High-flowability dental curable composition

Abstract

To provide a dental curable composition having X-ray opacity and high flowability, and exhibiting good operability when contained in a bottle container as well as excellent long-term stability.SOLUTION: A dental curable composition including (A) a polymerizable monomer, (B) a polymerization initiator, and (C) a filler, wherein the component (C) includes (C1) an inorganic filler having X-ray opacity and (C2) hydrophobized silica fine particles having a primary particle diameter of less than 0.1 μm, the component (C1) is surface-treated with a hydrophobic silane coupling agent such as, for example, 3-methacryloylpropyltrimethoxysilane, a mass ratio of the component (C1) to the silane coupling agent is 100:0.01 to 1, and the dental curable composition has a flowability of 10 mm or more, the flowability being a distance moved by the dental curable composition after 1 minute when 0.05 g of the dental curable composition is placed in a lump on a slide glass plane set horizontally and the slide glass is fixed vertically with respect to a horizontal plane.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to highly flowable dental hardenable compositions. [Background technology]

[0002] Highly fluid dental curable compositions are used in dental adhesives, dental composite resins, dental core buildup materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicures, dental 3D printer materials, and orthodontic materials.

[0003] Patent Document 1 discloses a dental adhesive composition having X-ray contrast properties, and Patent Document 2 discloses a two-component dental adhesive composition. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2006-219439 [Patent Document 2] Patent Publication No. 2022-120710 Summary of the Invention [Problem to be solved by the invention]

[0005] However, these compositions have had problems in terms of good handling and long-term stability when the curable composition having X-ray contrast properties is used in a bottle container.

[0006] An object of the present invention is to provide a dental curable composition that has X-ray contrast properties, high fluidity, good handling properties even when placed in a bottle container, and excellent long-term stability. [Means for solving the problem]

[0007] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by preparing a specific dental hardenable composition.

[0008] The present disclosure provides the following: (Item 1) A dental curable composition comprising (A) a polymerizable monomer, (B) a polymerization initiator, and (C) a filler, (C) Component (C1) Inorganic filler having X-ray contrast properties and (C2) Hydrophobized silica fine particles having a primary particle diameter of less than 0.1 μm, Component (C1) is surface-treated with a hydrophobic silane coupling agent of formula 1, the mass ratio of component (C1) to formula 1 (component (C1) : formula 1) is 100:0.01 to 1; A dental hardenable composition having a fluidity of 10 mm or more, which is the distance traveled by the dental hardenable composition after 1 minute from when 0.05 g of the composition is placed in a lump on the flat surface of a horizontally placed slide glass and the slide glass is fixed perpendicular to the horizontal surface. [Formula (1)] [ka] (In the formula, R1 represents an alkyl group having 1 to 11 carbon atoms which may have one or more selected from halogen, aromatic ring, aliphatic ring, polymerizable group, -O-, -S-, -NH-, -C(O)-O-, -OC(O)-, -C(O)-NH-, -OC(O)-NH-, and -NH-C(O)-O-; R2, R3, and R4 represent an alkoxy group having 1 to 4 carbon atoms, an alkyl group, or a halogen, and may be the same as or different from one another.) (Item 2) (C1) The dental hardenable composition according to Item 1, wherein the inorganic filler having radiopaque properties is an aluminosilicate glass containing one or more elements selected from strontium, barium, lanthanum, zirconium, ytterbium, and gadolinium. (Item 3) (C1) The dental curable composition according to Item 1, wherein the inorganic filler having X-ray contrast properties is surface-treated with an acidic compound and a silane coupling agent. (Item 4) (C1) The dental curable composition according to Item 2, wherein the inorganic filler having X-ray contrast properties has been surface-treated with an acidic compound and a silane coupling agent. (Item 5) 2. The dental curable composition according to item 1, wherein the amount of the surface treatment of the (C1) inorganic filler having X-ray contrast properties with a silane coupling agent is 0.01 to 0.50 parts by mass per 100 parts by mass of the (C1) inorganic filler having X-ray contrast properties. (Item 6) 3. The dental curable composition according to Item 2, wherein the amount of the surface treatment of the (C1) inorganic filler having X-ray contrast properties with a silane coupling agent is 0.01 to 0.50 parts by mass per 100 parts by mass of the (C1) inorganic filler having X-ray contrast properties. (Item 7) A two-step dental adhesive composition kit comprising a first agent and a second agent which is a dental curable composition, the kit being used by applying the first agent to an adherend and then further applying the second agent; The first agent is For 100 parts by mass of the first agent (A1) 2 to 30 parts by mass of a polymerizable monomer having an acidic group (A2) 0 to 50 parts by mass of a polymerizable monomer having no acidic group (D) 5 to 50 parts by mass of water, and (E) containing 0 to 50 parts by mass of a volatile organic solvent, The second agent is For 100 parts by mass of the polymerizable monomer (A) contained in the second agent (B) 0.5 to 5.0 parts by mass of a polymerization initiator (C1) 40 to 120 parts by mass of an inorganic filler having X-ray contrast properties, and (C2) 3 to 20 parts by mass of hydrophobic silica fine particles with a primary particle diameter of less than 0.1 μm 2. A dental adhesive composition comprising a first agent and a second agent according to item 1, characterized in that it comprises: (Item 8) A two-step dental adhesive composition kit comprising a first agent and a second agent which is a dental curable composition, the kit being used by applying the first agent to an adherend and then further applying the second agent; The first agent is For 100 parts by mass of the first agent (A1) 2 to 30 parts by mass of a polymerizable monomer having an acidic group (A2) 0 to 50 parts by mass of a polymerizable monomer having no acidic group (D) 5 to 50 parts by mass of water, and (E) containing 0 to 50 parts by mass of a volatile organic solvent, The second agent is For 100 parts by mass of the polymerizable monomer (A) contained in the second agent (B) 0.5 to 5.0 parts by mass of a polymerization initiator (C1) 40 to 120 parts by mass of an inorganic filler having X-ray contrast properties, and (C2) 3 to 20 parts by mass of hydrophobic silica fine particles with a primary particle diameter of less than 0.1 μm 3. A dental adhesive composition comprising a first agent and a second agent according to item 2, characterized in that it comprises: (Item 9) A two-step dental adhesive composition kit comprising a first agent and a second agent which is a dental curable composition, the kit being used by applying the first agent to an adherend and then further applying the second agent; The first agent is For 100 parts by mass of the first agent (A1) 2 to 30 parts by mass of a polymerizable monomer having an acidic group (A2) 0 to 50 parts by mass of a polymerizable monomer having no acidic group (D) 5 to 50 parts by mass of water, and (E) containing 0 to 50 parts by mass of a volatile organic solvent, The second agent is For 100 parts by mass of the polymerizable monomer (A) contained in the second agent (B) 0.5 to 5.0 parts by mass of a polymerization initiator (C1) 40 to 120 parts by mass of an inorganic filler having X-ray contrast properties, and (C2) 3 to 20 parts by mass of hydrophobic silica fine particles with a primary particle diameter of less than 0.1 μm 4. A dental adhesive composition comprising a first agent and a second agent according to item 3, characterized in that it comprises: (Item 10) A two-step dental adhesive composition kit comprising a first agent and a second agent which is a dental curable composition, the kit being used by applying the first agent to an adherend and then further applying the second agent; The first agent is For 100 parts by mass of the first agent (A1) 2 to 30 parts by mass of a polymerizable monomer having an acidic group (A2) 0 to 50 parts by mass of a polymerizable monomer having no acidic group (D) 5 to 50 parts by mass of water, and (E) containing 0 to 50 parts by mass of a volatile organic solvent, The second agent is For 100 parts by mass of the polymerizable monomer (A) contained in the second agent (B) 0.5 to 5.0 parts by mass of a polymerization initiator (C1) 40 to 120 parts by mass of an inorganic filler having X-ray contrast properties, and (C2) 3 to 20 parts by mass of hydrophobic silica fine particles with a primary particle diameter of less than 0.1 μm 5. A dental adhesive composition comprising a first agent and a second agent according to item 4, characterized in that it comprises: (Item 11) A two-step dental adhesive composition kit comprising a first agent and a second agent which is a dental curable composition, the kit being used by applying the first agent to an adherend and then further applying the second agent; The first agent is For 100 parts by mass of the first agent (A1) 2 to 30 parts by mass of a polymerizable monomer having an acidic group (A2) 0 to 50 parts by mass of a polymerizable monomer having no acidic group (D) 5 to 50 parts by mass of water, and (E) containing 0 to 50 parts by mass of a volatile organic solvent, The second agent is For 100 parts by mass of the polymerizable monomer (A) contained in the second agent (B) 0.5 to 5.0 parts by mass of a polymerization initiator (C1) 40 to 120 parts by mass of an inorganic filler having X-ray contrast properties, and (C2) 3 to 20 parts by mass of hydrophobic silica fine particles with a primary particle diameter of less than 0.1 μm 6. A dental adhesive composition comprising a first agent and a second agent according to item 5, characterized in that it comprises: (Item 12) A two-step dental adhesive composition kit comprising a first agent and a second agent which is a dental curable composition, the kit being used by applying the first agent to an adherend and then further applying the second agent; The first agent is For 100 parts by mass of the first agent (A1) 2 to 30 parts by mass of a polymerizable monomer having an acidic group (A2) 0 to 50 parts by mass of a polymerizable monomer having no acidic group (D) 5 to 50 parts by mass of water, and (E) containing 0 to 50 parts by mass of a volatile organic solvent, The second agent is For 100 parts by mass of the polymerizable monomer (A) contained in the second agent (B) 0.5 to 5.0 parts by mass of a polymerization initiator (C1) 40 to 120 parts by mass of an inorganic filler having X-ray contrast properties, and (C2) 3 to 20 parts by mass of hydrophobic silica fine particles with a primary particle diameter of less than 0.1 μm 7. A dental adhesive composition comprising a first agent and a second agent according to item 6, characterized in that it comprises: [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a dental curable composition that has X-ray contrast properties, high fluidity, good handling properties even when placed in a bottle container, and excellent long-term stability. [Brief explanation of the drawings]

[0010] [Figure 1] Bond container used in the example "Evaluation 3: Good dischargeability" [Figure 2] Bond container used in the example "Evaluation 3: Good dischargeability" [Figure 3] The spout cap of the bond container used in the example "Evaluation 3: Good drainability" [Figure 4]Bond container used in the example "Evaluation 3: Good dischargeability" MODE FOR CARRYING OUT THE INVENTION

[0011] Dental hardenable compositions are materials that can be used to restore the anatomical shape of carious areas or missing teeth, or to improve tooth alignment and occlusion. Various dental hardenable compositions are available depending on the application. When used to restore the anatomical shape of carious areas or missing teeth, dental hardenable compositions preferably have radiopaque properties. In clinical settings, X-ray photography is sometimes performed to diagnose secondary caries. This technique allows for diagnosis of carious areas because carious areas have reduced radiopaque properties compared to healthy teeth. When a dental hardenable composition with radiopaque properties is used to restore the anatomical shape of carious areas or missing teeth, even if caries occurs around the dental hardenable composition, diagnosis becomes easier due to the difference in radiopaque properties between the carious area and the dental hardenable composition.

[0012] On the other hand, when a dental hardenable composition is used to restore the anatomical shape of a carious area or a missing tooth, if the dental hardenable composition does not have sufficient radiopacity, the degree of radiopacity will be the same as that of the carious area, making diagnosis complicated. For this reason, dental hardenable compositions with radiopacity have been developed.

[0013] One known method for imparting radiopaque properties to dental hardenable compositions is to incorporate fillers containing elements such as strontium, barium, lanthanum, zirconium, ytterbium, and gadolinium into the dental hardenable compositions. However, fillers containing such elements tend to have a high specific gravity, resulting in a large difference in specific gravity between the filler and the polymerizable monomer, leading to sedimentation. On the other hand, if the filler is not hydrophobized to reduce its affinity with the polymerizable monomer, the dental hardenable composition may thicken or have a reduced fluidity, failing to achieve the desired fluidity. For these reasons, it has been difficult to achieve both radiopaque properties and the stability of the dental hardenable compositions.

[0014] As a result of investigations, the inventors have found that by allowing a filler to coexist with a smaller amount of a silane coupling agent than usual in the composition, and by including hydrophobic silica fine particles as a filler, the filler is less likely to settle, resulting in a dental hardenable composition with good operability, and have completed the present invention.

[0015] [(A) Polymerizable Monomer] The polymerizable monomer (A) (also referred to as "component (A)" in the present invention) contained in the dental adhesive composition of the present invention can be any known polymerizable monomer without any limitations. The polymerizable monomer (A) includes (A1) a polymerizable monomer having an acidic group and (A2) a polymerizable monomer not having an acidic group. In the polymerizable monomer described in the present invention, the polymerizable group preferably exhibits radical polymerizability. Specifically, from the viewpoint of ease of radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. In this specification, "(meth)acrylic" means acrylic and / or methacrylic, "(meth)acryloyl" means acryloyl and / or methacryloyl, "(meth)acrylate" means acrylate and / or methacrylate, and "(meth)acrylamide" means acrylamide and / or methacrylamide. Polymerizable monomers having a substituent at the α-position of the (meth)acrylic group and / or (meth)acrylamide group can also be preferably used. In this specification, silane coupling agents having a polymerizable group and particles surface-treated with a silane coupling agent having a polymerizable group are not classified as (A) polymerizable monomers.

[0016] [(A1) Polymerizable Monomer Having an Acidic Group] The dental adhesive composition of the present invention contains in the first agent (A1) a polymerizable monomer having an acidic group (also referred to as "component (A1)" in the present invention). The polymerizable monomer having an acidic group (A1) can be any polymerizable monomer having one or more polymerizable groups and at least one acidic group such as a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonate group, a sulfone group, or a carboxylic acid group, and the like, without any limitations. The inclusion of a polymerizable monomer having an acidic group can impart adhesion to tooth structures and prosthetic devices.

[0017] Specific examples of the polymerizable monomer having a phosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyethyl dihydrogen phosphate, 9-(meth)acryloyloxypropyl dihydrogen phosphate, 10-(meth)acryloyloxybutyl dihydrogen phosphate, 11-(meth)acryloyloxybutyl dihydrogen phosphate, 12-(meth)acryloyloxybutyl dihydrogen phosphate, 13-(meth)acryloyloxybutyl dihydrogen phosphate, 14-(meth)acryloyloxybutyl dihydrogen phosphate, 15-(meth)acryloyloxypentyl dihydrogen phosphate, 16-(meth)acryloyloxyhexyl dihydrogen phosphate, 17-(meth)acryloyloxyheptyl dihydrogen phosphate, 18-(meth)acryloyloxybutyl dihydrogen phosphate, 19-(meth)acryloyloxybutyl dihydrogen phosphate, 20-(meth)acryloyloxybutyl dihydrogen phosphate, 21-(meth)acryloyloxybutyl dihydrogen phosphate, 22-(meth)acryloyloxybutyl dihydrogen phosphate, 23-(meth)acryloyloxybutyl dihydrogen phosphate, 24-(meth)acryloyloxybutyl dihydrogen phosphate, 25-(meth)acryloyloxybutyl dihydrogen phosphate, 26-(meth)acryloyloxyhexyl dihydrogen phosphate, 27-(meth)acryloyloxyhexyl dihydrogen phosphate, Acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate , bis[2-(meth)acryloyloxyethyl]hydrogenphosphate, bis[4-(meth)acryloyloxybutyl]hydrogenphosphate, bis[6-(meth)acryloyloxyhexyl]hydrogenphosphate, bis[8-(meth)acryloyloxyoctyl]hydrogenphosphate, bis[9-(meth)acryloyloxynonyl]hydrogenphosphate, bis[10-(meth)acryloyloxydecyl]hydrogenphosphate, 1,3-di(meth)acryloyl and bis[2-(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; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0018] Specific examples of the polymerizable monomer having a pyrophosphate group include one or more selected from 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; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0019] Specific examples of polymerizable monomers 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, and 9-(meth)acryloyloxyno and (meth)acryloyloxycosyl dihydrogenthiophosphate; 1-(meth)acryloyloxydecyl dihydrogenthiophosphate; 10-(meth)acryloyloxydecyl dihydrogenthiophosphate; 11-(meth)acryloyloxyundecyl dihydrogenthiophosphate; 12-(meth)acryloyloxydodecyl dihydrogenthiophosphate; 16-(meth)acryloyloxyhexadecyl dihydrogenthiophosphate; 20-(meth)acryloyloxyicosyl dihydrogenthiophosphate; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0020] Specific examples of the polymerizable monomer having a phosphonic acid group include one or more selected from 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxydecyl-3-phosphonoacetate; acid chlorides, alkali metal salts, and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0021] Specific examples of polymerizable monomers having a sulfonic acid group include one or more selected from 2-(meth)acrylamide-2-methylpropanesulfonic acid, 2-sulfoethyl(meth)acrylate, and the like.

[0022] Polymerizable monomers having a carboxylic acid group are classified into (meth)acrylic compounds having one carboxyl group in the molecule, and (meth)acrylic compounds having multiple carboxyl groups in the molecule. Specific examples of (meth)acrylic compounds having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid, and 3-(meth)acryloyloxybenzoic acid. and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.Specific examples of the (meth)acrylic compound having multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, 4 ...4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 4-(meth and 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate; acid anhydrides and acid halides thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

[0023] [(A2) Polymerizable monomer having no acidic group] The (A2) polymerizable monomer having no acidic group (also referred to as "component (A2)" in the present invention) can be any polymerizable monomer having one or more polymerizable groups and no acidic group, and can be used without any restrictions. The (A2) polymerizable monomer having no acidic group includes one or more types selected from polymerizable monomers having one radically polymerizable group, polymerizable monomers having two radically polymerizable groups, and polymerizable monomers having three or more radically polymerizable groups.

[0024] Specific examples of (A2) polymerizable monomers having one radically polymerizable group among polymerizable monomers having no acidic group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, propylene glycol mono(meth)acrylate, glycerol mono(meth)acrylate, erythritol mono(meth)acrylate, N-methylol (meth)acrylamide, Examples of the acrylate include one or more selected from N-hydroxyethyl(meth)acrylamide, N,N-(dihydroxyethyl)(meth)acrylamide, methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, benzyl(meth)acrylate, lauryl(meth)acrylate, 2,3-dibromopropyl(meth)acrylate, 3-(meth)acryloyloxypropyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, and (meth)acrylamide.

[0025] (A2) Specific examples of polymerizable monomers having two radically polymerizable groups among polymerizable monomers having no acidic group include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, )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)acryloyloxydiethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyditriethoxyphenyl) 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, glycerol di(meth)acrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,Examples of the methacryloyloxy-2-hydroxypropoxy-ethane include one or more selected from 2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as "UDMA"), and 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane.

[0026] Specific examples of (A2) polymerizable monomers having three radically polymerizable groups among polymerizable monomers having no acidic group include one or more selected from trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate, and 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane.

[0027] In addition to these polymerizable monomers, oligomers or prepolymers having at least one polymerizable group in the molecule may be used without any limitation. Furthermore, there is no problem even if the same molecule has a substituent such as a fluoro group. The above-described polymerizable monomers may be used alone or in combination.

[0028] The dental curable composition of the present invention contains a polymerizable monomer (A). The dental curable composition of the present invention preferably contains only a polymerizable monomer (A2) that does not have an acidic group as the polymerizable monomer (A). When the dental curable composition contains a polymerizable monomer (A1) that has an acidic group, it is necessary to select an inorganic filler (C1) having radiopaque properties that does not interact with the polymerizable monomer (A1). If an inorganic filler that interacts with the polymerizable monomer (A1) is selected, the operability of the dental curable composition may be reduced. Regardless of the type of inorganic filler (C1) having radiopaque properties, the amount of the polymerizable monomer (A1) that can be blended is preferably 0 to 5 parts by mass, more preferably 0 to 1 part by mass, and even more preferably zero, per 100 parts by mass of the polymerizable monomer (A) contained in the dental curable composition.

[0029] <(B) Polymerization initiator> The dental curable composition of the present invention contains a polymerization initiator (B) (also referred to as "component (B)" in the present invention). Polymerization methods that can be suitably used for the dental curable composition of the present invention include photopolymerization, chemical polymerization, or dual polymerization that includes both of these. The dental curable composition of the present invention preferably contains a photopolymerization initiator.

[0030] [Photopolymerization initiator] When the dental curable composition of the present invention does not contain a chemical polymerization initiator, it contains a photopolymerization initiator. A photopolymerization initiator is a polymerization initiator that can initiate polymerization by irradiating light. The photopolymerization initiator that can be used in the dental adhesive composition of the present invention can be one or more selected from photosensitizers, photoacid generators, photopolymerization accelerators, etc. These can be any known compounds that are commonly used and can be used without any restrictions.

[0031] Specific examples of photosensitizers that can be used in the dental curable composition of the present invention include one or more selected from α-diketones, benzoin alkyl ethers, thioxanthones, benzophenones, acylphosphine oxides, and acylgermanium compounds. Examples of α-diketones include one or more selected from camphorquinone, camphorquinonecarboxylic acid, and camphorquinone sulfonic acid. Examples of benzoin alkyl ethers include one or more selected from benzoin, benzoin methyl ether, and benzoin ethyl ether. Examples of thioxanthones include one or more selected from 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone. Examples of benzophenones include one or more selected from benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone. Examples of the acylphosphine oxides include one or more selected from diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, etc. Examples of the acylgermanium compounds include one or more selected from bisbenzoyldiethylgermanium, bisbenzoyldimethylgermanium, etc.

[0032] Photoacid generators that can be used in the dental curable composition of the present invention include one or more compounds selected from the group consisting of triazine compounds, iodonium salt compounds, sulfonium salt compounds, and sulfonic acid ester compounds. Among these, one or more compounds selected from the group consisting of triazine compounds and iodonium salt compounds are preferred because of their high polymerizability when used in combination with a sensitizer. Specific examples of preferred iodonium salt compounds include one or more compounds selected from the group consisting of 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, bis(4-tert-butylphenyl)iodonium tetrakis(pentafluorophenyl)borate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, and diphenyliodonium-2-carboxylate monohydrate.

[0033] The photopolymerization accelerator that can be used in the dental curable composition of the present invention is an amine compound, such as one or more selected from p-dimethylaminobenzoic acid ethyl ester, triethanolamine, triisopropanolamine, tribenzylamine, dibenzylglycine ethyl ester, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, and N,N-diisopropylaminoethyl methacrylate.

[0034] A suitable combination of polymerization initiators for use in the dental curable composition of the present invention is a combination of a photosensitizer and an amine compound, more specifically, a combination of an α-diketone compound containing camphorquinone and a dialkylbenzoic acid ester compound containing p-dimethylaminobenzoic acid ethyl ester. In addition, it is preferable to include hydroxyl-containing amine compounds such as triethanolamine, triisopropanolamine, N,N-bis(2-hydroxyethyl)-p-toluidine, and N,N-bis(2-hydroxypropyl)-p-toluidine, or to include one or more photopolymerization accelerators selected from N,N-dimethylaminoethyl acrylate and N,N-diethylaminoethyl acrylate.

[0035] [Chemical polymerization initiator] The dental curable composition of the present invention can contain a chemical polymerization initiator. Chemical polymerization is a polymerization method that hardens the composition without requiring special equipment such as a light irradiator, and the chemical polymerization initiator is a polymerization initiator that can start chemical polymerization. Any commonly used known compound can be used as the chemical polymerization initiator without any restrictions.

[0036] Specific examples of transition metal compounds that can be preferably used in the dental hardenable composition of the present invention include copper (Cu) compounds and vanadium (V) compounds. As the copper (Cu) compound, one or more compounds selected from copper chloride (monovalent), copper bromide (monovalent), copper chloride (divalent), copper acetate (divalent), copper gluconate (divalent), copper acetylacetonate (divalent), and copper methacrylate (divalent) can be used. As the vanadium compound, one or more compounds selected from vanadium acetylacetonate (trivalent), divanadium tetroxide (tetravalent), vanadyl acetylacetonate (tetravalent), vanadium oxide stearate (tetravalent), vanadyl oxalate (tetravalent), vanadyl sulfate (tetravalent), oxobis(1-phenyl-1,3-butanedionato)vanadium (tetravalent), bis(maltolate)oxovanadium (tetravalent), vanadium pentoxide (pentavalent), and sodium metavanadate (pentavalent).

[0037] Specific examples of thiourea compounds that can be used in the dental curable composition of the present invention include one or more selected from dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl)thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, N-benzylthiourea, 1,3-dicyclohexylthiourea, N,N'-diphenylthiourea, 1,3-di(p-tolyl)thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea, and dicyclohexylthiourea. Among these, one or more selected from (2-pyridyl)thiourea, N-acetylthiourea, N-benzoylthiourea, and N-benzylthiourea can be preferably used.

[0038] The organic peroxide usable in the dental curable composition of the present invention may be at least one selected from diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, peroxyesters, peroxydicarbonates, and hydroperoxides, including at least one selected from t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, t-amylperoxy-2-ethylhexanoate, t-amylperoxyacetate, t-amylperoxybenzoate, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-amylperoxy)cyclohexane, dibenzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0039] Other examples of chemical polymerization initiators include one or more selected from phosphine compounds, sulfinic acid compounds, borate compounds, barbituric acid derivatives, and ascorbic acid compounds. Specific examples of phosphine compounds include one or more phosphine compounds selected from triphenylphosphine and 4-(phenylphosphino)benzoic acid. Specific examples of sulfinic acid compounds include one or more sulfinic acid compounds selected from sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate. Specific examples of borate compounds include one or more borate compounds selected from sodium salts, lithium salts, potassium salts, and tetrabutylammonium salts of tetraarylborate compounds. Specific examples of barbituric acid derivatives include one or more barbituric acid derivatives selected from 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, and the sodium or calcium salts of the aforementioned barbituric acid derivatives. Specific examples of the ascorbic acid compound include one or more ascorbic acid compounds selected from ascorbic acid, ascorbyl 6-palmitate, and salt compounds of the above-mentioned ascorbic acid compounds.

[0040] The polymerization initiator contained in the dental curable composition of the present invention may be subjected to secondary treatment such as pulverization, carrier adsorption, encapsulation in microcapsules, etc., if necessary. Furthermore, these various types of polymerization initiators can be used alone or in combination of two or more types, regardless of the polymerization mode or method.

[0041] The dental curable composition of the present invention preferably contains 0.5 to 5.0 parts by mass of a polymerization initiator relative to 100 parts by mass of the polymerizable monomer (A) contained in the dental curable composition. When the amount is 0.5 part by mass or more, the composition is cured well, and when the amount is 5.0 parts by mass or less, the color tone tends to be good.

[0042] <(C) Filler> The dental curable composition of the present invention contains a (C) filler (also referred to as "component (C)" in the present invention). Examples of the (C) filler include inorganic fillers, organic fillers, organic-inorganic composite fillers, and ion-releasing glass. The (C) filler contains (C1) an inorganic filler having X-ray contrast properties and (C2) hydrophobic silica fine particles having a primary particle diameter of less than 0.1 μm.

[0043] Specific examples of inorganic fillers include, but are not limited to, one or more selected from silicon dioxide, alumina, titania, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. In particular, one or more selected from barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, and fluoroaluminosilicate glass, which are used in dental glass ionomer cements, resin-reinforced glass ionomer cements, and resin cements, can be preferably used. The fluoroaluminosilicate glass referred to here has a basic skeleton of silicon oxide and aluminum oxide, and contains alkali metals for the introduction of non-bridging oxygen. It also contains alkaline earth metals, including strontium, and fluorine as modifying and coordinating ions. Furthermore, it is a composition in which lanthanide series elements are incorporated into the skeleton to impart further radiopacity. Depending on the composition range, these lanthanide series elements are also incorporated into the composition as modifying and coordinating ions.

[0044] Specific examples of organic fillers include one or more polymers selected from polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, polycarbonate, and the like.

[0045] Specific examples of organic-inorganic composite fillers include fillers whose surfaces are polymerized and coated with a polymerizable monomer; fillers obtained by mixing and polymerizing a filler and a polymerizable monomer and then pulverizing the mixture to an appropriate particle size; fillers in which a filler is previously dispersed in a polymerizable monomer and then emulsion-polymerized or suspension-polymerized; fillers in which a filler is previously dispersed in a polymerizable monomer and a solvent and then spray-dried and polymerized; and fillers in which a filler is previously dispersed in a solvent and then spray-dried, then impregnated with a polymerizable monomer and then polymerized. However, the present invention is not limited to these examples.

[0046] Specific examples of ion-releasing glasses include any ion-releasing glass that contains one or more glass-skeleton-forming elements that form the glass skeleton and one or more glass-modifying elements that modify the glass skeleton. These ion-releasing glasses can be used alone or in combination. Furthermore, in the present invention, glass amphoteric elements that function as both glass-skeleton-forming elements and glass-modifying elements depending on the glass composition are included in the category of glass-skeleton-forming elements. Specific examples of glass-skeleton-forming elements contained in ion-releasing glasses include one or more elements selected from silica, aluminum, boron, and phosphorus, and these elements can be used alone or in combination. Specific examples of glass-modifying elements include one or more elements selected from halogen elements, alkali metal elements, and alkaline earth metal elements. Examples of halogen elements include one or more elements selected from fluorine, bromine, iodine, and the like. Examples of alkali metal elements include one or more elements selected from sodium, lithium, and the like. Examples of alkaline earth metal elements include one or more selected from calcium, strontium, etc. These elements can be used alone or in combination. Among these, it is preferable to include one or more selected from silica, aluminum, and boron as the glass skeleton forming element and one or more selected from fluorine, sodium, and strontium as the glass modifying element. Specific examples include silica glass, fluoroaluminosilicate glass, fluoroborosilicate glass, and fluoroaluminoborosilicate glass containing one or more selected from strontium and sodium. Furthermore, from the viewpoint of gradually releasing fluorine ions, strontium ions, borate ions, and aluminum ions, fluoroaluminoborosilicate glass containing strontium is more preferable. More preferred examples of the glass composition range include SiO2: 10 to 40 mass%, Al2O3: 10 to 35 mass%, B2O3: 2.5 to 30 mass%, SrO: 15 to 50 mass%, F: 2.5 to 20 mass%, and Na2O: 0 to 15 mass%.This glass composition can be confirmed by using instrumental analysis such as elemental analysis, Raman spectroscopy, and X-ray fluorescence analysis, but there is no problem as long as the actually measured value by any of the analysis methods matches these composition ranges.

[0047] (C) The filler can be treated with a surface treatment agent, typically a silane coupling agent. The surface treatment agent and the surface treatment method are not particularly limited, and known methods can be used without limitation, such as a method of spraying the surface treatment agent while stirring the powdered filler, a method of dispersing and mixing the filler and the surface treatment agent in a solvent, or a method of supplying the silane coupling agent in a vapor or gaseous state to the surface of the filler. Preferred silane coupling agents used for the surface treatment of fillers include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, and hexamethyldisilazane. In addition to silane coupling agents, the surface treatment of fillers can also be carried out using a titanate-based coupling agent and / or an aluminate-based coupling agent.

[0048] The shape of the (C) filler is not particularly limited, and fillers of any shape such as spheres, needles, plates, crushed particles, scales, etc. The primary particle size of the filler is preferably in the range of 0.001 μm to 100 μm, more preferably in the range of 0.001 μm to 10 μm.

[0049] [(C1) Inorganic filler with X-ray contrast properties] The dental hardenable composition of the present invention contains (C1) an inorganic filler having X-ray contrast properties (also referred to as "component (C1)" in the present invention). When the dental hardenable composition contains the inorganic filler having X-ray contrast properties, it becomes easier to distinguish the dental hardenable composition from caries sites, and this is expected to have an auxiliary effect in diagnosing secondary caries and in monitoring the progress of the site to which the dental hardenable composition is applied.

[0050] (C1) The inorganic filler having X-ray contrast properties contains an element having X-ray shielding ability. Specifically, the inorganic filler has X-ray contrast properties when it contains one or more elements selected from chromium, iron, zinc, strontium, yttrium, zirconium, tin, tellurium, barium, lanthanum, gadolinium, ytterbium, tantalum, tungsten, and bismuth. Among these elements, it is preferable to contain one or more elements selected from strontium, barium, lanthanum, zirconium, ytterbium, and gadolinium, and more preferably, it is an aluminosilicate glass containing these elements. When it is an aluminosilicate glass, better long-term stability can be expected.

[0051] The level of X-ray contrast of (C1) inorganic fillers having X-ray contrast properties varies depending on the compound type, content, and blending method of the element having X-ray shielding ability. Therefore, (C1) inorganic fillers having X-ray contrast properties containing an element having X-ray shielding ability can be suitably used. On the other hand, the dental curable composition must have X-ray contrast properties, and the ratio of the X-ray contrast properties of a 1 mm plate of the hardened dental curable composition to that of a 1 mm plate of aluminum is preferably 0.5 times or more, more preferably 0.7 times or more, and even more preferably 1 time or more. When the ratio is 1 time or more, it becomes easy to distinguish the difference from the caries site. In general, the higher the X-ray contrast properties, the more preferable, with the upper limit being about 4 times. On the other hand, when the ratio is less than 0.5 times, it is not considered to have X-ray contrast properties.

[0052] (C1) The method for producing the inorganic filler having X-ray contrast properties is not particularly limited, and it can be produced by a melting method, a sol-gel method, or other manufacturing method. Among these, a melting method using a melting furnace is preferred from the viewpoint of ease of designing the glass composition, including the selection of raw materials. The inorganic filler having X-ray contrast properties used in the present invention has an amorphous structure, but there is no problem if it contains a partial crystalline structure, and there is also no problem if it is a mixture of glass having an amorphous structure and glass having a crystalline structure. Whether the glass structure is amorphous or not can be confirmed using analytical equipment such as X-ray diffraction analysis or a transmission electron microscope.

[0053] (C1) The inorganic filler having X-ray contrast properties is surface-treated with a hydrophobic silane coupling agent of Formula 1. Furthermore, apart from the surface treatment with the hydrophobic silane coupling agent of Formula 1, it can also be functionalized by a known surface treatment. Specific examples of surface treatment agents used for the surface treatment include surfactants, fatty acids, organic acids, inorganic acids, monomers, polymers, various coupling agents, metal alkoxide compounds, and partial condensates thereof. Among these surface treatment agents, a composite surface treatment using an acidic polymer and a silane compound is preferred.

[0054] The preferred primary particle size of the inorganic filler (C1) having X-ray contrast properties is 0.5 to 100 μm, and more preferably 0.5 to 5 μm. When surface treatment is performed, the filler may aggregate. In such cases, it is preferable to measure the particle size after deflocculating the aggregates, but this can be difficult to do. For this reason, the present invention specifies a preferred range for the primary particle size before surface treatment. When the primary particle size of component (C1) is 0.5 μm or more, the dental curable composition tends to have high fluidity and a good feel when handled. When the primary particle size of component (C1) is 100 μm or less, the dental curable composition tends to have good storage stability.

[0055] The structure of the silane coupling agent of formula 1 is shown below. [Formula (1)] [ka] (In the formula, R1 represents an alkyl group having 1 to 11 carbon atoms which may have one or more selected from halogen, aromatic ring, aliphatic ring, polymerizable group, -O-, -S-, -NH-, -C(O)-O-, -OC(O)-, -C(O)-NH-, -OC(O)-NH-, and -NH-C(O)-O-; R2, R3, and R4 represent an alkoxy group having 1 to 4 carbon atoms, an alkyl group, or a halogen, and may be the same as or different from one another.)

[0056] Specific examples of the alkyl group of formula 1 having 1 to 11 carbon atoms include linear alkyl groups, branched alkyl groups, and cyclic alkyl groups having 1 to 11 carbon atoms.

[0057] Specific examples of the alkoxy group and alkyl group having 1 to 4 carbon atoms in Formula 1 include linear alkoxy groups, branched alkoxy groups, cyclic alkoxy groups, linear alkyl groups, branched alkyl groups, and cyclic alkyl groups having 1 to 4 carbon atoms.

[0058] Specific examples of the compound of formula 1 include one or more selected from methylchlorosilane, octadecyltrimethoxysilane, octyltrimethoxysilane, 3-methacryloylpropyltrimethoxysilane, and 8-methacryloyloctyltrimethoxysilane. 3-Methacryloylpropyltrimethoxysilane is preferably used.

[0059] (C1) Inorganic fillers having X-ray contrast properties can also be functionalized by known surface treatments in addition to the surface treatment with the silane coupling agent of formula 1 (surface treatment with a hydrophobic surface treatment agent is also called "hydrophobization treatment"). Specific examples of surface treatment agents used for the surface treatment include surfactants, fatty acids, organic acids, inorganic acids, monomers, polymers, various coupling agents, metal alkoxide compounds, and partial condensates thereof. Among these surface treatment agents, composite surface treatment with an acidic polymer and a silane compound is preferred.

[0060] The inorganic filler (C1) having X-ray contrast properties is surface-treated with a hydrophobic silane coupling agent of formula 1. The blending mass ratio of component (C1) to formula 1 (component (C1) : formula 1) during the surface treatment is 100:0.01 to 1, more preferably 100:0.01 to 0.5. When the blending mass ratio of component (C1) to formula 1 (component (C1) : formula 1) during the surface treatment is 100:0.01 or more, the fluidity is less likely to change even after long-term storage, resulting in excellent long-term stability. When the blending mass ratio is 100:1 or less, the dental curable composition is expected to be uniform without separation or sedimentation even after long-term storage, and to provide a good feeling when the dental curable composition is dispensed from a bottle container that has been left standing for a long period of time.

[0061] Containers used to fill dental curable compositions include jars, syringes, bottles, and pouches. Among these, bottles offer advantages over syringes, such as an easier filling process and a more compact shape relative to the volume, as well as improved maneuverability compared to jars. Furthermore, among dental curable compositions that require a small amount to be dispensed and applied thinly, bottles are often used for dental adhesives and dental coating materials. When a dental curable composition is filled into a syringe, it can be expelled using plunger pressure, but this is difficult to achieve with a bottle. For example, a method of squeezing the bottle container to apply pressure and expel the dental curable composition contained therein through a nozzle is conceivable. However, if the dental curable composition does not have sufficient fluidity, a strong squeeze is required, making it difficult to operate. Furthermore, because of individual differences in the amount of force required to squeeze the bottle tightly to expel the dental curable composition, the amount of discharge may be uneven, making it difficult to dispense the appropriate amount desired by the user. For these reasons, dental curable compositions to be used in bottle containers preferably have high fluidity. On the other hand, materials with high fluidity are prone to sedimentation of inorganic fillers due to the low viscosity of the polymerizable monomer (A) used as the matrix. Furthermore, adding a large amount of a rheology control agent can suppress sedimentation of inorganic fillers, but can also reduce operability, making it difficult to achieve both long-term stability and operability. In particular, inorganic fillers with radiopaque properties tend to be prone to sedimentation because they have a higher specific gravity than silica particles or polymer particles. In the present invention, we have discovered that by incorporating hydrophobic silica microparticles (C2) with a primary particle diameter of less than 0.1 μm into a dental curable composition, sedimentation of inorganic fillers (C1) with radiopaque properties can be suppressed. On the other hand, if inorganic fillers (C1) with radiopaque properties are not treated with a silane coupling agent, their fluidity may decrease after long-term storage. While this depends on the primary particle size, the dental industry typically uses more than 1 part by weight of hydrophobic silane coupling agent per 100 parts by weight of inorganic filler for surface treatment.It has been found that the dental curable composition of the present invention can achieve both long-term stability and operability by surface treating the composition with a silane coupling agent in an amount less than that of a silane coupling agent commonly used in the dental industry.

[0062] The definition of high fluidity and the method for evaluating fluidity in the present invention are described below. To evaluate fluidity, 0.05 g of the dental hardenable composition is placed as a single mass on a horizontally placed flat glass slide. Next, the glass slide is fixed perpendicular to the horizontal surface, and the distance traveled by the dental hardenable composition is measured one minute later. This value is taken as the fluidity. In this case, the glass slide is not surface-treated and has no irregularities. The material of the glass slide is preferably soda glass. In the present invention, "placed as a single mass" refers to placing the dental hardenable composition as a single mass. 0.05 g of the dental hardenable composition should not be divided into two pieces or placed in a thin, spread state. It is preferable to place the dental hardenable composition in a shape close to a hemisphere. Furthermore, the time required from placing 0.05 g of the dental hardenable composition as a single mass on a horizontally placed flat glass slide to fixing it vertically is within 10 seconds, preferably within 5 seconds. The dental hardenable composition of the present invention has a fluidity of 10 mm or more, preferably 15 mm or more, and more preferably 15 mm to 35 mm. When the fluidity is 10 mm or more, the dental curable composition tends to have a good feel when used because it spreads appropriately over the application site.When the fluidity is 35 mm or less, the filler is less likely to settle, and storage stability tends to be good.

[0063] The surface treatment method using the silane coupling agent of formula 1 (component (C1)) can be any known method such as a wet pretreatment method, a dry pretreatment method, or an integral blend method. Of these, the integral blend method is the most preferred.

[0064] The pretreatment method refers to a method in which component (C1) is subjected to a hydrophobic treatment before the dental hardenable composition is produced. In the pretreatment method, a filler that has been hydrophobized so that the compounding ratio of component (C1) to formula 1 (component (C1) : formula 1) is 100:0.01 to 1, preferably 100:0.01 to 0.5, is used in the dental hardenable composition, and good long-term stability can be expected.

[0065] The integral blending method, unlike the wet and dry pretreatment methods, involves surface treatment during the mixing step of the polymerizable monomer (A) and the component (C1). In other words, the surface treatment is performed on the component (C1) during the production of the dental curable composition. In this process, the component (C1) may be mixed with all or a portion of the component (A) contained in the dental curable composition during the mixing step with the component (C1), or may be mixed with a matrix containing the polymerizable monomer (A) and the polymerization initiator (B). Furthermore, the component (C2) may be simultaneously blended during the mixing step. In the integral blending method, good long-term stability can be expected by using a filler that has been hydrophobized so that the blending ratio of the component (C1) to the formula (1) (component (C1) : formula 1) is 100:0.01 to 1, preferably 100:0.01 to 0.5, in the dental curable composition.

[0066] When the pretreatment method and the integral blending method are used in combination, the above-mentioned blending ratio can be calculated from the sum of the respective blending ratios. Even in this case, good long-term stability can be expected by using a dental hardenable composition that has been surface-treated so that the blending ratio of component (C1) to formula 1 (component (C1) : formula 1) is 100:0.01 to 1, preferably 100:0.01 to 0.5.

[0067] When surface treatment is performed using the integral blending method, it is preferable to not include any inorganic fillers other than component (C1) that have not been hydrophobized. In such cases, it may be difficult to control the degree of surface treatment of component (C1). On the other hand, when a hydrophobized filler such as component (C2) is included, the desired effect of the dental curable composition of the present invention is exhibited, so that the surface treatment of component (C1) is prioritized and the effects on other inorganic fillers can be essentially ignored in calculations. Furthermore, in the present invention, surface treatment with a hydrophobic silane coupling agent does not only refer to the formation of an irreversible chemical bond between the inorganic filler and the silane coupling agent, but also refers to any interaction such as a reversible chemical bond or physical adsorption.

[0068] The filler (C) used in the present invention may be coated with a polysiloxane on its surface to form a polysiloxane-coated filler.

[0069] A method for producing a polysiloxane-coated filler will now be described in detail. A silane compound represented by formula 2 is mixed into an aqueous dispersion containing a filler that has been finely pulverized to a desired primary particle size (D50) by grinding or other methods, and this is hydrolyzed or partially hydrolyzed in the system to form a silanol compound, which is then condensed to form a polysiloxane, which is then used to coat the filler surface and produce a polysiloxane-coated filler. Note that the layer formed when a filler is surface-treated with the silane compound represented by formula 2 is a polysiloxane coating layer, and because it has a hydrophilic surface, in the present invention the silane compound represented by formula 2 is distinguished from a hydrophobic silane coupling agent.

[0070] [Formula (2)] [ka]

[0071] (In the formula, X 1~4 is a hydroxy group, a halogen group, or an alkoxy group having 8 or less carbon atoms, and X 1~4 may be the same or different.)

[0072] Specific examples of the silane compound represented by formula 2 include one or more selected from tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, trimethoxychlorosilane, triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane, diethoxydichlorosilane, tetraphenoxysilane, tetrachlorosilane, and silicon hydroxide (silicon oxide hydrate), and more preferably tetramethoxysilane and / or tetraethoxysilane.

[0073] More preferably, it is a low-condensation product of the silane compound represented by formula 2. For example, it is a low-condensation silane compound obtained by partially hydrolyzing and condensing tetramethoxysilane and / or tetraethoxysilane. These compounds can be used alone or in combination.

[0074] The filler (C) used in the present invention may be surface-treated with an acidic compound. In particular, the inorganic filler (C1) having X-ray contrast properties is preferably surface-treated with an acidic compound. By performing the surface treatment with an acidic compound, the dental curable composition is less stringy when discharged from a bottle container, and has a good crispness when discharged.

[0075] Examples of methods for surface treatment of (C) fillers with an acidic compound are given below. Surface treatment of (C) fillers with an acidic compound is preferably performed on polysiloxane-coated fillers. For the acidic compound treatment, equipment commonly used in the industry can be used as long as it is a dry fluidization type agitator, such as a Henschel mixer, super mixer, or high-speed mixer. Treatment of (C) fillers with an acidic compound can be performed by contacting them with a solution containing the acidic compound by impregnation or spraying. For example, the (C) filler may be dry fluidized, and while still fluidized, the solution containing the acidic compound may be dispersed from above and thoroughly stirred. There are no particular limitations on the method for dispersing the solution containing the acidic compound, but a drip or spray method, which allows for uniform dispersion, is preferred.

[0076] After the dispersion step of the solution containing the acidic compound and the filler (C), it is preferable to remove the water and organic solvent contained therein. The heat treatment method for removing the water and organic solvent is not particularly limited and can be performed by a known, general method. The equipment used for the heat treatment is preferably a box-type hot air dryer or a rotary heat treatment device capable of uniform heating. The heat treatment temperature is in the range of room temperature to 200°C, more preferably 40 to 150°C. If the temperature is lower than this range, the aqueous medium is not sufficiently removed, while if the temperature is higher than this range, the acidic compound may decompose and discolor. The heat treatment time depends on the capacity of the dryer, etc., so there is no problem as long as the time is long enough to sufficiently remove the aqueous medium. After the heat treatment, the heat-treated product can be easily crushed by applying shear force or impact force, and the crushing method can be performed using the equipment used for the above reaction.

[0077] The solvent used to prepare the solution containing the acidic compound used in the reaction can be any solvent that dissolves the acidic compound, and examples thereof include one or more selected from water, ethanol, and acetone. Among these, one or more selected from water and ethanol are particularly preferred. The amount of the acidic compound added per 100 parts by mass of (C) filler is preferably in the range of 0.5 to 10 parts by mass.

[0078] The acidic compound used in the acidic compound treatment may be at least one selected from inorganic acids such as phosphoric acid and hydrochloric acid, organic acids such as acetic acid, polymerizable monomers (A1) having an acidic group, and acidic polymers. Of these, acidic polymers are most preferably used. The acidic polymer is a copolymer or homopolymer of a polymerizable monomer having, as an acidic group, one or more acidic groups selected from the group consisting of a phosphate residue, a pyrophosphate residue, a thiophosphate residue, a carboxylic acid residue, and a sulfonic acid group. Specific examples of these polymerizable monomers include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic anhydride, 5-(meth)acryloylaminopentylcarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 2-(meth)acryloyloxyethoxycarbonylphthalic acid ... and at least one selected from the group consisting of di(2-(meth)acryloyloxyethyl)phenyl phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, 1,3-di(meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl phosphate, 2-(meth)acryloyloxyethyl-2'-bromoethyl phosphate, (meth)acryloyloxyethyl phenyl phosphonate, di(2-(meth)acryloyloxyethyl)pyrophosphate, 2-(meth)acryloyloxyethyl dihydrogendithiophosphorate, and 10-(meth)acryloyloxydecyl dihydrogenthiophosphate. Among these, it is preferable to use a homopolymer or copolymer of an α-β unsaturated carboxylic acid, and more specifically, it is preferable to use one or more selected from an acrylic acid polymer, an acrylic acid-maleic acid copolymer, and an acrylic acid-itaconic acid copolymer.

[0079] The weight-average molecular weight of the acidic polymer is preferably in the range of 2000 to 50000, and more preferably in the range of 5000 to 40000. When treated with an acidic polymer having a weight-average molecular weight of 2000 or more, the dental curable composition tends to be less stringy when discharged from a bottle container and tends to have a good crispness when discharged, and when treated with an acidic polymer having a weight-average molecular weight of 50000 or less, the viscosity of the solution containing the acidic polymer is lower, making surface treatment easier.

[0080] The inorganic filler (C1) having X-ray contrast properties contained in the dental curable composition of the present invention is preferably contained in an amount of 40 to 120 parts by mass per 100 parts by mass of the polymerizable monomer (A) contained in the dental curable composition. If the blending amount is less than 40 parts by mass, sufficient X-ray contrast properties may not be exhibited, and if the blending amount is more than 120 parts by mass, appropriate fluidity may not be exhibited, resulting in poor operability when the composition is placed in a bottle container.

[0081] [(C2) Hydrophobized silica fine particles with a primary particle diameter of less than 0.1 μm] The dental curable composition of the present invention contains (C2) hydrophobized silica fine particles having a primary particle diameter of less than 0.1 μm (also referred to as "component (C2)" in the present invention). By containing the hydrophobized silica fine particles, the dental curable composition can have good operability even when filled in a bottle container, and can suppress sedimentation of the inorganic filler having X-ray contrast properties.

[0082] Specific methods for hydrophobizing hydrophobic silica fine particles include a surface treatment method using a modified silicone oil such as dimethylsilicone oil, and / or a surface treatment method using a silane coupling agent having one or more functional groups selected from a trimethylsilyl group, a dimethylsilyl group, a methylsilyl group, and an alkylsilyl group that may have a (meth)acryloyl group and has an alkyl chain having a carbon number of 3 to 18. The silane coupling agent preferably hydrophobicizes the silica fine particles via a covalent bond.

[0083] Specific examples of modified silicone oils and silane coupling agents include polydimethylsiloxane, hexamethyldisilazane, dimethylpolysiloxane, methylchlorosilane, alkyltrialkoxysilane, dialkyldialkoxysilane, alkylalkoxysilanes such as octadecylalkoxysilane and octylalkoxysilane, and (meth)acryloylalkylalkoxysilanes such as 3-methacryloylpropyltrimethoxysilane and 8-methacryloyloctyltrimethoxysilane.

[0084] To further improve the rheological properties, the silica microparticles may be hydrophobized by several methods, for example, by treating them with a silane coupling agent and / or modified silicone oil, or by treating them with a surface treatment agent simultaneously.

[0085] (C2) Hydrophobized silica fine particles having a primary particle diameter of less than 0.1 μm are exemplified by dry silica, silica aerogel, wet silica, etc., with dry silica being more preferred.

[0086] Among the hydrophobic silica particles listed above, dry silica is commercially available under the trade name Aerosil, for example, manufactured by Nippon Aerosil Co., Ltd. Examples include Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, and also silica fine powders whose surfaces have been subjected to hydrophobic treatment, such as Aerosil R972, Aerosil R974, Aerosil R976, Aerosil R976S, Aerosil R202, Aerosil R812, Aerosil R812S, Aerosil R805, Aerosil R104, Aerosil R106, RY200, RX200, R711, RY200S, RA200H, R8200, and RA200HS.

[0087] The blending amount of (C2) hydrophobized silica fine particles having a primary particle diameter of less than 0.1 μm is 3 to 20 parts by mass, preferably 5 to 15 parts by mass, per 100 parts by mass of (A) polymerizable monomer. When the blending amount is 3 parts by mass or more per 100 parts by mass of (A) polymerizable monomer, sedimentation of (C) filler contained in the dental curable composition tends to be less likely to occur, and when the blending amount is 20 parts by mass or less, the dental curable composition tends to have good handleability.

[0088] The primary particle size in the present invention refers to the average primary particle size. The primary particle size of the (C) filler can be an average calculated based on the particle size distribution measured, for example, by a laser diffraction particle size analyzer. For example, it can be measured using a laser diffraction particle size analyzer (Microtrac MT3300EXII, manufactured by Nikkiso Co., Ltd.). When measuring using a laser diffraction particle size analyzer, the measurement is performed after dispersing the filler uniformly using ultrasound or the like. Alternatively, the primary particle size can be measured using dynamic light scattering particle size measurement, or, for fillers in which primary particles are strongly aggregated to form secondary particles, using electron microscope photographs. For fillers with a primary particle size of less than 0.1 μm, it is preferable to calculate the primary particle size from electron microscope photographs, and for fillers with a primary particle size of 0.1 μm or more, it is preferable to calculate the primary particle size using a laser diffraction particle size analyzer.

[0089] The type of (C) filler is not limited as long as it is a known filler, and a filler appropriate for the intended use can be blended, and it is preferable to blend a filler such as an inorganic filler, an organic filler, an organic-inorganic composite filler, or an ion-releasing glass. The dental curable composition of the present invention may use the exemplified fillers alone or in combination of two or more.

[0090] <Other ingredients> The dental curable composition of the present invention may contain components other than the above components (A) to (C) as long as the effects of the present invention are not impaired. For example, the dental curable composition of the present invention may contain any of the following components as needed: benzophenone-based or benzotriazole-based ultraviolet absorbers; α-alkylstyrene compounds; mercaptan compounds such as n-butyl mercaptan or n-octyl mercaptan; chain transfer agents such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, or α-pinene; metal capture agents such as aminocarboxylic acid-based chelating agents or phosphonic acid-based chelating agents; discoloration inhibitors; polymerization inhibitors; antibacterial agents; color pigments; and other conventionally known additives.

[0091] The method for producing the dental curable composition of the present invention is not particularly limited. A typical method for producing a dental curable composition includes preparing a matrix by first mixing the (A) polymerizable monomer (excluding the (C) filler) and the (B) polymerization initiator, etc., using a known method such as a planetary mixer, a tumbler mixer, a mix rotor, a dissolver, or a planetary mixer. Then, the matrix and the (C) filler are kneaded using a known method such as a planetary mixer, a tumbler mixer, a mix rotor, a dissolver, or a planetary mixer, and air bubbles are removed under reduced pressure to form a uniform paste. In the present invention, the term "matrix" refers to a mixed solution prepared by mixing the components excluding the (C) filler. Specifically, it refers to a mixed solution prepared by premixing the (A) polymerizable monomer and the (B) polymerization initiator, etc. If one or more of the (A) polymerizable monomer and the (B) polymerization initiator do not dissolve uniformly in the matrix, the matrix may be free of one or more of them. The preferred method for incorporating the (A) polymerizable monomer and (B) polymerization initiator not contained in the matrix into the dental curable composition is to incorporate them when mixing the matrix and (C) filler. Components that do not dissolve in the matrix include components that do not dissolve even when mixed for 48 hours using a mix rotor at 100 rpm. In this case, components that can be mixed at high temperatures are preferably mixed at a temperature of 50°C. On the other hand, components that may deteriorate when heated, such as the (B) polymerization initiator, are preferably mixed at a temperature of 20 to 30°C. The most preferred production method is to premix the (A) polymerizable monomer and (B) polymerization initiator to prepare a uniform matrix, and then mix the (C) filler to produce the dental curable composition. The present invention can also be produced without any problems using the above production method.

[0092] The dental curable composition of the present invention may contain only (A) the polymerizable monomer, (B) the polymerization initiator, and (C) the filler, or may contain only one or more of the above-mentioned components as components other than (A) to (C).

[0093] The dental curable composition of the present invention can be used as a kit with a dental adhesive composition. More specifically, it is a kit of dental adhesive compositions that can be used by applying a first agent to an adherend, and then applying the dental curable composition of the present invention as a second agent without light irradiation.

[0094] The first agent included in the dental adhesive composition kit contains (A1) a polymerizable monomer having an acidic group. Suitable examples of the (A1) polymerizable monomer having an acidic group include one or more selected from 10-methacryloyloxydecyl dihydrogen phosphate, 6-methacryloxyhexyl phosphonoacetate, 4-methacryloxyethyl trimellitic acid, and 4-methacryloxyethyl trimellitic anhydride. The preferred amount of (A1) polymerizable monomer having an acidic group per 100 parts by mass of the first agent composition is 2 to 30 parts by mass. When the amount of (A1) polymerizable monomer having an acidic group included in the first agent is 2 parts by mass or more, good adhesive strength tends to be achieved, and when the amount is 30 parts by mass or less, good storage stability tends to be achieved.

[0095] The first agent included in the dental adhesive composition kit may contain (A2) a polymerizable monomer having no acidic group. Suitable examples of the (A2) polymerizable monomer having no acidic group include one or more selected from 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane, glycerol dimethacrylate, and triethylene glycol dimethacrylate. The amount of the (A2) polymerizable monomer having no acidic group is preferably 0 to 50 parts by mass per 100 parts by mass of the first agent composition.

[0096] The first agent included in the dental adhesive composition kit contains (D) water (also referred to as "component (D)" in the present invention). Specific examples of (D) water include one or more selected from deionized water and distilled water. The amount of (D) water is preferably 5 to 50 parts by mass per 100 parts by mass of the first agent composition. When the amount is 5 parts by mass or more, the adhesive strength to dentin tends to be good, and when the amount is 50 parts by mass or less, the solubility of the (A) polymerizable monomer included in the first agent may be good.

[0097] The first agent included in the dental adhesive composition kit may contain (E) a volatile organic solvent (also referred to as "component (E)" in the present invention). The (E) volatile organic solvent is typically an organic solvent having a boiling point of 150°C or less under normal pressure and a solubility in water at 25°C of 5% by mass or more, more preferably 30% by mass or more, and most preferably soluble in water at any desired ratio. Among these, water-soluble volatile organic solvents having a boiling point of 100°C or less under normal pressure are preferred, and specific examples thereof include one or more selected from ethanol, methanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane, and tetrahydrofuran. Of the aforementioned volatile organic solvents, one or more selected from ethanol, isopropyl alcohol, acetone, and methyl ethyl ketone are even more preferred. The blending amount of (E) the volatile organic solvent is preferably 0 to 50 parts by mass per 100 parts by mass of the first agent composition.

[0098] <Other ingredients> The first agent included in the dental adhesive composition kit may contain components other than the above-mentioned components (A1) and (D) as long as the effects of the present invention are not impaired. For example, components such as excipients typified by fumed silica, benzophenone-based and benzotriazole-based UV absorbers, α-alkylstyrene compounds, mercaptan compounds such as n-butyl mercaptan and n-octyl mercaptan, chain transfer agents such as terpenoid compounds such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, and α-pinene, metal capture agents such as aminocarboxylic acid-based chelating agents and phosphonic acid-based chelating agents, discoloration inhibitors, antibacterial agents, color pigments, and other conventionally known additives may be added as needed. [Example]

[0099] The materials used in the examples and comparative examples and their abbreviations are shown below. [(A) Polymerizable Monomer] <(A1) Polymerizable Monomer Having an Acidic Group> MDP: 10-methacryloyloxydecyl dihydrogen phosphate MET: 4-methacryloxyethyl trimellitate META: 4-Methacryloyloxyethoxycarbonylphthalic anhydride <(A2) Polymerizable Monomer Having No Acidic Group> BisGMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane UDMA: N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)ethanol]methacrylate TEGDMA: Triethylene glycol dimethacrylate GDMA: Glycerol dimethacrylate HEMA: Hydroxyethyl methacrylate <Hydrophobic silane coupling agent> MPTMS: (3-methacryloyloxypropyl)trimethoxysilane MPTES: (3-methacryloyloxypropyl)triethoxysilane

[0100] [(B) Polymerization initiator] CQ: Camphorquinone BAPO: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide DMBE: Ethyl N,N-dimethylaminobenzoate DHPPT: N,N-di(2-hydroxypropyl)-p-toluidine DEPT: N,N-di(2-hydroxyethyl)-p-toluidine

[0101] [(C) Filler] <(C1) Inorganic filler with X-ray contrast properties> (Filler C1: Amount of surface treatment with hydrophobic silane coupling agent: 0 parts by mass) Fluoroaluminoborosilicate glass (primary particle diameter 3 μm, SiO2: 22.5 wt%, Al2O3: 20.0 wt%, B2O3: 12.3 wt%, SrO: 35.7 wt%, Na2O: 2.5 wt%, F: 7.0 wt%) (Filler C2: Amount of surface treatment with hydrophobic silane coupling agent: 0 parts by mass) Fluoroaluminoborosilicate glass (primary particle diameter 1 μm, SiO2: 22.5 wt%, Al2O3: 20.0 wt%, B2O3: 12.3 wt%, SrO: 35.7 wt%, Na2O: 2.5 wt%, F: 7.0 wt%)

[0102] (Filler C3: Amount of surface treatment with hydrophobic silane coupling agent: 0 parts by mass) To 100 g of filler C2, 4.5 g of a low-condensation silane compound "MKC Silicate MS56S" (SiO2 content 56.0% by mass, degree of polymerization 2-100, manufactured by Mitsubishi Chemical Corporation) was added and mixed with stirring for approximately 90 minutes. After mixing for the specified time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours. It was then cooled to obtain a heat-treated product. The resulting heat-treated product was placed in a Henschel mixer and crushed at 1800 rpm for 5 minutes to obtain a polysiloxane-coated filler. 16.0 g of an aqueous solution containing the acidic compound polyacrylic acid (polymer concentration 13% by mass, weight-average molecular weight 10,000, manufactured by Nakarai) was sprayed onto 100 g of the polysiloxane-coated filler. After spraying, the powder removed from the mixer was heated at 100°C for 3 hours in a hot air dryer. After returning to room temperature, it was sieved to obtain filler C3.

[0103] (Filler C4: Amount of surface treatment with hydrophobic silane coupling agent: 0.2 parts by mass) To 100 g of filler C1, 5 g of water, 10 g of ethanol, and a silane coupling treatment solution containing 0.2 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were added, and the mixture was stirred and mixed for 2 hours. After that, the mixture was heat-treated at 90°C for 15 hours, and then sieved to obtain filler C4.

[0104] (Filler C5: Amount of surface treatment with hydrophobic silane coupling agent: 0.05 parts by mass) To 100 g of filler C2, 5 g of water, 10 g of ethanol, and a silane coupling treatment solution containing 0.05 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were added, and the mixture was stirred and mixed for 2 hours. After that, the mixture was heat-treated at 90°C for 15 hours, and then sieved to obtain filler C5.

[0105] (Filler C6: Amount of surface treatment with hydrophobic silane coupling agent: 0.1 parts by mass) To 100 g of filler C3, 5 g of water, 10 g of ethanol, and a silane coupling treatment solution containing 0.1 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were added, and the mixture was stirred and mixed for 2 hours. After that, the mixture was heat-treated at 90°C for 15 hours, and then sieved to obtain filler C6.

[0106] (Filler C7: Amount of surface treatment with hydrophobic silane coupling agent: 0.6 parts by mass) To 100 g of filler C3, 5 g of water, 10 g of ethanol, and a silane coupling treatment solution containing 0.6 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were added, and the mixture was stirred and mixed for 2 hours. After that, the mixture was heat-treated at 90°C for 15 hours, and then sieved to obtain filler C7.

[0107] (Filler C8: Amount of surface treatment with hydrophobic silane coupling agent: 1.5 parts by mass) To 100 g of filler C1, 5 g of water, 10 g of ethanol, and a silane coupling treatment solution containing 1.5 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were added, and the mixture was stirred and mixed for 2 hours. After that, the mixture was heat-treated at 90°C for 15 hours, and then sieved to obtain filler C8.

[0108] (Filler C9: Amount of surface treatment with hydrophobic silane coupling agent: 1.5 parts by mass) To 100 g of filler C3, 5 g of water, 10 g of ethanol, and a silane coupling treatment solution containing 1.5 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were added, and the mixture was stirred and mixed for 2 hours. After that, the mixture was heat-treated at 90°C for 15 hours, and then sieved to obtain filler C9.

[0109] (C2) Hydrophobic silica fine particles with a primary particle diameter of less than 0.1 μm (Filler D21) Aerosil R-972 (manufactured by Evonik, primary particle size 16 nm, hydrophobic silica surface-treated with dimethyldichlorosilane) (Filler D22) Aerosil R-974 (manufactured by Evonik, primary particle size 12 nm, hydrophobic silica surface-treated with dimethyldichlorosilane) (Filler D23) Aerosil R-711 (manufactured by Evonik, primary particle size 12 nm, hydrophobic silica surface-treated with methacrylsilyl)

[0110] [(D)Water] DW: Distilled water

[0111] [(E) Volatile organic solvent] EtOH: ethanol Acetone: Acetone

[0112] [others] [Polymerization inhibitor] MeHQ: p-Methoxyphenol BHT: Dibutylhydroxytoluene [UV absorber] OB: 2-hydroxy-4-(octyloxy)benzophenone [Fluorescent agent] FA: Diethyl 2,5-dihydroxyterephthalate

[0113] <Production Example 2-1: Production method of dental curable composition (second part) (2-1)> All ingredients except for the (C) filler shown in Table 1 were placed in a wide-mouth plastic container and mixed for 48 hours at 100 rpm using a VMRC-5 mix rotor to obtain a matrix. The matrix and (C) filler were then placed in a kneader, uniformly stirred, and degassed under vacuum to obtain dental curable composition (2-1). When the dental curable composition is used as a dental adhesive composition in combination with a first agent, it is used as the second agent. In Tables 1 to 3, the abbreviation for each component is followed by the mass part of each component in parentheses.

[0114] <Production Examples 2-2 to 2-18 and Comparative Production Examples 2-1 to 2-4: Production methods of dental curable compositions (second parts) (2-2) to (2-18) and (C2-1) to (C2-4)> In Production Examples 2-2 to 2-18 and Comparative Production Examples 2-1 to 2-4, dental curable compositions (2-2) to (2-18) and (C2-1) to (C2-4) were obtained in the same manner as in Production Example 2-1, except that the compositions were changed to those shown in Tables 1 to 3. The numbers of the Production Examples and the numbers of the dental curable compositions correspond to each other.

[0115] [Table 1]

[0116] [Table 2]

[0117] [Table 3]

[0118] <Production Example 1-1: Production method of first agent (1-1)> All ingredients shown in Table 4 were placed in a wide-mouth plastic container and mixed for 48 hours at 100 rpm using a VMRC-5 mix rotor to obtain the first agent (1-1). Note that in Table 4, the abbreviation for each component is followed by the mass part of each component in parentheses.

[0119] <Production Examples 1-2 to 1-9: Production Methods of First Agents (1-2) to (1-9)> In Production Examples 1-2 to 1-9, first agents (1-2) to (1-9) were obtained in the same manner as in Production Example 1-1, except that the compositions were changed to those shown in Table 4. The numbers of the Production Examples and the numbers of the first agents correspond to each other.

[0120] [Table 4]

[0121] <Evaluation 1: X-ray contrast> The dental curable composition was filled into a stainless steel mold (15φ×1mm: disc-shaped), and a cover glass was placed on top and pressed with a glass plate. The cover glass was cured by irradiating it with light for 1 minute using a photopolymerization irradiator (Grip Light II, manufactured by Matsufuku). The cured product was then removed from the mold, and the cover glass was removed. An X-ray transmission image was obtained using an aluminum step wedge and an X-ray inspection device (3MX-31M, manufactured by Shimadzu Corporation). The obtained X-ray images were analyzed using the image analysis software ImageJ. A calibration curve of the gray value for each thickness of the aluminum step wedge was created, and the ratio of the gray value of the dental curable composition to 1 mm of aluminum was used to determine the radiopacity of the dental curable composition. A radiopacity of 1.0 times or more relative to 1 mm of aluminum was considered to have sufficient radiopacity and was graded A; a radiopacity of 0.7 times or more but less than 1.0 times was considered to have normal radiopacity and was graded B; a radiopacity of 0.5 times or more but less than 0.7 times was considered to have low radiopacity and was graded C; and a radiopacity of less than 0.5 times was considered to have significantly low radiopacity and was graded D. Dental curable compositions with radiopacity are preferred because they aid in the observation of the prognosis of restored areas and the diagnosis of secondary caries.

[0122] <Rating 2: Liquidity> A 0.05 g sample of the initial dental curable composition or an accelerated test sample prepared by standing in an incubator set at 50°C for two weeks was placed as a mass on a horizontally placed glass slide (soda glass, 70 mm x 70 mm). Within 5 seconds, the glass slide was fixed vertically at a 90-degree angle to the horizontal. After 1 minute, the distance traveled by the dental curable composition was measured. This travel distance (unit: millimeters) was defined as fluidity. A fluidity of 15 mm or more was determined to have particularly good high fluidity. A fluidity of 10 mm or more but less than 15 mm was determined to have good high fluidity. A fluidity of less than 10 mm was determined to not have high fluidity. A change of less than 5 mm between the initial preparation and the accelerated test sample was rated A, indicating particularly excellent storage stability; a change of 5 mm or more but less than 10 mm was determined to have fair storage stability; and a change of 10 mm or more was determined to have poor storage stability and rated D. The dental curable composition of the present invention is preferably a highly fluid composition for use in a bottle container. Furthermore, it is preferable that the fluidity does not change after long-term storage, since this is expected to provide the desired operability.

[0123] <Rating 3: Good drainability> Five grams of the dental curable composition of the Example or Comparative Example was filled into a bonding container (FIGS. 1 to 4, nozzle diameter 3 mm, height 51 mm, width 22 mm). After filling, the bonding container was left standing for one week, and then the bonding container was inverted to evaluate the discharge feeling based on the time it took for the dental curable composition to be discharged from the nozzle. If the time it took for the composition to be discharged was within 30 seconds, the discharge feeling was rated as A, which was good; if it took 30 to 60 seconds, the discharge feeling was rated as B, which was normal; and if it took more than 60 seconds, the discharge feeling was rated as C, which was bad. If the dental curable composition is too thixotropic or has very high viscosity, the discharge feeling after being left standing for one week tends to be poor. A good discharge feeling is preferable because it allows the user to quickly discharge the dental curable composition from the bottle and use it when desired.

[0124] <Evaluation 4: Appearance check (check for floating liquid)> 30 g of the dental curable composition of each Example or Comparative Example was placed in a 50 mL light-shielding container and stored in an incubator at 50°C. After storage in the incubator at 50°C for one or two weeks, the appearance of the light-shielding container was inspected. A dental curable composition that maintained a uniform state without floating or settling even after two weeks of storage at 50°C was deemed to have good stability and was rated A. A dental curable composition that maintained a uniform state without floating or settling after one week of storage at 50°C, but that did not maintain a uniform state after two weeks of storage at 50°C, due to floating or settling, was deemed to have fair stability and was rated B. A dental curable composition that separated and / or settling occurred after one week of storage at 50°C was deemed to have poor storage stability and was rated D. A dental curable composition that is not sufficiently uniform requires an operation to homogenize the dental curable composition each time it is used, which is undesirable because it places a burden on the user.

[0125] <Evaluation 5: Adhesion strength> A bovine central incisor specimen embedded in epoxy resin was polished with #500 waterproof abrasive paper to remove the dentin surface. The first agent described in the Examples was then applied to the surface to be adhered, followed by air drying. The second agent was then applied to the surface to which the first agent had been applied, and the specimen was irradiated for 10 seconds with a dental polymerization LED light irradiator (Penbright, manufactured by Shofu Co., Ltd.). A φ2.38 mm hole mold (manufactured by Ultradent) was then placed on top, and dental filling flowable composite resin (Beauty Fill Flow Plus X, manufactured by Shofu Co., Ltd.) was filled in, followed by irradiating for 10 seconds with a dental polymerization LED light irradiator (Penbright, manufactured by Shofu Co., Ltd.). The mold was removed, and the prepared adhesive test specimen was immersed in 37°C water for 24 hours. Afterwards, a thermal shock tester (manufactured by Thomas Scientific Instruments) was used to measure the shear bond strength of the prepared specimens, immersing them in a cold water phase at 4°C and a hot water phase at 60°C for 30 seconds each, 5,000 times. The shear bond strength of the prepared test specimens was then measured using a universal testing machine (manufactured by Instron) at a crosshead speed of 1 mm / min. Bond strengths of 20 MPa or more were considered extremely good. Bond strengths of 10 MPa to less than 20 MPa were considered average, and bond strengths of less than 10 MPa were considered insufficient. Higher bond strengths are preferable, as they affect the long-term stability of the repaired area.

[0126] The results of each test shown in Tables 5 to 7 are described below.

[0127] [Table 5]

[0128] [Table 6]

[0129] [Table 7]

[0130] It was confirmed that the compositions described in the examples have X-ray contrast properties, have high fluidity, and are easy to handle and have excellent stability when placed in a bottle container.

[0131] Example 1, which contained a large amount of component (C1), had low fluidity and tended to have slightly low dentin adhesion. Examples 4 and 5, which contained a small amount of inorganic filler containing component (C1), tended to have low X-ray contrast properties. Furthermore, Example 4, which contained a large amount of component (C2), tended to have low fluidity. Examples 14 and 15, which contained a large amount of component (C1) surface-treated with the silane coupling agent of formula 1, tended to be prone to separation. Furthermore, Examples 9 to 12, which used component (C1) that was not surface-treated with an acidic compound, tended to have poorer removability than those using component (C1) that was surface-treated with an acidic compound (e.g., Example 8).

[0132] Example 6, which contained a small amount of component (B), tended to have slightly lower adhesive strength to dentin. Also, Example 17, which used Production Example 1-9, which contained a small amount of component (A1) in the dental adhesive composition used in the dentin adhesion test, tended to have lower adhesiveness to dentin.

[0133] Example 11, in which the dental hardenable composition contained component (A1), tended to have low fluidity.

[0134] Comparative Examples 1 and 3, in which the amount of surface treatment of component (C1) with the silane coupling agent of Formula 1 was excessive, exhibited strong liquid floating and thus poor storage stability. Comparative Example 2, which did not contain component (C1) that had been surface treated with the silane coupling agent of Formula 1, exhibited poor fluidity stability. Comparative Example 4, which did not contain component (C1), did not have X-ray contrast properties.

[0135] A dental adhesive composition was prepared by removing the polymerization initiator from the composition of Example 18, and not including the polymerization initiator (B) in the second agent (not shown in the table). When an attempt was made to cure it in the same manner as in the other examples and comparative examples, it did not cure.

[0136] The dental curable compositions evaluated in the examples can be used for dental adhesives, dental composite resins, dental core build-up materials, dental resin cements, dental coating materials, dental pit and fissure sealants, dental manicure materials, dental 3D printer materials, orthodontic materials, etc. Preferably, they can be used as a two-step dental adhesive composition kit containing a first agent and a second agent. [Industrial Applicability]

[0137] According to the present invention, the composition has X-ray contrast properties, high fluidity, and can achieve both good operability and stability even when placed in a bottle container.

Claims

1. A dental curable composition comprising (A) a polymerizable monomer, (B) a polymerization initiator, and (C) a filler, Component (C) (C1) an inorganic filler having X-ray contrast properties; and (C2) containing hydrophobized silica fine particles having a primary particle diameter of less than 0.1 μm, The component (C1) is surface-treated with a hydrophobic silane coupling agent of formula 1, the mass ratio of component (C1) to formula 1 (component (C1) : formula 1) is 100:0.01 to 1; A dental hardenable composition having a fluidity of 10 mm or more, which is the distance traveled by the dental hardenable composition after 1 minute from when 0.05 g of the dental hardenable composition is placed in a lump on the flat surface of a horizontally placed slide glass and the slide glass is fixed perpendicular to the horizontal surface. [Formula (1)] 【Chemistry 1】 (In the formula, R １ represents an alkyl group having 1 to 11 carbon atoms which may have one or more groups selected from halogen, an aromatic ring, an aliphatic ring, a polymerizable group, —O—, —S—, —NH—, —C(O)—O—, —O—C(O)—, —C(O)—NH—, —O—C(O)—NH—, and —NH—C(O)—O—; R ２ and R ３ and R ４ represents an alkoxy group, an alkyl group, or a halogen atom having 1 to 4 carbon atoms, and may be the same or different.

2. 2. The dental hardenable composition according to claim 1, wherein the inorganic filler (C1) having X-ray contrast properties is an aluminosilicate glass containing one or more elements selected from the group consisting of strontium, barium, lanthanum, zirconium, ytterbium, and gadolinium.

3. 2. The dental curable composition according to claim 1, wherein the inorganic filler (C1) having X-ray contrast properties has been surface-treated with an acidic compound and a silane coupling agent.

4. 3. The dental curable composition according to claim 2, wherein the inorganic filler (C1) having X-ray contrast properties has been surface-treated with an acidic compound and a silane coupling agent.

5. The dental curable composition according to claim 1, wherein the amount of the surface treatment of the inorganic filler (C1) having X-ray contrast properties with the silane coupling agent is 0.01 to 0.50 parts by mass per 100 parts by mass of the inorganic filler (C1) having X-ray contrast properties.

6. The dental curable composition according to claim 2, wherein the amount of the surface treatment of the inorganic filler (C1) having X-ray contrast properties with the silane coupling agent is 0.01 to 0.50 parts by mass per 100 parts by mass of the inorganic filler (C1) having X-ray contrast properties.

7. A two-step dental adhesive composition kit comprising a first agent and a second agent which is a dental curable composition, the kit being used by applying the first agent to an adherend and then further applying the second agent; The first agent is For 100 parts by mass of the first agent (A1) 2 to 30 parts by mass of a polymerizable monomer having an acidic group (A2) 0 to 50 parts by mass of a polymerizable monomer having no acidic group (D) 5 to 50 parts by mass of water, and (E) 0 to 50 parts by mass of a volatile organic solvent; The second agent per 100 parts by mass of the polymerizable monomer (A) contained in the second agent (B) 0.5 to 5.0 parts by mass of a polymerization initiator (C1) 40 to 120 parts by mass of an inorganic filler having X-ray contrast properties, and (C2) 3 to 20 parts by mass of hydrophobic silica fine particles having a primary particle diameter of less than 0.1 μm 2. A dental adhesive composition comprising the first and second parts according to claim 1, wherein the second part comprises:

8. A two-step dental adhesive composition kit comprising a first agent and a second agent which is a dental curable composition, the kit being used by applying the first agent to an adherend and then further applying the second agent; The first agent is For 100 parts by mass of the first agent (A1) 2 to 30 parts by mass of a polymerizable monomer having an acidic group (A2) 0 to 50 parts by mass of a polymerizable monomer having no acidic group (D) 5 to 50 parts by mass of water, and (E) 0 to 50 parts by mass of a volatile organic solvent; The second agent per 100 parts by mass of the polymerizable monomer (A) contained in the second agent (B) 0.5 to 5.0 parts by mass of a polymerization initiator (C1) 40 to 120 parts by mass of an inorganic filler having X-ray contrast properties, and (C2) 3 to 20 parts by mass of hydrophobic silica fine particles having a primary particle diameter of less than 0.1 μm 3. A dental adhesive composition comprising the first and second parts according to claim 2, wherein the second part comprises:

9. A two-step dental adhesive composition kit comprising a first agent and a second agent which is a dental curable composition, the kit being used by applying the first agent to an adherend and then further applying the second agent; The first agent is For 100 parts by mass of the first agent (A1) 2 to 30 parts by mass of a polymerizable monomer having an acidic group (A2) 0 to 50 parts by mass of a polymerizable monomer having no acidic group (D) 5 to 50 parts by mass of water, and (E) 0 to 50 parts by mass of a volatile organic solvent; The second agent per 100 parts by mass of the polymerizable monomer (A) contained in the second agent (B) 0.5 to 5.0 parts by mass of a polymerization initiator (C1) 40 to 120 parts by mass of an inorganic filler having X-ray contrast properties, and (C2) 3 to 20 parts by mass of hydrophobic silica fine particles having a primary particle diameter of less than 0.1 μm 4. A dental adhesive composition comprising the first and second parts according to claim 3, wherein the second part comprises:

10. A two-step dental adhesive composition kit comprising a first agent and a second agent which is a dental curable composition, the kit being used by applying the first agent to an adherend and then further applying the second agent; The first agent is For 100 parts by mass of the first agent (A1) 2 to 30 parts by mass of a polymerizable monomer having an acidic group (A2) 0 to 50 parts by mass of a polymerizable monomer having no acidic group (D) 5 to 50 parts by mass of water, and (E) 0 to 50 parts by mass of a volatile organic solvent; The second agent per 100 parts by mass of the polymerizable monomer (A) contained in the second agent (B) 0.5 to 5.0 parts by mass of a polymerization initiator (C1) 40 to 120 parts by mass of an inorganic filler having X-ray contrast properties, and (C2) 3 to 20 parts by mass of hydrophobic silica fine particles having a primary particle diameter of less than 0.1 μm 5. A dental adhesive composition comprising the first and second parts according to claim 4, wherein the second part comprises:

11. A two-step dental adhesive composition kit comprising a first agent and a second agent which is a dental curable composition, the kit being used by applying the first agent to an adherend and then further applying the second agent; The first agent is For 100 parts by mass of the first agent (A1) 2 to 30 parts by mass of a polymerizable monomer having an acidic group (A2) 0 to 50 parts by mass of a polymerizable monomer having no acidic group (D) 5 to 50 parts by mass of water, and (E) 0 to 50 parts by mass of a volatile organic solvent; The second agent per 100 parts by mass of the polymerizable monomer (A) contained in the second agent (B) 0.5 to 5.0 parts by mass of a polymerization initiator (C1) 40 to 120 parts by mass of an inorganic filler having X-ray contrast properties, and (C2) 3 to 20 parts by mass of hydrophobic silica fine particles having a primary particle diameter of less than 0.1 μm 6. A dental adhesive composition comprising the first and second parts according to claim 5, wherein the second part comprises:

12. A two-step dental adhesive composition kit comprising a first agent and a second agent which is a dental curable composition, the kit being used by applying the first agent to an adherend and then further applying the second agent; The first agent is For 100 parts by mass of the first agent (A1) 2 to 30 parts by mass of a polymerizable monomer having an acidic group (A2) 0 to 50 parts by mass of a polymerizable monomer having no acidic group (D) 5 to 50 parts by mass of water, and (E) 0 to 50 parts by mass of a volatile organic solvent; The second agent per 100 parts by mass of the polymerizable monomer (A) contained in the second agent (B) 0.5 to 5.0 parts by mass of a polymerization initiator (C1) 40 to 120 parts by mass of an inorganic filler having X-ray contrast properties, and (C2) 3 to 20 parts by mass of hydrophobic silica fine particles having a primary particle diameter of less than 0.1 μm 7. A dental adhesive composition comprising the first and second parts according to claim 6, wherein the second part comprises:

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