2 Paste-type Hardening Dental Composition

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

Technical Field

[0001] The present invention relates to a two-paste type dental curable composition.

Background Art

[0002] For the restoration and treatment of teeth, which are one of the living hard tissues, resin-based dental curable compositions composed of polymerizable monomers, polymerization initiators, etc. are widely used.

[0003] The polymerization initiators contained in dental curable compositions are mainly classified into photopolymerization initiators that are polymerized and cured by irradiating visible light, and chemical polymerization initiator systems in which a chemical polymerization initiator and a chemical polymerization accelerator are separately packaged and mixed immediately before use for polymerization and curing. Recently, products called dual-cure types containing both of these initiators have also been widely used in dental clinics. In addition, among dental curable compositions containing a chemical polymerization initiator system, two-paste type dental curable compositions in which both agents are pastes are generally used because of their excellent operability such as simplicity of operation.

[0004] Examples of the uses of two-paste type dental curable compositions include dental cements for fixing crown restorative materials made of metal or ceramics, called inlays and crowns, to teeth. Among these dental cements, in recent years, two-paste type dental cements containing polymerizable monomers having acidic groups such as phosphate groups or carboxy groups to impart self-adhesiveness to tooth substances and prostheses have been widely used because of the simplicity of operation that no pretreatment such as a primer is required.

[0005] By the way, compounds having an isocyanurate skeleton are known as components of dental curable compositions, and depending on the properties resulting from their structures, they are used as crosslinking agents and the like.

[0006] For example, Patent Document 1 discloses a two-paste type dental curable composition having clinically acceptable adhesive durability for dental adherends such as dental glass ceramics restorations without using a primer, and a specific compound having an isocyanurate skeleton is described as one of its crosslinking agent components. Further, Patent Document 2 discloses a composition of a polymerizable dental material, and a specific compound having an isocyanurate skeleton is described as one of its reactive paste formers.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] As a required property of a two-paste type self-adhesive dental cement, it is natural to have excellent adhesiveness to adherends such as tooth substance and prostheses. In addition, it is also important to have excellent handling properties. That is, a two-paste type dental curable composition such as dental cement is generally used by manually mixing and kneading two pastes in an appropriate quantitative ratio on a mixing paper using a spatula or the like. When accurately collecting each paste from a container such as a syringe in a desired amount of use, it is required to have excellent handling properties during paste collection, that is, a paste property with relatively low fluidity. Further, in order to more easily mix and knead the paste, an automix type in which a mixing tip is attached to the tip of a syringe and the two agents are automatically mixed has recently been widely used. In order to provide a uniform paste after mixing, it is required to have a paste property in which the viscosities of the two-agent pastes are similar and have an appropriate fluidity that is easy to mix.

[0009] However, as a result of investigations by the present inventors, although the two-paste type dental curable composition of Patent Document 1 is excellent in handleability during paste collection and has excellent self-adhesiveness to prostheses such as lithium disilicate glass, it has been found that there is still room for further improvement in the adhesiveness to dentin (hereinafter also referred to as "dentin adhesiveness").

[0010] In addition, as for the dental material of Patent Document 2, as a result of investigations by the present inventors, it has been found that the first paste containing triallyl isocyanurate and a reactive paste-forming agent having an acidic group has problems in handleability during paste collection. Furthermore, since two pastes with different paste properties are mixed and kneaded, it has been found that the paste after mixing and kneading is non-uniform, resulting in variations in the properties of the cured product including dentin adhesiveness.

[0011] Therefore, an object of the present invention is to provide a two-paste type dental curable composition that is excellent in dentin adhesiveness, handleability during paste collection, and fluidity after mixing and kneading, and has little variation in the properties of the cured product evaluated by dentin adhesiveness and the like.

Means for Solving the Problems

[0012] As a result of intensive investigations to solve the above problems, the present inventors have found that the above problems can be solved by using 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, and based on this finding, further investigations have been repeated to complete the present invention.

[0013] 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), It is composed 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 type dental curable composition, wherein one paste contains a chemical polymerization initiator (g) and the other paste contains a chemical polymerization accelerator (h). [Chemical formula] (In the formula, R 1 ~R 3 are each independently an organic group which may have a substituent, and at least one of R 1 ~R 3 is a hydrocarbon group having 3 or less carbon atoms, and the total number of carbon atoms of R 1 ~R 3 is 15 or less.) [2] The two-paste type dental curable composition according to [1], wherein the viscosity (30 ° C) of the second paste is 1000 to 35000 mPa·s. [3] The two-paste type dental curable composition according to [1] or [2], wherein the viscosities (30 ° C) of the first paste and the second paste are both 1000 to 35000 mPa·s. [4] The two-paste type dental curable composition according to any one of [1] to [3], wherein the ratio of the viscosities (30 ° C) of the first paste to the second paste (viscosity of the first paste / viscosity of the second paste) is 0.8 to 1.2. [5] The two-paste type dental curable composition according to any one of [1] to [4], wherein the content of the isocyanurate compound (e) is 0.5 to 7.0 parts by mass in 100 parts by mass of the total amount of the two-paste type dental curable composition. [6] The two-paste type dental curable composition according to any one of [1] to [5], wherein R 1 ~R 3 are all linear hydrocarbon groups having 3 or less carbon atoms. [7] The two-paste type dental curable composition according to any one of [1] to [6], further comprising a photoinitiator (i) in at least one of the first paste and the second paste. [8] The two-paste type dental curable composition according to any one of [1] to [7], wherein the isocyanurate compound (e) is triallyl isocyanurate. A dental cement comprising a two-paste type curable dental composition according to any one of [1] to [8].

Advantages of the Invention

[0014] According to the present invention, a two-paste type curable dental composition excellent in dentin adhesiveness, handleability at the time of paste collection, and fluidity after mixing and kneading, and having little variation in the properties of the cured product evaluated by dentin adhesiveness and the like can be provided.

Embodiments for Carrying Out the Invention

[0015] The two-paste type curable dental composition of the present invention is composed of a first paste containing a polymerizable monomer (a) having an acidic group, a polymerizable monomer (b) not having an acidic group, and a filler (c), and a second paste containing a polymerizable monomer (d) not having an acidic group, an isocyanurate compound (e) represented by the following general formula (1), and a filler (f), wherein one paste contains a chemical polymerization initiator (g) and the other paste contains a chemical polymerization accelerator (h).

[0016]

Chemical formula

[0017] The reason why the two-paste type dental curable composition of the present invention is excellent in dentin adhesiveness and handling properties during paste collection and has little variation in the properties of the cured product evaluated by dentin adhesiveness and the like is not necessarily clear, but the present inventors presume as follows. Conventional two-paste type dental curable compositions do not have high paste fluidity during paste collection, during paste mixing and kneading, and during paste application to the prosthesis. On the other hand, although the two-paste type dental curable composition of the present invention does not have high paste fluidity during paste collection, it has a moderate paste property with high paste fluidity during paste mixing and kneading, making it easy to mix and knead. Thus, it is presumed that since high paste fluidity enables uniform mixing and kneading, there is little variation in the properties of the cured product, and since the permeability to dentin is increased, the adhesiveness to dentin is improved. Also, the mechanism by which the composition of the present invention exhibits high fluidity after mixing and kneading 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 + coordinates to the isocyanurate skeleton. It is considered that the positively charged isocyanurate compound adsorbs on the surface of the filler, causing repulsion between the fillers, weakening the ionic interaction, and resulting in a paste having appropriate fluidity.

[0018] The first paste of the two-paste type dental curable composition of the present invention contains a polymerizable monomer (a) having an acidic group. Blending the polymerizable monomer (a) having an acidic group can impart excellent adhesiveness to dental prosthetic materials including dentin.

[0019] Examples of the polymerizable monomer (a) having an acidic group include polymerizable monomers having at least one acidic group such as a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group, and having at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group, and a styrene group. The polymerizable monomer (a) having an acidic group has an affinity for the adherend and has a decalcifying action on dentin. Specific examples of the polymerizable monomer (a) having an acidic group are described below. In the present specification, “(meth)acryl” means acrylic and methacrylic, and “(meth)acryloyl” means acryloyl and methacryloyl.

[0020] Examples of the polymerizable monomer having a phosphate group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-acryloyloxydecyl dihydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate (hereinafter sometimes abbreviated as "MDP"), 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyeicosyl 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] hydrogen phosphate, bis[10-(meth)acryloyloxydecyl] hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl] hydrogen phosphate, and acid chlorides, alkali metal salts, ammonium salts, etc. thereof.

[0021] Examples of the polymerizable monomer having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, and their acid chlorides, alkali metal salts, ammonium salts and the like.

[0022] Examples of the polymerizable monomer having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogen thiophosphate, 3-(meth)acryloyloxypropyl dihydrogen thiophosphate, 4-(meth)acryloyloxybutyl dihydrogen thiophosphate, 5-(meth)acryloyloxypentyl dihydrogen thiophosphate, 6-(meth)acryloyloxyhexyl dihydrogen thiophosphate, 7-(meth)acryloyloxyheptyl dihydrogen thiophosphate, 8-(meth)acryloyloxyoctyl dihydrogen thiophosphate, 9-(meth)acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, 20-(meth)acryloyloxyeicosyl dihydrogen thiophosphate, and their acid chlorides, alkali metal salts, ammonium salts and the like.

[0023] Examples of the polymerizable monomer having a phosphonic acid group include 2-(meth)acryloyloxyethyl phenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl phosphonoacetate, 10-(meth)acryloyloxydecyl phosphonoacetate, and their acid chlorides, alkali metal salts, ammonium salts, etc.

[0024] Examples of the polymerizable monomer having a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, 2-sulfoethyl (meth)acrylate, etc.

[0025] Examples of the polymerizable monomer having a carboxylic acid group include a polymerizable monomer having one carboxy group in the molecule and a polymerizable monomer having a plurality of carboxy groups in the molecule.

[0026] Examples of the polymerizable monomer having one carboxy group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen maleate, and their acid halides, etc.

[0027] Examples of the polymerizable monomer having a plurality of carboxy groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytetradecane-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 acid anhydrides or acid halides thereof, etc.

[0028] The polymerizable monomer (a) having the above acidic group may be used alone or in combination of two or more. Among these polymerizable monomers (a) having acidic groups, one or more selected from the group consisting of a polymerizable monomer having a phosphate group, a polymerizable monomer having a carboxylic acid group, and a polymerizable monomer having a sulfonic acid group are preferable in terms of having a large adhesive strength to dental adherends. One or more selected from the group consisting of a polymerizable monomer having a phosphate group having two or more hydroxyl groups bonded to a phosphorus atom, a polymerizable monomer having a plurality of carboxy groups in the molecule, and a polymerizable monomer having a sulfonic acid group are more preferable. One or more selected from the group consisting of 10-(meth)acryloyloxydecyl dihydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogen 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 even more preferable.

[0029] The content of the polymerizable monomer (a) having an acidic group is preferably 1 to 50 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 2 to 15 parts by mass in 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. 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 the acidic group-containing polymerizable monomer (a) is 50 parts by mass or less, it is easy to maintain the balance between polymerizability and adhesiveness. In particular, by setting it to 2 to 15 parts by mass, a paste having appropriate fluidity can be obtained after kneading with the second paste. In the present invention, the total amount of the polymerizable monomer components in the two-paste type dental curable composition means the total amount of the polymerizable monomer (a) having an acidic group contained in the first paste and the polymerizable monomers (b) and (d) having no acidic group contained in the first paste and the second paste.

[0030] The two-paste type dental curable composition of the present invention contains polymerizable monomers having no acidic group in both the first paste and the second paste (the one contained in the first paste is referred to as "polymerizable monomer (b) having no acidic group", and the one contained in the second paste is referred to as "polymerizable monomer (d) having no acidic group"). The polymerizable monomer having no acidic group is a polymerizable monomer in which a radical polymerization reaction proceeds by a polymerization initiator to form a polymer. 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.

[0031] The water-soluble polymerizable monomer means a polymerizable monomer having a solubility in water at 25 ° C of 10% by mass or more. Those having a solubility of 30% by mass or more are preferred, and those that can be dissolved in water at an arbitrary ratio at 25 ° C are more preferred. The water-soluble polymerizable monomer promotes the penetration of the components of the two-paste type dental curable composition into the dentin, and also penetrates into the dentin and adheres to the organic components (collagen) in the dentin. Examples of the water-soluble polymerizable monomer 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 (the number of oxyethylene groups is 9 or more), N-methacryloyloxyethyl acrylamide, etc., and 2-hydroxyethyl (meth) acrylate is preferred.

[0032] The 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 the crosslinkable polymerizable monomer include aromatic compound-based bifunctional polymerizable monomers, aliphatic compound-based bifunctional polymerizable monomers, trifunctional or higher functional polymerizable monomers, and the like. The hydrophobic polymerizable monomer improves the mechanical strength, handleability, etc. of the two-paste type dental curable composition.

[0033] Examples of the aromatic compound-based bifunctional polymerizable monomer include the following general formula (2) [Chemical formula] (In the formula, 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, w, x, y, and z are integers from 0 to 6, and may be the same or different from each other. Also, n and m are integers from 0 to 8, and may be the same or different from each other.) Examples thereof include aromatic di(meth)acrylates represented by . Examples of the aromatic compound-based bifunctional polymerizable monomer include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-acryloyloxy-2-hydroxypropoxy)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)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 and 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (hereinafter sometimes abbreviated as "D2.6E") (average number of moles of added ethoxy groups: 2.6) are preferred.

[0034] Examples of the aliphatic compound-based bifunctional polymerizable monomer include erythritol di(meth)acrylate, sorbitol di(meth)acrylate, mannitol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol di(meth)acrylate, glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2,2,4-trimethylhexamethylene bis(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-trimethylhexamethylene bis(2-carbamoyloxyethyl) dimethacrylate, and 1,2-bis(3-methacryloyloxy-2-hydroxypropyloxy)ethane are preferred.

[0035] Examples of the polymerizable monomer having a functionality of 3 or more 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.

[0036] Each of the polymerizable monomers (b) and (d) having no acidic group may be blended alone or in combination of two or more. The total amount of the polymerizable monomers (b) and (d) having no acidic group is preferably 50 to 99 parts by mass, more preferably 70 to 98 parts by mass, and even more preferably 85 to 98 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the two-paste type dental curable composition of the present invention. The content of the water-soluble polymerizable monomer in the polymerizable monomers (b) and (d) having no acidic group 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 100 parts by mass of the total amount of the polymerizable monomers (b) and (d) having no acidic group. Further, the content of the hydrophobic polymerizable monomer in the polymerizable monomers (b) and (d) having no acidic group 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 100 parts by mass of the total amount of the polymerizable monomers (b) and (d) having no acidic group.

[0037] The two-paste type dental curable composition of the present invention contains fillers in both the first paste and the second paste (the filler contained in the first paste is referred to as "filler (c)", and the filler contained in the second paste is referred to as "filler (f)"). As filler (c) and (f), any filler can be used as long as the effects of the present invention are not impaired, and examples include inorganic fillers, organic fillers, and composite fillers of inorganic fillers and organic fillers. Filler (c) and (f) may be the same or different. Filler (c) and (f) may each be blended alone or in combination of two or more.

[0038] Examples of inorganic fillers include silica; minerals based on silica such as kaolin, clay, mica, and mica; ceramics and glasses based on silica and containing Al2O3, B2O3, TiO2, ZrO2, BaO, La2O3, SrO, ZnO, CaO, P2O5, Li2O, Na2O, etc. Examples of glasses include lithium borosilicate glass, borosilicate glass, bioglass, lanthanum glass, barium glass, strontium glass, soda glass, zinc glass, and fluoroaluminosilicate glass. Also, 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 preferably used. In terms of adhesion and handleability, fine particle silica with an average particle diameter of 0.001 to 10 μm is preferably used. 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 of the above are product names manufactured by Nippon Aerosil Co., Ltd.).

[0039] Examples of the organic filler include polymers of polymethyl methacrylate, polyethyl methacrylate, polyfunctional methacrylate, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber.

[0040] Examples of the composite filler of the inorganic filler and the organic filler include those in which the inorganic filler is dispersed in the organic filler and the inorganic / organic composite filler in which the inorganic filler is coated with various polymers.

[0041] In the present specification, the average particle diameters of the fillers (c) and (f) can be determined by the laser diffraction scattering method or electron microscopic observation of the particles. Specifically, the laser diffraction scattering method is convenient for measuring the particle diameters of particles of 0.1 μm or more, and electron microscopic observation is convenient for measuring the particle diameters of ultrafine particles of less than 0.1 μm. 0.1 μm means the value measured by the laser diffraction scattering method.

[0042] The laser diffraction scattering method can be measured, for example, by a laser diffraction particle size distribution measuring device (SALD-2300: manufactured by Shimadzu Corporation) using an aqueous solution of 0.2% sodium hexametaphosphate as a dispersion medium.

[0043] For electron microscopic observation, for example, a scanning electron microscope (S-4000 type, manufactured by Hitachi, Ltd.) photograph of the filler particles is taken, and the particle diameters of the particles (200 or more) observed in the unit visual field of the photograph are measured using image analysis type particle size distribution measurement software (Mac-View (manufactured by Mountech Co., Ltd.)). At this time, the particle diameter of the particle is obtained as the arithmetic mean value of the longest length and the shortest length of the particle, and the average particle diameter is calculated from the number of particles and the particle diameter thereof.

[0044] In order to improve the hardness, mechanical strength, and handleability, fillers (c) and (f) may be surface-treated in advance with a known surface treatment agent such as a silane coupling agent and then used. Examples of the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, and the like.

[0045] The content of filler (c) in the first paste is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 50 to 80 parts by mass with respect to 100 parts by mass of the first paste. By being 10 parts by mass or more, the strength of the cured composition can be improved, and by being 90 parts by mass or less, a paste property with good handleability can be obtained. Also, the content of filler (f) in the second paste is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 50 to 80 parts by mass with respect to 100 parts by mass of the second paste. By being 10 parts by mass or more, the strength of the cured composition can be improved, and by being 90 parts by mass or less, a paste property with good handleability can be obtained.

[0046] The two-paste type curable dental composition of the present invention contains an isocyanurate compound (e) in the second paste. In order to achieve 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 curable dental 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). Further, the second paste contains the isocyanurate compound (e) and substantially does not contain the polymerizable monomer having an acidic group. In the present specification, "substantially does not contain" means that the content is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less, and particularly preferably 0% by mass.

[0047] The isocyanurate compound (e) used in the present invention is a compound represented by the following general formula (1).

Chemical formula

[0048] R 1 ~R 3 may be the same or different. As the organic group of R 1 ~R 3 , it may be an organic group having a polymerizable group or an organic group not having a polymerizable group. Examples of the polymerizable group include a vinyl group, a (meth)acryloyl group, and an epoxy group. As the organic group, a linear or branched hydrocarbon group is preferable. Examples of the linear or branched hydrocarbon group having a polymerizable group include an allyl group and a glycidyl group. The number of carbon atoms of each organic group of R 1 ~R 3 is R1 ~R 3 at least one of them has 3 or less carbon atoms, and R 1 ~R 3 is not particularly limited as long as the total number of carbon atoms is 15 or less, and may be, for example, 6 or less. R 1 ~R 3 Examples of the substituent of ~R 1 ~R 3 include a halogen atom, a cyano group, an alkoxysilyl group (such as a methoxysilyl group, an ethoxysilyl group, etc.), an alkoxy group (such as a methoxy group, an ethoxy group, etc.), an amino group, and the like. R 1 ~R 3 is preferably 14 or less, more preferably 12 or less in total carbon number. R 1 ~R 3 at least one of them is a linear hydrocarbon group having 3 or less carbon atoms, and R 1 ~R 3 is preferably 15 or less in total carbon number, is a linear hydrocarbon group having a polymerizable group of 3 or less carbon atoms, and R 1 ~R 3 is more preferably 15 or less in total carbon number. On the other hand, like tris(2-(meth)acryloxyethyl)isocyanurate, etc., when R 1 ~R 3 are all organic groups other than hydrocarbon groups, or when R 1 ~R 3 are all linear hydrocarbon groups having 4 or more carbon atoms, or when R 1 ~R 3 is a compound having a total carbon number exceeding 15, the viscosity when made into a paste becomes high and the fluidity becomes low, so that no clear improvement in fluidity after kneading is observed and the effects of the present invention cannot be obtained. Also, R 1 ~R 3 at least one of them needs to be a hydrocarbon group that hardly interacts with the filler. For example, tris(trimethoxysilylpropyl)isocyanurate used in Comparative Examples described later, etc., when R 1 ~R 3 all have substituents such as methoxysilyl groups that easily act with the filler, repulsion between the fillers does not occur and the fluidity does not increase, so that the effects of the present invention cannot be obtained.

[0049] As the isocyanurate compound (e) used in the present invention, triallyl isocyanurate, tripropyl isocyanurate, mono(trimethoxysilylpropyl) diallyl isocyanurate, 1,3-bis(2-allyloxyethyl)-5-methyl isocyanurate, 1-(2-allyloxyethyl)-3,5-dimethyl isocyanurate, 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-dimethyl isocyanurate, 1,3-diacryloyl-5-methyl isocyanurate, 1,3-dimethacryloyl-5-methyl isocyanurate, and 1,3-bis(2-allyloxyethyl)-5-methyl isocyanurate, etc. may be mentioned. Among these, from the viewpoint of the fluidity of the paste after kneading, it is preferable that two or more of R 1 ~R 3 are linear hydrocarbon groups having 3 or less carbon atoms, and it is more preferable that all of R 1 ~R 3 are linear hydrocarbon groups having 3 or less carbon atoms. Such compounds include, for example, triallyl isocyanurate, tripropyl isocyanurate, etc., and among these, triallyl isocyanurate is more preferable. 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, it can be produced by the production method described in JP-A-2015-051972.

[0050] The isocyanurate compound (e) is preferably 0.5 to 7.0 parts by mass, more preferably 1.5 to 3.0 parts by mass, based on 100 parts by mass of the total amount of the two-paste type dental curable composition of the present invention, from the viewpoint of reducing the paste properties, dentin adhesiveness, and variations in the properties of the cured product. Further, in order to enhance the fluidity after mixing and kneading with the first paste, the mass ratio [(a):(e)] of the polymerizable monomer (a) having an acidic group to the isocyanurate compound (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, and even more preferably in the range of 1.0:0.8 to 1.0:1.2.

[0051] 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.

[0052] Typical organic peroxides include hydroperoxides, peroxy esters, ketone peroxides, peroxyketals, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and the like. Among these, hydroperoxides and peroxy esters are preferred, and peroxy esters are particularly preferred because the variation in the working time is small even when the two-paste type dental curable composition of the present invention is stored for a long time. The organic peroxide may be used alone or in combination of two or more.

[0053] Examples of the hydroperoxide include cumene hydroperoxide, t-butyl hydroperoxide, t-hexyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide (hereinafter sometimes abbreviated as "THP"), and the like.

[0054] As the peroxyester, any known peroxyester 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-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-bis(m-toluoylperoxy)hexane, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butyl peroxyacetate, t-butyl peroxy-m-toluoylbenzoate, t-butyl peroxybenzoate (hereinafter sometimes abbreviated as "BPB"), bis(t-butylperoxy)isophthalate, and the like. These can be used alone or in appropriate combinations of two or more.Among these, from the viewpoints of storage stability and reactivity, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, and t-butyl peroxyacetate are preferred, and t-butyl peroxybenzoate is more preferred.

[0055] Examples of the ketone peroxide include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, and the like.

[0056] Examples of the peroxyketal 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.

[0057] Examples of the dialkyl peroxide include α,α-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butyl cumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)3-hexyne, and the like.

[0058] Examples of the diacyl peroxide include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide, m-toluoylbenzoyl peroxide, benzoyl peroxide and the like.

[0059] Examples of the peroxydicarbonate include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, 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.

[0060] Examples of the inorganic peroxide include peroxodisulfate and peroxodiphosphate. Among these, peroxodisulfate is preferable from the viewpoint of curability. Specific examples of the peroxodisulfate include sodium peroxodisulfate, potassium peroxodisulfate (hereinafter sometimes abbreviated as KPS), aluminum peroxodisulfate, and ammonium peroxodisulfate.

[0061] From the viewpoint of curability, the organic peroxide and the inorganic peroxide are preferably 0.01 to 5 parts by mass, more preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer component in the two-paste type dental curable composition of the present invention.

[0062] Examples of the transition metal complex include copper compounds and vanadium compounds.

[0063] As the copper compound, a compound soluble in the polymerizable monomer component is preferred. Specific examples thereof include, as copper carboxylates, copper(II) acetate, copper(II) isobutyrate, copper(II) gluconate, copper(II) citrate, copper(II) phthalate, copper(II) tartrate, copper(II) oleate, copper(II) octylate, copper(II) octenoate, copper(II) naphthenate, copper(II) methacrylate, copper(II) 4-cyclohexylbutyrate; as copper β-diketones, copper(II) acetylacetonate, copper(II) trifluoroacetylacetonate, copper(II) hexafluoroacetylacetonate, copper(II) 2,2,6,6-tetramethyl-3,5-heptanedionate, copper(II) benzoylacetonate; as copper β-ketoesters, copper(II) ethyl acetoacetate; as copper alkoxides, copper(II) methoxide, copper(II) ethoxide, copper(II) isopropoxide, copper(II) 2-(2-butoxyethoxy)ethoxide, copper(II) 2-(2-methoxyethoxy)ethoxide; as copper dithiocarbamate, copper(II) dimethyldithiocarbamate; as salts of copper and inorganic acids, copper(II) nitrate; and copper(II) chloride. These may be used alone or in appropriate combinations of two or more. Among these, from the viewpoints of solubility and reactivity with the polymerizable monomer, copper(II) carboxylates, copper(II) β-diketones, and copper(II) β-ketoesters are preferred, and copper(II) acetate and copper(II) acetylacetonate are particularly preferred.

[0064] From the viewpoint of curability, the content of the copper compound is preferably 0.000005 to 1 part by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the two-paste type dental curable composition of the present invention.

[0065] Examples of the vanadium compound include vanadium acetylacetonate, vanadyl acetylacetonate (hereinafter sometimes abbreviated as "VOAA"), vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, etc., and vanadium acetylacetonate and vanadyl acetylacetonate are particularly preferred.

[0066] From the viewpoint of curability, the content of the vanadium compound is preferably 0.005 to 1 part by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the two-paste type dental curable composition of the present invention.

[0067] 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 the chemical polymerization accelerator (h) include aromatic amines, aliphatic amines, aromatic sulfinate salts, reducing inorganic compounds having sulfur, thiourea derivatives, benzotriazole compounds, and benzimidazole compounds. The chemical polymerization accelerator (h) may be used alone or in combination of two or more.

[0068] As the aromatic amine, known aromatic secondary amines, aromatic tertiary amines, etc. may be used. Examples of the aromatic secondary amine or aromatic tertiary amine 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-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-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 preferable from the viewpoint of redox reactivity.

[0069] Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine, and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine, and N-methylethanolamine; and tertiary aliphatic amines such as N-methyldiethanolamine, N-ethyldiethanolamine, N-n-butyldiethanolamine, N-lauryl diethanolamine, 2-(dimethylamino)ethyl (meth)acrylate, N-methyldiethanolamine di(meth)acrylate, N-ethyldiethanolamine di(meth)acrylate, triethanolamine tri(meth)acrylate, triethanolamine, trimethylamine, triethylamine, and tributylamine. Among these, in terms of redox reactivity, tertiary aliphatic amines are preferred, and among them, N-methyldiethanolamine, triethanolamine, and 2-(dimethylamino)ethyl methacrylate are particularly preferred.

[0070] The content of the aromatic amine or aliphatic amine is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 5 parts by mass, and even more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the two-paste type dental curable composition of the present invention. If the content is 0.01 part 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 more favorably exhibited. Further, if the content is 10 parts by mass or less, it is less likely to affect the color tone stability of the obtained two-paste type dental curable composition.

[0071] Examples of the aromatic sulfinate salts include lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, calcium salts, strontium salts, iron salts, zinc salts, ammonium salts, tetramethylammonium salts, and tetraethylammonium salts of benzenesulfinic acid, p-toluenesulfinic acid, o-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, 2,4,6-trimethylbenzenesulfinic acid, 2,4,6-triisopropylbenzenesulfinic acid (the sodium salt may be abbreviated as "TPBSS" hereinafter), chlorobenzenesulfinic acid, naphthalenesulfinic acid, etc. Among these, from the viewpoints of the curability and storage stability of the composition, lithium salts, sodium salts, potassium salts, magnesium salts, and calcium salts of 2,4,6-trimethylbenzenesulfinic acid and 2,4,6-triisopropylbenzenesulfinic acid are preferred, and lithium salts, sodium salts, potassium salts, magnesium salts, and calcium salts of 2,4,6-triisopropylbenzenesulfinic acid are more preferred.

[0072] From the viewpoint of the mechanical strength of the cured product of the two-paste type dental curable composition obtained, the content of the aromatic sulfinate salt is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 4 parts by mass, and still more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the two-paste type dental curable composition of the present invention.

[0073] Examples of the sulfur-containing reducing inorganic compound include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, dithionites, etc. 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, etc. The sulfur-containing reducing inorganic compound may be used alone or in combination of two or more.

[0074] As the content of the reducing inorganic compound, 0.01 to 15 parts by mass, more preferably 0.05 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass, are preferable with respect to 100 parts by mass of the total amount of the polymerizable monomer component in the two-paste type dental curable composition of the present invention. When the content is 0.01 part by mass or more, it hardly affects the adhesive strength of the obtained two-paste type dental curable composition to a wet body such as dentin. Further, when the content is 15 parts by mass or less, it hardly reduces the mechanical strength of the cured product of the obtained two-paste type dental curable composition.

[0075] Examples of the thiourea derivative include ethylene thiourea, 4,4-dimethylethylene thiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, dicyclohexylthiourea, tetracyclohexylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea, pyridylthiourea, etc. Among these, 4,4-dimethylethylene thiourea, pyridylthiourea, and N-benzoylthiourea are preferable.

[0076] Examples of the benzotriazole compound and / or benzimidazole compound include the compounds represented by the following general formula (3) and (4), respectively.

[0077]

Chemical formula

[0078]

Chemical formula

[0079] In the above general formulas (3) and (4), R 8 ~R 15Each 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.

[0080] R 8 ~R 15 The alkyl group represented by 8 ~ 15 may be linear, branched, or cyclic, and preferably has 1 to 10 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a cyclopentyl group, an n-hexyl group, an isohexyl group, a cyclohexyl group, an n-heptyl group, a cycloheptanyl group, an n-octyl group, a 2-ethylhexyl group, a cyclooctyl group, an n-nonyl group, a cyclononyl group, an n-decyl group, etc. Among these, a methyl group and an ethyl group are particularly preferred.

[0081] R 8 ~R 15 The aryl group represented by 8 ~ 15 preferably has 6 to 10 carbon atoms, and examples include a phenyl group, a naphthyl group, an anthryl group, etc.

[0082] R 8 ~R 15 The alkoxy group represented by 8 ~ 15 may be linear, branched, or cyclic, and preferably has 1 to 8 carbon atoms. Specific examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an n-hexyloxy group, a cyclohexyloxy group, an n-octyloxy group, a 2-ethylhexyloxy group, etc.

[0083] R 8 ~R 15The alkenyl group represented by may be linear, branched, or cyclic, and those having 2 to 6 carbon atoms are preferred. Specific examples include vinyl group, allyl group, methylvinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, and the like.

[0084] R 8 ~R 15 Examples of the aralkyl group represented by include an alkyl group (particularly an alkyl group having 1 to 10 carbon atoms) substituted with an aryl group (particularly an aryl group having 6 to 10 carbon atoms), and specifically, a benzyl group and the like can be mentioned.

[0085] R 8 ~R 15 Examples of the halogen atom represented by include a chlorine atom, a bromine atom, an iodine atom, and the like.

[0086] R 8 ~R 15 Preferably, it is a hydrogen atom or a methyl group. Also, R 8 ~R 15 may be the same or different from each other.

[0087] The benzotriazole compound and the benzimidazole compound may be used alone or in combination of two or more. Specific examples of the benzotriazole compound and the benzimidazole compound include 1H-benzotriazole (hereinafter, may be 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 in terms of the color tone and storage stability of the composition.

[0088] As a method of separately packaging the chemical polymerization initiator (g) and the chemical polymerization accelerator (h) for the two pastes of the two-paste type dental curable composition of the present invention, there is no particular limitation as long as at least the chemical polymerization initiator (g) is contained in one paste and at least the chemical polymerization accelerator (h) is contained in the other paste. However, since solidification may occur during storage if both are present in the same paste, it is preferable that one paste contains only the chemical polymerization initiator (g) (not containing the chemical polymerization accelerator (h)) and the other paste contains only the chemical polymerization accelerator (h) (not containing the chemical polymerization initiator (g)). Further, 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).

[0089] The two-paste type dental curable composition of the present invention may further contain a photoinitiator (i) in at least one of the first paste and the second paste.

[0090] The photoinitiator (i) may be used alone or in combination of two or more. The content of the photoinitiator (i) is preferably in the range of 0.005 to 10 parts by mass, more preferably in the range of 0.01 to 5 parts by mass, 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.

[0091] In addition, in order to enhance the photocurability, a photopolymerization initiator (i) and a polymerization accelerator for a photopolymerization initiator such as aldehydes, thiol compounds, amine compounds, and triazine compounds substituted with a trihalomethyl group may be used in combination. Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, p-n-octyloxybenzaldehyde, and the like. Examples of thiol compounds include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, thiobenzoic acid, and the like. Examples of amine compounds include ethyl 4-(N,N-dimethylamino)benzoate and the like. Note that some amine compounds used as a polymerization accelerator for a photopolymerization initiator also have the function as the chemical polymerization accelerator (h). As the triazine compound substituted with a trihalomethyl group, any known compound can be used without any limitation as long as it is an s-triazine compound having at least one trihalomethyl group such as a trichloromethyl group and a tribromomethyl group. The polymerization accelerator may be used alone or in combination of two or more.

[0092] The polymerization accelerators for a photopolymerization initiator such as aldehydes, thiol compounds, amine compounds, and triazine compounds substituted with a trihalomethyl group may be used alone or in combination of two or more compounds as necessary. The content of the polymerization accelerator for the photopolymerization initiator is 0.005 to 0.3 parts by mass, preferably 0.008 to 0.2 parts by mass, and more preferably 0.01 to 0.1 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.

[0093] In the two-paste type curable dental composition of the present invention, a fluoride ion-releasing substance may be blended for the purpose of imparting acid resistance to dentin. Examples of the fluoride ion-releasing substance include fluoride ion-releasing polymers such as copolymers of methyl methacrylate and methyl methacrylate fluoride; hydrogen fluoride salts of aliphatic or alicyclic primary, secondary or tertiary amines such as cetylamine hydrogen fluoride salt, cyclohexylamine hydrogen fluoride salt, diisobutylamine hydrogen fluoride salt, and triethylamine hydrofluoride salt; and inorganic fillers. Examples of the inorganic filler include the aforementioned fluoroaluminosilicate glass, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, ytterbium fluoride, and the like.

[0094] In the two-paste type curable dental composition of the present invention, a silane coupling agent such as 3-methacryloyloxypropyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, 11-methacryloxyundecyltrimethoxysilane, a silanol condensation catalyst, and a crosslinking agent may be blended.

[0095] In the two-paste type curable dental composition of the present invention, additives such as a stabilizer (polymerization inhibitor) such as 2,6-di-t-butyl-4-methylphenol, a colorant (dye, pigment), a fluorescent agent, and an ultraviolet absorber may be blended. Further, antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxydodecylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydodecylammonium chloride, and triclosan may be blended.

[0096] 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, still more preferably 5000 to 10000 Pa·s, and particularly preferably 6000 to 8000 Pa·s from the viewpoint of handleability at the time of paste collection.

[0097] The viscosity (at 30°C) of the second paste of the two-paste type dental curable composition of the present invention is preferably 1,000 to 35,000 Pa·s, more preferably 3,000 to 20,000 Pa·s, even more preferably 5,000 to 10,000 Pa·s, and particularly preferably 6,000 to 8,000 Pa·s from the viewpoint of handleability at the time of paste collection. Further, it is preferable that the viscosities (at 30°C) of both the first paste and the second paste are 1,000 to 35,000 Pa·s, more preferably both are 3,000 to 20,000 Pa·s, even more preferably both are 5,000 to 10,000 Pa·s, and particularly preferably both are 6,000 to 8,000 Pa·s.

[0098] The ratio of the viscosities (at 30°C) of the first paste and the second paste of the two-paste type dental curable composition of the present invention (viscosity of the first paste / viscosity of the second paste) is preferably 0.8 to 1.2, and more preferably 0.9 to 1.1 from the viewpoint of easy collection in a desired quantitative ratio. The viscosities of the viscosity of the first paste (at 30°C) and the viscosity of the second paste (at 30°C) and the ratio of their viscosities (viscosity of the first paste / viscosity of the second paste) can be adjusted, for example, by selecting the types and contents of the polymerizable monomers and fillers blended in each paste. The method for measuring the viscosity of the composition described in this specification is as described in the examples below.

[0099] The two-paste type dental curable composition of the present invention can be produced, for example, by mixing components other than the powdery components (such as fillers (c) and (f)), obtaining a solution, and adding the powdery components.

[0100] The present invention includes embodiments in which the above configurations are variously combined within the scope of the technical idea of the present invention as long as the effects of the present invention are achieved.

Examples

[0101] Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples, and many modifications are possible by those with ordinary knowledge in the art within the scope of the technical idea of the present invention. The abbreviations and symbols used below are as follows.

[0102] [Polymerizable monomer (a) having an acidic group] MDP: 10-Methacryloyloxydecyl dihydrogen phosphate

[0103] [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)

[0104] [Fillers (c) and (f)] F1: Silane-treated quartz powder: Quartz (manufactured by MARUWA QUARTZ) was pulverized with a ball mill to obtain quartz powder with an average particle diameter of about 4.5 μm. 3 parts by mass of 3-methacryloyloxypropyltrimethoxysilane was used to perform surface treatment on 100 parts by mass of this quartz powder to obtain silane-treated quartz powder. R972: Fine particle silica "Aerosil (registered trademark) R972" manufactured by Nippon Aerosil Co., Ltd., average particle diameter: 16 nm F2: Silane-treated barium glass powder: Barium glass (manufactured by Estec Co., product code "Raysorb E-3000") was pulverized with a ball mill to obtain barium glass powder with an average particle diameter of about 2.4 μm. 3 parts by mass of 3-methacryloyloxypropyltrimethoxysilane was used to perform surface treatment on 100 parts by mass of this barium glass powder to obtain silane-treated barium glass powder. Alumina: manufactured by Nippon Aerosil Co., Ltd., product name "AEROXIDE (registered trademark) AluC", average particle diameter: 20 nm

[0105] [Isocyanurate compound (e)] TAIC: Triallyl isocyanurate MSPI: Mono(trimethoxysilylpropyl)diallyl isocyanurate TSPI: Tris(trimethoxysilylpropyl) isocyanurate

[0106] [Chemical polymerization initiator (g)] Copper(II) acetate BPB: t-Butyl peroxybenzoate KPS: Potassium peroxydisulfate

[0107] [Chemical polymerization accelerator (h)] TPBSS: Sodium 2,4,6-triisopropylbenzenesulfinate DEPT: N,N-Bis(2-hydroxyethyl)-p-toluidine BTA: 1H-Benzotriazole NAA: Sodium sulfite

[0108] [Photoinitiator (i)] CQ: Camphorquinone

[0109] [Others] 11-MUS: 11-Methacryloyloxyundecyltrimethoxysilane (silane coupling agent) PDE: Ethyl 4-(N,N-dimethylamino)benzoate (polymerization accelerator for photoinitiator) BHT: 2,6-Di-t-butyl-4-methylphenol (stabilizer)

[0110] [Examples 1 to 5 and Comparative Examples 1 to 4] The first paste and the second paste having the compositions shown in Table 1 were prepared. The first paste was prepared by formulating components other than the powdery components (fillers), stirring to obtain a uniform solution, kneading the powdery components, and defoaming. The powdery components in the first paste were in a dispersed state in the powdery state. Also, the second paste was prepared by formulating components other than the powdery components (fillers and TPBSS), stirring to obtain a uniform solution, kneading the powdery components, and defoaming. The powdery components in the second paste were in a dispersed powdery state. The two agents were mixed at a mass ratio of 1:1, and the mixture was used for evaluation as a dental curable composition. The shear bond strength to dentin, the viscosities of the first paste and the second paste, and the fluidity immediately after mixing and kneading the first paste and the second paste were tested by the method shown below. The results are shown in Table 1.

[0111] 〔Shear bond strength to dentin〕 The labial surface of the bovine mandibular anterior teeth was polished with #80 silicon carbide paper (manufactured by Nippon Gainen Co., Ltd.) under running water to expose the flat surface of the dentin. The teeth were embedded in dental composite resin in a stainless-steel ring so that this flat surface was exposed, and the flat surface was further polished with silicon carbide paper up to #1000 (manufactured by Nippon Gainen Co., Ltd.) under running water to obtain a smooth surface of the dentin. The first paste and the second paste of the curable dental composition of the present invention were mixed and kneaded with a spatula for 10 seconds, and the mixture was placed on one end face (circular cross-section) of a stainless-steel cylindrical chip (diameter 3 mm, length 1.0 cm). The end face on which the curable dental composition was placed was placed on the smooth surface of the dentin. Then, a load of 500 g was applied vertically from above the stainless-steel cylindrical chip, and the margin part between the stainless-steel cylindrical chip and the smooth surface was irradiated with a dental polymerization light irradiator (Pentacure 2000, manufactured by Morita Corporation) for 2 to 5 seconds to remove the excess cement. Then, it was irradiated with a dental polymerization light irradiator (Pentacure 2000, manufactured by Morita Corporation) for 10 seconds. After 10 minutes, the 500 g load was removed to obtain a test sample. Five test samples were prepared. The test samples were immersed in water at 37°C for 24 hours, and then the shear bond strength was examined. This shear bond strength represents the initial shear bond strength. The shear bond strength was measured using a universal testing machine (manufactured by Shimadzu Corporation, trade name "AG-I 100kN") under the condition of a crosshead speed of 1 mm / min. The shear bond strength in the table is the average value of the measured values for each of the five test samples. This value of the shear bond strength to the dentin was used as an index of the shear bond strength to the dental tissue, and the variation value of the shear bond strength (CV value (coefficient of variation) = standard deviation / average value) was calculated. The shear bond strength to the dental tissue is preferably 7 MPa or more, more preferably 9 MPa or more, and even more preferably 11 MPa or more. The variation value of the shear bond strength (CV value (coefficient of variation)) is preferably 0.45 or less, more preferably 0.40 or less, and even more preferably 0.35 or less.

[0112] 〔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, conforming to JIS K-7117-2:1999, cone-plate type), with a cone rotor of 0.8°×R12, the measurement was carried out at a sample volume of 0.5 mL and 30 °C. After performing preheating for 1 minute, the measurement was started, and the measured value after 3 minutes was taken as its viscosity. The viscosities in the table are the average values when each sample was measured three times. If the paste viscosity (30 °C) before mixing is 1000 to 35000 Pa·s, it is a paste property that is easy to collect. If the ratio of the viscosities (30 °C) of the first paste to the second paste (viscosity of the first paste / viscosity of the second paste) is 0.8 to 1.2, it is easy to collect an equal amount when extruded simultaneously from the syringe, has good handling properties, and stable performance can be obtained.

[0113] 〔Flowability after mixing and kneading〕 The first paste and the second paste were mixed and kneaded on a kneading paper with a spatula for 10 seconds and evaluated by hand feeling (N = 1). <Judgment criteria> ◎: There is no resistance during mixing and kneading, the fluidity after mixing and kneading is high, and it spreads by its own weight when the paste is gathered. 〇: There is no resistance during mixing and kneading, the fluidity after mixing and kneading is high, but a part of the shape remains when the paste is gathered. ×: There is resistance during mixing and kneading, the fluidity after mixing and kneading is low, and the shape remains when the paste is gathered.

[0114]

Table 1

[0115] As shown in Table 1, the two-paste type dental curable compositions of Examples 1 to 5 showed excellent adhesiveness to dentin and high fluidity after mixing and kneading. In addition, since the viscosity of each paste was also within a specific range, the handling property during paste collection was also excellent. On the other hand, although the two-paste type dental curable compositions prepared in Comparative Examples 1 to 3 had excellent handling properties during paste collection, their fluidity after mixing and kneading was low, the variation in adhesive strength was large, and stable adhesiveness to dentin could not be obtained. Also, in Comparative Examples 1 and 2 that did not contain an isocyanurate compound in the second paste, sufficient fluidity after mixing and kneading could not be obtained, the CV value of the adhesiveness to dentin was also higher than that of Examples 1 to 5, and it was shown that there was a large variation in the properties of the cured product. Comparative Example 3 used an isocyanurate compound in which none of R 1 ~R 3 was a linear hydrocarbon group having 3 or less carbon atoms, but the fluidity after mixing and kneading was low, stable adhesiveness to dentin could not be obtained, the CV value of the adhesiveness to dentin was also higher than that of Examples 1 to 5, and it was shown that there was also a large variation in the properties of the cured product. In Comparative Example 4, since the polymerizable monomer having an acidic group and the isocyanurate compound were contained in the first paste, the viscosities of the first paste and the second paste were greatly different, the handling property during paste collection was poor, and it was difficult to uniformly mix the paste even during mixing and kneading. Stable adhesion to dentin could not be obtained, the CV value of the adhesiveness to dentin was also higher than that of Examples 1 to 5, and it was shown that there was a large variation in the properties of the cured product.

Industrial Applicability

[0116] The two-paste type dental curable composition of the present invention can be suitably used for dental restoration treatment. Further, the two-paste type dental curable composition of the present invention can be suitably used as a dental cement, and particularly suitably used as a self-adhesive cement.

Claims

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); It is composed of a second paste containing a polymerizable monomer (d) having no acidic group, an isocyanurate compound (e), and a filler (f), One of the pastes contains a chemical polymerization initiator (g), and the other paste contains a chemical polymerization accelerator (h), The isocyanurate compound (e) is at least one selected from the group consisting of triallyl isocyanurate, tripropyl isocyanurate, mono(trimethoxysilylpropyl)diallyl isocyanurate, 1,3-bis(2-allyloxyethyl)-5-methyl isocyanurate, 1-(2-allyloxyethyl)-3,5-dimethyl isocyanurate, 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-dimethyl isocyanurate, 1,3-diacryloyl-5-methyl isocyanurate, 1,3-dimethacryloyl-5-methyl isocyanurate, and 1,3-bis(2-allyloxyethyl)-5-methyl isocyanurate, A two-paste type dental curable composition.

2. The two-paste type dental curable composition according to Claim 1, wherein the viscosity (30°C) of the second paste is 1000 to 35000 mPa·s.

3. The two-paste type dental curable composition according to Claim 1 or 2, wherein the viscosities (30°C) of the first paste and the second paste are both 1000 to 35000 mPa·s.

4. The two-paste type dental curable composition according to any one of Claims 1 to 3, wherein the ratio of the viscosities (30°C) of the first paste to the second paste (viscosity of the first paste / viscosity of the second paste) is 0.8 to 1.

2.

5. The 2-paste type dental curable composition 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 in 100 parts by mass of the total amount of the 2-paste type dental curable composition.

6. The 2-paste type dental curable composition according to any one of claims 1 to 5, further comprising a photopolymerization initiator (i) in at least one of the first paste and the second paste.

7. The 2-paste type dental curable composition according to any one of claims 1 to 6, wherein the isocyanurate compound (e) is triallyl isocyanurate.

8. A dental cement comprising the 2-paste type dental curable composition according to any one of claims 1 to 7.

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