Portion-packaged dental adhesive composition

Abstract

To provide a dental adhesive composition that exhibits excellent paste properties while maintaining stability of adhesive performance during storage.SOLUTION: A portion-packaged dental adhesive composition comprises: a first paste containing (A) polymerizable monomers comprising (A1) polymerizable monomers having an acidic group and (A2) polymerizable monomers free of acidic groups, (B1) a transition metal compound, (B2) a thiourea compound, (C) a polymerization inhibitor, and (D1) a hydrophobically treated basic filler that is free of Al2O3; and a second paste comprising (A2) a polymerizable monomer free of acidic groups, (B3) a hydroperoxide, (C) a polymerization inhibitor, and (D) a filler. Relative to 100 pts.mass of the (A) polymerizable monomers comprising (A1) and (A2), included in the first paste, (D1) is contained by 50 pts.mass or more in the first paste. After adding 1 g of (D1) to a mixed solution of 40 g of distilled water and 10 g of ethanol and then stirring for 1 hour, the mixed solution exhibits a pH of 8.0 to 11.0.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a dental adhesive composition in a packaged form. [Background technology]

[0002] In the dental field, dental adhesive compositions are widely used as dental resin cements, dental core building materials, dental filling materials, orthodontic materials, and the like.

[0003] Patent Documents 1 and 2 propose dental compositions containing a basic filler. Patent Document 3 proposes a manufacturing method and a dental composition containing inorganic particles treated with a chelate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6393393 [Patent Document 2] Patent Publication No. 2023-42510 [Patent Document 3] Patent Publication No. 2023-50935 Summary of the Invention [Problem to be solved by the invention]

[0005] However, these compositions have had a problem in terms of achieving both paste properties and long-term stability of adhesiveness. [Means for solving the problem]

[0006] As a result of extensive research, the present inventors have found that the above problems can be solved by using a specific composition.

[0007] The present disclosure provides the following: (Item 1) A dental adhesive composition in a package form, (A) a polymerizable monomer including (A1) a polymerizable monomer having an acidic group and (A2) a polymerizable monomer not having an acidic group, (B1) a transition metal compound, (B2) a thiourea compound, (C) a polymerization inhibitor, and (D1) Al 2 O 3 a first paste containing a hydrophobically treated basic filler that does not contain a second paste including (A2) a polymerizable monomer having no acidic group, (B3) a hydroperoxide, (C) a polymerization inhibitor, and (D) a filler; (D1) Al is added to 100 parts by mass of the polymerizable monomer (A) including the polymerizable monomer (A1) having an acidic group and the polymerizable monomer (A2) not having an acidic group, contained in the first paste. 2 O 3 The hydrophobized basic filler not including (D1)Al 2 O 3 A sachet-type dental adhesive composition, characterized in that when 1 g of a hydrophobically treated basic filler not containing EDTA is added to a mixed solution of 40 g of distilled water and 10 g of ethanol and stirred for 1 hour, the mixed solution has a pH of 8.0 to 11.0. (Item 2) (D1)Al 2 O 3 The hydrophobized basic filler is a filler containing zirconia and silica, and the specific surface area of ​​the basic filler before the hydrophobization treatment is 100 m 2 2. The packaged dental adhesive composition according to item 1, wherein the composition has a viscosity of 1.0 μm or more. (Item 3) 2. The packaged dental adhesive composition according to item 1, wherein the first paste contains 0.01 to 5 parts by mass of (E) water per 100 parts by mass of (A) polymerizable monomer. (Item 4) 3. The packaged dental adhesive composition according to item 2, wherein the first paste contains 0.01 to 5 parts by mass of (E) water per 100 parts by mass of (A) polymerizable monomer. (Item 5) 2. The packaged dental adhesive composition according to item 1, wherein the first paste contains 0.25 to 2 parts by mass of the polymerization inhibitor (C) per 100 parts by mass of the polymerizable monomer (A). (Item 6) 3. The packaged dental adhesive composition according to item 2, wherein the first paste contains 0.25 to 2 parts by mass of the polymerization inhibitor (C) per 100 parts by mass of the polymerizable monomer (A). (Item 7) 4. The individually packaged dental adhesive composition according to item 3, wherein the first paste contains 0.25 to 2 parts by mass of the polymerization inhibitor (C) per 100 parts by mass of the polymerizable monomer (A). (Item 8) 5. The individually packaged dental adhesive composition according to item 4, wherein the first paste contains 0.25 to 2 parts by mass of the polymerization inhibitor (C) per 100 parts by mass of the polymerizable monomer (A). (Item 9) The volume ratio of the first paste to the second paste ([first paste:second paste]) is 1:0.8 to 1.2, The first paste and the second paste are pastes containing a matrix and a (D) filler, In 100 parts by mass of the polymerizable monomer (A) contained in the first paste, (A1) 1 to 30 parts by mass of a polymerizable monomer having an acidic group, and (A2) 70 to 99 parts by mass of a polymerizable monomer having no acidic group, Relative to 100 parts by mass of the polymerizable monomer (A) contained in the first paste, (B1) 0.001 to 0.5 parts by mass of a transition metal compound, (B2) 0.1 to 5 parts by mass of a thiourea compound, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, (D1)Al 2 O 3 50 to 400 parts by mass of a hydrophobized basic filler not containing Relative to 100 parts by mass of the polymerizable monomer (A) contained in the second paste, (B3) 0.5 to 5 parts by mass of hydroperoxide, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, 6. The individually packaged dental adhesive composition according to item 5, comprising 50 to 400 parts by mass of (D) a filler. (Item 10) The volume ratio of the first paste to the second paste ([first paste:second paste]) is 1:0.8 to 1.2, The first paste and the second paste are pastes containing a matrix and a (D) filler, In 100 parts by mass of the polymerizable monomer (A) contained in the first paste, (A1) 1 to 30 parts by mass of a polymerizable monomer having an acidic group, and (A2) 70 to 99 parts by mass of a polymerizable monomer having no acidic group, For 100 parts by mass of the polymerizable monomer (A) contained in the first paste (B1) 0.001 to 0.5 parts by mass of a transition metal compound, (B2) 0.1 to 5 parts by mass of a thiourea compound, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, and (D1)Al 2 O 3 50 to 400 parts by mass of a hydrophobized basic filler not containing Relative to 100 parts by mass of the polymerizable monomer (A) contained in the second paste, (B3) 0.5 to 5 parts by mass of hydroperoxide, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, 7. The individually packaged dental adhesive composition according to item 6, comprising 50 to 400 parts by mass of (D) a filler. (Item 11) The volume ratio of the first paste to the second paste ([first paste:second paste]) is 1:0.8 to 1.2, The first paste and the second paste are pastes containing a matrix and a (D) filler, In 100 parts by mass of the polymerizable monomer (A) contained in the first paste, (A1) 1 to 30 parts by mass of a polymerizable monomer having an acidic group, and (A2) 70 to 99 parts by mass of a polymerizable monomer having no acidic group, For 100 parts by mass of the polymerizable monomer (A) contained in the first paste (B1) 0.001 to 0.5 parts by mass of a transition metal compound, (B2) 0.1 to 5 parts by mass of a thiourea compound, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, and (D1)Al 2 O 3 50 to 400 parts by mass of a hydrophobized basic filler not containing Relative to 100 parts by mass of the polymerizable monomer (A) contained in the second paste, (B3) 0.5 to 5 parts by mass of hydroperoxide, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, 8. The individually packaged dental adhesive composition according to item 7, comprising 50 to 400 parts by mass of (D) a filler. (Item 12) The volume ratio of the first paste to the second paste ([first paste:second paste]) is 1:0.8 to 1.2, The first paste and the second paste are pastes containing a matrix and a (D) filler, In 100 parts by mass of the polymerizable monomer (A) contained in the first paste, (A1) 1 to 30 parts by mass of a polymerizable monomer having an acidic group, and (A2) 70 to 99 parts by mass of a polymerizable monomer having no acidic group, For 100 parts by mass of the polymerizable monomer (A) contained in the first paste (B1) 0.001 to 0.5 parts by mass of a transition metal compound, (B2) 0.1 to 5 parts by mass of a thiourea compound, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, and (D1)Al 2 O 3 50 to 400 parts by mass of a hydrophobized basic filler not containing Relative to 100 parts by mass of the polymerizable monomer (A) contained in the second paste, (B3) 0.5 to 5 parts by mass of hydroperoxide, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, 9. The individually packaged dental adhesive composition according to item 8, comprising 50 to 400 parts by mass of (D) a filler. (Item 13) 13. The orthodontic adhesive composition according to any one of items 1 to 12. Effect of the Invention

[0008] An object of the present invention is to provide a dental adhesive composition which combines good paste properties with good long-term stability of adhesiveness. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The dental adhesive composition of the present invention is a material that can be used to restore the anatomical form of carious areas or missing teeth, or to improve tooth alignment and occlusion. The dental adhesive composition can be cured by polymerization reaction to obtain properties suitable for the desired application, that is, mechanical strength and adhesive strength that can withstand occlusal pressure. The polymerization reaction of the dental adhesive composition is roughly divided into photopolymerization, in which polymerization is initiated by irradiation with light, and chemical polymerization, in which polymerization is initiated by a chemical polymerization initiator and a chemical polymerization accelerator. Photopolymerization can be polymerized at any time by the surgeon by irradiating light, but the parts that the light does not reach cannot be polymerized at all. On the other hand, chemical polymerization, although the curing time depends on the type and amount of the chemical polymerization initiator and chemical polymerization accelerator, can also polymerize the parts that the light does not reach, and is therefore adopted in many dental materials. In addition, dental materials are required to have high storage stability that does not decrease the hardening property or change the properties regardless of the application.

[0010] Among dental adhesive compositions, orthodontic adhesive compositions are used for bonding orthodontic devices such as brackets and orthodontic crowns, attachments in aligner orthodontics, bite-up cases, etc. While a dental adhesive composition with high adhesive strength is required for bonding orthodontic devices that are subject to heavy loads, the orthodontic devices must be removed at the end of orthodontic treatment, and therefore removal of the orthodontic devices may be complicated if the adhesive strength is extremely high.

[0011] As described above, dental adhesive compositions containing a chemical polymerization initiator are preferable for bonding orthodontic devices such as metal brackets and orthodontic crowns that cannot be reached by light, but conventional dental adhesive compositions may suffer from reduced adhesiveness or changes in paste properties due to deterioration of the chemical polymerization initiator or alteration of polymerizable monomers having an acidic group, etc. Furthermore, when an orthodontic adhesive composition is made specifically for orthodontic crowns among orthodontic devices, the frequency of cases may be lower than when the composition is used for prosthetic devices such as crowns and inlays, and therefore it is necessary to be able to be used for a long period of time, and therefore there are cases in which extremely high storage stability is required compared to conventional cases.

[0012] The inventors have found that the above problems can be solved by using a specific filler, and have completed the present invention.

[0013] [(A) Polymerizable monomer] The (A) polymerizable monomer contained in the dental adhesive composition of the present invention can be used without any restriction as long as it is a known one. The (A) polymerizable monomer can be exemplified by one or more selected from (A1) polymerizable monomers having an acidic group and (A2) polymerizable monomers not having an acidic group. In the polymerizable monomer described in the present invention, the polymerizable group is preferably one that exhibits radical polymerizability, and specifically, from the viewpoint of easiness of radical polymerization, the polymerizable group is preferably a (meth)acrylic group and / or a (meth)acrylamide group. In this specification, "(meth)acrylic" means acryl and / or methacryl, "(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.

[0014] [(A1) Polymerizable monomer having an acidic group] The dental adhesive composition of the present invention contains in the first paste (A1) a polymerizable monomer having an acidic group. (A1) The polymerizable monomer having an acidic group can be used without any restrictions as long as it has one or more polymerizable groups and at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, or a carboxylic acid group. By containing a polymerizable monomer having an acidic group, it is possible to impart adhesion to teeth and prosthetic devices.

[0015] Specific examples of polymerizable monomers 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)acryloyloxypentyl dihydrogen phosphate, 14-(meth)acryloyloxyhexyl dihydrogen phosphate, 15-(meth)acryloyloxyhexyl dihydrogen phosphate, 16-(meth)acryloyloxyhexyl dihydrogen phosphate, 17-(meth)acryloyloxyheptyl dihydrogen phosphate, 18-(meth)acryloyloxyhexyl dihydrogen phosphate, 19-(meth)acryloyloxyhexyl dihydrogen phosphate, 20-(meth)acryloyloxyhexyl dihydrogen phosphate, 21-(meth)acryloyloxyhexyl dihydrogen phosphate, 22-(meth)acryloyloxyhexyl dihydrogen phosphate, 23-(meth)acryloyloxyhexyl dihydrogen phosphate, 24-(meth)acryloyloxyhexyl dihydrogen phosphate, 25-(meth)acryloyloxyhexyl dihydrogen phosphate, 26-(meth)acryloyloxyhexyl dihydrogen phosphate, 27-(meth)acrylo 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 phosphate, bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl]hydrogen phosphate, bis[9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di( Examples of the 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.

[0016] Specific examples of polymerizable monomers having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl]pyrophosphate, bis[4-(meth)acryloyloxybutyl]pyrophosphate, bis[6-(meth)acryloyloxyhexyl]pyrophosphate, bis[8-(meth)acryloyloxyoctyl]pyrophosphate, bis[10-(meth)acryloyloxydecyl]pyrophosphate; 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.

[0017] 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)acryloyloxyhexyl dihydrogen thiophosphate. Examples of the acryloyloxynonyl dihydrogen thiophosphate include 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, and 20-(meth)acryloyloxyicosyl dihydrogen thiophosphate; 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 phosphonic acid group include 2-(meth)acryloyloxyethyl phenyl phosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-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.

[0019] Specific examples of the polymerizable monomer having a sulfonic acid group include 2-(meth)acrylamide-2-methylpropanesulfonic acid, 2-sulfoethyl(meth)acrylate, and the like.

[0020] 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, 3-(meth)acryloyloxybenzoic acid, and 4-(meth)acryloyloxybenzoic acid. Examples of the acryloyloxybenzoic acid include 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxyethyl hydrogen malate; acid halides thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.Specific examples of (meth)acrylic compounds 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) p) acryloyloxyethyl trimellitic acid, 4-(meth)acryloyloxybutyl trimellitic acid, 4-(meth)acryloyloxyhexyl trimellitic acid, 4-(meth)acryloyloxydecyl trimellitic acid, 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.

[0021] The polymerizable monomer having an acidic group (A1) contained in the dental adhesive composition of the present invention is at least one selected from a polymerizable monomer having a phosphoric acid group, a polymerizable monomer having a phosphonic acid group, and a polymerizable monomer having a carboxylic acid group, and more preferably at least one selected from 10-methacryloyloxydecyl dihydrogen phosphate, 6-methacryloyloxyhexyl-3-phosphonoacetate, 4-methacryloyloxyethyl trimellitic acid, and 4-methacryloxyethyl trimellitic anhydride can be suitably used. It is preferable that the polymerizable monomer having an acidic group (A1) is contained in 100 parts by mass of the polymerizable monomer (A) contained in the first paste of the dental adhesive composition of the present invention from 1 to 30 parts by mass. When the blending amount of the polymerizable monomer having an acidic group (A1) is 1 part by mass or more relative to 100 parts by mass of the polymerizable monomer (A) contained in the first paste of the dental adhesive composition of the present invention, good adhesive strength tends to be expressed, and when it is 30 parts by mass or less, the stability of the paste property tends to be good. Furthermore, when the first paste of the dental adhesive composition of the present invention does not contain the polymerizable monomer having an acidic group (A1), good adhesive strength is not exhibited.

[0022] [(A2) Polymerizable monomer having no acidic group] The dental adhesive composition of the present invention contains (A2) a polymerizable monomer having no acidic group in the first paste and the second paste. The (A2) polymerizable monomer having no acidic group can be used without limitation as long as it has one or more polymerizable groups and does not have an acidic group. The (A2) polymerizable monomer having no acidic group includes those having one radical polymerizable group, those having two radical polymerizable groups, and those having three or more radical polymerizable groups. The (A2) polymerizable monomer having no acidic group may have a functional group (e.g., one or more selected from an alkoxysilyl group, a urethane, and an ether).

[0023] Specific examples of the polymerizable monomer having one radical polymerizable group among the polymerizable monomers having no acidic group (A2) 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)acrylate, and the like. Examples of the acryloylamide include 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.

[0024] Specific examples of polymerizable monomers having two radical polymerizable groups among the polymerizable monomers having no acidic group (A2) 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 such methacryloyloxy-2-hydroxypropoxy compounds include 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.

[0025] (A2) Specific examples of polymerizable monomers having three radically polymerizable groups among polymerizable monomers having no acidic group include 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, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane, and the like.

[0026] (A2) Specific examples of polymerizable monomers having an alkoxysilyl group among the polymerizable monomers not having an acidic group include (meth)acrylic compounds and (meth)acrylamide compounds having one alkoxysilyl group in the molecule, and (meth)acrylic compounds and (meth)acrylamide compounds having multiple alkoxysilyl groups in the molecule. Examples of the silane include 2-(meth)acryloxyethyl trimethoxysilane, 3-(meth)acryloxypropyl trimethoxysilane, 3-(meth)acryloxypropyl triethoxysilane, 3-(meth)acryloxypropyl methyl dimethoxysilane, 4-(meth)acryloxybutyl trimethoxysilane, 5-(meth)acryloxypentyl trimethoxysilane, 6-(meth)acryloxyhexyl trimethoxysilane, 7-(meth)acryloxyheptyl trimethoxysilane, 8-(meth)acryloxyoctyl trimethoxysilane, 9-(meth)acryloxynonyl trimethoxysilane, 10-(meth)acryloxydecyl trimethoxysilane, and 11-(meth)acryloxyundecyl trimethoxysilane.Furthermore, examples of compounds having a urethane group or an ether group include 3,3-dimethoxy-8,37-dioxo-2,9,36-trioxa-7,38-diaza-3-silatetracontan-40-yl(meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,18-trioxa-7-aza-3-silanonadecan-19-oyl)amino)-2-methylpropane-1,3-diyldi(meth)acrylate, and 3,3-dimethoxy-8,19-dioxo-2,9,18-trioxa-7,20-diaza-3-siladocosan-22-yl(meth)acrylate. acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21-hexaoxa-7,23-diaza-3-silapentacosan-25-yl (meth)acrylate, 3,3-dimethoxy-8,22-dioxo-2,9,12,15,18,21,26-heptaoxa-7,23-diaza-3-silaoctacosan-28-yl (meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18-pentaoxa-7,20-diaza-3-siladocosane-22-yl (meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18-pentaoxa-7,20-diaza-3-siladocosane-22-yl (meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,12,15,18-pentaoxa-7-aza-3-silanonadecane-19-yl)amino)-2-methylpropane-1,3-diyl di(meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosane-23-yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosane-23-yl (meth)acrylate 4,4-diethoxy-13-oxo-3,12,17-trioxa-14-aza-4-silanonadecan-19-yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silaicosan-20-yl (meth)acrylate, and 2-methyl-2-((11-(triethoxysilyl)undecyloxy)carbonylamino)propane-1,3-diyl di(meth)acrylate.

[0027] In addition to these polymerizable monomers, there is no limitation in using oligomers or prepolymers having at least one polymerizable group in the molecule. In addition, there is no problem in having a substituent such as a fluoro group in the same molecule. The above-mentioned polymerizable monomers can be used alone or in combination.

[0028] The dental adhesive composition of the present invention preferably contains 70 to 99 parts by mass of the polymerizable monomer (A2) having no acidic group in 100 parts by mass of the polymerizable monomer (A) contained in the first paste. Also, it is preferable that the composition contains 95 to 100 parts by mass of the polymerizable monomer (A2) having no acidic group in 100 parts by mass of the polymerizable monomer (A) contained in the second paste, and more preferably contains 99 to 100 parts by mass. A smaller amount of the polymerizable monomer (A2) having no acidic group contained in the second paste means that the amount of the polymerizable monomer (A1) having an acidic group is increased, and it is preferable that the amount of the polymerizable monomer (A1) having an acidic group contained in the second paste is 5 parts by mass or less, since the adhesive strength after long-term storage is better than when the amount exceeds 5 parts by mass.

[0029] <(B) Chemical Polymerization Initiator> The dental adhesive composition of the present invention contains a chemical polymerization initiator. Chemical polymerization is a polymerization method that hardens without requiring special equipment such as a light irradiator, and a chemical polymerization initiator is a polymerization initiator that can start chemical polymerization. As chemical polymerization initiators, the dental adhesive composition of the present invention contains a transition metal compound (B1) and a thiourea compound (B2) in the first paste, and a hydroperoxide (B3) in the second paste. These can be any known compounds that are commonly used without any restrictions.

[0030] [(B1) Transition metal compound] The dental adhesive composition of the present invention contains a transition metal compound (B1). In the present invention, the transition metal compound (B1) is used as a chemical polymerization initiator. As specific examples of the transition metal compound (B1) that can be used in the dental adhesive composition of the present invention, a copper (Cu) compound or a vanadium (V) compound can be preferably used. Examples of copper (Cu) compounds that can be used include copper chloride (monovalent), copper bromide (monovalent), copper chloride (divalent), copper acetate (divalent), copper gluconate (divalent), copper acetylacetonate (divalent), and copper methacrylate (divalent). Examples of vanadium compounds that can be used include vanadium acetylacetonate (trivalent), divanadium tetroxide (tetravalent), vanadyl acetylacetonate (tetravalent), vanadyl stearate oxide (tetravalent), vanadyl oxalate (tetravalent), vanadyl sulfate (tetravalent), oxo-bis(1-phenyl-1,3-butanedionato)vanadium (tetravalent), bis(maltolato)oxo-vanadium (tetravalent), vanadium pentoxide (pentavalent), and sodium metavanadate (pentavalent). Among these, copper acetate (divalent), copper gluconate (divalent), copper acetylacetonate (divalent), copper methacrylate (divalent), vanadium acetylacetonate (trivalent), vanadyl acetylacetonate (tetravalent), vanadium oxide stearate (tetravalent), and bis(maltolato)oxovanadium (tetravalent) can be preferably used. As the transition metal compound, any known transition metal compound can be used without limitation. These transition metal compounds may be used in combination with a plurality of types as necessary. The blending amount of the transition metal compound is preferably 0.001 to 0.5 parts by mass relative to 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the first paste. When the blending amount is 0.001 parts by mass or more, the adhesive strength tends to be good due to a certain level of chemical polymerizability, and when the blending amount is 0.5 parts by mass or less, the paste properties tend to be stable during long-term storage.

[0031] [(B2) Thiourea compounds] The dental adhesive composition of the present invention contains a thiourea compound. In the present invention, the thiourea compound (B2) is used as a chemical polymerization initiator. Specific examples of the thiourea compound (B2) that can be used in the dental adhesive composition of the present invention include 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, (2-pyridyl)thiourea, N-acetylthiourea, N-benzoylthiourea, and N-benzylthiourea are preferably used. As the thiourea compound, any known thiourea derivative can be used without limitation. A plurality of types of these thiourea derivatives may be used in combination as necessary. The amount of the thiourea derivative is preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the first paste. If the amount is 0.1 part by mass or more, the adhesive strength tends to be good because the compound has a certain level of chemical polymerizability, and if the amount is 5 parts by mass or less, the dispersibility in the polymerizable monomer tends to be good.

[0032] [(B3) Hydroperoxide] The dental adhesive composition of the present invention contains a hydroperoxide (B3). In the present invention, the hydroperoxide (B3) is used as a chemical polymerization initiator. Specific examples of the hydroperoxide (B3) that can be used in the dental adhesive composition of the present invention include 2,5-dimethylhexane-2,5-dihydroperoxide, tert-amyl hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and the like. Among these, 1,1,3,3-tetramethylbutyl hydroperoxide and cumene hydroperoxide are preferably used. As the hydroperoxide, any known hydroperoxide can be used without any restrictions. A plurality of types of these hydroperoxides may be used in combination as necessary. The amount of the hydroperoxide is preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the second paste. When it is 0.5 parts by mass or more, the adhesive strength tends to be good due to a certain level of chemical polymerizability, and when it is 5 parts by mass or less, the stability of the paste properties during long-term storage tends to be good.

[0033] The polymerization initiators (B1) transition metal compounds, (B2) thiourea compounds, and (B3) hydroperoxides may be subjected to secondary treatments such as fine pulverization, carrier adsorption, and encapsulation in microcapsules, if necessary, without any problems. Furthermore, these various types of chemical polymerization initiators can be used alone or in combination of two or more types, regardless of the polymerization mode or polymerization method.

[0034] Examples of the (B) chemical polymerization initiator other than the (B1) transition metal compound, (B2) thiourea compound, and (B3) hydroperoxide contained in the (B) chemical polymerization initiator include amine compounds, phosphine compounds, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, halogen compounds, and ascorbic acid compounds.

[0035] Specific examples of the amine compound include pN,N-dihydroxyethyl-toluidine and pN,N-dihydroxypropyl-toluidine. Specific examples of the phosphine compound include triphenylphosphine and 4-(phenylphosphino)benzoic acid. Specific examples of the sulfinic acid and its salts include sodium benzenesulfinate, sodium p-toluenesulfinate and sodium 2,4,6-triisopropylbenzenesulfinate. Examples of the borate compound include sodium salts, lithium salts, potassium salts and tetrabutylammonium salts of tetraarylborate compounds. Examples of the barbituric acid derivatives include sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate and sodium 1-cyclohexyl-5-ethylbarbiturate and their sodium salts or calcium salts. Specific examples of the ascorbic acid compound include ascorbic acid, ascorbyl 6-palmitate and their salt compounds.

[0036] The dental adhesive composition of the present invention may contain, as a chemical polymerization initiator, (B) a chemical polymerization initiator other than (B1) a transition metal compound, (B2) a thiourea compound, and (B3) a hydroperoxide.

[0037] [(C) Polymerization inhibitor] The dental adhesive composition of the present invention contains a polymerization inhibitor (C). The type of polymerization inhibitor (C) is not limited as long as it is a known polymerization inhibitor such as a phenolic compound, a phosphorus compound, a sulfur compound, or an amine compound, and a polymerization inhibitor can be blended according to the application.

[0038] Suitable polymerization inhibitors that can be used in the present invention include phenol-based polymerization inhibitors. Specific examples thereof include 4-methoxyphenol, 6-tert-butyl-2,4-xylenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methoxyphenol, 2,6-di-tert-butyl-4-ethylphenol, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate stearyl ... 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) )-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-tert-butyl-4,6-dimethylphenol, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] Among these, hindered phenol-based polymerization inhibitors are preferred, and more preferred are 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene, and 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate.

[0039] If the dental adhesive composition of the present invention does not contain the polymerization inhibitor (C), changes in paste properties and gelation of the paste may occur after long-term storage. The dental adhesive composition of the present invention preferably contains 0.03 to 2 parts by mass of the polymerization inhibitor (C) per 100 parts by mass of the polymerizable monomer (A) contained in the first paste, and more preferably 0.25 to 2 parts by mass. When the polymerization inhibitor (C) is 0.03 parts by mass or more, the storage stability tends to be good, and when it is 2 parts by mass or less, the adhesive strength tends to be good. In addition, the higher the content of the polymerization inhibitor (C), the higher the Al (D1) contained in the first paste. 2 O 3 This is preferable because long-term stability of the paste properties can be expected regardless of the type of hydrophobized basic filler that does not contain (A). In addition, the dental adhesive composition of the present invention preferably contains 0.03 to 2 parts by mass of (C) a polymerization inhibitor per 100 parts by mass of (A) a polymerizable monomer contained in the second paste.

[0040] [(D) Filler] The dental adhesive composition of the present invention contains a filler (D). The filler (D) is (D1) Al 2 O 3 Hydrophobically treated basic filler not containing (D2)Al 2 O 3 Examples of the filler include one or more inorganic fillers other than hydrophobically treated basic fillers not containing

[0041] (D) The type of filler is not limited as long as it is a known filler, and a filler according to its application can be blended, and it is preferable to blend a filler such as an inorganic filler, an organic filler, or an organic-inorganic composite filler. An example of an inorganic filler is ion-releasing glass. The dental adhesive composition of the present invention may use the exemplified fillers alone or in combination of two or more kinds.

[0042] The inorganic filler is not particularly limited in its chemical composition, but specific examples include 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, strontium calcium fluoroaluminosilicate glass, etc. In particular, fluoroaluminosilicate barium glass, fluoroaluminosilicate strontium glass, fluoroaluminosilicate glass, etc., which are used in dental glass ionomer cement, resin-reinforced glass ionomer cement, resin cement, etc., can also be suitably used. The fluoroaluminosilicate glass referred to here has a basic skeleton of silicon oxide and aluminum oxide, and contains an alkali metal for the introduction of non-bridging oxygen. It also contains alkaline earth metals including strontium and fluorine as modifying and coordinating ions. It is also a composition in which a lanthanide series element is incorporated into the skeleton to provide further X-ray opacity. This lanthanide series element is also incorporated into the composition as a modifying and coordinating ion depending on the composition range.

[0043] The inorganic filler may contain hydrophobized inorganic fine particles. The hydrophobized inorganic fine particles preferably have an average primary particle diameter of 0.1 to 50 nm, and are preferably hydrophobized by treatment with a silane coupling agent and / or modified silicone oil. By blending the hydrophobized inorganic fine particles, it is expected that the precipitation of the inorganic filler is suppressed and rheological properties are imparted in addition to improving the bending strength.

[0044] Specific examples of organic fillers include polymers such as 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, and polycarbonate.

[0045] Examples of organic-inorganic composite fillers include, but are not limited to, inorganic fillers whose surfaces are coated with a polymerizable monomer; inorganic fillers and polymerizable monomers are mixed and polymerized, and then pulverized to an appropriate particle size; inorganic fillers that have been previously dispersed in polymerizable monomers and then emulsion-polymerized or suspension-polymerized; inorganic fillers that have been previously dispersed in polymerizable monomers and solvents, then spray-dried, and then polymerized; and inorganic fillers that have been previously dispersed in a solvent, then spray-dried, then impregnated with a polymerizable monomer, and then polymerized.

[0046] The ion-releasing glass is characterized by releasing at least one of fluorine ions, strontium ions, borate ions, and aluminum ions, and it is preferable that a plurality of these ions are released simultaneously.

[0047] The ion-releasing glass used in the present invention can be any ion-releasing glass without any limitation as long as it contains one or more glass skeleton forming elements that form a 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 of a plurality of ion-releasing glasses. In addition, in the present invention, glass amphoteric elements that play the role of either a glass skeleton forming element or a glass modifying element 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 glass include silica, aluminum, boron, phosphorus, etc., and these can be used alone or in combination of a plurality of elements. Specific examples of glass modifying elements include halogen elements such as fluorine, bromine, and iodine, alkali metal elements such as sodium and lithium, and alkaline earth metal elements such as calcium and strontium, and these can be used alone or in combination of a plurality of elements. Among these, it is preferable to include silica, aluminum, and boron as glass skeleton forming elements and fluorine, sodium, and strontium as glass modifying elements, and specific examples include silica glass, fluoroaluminosilicate glass, fluoroborosilicate glass, and fluoroaluminoborosilicate glass containing 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. Specific examples of more preferable glass composition ranges include SiO 2 :10~40% by mass, Al 2 O 3 :10~35% by mass, B 2 O 3 :2.5~30% by mass, SrO:15~50% by mass, F:2.5~20% by mass, Na 2 O: 0 to 15 mass %. This glass composition can be confirmed by using instrumental analysis such as elemental analysis, Raman spectroscopy, and fluorescent X-ray analysis, but there is no problem if the actual measured value by any of the analysis methods matches this composition range.

[0048] The manufacturing method of these ion-releasing glasses is not particularly limited, and they can be manufactured by a manufacturing method such as a melting method or a sol-gel method. Among them, the manufacturing method using a melting furnace is preferable from the viewpoint of ease of glass composition design including the selection of raw materials. The ion-releasing glass used in the present invention has an amorphous structure, but there is no problem even if it contains a part of a crystalline structure, and there is no problem even if it is a mixture of glass having an amorphous structure and glass having a crystalline structure. The judgment of whether the glass structure is amorphous or not can be confirmed using an analytical instrument such as X-ray diffraction analysis or a transmission electron microscope. Among them, the ion-releasing glass used in the present invention is preferably an amorphous structure, which is a homogeneous structure, since various ions are gradually released due to the equilibrium relationship with the ion concentration in the external environment.

[0049] Furthermore, in order to enhance the ion release from the ion-releasing glass, it is preferable to perform a surface treatment on the glass surface to functionalize it and improve the ion release. Specific examples of surface treatment materials used for the surface treatment include surfactants, fatty acids, organic acids, inorganic acids, monomers, polymers, various coupling materials, silane compounds, metal alkoxide compounds, and partial condensates thereof. Among these surface treatment materials, it is preferable to perform a composite surface treatment using an acidic polymer and a silane compound.

[0050] This composite surface treatment is a method in which the surface of the ion-releasing glass is coated with a silane compound, and then the surface is treated with an acidic polymer, as will be specifically described below. A silane compound is mixed into an aqueous dispersion containing ion-releasing glass that has been finely pulverized to a desired average particle size by grinding or the like, 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 coated on the surface of the ion-releasing glass to form a polysiloxane-coated ion-releasing glass.

[0051] Specific examples of silane compounds that can be used for the polysiloxane coating include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraallyloxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, trimethoxychlorosilane, triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane, diethoxydichlorosilane, tetraphenoxysilane, tetrachlorosilane, silicon hydroxide (silicon oxide hydrate), and the like, with tetramethoxysilane and tetraethoxysilane being more preferred.

[0052] Furthermore, it is more preferable that the silane compound used for the polysiloxane coating is a low condensation compound. For example, a low condensation silane compound obtained by partially hydrolyzing and condensing tetramethoxysilane and tetraethoxysilane. These compounds can be used alone or in combination.

[0053] The polysiloxane-coated ion-releasing glass obtained in the previous step can be subjected to an acidic polymer treatment to react with an acidic polymer to obtain an ion-releasing glass. The acidic polymer treatment can be performed using equipment commonly used in the industry as long as it is a dry-fluidized mixer, such as a Henschel mixer, a super mixer, or a high-speed mixer. The reaction of the acidic polymer with the ion-releasing glass on which the polysiloxane coating has been formed can be performed by contacting the glass with an acidic polymer solution by impregnation or spraying. For example, the polysiloxane-coated ion-releasing glass is dry-fluidized, and the acidic polymer solution is dispersed from the top while the glass is in the fluidized state, and the glass is sufficiently stirred. There is no particular restriction on the method of dispersing the acidic polymer solution, but a dripping or spraying method that allows uniform dispersion is more preferable. The reaction is preferably performed at around room temperature, and as the temperature increases, the reaction between the acid-reactive element and the acidic polymer becomes faster, resulting in non-uniform formation of the cement phase.

[0054] It is preferable to remove moisture in the cement reaction phase by performing heat treatment after the reaction. If moisture remains in the cement reaction phase, it is disadvantageous in terms of strength, but the filler of the present invention is suppressed from decreasing in mechanical strength by the polysiloxane coating. The heat treatment method after the acidic polymer treatment 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 in the range of 40 to 150°C. If the temperature is lower than this range, the aqueous medium is not sufficiently removed, and if it is higher than this range, the organic layer of the acidic polymer may decompose or discolor. Since the heat treatment time depends on the capacity of the dryer, etc., there is no problem as long as the aqueous medium can be sufficiently removed. After the heat treatment, the heat-treated product can be easily crushed by applying a shear force or an impact force, and the crushing method can be performed using the equipment used in the above reaction.

[0055] The solvent used in the preparation of the acidic polymer solution used in the reaction can be any solvent that dissolves the acidic polymer, including water, ethanol, acetone, etc. Among these, water is particularly preferred, since it allows the acidic groups of the acidic polymer to dissociate and react uniformly with the surface of the basic filler, which is the core.

[0056] The weight-average molecular weight of the acidic polymer is in the range of 2000 to 50000, preferably in the range of 5000 to 40000. When treated with an acidic polymer having a weight-average molecular weight of less than 2000, an acidic polymer reaction phase is not formed in the polysiloxane-coated ion-release glass, and as a result, the ion-release property tends to be reduced. On the other hand, when treated with an acidic polymer having a weight-average molecular weight of more than 50000, the viscosity of the acidic polymer solution increases, making it difficult to uniformly treat the polysiloxane-coated ion-release glass. In addition, the acidic polymer concentration in 100 parts by mass of the acidic polymer solution is preferably in the range of 3 to 25 parts by mass, more preferably in the range of 8 to 20 parts by mass. When the acidic polymer concentration is less than 3 parts by mass, the acidic polymer reaction phase described above becomes fragile, and the effect of improving the ion-release property cannot be obtained. Furthermore, if the acidic polymer concentration exceeds 25 parts by mass, it is difficult to uniformly diffuse the polysiloxane layer (porous), and a homogeneous acidic polymer reaction phase cannot be obtained. In addition, since the reaction occurs immediately upon contact with the polysiloxane-coated ion-releasing glass, problems such as the formation of strongly reacted aggregates occur. Furthermore, the amount of the acidic polymer solution added to the polysiloxane-coated ion-releasing glass is preferably in the range of 6 to 40 parts by mass, more preferably 10 to 30 parts by mass. Converted based on this amount of addition, the optimal amount of acidic polymer and the optimal amount of water are 1 to 7 parts by mass and 10 to 25 parts by mass, respectively, relative to the polysiloxane-coated ion-releasing glass.

[0057] The acidic polymer that can be used to form an acidic polymer reaction phase on the surface of the polysiloxane-coated ion-releasing glass by the above-mentioned method can be any copolymer or homopolymer of a polymerizable monomer having an acidic group such as a phosphate residue, a pyrophosphate residue, a thiophosphate residue, a carboxylic acid residue, or a sulfonic acid residue as the acidic 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)acryloyloxyethyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, and the like. Examples of the dihydrogen phosphate include 20-(meth)acryloyloxyeicosyl dihydrogen phosphate, 1,3-di(meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl phosphate, 2-(meth)acryloyloxyethyl-2'-bromoethyl phosphate, (meth)acryloyloxyethyl phenyl phosphonate, di(2-(meth)acryloyloxyethyl) pyrophosphate, 2-(meth)acryloyloxyethyl dihydrogen dithiophosphorate, and 10-(meth)acryloyloxydecyl dihydrogen thiophosphate. Among the polymers (co)polymerized using these polymerizable monomers, it is preferable to use a homopolymer or copolymer of an α-β unsaturated carboxylic acid, which has a relatively slow acid-base reaction with the acid-reactive element contained in the polysiloxane-coated ion-releasing glass, and specifically, examples thereof include an acrylic acid polymer, an acrylic acid-maleic acid copolymer, and an acrylic acid-itaconic acid copolymer.

[0058] The above-mentioned (D) filler can be treated with a surface treatment material, typically a silane coupling agent, for the purpose of improving the affinity with the polymerizable monomer, dispersibility in the polymerizable monomer, and mechanical strength and water resistance of the cured product. Such surface treatment material and surface treatment method are not particularly limited, and known methods can be used without limitation, such as a method of spraying the surface treatment material while stirring the powdered filler, a method of dispersing and mixing the filler and the surface treatment material in a solvent, and a method of supplying the silane coupling agent in a vapor or gaseous state to the filler surface. As the silane coupling agent used for the surface treatment of the filler, 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 or hexamethyldisilazane are preferred. In addition to the silane coupling agent, the surface treatment of the filler can be performed by a method using a titanate-based coupling agent or an aluminate-based coupling agent. The amount of the treatment with the surface treatment agent in the filler is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the filler before treatment.

[0059] The shape of the (D) filler is not particularly limited, and fillers of any shape such as spheres, needles, plates, crushed pieces, scales, etc. The average particle size of the filler is preferably in the range of 0.01 μm to 50 μm, more preferably 0.01 μm to 30 μm, still more preferably 0.05 μm to 20 μm, and even more preferably 0.05 μm to 10 μm.

[0060] [(D1)Al 2 O 3 Hydrophobically treated basic filler that does not contain The dental adhesive composition of the present invention comprises in the first paste (D1) Al 2 O 3 (D1) Contains a hydrophobized basic filler that does not contain Al. 2 O 3 By including the hydrophobically treated basic filler that does not contain any of the above, the dental adhesive composition can maintain good adhesive strength and paste properties for a long period of time.

[0061] (D1)Al 2 O 3 It is not clear why the dental adhesive composition exhibits good long-term stability by using a hydrophobically treated basic filler that does not contain (B1). When one or more compounds selected from transition metal compounds, (B2) thiourea compounds, and (B3) hydroperoxides are stored in the same composition as the polymerizable monomer having an acidic group (A1), the storage stability may be poor. This is believed to be due to the reaction between the acidic component of the polymerizable monomer having an acidic group (A1) and the chemical polymerization initiator. Therefore, (D1) Al is added as a component that can moderately interact with the polymerizable monomer having an acidic group (A1). 2 O 3 We believe that the hydrophobic treated basic packing material that does not contain Al is functioning. 2 O 3 Since the hydrophobized basic filler that does not contain Al is hydrophobized, it does not bond strongly to the polymerizable monomer having an acidic group (A1), and therefore the adhesion is stable for a long period of time. 2 O 3 It is presumed that when the first paste contains (A1), aluminum ions may be partially released, causing the polymerizable monomer having an acidic group (A1) to crosslink three-dimensionally, resulting in a decrease in long-term stability. In addition, the reason why the first paste does not contain the polymerizable monomer having an acidic group (A1) and the hydroperoxide (B3) is that when the amount of the polymerizable monomer having an acidic group (A1) blended is extremely high, the long-term stability may be inferior to that when the transition metal compound (B1) and the thiourea compound (B2) are coexisting.

[0062] (D1)Al2 O 3 Hydrophobically treated basic filler that does not contain Al 2 O 3 As a result of the inventor's investigation, 2 O 3 It was confirmed that when a hydrophobized basic filler containing (D1) Al was blended with (A1) a first paste containing a polymerizable monomer having an acidic group, the adhesiveness and long-term stability of the paste properties decreased. In particular, there was a tendency for stability to decrease significantly when the blending amount was large. On the other hand, (D1) Al 2 O 3 When using a hydrophobically treated basic filler that does not contain Al, good paste properties and long-term stability of adhesiveness tended to be exhibited. 2 O 3 Hydrophobically treated basic filler containing no Al 2 O 3 The content of Al in the basic filler before the hydrophobization treatment is preferably 1% by weight or less, more preferably 0.1% by weight or less, and further preferably it is completely absent. 2 O 3 Hydrophobically treated basic filler containing no Al 2 O 3 When the amount is small relative to the amount of the basic filler before the hydrophobization treatment, it does not have a significant effect on the long-term stability.

[0063] (D1)Al 2 O 3The hydrophobic treatment in the hydrophobic treated basic filler not containing refers to a surface treatment with a surfactant or a coupling agent. The hydrophobic treatment using a silane coupling agent is preferable, and examples of the silane coupling agent used in the hydrophobic treatment include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxyoctyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, and hexamethyldisilazane. The hydrophobic treatment is preferably performed using 1 part by mass or more of a surfactant or a coupling agent per 100 parts by mass of the filler.

[0064] (D1)Al 2 O 3 A basic filler in a hydrophobized basic filler not containing (D1)Al is defined as a filler having a pH of 8.0 to 11.0 when 1 g of the filler is added to a mixed solution of 40 g of distilled water and 10 g of ethanol and stirred for 1 hour under the condition of 23°C ± 3°C. If the pH is less than 8.0, the filler is not basic enough, so that the expected effect of adhesive strength and long-term stability of paste properties when blended in a dental adhesive composition is not fully exhibited, and if the pH exceeds 11.0, although it is a basic filler, it may cause a decrease in adhesive strength when blended in a dental adhesive composition due to its excessive basicity. 2 O 3 The more preferred pH of the dispersion when 1 g of a hydrophobized basic filler not containing (D1)Al is added to a mixed solution of 40 g of distilled water and 10 g of ethanol and stirred for 1 hour is 9.0 to 10.5. 2 O 3 A dental adhesive composition containing a basic filler in the hydrophobically treated basic filler not containing any of the above can be expected to have particularly good adhesive strength and long-term stability of paste properties.

[0065] (D1)Al 2O 3 The basic fillers in the hydrophobically treated basic fillers that do not contain Al are 2 O 3 The chemical composition is not particularly limited as long as it does not contain (D1). Specific examples include silicon dioxide, titania, silica-titania, silica-titania-barium oxide, silica-zirconia, lanthanum glass, borosilicate glass, and barium glass. Among these, silica-zirconia is preferable. (D2) Al 2 O 3 In the hydrophobized basic filler not containing, it is preferable that 95 parts by mass or more of 100 parts by mass of the basic filler is composed of silica or zirconia, and more preferably 99 parts by mass or more of the basic filler is composed of silica or zirconia.

[0066] (D1)Al 2 O 3 The average particle size of the basic filler before hydrophobic treatment constituting the hydrophobic treated basic filler not containing 2 / g or more, and particularly preferably 100m 2 / g or more. 2 / g or more, the stability of the paste properties is particularly favorable. Furthermore, when used in orthodontic adhesives, it is expected to produce an appropriate adhesive strength. Particle size can be measured using a laser diffraction particle size distribution measuring device or an electron microscope. Furthermore, the specific surface area can be measured by the BET method. For example, the specific surface area can be measured by the gas adsorption method using a gas adsorption analyzer.

[0067] The dental adhesive composition of the present invention comprises, for every 100 parts by mass of the polymerizable monomer (A) contained in the first paste, (D1) Al in the first paste. 2 O 3 (D1) Contains 50 parts by mass or more of a hydrophobized basic filler that does not contain Al. 2 O 3When the hydrophobized basic filler does not contain (D1)Al and the basic filler contains 50 parts by mass or more, good storage stability is exhibited. 2 O 3 When the amount of the hydrophobic basic filler not containing Al is less than 50 parts by mass, sufficient storage stability may not be exhibited. 2 O 3 Hydrophobically treated basic filler containing Al 2 O 3 In the case of non-hydrophobized basic fillers that do not contain Al, the adhesive strength and paste property stability may decrease. 2 O 3 Hydrophobically treated basic filler containing Al 2 O 3 The amount of the non-hydrophobic treated basic filler not containing Al is proportional to the amount of the non-hydrophobic treated basic filler. 2 O 3 Hydrophobically treated basic filler containing Al 2 O 3 The amount of the non-hydrophobized basic filler not containing (A) is preferably 50 parts by mass or less, more preferably 10 parts by mass or less, and most preferably none, per 100 parts by mass of the (A) polymerizable monomer contained in the first paste.

[0068] The dental adhesive composition of the present invention contains 50 to 400 parts by mass of (D) filler per 100 parts by mass of (A) polymerizable monomer contained in each of the first paste and the second paste.

[0069] [(E)Wed] The dental adhesive composition of the present invention may contain water (E). The water (E) is not limited to distilled water, ion-exchanged water, or other common water. The dental adhesive composition of the present invention may have high adhesive strength by containing water (E) in the first paste. The dental adhesive composition of the present invention has a curing mechanism mainly caused by radical polymerization by a chemical polymerization initiator (B). On the other hand, the glass ionomer cement has a curing mechanism mainly caused by a glass ionomer reaction by polyacrylic acid, water, and fluoroaluminosilicate. The dental adhesive composition of the present invention is clearly distinguished from glass ionomer cement because it cures sufficiently even when it does not contain water (E), and the preferred blending amount of water (E) is also clearly less than that of glass ionomer cement. The dental adhesive composition of the present invention preferably contains 0.01 to 5 parts by mass of water (E) relative to 100 parts by mass of polymerizable monomer (A) contained in the first paste, and more preferably contains 0.01 to 2 parts by mass of water. When the blending amount of (E) water is 0.01 parts by mass or more, the adhesive strength tends to be excellent, and when it contains 5 parts by mass or less, the mechanical strength and adhesive strength tend to be excellent.

[0070] [Photopolymerization initiator] The dental adhesive composition of the present invention may contain a photopolymerization initiator. The photopolymerization initiator is a polymerization initiator that can initiate polymerization by irradiation with light. Examples of photopolymerization initiators that can be used in the dental adhesive composition of the present invention include photosensitizers, photoacid generators, and photopolymerization accelerators. These can be any known compounds that are generally used without any restrictions.

[0071] Specific examples of photosensitizers that can be used in the dental adhesive composition of the present invention include α-diketones such as camphorquinone, camphorquinone carboxylic acid, and camphorquinone sulfonic acid; benzoin alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; thioxanthones such as 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone; benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone; acylphosphine oxides such as diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; and acylgermanium compounds such as bisbenzoyldiethylgermanium and bisbenzoyldimethylgermanium.

[0072] Examples of photoacid generators that can be used in the dental adhesive composition of the present invention include triazine compounds, iodonium salt compounds, sulfonium salt compounds, and sulfonic acid ester compounds. Among these, triazine compounds and iodonium salt compounds are preferred because they have high polymerizability when used in combination with a sensitizer. Specific examples of preferred iodonium salt compounds include 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.

[0073] The photopolymerization accelerator that can be used in the dental adhesive composition of the present invention is an amine compound, such as p-dimethylaminobenzoic acid ethyl ester, triethanolamine, triisopropanolamine, tribenzylamine, dibenzylglycine ethyl ester, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, and N,N-diisopropylaminoethyl methacrylate.

[0074] <Other ingredients> In addition, the dental adhesive composition of the present invention may contain components other than the above components (A) to (E) as long as the effects of the present invention are not impaired. For example, excipients such as fumed silica, benzophenone-based and benzotriazole-based ultraviolet absorbers, α-alkylstyrene compounds, mercaptan compounds such as n-butyl mercaptan and n-octyl mercaptan, chain transfer materials such as terpenoid compounds such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene, and α-pinene, metal capture materials such as aminocarboxylic acid-based chelating agents and phosphonic acid-based chelating agents, discoloration inhibitors, antibacterial agents, color pigments, and other conventionally known additives can be added as necessary.

[0075] The method for producing the dental adhesive composition of the present invention is not particularly limited. A general method for producing a dental adhesive composition includes a method in which (A) polymerizable monomers excluding (D) filler, (B) chemical polymerization initiators, (C) polymerization inhibitors, etc. are mixed in advance by a known method such as a rotation-revolution mixer, a tumbler mixer, a mix rotor, a dissolver, a planetary mixer, etc. to prepare a matrix, and then this matrix and (D) filler are kneaded by a known method such as a rotation-revolution mixer, a tumbler mixer, a mix rotor, a dissolver, a planetary mixer, etc., and air bubbles are removed under reduced pressure to prepare a uniform paste. In the present invention, the matrix refers to a mixed solution prepared by mixing components excluding (D) filler, and specifically refers to a mixed solution prepared by mixing (A) polymerizable monomers, (B) chemical polymerization initiators, (C) polymerization inhibitors, etc. in advance. If any of (A) polymerizable monomers, (B) chemical polymerization initiators, and (C) polymerization inhibitors does not dissolve uniformly in the matrix, the matrix may not contain one or more of these. As a method of blending the dental adhesive composition of the (A) polymerizable monomer, (B) chemical polymerization initiator, and (C) polymerization inhibitor not contained in the matrix, it is preferable to blend them when mixing the matrix and (D) filler. The 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, it is preferable to mix at a temperature of 50°C for those that can be mixed at high temperatures. On the other hand, it is preferable to mix at a temperature of 25±5°C for those that may deteriorate due to heating, such as (B) chemical polymerization initiator. The most preferable manufacturing method is a method in which the (A) polymerizable monomer, (B) chemical polymerization initiator, (C) polymerization inhibitor, etc. are mixed in advance to prepare a uniform matrix, and then the (D) filler is mixed to manufacture the dental adhesive composition. In the present invention, the above manufacturing method can be used to manufacture the dental adhesive composition without any problems.

[0076] The dental adhesive composition of the present invention is used by mixing the first paste and the second paste. As a mixing method, a method of discharging equal amounts of the first paste and the second paste filled in a double syringe and mixing them using a spatula, or a method of attaching a static mixer to a double syringe and pushing in the plunger to mix the first paste and the second paste can be used, but any known mixing method can be used. The mixing ratio of the first paste and the second paste is preferably 1:0.8 to 1.2 in volume ratio ([first paste:second paste]), and more preferably 1:1. The mass ratio ([first paste:second paste]) is preferably 1:0.7 to 1.3, and more preferably 1:1.

[0077] The dental adhesive composition of the present invention comprises (A) a polymerizable monomer, (B) a chemical polymerization initiator, (C) a polymerization inhibitor, and (D1) Al. 2 O 3 It may contain only the filler (D) containing a hydrophobically treated basic filler that does not contain any of the following: Also, it may contain only one or more of the above-mentioned components as components other than (A) to (D). EXAMPLES

[0078] 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-Methacryloxyethyltrimellitic acid ·MHPA: (6-methacryloyloxy)hexyl phosphonoacetate META: 4-Methacryloyloxyethoxycarbonylphthalic anhydride <(A2) Polymerizable monomer having no acidic group> BisGMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane 2.6E: 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane having an average molar number of ethoxy groups of 2.6. ·UDMA: N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)ethanol]methacrylate TEGDMA: Triethylene glycol dimethacrylate ·GDMA: Glycerol dimethacrylate ·HEMA: Hydroxyethyl methacrylate ·MOTMS: Methacryloyl octyl trimethoxysilane

[0079] [(B) Chemical polymerization initiator] <(B1) Transition metal compound> CAA: Copper(II) acetylacetonate COA: Copper(II) acetate monohydrate VOA: Vanadyl acetylacetonate VAA: Vanadium(III) acetylacetonate <(B2) Thiourea compounds> BTU: Benzoylthiourea PTU: Pyridylthiourea BzTU: Benzylthiourea <(B3) Hydroperoxide> ·CHP: Cumene hydroperoxide TMBH: 1,1,3,3-Tetramethylbutylhydroperoxide ·TAH: tert-amyl hydroperoxide

[0080] [(C) Polymerization inhibitor] BHT: Dibutyl hydroxytoluene TTHP: Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] TBHT: 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene ODBH: 3-(3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate

[0081] [(E)Wed] DW: Distilled water

[0082] [(D) Filler] <(D1)Al 2 O 3 Hydrophobically treated basic filler that does not contain (Filler D1) Zirconium silicate filler (average particle size 3 μm: zirconia 20 wt%, silica 80 wt%, specific surface area: 170 m 2 To 100 g of the powder (100 g / g), 50 g of water, 35 g of ethanol, and a silane coupling treatment solution containing 20 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 a sieving process was carried out to obtain filler D1. (Filler D2) Zirconium silicate filler (average particle size 2 μm: zirconia 20 wt%, silica 80 wt%, specific surface area: 110 m 2 To 100 g of the powder (100 g / g), 50 g of water, 35 g of ethanol, and a silane coupling treatment solution containing 15 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 a sieving process was carried out to obtain filler D2. (Filler D3) Zirconium silicate filler (average particle size 1 μm: zirconia 20 wt%, silica 80 wt%, specific surface area: 80 m 2 To 100 g of the powder (100 g / g), 50 g of water, 35 g of ethanol, and a silane coupling treatment solution containing 4 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 a sieving process was carried out to obtain filler D3. (Filler D4) Zirconium silicate filler (average particle size 2 μm: zirconia 20 wt%, silica 80 wt%, specific surface area: 30 m 2 To 100 g of the powder (100 g / g), 50 g of water, 35 g of ethanol, and a silane coupling treatment solution containing 3 g of 8-methacryloyl octyl trimethoxy silane 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 a sieving process was carried out to obtain filler D4. (Filler D5) Zirconium silicate filler (average particle size 3 μm: zirconia 7 wt%, silica 93 wt%, specific surface area: 30 m 2 To 100 g of the powder (100 g / g), 50 g of water, 35 g of ethanol, and a silane coupling treatment solution containing 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 a sieving process was carried out to obtain filler D5. <(D2)Al 2 O 3 Inorganic fillers other than hydrophobized basic fillers that do not contain (Filler D6) Barium silicate filler (average particle size 1 μm, Al 2 O 3 : 10wt%, B 2 O 3 : 10wt%, BaO: 25wt%, SiO 2 To 100 g of the powder (55 wt%), 50 g of water, 35 g of ethanol, and a silane coupling treatment liquid containing 15 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 a sieving process was carried out to obtain filler D6. (Filler D7) Fluoroaluminoborosilicate glass (average particle size 1 μm, SiO 2 : 22.5wt%, Al 2 O 3 : 20.0wt%, B 2 O 3 : 12.3wt%, SrO: 35.7wt%, Na 2To 100 g of (O: 2.5 wt%, F: 7.0 wt%), 50 g of water, 35 g of ethanol, and a silane coupling treatment liquid containing 15 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 a sieving process was performed to obtain filler D7. (Filler D8) Fluoroaluminoborosilicate glass (average particle size 1 μm, SiO 2 : 22.5wt%, Al 2 O 3 : 20.0wt%, B 2 O 3 : 12.3wt%, SrO: 35.7wt%, Na 2 O: 2.5 wt%, F: 7.0 wt%), 100 g of low condensation product of silane compound "MKC Silicate MS56S" (SiO 2 4.5 g of 56.0% by mass, polymerization degree 2-100, manufactured by Mitsubishi Chemical Corporation) was added and mixed by stirring for about 90 minutes. After mixing for a predetermined time, the obtained treated slurry was aged at 50°C for 40 hours in a hot air dryer, then heated to 150°C and held for 6 hours, and then cooled to obtain a heat-treated product. The obtained heat-treated product was placed in a Henschel mixer and crushed at 1800 rpm for 5 minutes. To 100 g of the produced filler, 100 g of water, 80 g of ethanol, and 6 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours, and the obtained silane coupling treatment liquid was added and mixed by stirring for 30 minutes. Then, heat treatment was performed at 90°C for 15 hours to obtain filler D8. (Filler D9) Fluoroaluminoborosilicate glass (average particle size 1 μm, SiO 2 : 22.5wt%, Al 2 O 3 : 20.0wt%, B 2 O 3 : 12.3wt%, SrO: 35.7wt%, Na 2 O: 2.5 wt%, F: 7.0 wt%), 100 g of low condensation product of silane compound "MKC Silicate MS56S" (SiO 24.5 g of polyacrylic acid (polymer concentration 13% by mass, weight average molecular weight 10,000: manufactured by Nakarai) was added and mixed with stirring for about 90 minutes. After mixing for a predetermined time, the obtained treated slurry was aged at 50°C for 40 hours in a hot air dryer, then heated to 150°C and held for 6 hours, and then cooled to obtain a heat-treated product. The obtained heat-treated product was placed in a Henschel mixer and crushed at 1800 rpm for 5 minutes. Next, 16.0 g of an aqueous polyacrylic acid solution (polymer concentration 13% by mass, weight average molecular weight 10,000: manufactured by Nakarai) was sprayed from above. After spraying, the powder removed from the mixer was heated at 100°C for 3 hours in a hot air dryer. To 100 g of the produced filler, 100 g of water, 80 g of ethanol, and 9 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours, and the obtained silane coupling treatment liquid was added and mixed with stirring for 30 minutes. Thereafter, heat treatment was carried out at 90° C. for 15 hours to obtain filler D9. (Filler D10) Zirconium silicate filler (average particle size 3 μm: zirconia 5 wt%, silica 95 wt%, specific surface area: 30 m 2 To 100 g of cellulose acetate (100 g / g), 50 g of water, 35 g of ethanol, and a silane coupling treatment solution containing 7 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 a sieving process was carried out to obtain filler D10. (Filler D11) Fluoroaluminosilicate glass (average particle size 1 μm, SiO 2 : 30wt%, Al 2 O 3 : 25wt%, SrO: 20wt%, P 2 O 5 : 15.0wt%, F: 9wt%, Na 2 O:1.0wt%), 100g of low condensation product of silane compound "MKC Silicate MS56S" (SiO 24.5 g of 56.0% by mass, polymerization degree 2-100, manufactured by Mitsubishi Chemical Corporation) was added and mixed by stirring for about 90 minutes. After mixing for a predetermined time, the obtained treated slurry was aged at 50°C for 40 hours in a hot air dryer, then heated to 150°C and held for 6 hours, and then cooled to obtain a heat-treated product. The obtained heat-treated product was placed in a Henschel mixer and crushed at 1800 rpm for 5 minutes. To 100 g of the produced filler, 100 g of water, 80 g of ethanol, and 6 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours, and the obtained silane coupling treatment liquid was added and mixed by stirring for 30 minutes. Then, heat treatment was performed at 90°C for 15 hours to obtain filler D11. (Filler D12) Titanium oxide (average particle size 0.25 μm) (Filler D13) Zirconia oxide (average particle size 0.03 μm) (Filler D14) Aerosil R-8200 (manufactured by Evonik) (Filler D15) Aerosil R-7200 (manufactured by Evonik) (Filler D16) Aerosil R-711 (Evonik) (Filler D17) Ytterbium fluoride (average particle size 0.1 nm)

[0083] [Photopolymerization initiator] CQ: Camphorquinone BAPO: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide DMBE: Ethyl N,N-dimethylaminobenzoate [Ultraviolet absorber] OB: 2-Hydroxy-4-(octyloxy)benzophenone [Fluorescent agent] FA: Diethyl 2.5-dihydroxyterephthalate

[0084] [Pigment] UB: Ultramarine (blue pigment)

[0085] The yellow, red and black pigments are not included in the calculations and are not shown in the table because their amounts per 100 parts by mass of the composition are less than 0.05 parts by mass and their effect on storage stability and mechanical properties is extremely small.

[0086] <(D) Confirmation of basicity of packing material> The basicity of each packing material was evaluated by adding 1 g of packing material to a mixed solution of 40 g of distilled water and 10 g of ethanol, and measuring the pH of the mixed solution after stirring for 1 hour at 23±3°C. Packing materials with a pH of 8.0 or higher were considered basic.

[0087] [Table 1]

[0088] <Method for producing dental adhesive composition> All ingredients except for the (D) filler shown in Tables 2 to 7 were placed in a wide-mouthed plastic container and mixed for 48 hours at 100 rpm using a mix rotor VMRC-5 to obtain a matrix. The matrix and (D) filler were then placed in a kneader and uniformly stirred, and then degassed under vacuum to obtain pastes 1 and 2. Pastes 1 and 2 were then filled into a Mixpack double syringe (5 mL) to prepare dental adhesive compositions. In Tables 2 to 7, the mass parts of each ingredient are listed in parentheses after the abbreviation of each ingredient.

[0089] [Table 2]

[0090] [Table 3]

[0091] [Table 4]

[0092] [Table 5]

[0093] [Table 6]

[0094] [Table 7]

[0095] <Storage test method> The dental adhesive composition was filled in a double syringe (5 mL) manufactured by Mixpack Co., Ltd. and stored in a storage cabinet (Yamato Scientific Co., Ltd.) set at 40° C. for 5 months.

[0096] <Evaluation 1: Adhesive strength to tooth structure> The epoxy resin-embedded bovine tooth test piece was polished with waterproof abrasive paper #500 to remove the enamel or dentin plane. The adhesion surface of the stainless steel rod (φ4.0 mm) was sandblasted with alumina (50 μm) (0.2 MPa, 5 seconds), washed with water, dried, and coated with a metal adhesive primer (Metal Link, Matsufu). The dental adhesive composition of the Example or Comparative Example was applied to the adhesion surface of the stainless steel rod in an appropriate amount after thoroughly mixing the corresponding first paste and second paste in equal masses, and the bovine tooth test piece and the stainless steel rod were bonded together. A load of 200 g was applied vertically to the stainless steel rod, and excess cement was wiped off with a cloth. Thereafter, the adhesive test specimen was irradiated with light for 10 seconds using a dental polymerization LED light irradiator (Penbright, manufactured by Matsufu) and the load was removed. The adhesive test specimen was then immersed in water at 37°C for 24 hours, and the shear adhesive strength was measured using a universal testing machine (manufactured by Instron) at a crosshead speed of 1mm / min. With respect to enamel, it was judged that the adhesive strength was excellent when it showed an adhesive strength of 10 MPa or more, and that it was judged that it was very high when it showed an adhesive strength of 30 MPa or more. On the other hand, it was judged that the adhesive strength was low when it was less than 5 MPa. With respect to dentin, it was judged that the adhesive strength was excellent when it showed an adhesive strength of 7 MPa or more. On the other hand, it was judged that the adhesive strength was low when it was less than 2 MPa. The adhesive strength measured after preparing the dental adhesive composition of the examples or comparative examples was taken as the adhesive strength of the initial preparation. On the other hand, the adhesive strength measured after storing the dental adhesive composition of the examples or comparative examples at 40°C for 5 months was taken as the adhesive strength of the accelerated test product. High adhesive strength is preferable because it reduces the risk of detachment of prosthetic devices, orthodontic devices, etc. On the other hand, when it comes to orthodontic adhesives, if the adhesive strength to enamel is very high, it may be difficult to remove, especially when removing orthodontic devices such as orthodontic crowns, so it may be preferable for the adhesive to have a moderately excellent adhesive strength. It is important for the adhesive strength to remain the same between the initial preparation and the accelerated test product in order to continue stable use. Furthermore, in cases where excessively high adhesive strength is not required, such as orthodontic adhesives and wearable adhesives, it is important that the adhesive continues to show a constant adhesive strength over a long period of time.

[0097] <Rating 2: Consistency> 0.5 mL of the first paste of the dental adhesive composition of the embodiment or comparative example was taken, sandwiched between 50 mm x 50 mm glass plates, and left to stand for 1 minute with a load of 200 g placed on it. Thereafter, the dental adhesive composition was placed on graph paper while still sandwiched between the glass plates, and the length of the dental adhesive composition was measured in the horizontal direction, which was 90° different from the vertical axis direction with respect to the graph paper. The average value of the measured length was taken as the consistency. When the dental adhesive composition was stored at 40 ° C for 5 months, the consistency change rate was within ± 2 mm with respect to the consistency measured within 30 days after the preparation of the dental adhesive composition, A was taken, when it was within ± 3 mm, when it was within ± 4 mm, C was taken, and when it exceeded ± 4 mm, D was taken. The dental adhesive composition of the present invention is used by kneading the first paste and the second paste, but if the consistency of the first paste changes, the consistency of the kneaded product of the first paste and the second paste also changes. In addition, it is not preferable because it affects the feeling and kneadability when kneading the first paste and the second paste. If the consistency of the dental adhesive composition changes significantly, the dischargeability from the syringe may decrease, the paste may drip when applied to a prosthetic device or an orthodontic appliance, etc., and the operability may be poor, or the paste may not spread sufficiently when pressed against the surface, and the adhesive strength that should be expressed by design may not be fully expressed. Since the consistency is appropriately adjusted for each application, a dental adhesive composition with a small change in consistency and high paste stability can be used for a long time, which is preferable.

[0098] The results of each test are shown in Tables 8 and 9.

[0099] [Table 8]

[0100] [Table 9]

[0101] It was confirmed that the adhesive strength and consistency of the compositions described in the Examples were stable both at the initial stage of preparation and after the accelerated test.

[0102] First paste (D1) Al 2 O 3 Among hydrophobically treated basic packing materials that do not contain 2 The compositions containing D1 and D2, in which the filler having an Al content of 1000 g or more has been hydrophobized, tended to have particularly excellent consistency stability. 2 O 3 Among hydrophobically treated basic packing materials that do not contain 2 Examples 3 to 6, which contained D3 to 5 in which the fillers having an Al content of less than 1.0 wt. / g were hydrophobized, tended to have slightly inferior consistency stability to the compositions containing D1 and D2. On the other hand, Examples 16 to 20, which contained 0.5 to 2.0 parts by mass of the polymerization inhibitor (C), tended to have good consistency stability even when they contained fillers D3 to D5. 2 O 3 Examples 7 and 10, which contained basic fillers D6 and D10, tended to have poor consistency stability.

[0103] Among Examples 21 to 26 in which the first paste contained water (E), Examples 21 to 25 in which the content of water (E) was 0.01 to 2 parts by mass tended to exhibit good adhesive strength, whereas Example 26 in which the content of water (E) exceeded 2 parts by mass tended to exhibit poor consistency stability.

[0104] Example 14, in which the amount of the polymerizable monomer having an acidic group (A1) contained in the first paste was less than 2 parts by mass, tended to have poor adhesive strength, while Example 15, in which the amount of the polymerizable monomer having an acidic group (A1) contained in the first paste was more than 40 parts by mass, tended to have poor consistency stability.

[0105] (D1) Al contained in the first paste relative to 100 parts by mass of (A) polymerizable monomer contained in the first paste 2 O 3Comparative Examples 1 to 8, in which the amount of hydrophobized basic filler not containing (A1) was less than 50 parts by mass, had extremely poor consistency stability or tended to gel after the accelerated test. Comparative Example 9, which did not contain (A1) a polymerizable monomer having an acidic group, tended to have extremely poor adhesive strength. Comparative Example 10, which did not contain (B1) a transition metal compound or (B2) a thiourea compound, and Comparative Example 11, which did not contain (B3) a hydroperoxide, did not cure sufficiently, so that the adhesive strength could not be measured. Comparative Example 12, which did not contain (C) a polymerization inhibitor, gelled both the first paste and the second paste after the accelerated test. Comparative Examples 13 and 14, in which the first paste contained (C) a hydroperoxide, tended to gel after the accelerated test.

[0106] The dental adhesive composition of the present invention evaluated in the examples can be used without any problems in any known dental adhesive composition, such as dental resin cement, dental abutment material, dental filling material, orthodontic material, etc. [Industrial Applicability]

[0107] According to the present invention, it is possible to provide a dental adhesive composition which combines good paste properties with good storage stability of adhesiveness.

Claims

1. A dental adhesive composition in a package form, (A) a polymerizable monomer including (A1) a polymerizable monomer having an acidic group and (A2) a polymerizable monomer not having an acidic group, (B1) a transition metal compound, (B2) a thiourea compound, (C) a polymerization inhibitor, and (D1) Al ２ O ３ a first paste containing a hydrophobically treated basic filler that does not contain a second paste including (A2) a polymerizable monomer having no acidic group, (B3) a hydroperoxide, (C) a polymerization inhibitor, and (D) a filler; (D1) Al is added to 100 parts by mass of the polymerizable monomer (A) containing (A1) a polymerizable monomer having an acidic group and (A2) a polymerizable monomer not having an acidic group, which is contained in the first paste. ２ O ３ The hydrophobized basic filler not including (D1) Al ２ O ３ The dental adhesive composition of the present invention is characterized in that, when 1 g of a hydrophobized basic filler not containing , is added to a mixed solution of 40 g of distilled water and 10 g of ethanol, and the mixed solution is stirred for 1 hour, the pH of the mixed solution is 8.0 to 11.

0.

2. (D1) Al ２ O ３ The hydrophobized basic filler not containing is a filler containing zirconia and silica, and the specific surface area of ​​the basic filler before the hydrophobization treatment is 100 m ２ 2. The packaged dental adhesive composition according to claim 1, wherein the adhesive strength is 1 / g or more.

3. 2. The packaged dental adhesive composition according to claim 1, wherein the first paste contains 0.01 to 5 parts by mass of water (E) per 100 parts by mass of the polymerizable monomer (A).

4. 3. The packaged dental adhesive composition according to claim 2, wherein the first paste contains 0.01 to 5 parts by mass of water (E) per 100 parts by mass of the polymerizable monomer (A).

5. 2. The packaged dental adhesive composition according to claim 1, wherein the first paste contains 0.25 to 2 parts by mass of the polymerization inhibitor (C) per 100 parts by mass of the polymerizable monomer (A).

6. 3. The packaged dental adhesive composition according to claim 2, wherein the first paste contains 0.25 to 2 parts by mass of the polymerization inhibitor (C) per 100 parts by mass of the polymerizable monomer (A).

7. 4. The packaged dental adhesive composition according to claim 3, wherein the first paste contains 0.25 to 2 parts by mass of the polymerization inhibitor (C) per 100 parts by mass of the polymerizable monomer (A).

8. 5. The packaged dental adhesive composition according to claim 4, wherein the first paste contains 0.25 to 2 parts by mass of the polymerization inhibitor (C) per 100 parts by mass of the polymerizable monomer (A).

9. The volume ratio of the first paste to the second paste ([first paste:second paste]) is 1:0.8 to 1.2, The first paste and the second paste are pastes containing a matrix and a filler (D), In 100 parts by mass of the polymerizable monomer (A) contained in the first paste, (A1) 1 to 30 parts by mass of a polymerizable monomer having an acidic group, and (A2) 70 to 99 parts by mass of a polymerizable monomer having no acidic group, Relative to 100 parts by mass of the polymerizable monomer (A) contained in the first paste, (B1) 0.001 to 0.5 parts by mass of a transition metal compound, (B2) 0.1 to 5 parts by mass of a thiourea compound, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, (D1) Al ２ O ３ 50 to 400 parts by mass of a hydrophobized basic filler not containing Relative to 100 parts by mass of the polymerizable monomer (A) contained in the second paste, (B3) 0.5 to 5 parts by mass of a hydroperoxide, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, 6. The packaged dental adhesive composition according to claim 5, further comprising 50 to 400 parts by mass of a filler (D).

10. The volume ratio of the first paste to the second paste ([first paste:second paste]) is 1:0.8 to 1.2, The first paste and the second paste are pastes containing a matrix and a filler (D), In 100 parts by mass of the polymerizable monomer (A) contained in the first paste, (A1) 1 to 30 parts by mass of a polymerizable monomer having an acidic group, and (A2) 70 to 99 parts by mass of a polymerizable monomer having no acidic group, With respect to 100 parts by mass of the polymerizable monomer (A) contained in the first paste (B1) 0.001 to 0.5 parts by mass of a transition metal compound, (B2) 0.1 to 5 parts by mass of a thiourea compound, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, and (D1) Al ２ O ３ 50 to 400 parts by mass of a hydrophobized basic filler not containing Relative to 100 parts by mass of the polymerizable monomer (A) contained in the second paste, (B3) 0.5 to 5 parts by mass of a hydroperoxide, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, 7. The packaged dental adhesive composition according to claim 6, further comprising 50 to 400 parts by mass of a filler (D).

11. The volume ratio of the first paste to the second paste ([first paste:second paste]) is 1:0.8 to 1.2, The first paste and the second paste are pastes containing a matrix and a filler (D), In 100 parts by mass of the polymerizable monomer (A) contained in the first paste, (A1) 1 to 30 parts by mass of a polymerizable monomer having an acidic group, and (A2) 70 to 99 parts by mass of a polymerizable monomer having no acidic group, With respect to 100 parts by mass of the polymerizable monomer (A) contained in the first paste (B1) 0.001 to 0.5 parts by mass of a transition metal compound, (B2) 0.1 to 5 parts by mass of a thiourea compound, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, and (D1) Al ２ O ３ 50 to 400 parts by mass of a hydrophobized basic filler not containing Relative to 100 parts by mass of the polymerizable monomer (A) contained in the second paste, (B3) 0.5 to 5 parts by mass of a hydroperoxide, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, 8. The packaged dental adhesive composition according to claim 7, further comprising 50 to 400 parts by mass of a filler (D).

12. The volume ratio of the first paste to the second paste ([first paste:second paste]) is 1:0.8 to 1.2, The first paste and the second paste are pastes containing a matrix and a filler (D), In 100 parts by mass of the polymerizable monomer (A) contained in the first paste, (A1) 1 to 30 parts by mass of a polymerizable monomer having an acidic group, and (A2) 70 to 99 parts by mass of a polymerizable monomer having no acidic group, With respect to 100 parts by mass of the polymerizable monomer (A) contained in the first paste (B1) 0.001 to 0.5 parts by mass of a transition metal compound, (B2) 0.1 to 5 parts by mass of a thiourea compound, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, and (D1) Al ２ O ３ 50 to 400 parts by mass of a hydrophobized basic filler not containing Relative to 100 parts by mass of the polymerizable monomer (A) contained in the second paste, (B3) 0.5 to 5 parts by mass of a hydroperoxide, (C) 0.03 to 2 parts by mass of a polymerization inhibitor, 9. The packaged dental adhesive composition according to claim 8, further comprising 50 to 400 parts by mass of a filler (D).

13. The orthodontic adhesive composition according to any one of claims 1 to 12.

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