JP2008189580A - Multifunctional hydrophilic polymerizable monomer-containing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition which is suitable as a dental composition, and comprises a polymerizable monomer having at least one acidic group selected from the group consisting of a phosphoric acid group, pyrophosphoric acid group, thiophosphoric acid group, phosphonic acid group and carboxylic acid group, a multifunctional polymerizable monomer having two or more polymerizable groups and two or more primary hydroxy groups, and water. <P>SOLUTION: This composition comprising a polymerizable monomer (a) having at least one acidic group selected from the group consisting of a phosphoric acid group, pyrophosphoric acid group, thiophosphoric acid group, phosphonic acid group and carboxylic acid group, a polymerizable monomer (b) having two or more polymerizable groups and two or more primary hydroxy groups, and (c) water, is characterized in that the polymerizable monomer (a), the polymerizable monomer (b) and the water (c) are contained in amounts of 2 to 98 pts.wt., 2 to 98 pts.wt. and 1 to 2,000 pts.wt, respectively, per 100 pts.wt. of the total amount of the polymerizable monomer components. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polymerizable monomer having at least one acidic group selected from the group consisting of a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, and a carboxylic acid group, and two or more polymerizable groups And a polyfunctional polymerizable monomer having two or more primary hydroxyl groups, and a composition containing water.

  A dental adhesive is usually used when filling or coating a restoration in a tooth defect. As dental adhesives, those containing a polymerizable monomer having an acidic group and a polymerizable monomer having a polymerizable group and a hydroxyl group are known.

For example, US Pat. No. 5,658,963 contains a polymerizable component, a polymerization initiator system, and an antimicrobial agent selected from salicylic acid, 4-aminosalicylic acid, salicylic acid ester, 4-aminosalicylic acid ester or sulfanilamide. A dental restorative composition comprising 0.1 to 5% by weight of the antibacterial agent based on the total amount of the composition, and the water absorption of the cured body of the dental restorative composition is 50 μg / mm A dental restorative composition for a primer, adhesive, lining material, primer / adhesive, cement or filler, characterized in that it is less than ³ / week. According to this, it is possible to provide a dental restorative composition that has minimal adverse effects on living tissue and surrounding tissues, does not affect the restorative properties of the composition, and further maintains an antibacterial action for a long period of time. Has been. However, the adhesive strength to enamel and dentin is not always good, and improvement has been desired.

  Here, when such a dental adhesive is allowed to act on the dentin, a decalcification action that dissolves the dentin surface with an acidic component, a penetration action that the monomer component penetrates into the collagen layer of the dentin, and It is important that the infiltrated monomer component is hardened and has a curing action to form a hybrid layer with collagen (hereinafter sometimes referred to as “resin-impregnated layer”).

  From the three-liquid three-step type in which the decalcification action, the osmosis action, and the curing action are sequentially applied to date, the two-liquid two-step type that unifies the decalcification action and the osmosis action, and the deashing action, Studies are being conducted to simplify the usage of dental adhesives into a one-pack, one-step type that integrates all of the penetrating action and the hardening action. In any use mode, a composition that can be used as a dental adhesive having excellent adhesiveness is required.

US Pat. No. 5,658,963

  The present invention has been made to solve the above-mentioned problems, and is at least selected from the group consisting of a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonic acid group, and a carboxylic acid group suitable for a dental composition. Provided is a composition comprising a polymerizable monomer having one kind of acidic group, a polyfunctional polymerizable monomer having two or more polymerizable groups and two or more primary hydroxyl groups, and water. It is intended to do.

  The above-mentioned problem is a polymerizable monomer (a) having at least one acidic group selected from the group consisting of a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group and a carboxylic acid group, a polymerizable group A composition comprising a polymerizable monomer (b) having two or more and two or more primary hydroxyl groups and water (c), wherein the total amount of the polymerizable monomer components is 100 parts by weight. On the other hand, it comprises 2 to 98 parts by weight of the polymerizable monomer (a), 2 to 98 parts by weight of the polymerizable monomer (b), and 1 to 2000 parts by weight of water (c). This is solved by providing a composition.

  At this time, 1 to 90 parts by weight of the polymerizable monomer (d) having one polymerizable group and one or more hydroxyl groups is further contained with respect to 100 parts by weight of the total amount of the polymerizable monomer components. And the polymerizable monomer (a) is 10-methacryloyloxydecyl phosphoric acid, 1,3-dimethacryloyloxypropyl-2-phosphoric acid, 2-methacryloyloxyethyl phosphoric acid, 4-methacryloyloxyethyl It is preferably at least one selected from the group consisting of trimellitic anhydride, 4-methacryloyloxyethyl trimellitic acid and 11-methacryloyloxyundecane-1,1-dicarboxylic acid. The polymerizable monomer (b) is preferably at least one selected from the group consisting of pentaerythritol di (meth) acrylate and dipentaerythritol di, tri, and tetra (meth) acrylate. It is preferable that the organic solvent (e) is contained in an amount of 1 to 2000 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer components, and the organic solvent (e) is a water-soluble organic solvent. Is preferred. It is preferable to contain 0.001 to 30 parts by weight of a polymerization initiator (f) with respect to 100 parts by weight of the total amount of polymerizable monomer components, and 100 parts by weight of the total amount of polymerizable monomer components. On the other hand, it is preferable to contain 0.001-30 weight part of polymerization accelerators (g). Moreover, it is also suitable to contain 1-1000 weight part of fillers (h) with respect to 100 weight part of whole quantity of a polymerizable monomer component.

  A preferred embodiment of such a composition is a dental composition, particularly suitable as a primer or a bonding material.

  The composition of the present invention comprises a polymerizable monomer having at least one acidic group selected from the group consisting of a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, and a carboxylic acid group, a polymerizable group A polyfunctional polymerizable monomer having two or more and two or more primary hydroxyl groups, and water are contained. When the composition of the present invention is used for dental use, it exhibits excellent adhesive strength. Therefore, it is suitable as a dental composition, and particularly suitable as a primer and a bonding material.

  The composition of the present invention comprises a polymerizable monomer (a) having at least one acidic group selected from the group consisting of a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, and a carboxylic acid group, It contains a polymerizable monomer (b) having two or more polymerizable groups and two or more primary hydroxyl groups, and water (c), and is useful as a dental composition.

  The polymerizable monomer (a) used in the present invention has at least a polymerizable group and is at least selected from the group consisting of a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonic acid group, and a carboxylic acid group. It is a polymerizable monomer having one kind of acidic group.

  When the polymerizable monomer (a) used in the present invention has a polymerizable group, radical polymerization becomes possible and copolymerization with other monomers becomes possible. From the viewpoint of easy radical polymerization, the polymerizable group is preferably a (meth) acryl group or a (meth) acrylamide group. The polymerizable monomer (a) is preferably used as a component of the dental composition. However, since the oral cavity is a moist environment, there is a possibility that the polymerizable group may be eliminated by hydrolysis or the like. In consideration of the irritation to the living body of the detached polymerizable group, the polymerizable group is preferably a methacryl group or a methacrylamide group. The polymerizable monomer (a) may be a monofunctional monomer or a polyfunctional monomer.

  The polymerizable monomer (a) is selected from the group consisting of a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group and a carboxylic acid group in addition to having a polymerizable group as described above. Having at least one acidic group. Therefore, when the composition containing the polymerizable monomer (a) is used as a dental composition, the polymerizable monomer (a) itself has an acid etching effect and a primer treatment effect. There is an advantage that no pretreatment such as primer treatment is required.

  Examples of the polymerizable monomer (a) having a phosphoric acid group include, for example, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meta ) Acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (Meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11 (Meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyl dihydrogen phosphate, 20- (meth) acryloyloxyicosyl dihydro Genphosphate, 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) [Chloroyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromo Examples thereof include ethyl hydrogen phosphate, bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl] hydrogen phosphate, and acid chlorides, alkali metal salts, ammonium salts and the like thereof.

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

  Examples of the polymerizable monomer (a) having a thiophosphate group include 2- (meth) acryloyloxyethyl dihydrogenthiophosphate, 3- (meth) acryloyloxypropyl dihydrogenthiophosphate, 4- ( (Meth) acryloyloxybutyl dihydrogenthiophosphate, 5- (meth) acryloyloxypentyl dihydrogenthiophosphate, 6- (meth) acryloyloxyhexyl dihydrogenthiophosphate, 7- (meth) acryloyloxyheptyl dihydrogen Thiophosphate, 8- (meth) acryloyloxyoctyl dihydrogen thiophosphate, 9- (meth) acryloyloxynonyl dihydrogen thiophosphate, 10- (meth) acryloyloxydecyl Hydrogenthiophosphate, 11- (meth) acryloyloxyundecyl dihydrogenthiophosphate, 12- (meth) acryloyl oxide decyl dihydrogenthiophosphate, 16- (meth) acryloyloxyhexadecyl dihydrogenthiophosphate, 20 -(Meth) acryloyloxyicosyl dihydrogenthiophosphate, and acid chlorides, alkali metal salts, ammonium salts and the like thereof are exemplified.

  Examples of the polymerizable monomer (a) having a phosphonic acid group include, for example, 2- (meth) acryloyloxyethyl phenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, 6- (Meth) acryloyloxyhexyl-3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonoacetate, 10- ( Examples thereof include (meth) acryloyloxydecyl-3-phosphonoacetate, and acid chlorides, alkali metal salts, and ammonium salts thereof.

  The polymerizable monomer (a) having a carboxylic acid group is not particularly limited, but a monofunctional polymerizable monomer having one carboxyl group or its acid anhydride group in the molecule, and a plurality of monomers in the molecule. And monofunctional polymerizable monomers having a carboxyl group or an acid anhydride group thereof.

  Examples of monofunctional polymerizable monomers having one carboxyl group or acid anhydride group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, and N- (meth) acryloyl. Aspartic acid, N- (meth) acryloyl-5-aminosalicylic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydrogenma Rate, 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid, O- (meth) acryloyl tyrosine, N- (meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) Acryloyl-p-aminobenzoic acid, N- ( T) Acrylyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meta) ) Acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, etc. and acid anhydrides or acid halides of the above (radical) polymerizable monomers.

  Examples of monofunctional polymerizable monomers having a plurality of carboxyl groups or acid anhydride groups in the molecule include 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 9- (meta ) Acryloyloxynonane-1,1-dicarboxylic acid, 10- (meth) acryloyloxydecane-1,1-dicarboxylic acid, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 12- (meth) acryloyl Oxidodecane-1,1-dicarboxylic acid, 13- (meth) acryloyloxytridecane-1,1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxyethyl trimellitate Anhydride, 4- (meth) acryloyloxybutyl trimellitate, 4- (meth) a Liloyloxyhexyl trimellitate, 4- (meth) acryloyloxydecyl trimellitate, 2- (meth) acryloyloxyethyl-3′-methacryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) propyl succin Nate, 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid anhydride, 6- (meth) acryloyloxyethylnaphthalene-2,3,6-tricarboxylic acid anhydride, 4- (meth) acryloyl Examples include oxyethylcarbonylpropionoyl-1,8-naphthalic anhydride, 4- (meth) acryloyloxyethylnaphthalene-1,8-tricarboxylic acid anhydride, and the like.

  Among the polymerizable monomers (a) having an acidic group described above, the polymerizable monomer (a) is a phosphate group or a carboxylic acid from the viewpoint of good adhesive strength when used as a dental composition. It preferably has a group. Specifically, the polymerizable monomer (a) is 10-methacryloyloxydecyl phosphate, 1,3-dimethacryloyloxypropyl-2-phosphate, 2-methacryloyloxyethyl phosphate, 4-methacryloyloxyethyltri It is preferably at least one selected from the group consisting of merit acid anhydride, 4-methacryloyloxyethyl trimellitic acid and 11-methacryloyloxyundecane-1,1-dicarboxylic acid.

  The composition of the present invention contains 2 to 98 parts by weight of the polymerizable monomer (a) with respect to 100 parts by weight of the total amount of the polymerizable monomer components. When a composition in which the blending amount of the polymerizable monomer (a) is in such a range is used as a dental composition, the polymerizable monomer (a) itself has an acid etching effect and a primer treatment effect. Therefore, there is an advantage that no pretreatment such as acid etching treatment or primer treatment is required. Therefore, when the composition of the present invention contains the polymerizable monomer (a), it is possible to provide a primer or a bonding material that is simple and has good adhesive strength. When the compounding amount of the polymerizable monomer (a) is less than 2 parts by weight, the acid etching effect or the primer treatment effect may not be obtained. The compounding amount of the polymerizable monomer (a) is 3 parts by weight. Preferably, it is preferably 5 parts by weight or more, more preferably 10 parts by weight or more. On the other hand, when the compounding amount of the polymerizable monomer (a) exceeds 98 parts by weight, the polymerizability of the composition may decrease and the adhesive strength may decrease, and the compounding amount of the polymerizable monomer (a) may decrease. Is preferably 85 parts by weight or less, more preferably 80 parts by weight or less, still more preferably 60 parts by weight or less, and particularly preferably 50 parts by weight or less.

  The composition of the present invention contains a polymerizable monomer (b) having two or more polymerizable groups and two or more primary hydroxyl groups in addition to the polymerizable monomer (a) having an acidic group. It is characterized by doing. By this, when the composition of this invention is used as a dental composition, the outstanding adhesive strength is shown. Since the polymerizable monomer (b) used in the present invention is a polyfunctional polymerizable monomer having two or more polymerizable groups, it has high polymerizability and good crosslinkability. When the polymerizable monomer (b) has a polymerizable group, radical polymerization becomes possible and copolymerization with other monomers becomes possible. From the viewpoint of easy radical polymerization, the polymerizable group is preferably a (meth) acryl group or a (meth) acrylamide group. The polymerizable monomer (b) is preferably used as a component of the dental composition. However, since the oral cavity is a moist environment, there is a possibility that the polymerizable group may be detached by hydrolysis or the like. In consideration of the irritation to the living body of the detached polymerizable group, the polymerizable group is preferably a methacryl group or a methacrylamide group.

  Moreover, since the polymerizable monomer (b) has two or more primary hydroxyl groups in addition to having two or more polymerizable groups, it has high hydrophilicity, and the composition of the present invention described later is dental. When used as a composition for use, the penetration of dentin into the collagen layer is good and the adhesive strength is high. Actually, as is clear from the comparison between Examples 1 to 6 and Comparative Examples 1 to 4 in the examples described later, one or two secondary hydroxyl groups or one primary hydroxyl group is present. When only the monomer is used, sufficient adhesive strength cannot be obtained. By using a polymerizable monomer (b) having two or more polymerizable groups and two or more primary hydroxyl groups as a component of the dental composition, it has excellent adhesive strength to the tooth. Show. As the polymerizable monomer (b), a larger number of polymerizable groups and primary hydroxyl groups per molecular weight is preferable from the viewpoint of permeability and crosslink density, but the compound can be easily obtained and obtained. From the viewpoint of good handleability of the composition, the number of polymerizable groups is preferably 6 or less, and the number of primary hydroxyl groups is preferably 6 or less.

  Such a polymerizable monomer (b) is not particularly limited as long as it is a polymerizable monomer having two or more polymerizable groups and two or more primary hydroxyl groups, but collagen formed after polymerization. From the viewpoint of good strength of the hybrid layer and good adhesive strength, at least selected from the group consisting of pentaerythritol di (meth) acrylate and dipentaerythritol di, tri, and tetra (meth) acrylate One type is preferable.

  The composition of the present invention comprises 2 to 98 parts by weight of the polymerizable monomer (b) with respect to 100 parts by weight of the total amount of the polymerizable monomer components. When a composition in which the blending amount of the polymerizable monomer (b) is in such a range is used as a dental composition, there is an advantage that a product having excellent adhesive strength can be obtained. Therefore, when the composition of the present invention contains the polymerizable monomer (b), it is possible to provide a primer or a bonding material that is simple and has good adhesive strength. When the blending amount of the polymerizable monomer (b) is less than 2 parts by weight, the adhesive strength may be lowered, and the blending amount of the polymerizable monomer (b) is preferably 5 parts by weight or more. The amount is more preferably 10 parts by weight or more, and further preferably 20 parts by weight or more. On the other hand, when the compounding amount of the polymerizable monomer (b) exceeds 98 parts by weight, the adhesive force may be reduced, and the compounding amount of the polymerizable monomer (b) is 90 parts by weight or less. Preferably, it is 80 parts by weight or less, more preferably 70 parts by weight or less, and particularly preferably 60 parts by weight or less.

  The composition of the present invention comprises 1 to 2000 parts by weight of water (c) with respect to 100 parts by weight of the total amount of polymerizable monomer components. By including such a blending amount of water (c), excellent adhesive strength is exhibited when the composition of the present invention is used as a dental composition. When the blending amount of water (c) is less than 1 part by weight, the acid etching effect and primer treatment effect of the composition may be reduced, and the adhesive strength may be reduced. The blending amount of water (c) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and further preferably 20 parts by weight or more. On the other hand, when the amount of water (c) exceeds 2000 parts by weight, the polymerizability of the monomer is lowered, and the adhesive strength may be lowered. The amount of water (c) is preferably 1000 parts by weight or less, more preferably 500 parts by weight or less, further preferably 200 parts by weight or less, and particularly preferably 100 parts by weight or less. preferable. Moreover, it is preferable that the water (c) does not contain impurities that have an adverse effect, and distilled water or ion-exchanged water is preferable. The water (c) may be used alone or as a mixed solvent of water (c) and an organic solvent (e) described later.

  The composition of the present invention preferably contains a polymerizable monomer (d) having one polymerizable group and one or more hydroxyl groups. In addition to the polymerizable monomer (a), the polymerizable monomer (b) and the water (c), the composition of the present invention can be used in the dental treatment by further containing such a polymerizable monomer (d). When used as a composition for an adhesive, the adhesive strength is good, which is preferable. When the polymerizable monomer (d) has a polymerizable group, radical polymerization becomes possible and copolymerization with other monomers becomes possible. From the viewpoint of easy radical polymerization, the polymerizable group is preferably a (meth) acryl group or a (meth) acrylamide group. The polymerizable monomer (d) is preferably used as a component of the dental composition. However, since the oral cavity is a moist environment, there is a possibility that the polymerizable group may be detached by hydrolysis or the like. In consideration of the irritation to the living body of the detached polymerizable group, the polymerizable group is preferably a methacryl group or a methacrylamide group.

  The polymerizable monomer (d) has one or more hydroxyl groups, has good hydrophilicity, and is a monofunctional polymer monomer having one polymerizable group. In addition to the body (a), the polymerizable monomer (b) and the water (c), when the composition of the present invention further containing the polymerizable monomer (d) is used as a dental composition, It is preferable because the permeability of the dentin into the collagen layer is more excellent.

  Examples of such a polymerizable monomer (d) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 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) (meth) acrylamide and the like can be mentioned. Among these, 2-hydroxyethyl (meth) acrylate, (3-hydroxypropyl (meth) acrylate, glycerol mono (meth) Acrylate, erythritol mono (meth) acrylate) are preferable, particularly preferably 2-hydroxyethyl methacrylate.

  Although the compounding quantity of the polymerizable monomer (d) used by this invention is not specifically limited, 1 to 90 weight of polymerizable monomers (d) are with respect to 100 weight part of whole quantity of a polymerizable monomer component. It is preferable to contain a part. When a composition in which the blending amount of the polymerizable monomer (d) is within such a range is used as a dental composition, the penetration of dentin into the collagen layer is good and the adhesive strength is good. Therefore, it is preferable. Therefore, when the composition of the present invention contains the polymerizable monomer (d), it is possible to provide a primer or a bonding material that is simple and has good adhesive strength. When the blending amount of the polymerizable monomer (d) is less than 1 part by weight, there is a possibility that contribution of penetration of the dentin into the collagen layer by the polymerizable monomer (d) may not be obtained, and the adhesive strength is The blending amount of the polymerizable monomer (d) is more preferably 5 parts by weight or more, further preferably 10 parts by weight or more, and particularly preferably 30 parts by weight or more. preferable. On the other hand, when the compounding amount of the polymerizable monomer (d) exceeds 90 parts by weight, the mechanical strength of the cured product may be decreased and the adhesive strength may be decreased. The amount is more preferably 80 parts by weight or less, further preferably 75 parts by weight or less, and particularly preferably 70 parts by weight or less.

  The composition of the present invention has a crosslinking property other than the polymerizable monomer (a), the polymerizable monomer (b) and the polymerizable monomer (d) to the extent that the effects of the present invention are not impaired. You may further contain a functional polymerizable monomer.

  The polyfunctional polymerizable monomer having crosslinkability other than (a), (b) and (d) is not particularly limited. Examples thereof include a bifunctional polymerizable monomer of a system and a polymerizable monomer having a trifunctional or higher functionality.

  Examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis ((meth) acryloyloxyphenyl) propane and 2,2-bis [4- (3- (meth) acryloyloxy). -2-hydroxypropoxyphenyl] propane (commonly referred to as “BisGMA”), 2,2-bis (4- (meth) acryloyloxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane), 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meta ) Acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxypheny) ) 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, etc. Is mentioned.

  Examples of aliphatic compound-based bifunctional polymerizable monomers include 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-decandiol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, 2,2,4-trimethylhexamethylene Screw( - such carbamoyloxyethyl) dimethacrylate (commonly known as "UDMA"), among others.

  Examples of tri- or higher functional polymerizable monomers 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 And 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane.

  It is preferable that the composition of this invention contains the organic solvent (e) depending on the specific embodiment. Examples of the organic solvent (e) include methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, hexane, toluene, chloroform, ethyl acetate, butyl acetate and the like. Among these, in consideration of both safety to the living body and ease of removal based on volatility, the organic solvent (e) is preferably a water-soluble organic solvent. Specifically, ethanol and acetone are Preferably used. The compounding quantity of the said organic solvent (e) is not specifically limited, Depending on embodiment, there exists a thing which does not require the mixing | blending of the said organic solvent (e). In the embodiment using the organic solvent (e), it is preferable to contain 1 to 2000 parts by weight of the organic solvent (e) with respect to 100 parts by weight of the total amount of the polymerizable monomer components. Since the suitable compounding amount of the organic solvent (e) varies greatly depending on the embodiment used, the organic solvent according to each embodiment is described in conjunction with the description of specific embodiments of the composition of the present invention described later. A suitable blending amount of the solvent (e) will be shown.

  As a polymerization initiator (f) used for this invention, it can select and use from the polymerization initiator used in the general industry, and the polymerization initiator used for a dental use is used preferably especially. In particular, polymerization initiators for photopolymerization and chemical polymerization are used alone or in combination of two or more.

  Among the polymerization initiator (f) used in the present invention, as the photopolymerization initiator, (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, Examples include α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, α-amino ketone compounds, and the like.

  Among the (bis) acylphosphine oxides contained in the photopolymerization initiator used in the present invention, acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 2,6-dimethoxybenzoyldiphenylphosphine. Oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenyl Examples thereof include phosphine oxide and benzoyl di- (2,6-dimethylphenyl) phosphonate. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, and the like (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide.

  The water-soluble acyl phosphine oxides contained in the photopolymerization initiator used in the present invention preferably have an alkali metal ion, alkaline earth metal ion, pyridinium ion or ammonium ion in the acyl phosphine oxide molecule. For example, water-soluble acylphosphine oxides are disclosed in European Patent No. It can be synthesized by the method disclosed in Japanese Patent No. 0009348 or Japanese Patent Application Laid-Open No. 57-197289.

  Specific examples of the water-soluble acyl phosphine oxides include monomethyl acetyl phosphonate / sodium, monomethyl (1-oxopropyl) phosphonate / sodium, monomethyl benzoyl phosphonate / sodium, monomethyl (1-oxobutyl) phosphine. Phosphonate sodium, monomethyl (2-methyl-1-oxopropyl) phosphonate sodium, acetyl phosphonate sodium, monomethyl acetyl phosphonate sodium, acetyl methyl phosphonate sodium, methyl 4- (hydroxy Methoxyphosphinyl) -4-oxobutanoate sodium salt, methyl-4-oxophosphonobutanoate mononatrium salt, acetyl phenyl phosphinate Sodium salt, (1-oxopropyl) pentylphosphinate sodium, methyl-4- (hydroxypentylphosphinyl) -4-oxobutanoate sodium salt, acetylpentylphosphinate sodium, acetylethylphosphite Nate sodium, methyl (1,1-dimethyl) methyl phosphinate sodium, (1,1-diethoxyethyl) methyl phosphinate sodium, (1,1-diethoxyethyl) methyl phosphinate sodium Methyl-4- (hydroxymethylphosphinyl) -4-oxobutanoate lithium salt, 4- (hydroxymethylphosphinyl) -4-oxobutanoic acid dilithium salt, methyl (2-methyl- 1,3-dioxolan-2-yl) Phosphinate sodium salt, methyl (2-methyl-1,3-thiazolidin-2-yl) phosphonite sodium salt, (2-methylperhydro-1,3-diazin-2-yl) phosphonite sodium Salt, acetyl phosphinate sodium salt, (1,1-diethoxyethyl) phosphonite sodium salt, (1,1-diethoxyethyl) methyl phosphonite sodium salt, methyl (2-methyloxathio) Lan-2-yl) phosphinate sodium salt, methyl (2,4,5-trimethyl-1,3-dioxolan-2-yl) phosphinate sodium salt, methyl (1,1-propoxyethyl) phos Finate sodium salt, (1-methoxyvinyl) methyl phosphinate sodium salt, (1-ethylthiovinyl) methyl phosphinate sodium salt, methyl (2-methylperhydro-1,3-diazin-2-yl) phosphinate sodium salt, methyl (2-methylperhydro-1, 3-thiazin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-diazolidin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-thiazolidine- 2-yl) phosphinate sodium salt, (2,2-dicyano-1-methylethynyl) phosphinate sodium salt, acetyl methyl phosphinate oxime natrium salt, acetyl methyl phosphinate-O-benzyl Oxime sodium salt, 1-[(N-ethoxyimino) ethyl] methyl phosphinate na Lithium salt, methyl (1-phenyliminoethyl) phosphinate sodium salt, methyl (1-phenyl hydrazone ethyl) phosphinate sodium salt, [-(2,4-dinitrophenylhydrazono) ethyl] methyl phosphine Finate sodium salt, acetyl methyl phosphinate semicarbazone sodium salt, (1-cyano-1-hydroxyethyl) methyl phosphinate sodium salt, (dimethoxymethyl) methyl phosphinate sodium salt, formyl Methyl phosphinate sodium salt, (1,1-dimethoxypropyl) methyl phosphinate sodium salt, methyl (1-oxopropyl) phosphinate sodium salt, (1,1-dimethoxypropyl) methyl phosphinate・ Dodeci Guanidine salt, (1,1-dimethoxypropyl) methylphosphinate-isopropylamine salt, acetylmethylphosphinate thiosemicarbazone sodium salt, 1,3,5-tributyl-4-methylamino-1,2, 4-triazolium (1,1-dimethoxyethyl) -methylphosphinate, 1-butyl-4-butylaminomethylamino-3,5-dipropyl-1,2,4-triazolium (1,1-dimethoxyethyl)- Methyl phosphinate, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide potassium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide ammonium salt Etc. Furthermore, the compound described in Unexamined-Japanese-Patent No. 2000-159621 is also mentioned.

  Among these (bis) acylphosphine oxides and water-soluble acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2 , 4,6-Trimethylbenzoyl) acylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are particularly preferred.

  Examples of thioxanthones or quaternary ammonium salts of thioxanthones contained in the photopolymerization initiator used in the present invention include thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3- (9- Oxy-9H-thioxanthen-4-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (1-methyl-9-oxy-9H-thioxanthen-4-yloxy)- N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy -3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N Trimethyl-1-propaneaminium chloride, 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, 2-hydroxy -3- (1,3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride and the like can be used.

  Among these thioxanthones or quaternary ammonium salts of thioxanthones, a particularly preferred thioxanthone is 2-chlorothioxanthen-9-one, and a particularly preferred quaternary ammonium 厶 salt of thioxanthones is 2 -Hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride.

  Examples of ketals contained in the photopolymerization initiator used in the present invention include benzyl dimethyl ketal and benzyl diethyl ketal.

  Examples of the α-diketone contained in the photopolymerization initiator used in the present invention include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4 , 4′-oxybenzyl, acenaphthenequinone and the like. Among these, camphorquinone is particularly preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.

  Examples of the coumarin compound contained in the photopolymerization initiator used in the present invention include 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin, 3 -Benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3- (p -Nitrobenzoyl) coumarin, 3- (p-nitrobenzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3 '-Carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, Zoylbenzo [f] coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo [f] coumarin, 7 -Methoxy-3- (p-nitrobenzoyl) coumarin, 3- (p-nitrobenzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin, 7-dimethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-diethylamino) coumarin, 7-methoxy-3- (4 -Methoxybenzoyl) coumarin, 3- (4- Trobenzoyl) benzo [f] coumarin, 3- (4-ethoxycinnamoyl) -7-methoxycoumarin, 3- (4-dimethylaminocinnamoyl) coumarin, 3- (4-diphenylaminocinnamoyl) coumarin, 3- [(3-Dimethylbenzothiazol-2-ylidene) acetyl] coumarin, 3-[(1-methylnaphtho [1,2-d] thiazol-2-ylidene) acetyl] coumarin, 3,3′-carbonylbis (6- Methoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin), 3,3′-carbonylbis (7-dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3- (2-Benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2-benzoimidazoloyl) -7- (Diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dioctylamino) coumarin, 3-acetyl-7- (dimethylamino) coumarin, 3,3-carbonylbis (7-dibutylaminocoumarin), 3 , 3'-carbonyl-7-diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3 6,7-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one, 10- (2-benzothiazoyl) -2 , 3,6,7-tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one, etc. Rights 9-3109, JP-compounds described in JP-A-10-245525 can be cited.

  Among the above-mentioned coumarin compounds, 3,3′-carbonylbis (7-diethylaminocoumarin) and 3,3′-carbonylbis (7-dibutylaminocoumarin) are particularly preferable.

  Examples of anthraquinones contained in the photopolymerization initiator used in the present invention include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2- Examples include ethyl anthraquinone and 1-hydroxyanthraquinone.

  Examples of benzoin alkyl ethers contained in the photopolymerization initiator used in the present invention include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of α-aminoketones contained in the photopolymerization initiator used in the present invention include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

  Among these photopolymerization initiators, it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides and salts thereof, α-diketones, and coumarin compounds. As a result, it has excellent photocurability in the visible and near-ultraviolet regions, and has an adhesive property including the compound (b) that exhibits sufficient photocurability using any light source of a halogen lamp, a light emitting diode (LED), or a xenon lamp A composition is obtained.

  Of the polymerization initiator (f) used in the present invention, an organic peroxide is preferably used as the chemical polymerization initiator. The organic peroxide used for said chemical polymerization initiator is not specifically limited, A well-known thing can be used. Typical organic peroxides include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, peroxydicarbonate and the like.

  Examples of the ketone peroxide include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.

  Examples of the hydroperoxide include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide.

  Examples of the diacyl peroxide include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. Is mentioned. Dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3- Examples include bis (t-butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne.

  Examples of the peroxyketal include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t -Butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 4,4-bis (t-butylperoxy) valeric acid-n-butyl ester and the like.

  Examples of the peroxyester include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexa Noate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate , T-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate and t-butylperoxymaleic acid.

  Examples of the peroxydicarbonate include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, di- Examples include n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate and diallyl peroxydicarbonate.

  Among these organic peroxides, diacyl peroxide is preferably used from the comprehensive balance of safety, storage stability, and radical generating ability, and among them, benzoyl peroxide is particularly preferably used.

  The blending amount of the polymerization initiator (f) used in the present invention is not particularly limited, but from the viewpoint of curability and the like of the resulting composition, polymerization is started with respect to 100 parts by weight of the total amount of the polymerizable monomer components. It is preferable to contain 0.001-30 weight part of agents (f). When the blending amount of the polymerization initiator (f) is less than 0.001 part by weight, the mechanical strength of the cured product may decrease and the adhesive strength may decrease, and more preferably 0.01 part by weight or more. More preferably, it is 0.1 parts by weight or more, and particularly preferably 1 part by weight or more. On the other hand, when the compounding quantity of a polymerization initiator (f) exceeds 30 weight part, there exists a possibility that adhesive strength may fall, More preferably, it is 15 weight part or less, More preferably, it is 5 weight part or less.

  In a preferred embodiment, the polymerization initiator (f) described above is used with a polymerization accelerator (g). Examples of the polymerization accelerator (g) used in the present invention include amines, sulfinic acid and salts thereof, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, and thiols. Compounds and the like.

  The amines contained in the polymerization accelerator (g) used in the present invention are classified into aliphatic amines and aromatic amines. Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methyldiethanolamine; N -Methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, Tertiary fats such as triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine Such as family amines. Among these, tertiary aliphatic amines are preferable from the viewpoint of curability and storage stability of the composition, and among these, N-methyldiethanolamine and triethanolamine are more preferably used.

  Examples of the aromatic amine include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, and N, N-bis. (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl)- 3,5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N , N-dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylamino Benzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid 2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone, 4- Examples include butyl dimethylaminobenzoate. Among these, N, N-di (2-hydroxyethyl) -p-toluidine, 4-N, N-dimethylaminobenzoic acid ethyl ester, N, N- from the viewpoint of imparting excellent curability to the composition. At least one selected from the group consisting of dimethylaminobenzoic acid n-butoxyethyl ester and 4-N, N-dimethylaminobenzophenone is preferably used.

  Examples of the sulfinic acid and salts thereof included in the polymerization accelerator (g) used in the present invention include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, and lithium p-toluenesulfinate P-toluenesulfinate calcium, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethyl Sodium benzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-to Ethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate Calcium, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfin Examples include lithium acid, calcium 2,4,6-triisopropylbenzenesulfinate, sodium benzenesulfinate, sodium p-toluenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate Particularly preferred.

  The borate compound contained in the polymerization accelerator (g) used in the present invention is preferably an aryl borate compound. Specific examples of suitably used aryl borate compounds include trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluoro) as borate compounds having one aryl group in one molecule. Phenyl) boron, trialkyl (3,5-bistrifluoromethyl) phenylboron, trialkyl [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl ] Boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl (p-butyloxy) Phenyl) boron, trialkyl (m-butyloxyphenyl) boron, Alkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (the alkyl group is at least one selected from the group consisting of n-butyl, n-octyl, n-dodecyl, etc.) A) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinori Examples thereof include a nium salt and a butyl quinolinium salt.

  Examples of the borate compound having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, and dialkyldi (3,5-bistrifluoromethyl) phenyl. Boron, dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron, dialkyldi (m-nitro Phenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-octyloxyphenyl) Boron and di Sodium salt, lithium salt, potassium salt of rualkyldi (m-octyloxyphenyl) boron (the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, n-dodecyl group, etc.) Magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt and butylquinolinium salt It is done.

  Further, borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3 , 5-Bistrifluoromethyl) phenyl boron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, monoalkyltri ( p-nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p-butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri (p-butyloxyphenyl) Boron, monoalkyltri (m-butyloxyphenyl) boron, monoal Rutri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (the alkyl group is one selected from n-butyl group, n-octyl group, n-dodecyl group, etc.) Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, A butyl quinolinium salt etc. are mentioned.

  Further, borate compounds having four aryl groups in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenylboron. Tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m-nitrophenyl) ) Boron, Tetrakis (p-butylphenyl) boron, Tetrakis (m-butylphenyl) boron, Tetrakis (p-butyloxyphenyl) boron, Tetrakis (m-butyloxyphenyl) boron, Tetrakis (p-octyloxyphenyl) boron , Tetrakis (m-octyloxyf Nyl) boron, (p-fluorophenyl) triphenylboron, (3,5-bistrifluoromethyl) phenyltriphenylboron, (p-nitrophenyl) triphenylboron, (m-butyloxyphenyl) triphenylboron, ( p-butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron and sodium salt of (p-octyloxyphenyl) triphenylboron, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetra Examples thereof include methylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, and butylquinolinium salt.

  Among these aryl borate compounds, it is more preferable to use a borate compound having 3 or 4 aryl groups in one molecule from the viewpoint of storage stability. These aryl borate compounds may be used alone or in combination of two or more.

  Examples of the barbituric acid derivative contained in the polymerization accelerator (g) used in the present invention include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid. 5-butyl barbituric acid, 5-ethyl barbituric acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbi Tool acid, 1,3-dimethyl-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid 1,3-dimethyl-5-cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, Rohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methyl Barbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, and These salts (especially preferred are alkali metals or alkaline earth metals). It is, as the salts of these barbituric acids include sodium 5-butyl barbituric acid, 1,3,5-trimethyl barbituric acid sodium and 1-cyclohexyl-5-ethyl barbituric sodium tools acids and the like.

  Particularly preferred barbituric acid derivatives include 5-butyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, And sodium salts of these barbituric acids.

  Examples of the triazine compound contained in the polymerization accelerator (g) used in the present invention include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl)- s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (Trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis ( Lichloromethyl) -s-triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s- Triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -Styryl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (O-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-butoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) ) -S-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-tri Methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-biphenylyl)- 4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-bis (2-hydroxyethyl) amino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-ethylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-methylamino} ester Toxi] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine and the like are exemplified. The

  Among the triazine compounds exemplified above, 2,4,6-tris (trichloromethyl) -s-triazine is particularly preferable from the viewpoint of polymerization activity, and 2-phenyl-4 is preferable from the viewpoint of storage stability. , 6-Bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (4-biphenylyl) -4,6-bis ( Trichloromethyl) -s-triazine. You may use the said triazine compound 1 type or in mixture of 2 or more types.

  As the copper compound contained in the polymerization accelerator (g) used in the present invention, for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.

  Examples of the tin compound contained in the polymerization accelerator (g) used in the present invention include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyl. Examples thereof include tin dilaurate. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

  The vanadium compound contained in the polymerization accelerator (g) used in the present invention is preferably IV-valent and / or V-valent vanadium compounds. Examples of the IV-valent and / or V-valent vanadium compounds include divanadium tetroxide (IV), vanadium oxide acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1- Japanese Patent Application Laid-Open Publication No. 2003, such as phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), and ammonium metavanadate (V) The compound described in -96122 is mentioned.

  Examples of the halogen compound contained in the polymerization accelerator (g) used in the present invention include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, di Lauryldimethylammonium bromide or the like is preferably used.

  Examples of aldehydes contained in the polymerization accelerator (g) used in the present invention include terephthalaldehyde and benzaldehyde derivatives. Examples of the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like. Among these, pn-octyloxybenzaldehyde is preferably used from the viewpoint of curability.

  Examples of the thiol compound contained in the polymerization accelerator (g) used in the present invention include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

  Although the compounding quantity of the polymerization accelerator (g) used for this invention is not specifically limited, From viewpoints, such as sclerosis | hardenability of the composition obtained, superposition | polymerization acceleration | stimulation is carried out with respect to 100 weight part of whole quantity of a polymerizable monomer component. It is preferable to contain 0.001-30 weight part of agents (g). When the blending amount of the polymerization accelerator (g) is less than 0.001 part by weight, the mechanical strength of the cured product may decrease and the adhesive strength may decrease, and more preferably 0.01 part by weight or more. More preferably, it is 0.1 parts by weight or more. On the other hand, when the blending amount of the polymerization accelerator (g) exceeds 30 parts by weight, there is a possibility that the adhesive strength may be reduced, the color tone of the composition may be deteriorated, or the cured product may be discolored. It is 20 parts by weight or less, more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less.

  The composition of the present invention preferably contains a filler (h). Such fillers are generally roughly classified into organic fillers, inorganic fillers, and organic-inorganic composite fillers. Examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene, and chloroprene. Examples include rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and these are used alone or as a mixture of two or more. Can be used. 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 handling properties and mechanical strength of the resulting composition, the average particle diameter of the organic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

  Inorganic fillers include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, alumino Examples thereof include silicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. 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 and mechanical strength of the resulting composition, the average particle size 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 composition, it is preferable to use a spherical filler as the inorganic filler. Furthermore, when the spherical filler is used, there is an advantage that a composite resin excellent in surface lubricity can be obtained when the composition of the present invention is used as a dental composite resin. 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 size is less than 0.1 μm, the filling rate of the spherical filler in the composition is lowered, and the mechanical strength 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 | liquidity of a composition, you may use the said inorganic filler, after surface-treating beforehand with well-known surface treatment agents, such as a silane coupling agent, as needed. Examples of the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane. , Γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like.

  The organic-inorganic composite filler used in the present invention is obtained by previously adding a polymerizable monomer to the above-described inorganic filler, 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 and mechanical strength of the resulting composition, the average particle size of the organic-inorganic composite filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

  The blending amount of the inorganic filler (h) used in the present invention is not particularly limited, and may be 1 to 1000 parts by weight of the filler (h) with respect to 100 parts by weight of the total amount of the polymerizable monomer components. preferable. Since the suitable compounding amount of the filler (h) varies greatly depending on the embodiment to be used, the filler (h) according to each embodiment is described together with the description of specific embodiments of the composition of the present invention described later. The preferred blending amount is shown.

  In addition, the composition of the present invention may contain 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.

  The polymerizable monomer (a) having an acidic group of the present invention, a polymerizable monomer (b) having two or more polymerizable groups and two or more primary hydroxyl groups, and water (c) are contained. The composition obtained is suitably used as a dental composition. The dental composition comprising the composition of the present invention includes a primer, a bonding material, a composite resin, a cement (resin cement, glass ionomer cement, resin reinforced glass ionomer cement), a foveal fissure filling material, a denture base resin, and the like. Among them, the dental composition comprising the composition of the present invention is suitably used as a primer or a bonding material. Hereinafter, each embodiment will be described in detail.

  As described above, a dental adhesive is usually used when filling or covering a restoration on a tooth defect. Typically, the dental adhesive is acted on the dentin. Here, when such a dental adhesive is allowed to act on dentin, a decalcification action that dissolves the dentin surface with an acidic component, a penetration action that the monomer component penetrates into the collagen layer of dentin, and It is important that the infiltrated monomer component is hardened and has a hardening action to form a hybrid layer with collagen (hereinafter sometimes referred to as “resin impregnated layer”). An adhesion system that performs these three steps of “demineralization”, “penetration”, and “curing” separately is usually called a “three-step adhesion system”. Basically, the product used in the infiltration process is a primer, and the product used in the curing process is a bonding material.

  In recent years, in order to simplify the work process, a product that combines the decalcification process and the infiltration process in one step has been developed and put into practical use, and the product is called a “self-etching primer”. . An adhesion system using a self-etching primer and a bonding material is usually called a “two-step adhesion system”. Since the polymerizable monomer (b) used in the present invention has two or more hydroxyl groups and high hydrophilicity, it easily penetrates into the dentin collagen layer. For this reason, it is preferable to use the composition of this invention containing a polymerizable monomer (b) as a dental primer, and it is preferable to use it as a dental self-etching primer.

  The primer containing the composition of the present invention comprises a polymerizable monomer (a), a polymerizable monomer (b) having two or more polymerizable groups and two or more primary hydroxyl groups, water (c), A composition containing a polymerizable monomer (d) having one polymerizable group and one or more hydroxyl groups, a polymerization initiator (f), and a polymerization accelerator (g) is preferred. The amount of each component is (a) 5 to 80 parts by weight, (b) 10 to 95 parts by weight, and (d) 5 to 80 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer components. Preferably, (a) 5 to 60 parts by weight, (b) 10 to 90 parts by weight, and (d) 10 to 80 parts by weight, (a) 10 to 50 parts by weight, (b) 20 More preferably, it is -80 weight part and (d) 30-80 weight part. Moreover, (c) 5-1000 weight part, (f) 0.01-30 weight part, and (g) 0.01-20 weight part are contained with respect to 100 weight part of whole quantity of a polymerizable monomer component. Preferably, (c) 10 to 500 parts by weight, (f) 0.1 to 30 parts by weight, and (g) 0.01 to 10 parts by weight, (c) 20 to 200 parts by weight, (f) More preferably, it contains 0.1 to 5 parts by weight and (g) 0.01 to 5 parts by weight.

  The polymerizable monomer (b) used in the present invention has two or more hydroxyl groups in the molecule, and the polymerizable monomer (d) used in the present invention has one hydroxyl group in the molecule. Since it has the above, the hydrophilic property of the composition of this invention can be improved and the permeability to the collagen layer of dentine can be improved. Similarly, amines are preferred as the polymerization accelerator (g).

  The composition of the present invention is preferably used as a bonding material. As the bonding material in the “two-step adhesion system”, the polymerizable monomer (a), the polymerizable monomer (b) having two or more polymerizable groups and two or more primary hydroxyl groups, water (C), a composition comprising a polymerizable monomer (d) having one polymerizable group and one or more hydroxyl groups, a polymerization initiator (f), a polymerization accelerator (g) and a filler (h). It is preferable. The amount of each component is (a) 5 to 80 parts by weight, (b) 10 to 95 parts by weight, and (d) 5 to 80 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer components. Preferably, (a) 5 to 60 parts by weight, (b) 10 to 90 parts by weight, and (d) 10 to 80 parts by weight, (a) 5 to 50 parts by weight, (b) 20 More preferably, it is -90 weight part and (d) 20-80 weight part. As in (b) used in the present invention, the mechanical strength of the cured product obtained by having two polymerizable groups can be increased. Further, (c) 1 to 100, (f) 0.01 to 30 parts by weight, (g) 0.01 to 20 parts by weight and (h) 1 with respect to 100 parts by weight of the total amount of the polymerizable monomer components. It is preferable to contain ~ 100 parts by weight, more preferably (c) 1-50, (f) 0.1-30 parts by weight, (g) 0.01-10 parts by weight and (h) 5-50 parts by weight. Preferably, (c) 1 to 30, (f) 1 to 15 parts by weight, (g) 0.1 to 10 parts by weight, and (h) 10 to 30 parts by weight are further included.

  In recent years, there has been a demand for further simplification of work, so products that implement the three steps of "decalcification", "penetration" and "curing" in one step have been developed. It is called “adhesion system”. As a bonding material used in such a one-step bonding system, a so-called “1” which is provided in the form of a bonding material used by mixing two liquids divided into A liquid and B liquid immediately before use, and one liquid from the beginning. Two types of bonding materials for liquid type one-step bonding systems are typical products. Among these, the one-pack type has a greater merit in use because the process is more simplified. When the composition of the present invention is used as a bonding material for the one-component one-step adhesive system, the composition is (a), (b), (c), (d), (e), (f), ( A composition containing g) and (h) is preferred. The amount of each component is (a) 5 to 80 parts by weight, (b) 10 to 95 parts by weight, and (d) 5 to 80 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer components. Preferably, (a) 5 to 60 parts by weight, (b) 10 to 90 parts by weight, and (d) 10 to 80 parts by weight, (a) 10 to 50 parts by weight, (b) 20 More preferably, it is -90 parts by weight and (d) 30-80 parts by weight. In the one-component one-step adhesive system, since “penetration” and “curing” are performed at the same time, as shown in (b), it has two or more polymerizable groups and has two primary hydroxyl groups. It is significant to use a polymerizable monomer having at least one and a polymerizable monomer having one polymerizable group and having at least one hydroxyl group as in (d). Moreover, (c) 1-1000 weight part, (e) 1-1000 weight part, (f) 0.01-30 weight part, (g) 0 with respect to 100 weight part of whole quantity of a polymerizable monomer component. 0.01 to 20 parts by weight and (h) 1 to 100 parts by weight, (c) 1 to 500 parts by weight, (e) 1 to 500 parts by weight, (f) 0.1 to 30 parts by weight, ( g) More preferably 0.01 to 10 parts by weight and (h) 5 to 50 parts by weight, (c) 5 to 100 parts by weight, (e) 5 to 100 parts by weight, (f) 1 to 15 parts by weight (G) 0.1 to 10 parts by weight and (h) 10 to 30 parts by weight are more preferable.

  In the bonding material of the one-component one-step adhesive system, the organic solvent (e) is preferably used in the form of a mixed solvent with water (c). The content of water (c) in the mixed solvent is not particularly limited, but is preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 20% by weight or more.

  Hereinafter, the present invention will be described more specifically with reference to examples. Abbreviations used below are as follows.

[Polymerizable monomer having acidic group (a)]
MDP: 10-methacryloyloxydecyl phosphate (10-methacryloyloxydecyl dihydrogen phosphate)
GDMP: 1,3-dimethacryloyloxypropyl-2-phosphate (1,3-dimethacryloyloxypropyl dihydrogen phosphate)
Phosmer: 2-methacryloyloxyethyl phosphate (2-methacryloyloxyethyl dihydrogen phosphate)
4-META: 4-methacryloyloxyethyl trimellitic anhydride MAC-10: 11-methacryloyloxyundecane-1,1-dicarboxylic acid

[Polymerizable monomer having sulfonic acid group]
AMPS: 2-acrylamido-2-methylpropanesulfonic acid

[Polymerizable monomer (b) having two polymerizable groups and two primary hydroxyl groups]
ErMA: Pentaerythritol dimethacrylate

[Polymerizable monomer having 5 polymerizable groups and 1 primary hydroxyl group]
DPEPA: Dipentaerythritol pentaacrylate

[Polymerizable monomer having two polymerizable groups and one secondary hydroxyl group]
GDMA: Glycerol dimethacrylate

[Polymerizable monomer having two polymerizable groups and two secondary hydroxyl groups]
# 801: 1,2-bis (3-methacryloyloxy-2-hydroxypropyloxy) ethane BisGMA: bisphenol A diglycidyl methacrylate

[Polymerizable monomer having two polymerizable groups but no hydroxyl group]
NPG: Neopentyl glycol dimethacrylate

[Polymerizable monomer (d) having one polymerizable group and one hydroxyl group]
HEMA: 2-hydroxyethyl methacrylate

[Photopolymerization initiator]
CQ: dl-camphorquinone TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

[Polymerization accelerator]
DBB: N, N-dimethylaminobenzoic acid n-butoxyethyl ester

[Polymerization inhibitor]
BHT: 2,6-di-tert-butyl-4-methylphenol

[Inorganic filler]
Inorganic filler 1: Nippon Aerosil silica "R972"
Inorganic filler 2: Silica “Ar380” made by Nippon Aerosil

[Preparation of one-component dental composition]
(Example 1)
The following components were mixed at room temperature to prepare a one-pack type bonding material composition, which is a one-pack type dental composition, and the adhesive strength with bovine enamel and bovine dentin was measured.
One-component bonding material composition:
GDMP 10 parts by weight ErMA 40 parts by weight HEMA 40 parts by weight Water 10 parts by weight CQ 2 parts by weight TMDPO 3 parts by weight DBB 1 part by weight BHT 0.5 part by weight Inorganic filler 1 10 parts by weight

[Method for evaluating adhesion to bovine enamel and bovine dentin]

  The lip surface of bovine mandibular anterior teeth was polished with # 80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to expose the enamel flat surface and the dentin flat surface. 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 thickness of about 150 μm having a round hole with a diameter of 3 mm was attached to the smooth surface after drying to define the adhesion area.

  The prepared one-component bonding material composition is applied to the round hole using a brush, left for 20 seconds, and then air blown over the surface, thereby eliminating the fluidity of the applied one-component bonding material composition. Until dried. Next, the applied one-part bonding material composition was cured by irradiating light for 10 seconds with a dental visible light irradiator “JET Light 3000” (manufactured by J. Morita USA).

  A dental filling composite resin (manufactured by Kuraray Medical Co., Ltd., trade name “Clearfill AP-X” (registered trademark)) was applied to the surface of the cured product of the obtained one-component bonding material composition, and a release film ( Polyester). Subsequently, a glass slide was placed on the release film and pressed to smooth the coated surface of the composite resin. Subsequently, the composite resin was irradiated with light using the irradiator “JET Light 3000” for 20 seconds through the release film to cure the composite resin.

  A stainless steel cylindrical rod (diameter 7 mm, length) using a commercially available dental resin cement (trade name “Panavia 21” manufactured by Kuraray Medical Co., Ltd.) on the surface of the cured product of the obtained dental filling composite resin. One end face (circular cross section) of 2.5 cm) was bonded. After bonding, the sample was allowed to stand at room temperature for 30 minutes and then immersed in distilled water. The sample immersed in the distilled water was allowed to stand in a thermostat kept at 37 ° C. for 24 hours to prepare a test sample for adhesion test. A total of five samples for adhesion test were prepared.

[Measurement of adhesive strength]
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. . The bond strength with bovine enamel was 17 MPa, and the bond strength with bovine dentin was 14 MPa. The obtained results are summarized in Table 1.

(Example 2)
In Example 1, instead of using 10 parts by weight of “GDMP” which is the polymerizable monomer (a), a one-component bonding material composition was used in the same manner as in Example 1 except that 10 parts by weight of “MDP” was used. The product was prepared, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 1.

(Example 3)
In Example 1, instead of using 10 parts by weight of “GDMP” which is the polymerizable monomer (a), the same composition as in Example 1 was used, except that 10 parts by weight of “phosmer” was used. The product was prepared, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 1.

Example 4
In Example 1, instead of using 10 parts by weight of the polymerizable monomer (a) “GDMP”, 10 parts by weight of “4-META” was used. A material composition was prepared, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 1.

(Example 5)
In Example 1, instead of using 10 parts by weight of the polymerizable monomer (a) “GDMP”, 10 parts by weight of “MAC-10” was used. A material composition was prepared, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 1.

(Example 6)
In Example 1, instead of using 40 parts by weight of the polymerizable monomer (d) “HEMA”, the same as Example 1 except that 30 parts by weight of “HEMA” was used and 10 parts by weight of ethanol was used. Thus, a one-component bonding material composition was prepared, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 1.

(Comparative Example 1)
In Example 1, instead of using 40 parts by weight of “ErMA” which is the polymerizable monomer (b), a one-component bonding material composition was used in the same manner as in Example 1 except that 40 parts by weight of “GDMA” was used. The product was prepared, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 1.

(Comparative Example 2)
In Example 1, instead of using 40 parts by weight of “ErMA” that is the polymerizable monomer (b), 40 parts by weight of “# 801” was used. A composition was prepared, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 1.

(Comparative Example 3)
In Example 1, instead of using 10 parts by weight of “GDMP” which is a polymerizable monomer (a), 10 parts by weight of “AMPS” which is a polymerizable monomer having a sulfonic acid group was used. A one-component bonding material composition was prepared in the same manner as in Example 1, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 1.

(Comparative Example 4)
In Example 1, instead of using 40 parts by weight of “ErMA” which is the polymerizable monomer (b), the same composition as in Example 1 was used except that 40 parts by weight of “DPEPA” was used. The product was prepared, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 1.

(Comparative Example 5)
In Example 1, instead of using 10 parts by weight of “GDMP” as the polymerizable monomer (a), 1 part by weight of “GDMP” was used, and “ErMA” as the polymerizable monomer (b) was used. Instead of using 40 parts by weight, a one-component type bonding material composition was prepared in the same manner as in Example 1 except that 49 parts by weight of “ErMA” was used, and the adhesive strength with bovine enamel and bovine dentin The adhesive strength was measured. The obtained results are summarized in Table 1.

(Comparative Example 6)
In Example 1, instead of using 10 parts by weight of “GDMP” that is the polymerizable monomer (a), 49 parts by weight of “GDMP” is used, and “ErMA” that is the polymerizable monomer (b) is used. Instead of using 40 parts by weight, a one-component bonding material composition was prepared in the same manner as in Example 1 except that 1 part by weight of “ErMA” was used, and the adhesive strength with bovine enamel and bovine dentin The adhesive strength was measured. The obtained results are summarized in Table 1.

  From Table 1, 2 to 98 parts by weight of the polymerizable monomer (a) having an acidic group, two or more polymerizable groups and a primary hydroxyl group 2 with respect to 100 parts by weight of the total amount of the polymerizable monomer components. In Examples 1 to 5 using a composition comprising 2 to 98 parts by weight of the polymerizable monomer (b) having 1 or more and 1 to 2000 parts by weight of water (c), the composite resin and Both the adhesive strength with the enamel and the adhesive strength between the composite resin and the dentin are good, and it can be seen that it is useful as a dental composition. In contrast, Comparative Examples 1, 2, and 4 in which the polymerizable monomer (b) was not used, Comparative Example 3 in which the polymerizable monomer (a) was not used, and the content of the polymerizable monomer (a) In Comparative Example 5 in which the amount was 1 part by weight and Comparative Example 6 in which the content of the polymerizable monomer (b) was 1 part by weight, the adhesive strength between the composite resin and enamel, and the composite resin and ivory The adhesive strength with the quality was both very poor.

[Preparation of two-component dental composition]
(Example 7)
The following components were mixed at room temperature to prepare a primer composition and a bonding material composition, and the adhesion strength with bovine enamel and bovine dentin was measured.
Primer composition:
GDMP 15 parts by weight ErMA 35 parts by weight HEMA 30 parts by weight Water 20 parts by weight CQ 0.2 part by weight TMDPO 0.3 part by weight DBB 0.1 part by weight BHT 0.05 part by weight

Bonding material composition:
BisGMA 40 parts by weight HEMA 40 parts by weight NPG 20 parts by weight TMDPO 3 parts by weight Inorganic filler 1 5.5 parts by weight Inorganic filler 2 1.5 parts by weight

[Method for evaluating adhesion to bovine enamel and bovine dentin]

  The lip surface of bovine mandibular anterior teeth was polished with # 80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to expose the enamel flat surface and the dentin flat surface. 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 thickness of about 150 μm having a round hole with a diameter of 3 mm was attached to the smooth surface after drying to define the adhesion area.

  The prepared primer composition was applied in the round hole using a brush, left for 20 seconds, and then air blown on the surface to dry the applied primer composition until the fluidity of the primer composition disappeared. Subsequently, the above-mentioned bonding material composition was applied repeatedly on the tooth surface to which the primer was applied and dried. Subsequently, the applied primer composition and the bonding material composition were cured by irradiating light for 10 seconds with a dental visible light irradiator “JET Light 3000” (manufactured by J. Morita USA).

  A composite resin for dental filling (Kuraray Medical Co., Ltd., trade name “Clearfill AP-X” (registered trademark)) is applied to the surface of the cured product of the obtained bonding material composition, and a release film (polyester) is used. Covered. Subsequently, a glass slide was placed on the release film and pressed to smooth the coated surface of the composite resin. Subsequently, the composite resin was irradiated with light using the irradiator “JET Light 3000” for 20 seconds through the release film to cure the composite resin.

  A stainless steel cylindrical rod (diameter 7 mm, length) using a commercially available dental resin cement (trade name “Panavia 21” manufactured by Kuraray Medical Co., Ltd.) on the surface of the cured product of the obtained dental filling composite resin. One end face (circular cross section) of 2.5 cm) was bonded. After bonding, the sample was allowed to stand at room temperature for 30 minutes and then immersed in distilled water. The sample immersed in the distilled water was allowed to stand in a thermostat kept at 37 ° C. for 24 hours to prepare a test sample for adhesion test. A total of five samples for adhesion test were prepared.

[Measurement of adhesive strength]
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. . The bond strength with bovine enamel was 19 MPa, and the bond strength with bovine dentin was 18 MPa. The obtained results are summarized in Table 2.

(Example 8)
In Example 7, instead of using 15 parts by weight of “GDMP” which is the polymerizable monomer (a), a primer composition and a bonding material were used in the same manner as in Example 7 except that 15 parts by weight of “MDP” was used. A composition was prepared, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 2.

Example 9
In Example 7, instead of using 15 parts by weight of the polymerizable monomer (a) “GDMP”, the primer composition and the primer composition were the same as in Example 7 except that 15 parts by weight of “4-META” was used. A bonding material composition was prepared, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 2.

(Comparative Example 7)
In Example 7, instead of using 15 parts by weight of “GDMP” which is a polymerizable monomer (a), 15 parts by weight of “AMPS” which is a polymerizable monomer having a sulfonic acid group was used. A primer composition and a bonding material composition were prepared in the same manner as in Example 7, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 2.

(Comparative Example 8)
In Example 7, instead of using 35 parts by weight of “ErMA” which is the polymerizable monomer (b), a primer composition and a bonding material were used in the same manner as in Example 7 except that 35 parts by weight of “DPEPA” was used. A composition was prepared, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 2.

(Comparative Example 9)
In Example 7, instead of using 35 parts by weight of “ErMA” which is the polymerizable monomer (b), the primer composition and the bonding material were the same as in Example 7 except that 35 parts by weight of “GDMA” was used. A composition was prepared, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 2.

(Comparative Example 10)
In Example 7, instead of using 35 parts by weight of “ErMA” which is the polymerizable monomer (b), the primer composition and bonding were performed in the same manner as in Example 7 except that 35 parts by weight of “# 801” was used. A material composition was prepared, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 2.

(Comparative Example 11)
In Example 7, instead of using 15 parts by weight of “GDMP” as the polymerizable monomer (a), 1 part by weight of “GDMP” was used, and “ErMA” as the polymerizable monomer (b) was used. Instead of using 35 parts by weight, a primer composition and a bonding material composition were prepared in the same manner as in Example 7 except that 49 parts by weight of “ErMA” was used, and adhesion strength with bovine enamel and bovine ivory The adhesive strength with the quality was measured. The obtained results are summarized in Table 2.

(Comparative Example 12)
In Example 7, instead of using 15 parts by weight of “GDMP” as the polymerizable monomer (a), 49 parts by weight of “GDMP” was used, and “ErMA” as the polymerizable monomer (b) was used. Instead of using 35 parts by weight, a primer composition and a bonding material composition were prepared in the same manner as in Example 7 except that 1 part by weight of “ErMA” was used, and the adhesive strength with bovine enamel and bovine ivory The adhesive strength with the quality was measured. The obtained results are summarized in Table 2.

  From Table 2, 2 to 98 parts by weight of the polymerizable monomer (a) having an acidic group, two or more polymerizable groups and a primary hydroxyl group 2 with respect to 100 parts by weight of the total amount of polymerizable monomer components. In Examples 7, 8 and 9 using compositions containing 2 to 98 parts by weight of polymerizable monomer (b) having 1 or more and 1 to 2000 parts by weight of water (c) Both the adhesive strength between the resin and the enamel and the adhesive strength between the composite resin and the dentin are good, and it can be seen that it is useful as a dental composition. On the other hand, in Comparative Example 7 in which the polymerizable monomer (a) was not used, the adhesive strength between the composite resin and the dentin was greatly inferior, and Comparative Examples 8 to 8 in which the polymerizable monomer (b) was not used. 10. In Comparative Example 11 in which the content of the polymerizable monomer (a) is 1 part by weight, and in Comparative Example 12 in which the content of the polymerizable monomer (b) is 1 part by weight, the composite resin and the enamel And the adhesive strength between the composite resin and the dentin were both greatly inferior.

Claims (12)

  A polymerizable monomer (a) having at least one acidic group selected from the group consisting of a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group and a carboxylic acid group, and two or more polymerizable groups; A composition comprising a polymerizable monomer (b) having two or more primary hydroxyl groups and water (c), which is polymerized with respect to 100 parts by weight of the total amount of polymerizable monomer components. 2 to 98 parts by weight of the polymerizable monomer (a), 2 to 98 parts by weight of the polymerizable monomer (b), and 1 to 2000 parts by weight of water (c). .   2 to 90 parts by weight of a polymerizable monomer (d) having one polymerizable group and one or more hydroxyl groups with respect to 100 parts by weight of the total amount of the polymerizable monomer components. The composition as described.   The polymerizable monomer (a) is 10-methacryloyloxydecyl phosphoric acid, 1,3-dimethacryloyloxypropyl-2-phosphoric acid, 2-methacryloyloxyethyl phosphoric acid, 4-methacryloyloxyethyl trimellitic anhydride, The composition according to claim 1 or 2, which is at least one selected from the group consisting of 4-methacryloyloxyethyl trimellitic acid and 11-methacryloyloxyundecane-1,1-dicarboxylic acid.   The polymerizable monomer (b) is at least one selected from the group consisting of pentaerythritol di (meth) acrylate and dipentaerythritol di, tri, and tetra (meth) acrylate. Or a composition according to claim 1.   The composition according to any one of claims 1 to 4, comprising 1 to 2000 parts by weight of the organic solvent (e) with respect to 100 parts by weight of the total amount of the polymerizable monomer components.   The composition according to claim 5, wherein the organic solvent (e) is a water-soluble organic solvent.   The composition according to any one of claims 1 to 6, comprising 0.001 to 30 parts by weight of a polymerization initiator (f) with respect to 100 parts by weight of the total amount of the polymerizable monomer components.   The composition according to any one of claims 1 to 7, comprising 0.001 to 30 parts by weight of a polymerization accelerator (g) with respect to 100 parts by weight of the total amount of the polymerizable monomer components.   The composition according to any one of claims 1 to 8, comprising 1 to 1000 parts by weight of filler (h) with respect to 100 parts by weight of the total amount of polymerizable monomer components.   A dental composition comprising the composition according to claim 1.   A primer comprising the dental composition according to claim 10.   A bonding material comprising the dental composition according to claim 10.