JP5955329B2 - Adhesion kit - Google Patents

Description

  The present invention relates to an adhesive kit that includes a pretreatment material and an adhesive and is suitable for dental use, and particularly suitable as a dental cement kit.

  Dental cement is used as a material for attaching a prosthesis such as a crown, an inlay, or a bridge to a defective part of a tooth affected part.

  In many cases, materials such as metals and ceramics are used for prosthesis, and dental cement has high adhesion to these materials, but often has low adhesion to teeth. Further, when only the dental cement is cured, the initiator is uniformly dispersed in the dental cement, so that radicals are generated uniformly and a shrinkage force is generated toward the center of the dental cement. . Since this contraction force is a force in a direction in which the dental cement is peeled off from the tooth material, this also reduces the adhesiveness.

  Therefore, a dental cement kit in which a primer and dental cement are combined is widely used. The primer used in the dental cement kit exhibits high adhesion to the tooth by penetrating into the tooth. Moreover, when hardening a primer and dental cement, many radicals generate | occur | produce on the tooth surface to which the primer was apply | coated, and more polymerization hardening progresses on a tooth surface. In this case, the shrinkage force is generated in the direction of the tooth surface of the cement, so that the adhesiveness is not reduced. Therefore, according to the dental cement kit, it is possible to obtain high adhesion to both the tooth and the prosthesis.

  As an adhesive kit that can be used as a dental cement kit, Patent Document 1 discloses a dental primer containing (meth) acrylate having an acid group, water, a water-soluble and volatile organic solvent, and a vanadium compound, and an acid group. A (meth) acrylate having an acid group, a (meth) acrylate having no acid group, a hydroperoxide as a polymerization initiator, a thiourea derivative as a reducing agent, and a dental adhesive containing a vanadium compound as a polymerization accelerator. A dental restorative material set is disclosed.

  Patent Document 2 discloses a primer having a pH value of less than 4.5, a polymerizable monomer, a pyridylthiourea compound, a hydroperoxide compound having at least one hydroperoxide group bonded to a tertiary carbon, And a dental cement kit comprising a two-part dental composition comprising a fine filler.

JP 2010-280630 A European Patent Publication No. 1693046

  However, according to the study by the present inventors, according to the dental restorative material set described in Patent Document 1, although high adhesiveness to the tooth can be obtained, the polymerization curing proceeds in a short time. However, it has been found that the time for preparing the position of the prosthesis is shortened, and there is a problem that sufficient operation margin time cannot be taken after the contact between the primer and the adhesive. On the other hand, although the dental cement kit of patent document 2 has the favorable operation allowance time after contact of a primer and an adhesive material, it turned out that the adhesiveness with respect to a tooth substance is inadequate.

  In general, when the curability of a dental cement kit is increased, high adhesiveness can be obtained, while an operation margin time after contact between a primer and an adhesive is shortened. For this reason, it is difficult to achieve both high adhesiveness and sufficient operation margin time.

  Then, an object of this invention is to provide the adhesion | attachment kit which is excellent in both the adhesiveness with a tooth substance, and the operation surplus time after the contact of a pretreatment material and an adhesive material.

The present invention includes an acidic group-containing radical polymerizable monomer (a1), a vanadium compound (a2), a solvent (a3), and a hydrophilic radical polymerizable monomer (a4) having no acidic group. Processing material (A);
A radically polymerizable monomer (b1) having no acidic group, a hydroperoxide compound (b2) having 5 or more carbon atoms having at least one hydroperoxide group bonded to a tertiary carbon, pyridylthiourea or a derivative thereof ( b3), an adhesive containing 0 to 3 parts by weight of filler (b4) as an essential component and acidic compound (b5) with respect to a total of 100 parts by weight of (b1), (b2), and (b3) Material (B);
It is the adhesion kit containing.

  In the present invention, it is a preferred embodiment that the adhesive (B) further contains a vanadium compound (b6). In the present invention, it is also a preferred embodiment that the adhesive (B) further contains a copper compound (b7).

  In the present invention, the hydroperoxide compound (b2) is preferably cumene hydroperoxide and / or 1,1,3,3-tetramethylbutyl hydroperoxide. The content of the acidic compound (b5) in the adhesive (B) is preferably 0 part by weight. The pretreatment material (A) further contains 0.2 to 5% by weight of a polymerization inhibitor (a5), and the weight ratio (a2) / (a5) of the vanadium compound (a2) to the polymerization inhibitor (a5). Is preferably 2/1 to 1/10. The pyridylthiourea or derivative (b3) thereof is preferably a compound represented by the following formula.

Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, hydroxyl group, alkyl group, cycloalkyl group, alkoxyl group, aryl group, acyl group, alkenyl group, aralkyl group, or oxygen A monovalent heterocyclic group containing an atom, sulfur atom or nitrogen atom.)

  The adhesive kit of the present invention is suitable for dental use. In particular, it is preferable to constitute a dental cement kit in which the pretreatment material (A) is a primer and the adhesive (B) is cement.

  The adhesive kit of the present invention is excellent in both the adhesiveness to the tooth substance and the operation margin time after the contact between the pretreatment material and the adhesive material. Therefore, it is suitable for dental use, and particularly suitable for a dental cement kit.

  The adhesion kit of the present invention includes a pretreatment material (A) and an adhesive material (B). First, the pretreatment material (A) will be described. The pretreatment material (A) comprises an acidic group-containing radical polymerizable monomer (a1), a vanadium compound (a2), a solvent (a3), and a hydrophilic radical polymerizable monomer (a4) having no acidic group. Containing.

  Examples of the acidic group-containing radical polymerizable monomer (a1) used in the present invention include acidic groups such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a carboxylic acid group, and a sulfonic acid group. Examples thereof include polymerizable monomers having at least one and having at least one radical polymerizable group such as acryloyl group, methacryloyl group, vinyl group and styrene group. The acidic group-containing radical polymerizable monomer (a1) preferably has a (meth) acryloyl group from the viewpoint of radical polymerizability and safety. The acidic group-containing radically polymerizable monomer (a1) can be used alone or in appropriate combination of two or more. Specific examples of the acidic group-containing radical polymerizable monomer (a1) will be described below. In the present specification, the description of (meth) acryl is a general term for methacryl and acryl.

  Examples of phosphoric acid group-containing radical polymerizable monomers 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) acryloyloxyoctyldi Hydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acetate Royloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyl dihydrogen phosphate, 20- (meth) acryloyloxyicosyl dihydrogen phosphate, Bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- ( (Meth) acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyloxynonyl] hydrogen phosphate, bis [10- (meth) acryloylo Sidecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl 2-bromoethyl hydrogen phosphate 2-methacryloyloxyethyl- (4-methoxyphenyl) hydrogen phosphate, 2-methacryloyloxypropyl- (4-methoxyphenyl) hydrogen phosphate and acid chlorides, alkali metal salts and amine salts thereof.

  Pyrophosphate group-containing radical polymerizable monomers include bis [2- (meth) acryloyloxyethyl pyrophosphate], bis [4- (meth) acryloyloxybutyl pyrophosphate], and bis [6- (meth) pyrophosphate. Examples include acryloyloxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate, and acid chlorides, alkali metal salts and amine salts thereof.

  As the thiophosphate group-containing radical polymerizable monomer, 2- (meth) acryloyloxyethyl dihydrogenthiophosphate, 3- (meth) acryloyloxypropyl dihydrogenthiophosphate, 4- (meth) acryloyloxybutyldi Hydrogenthiophosphate, 5- (meth) acryloyloxypentyl dihydrogenthiophosphate, 6- (meth) acryloyloxyhexyl dihydrogenthiophosphate, 7- (meth) acryloyloxyheptyl dihydrogenthiophosphate, 8- ( (Meth) acryloyloxyoctyl dihydrogenthiophosphate, 9- (meth) acryloyloxynonyl dihydrogenthiophosphate, 10- (meth) acryloyloxydecyl dihydrodi Thiophosphate, 11- (meth) acryloyloxyundecyl dihydrogen thiophosphate, 12- (meth) acryloyl oxide decyl dihydrogen thiophosphate, 16- (meth) acryloyloxy hexadecyl dihydrogen thiophosphate, 20- (Meth) acryloyloxyicosyl dihydrogenthiophosphate and acid chlorides, alkali metal salts and ammonium salts thereof are exemplified.

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

  Carboxylic acid group-containing radical polymerizable monomers include monofunctional radical polymerizable monomers having one carboxyl group or acid anhydride group in the molecule, and a plurality of carboxyl groups or acid anhydrides in the molecule. And monofunctional radically polymerizable monomers having a physical group.

  Examples of monofunctional radically polymerizable monomers having one carboxyl group or acid anhydride group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloyl. Aspartic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydrogen maleate, O- (meth) acryloyl tyrosine, N- (Meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2- (meta ) Acrylyloxybenzoic acid, 3- (meth) acryloyloxy Benzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid and the like, and carboxyl groups of these compounds are acid anhydride grouped Compounds.

  Examples of monofunctional radically polymerizable monomers having a plurality of carboxyl groups or acid anhydride groups in the molecule include, for example, 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) Acryloyl oxide decane-1,1-dicarboxylic acid, 13- (meth) acryloyloxytridecane-1,1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxyethyl trimellitate Tate anhydride, 4- (meth) acryloyloxybutyl trimellitate, 4- (meta Acryloyloxyhexyl trimellitate, 4- (meth) acryloyloxydecyl trimellitate, 2- (meth) acryloyloxyethyl-3 ′-(meth) acryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) Propyl succinate, 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic anhydride, 6- (meth) acryloyloxyethylnaphthalene-2,3,6-tricarboxylic anhydride, 4- (meth And acryloyloxyethylcarbonylpropionoyl-1,8-naphthalic anhydride, 4- (meth) acryloyloxyethylnaphthalene-1,8-tricarboxylic acid anhydride, and the like.

  Examples of the sulfonic acid group-containing radical polymerizable monomer include 2- (meth) acrylamide-2-methylpropane sulfonic acid, styrene sulfonic acid, and 2-sulfoethyl (meth) acrylate.

  Among the above-mentioned acidic group-containing radical polymerizable monomers (a1), from the viewpoint of adhesiveness, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 4- (meth) acryloyloxyethyl trimellitate anhydride, 4- (meth) acryloyloxyethyl trimellitate, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, and 2- (meth) acrylamido-2-methylpropanesulfonic acid are preferred.

  The amount of the acidic group-containing radical polymerizable monomer (a1) in the pretreatment material (A) is preferably 3 to 35% by weight, more preferably 5 to 30% by weight, More preferably, it is 25% by weight. By making the blending amount of (a1) 3% by weight or more, the decalcification of the tooth by the pretreatment material (A) is further promoted, which contributes to the improvement of the adhesion of the tooth. On the other hand, when the blending amount of (a1) is 35% by weight or less, it becomes easier to make the pretreatment material (A) a uniform solution, which leads to improvement in handling properties and tooth adhesion.

  The vanadium compound (a2) used in the present invention is a component that serves as a polymerization accelerator for redox polymerization.

  Examples of the vanadium compound (a2) include vanadium acetylacetonate, vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, vanadyl oxalate, bis (maltolate) oxovanadium (IV), oxobis (1 -Phenyl-1,3-butanedionate) vanadium (IV), vanadium (V) oxytriisopropoxide, ammonium metavanadate (V), sodium metavanadate (V), vanadium pentoxide (V), ditetraoxide Examples thereof include vanadium (IV) and vanadyl sulfate (IV). Among them, from the viewpoint of solubility in the solvent (a3), vanadium acetylacetonate, vanadyl acetylacetonate, bis (maltolate) oxovanadium (IV Preferably, vanadyl acetylacetonate and bis (Marutorato) oxovanadium (IV) is more preferable. A vanadium compound (a2) can be used individually by 1 type or in combination of 2 or more types.

  If the blending amount of the vanadium compound (a2) in the pretreatment material (A) is too small, the adhesiveness to the tooth tends to decrease, and if it is too large, the operation margin time tends to be shortened. Therefore, the amount of the vanadium compound (a2) in the pretreatment material (A) is preferably 0.1 to 1% by weight, more preferably 0.2 to 0.7% by weight, More preferably, it is 3 to 0.6% by weight.

  The solvent (a3) used in the present invention improves the compatibility of the components of the pretreatment material and improves the permeability of the components of the pretreatment material into the tooth. As the solvent (a3), water and a water-soluble organic solvent can be suitably used. As the water-soluble organic solvent, the boiling point under normal pressure is usually 150 ° C. or lower, and the solubility in water at 25 ° C. is 5% by weight or more, more preferably 30% by weight or more, and most preferably in any proportion. Soluble organic solvents are used. Among them, a water-soluble organic solvent having a boiling point of 100 ° C. or less under normal pressure is preferable, and specific examples thereof include ethanol, methanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxyethane, 1,2- Examples include diethoxyethane and tetrahydrofuran. A solvent (a3) can be used individually by 1 type or in combination of 2 or more types. When the solvent (a3) contains water, excessive evaporation of the solvent can be prevented, and adhesion to dentin can be improved. Accordingly, the solvent (a3) preferably contains water. The content of water in the solvent (a3) is preferably 60% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and most preferably 100% by weight.

  The blending amount of the solvent (a3) in the pretreatment material (A) is preferably 10 to 60% by weight, more preferably 25 to 50% by weight, and further preferably 30 to 45% by weight. preferable. When the compounding amount of the solvent (a3) is 10% by weight, the pretreatment material (A) has a more appropriate tooth demineralization ability, and contributes to the improvement of tooth adhesion. Further, when the blending amount is 60% by weight or less, the transpiration of the solvent (a3) after applying the pretreatment material (A) to the adherend becomes easier, and the variation due to the procedure of each operator is reduced. There is an advantage that more stable adhesiveness can be obtained.

  The hydrophilic radically polymerizable monomer (a4) having no acidic group used in the present invention penetrates into the tooth, improves the degree of polymerization of the cured product, and improves the adhesive force.

  The hydrophilic radical polymerizable monomer (a4) having no acidic group is a hydrophilic radical polymerizable monomer having no acidic group having a solubility in water at 25 ° C. of 5% by weight or more in this specification. And those having the same solubility of 10% by weight or more are more preferable, and those having the same solubility of 30% by weight or more are more preferable.

  As the hydrophilic radical polymerizable monomer (a4) having no acidic group, for example, the hydrophilic radical polymerizable monomer (a4) having solubility in water as described above and having an acidic group (phosphate group, pyrophosphate group, thiophosphate group, And those having at least one radical polymerizable group (acryloyl group, methacryloyl group, vinyl group, styrene group, etc.) without having a phosphonic acid group, a carboxylic acid group, a sulfonic acid group and the like. The hydrophilic radically polymerizable monomer (a4) having no acidic group preferably has a (meth) acryloyl group from the viewpoint of radical polymerizability and safety.

  The hydrophilic radically polymerizable monomer (a4) having no acidic group is any of monofunctional (a4-1), bifunctional (a4-2), and trifunctional or higher (a4-3). It may be. In the present specification, “monofunctional”, “bifunctional” and “trifunctional or higher” mean having one, two and three or more radical polymerizable groups, respectively.

  Specific examples of the monofunctional hydrophilic radical polymerizable monomer (a4-1) having no acidic group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl. (Meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate , Erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide, methoxypolyethylene glycol (meth) acrylate, ( And acryloylmorpholine, diethyl (meth) acrylamide, and the like. Among these, 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) are preferred from the viewpoint of improving the penetration of dentin into the collagen layer. Preferred are acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, (meth) acryloylmorpholine, and diethyl (meth) acrylamide, and particularly preferably 2-hydroxyethyl methacrylate.

  Examples of the bifunctional hydrophilic radical polymerizable monomer (a4-2) having no acidic group include erythritol di (meth) acrylate, sorbitol di (meth) acrylate, mannitol di (meth) acrylate, and pentaerythritol. Di (meth) acrylate, dipentaerythritol di (meth) acrylate, glycerol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane, ethylene bis (meth) acrylamide, propylene bis (Meth) acrylamide, butylene bis (meth) acrylamide, N, N ′-(dimethyl) ethylenebis (meth) acrylamide, N, N′-diethyl-1,3-propylenebis (meth) acrylamide, bis [2- (2 -Methyl- (meth) acryla No. ethoxycarbonyl] hexamethylenediamine, 2,2,4-trimethylhexamethylene-1,6-bis (meth) acrylamide, and the like, among these, the viewpoint of the balance of penetrability and crosslinkability into the tooth To glycerol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane, propylene bis (meth) acrylamide, N, N ′-(dimethyl) ethylenebis (meth) acrylamide and N , N′-diethyl-1,3-propylenebis (meth) acrylamide is preferred, and 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane is more preferred.

  Examples of the trifunctional or higher hydrophilic radical polymerizable monomer (a4-3) having no acidic group include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri ( (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like. Among these, dipentaerythritol tetra (meth) from the viewpoint of the balance between penetrability and crosslinkability. ) Acrylate and dipentaerythritol penta (meth) acrylate are preferred.

  The blending amount of the hydrophilic radical polymerizable monomer (a4) having no acidic group in the pretreatment material (A) is preferably 35 to 85% by weight, and preferably 37 to 75% by weight. More preferably, it is 40 to 65% by weight. When the blending amount of (a4) is 35% by weight or more, the blending effect of (a4), which is an improvement in adhesiveness, can be exhibited more remarkably. On the other hand, when the blending amount of (a4) is 85% by weight or less, the decalcification ability of the tooth of the pretreatment material (A) can be expressed at a high level without impairing the blending effect of (a4). .

  In a preferred embodiment, the hydrophilic radical polymerizable monomer (a4) having no acidic group includes a bifunctional hydrophilic radical polymerizable monomer (a4-2) having no acidic group. In this case, the adhesiveness with a tooth substance, especially the adhesiveness with dentin becomes higher. In a more preferred embodiment, the hydrophilic radical polymerizable monomer (a4) having no acidic group is a bifunctional hydrophilic radical polymerizable monomer (a4-2) or a monofunctional hydrophilic radical polymerizable monomer. Any of monomer (a4-1) is included. By allowing both to coexist, the penetration of the pretreatment material (A) into the tooth becomes better, and the adhesiveness is further improved.

  The blending amount of the bifunctional hydrophilic radical polymerizable monomer (a4-2) having no acidic group is 100 parts by weight of the total amount of the radical polymerizable monomer contained in the pretreatment material (A). It is preferable that it is 1-20 weight part, More preferably, it is 2-15 weight part, More preferably, it is 5-12 weight part. In addition, as described above, (a4) includes both the bifunctional hydrophilic radical polymerizable monomer (a4-2) and the monofunctional hydrophilic radical polymerizable monomer (a4-1). preferable. In this case, the blending amount of (a4-2) is preferably 1 to 35 parts by weight, more preferably 100 parts by weight of the total amount of radical polymerizable monomers contained in the pretreatment material (A). 2 to 15 parts by weight, more preferably 5 to 12 parts by weight. Moreover, it is preferable that the compounding quantity of (a4-1) is 20-85 weight part in 100 weight part of whole quantity of the radically polymerizable monomer contained in a pretreatment material (A), More preferably, it is 40. It is -72 weight part, More preferably, it is 45-69 weight part.

  The pretreatment material (A) may further contain a polymerization accelerator. Polymerization accelerators include amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, halogen compounds, aldehydes, thiol compounds, sulfites, bisulfites, thioureas Compound etc. are mentioned.

  The pretreatment material (A) may further contain a polymerization inhibitor (a5) from the viewpoint of storage stability. Examples of the polymerization inhibitor include 3,5-di-t-butyl-4-hydroxytoluene, hydroquinone, dibutyl hydroquinone, dibutyl hydroquinone monomethyl ether, 2,6-t-butylphenol, and 4-methoxyphenol. One or more of these may be blended. The blending amount of the polymerization inhibitor in the pretreatment material (A) is preferably 0.2 to 5% by weight, more preferably 0.4 to 5% by weight, still more preferably 0.7 to 3% by weight, 2% by weight is even more preferred. If the blending amount of the polymerization inhibitor (a5) in the pretreatment material (A) is less than 0.4% by weight, the storage stability of the pretreatment material may not be sufficient and the color may be changed. When it is more than 5% by weight, the polymerization inhibitor may not be dissolved in the pretreatment material composition, and the polymerization inhibitor may precipitate during storage or composition preparation.

  In the pretreatment material (A), the weight ratio (a2) / (a5) between the vanadium compound (a2) and the polymerization inhibitor (a5) is preferably 2/1 to 1/10, and 1/1 to It is more preferably 1/6, and further preferably 1/2 to 1/4. The polymerization inhibitor is more preferably contained than the vanadium compound. When the amount of the polymerization inhibitor is less than the vanadium compound, the storage stability of the pretreatment material is deteriorated and the color may be changed during storage.

  The pretreatment material (A) may further contain a filler. As an example of a filler, it is the same as that of the filler (b4) contained in the below-mentioned adhesive material (B).

  In addition, the pretreatment material (A) may contain a pH adjuster, an ultraviolet absorber, a thickener, a colorant, an antibacterial agent, a fragrance and the like as long as the effects of the present invention are not impaired.

  Next, the adhesive material (B) included in the adhesive kit of the present invention will be described. The adhesive (B) includes a radical polymerizable monomer (b1) having no acidic group, a hydroperoxide compound having 5 or more carbon atoms (b2) having at least one hydroperoxide group bonded to a tertiary carbon. , Pyridylthiourea or a derivative thereof (b3), and filler (b4) as essential components, and the acidic compound (b5) is added to 100 parts by weight of the total of (b1), (b2), and (b3). Contains 3 parts by weight.

  Examples of the radical polymerizable monomer (b1) having no acidic group include an aromatic radical polymerizable monomer (b1-1) having no acidic group and an aliphatic radical polymerizable monomer having no acidic group. It is divided roughly into a monomer (b1-2).

  The aromatic radical polymerizable monomer (b1-1) having no acidic group may be monofunctional, bifunctional, or trifunctional or higher.

  Examples of the monofunctional aromatic radical polymerizable monomer (b1-1-1) having no acidic group include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and phenoxy. Polyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, neopentyl glycol- (meth) acrylic acid-benzoic acid Examples include esters.

  The bifunctional aromatic radical polymerizable monomer (b1-1-2) having no acidic group has a hydroxyl group in the molecule (b1-1-2-OH) and a hydroxyl group in the molecule. It is roughly divided into those not (b1-1-2-NonOH). Specific examples of those having a hydroxyl group in the molecule (b1-1-2-OH) include 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane (common name “ Bis-GMA "), 2,2-bis [4- (4- (meth) acryloyloxy) -3-hydroxybutoxyphenyl] propane, 2,2-bis [4- (4- (meth) acryloyloxy)- 2-hydroxybutoxyphenyl] propane and 2,2-bis [4- (5- (meth) acryloyloxy) -4-hydroxypentoxyphenyl] propane. On the other hand, specific examples of those having no hydroxyl group and acidic group (b1-1-2-NonOH) in the molecule include 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis ( 4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxy Phenyl) -2- (4- (meth) acryloyloxyethoxyphenyl) propane, 2- (4- (meth) Acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2- (4- (meth) Acryloyloxydipropoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- ( And (meth) acryloyloxydipropoxyphenyl) propane and 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane. Among 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, a compound having an average addition mole number of ethoxy groups of 2.6 (common name “D2.6E”) is preferable.

  Among these, it is preferable to use a bifunctional aromatic radical polymerizable monomer (b1-1-2). In a preferred embodiment, the aromatic radical polymerizable monomer (b1-1) includes (b1-1-2-OH) and (b1-1-2-NonOH), and the (b1-1-2-OH) ) And (b1-1-2-NonOH) is a weight ratio (b1-1-2-OH) / (b1-1-2-NonOH) of 5/95 to 70/30, 25/75 to 60/40 is more preferable, and 27/73 to 50/50 is even more preferable. At this time, adhesiveness with the tooth substance of the adhesion kit obtained becomes especially high.

  The radical polymerizable monomer (b1) having no acidic group preferably includes an aliphatic radical polymerizable monomer (b1-2) having no acidic group. Aliphatic hydrophilic radical polymerizable monomer (b1-2) having no acidic group is monofunctional (b1-2-1), bifunctional (b1-2-2), trifunctional or more ( Any of b1-2-3) may be used.

  The monofunctional aliphatic radical polymerizable monomer (b1-2-1) having no acidic group has a hydroxyl group in the molecule (b1-2-1-OH) and a hydroxyl group in the molecule. It is roughly divided into those not (b1-2-1-NonOH). Specific examples of those having a hydroxyl group in the molecule (b1-2-1-OH) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1 , 3-Dihydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol Mono (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (me ) Acrylamide and the like, among these, from the viewpoint of adhesion to the tooth of the obtained adhesion kit, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, Erythritol mono (meth) acrylate is preferable, and 2-hydroxyethyl methacrylate is particularly preferable. On the other hand, specific examples of the monofunctional aliphatic radical polymerizable monomer (b1-2-1-NonOH) having no hydroxyl group or acidic group in the molecule include methyl (meth) acrylate and ethyl (meth) acrylate. , Isobutyl (meth) acrylate, lauryl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acryloylmorpholine, diethyl (meth) Among these, methoxypolyethylene glycol (meth) acrylate, (meth) acryloylmorpholine, and diethyl (meth) acrylamide are preferable from the viewpoint of adhesion to the tooth of the obtained adhesion kit.

  The bifunctional aliphatic radical polymerizable monomer (b1-2-2) having no acidic group also has a hydroxyl group in the molecule (b1-2-2-OH) and a hydroxyl group in the molecule. It is divided roughly into what is not (b1-2-2-NonOH). Examples of those having a hydroxyl group in the molecule (b1-2-2-OH) include erythritol di (meth) acrylate, sorbitol di (meth) acrylate, mannitol di (meth) acrylate, pentaerythritol di (meth) acrylate, Examples include dipentaerythritol di (meth) acrylate, glycerol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane, and among these, the mechanical properties of the resulting adhesive kit Glycerol di (meth) acrylate and 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane are preferable from the viewpoint of strength and adhesiveness to teeth, and 1,2-bis (3-methacryloyloxy- 2-hydroxypropyloxy) Emissions is more preferable. On the other hand, examples of those having no hydroxyl group or acidic group in the molecule (b1-2-2-NonOH) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth). Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,5 -Pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) Dimetac Rate (commonly known as “UDMA”), tricyclodecane dimethanol di (meth) acrylate, ethylene bis (meth) acrylamide, propylene bis (meth) acrylamide, butylene bis (meth) acrylamide, N, N ′-(dimethyl) ethylene bis ( (Meth) acrylamide, N, N′-diethyl-1,3-propylenebis (meth) acrylamide, bis [2- (2-methyl- (meth) acrylamino) ethoxycarbonyl] hexamethylenediamine, 2,2,4- Examples include trimethylhexamethylene-1,6-bis (meth) acrylamide, and among them, triethylene glycol di (meth) acrylate, neo from the viewpoint of mechanical strength of the obtained adhesion kit and adhesion to the tooth. Pentyl glycol di (meth) acrylate, , 2,4-hexamethylene bis (2-carbamoyloxyethyl) dimethacrylate are more preferred.

  Examples of the trifunctional or higher functional aliphatic radical polymerizable monomer (b1-2-3) having no acidic group include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, Methylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate N, N- (2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6 -Tetraacryloyloxy Chill-4-oxy-heptane, and the like.

  Among these, it is preferable to use the bifunctional aliphatic radical polymerizable monomer (b1-2-2) from the viewpoint of the mechanical strength of the obtained adhesion kit and the adhesiveness to the tooth.

  In a preferred embodiment, the adhesive (B) of the present invention contains (b1-2-2-OH) and (b1-2-2-NonOH) as radically polymerizable monomers (b1) having no acidic group. including. By using both in combination, the adhesiveness to the dentin, particularly the adhesiveness to the dentin, is further enhanced. The content of (b1-2-2-OH) is preferably 1 to 20 parts by weight, more preferably 2 to 100 parts by weight of the total amount of radical polymerizable monomers contained in the adhesive (B). 14 parts by weight, more preferably 2.5 to 10 parts by weight. Further, the content of (b1-2-2-NonOH) is preferably 5 to 50 parts by weight, more preferably 100 parts by weight of the total amount of radical polymerizable monomers contained in the adhesive (B). The amount is 10 to 35 parts by weight, more preferably 14 to 28 parts by weight.

  The radical polymerizable monomer (b1) having no acidic group includes an aromatic radical polymerizable monomer (b1-1) having no acidic group and an aliphatic radical polymerizable monomer having no acidic group. Body (b1-2), and the weight ratio (b1-1) / (b1) of the aromatic radical polymerizable monomer (b1-1) and the aliphatic radical polymerizable monomer (b1-2). -2) is preferably 50/50 to 90/10, more preferably 60/40 to 85/15, and even more preferably 65/35 to 80/20. At this time, the transparency and mechanical strength of the cured product of the obtained adhesion kit are particularly high.

  The blending amount of the radical polymerizable monomer (b1) having no acidic group in the adhesive (B) is preferably 14 to 60% by weight, and 19 to 50% by weight from the viewpoint of the viscosity and mechanical strength. Is more preferable, and 24-48 weight% is further more preferable.

  The hydroperoxide compound (b2) having 5 or more carbon atoms and having at least one hydroperoxide group bonded to a tertiary carbon is a component that serves as an oxidizing agent for the redox polymerization initiator. When the number of carbon atoms of the hydroperoxide compound having at least one hydroperoxide group bonded to the tertiary carbon is less than 5, both the adhesion to the tooth and the operation margin time are insufficient. Therefore, in the present invention, a hydroperoxide compound (b2) having 5 or more carbon atoms is used.

  Examples of the hydroperoxide compound (b2) having 5 or more carbon atoms having at least one hydroperoxide group bonded to a tertiary carbon used in the present invention include cumene hydroperoxide, t-amyl hydroperoxide, 1,1 , 3,3-tetramethylbutyl hydroperoxide, 2,5-dimethyl-2,5-di (hydroperoxy) hexane, p-diisopropylbenzene monohydroperoxide, p-menthane hydroperoxide, pinane hydroperoxide These can be used alone or in combination of two or more. Among them, it is preferable to use cumene hydroperoxide and / or 1,1,3,3-tetramethylbutyl hydroperoxide.

  As a compounding quantity of the hydroperoxide compound (b2) in adhesive material (B), it is preferable that it is 0.01 to 10 weight% of the whole adhesive material (B), More preferably, it is 0.05 to 5 weight%. is there. When the blending amount is less than 0.01% by weight, the function as a redox polymerization initiator may be insufficient, and when it exceeds 10% by weight, (b1) in the adhesive (B) is easily polymerized. There exists a tendency and there exists a possibility that the storage stability of an adhesive material (B) may fall.

  Pyridylthiourea or its derivative (b3) is a component that serves as a reducing agent for the redox polymerization initiator.

  The pyridylthiourea or its derivative (b3) is not particularly limited as long as the thiourea has a pyridyl group as a substituent, and a compound represented by the following formula is used.

Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, hydroxyl group, alkyl group, cycloalkyl group, alkoxyl group, aryl group, acyl group, alkenyl group, aralkyl group, or oxygen A monovalent heterocyclic group containing an atom, sulfur atom or nitrogen atom.)

The alkyl group represented by R ^{1 to} R ³ may be linear or branched, and preferably has 1 to 12 carbon atoms. Examples thereof include a methyl group, an ethyl group, and an n-propyl group. , Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, n-heptyl group N-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.

The cycloalkyl group represented by R ^{1 to} R ³ is preferably one having 3 to 10 carbon atoms, and examples include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptanyl group, cyclooctanyl group, and cyclononanyl. Groups and the like.

The alkoxyl group represented by R ^{1 to} R ³ is preferably an alkoxyl group having 1 to 8 carbon atoms, and examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a t-butoxy group, A pentyloxy group, a hexyloxy group, etc. are mentioned.

The aryl group represented by R ^{1 to} R ³ is preferably an aryl group having 6 to 16 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

The acyl group represented by R ^{1 to} R ³ is preferably one having 1 to 10 carbon atoms, and examples include formyl group, acetyl group, propanoyl group, butanoyl group, benzoyl group and the like.

The alkenyl group represented by R ^{1 to} R ³ may be either linear or branched, and preferably has 2 to 8 carbon atoms, such as vinyl group, allyl group, methylvinyl group, propenyl group, butenyl. Group, pentenyl group, hexenyl group and the like.

The aralkyl group represented by R ^{1 to} R ³ is preferably one having 7 to 16 carbon atoms, and examples include an aryl group substituted with a lower alkyl group (particularly an alkyl group having 1 to 6 carbon atoms). Specific examples include a methylphenyl group, an ethylphenyl group, a butylphenyl group, a dimethylphenyl group, a dibutylphenyl group, and a methylnaphthyl group.

As a monovalent heterocyclic group containing an oxygen atom, a sulfur atom or a nitrogen atom represented by R ^{1 to} R ³ , those having 4 to 10 carbon atoms are preferable, for example, a pyridyl group, an imidazolyl group, a piperidyl group, a thienyl group. Thiopyranyl group, furyl group, pyranyl group and the like.

As R < ¹ > -R < ³ >, a hydrogen atom, an alkyl group, and an acyl group are preferable, and a hydrogen atom is more preferable.

  As a compounding quantity of the pyridyl thiourea or its derivative (b3) in an adhesive material (B), it is preferable that it is 0.003 to 5 weight% of the whole adhesive material (B), More preferably, it is 0.008 to 1 weight. %, More preferably 0.1 to 0.35% by weight. If the blending amount is less than 0.003% by weight, the function as a redox polymerization initiator may be insufficient, and if it exceeds 5% by weight, the curing start time may be shortened and an appropriate margin for operation may not be obtained. is there.

  As a filler (b4) used for this invention, the filler used for a dental use is used suitably. Fillers used for dental use are generally roughly classified into organic fillers, inorganic fillers, and organic-inorganic composite fillers. Examples of the organic filler material include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, and polystyrene. Chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and the like. These may be used alone or in combination of two or more. Can be used as a mixture. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used. From the viewpoint of the handling property of the obtained adhesive kit and the mechanical strength of the cured product, the average particle diameter of the organic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm. .

  Inorganic filler materials include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, and 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. . These can also be used individually or in mixture of 2 or more types. The shape of the inorganic filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used. From the viewpoint of handling properties of the obtained adhesion kit and mechanical strength of the cured product, the average particle diameter of the inorganic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

  Examples of the shape of the inorganic filler include an amorphous filler and a spherical filler. From the viewpoint of improving the mechanical strength of the cured product of the obtained adhesion kit, it is preferable to use a spherical filler as the inorganic filler. Here, the spherical filler is a particle diameter in a direction perpendicular to the maximum diameter, in which a photograph of the filler is taken with a scanning electron microscope (hereinafter abbreviated as SEM), and the particles observed in the unit field of view are rounded. Is a filler having an average homogeneity of 0.6 or more divided by its maximum diameter. The average particle diameter of the spherical filler is preferably 0.1 to 5 μm. When the average particle diameter is less than 0.1 μm, the filling rate of the spherical filler of the adhesive (B) is lowered, and the mechanical strength of the obtained cured product may be lowered. On the other hand, when the average particle diameter exceeds 5 μm, the surface area of the spherical filler is reduced, and a cured product having high mechanical strength may not be obtained.

  In order to adjust the fluidity of the adhesive (B), the inorganic filler may be used after surface treatment with a known surface treatment agent such as a silane coupling agent as necessary. Examples of the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, and 11-methacryloyloxyundecyltrimethoxysilane. , Γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like.

  The organic-inorganic composite filler is obtained by adding a monomer compound to the above-mentioned inorganic filler in advance, forming a paste, polymerizing, and pulverizing. As the organic-inorganic composite filler, for example, TMPT filler (trimethylolpropane methacrylate and silica filler mixed and polymerized and then pulverized) can be used. The shape of the organic-inorganic composite filler is not particularly limited, and the particle diameter of the filler can be appropriately selected and used. From the viewpoint of handling properties of the obtained adhesion kit and mechanical strength of the cured product, the average particle size of the organic-inorganic composite filler is preferably 0.001 to 50 μm, and preferably 0.001 to 10 μm. Is more preferable.

  When it is desired to give fluorine release property to the adhesive kit of the present invention, as filler (b4), fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass and strontium calcium fluoroalumino It is preferable to use at least one selected from the group consisting of silicate glass, and it is more preferable to use fluoroaluminosilicate glass and / or barium fluoroaluminosilicate glass. On the other hand, when it is desired to impart X-ray contrast properties to the cement, as the filler (b4), barium glass, strontium glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, strontium fluoroaluminosilicate glass and barium fluoroaluminosilicate glass It is preferable to use at least one selected from the group consisting of: barium glass and / or barium fluoroaluminosilicate glass.

  As a compounding quantity of the filler (b4) in an adhesive material (B), it is preferable that it is 0.5 to 85 weight%. When the filler compounding amount is less than 0.5% by weight, there is a possibility that the filler compounding effect of adjusting the viscosity of the adhesive (B) and improving the mechanical strength of the cured adhesive (B) cannot be obtained. On the other hand, when it exceeds 85 weight%, there exists a possibility that the viscosity of an adhesive material (B) may become large too much and operativity may fall. As will be described later, the adhesive (B) of the present invention is preferably used for dental bonding materials, dental composite resins, dental cements and the like. When the adhesive (B) is used as a dental composite resin or dental cement, from the viewpoint of the viscosity of the adhesive (B) and the mechanical strength of the adhesive (B) after curing, The blending amount of the filler (b4) is preferably 45 to 85% by weight, more preferably 47 to 80% by weight, and further preferably 50 to 75% by weight.

  The acidic compound (b5) is a component that activates the hydroperoxide compound (b2). When the hydroperoxide compound (b2) is excessively activated, the storage stability and operation margin time of the adhesion kit are impaired. Therefore, in the present invention, the blending amount is limited.

  Examples of the acidic compound (b5) include phosphoric acid group, phosphoric acid monoester group, pyrophosphoric acid group, thiophosphoric acid group, phosphonic acid group, phosphonic acid monoester group, carboxylic acid group, acid anhydride group, sulfonic acid group, sulfine. Examples thereof include organic compounds having an acidic group such as an acid group, and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid.

  The compounding amount of the acidic compound (b5) is a radical polymerizable monomer having no acidic group (b1), which is contained in the adhesive (B), from the viewpoint of storage stability of the adhesive kit and operation allowance time. It is 0-3 weight part with respect to a total of 100 weight part of hydroperoxide compound (b2) and pyridyl thiourea or its derivative (b3), Preferably it is 0-1 weight part, More preferably, it is 0-0. It is 5 parts by weight, more preferably 0 to 0.1 part by weight, which is an amount that can be mixed as an impurity, and most preferably 0 part by weight (not including the acidic compound (b5)).

  In the present invention, the adhesive (B) may contain a vanadium compound (b6) as a polymerization accelerator for redox polymerization. When the adhesive (B) contains the vanadium compound (b6), the elastic modulus of the cured product of the adhesive kit is improved, the water resistance is improved, and the hydrogen sulfide produced by caries bacteria in the oral cavity environment It can suppress that the hardened | cured material of an adhesion | attachment kit discolors. The vanadium compound (b6) that can be used is the same as the vanadium compound (a2) contained in the pretreatment material (A).

  If the blending amount of the vanadium compound (b6) is too small, the effect of blending the vanadium compound (b6) may not be obtained, and if it is too large, (b1) in the adhesive (B) is easily polymerized. There exists a tendency and there exists a possibility that the storage stability of an adhesive material (B) may fall. Therefore, the compounding amount of the vanadium compound (b6) is preferably 0.005 to 0.15 parts by weight with respect to 100 parts by weight of the radical polymerizable monomer contained in the adhesive (B), and is 0.008 to 0.00. 10 parts by weight is more preferable, and 0.01 to 0.08 part by weight is further preferable.

  In the present invention, the adhesive (B) may contain a copper compound (b7) as a polymerization accelerator for redox polymerization. When the adhesive (B) contains a copper compound (b7), the elastic modulus of the cured product of the adhesive kit is improved and the water resistance is improved, and the pretreatment material (A) and the adhesive (B) Especially, the operation surplus time after the contact is made is excellent.

  As the copper compound (b7), a compound soluble in a radical polymerizable monomer is preferable. Specific examples thereof include copper acetate, copper isobutyrate, copper gluconate, copper citrate, copper phthalate, copper tartrate, copper oleate, copper octylate, copper octenoate, copper naphthenate, methacrylate Acid copper, 4-cyclohexyl butyrate copper; β-diketone copper: acetylacetone copper, trifluoroacetylacetone copper, hexafluoroacetylacetone copper, 2,2,6,6-tetramethyl-3,5-heptanedionate copper, benzoylacetone copper; [beta] -ketoester copper, copper acetoacetate; copper alkoxide, copper methoxide, copper ethoxide, copper isopropoxide, copper 2- (2-butoxyethoxy) ethoxide, copper 2- (2-methoxyethoxy) ethoxide; dithiocarbamic acid As copper, copper dimethyldithiocarbamate; salts of copper and inorganic acids And copper nitrate; and copper chloride. These may be used alone or in combination of two or more. Among these, from the viewpoint of solubility and reactivity with respect to the radical polymerizable monomer, carboxylate copper, β-diketone copper, and β-ketoester copper are preferable, and copper acetate and acetylacetone copper are particularly preferable.

  If the blending amount of the copper compound (b7) is too small, the effect of blending the copper compound (b7) may not be obtained, and if it is too large, (b1) in the adhesive (B) is easily polymerized. There exists a tendency and there exists a possibility that the storage stability of an adhesive material (B) may fall. Therefore, the compounding amount of the copper compound (b7) is preferably 0.0001 to 0.01 parts by weight, and 0.0002 to 0 parts per 100 parts by weight of the radical polymerizable monomer contained in the adhesive (B). 0.005 part by weight is more preferable, and 0.0003 to 0.003 part by weight is further preferable.

  The adhesive (B) may further contain a photopolymerization initiator in order to constitute the adhesive kit as a dual cure type material. Photopolymerization initiators include (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyls Examples include ether compounds and α-aminoketone compounds. Further, it may further contain a chemical polymerization initiator.

  The adhesive material (B) may further contain a polymerization accelerator. Examples of the polymerization accelerator include amines, sulfinic acid and salts thereof, borate compounds, barbituric acid derivatives, triazine compounds, tin compounds, halogen compounds, aldehydes, thiol compounds, sulfites, and bisulfites.

  In addition, the adhesive (B) may be blended with a pH adjuster, a polymerization inhibitor, an ultraviolet absorber, a thickener, a colorant, an antibacterial agent, a fragrance and the like as long as the effects of the present invention are not impaired. .

  In the adhesive kit of the present invention, the adhesive (B) is formed in a form in which the hydroperoxide compound (b2) and pyridylthiourea or a derivative thereof (b3) are packaged in separate agents from the viewpoint of storage stability. Is preferred. When the agent containing hydroperoxide compound (b2) is agent A and the agent containing pyridylthiourea or its derivative (b3) is agent B, both agent A and agent B are in a paste form so that agent A and agent B It is preferable to blend a radically polymerizable monomer (b1) having no acidic group with each. A filler (b4) may be mix | blended with any of A agent and B agent, and may be mix | blended with both agents. Moreover, when an adhesive material (B) contains an acidic compound (b5), it is preferable that an acidic compound (b5) is contained only in A agent. Further, when the adhesive (B) contains the vanadium compound (b6) or the copper compound (b7), the vanadium compound (b6) and the copper compound (b7) are preferably contained only in the B agent. . When the vanadium compound (b6) is blended with the B agent of the adhesive (B), the blending amount is preferably 0.003 to 0.05% by weight based on the total weight of the components of the B agent. More preferably, it is 0.005 to 0.04% by weight. When the copper compound (b7) is blended with the B agent of the adhesive (B), the blending amount is preferably 0.00005 to 0.0008% by weight with respect to the total weight of the components of the B agent. More preferably, it is 0.0001 to 0.0006% by weight.

  As described above, a vanadium compound is blended in a pretreatment material as a polymerization accelerator for redox polymerization, and a specific hydroperoxide compound and a specific thiourea compound are blended in an adhesive as a redox polymerization initiator, and further an acidic compound The adhesive kit of the present invention in which the amount is limited is excellent in both the adhesiveness to the tooth and the operation margin time after the contact between the pretreatment material and the adhesive. In addition, the storage stability is high, and when the adhesive (B) is a package type, the operation margin time after mixing and preparing the adhesive (B) is also excellent. Furthermore, the cured product has high transparency. Therefore, it is suitable for dental use. When the adhesive kit of the present invention is applied to dental applications, the pretreatment material (A) is used as a dental primer, and the adhesive material (B) is configured as a dental bonding material, a dental composite resin, a dental cement, or the like. In particular, it is a preferable embodiment to constitute a dental cement kit in which the pretreatment material (A) is a dental primer and the adhesive (B) is a dental cement.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples. The abbreviations and abbreviations used below are as follows.

[Acid group-containing polymerizable monomer]
MDP: 10-methacryloyloxydecyl dihydrogen phosphate 4-MET: 4-methacryloyloxyethyl trimellitate [polymerizable monomer having no acidic group]
# 801: 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane GDMA: glycerol dimethacrylate (1,3-dimethacryloyloxy-2-propanol)
HEMA: 2-hydroxyethyl methacrylate BisGMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane D2.6E: 2,2-bis (4-methacryloyloxypolyethoxyphenyl) Propane 3G: Triethylene glycol dimethacrylate [vanadium compound]
VOAA: vanadyl acetylacetonate BMOV: bis (maltolate) oxovanadium (IV)
[Polymerization inhibitor]
BHT: 3,5-di-t-butyl-4-hydroxytoluene [hydroperoxide compound]
THP: 1,1,3,3-tetramethylbutyl hydroperoxide CHP: cumene hydroperoxide BHP: t-butyl hydroperoxide (4 carbon atoms)
[Organic peroxide]
BPO: Benzoyl peroxide [UV absorber]
TN236: Tinuvin 236 (Ciba Specialty Chemicals)
[Filler]
Ba glass: Silane-treated barium glass powder Barium glass (product code “E-3000”, manufactured by ESTEC Co., Ltd.) was pulverized with a ball mill to obtain barium glass powder having an average particle diameter of about 2.5 μm. Silane-treated barium glass powder obtained by surface treatment with 3 parts by weight of 3-methacryloyloxypropyltrimethoxysilane by a conventional method with respect to parts by weight is used. The average particle size of the barium glass powder was measured using a laser diffraction particle size distribution analyzer (SALD-2100: manufactured by Shimadzu Corporation), and using a 0.2% sodium hexametaphosphate aqueous solution as a dispersion medium.
Ar380: Fine particle silica “AEROSIL (registered trademark) 380” manufactured by Nippon Aerosil Co., Ltd.
[Thiourea derivatives]
2-PyTU: 1- (2-pyridyl) -2-thiourea BzTU: N-benzoylthiourea AcTU: 1-acetyl-2-thiourea [copper compound]
CuAA ₂ : acetylacetone copper (II)
[Photopolymerization initiator]
CQ: Camphorquinone [Others]
DMAEMA: N, N-dimethylaminoethyl methacrylate JA: 4-N, N-dimethylaminobenzoic acid ethyl ester DEPT: N, N-di (2-hydroxyethyl) -p-toluidine

Examples 1 to 75 and Comparative Examples 1 to 13
Adhesion kits containing the pretreatment material (A) and the adhesive material (B) of each Example and Comparative Example were prepared as follows, and their characteristics were evaluated. The results are shown in Tables 2-15.

[Preparation of pretreatment material (A)]
Each component described in Tables 2 to 15 was mixed at a normal temperature in the weight ratio described in the table to prepare a primer composition as a pretreatment material (A). The obtained pretreatment material (A) was used by filling a container of “Clearfill (registered trademark) Megabond (registered trademark) primer” (manufactured by Kuraray Medical Co., Ltd.).

[Preparation of adhesive (B)]
The components described in Tables 2 to 15 were mixed at room temperature in the weight ratios described in the table to prepare A paste and B paste. Subsequently, 15 g each was transferred to a resin container of “Clear Fill (registered trademark) FII” (manufactured by Kuraray Medical Co., Ltd.) only with B paste, covered with a container, and left in a 60 ° C. incubator for 24 hours. Then, it was used after returning to room temperature. The A paste and B paste obtained as described above were filled in a paste container of “Clearfill (registered trademark) Esthetic cement” (manufactured by Kuraray Medical Co., Ltd.), which is an automix syringe. When mixing A paste and B paste to obtain a composition, a mixing chip (“Clear Fill (registered trademark) Esthetic cement mixing chip, manufactured by Kuraray Medical Co., Ltd.) is attached to the tip of the paste container. Using the mixing chip, A paste and B paste were mixed in an equal volume ratio of 1: 1 to obtain a composition.

[Method for evaluating adhesion to bovine enamel and bovine dentin]
The lip surface of the bovine mandibular anterior teeth is polished with silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water (# 80), and the flat surface of the enamel and the flat surface of the dentin are exposed. Each sample was obtained. Each obtained sample was further polished with # 1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water. After polishing, the surface water was dried by air blowing. An adhesive tape having a round hole with a diameter of 3 mm and having a thickness of about 150 μm was attached to the smooth surface after drying to define the adhesion area.

  The prepared pretreatment material (A) is applied in the round hole with a brush, left for 20 seconds, and then air blown on the surface to dry the applied pretreatment material (A) until the fluidity is lost. did.

  Composition obtained by kneading A paste and B paste of adhesive (B) at a volume ratio of 1: 1 using a mixing chip as described above on the coated surface of the obtained pretreatment material (A). The product was placed and covered with a release film (trade name “EVAL” manufactured by Kuraray Co., Ltd.), and then allowed to stand at room temperature for 1 hour to be cured. Next, one end face (circular shape) of a stainless steel cylindrical rod (diameter 7 mm, length 2.5 cm) is used for this hardened surface using a dental resin cement (trade name “Panavia 21” manufactured by Kuraray Medical Co., Ltd.). The cross section) was bonded and allowed to stand for 30 minutes. Then, after removing the excess cement composition which protruded from the circumference | surroundings of stainless steel cylindrical rods, it was immersed in distilled water. The test sample immersed in distilled water was allowed to stand for 24 hours in a thermostatic chamber maintained at 37 ° C. to obtain a test piece. A total of five samples for adhesion test were prepared.

  Tensile bond strength of the above five adhesion test samples was measured with a universal testing machine (manufactured by Shimadzu Corporation) with the crosshead speed set to 2 mm / min, and the average value was taken as the tensile bond strength. .

[Measurement of operation surplus time at the time of primer contact]
The lip surface of the bovine mandibular anterior teeth was polished with silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water (# 80) to obtain a sample in which the flat surface of dentin was exposed. The flat surface was sized so that a bottom surface of a cylinder having a diameter of 9 mm was sufficiently placed thereon. The obtained flat surface was further polished with # 1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) and then immersed in distilled water. Subsequently, a circular cross section of a cylindrical SUS chip (diameter 9 mm and height about 7 mm) was polished with # 1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.). The bovine teeth soaked in distilled water and the polished SUS chip obtained as described above were allowed to stand in an open chamber set at 35 ° C. for 2 hours and then used for the test.

  After drying the bovine teeth after standing in an open chamber by air blowing the surface water, it is fixed on the glass slide using utility wax (manufactured by GC Corporation) so that the smooth surface is on top. did. The slide glass on which the bovine teeth were placed was placed on the work surface of the open chamber, and the position of the bovine teeth was adjusted so that the work surface and the smooth surface of the bovine teeth were parallel. Subsequently, the pretreatment material (A) is applied to the above smooth surface using a brush, left for 20 seconds, and then air-blowed on the surface to dry until the fluidity of the applied pretreatment material (A) is lost. did.

  On the polished surface of the SUS chip, a composition obtained by kneading the A paste and B paste of the adhesive (B) at a volume ratio of 1: 1 using a mixing chip as described above was placed. The SUS tip was gently placed on the bovine teeth so that the surface to which the object was applied was in contact with the smooth surface of the bovine teeth. Immediately thereafter, 150 g of a cylindrical weight (diameter 3 cm) was placed on the SUS chip for 1 second, and then the weight was removed. This time was taken as the measurement start time. After 30 seconds from the start of measurement, lightly touch with your finger to check whether the SUS tip moves, then repeat the same operation every 10 seconds, and the place where the SUS tip stops moving is the operation allowance time when the primer contacts did.

[Evaluation of storage stability of primer]
After filling the prepared various primers as the pretreatment material (A) into the container, the sample was left in a thermostat at 4 ° C. and 50 ° C. for 1 week and 4 weeks. The primer after storage at each temperature was dropped on the mixing dish one by one, and the change in the appearance of the 50 ° C. stored product with respect to the 4 ° C. stored product was visually observed and evaluated according to the following criteria.

[Measurement of 23 ° C operation margin time (initial)]
Except that the composition obtained by kneading the A paste and B paste of the adhesive (B) at a volume ratio of 1: 1 using a mixing chip was kneaded and immediately left in the resin container, JIS T6523: According to the description of “6.5 Operation time test” in 2005, the 23 ° C. operation margin time (initial) of the adhesive (B) was measured.

[Measurement of 23 ° C operation margin time (50 ° C, after storage for 2 weeks)]
The automix syringe filled with the adhesive (B) was stored in a thermostat at 50 ° C. for 2 weeks, and then the operation allowance time was measured by the same method as “23 ° C. operation allowance time (initial)”.

[Measurement of transparency (ΔL *) of cured paste]
Using the adhesive (B), a disk-shaped sample (diameter of about 2 cm and thickness of 1 mm) was produced as follows. That is, a cover glass was placed on a slide glass, and two plate-like stainless steel spacers having a thickness of 1 mm were placed on the slide glass at positions separated from each other by 2.5 cm or more. Between these two spacers, a composition obtained by kneading A paste and B paste of adhesive (B) at a volume ratio of 1: 1 using a mixing chip is placed in a hemisphere, and the composition Another cover glass and slide glass were placed on the object from above. The composition was sandwiched between two glass slides and pressed into a disk shape, and the pressed composition was allowed to stand in a thermostat at 37 ° C. for 1 hour to be completely cured. Since the value in the test greatly fluctuates depending on the thickness of the sample, the thickness of the sample was regulated within a range of 0.99 to 1.00 mm (maximum thickness portion 1.00 mm, minimum thickness portion 0.99 mm).

  Using a spectral color difference meter (trade name “SE 6000”, manufactured by Nippon Denshoku Industries Co., Ltd.) that satisfies the conditions described in JIS-Z8729, the standard is behind the test piece under the conditions of a D65 light source and a colorimetric field of view of 2 degrees. The brightness (Lw *) when measuring the chromaticity with a white plate and the brightness (Lb *) when measuring the chromaticity with a standard blackboard placed behind the same test piece are measured, and the difference between the two (Δ L * = (Lw *) − (Lb *)) was defined as the transparency (ΔL *) of the paste cured product.

[Underwater discoloration test of cured paste]
Spectral color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.) satisfying the conditions described in JIS-Z8729 for a disk-shaped sample (diameter: about 2 cm and thickness: 1 mm) of the paste cured product made of the adhesive (B) produced above. Chromaticity in the L *, a *, b * color system with a standard white plate placed behind the test piece under the conditions of a D65 light source and a colorimetric field of view of 2 degrees using the product name “SE 6000”) Were measured, and these were designated L * 0, a * 0, and b * 0. Subsequently, the sample was transferred into a screw tube and filled with distilled water, and then the lid was firmly tightened and left in a thermostat at 70 ° C. for 2 weeks. For the sample after standing, the chromaticity in the L *, a *, b * color system was measured in the same manner, and these were designated L * 1, a * 1, and b * 1. Each obtained value was substituted into the following equation to obtain ΔE * which is an index of discoloration.
ΔE * = {(L * 1-L * 0) ² + (a * 1-a * 0) ² + (b * 1-b * 0) ² } ^1/2

[H ₂ S discoloration test of cured paste]
L * 0, a * 0 of a disk-shaped sample (approximately 2 cm in diameter and 1 mm in thickness) of a paste cured product made of the adhesive (B) according to the method described in the above-mentioned [Underwater Discoloration Test of Paste Cured Product]. , B * 0 was measured. Subsequently, 0.6955 g of sodium sulfide 9 hydrate (special grade reagent) was dissolved in distilled water to prepare 2 ml of an aqueous sodium sulfide solution. Also, distilled water was added to 6.33 ml of 35 wt% concentrated hydrochloric acid to prepare 100 ml of diluted hydrochloric acid. 1 ml of the aqueous sodium sulfide solution was placed in a 10 ml sample tube, and 4 ml of the diluted hydrochloric acid was added thereto and shaken to generate hydrogen sulfide. The pH of the liquid (hydrogen sulfide aqueous solution) in the sample tube when hydrogen sulfide was generated was 7.0 to 7.7. A simple pH meter (trade name “Twin pH B-212”, manufactured by HORIBA, Ltd.) was used for pH measurement, but the pH of the solution increased as hydrogen sulfide evolved. The discoloration test was started 10 minutes after mixing. The sample tube was covered except when measuring the pH or when the sample was put into the sample tube, and a polytetrafluoroethylene sealing tape was wrapped around the joint between the lid and the sample tube to completely seal the sample tube. . The lid opening operation at the time of pH measurement or sample introduction was performed in a short time of 15 seconds or less in order to prevent the hydrogen sulfide from scattering and flowing out of the sample tube.

The disc-shaped sample of the cured paste was poured so as to be completely immersed in the liquid (hydrogen sulfide aqueous solution) in the sample tube, and then the sample tube was stored in a 60 ° C. incubator for 24 hours. After removing the sample from the sample tube and wiping off the droplets adhering to the surface, using a spectral color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name “SE 6000”), the conditions for a D65 light source and a colorimetric field of view of 2 degrees are used. , The chromaticity in the L *, a *, b * color system is measured with a standard white plate placed behind the test piece, and the chromaticity L * 1, a * 1, b * after storage is measured. It was set to 1. Discoloration due to reaction with hydrogen sulfide tends to decrease when the sample is left in a clean atmosphere. Therefore, the chromaticity after storage should be measured within 10 minutes after removing the sample from the solution. I made it. Each obtained value was substituted into the following equation to obtain ΔE * which is an index of discoloration.
ΔE * = {(L * 1-L * 0) ² + (a * 1-a * 0) ² + (b * 1-b * 0) ² } ^1/2

[Measurement of bending strength and elastic modulus of cured paste]
A polyester film was laid on a slide glass plate, and a stainless steel mold 2 mm long × 25 mm wide × 2 mm deep was placed thereon. Next, a composition obtained by kneading the paste A and B paste of the adhesive (B) at a volume ratio of 1: 1 using a mixing chip is filled into a mold, and the surface of the composition in the mold is covered. The two glass slides were fixed using a double clip having a width of 25 mm by pressing with a glass slide through a polyester film. The sample fixed with the double clip was allowed to stand in a 37 ° C. incubator for 1 hour to be polymerized and cured, and then the sample was taken out of the incubator and the polymerized and cured product of the composition was removed from the mold. The polymerized cured product was immersed in distilled water at 37 ° C. for 24 hours and stored, and then subjected to a bending test. The bending strength and the flexural modulus were measured by performing a three-point bending test with a universal testing machine at a span of 20 mm and a crosshead speed of 1 mm / min. The average values of the bending strength and the bending elastic modulus for the five samples were taken as the bending strength and bending elastic modulus of the sample.

  The adhesive kit of the present invention is suitable for dental use, and particularly suitable for a dental cement kit.

Claims (8)

Pretreatment material (A) containing an acidic group-containing radical polymerizable monomer (a1), a vanadium compound (a2), a solvent (a3), and a hydrophilic radical polymerizable monomer (a4) having no acidic group )When,
A radically polymerizable monomer (b1) having no acidic group, a hydroperoxide compound (b2) having 5 or more carbon atoms having at least one hydroperoxide group bonded to a tertiary carbon, pyridylthiourea or a derivative thereof ( b3), an adhesive containing 0 to 3 parts by weight of filler (b4) as an essential component and acidic compound (b5) with respect to a total of 100 parts by weight of (b1), (b2), and (b3) Material (B);
Only contains the pyridylthio urea or its derivative (b3) is a compound represented by the following formula, the adhesive kit.

Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, hydroxyl group, alkyl group, cycloalkyl group, alkoxyl group, aryl group, acyl group, alkenyl group, aralkyl group, or oxygen A monovalent heterocyclic group containing an atom, sulfur atom or nitrogen atom.)   The adhesion kit according to claim 1, wherein the adhesive (B) further contains a vanadium compound (b6). The adhesion kit according to claim 1 or 2 , wherein the adhesive (B) further contains a copper compound (b7). The adhesion kit according to any one of claims 1 to 3, wherein the hydroperoxide compound (b2) is cumene hydroperoxide and / or 1,1,3,3-tetramethylbutyl hydroperoxide. The adhesive kit according to any one of claims 1 to 4 , wherein the content of the acidic compound (b5) in the adhesive (B) is 0 parts by weight. The pretreatment material (A) further contains 0.2 to 5% by weight of a polymerization inhibitor (a5),
The adhesion kit according to any one of claims 1 to 5, wherein a weight ratio (a2) / (a5) between the vanadium compound (a2) and the polymerization inhibitor (a5) is 2/1 to 1/10. The adhesion kit according to any one of claims 1 to 6, which is for dental use. The adhesive kit according to claim 7 , wherein the pretreatment material (A) is a primer, and the adhesive material (B) is cement.