copper(II) ethoxide, copper(II) isopropoxide, copper(II) 2-(2-butoxyethoxy ) ethoxide, copper(II) 2-(2-methoxyethoxy)ethoxide; copper(II) dimethyldithiocarbamate as copper dithiocarbamate; copper(II) nitrate as salt of copper and inorganic acids; and copper(II) chloride. is mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate. Among these, carboxylic acid copper (II), β-diketone copper (II), β-ketoester copper (II) are preferable from the viewpoint of solubility and reactivity with respect to the polymerizable monomer, and copper (II) acetate , acetylacetone copper(II) are particularly preferred.

From the viewpoint of curability, the content of the copper compound is 0.000005 to 1 part by mass with respect to 100 parts by mass as the total amount of the polymerizable monomer components in the two-paste type dental curable composition of the present invention. is preferred.

Examples of vanadium compounds include vanadium acetylacetonate, vanadyl acetylacetonate (hereinafter sometimes abbreviated as "VOAA"), vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, and vanadium acetylacetonate. Acetonate, vanadyl acetylacetonate are preferred.

From the viewpoint of curability, the content of the vanadium compound is 0.005 to 1 part by mass with respect to 100 parts by mass as the total amount of the polymerizable monomer components in the two-paste type dental curable composition of the present invention. is preferred.

The two-paste type dental curable composition of the present invention contains a chemical polymerization accelerator (h) in at least one of the first paste and the second paste. Examples of chemical polymerization accelerators (h) include aromatic amines, aliphatic amines, aromatic sulfinates, sulfur-containing reducing inorganic compounds, thiourea derivatives, benzotriazole compounds, and benzimidazole compounds. . The chemical polymerization accelerator (h) may be used singly or in combination of two or more.

As aromatic amines, known aromatic secondary amines, aromatic tertiary amines, and the like may be used. Examples of aromatic secondary amines or aromatic tertiary amines include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(2-hydroxyethyl)-p -toluidine (hereinafter sometimes abbreviated as "DEPT"), N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis(2-hydroxyethyl)-4-ethyl Aniline, 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-isopropylaniline, N,N-dimethyl-4-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline. Among these, N,N-bis(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; N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl (meth)acrylate, N-methyldiethanolamine di(meth)acrylate, N-ethyldiethanolamine di( tertiary aliphatic amines such as meth)acrylates, triethanolamine tri(meth)acrylates, triethanolamine, trimethylamine, triethylamine, tributylamine; Among these, tertiary aliphatic amines are preferred from the viewpoint of redox reactivity, and among these, N-methyldiethanolamine, triethanolamine, and 2-(dimethylamino)ethyl methacrylate are particularly preferred.

The content of the aromatic amine or aliphatic amine is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer components in the two-paste type curable dental composition of the present invention. 0.02 to 5 parts by mass is more preferable, and 0.05 to 2 parts by mass is even more preferable. When the content is 0.01 parts by mass or more, the adhesive strength of the obtained two-paste type dental curable composition to a wet body such as tooth substance can be exhibited more favorably. Also, if the content is 10 parts by mass or less, it is less likely to affect the color tone stability of the resulting two-paste type dental curable composition.

Aromatic sulfinates include benzenesulfinic acid, p-toluenesulfinic acid, o-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, 2 , 4,6-triisopropylbenzenesulfinic acid (sodium salt may be abbreviated as "TPBSS" hereinafter), chlorobenzenesulfinic acid, naphthalenesulfinic acid and other lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, calcium salts, strontium salts, iron salts, zinc salts, ammonium salts, tetramethylammonium salts, tetraethylammonium salts. Among these, lithium salts, sodium salts, potassium salts and magnesium salts of 2,4,6-trimethylbenzenesulfinic acid and 2,4,6-triisopropylbenzenesulfinic acid are used in terms of curability and storage stability of the composition. Salts and calcium salts are preferred, and lithium, sodium, potassium, magnesium and calcium salts of 2,4,6-triisopropylbenzenesulfinic acid are more preferred.

The content of the aromatic sulfinate is the polymerizable monomer in the two-paste-type dental curable composition of the present invention, from the viewpoint of the mechanical strength of the cured product of the resulting two-paste-type dental curable composition. It is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the total amount of the components.

Examples of reducing inorganic compounds containing sulfur include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, and dithionites. Among these, sulfites and bisulfites are preferred. Specific examples include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite and potassium hydrogen sulfite. The reducing inorganic compounds having sulfur may be used singly or in combination of two or more.

The content of the reducing inorganic compound is preferably from 0.01 to 15 parts by mass with respect to 100 parts by mass as the total amount of the polymerizable monomer components in the two-paste type curable dental composition of the present invention. 05 to 10 parts by mass is more preferable, and 0.1 to 5 parts by mass is even more preferable. When the content is 0.01 parts by mass or more, the adhesive strength of the resulting two-paste type dental curable composition to wet bodies such as tooth substance is less likely to be affected. Further, when the content is 15 parts by mass or less, the mechanical strength of the resulting hardened two-paste type dental curable composition is less likely to decrease.

Thiourea derivatives include ethylenethiourea, 4,4-dimethylethylenethiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, dicyclohexylthiourea, tri methylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, dicyclohexylthiourea, tetracyclohexylthiourea, N-acetylthiourea, N-benzoylthio Urea, diphenylthiourea, pyridylthiourea and the like can be mentioned, and among these, 4,4-dimethylethylenethiourea, pyridylthiourea and N-benzoylthiourea are preferred.

Benzotriazole compounds and/or benzimidazole compounds include compounds represented by the following general formulas (3) and (4), respectively.

In general formulas (3) and (4) above, each of R ⁸ to R ¹⁵ independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an alkenyl group, an aralkyl group, or a halogen atom.

The alkyl groups represented by R ⁸ to R ¹⁵ may be linear, branched or cyclic, and preferably have 1 to 10 carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group and isopentyl. group, 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 , cyclononyl group, n-decyl group and the like. Among these, a methyl group and an ethyl group are particularly preferred.

The aryl group represented by R ⁸ to R ¹⁵ preferably has 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.

The alkoxy groups represented by R ⁸ to R ¹⁵ may be linear, branched or cyclic, and preferably have 1 to 8 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, n-hexyloxy, cyclohexyloxy, n-octyloxy, and 2-ethylhexyloxy. and the like.

The alkenyl groups represented by R ⁸ to R ¹⁵ may be linear, branched or cyclic, and preferably have 2 to 6 carbon atoms. Specific examples include vinyl, allyl, methylvinyl, propenyl, butenyl, pentenyl, hexenyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl groups.

Examples of the aralkyl group represented by R ⁸ to R ¹⁵ include an alkyl group (especially an alkyl group having 1 to 10 carbon atoms) substituted with an aryl group (especially an aryl group having 6 to 10 carbon atoms). Specific examples include a benzyl group and the like.

Examples of halogen atoms represented by R ⁸ to R ¹⁵ include chlorine, bromine and iodine atoms.

R ⁸ to R ¹⁵ are preferably hydrogen atoms or methyl groups. Also, R ⁸ to R ¹⁵ may be the same or different.

A benzotriazole compound and a benzimidazole compound may be used individually by 1 type, and may use 2 or more types together. Specific examples of benzotriazole compounds and benzimidazole compounds include 1H-benzotriazole (hereinafter sometimes abbreviated as "BTA"), 5-methyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazole. , benzimidazole, 5-methylbenzimidazole, 5,6-dimethylbenzimidazole, and the like. Among these, 1H-benzotriazole and 5-methyl-1H-benzotriazole are preferred from the viewpoint of the color tone and storage stability of the composition.

As a method for packaging the chemical polymerization initiator (g) and the chemical polymerization accelerator (h) for the two pastes of the two-paste type curable dental composition of the present invention, one paste contains at least the chemical polymerization initiator (g). ), and the other paste is not particularly limited as long as it contains at least the chemical polymerization accelerator (h). Containing only the chemical polymerization initiator (g) (not containing the chemical polymerization accelerator (h)), and the other paste containing only the chemical polymerization accelerator (h) (not containing the chemical polymerization initiator (g)) is preferred. From the viewpoint of storage stability, it is more preferable that the first paste of the present invention contains only the chemical polymerization initiator (e) and the second paste contains only the chemical polymerization accelerator (f).

The two-paste type curable dental composition of the present invention may further contain a photopolymerization initiator (i) in at least one of the first paste and the second paste.

The photopolymerization initiator (i) may be used alone or in combination of two or more. The content of the photopolymerization initiator (i) is in the range of 0.005 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer components in the two-paste type dental curable composition of the present invention. Preferably, the range of 0.01 to 5 parts by mass is more preferable.

In order to enhance photocurability, a photopolymerization initiator (i) and a polymerization accelerator for photopolymerization initiators such as aldehydes, thiol compounds, amine compounds, and triazine compounds substituted with a trihalomethyl group are used. may be used together. Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, pn-octyloxybenzaldehyde and the like. Examples of thiol compounds include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, thiobenzoic acid and the like. Examples of the amine compound include ethyl 4-(N,N-dimethylamino)benzoate. Some of the amine compounds used as polymerization accelerators for photopolymerization initiators also have the function of the chemical polymerization accelerator (h). As the triazine-based compound substituted with a trihalomethyl group, known s-triazine compounds having at least one trihalomethyl group such as trichloromethyl group and tribromomethyl group can be used without any limitation. The polymerization accelerator may be used singly or in combination of two or more.

Polymerization accelerators for photopolymerization initiators, such as aldehydes, thiol compounds, amine compounds, and triazine compounds substituted with trihalomethyl groups, may be used singly or in combination of two or more compounds as necessary. may be used. The content of the polymerization accelerator for the photopolymerization initiator is 0.005 to 0.3 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer components in the two-paste type dental curable composition of the present invention. 0.008 to 0.2 parts by mass is preferable, and 0.01 to 0.1 parts by mass is more preferable.

A fluoride ion-releasing substance may be added to the two-paste type dental curable composition of the present invention for the purpose of imparting acid resistance to dentin. Fluoride ion-releasing substances include fluoride ion-releasing polymers such as copolymers of methyl methacrylate and methacrylic acid fluoride; hydrofluorides of aliphatic or alicyclic primary, secondary or tertiary amines such as triethylamine trihydrofluoride; inorganic fillers; Examples of inorganic fillers include the aforementioned fluoroaluminosilicate glass, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride.

Silane coupling agents such as 3-methacryloyloxypropyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 11-methacryloxyundecyltrimethoxysilane, and silanol are added to the two-paste type dental curable composition of the present invention. A condensation catalyst and a cross-linking agent may be blended.

The two-paste type curable dental composition of the present invention is added with a stabilizer (polymerization inhibitor) such as 2,6-di-t-butyl-4-methylphenol, a coloring agent (dye, pigment), a fluorescent agent, and an ultraviolet ray. Additives such as absorbents may be added. Antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxide decylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydecylammonium chloride, and triclosan may also be added. good.

The viscosity (30° C.) of the first paste of the two-paste type curable dental composition of the present invention is preferably 1000 to 35000 Pa·s, more preferably 3000 to 20000 Pa·s, from the viewpoint of handleability when collecting the paste. is more preferable, 5000 to 10000 Pa.s is even more preferable, and 6000 to 8000 Pa.s is particularly preferable.

The viscosity (30° C.) of the second paste of the two-paste type curable dental composition of the present invention is preferably 1,000 to 35,000 Pa·s, more preferably 3,000 to 20,000 Pa·s, from the viewpoint of handling during paste collection. is more preferable, 5000 to 10000 Pa.s is even more preferable, and 6000 to 8000 Pa.s is particularly preferable.
In addition, the viscosity (30 ° C.) of the first paste and the second paste is preferably 1000 to 35000 Pa s, more preferably 3000 to 20000 Pa s, and 5000 to 10000 Pa s. and more preferably 6000 to 8000 Pa·s.

The ratio of the viscosities (30° C.) of the first paste and the second paste (viscosity of the first paste/viscosity of the second paste) of the two-paste type dental curable composition of the present invention is easy to obtain at a desired amount ratio. From the viewpoint, it is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. The viscosity of the first paste (30 ° C.) and the viscosity of the second paste (30 ° C.) and the ratio of those viscosities (viscosity of the first paste/viscosity of the second paste) are, for example, blended in each paste. The type and content of the polymerizable monomer and filler can be selected and adjusted. The method for measuring the viscosity of the composition described in this specification is as described in Examples below.

The two-paste type curable dental composition of the present invention can be produced, for example, by mixing powdery components (such as fillers (c) and (f)), obtaining a solution, and adding the powdery components. can be done.

The present invention includes embodiments in which the above configurations are combined in various ways within the scope of the technical idea of the present invention as long as the effects of the present invention are exhibited.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples, and many modifications are possible within the scope of the technical idea of the present invention. It is possible by those who have ordinary knowledge in the field. The abbreviations and abbreviations used below are as follows.

[Polymerizable monomer (a) having an acidic group]
MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[Polymerizable monomers (b) and (d) having no acidic group]
HEMA: 2-hydroxyethyl methacrylate Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane D2.6E: 2,2-bis(4-methacryloyloxypolyethoxyphenyl ) Propane (average number of added moles of ethoxy group: 2.6)

[Fillers (c) and (f)]
F1: Silane-treated quartz powder:
Quartz (manufactured by MARUWA QUARTZ) was pulverized with a ball mill to obtain quartz powder having 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 in a conventional manner to obtain silane-treated quartz powder.
R972: Nippon Aerosil Co., Ltd. Fine particle silica "Aerosil (registered trademark) R972", average particle size: 16 nm
F2: Silane-treated barium glass powder:
Barium glass (manufactured by Estech, product code “Raysorb E-3000”) was pulverized with a ball mill to obtain barium glass powder having 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 in a conventional manner to obtain silane-treated barium glass powder.
Alumina: Nippon Aerosil Co., Ltd., trade name "AEROXIDE (registered trademark) AluC", average particle size: 20 nm

[Isocyanurate compound (e)]
TAIC: triallyl isocyanurate MSPI: mono(trimethoxysilylpropyl) diallyl isocyanurate TSPI: tris(trimethoxysilylpropyl) isocyanurate

[Chemical polymerization initiator (g)]
Copper(II) acetate
BPB: t-butyl peroxybenzoate KPS: potassium peroxodisulfate

[Chemical polymerization accelerator (h)]
TPBSS: sodium 2,4,6-triisopropylbenzenesulfinate DEPT: N,N-bis(2-hydroxyethyl)-p-toluidine BTA: 1H-benzotriazole NAA: sodium sulfite

[Photoinitiator (i)]
CQ: Camphorquinone

〔others〕
11-MUS: 11-methacryloyloxyundecyltrimethoxysilane (silane coupling agent)
PDE: 4-(N,N-dimethylamino) ethyl benzoate (polymerization accelerator for photopolymerization initiator)
BHT: 2,6-di-t-butyl-4-methylphenol (stabilizer)

[Examples 1 to 5 and Comparative Examples 1 to 4]
A first paste and a second paste having compositions shown in Table 1 were prepared. The first paste was prepared by mixing components other than the powdery component (filler), stirring the mixture to obtain a uniform solution, and then kneading the powdery component and defoaming. The powdery component in the first paste was in a state of being dispersed in powder form. The second paste was prepared by blending components other than the powdery components (filler and TPBSS), stirring the mixture to form a uniform solution, and then kneading the powdery components into the solution and defoaming. The powdery component in the second paste was in a powdery dispersed state. The two agents were mixed at a mass ratio of 1:1, and the resulting mixture was used for evaluation as a dental curable composition. The shear adhesive strength to dentin, the viscosity of the first and second pastes, and the fluidity immediately after mixing and kneading the first and second pastes were tested by the methods described below. Table 1 shows the results.

[Shear adhesive strength to dentin]
The lip surface of the bovine mandibular anterior tooth was polished with #80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to expose the flat surface of the dentin. The flat surface was embedded in a stainless steel ring with a dental composite resin so that it was exposed, and then the flat surface was polished under running water using silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) up to #1000. A smooth surface of good quality was obtained. The first paste and the second paste of the dental curable composition of the present invention were mixed and kneaded with a spatula for 10 seconds. cross section), and the end face of the side on which the curable dental composition was built up was placed on the smooth surface of the dentin. After that, a load of 500 g is applied vertically from the top of the stainless steel cylindrical tip, and the margin between the stainless steel cylindrical tip and the smooth surface is irradiated with a dental polymerization light irradiation device (Pencure 2000, manufactured by Morita Co., Ltd.) for 2 to 5 times. Excess cement was removed by irradiating for seconds. After that, irradiation was performed for 10 seconds with a dental polymerization light irradiator (Pencure 2000, manufactured by Morita Co., Ltd.). After 10 minutes, the load of 500 g was removed and a test sample was obtained. Five test samples were produced. The test samples were immersed in water at 37° C. for 24 hours and then examined for shear bond strength. This shear bond strength represents the initial shear bond strength. The shear bond strength was measured using a universal tester (manufactured by Shimadzu Corporation, trade name "AG-I 100 kN") at a crosshead speed of 1 mm/min. The shear bond strength in the table is the mean value of measurements on 5 test samples each. This value of shear bond strength to dentin was used as an index of shear bond strength to tooth substance, and the value of variation in shear bond strength (CV value (variation coefficient) = standard deviation/average value) was calculated. The shear bond strength to tooth substance is preferably 7 MPa or more, more preferably 9 MPa or more, and even more preferably 11 MPa or more. The variation in shear bond strength (CV value (variation coefficient)) is preferably 0.45 or less, more preferably 0.40 or less, and even more preferably 0.35 or less.

[Viscosity of each paste]
For each of the first paste and the second paste, using a viscometer (manufactured by Toki Sangyo Co., Ltd., TV-30E type viscometer, JIS K-7117-2: 1999, cone plate type). Measured at 30° C. with a sample volume of 0.5 mL using an 8°×R12 cone rotor. After preheating for 1 minute, the measurement was started, and the measured value after 3 minutes was taken as the viscosity. The viscosities in the table are the average values of 3 measurements for each sample. If the paste viscosity (30 ° C.) before mixing is 1000 to 35000 Pa s, the paste properties are easy to collect, and the ratio of the viscosity (30 ° C.) of the first paste and the second paste (viscosity of the first paste / second paste If the viscosity of the paste) is 0.8 to 1.2, it is easy to collect the same amount when simultaneously extruded from a syringe, good handleability, and stable performance can be obtained.

[Fluidity after mixing and kneading]
The first paste and the second paste were mixed and kneaded on kneading paper with a spatula for 10 seconds, and evaluated by hand feeling (N=1).
<Judgment Criteria>
A: There is no resistance during mixing and kneading, the fluidity after mixing and kneading is high, and the paste spreads by its own weight when it is collected.
○: No resistance during mixing and kneading, high fluidity after mixing and kneading, but some shape remains when the paste is put together.
x: There is resistance during mixing and kneading, the fluidity after mixing and kneading is low, and the shape remains when the paste is put together.

As shown in Table 1, the two-paste type curable dental compositions of Examples 1 to 5 exhibited excellent adhesiveness to tooth structure and high fluidity after mixing and kneading. Since the viscosity of the paste was also within a specific range, it was excellent in handleability at the time of paste collection. On the other hand, the two-paste type curable dental compositions prepared in Comparative Examples 1 to 3 had excellent handling properties when the paste was collected, but had low fluidity after mixing and kneading, and had large variations in adhesive strength. , it was not possible to obtain stable adhesion to tooth substance. In addition, in Comparative Examples 1 and 2, in which the second paste does not contain an isocyanurate compound, sufficient fluidity after mixing and kneading is not obtained, and the CV value of adhesiveness to dentin is also lower than that of Examples 1 to 5. It was shown that the properties of the cured product were highly variable. Comparative Example 3 uses an isocyanurate compound which is the same compound as in Example 4 of Patent Document 1 and none of R ¹ to R ³ is a linear hydrocarbon group having 3 or less carbon atoms. Fluidity after mashing is low, stable adhesion to tooth substance cannot be obtained, the CV value of adhesion to tooth substance is higher than that of Examples 1 to 5, and the properties of the cured product vary greatly. was shown. In Comparative Example 4, since the first paste contains a polymerizable monomer having an acidic group and an isocyanurate compound, the viscosities of the first paste and the second paste are significantly different, resulting in poor handleability when the paste is collected. Furthermore, it was difficult to mix the paste uniformly during mixing and kneading, and stable adhesion to the tooth substance could not be obtained. A high value was obtained, indicating that the properties of the cured product varied widely.

The two-paste type dental curable composition of the present invention can be suitably used for dental restorative treatment. In addition, the two-paste type dental curable composition of the present invention can be suitably used as a dental cement, particularly as a self-adhesive cement.

Claims (9)

a first paste containing a polymerizable monomer (a) having an acidic group, a polymerizable monomer (b) having no acidic group, and a filler (c);
Consists of a second paste containing a polymerizable monomer (d) having no acidic group, an isocyanurate compound (e) represented by the following general formula (1), and a filler (f),
A two-paste dental curable composition, wherein one paste contains a chemical polymerization initiator (g) and the other paste contains a chemical polymerization accelerator (h).

(wherein R ¹ to R ³ are each independently an optionally substituted organic group, at least one of R ¹ to R ³ is a hydrocarbon group having 3 or less carbon atoms, and The total carbon number of R ¹ to R ³ is 15 or less.) 2. The two-paste type dental curable composition according to claim 1, wherein the second paste has a viscosity (30° C.) of 1000 to 35000 mPa·s. 3. The two-paste type dental curable composition according to claim 1, wherein the viscosity (30° C.) of the first paste and the second paste is 1000 to 35000 mPa·s. The ratio of the viscosities (30° C.) of the first paste and the second paste (viscosity of the first paste/viscosity of the second paste) is 0.8 to 1.2, according to any one of claims 1 to 3. 2-paste type dental hardening composition. 5. The content of the isocyanurate compound (e) according to any one of claims 1 to 4, wherein the content of the isocyanurate compound (e) is 0.5 to 7.0 parts by mass with respect to the total amount of 100 parts by mass of the two-paste type dental curable composition. A two-paste dental hardenable composition of 6. The two-paste type dental curable composition according to any one of claims 1 to 5, wherein each of R ¹ to R ³ is a linear hydrocarbon group having 3 or less carbon atoms. The two-paste type dental curable composition according to any one of claims 1 to 6, wherein at least one of the first paste and the second paste further contains a photopolymerization initiator (i). The two-paste dental curable composition according to any one of claims 1 to 7, wherein the isocyanurate compound (e) is triallyl isocyanurate. A dental cement comprising the two-paste type dental curable composition according to any one of claims 1 to 8.