JP5162138B2 - Polyfunctional hydrophilic polymerizable monomer-containing composition - Google Patents

Description

  The present invention relates to a composition comprising a polymerizable monomer having a carboxylic acid group, a polyfunctional polymerizable monomer having two or more polymerizable groups and two or more primary hydroxyl groups, and a filler. .

  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 hardening 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 permeation action, and the curing action are applied in order up to the present, the two-liquid two-step type that unifies the decalcification action and the permeation action, and further the decalcification action, Studies are being made to simplify the use 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 excellent in adhesiveness is required. In addition, a composite resin in which an adhesive property is given to a filling composite resin has been developed, and studies are being made to further simplify the usage mode of the dental composition.

US Pat. No. 5,658,963

  The present invention has been made in order to solve the above-described problems, and includes a polymerizable monomer having a carboxylic acid group suitable for a dental composition, two or more polymerizable groups and two or more primary hydroxyl groups. An object of the present invention is to provide a composition comprising a multifunctional polymerizable monomer and a filler.

The subject is at least one selected from the group consisting of a polymerizable monomer having a carboxylic acid group (a), pentaerythritol di (meth) acrylate, and dipentaerythritol di, tri and tetra (meth) acrylate. The polymerizable monomer (b) and the filler (c) are contained in the polymerizable monomer component in a total amount of 100 parts by weight of the polymerizable monomer component (5). This is solved by providing a composition comprising -95 parts by weight, 5-95 parts by weight of the polymerizable monomer (b) and 1-1000 parts by weight of the filler (c).

At this time, it is preferable that 1 to 90 parts by weight of the polymerizable monomer (d) other than (a) and (b) 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 selected from the group consisting of 4-methacryloyloxyethyl trimellitic anhydride, 4-methacryloyloxyethyl trimellitic acid and 11-methacryloyloxyundecane-1,1-dicarboxylic acid. It is preferred that there is at least one . It is preferable to contain 0.001 to 30 parts by weight of the polymerization initiator (e) 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 (f). In addition, it is preferable to contain 1 to 2000 parts by weight of the solvent (g) with respect to 100 parts by weight of the total amount of the polymerizable monomer components, and it is also preferable that the solvent (g) is a water-soluble solvent. It is.

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

  The composition of the present invention comprises a polymerizable monomer having a carboxylic acid group, a polyfunctional polymerizable monomer having two or more polymerizable groups and two or more primary hydroxyl groups, and a filler. Is. 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 composite resin, cement and bonding material.

  The composition of the present invention comprises a polymerizable monomer (a) having a carboxylic acid group, a polymerizable monomer (b) having two or more polymerizable groups and two or more primary hydroxyl groups, and a filler (c ) And is useful as a dental composition.

  The polymerizable monomer (a) used in the present invention is a polymerizable monomer having a polymerizable group and an acidic group composed of a carboxylic acid 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 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.

  In addition to having a polymerizable group as described above, the polymerizable monomer (a) has an acidic group composed of a carboxylic acid 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, so that the acid etching treatment is performed. And the advantage that pretreatment such as primer treatment is not required.

  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, 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) Acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meta) And acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid and the like, 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 4-methacryloyloxyethyltrimethyl from the viewpoint of good adhesive strength when used as a dental composition. 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 comprises 5 to 95 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 composite resin, cement or bonding material that is simple and has good adhesive strength. If the blending amount of the polymerizable monomer (a) is less than 5 parts by weight, the acid etching effect or the primer treatment effect may not be obtained, and the blending amount of the polymerizable monomer (a) is 10 parts by weight. Preferably, it is 15 parts by weight or more, and more preferably 20 parts by weight or more. On the other hand, when the compounding amount of the polymerizable monomer (a) exceeds 95 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 70 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 comprises 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 a carboxylic acid group. It is characterized by containing. 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 is possible and copolymerization with other monomers is 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 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 comparison between Examples 1 and 2 in Examples described later and Comparative Examples 1 to 3, one or two monomers of the secondary hydroxyl group or one primary hydroxyl group is present. When only the monomer is used, sufficient adhesive strength cannot be obtained. By using the 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 5 to 95 parts by weight of the polymerizable monomer (b) with respect to 100 parts by weight of the total amount of the polymerizable monomer components. If the amount of the polymerizable monomer (b) is using the composition in such a range as a dental composition has the advantage that the adhesive strength is excellent is obtained. Therefore, it is possible compositions of the present invention by containing a polymerizable monomer (b), convenient and the adhesive strength to provide good composite resin, cement or bonding material. When the amount of the polymerizable monomer (b) is less than 5 parts by weight, there is a possibility that the adhesive strength decreases, the amount of the polymerizable monomer (b) is preferably 10 parts by weight or more 15 parts by weight or more, more preferably 20 parts by weight or more. On the other hand, if the amount of the polymerizable monomer (b) exceeds 95 parts by weight also, there is a possibility that the adhesive force decreases, the amount of the polymerizable monomer (b) is below 90 parts by weight 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 is blended with filler (c). 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, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene, Examples include chloroprene 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 as 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, and 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 composition of the present invention comprises 1 to 1000 parts by weight of filler (c) with respect to 100 parts by weight of the total amount of polymerizable monomer components. By including such a blending amount of the filler (c), the mechanical strength of the composition of the present invention can be improved and handling properties suitable for each application can be imparted. When the blending amount of the filler (c) is less than 1 part by weight, the mechanical strength of the cured product obtained by curing the composition of the present invention may be insufficient. On the other hand, when the blending amount of the filler (c) exceeds 1000 parts by weight, it becomes difficult to uniformly disperse the filler (c) in the total amount of the polymerizable monomer component, which is not good in terms of mechanical strength and handling properties. There is a risk of becoming a sufficient composition. Since the suitable compounding amount of the filler (c) varies greatly depending on the embodiment to be used, the filler (c) 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.

  The composition of the present invention preferably further comprises a polymerizable monomer (d) other than the polymerizable monomer (a) and the polymerizable monomer (b). The polymerizable monomer (d) is not particularly limited, and includes a polyfunctional polymerizable monomer having crosslinkability other than (a) and (b), one polymerizable group and one or more hydroxyl groups. And monofunctional polymerizable monomers.

  The polyfunctional polymerizable monomer having crosslinkability other than (a) and (b) is not particularly limited, but is an aromatic compound-based bifunctional polymerizable monomer or an aliphatic compound-based bifunctional monomer. Polymerizable monomers and trifunctional or higher functional monomers.

  Examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis ((meth) acryloyloxyphenyl) propane, 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 trifunctional or higher 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.

  Monofunctional polymerizable monomers having one polymerizable group and one or more hydroxyl groups include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meta ) Acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide N-hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide and the like.

  The blending amount of the polymerizable monomer (d) is not particularly limited, but the polymerizable monomer (d) other than (a) and (b) is 100 parts by weight based on the total amount of the polymerizable monomer components. It is preferable that 1-90 weight part is further contained. When a composition in which the blending amount of the polymerizable monomer (d) is in such a range is used as a dental composition, it is preferable because the adhesive strength is good. In particular, when a polyfunctional polymerizable monomer having crosslinkability other than (a) and (b) is used, the adhesive strength is further improved, and preferably one polymerizable group and one or more hydroxyl groups In the case of using a monofunctional polymerizable monomer having, it is preferable because the permeability to the dentin collagen layer is more excellent. Therefore, when the composition of the present invention contains the polymerizable monomer (d), it is possible to provide a composite resin, cement or 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, the adhesive strength may be lowered, and the blending amount of the polymerizable monomer (d) is more than 5 parts by weight. Preferably, it is 10 parts by weight or more, more preferably 25 parts by weight or more. 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.

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

  Among the polymerization initiator (e) 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-aminoketone 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) phosphonate 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 (e) 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, methyl cyclohexanone 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 thereof 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-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, di- Examples include n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate.

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

  Although the compounding quantity of the polymerization initiator (e) used for this invention is not specifically limited, From viewpoints, such as sclerosis | hardenability of the composition obtained, a polymerization start is 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 (e). When the blending amount of the polymerization initiator (e) 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 compounding quantity of a polymerization initiator (e) exceeds 30 weight part, there exists a possibility that adhesive strength may fall, More preferably, it is 10 weight part or less, More preferably, it is 5 weight part or less.

  In a preferred embodiment, the above-described polymerization initiator (e) is used together with a polymerization accelerator (f). Examples of the polymerization accelerator (f) 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. Compound etc. are mentioned.

  The amines contained in the polymerization accelerator (f) 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 them, 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 its salt contained in the polymerization accelerator (f) 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 (f) 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 dialkyldiphenyl boron, 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, butylquinolinium salt, etc. 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, n-octyl, n-dodecyl, 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 (p-octyloxyphenyl) triphenylboron sodium salt, 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 babituric acid derivative contained in the polymerization accelerator (f) 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 (f) 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 a copper compound contained in the polymerization accelerator (f) 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 (f) 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 (f) 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 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 (f) 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 (f) 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 (f) used in the present invention include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

  Although the compounding quantity of the polymerization accelerator (f) used for this invention is not specifically limited, From viewpoints, such as sclerosis | hardenability of the composition obtained, superposition | polymerization acceleration | stimulation 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 (f). When the blending amount of the polymerization accelerator (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. On the other hand, when the blending amount of the polymerization accelerator (f) 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.

  It is preferable that the composition of this invention contains a solvent (g) depending on the specific embodiment. Examples of the solvent (g) include water and organic solvents. Examples of the organic solvent include methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, hexane, toluene, chloroform, ethyl acetate, butyl acetate and the like. Among these, the solvent (g) is preferably a water-soluble solvent, that is, water and a water-soluble organic solvent, taking into consideration both safety to the living body and ease of removal based on volatility. Is preferably at least one selected from the group consisting of water, ethanol and acetone. Especially, it is preferable that the composition of this invention contains water depending on uses, such as the bonding material of the 1 liquid type 1 step adhesion system mentioned later, glass ionomer cement, and resin reinforced glass ionomer cement. By containing water, when the composition of the present invention is used as a dental composition, there are advantages such as excellent adhesive strength. As water, it is preferable not to contain the impurity which has a bad influence, and distilled water or ion-exchange water is preferable. The water may be used alone or as a mixed solvent of water and the organic solvent. The compounding quantity of the said solvent (g) is not specifically limited, Depending on embodiment, there exists a thing which does not require the mixing | blending of the said solvent (g). In the embodiment using the solvent (g), it is preferable to contain 1 to 2000 parts by weight of the solvent (g) with respect to 100 parts by weight of the total amount of the polymerizable monomer components. Since the suitable compounding amount of the solvent (g) varies greatly depending on the embodiment to be used, the solvent ( A suitable blending amount of g) will be 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 a filler (c) are contained. The resulting composition 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 composite resin, cement or 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 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 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.

  The composition of the present invention is preferably used as a bonding material. As a bonding material in the above-mentioned “two-step adhesion system”, a polymerizable monomer (a), a polymerizable monomer (b) having two or more polymerizable groups and two or more primary hydroxyl groups, a filler A composition containing (c), a polymerizable monomer (d), a polymerization initiator (e) and a polymerization accelerator (f) is preferred. The amount of each component is (a) 5 to 80 parts by weight, (b) 10 to 95 parts by weight, and (d) 10 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. Moreover, (c) 1-100 weight part, (e) 0.01-30 weight part, and (f) 0.01-20 weight part are included with respect to 100 weight part of whole quantity of a polymerizable monomer component. Preferably, (c) 5 to 50 parts by weight, (e) 0.1 to 30 parts by weight, and (f) 0.01 to 10 parts by weight, (c) 10 to 30 parts by weight, (e) More preferably, it contains 1 to 15 parts by weight and (f) 0.1 to 10 parts by weight.

  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 comprises (a), (b), (c), (d), (e), (f) and (f) A composition comprising 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 -90 parts by weight and (d) 30-80 parts by weight. In the one-pack type one-step adhesive system, since “penetration” and “curing” are performed at a time, it has two or more polymerizable groups and has two primary hydroxyl groups as shown in (b). The significance of using at least one polymerizable monomer is great. Moreover, (c) 1 to 100 parts by weight, (e) 0.01 to 30 parts by weight, (f) 0.01 to 20 parts by weight and (g) with respect to 100 parts by weight of the total amount of the polymerizable monomer components. 1) to 1000 parts by weight, (c) 5 to 50 parts by weight, (e) 0.1 to 30 parts by weight, (f) 0.01 to 10 parts by weight and (g) 1 to 500 parts by weight More preferably, it contains (c) 10-30 parts by weight, (e) 1-15 parts by weight, (f) 0.1-10 parts by weight, and (g) 5-100 parts by weight.

  The composition of the present invention is preferably used as a composite resin. In particular, in recent years, composite resins have been developed in which adhesive properties are added to the filling composite resin. Since the process is further simplified than the one-step adhesive system described above, the advantages in use are great. It is called “composite resin”. When the composition of the present invention is used as a composite resin, the composition is preferably a composition containing (a), (b), (c), (d), (e), and (f). The composite resin is usually used in such a form that it is filled in the cavity after cutting the carious site and forming the cavity. Thereafter, the filled composite resin is usually cured by photopolymerization. For this reason, as said (e), it is preferable to use a photoinitiator. In addition, since the composite resin filled and cured as described above receives an occlusal pressure in the oral cavity, excellent mechanical strength is required. For this reason, it is preferable that the said composition contains 40-900 weight part of filler (c) with respect to 100 weight part of whole quantity of a polymerizable monomer component, It is more preferable that 60-600 weight part is included, 150 More preferably, it contains ~ 400 parts by weight. When content of a filler (c) is less than 40 weight part, there exists a possibility that the mechanical strength of hardened | cured material may become inadequate. On the other hand, when the content of the filler (c) exceeds 900 parts by weight, it becomes difficult to uniformly disperse the filler (c) in the total amount of the polymerizable monomer component, and in terms of mechanical strength and handling properties. There is a risk of insufficient composition. The amount of each component is (a) 10 to 70 parts by weight, (b) 10 to 80 parts by weight, and (d) 15 to 75 parts by weight based on 100 parts by weight of the total amount of polymerizable monomer components. (A) 15 to 60 parts by weight, (b) 15 to 70 parts by weight, and (d) 20 to 65 parts by weight, more preferably (a) 20 to 50 parts by weight, (b) 20 More preferably, it is -60 weight part and (d) 25-55 weight part. Moreover, (c) 40-900 weight part, (e) 0.01-10 weight part, and (f) 0.01-10 weight part are included with respect to 100 weight part of whole quantity of a polymerizable monomer component. Preferably, (c) 60 to 600 parts by weight, (e) 0.1 to 5 parts by weight, and (f) 0.1 to 5 parts by weight, (c) 150 to 400 parts by weight, (e) More preferably, it contains 0.1 to 5 parts by weight and (f) 0.1 to 5 parts by weight.

  It is also one preferred embodiment to use the composition of the present invention as a dental cement. Preferred examples of the cement include resin cement, glass ionomer cement, and resin reinforced glass ionomer cement. When using the composition of this invention as a resin cement, it is preferable that the said composition is a composition containing (a), (b), (c), (d), (e), and (f). For example, dental cement is preferably used as a bonding material for fixing a dental restoration material made of metal or ceramic called an inlay or crown to a tooth. Like (b) used by this invention, the mechanical strength of the hardened | cured material obtained by having two polymeric groups can be raised, and it can endure occlusal pressure etc. Moreover, in the case of the above usage forms, since most of the restoration materials for crowns are light-impermeable, it is not easy to cure the cement by photopolymerization. For this reason, it is preferable to use a chemical polymerization initiator as said (e). And when it superposes | polymerizes using a chemical polymerization initiator, in order to raise the reactivity, it is preferable to use amines and / or sulfinic acid, and its salt as said (f), and amines, sulfinic acid, and its It is more preferable to use the salt at the same time. In addition, the composition of the present invention contains a filler (c), and when it is desired to impart a sustained release of fluorine to the cement, as the filler (c), fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoro It is preferable to use at least one selected from the group consisting of aluminosilicate glass, barium fluoroaluminosilicate glass and strontium calcium fluoroaluminosilicate glass, and more preferable to use fluoroaluminosilicate glass and / or barium fluoroaluminosilicate glass. . On the other hand, when it is desired to give X-ray contrast properties to the cement, the filler (c) includes barium glass, strontium glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, strontium fluoroaluminosilicate glass, and barium fluoroaluminosilicate. It is preferable to use at least one selected from the group consisting of glasses, and it is more preferable to use barium glass and / or barium fluoroaluminosilicate glass.

  Moreover, when using a chemical polymerization initiator, it is preferable to store said (e) and said (f) in a respectively separate container from a viewpoint of storage stability. That is, in a preferred embodiment, the resin cement is used in a two-part form, and in a more preferred embodiment, the resin cement is used in a two-paste form. It is preferable to store each paste in a state where the pastes are separated from each other, knead the two pastes immediately before use, and advance the chemical polymerization to cure. The paste is prepared by kneading a liquid component such as a polymerizable monomer and a filler (c) (powder). When amines and / or sulfinic acid and salts thereof are used as (f), it is preferable to store (a) and (f) in separate containers from the viewpoint of storage stability. . When the above two pastes are referred to as A paste and B paste, respectively, the A paste includes (a), (b), (c), (d) and (e), and the B paste is (b) , (C), (d) and (f) are particularly preferably used.

  The blending amount of each component when the composition of the present invention is used as dental cement is not particularly limited, but (a) 10 to 70 parts by weight, (b) with respect to 100 parts by weight of the total amount of polymerizable monomer components. 10) -80 parts by weight and (d) 15-75 parts by weight, (a) 15-60 parts by weight, (b) 15-70 parts by weight, and (d) 20-65 parts by weight. Are more preferable, (a) 20 to 50 parts by weight, (b) 20 to 60 parts by weight, and (d) 25 to 55 parts by weight are more preferable. In addition, as the blending amounts of the (e) and (f), when considering that an appropriate curing time can be obtained, (e) 0. It is preferable to contain 01 to 10 parts by weight and (f) 0.01 to 10 parts by weight, more preferably (e) 0.1 to 5 parts by weight and (f) 0.1 to 5 parts by weight, More preferably, (e) 0.5 to 5 parts by weight and (f) 0.2 to 5 parts by weight are included.

  Furthermore, the filler (c) is preferably contained in an amount of 40 to 900 parts by weight, more preferably 60 to 600 parts by weight, and more preferably 150 to 400 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer components. Is more preferable. When the content of the filler (c) is less than 40 parts by weight, the mechanical strength of the cured product may be insufficient. On the other hand, when the content of the filler (c) exceeds 900 parts by weight, the flowability of the paste is insufficient when the resin cement is used as a two-paste type cement which is a preferred embodiment thereof. Since it becomes difficult to perform proper mixing, the strength of the cured product may be reduced.

  The composition of the present invention is preferably used as a glass ionomer cement, and more preferably used as a resin reinforced glass ionomer cement. The glass ionomer cement is typically one in which an inorganic filler such as fluoroaluminosilicate glass and a polyalkenoic acid such as polyacrylic acid react and harden by an acid-base reaction. And it is thought that an adhesive function expresses when the polyacrylic acid and calcium in the hydroxyapatite constituting the tooth interact with each other. When the composition of the present invention is used as a glass ionomer cement, particularly preferably as a resin-reinforced glass ionomer cement, the composition is (a), (b), (c), (d), (e), (f ), (G) and a polyalkenoic acid-containing composition.

  The polyalkenoic acid is a polymer of unsaturated monocarboxylic acid or unsaturated dicarboxylic acid. Specific examples of the polyalkenoic acid include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 2-cyanoacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, A homopolymer such as uraconic acid or a copolymer with a monomer copolymerizable with these unsaturated carboxylic acids can be mentioned. In the case of a copolymer, the proportion of unsaturated carboxylic acid units is preferably 50 mol% or more based on the total structural units. The copolymerizable monomer is preferably an ethylenically unsaturated polymerizable monomer, such as styrene, acrylamide, acrylonitrile, methyl methacrylate, acrylates, vinyl chloride, allyl chloride, vinyl acetate, 1,1,6. -A trimethyl hexamethylene dimethacrylate ester etc. can be mentioned. Among these polyalkenoic acids, homopolymers or copolymers of acrylic acid or maleic acid are preferred. When these polyalkenoic acids have a weight average molecular weight of less than 5,000, the strength of the cured product of the dental cement composition is lowered, and the durability may be inferior. On the other hand, when the weight average molecular weight exceeds 40,000, the consistency of the dental cement composition at the time of kneading becomes hard and the operability may be lowered. Accordingly, the preferred polyalkenoic acid has a weight average molecular weight of 5,000 to 40,000.

  The filler (c) used is fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass from the viewpoints of curability in acid-base reaction and sustained release of fluorine in the composition. And at least one selected from the group consisting of strontium calcium fluoroaluminosilicate glass, and more preferably fluoroaluminosilicate glass and / or barium fluoroaluminosilicate glass.

  Moreover, as a solvent (g) used, it is preferable that it is a water-soluble solvent, and it is preferable that the said solvent (g) contains water from a viewpoint which advances an acid-base reaction smoothly. The content of water in the solvent (g) is preferably 50% by weight or more, more preferably 70% by weight or more, further preferably 90% by weight or less, and the solvent (g) Most preferably, consists essentially of water.

  The amount of each component when the composition of the present invention is used as a glass ionomer cement, particularly preferably a resin-reinforced glass ionomer cement, is not particularly limited, but with respect to 100 parts by weight of the total amount of polymerizable monomer components, a) 5 to 50 parts by weight, (b) 5 to 80 parts by weight, and (d) 5 to 70 parts by weight, (a) 5 to 40 parts by weight, (b) 15 to 70 parts by weight and ( d) More preferably 10 to 60 parts by weight, (a) 5 to 30 parts by weight, (b) 25 to 60 parts by weight and (d) 20 to 50 parts by weight are more preferable. In addition, as the blending amounts of the (e) and (f), when considering that an appropriate curing time can be obtained, (e) 0. It is preferable to contain 01 to 10 parts by weight and (f) 0.01 to 10 parts by weight, more preferably (e) 0.1 to 5 parts by weight and (f) 0.1 to 5 parts by weight, More preferably, (e) 0.5 to 5 parts by weight and (f) 0.2 to 5 parts by weight are included. Furthermore, the filler (c) is preferably contained in an amount of 40 to 900 parts by weight, more preferably 60 to 600 parts by weight, and more preferably 150 to 400 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer components. Is more preferable. When the content of the filler (c) is less than 40 parts by weight, the mechanical strength of the cured product may be insufficient. On the other hand, when the content of the filler (c) exceeds 900 parts by weight, the fluidity of the composition paste decreases and it becomes difficult to perform sufficient mixing, so that the acid-base reaction does not proceed smoothly. There is a case. As a result, the strength of the cured product may be reduced.

  Moreover, it is preferable that 5-500 weight part of solvent (g) is included with respect to 100 weight part of whole quantity of a polymerizable monomer component, It is more preferable that 10-300 weight part is included, 20-20 weight part is included. Is more preferable. (By containing the solvent (g) in such a range, the acid-base reaction can proceed smoothly, and the mechanical strength of the resulting cured product and the adhesiveness to the tooth will be good. .

  The polyalkenoic acid is preferably contained in an amount of 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, even more preferably 10 to 50 parts by weight, based on 100 parts by weight of the total amount of the polymerizable monomer components. . By containing the polyalkenoic acid in such a range, curing due to the acid-base reaction proceeds smoothly, and disintegration due to hydrolysis in the oral cavity of the obtained cured product can be reduced.

  As described above, since the glass ionomer cement is cured by the progress of the acid-base reaction, from the viewpoint of storage stability, the filler (c) and the polyalkenoic acid are packaged in separate containers and mixed immediately before use. It is preferable to be used. As a product form, a so-called powder-liquid type product form is also preferably used, but from the viewpoint of improving handling properties, it is more preferable to take the form of a so-called two-paste glass ionomer cement containing two types of paste. In the case of the two-paste type product form, when the above two pastes are referred to as A paste and B paste, respectively, the A paste is (a), (b), (c), (d), (f) , (G) and polyalkenoic acid, wherein the B paste comprises (b), (c), (d) and (e). The A paste includes (a), (b), (c), (d), (e), (g) and polyalkenoic acid, and the B paste includes (b), (c), (d). And embodiments comprising (f) are preferably used as well. In any embodiment, since polyalkenoic acid is contained on the A paste side, as the filler (c) contained in the B paste, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoro It is preferable to use at least one selected from the group consisting of aluminosilicate glass and strontium calcium fluoroaluminosilicate glass, and it is more preferable to use fluoroaluminosilicate glass and / or barium fluoroaluminosilicate glass. On the other hand, as the filler (c) contained in the A paste, it is preferable to use a filler that does not react with polyalkenoic acid, and quartz is particularly preferably used.

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

[Polymerizable monomer having carboxylic acid group (a)]
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

[Polymerizable monomer (d)]
3G: Triethylene glycol dimethacrylate

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

[Polymerization accelerator]
DBB: N, N-dimethylaminobenzoic acid n-butoxyethyl ester DEPT: N, N-di (2-hydroxyethyl) -p-toluidine TPBSS: sodium 2,4,6-triisopropylbenzenesulfinate

[Chemical polymerization catalyst]
BPO: Benzoyl peroxide

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

[Inorganic filler]
Inorganic filler 1: Nippon Aerosil silica "R972"
Inorganic filler 2: Silanized quartz powder (Preparation of inorganic filler 2)
Quartz (manufactured by MARUWA QUARTZ) was pulverized with a ball mill to obtain quartz powder. It was 4.5 micrometers when the average particle diameter of the obtained quartz powder was measured using the laser diffraction type particle size distribution measuring apparatus (Shimadzu Corporation make, model "SALD-2100"). With respect to 100 parts by weight of the quartz powder, surface treatment was performed with 3 parts by weight of 3-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain silanized quartz powder.

[Preparation of adhesive composite resin]
Example 1
The following components were mixed at room temperature to prepare an adhesive composite resin as a dental composition, and the adhesive strength with bovine enamel and bovine dentin was measured.
Adhesive composite resin:
4-META 25 parts by weight ErMA 30 parts by weight 3G 45 parts by weight CQ 2 parts by weight TMDPO 3 parts by weight DBB 1 part by weight BHT 0.5 parts by weight Inorganic filler 1 15 parts by weight Inorganic filler 2 385 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. The obtained sample was further polished with # 1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water. After polishing, ultrasonic cleaning was performed, and the surface water was dried by air blowing. An adhesive tape having a round hole with a diameter of 3 mm and having a thickness of about 150 μm was attached to the smooth surface after drying to define the adhesion area.

  The prepared adhesive composite resin was applied in the round hole and covered with a release film (polyester). Next, a glass slide was placed on the release film and pressed to smooth the application surface of the adhesive composite resin. Subsequently, the adhesive composite resin is irradiated with light for 20 seconds using the irradiator “JET Light 3000” (manufactured by J. Morita USA) through the release film, and the adhesive composite resin is obtained. Cured.

  A stainless steel cylindrical rod (diameter 7 mm, length 2) 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 adhesive composite resin. 0.5 cm) was bonded to one end face (circular cross section). 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 for 24 hours in a thermostat maintained at 37 ° C., thereby preparing a 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 10 MPa, and the bond strength with bovine dentin was 8 MPa. The obtained results are summarized in Table 1.

(Example 2)
In Example 1, instead of using 25 parts by weight of “4-META” which is the polymerizable monomer (a), adhesiveness was obtained in the same manner as in Example 1 except that 25 parts by weight of “MAC-10” was used. A composite resin 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 30 parts by weight of “ErMA” which is a polymerizable monomer (b), “GDMA” which is a polymerizable monomer having two polymerizable groups and one secondary hydroxyl group is used. An adhesive composite resin was prepared in the same manner as in Example 1 except that 30 parts by weight were used, 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 30 parts by weight of “ErMA” which is the polymerizable monomer (b), it is a polymerizable monomer having two polymerizable groups and two or more secondary hydroxyl groups. An adhesive composite resin was prepared in the same manner as in Example 1 except that 30 parts by weight of “# 801” was used, 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 30 parts by weight of the polymerizable monomer (b) “ErMA”, “DPEPA” is a polymerizable monomer having 5 polymerizable groups and 1 primary hydroxyl group. An adhesive composite resin was prepared in the same manner as in Example 1 except that 30 parts by weight were used, 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 25 parts by weight of “4-META” which is the polymerizable monomer (a), 25 parts by weight of “AMPS” which is a polymerizable monomer having a sulfonic acid group was used. Prepared an adhesive composite resin in the same manner as in Example 1, and measured the adhesive strength with bovine enamel and the adhesive strength with bovine dentin. The obtained results are summarized in Table 1.

(Comparative Example 5)
In Example 1, instead of using 25 parts by weight of “4-META” which is a polymerizable monomer (a), 3 parts by weight of “4-META” is used, and the polymerizable monomer (b) is used. Instead of using 30 parts by weight of “ErMA”, an adhesive composite resin was prepared in the same manner as in Example 1 except that 52 parts by weight of “ErMA” was used. The adhesive strength with the quality was measured. The obtained results are summarized in Table 1.

(Comparative Example 6)
In Example 1, instead of using 25 parts by weight of “4-META” which is a polymerizable monomer (a), 52 parts by weight of “4-META” is used, and the polymerizable monomer (b) is used. Instead of using 30 parts by weight of “ErMA”, an adhesive composite resin was prepared in the same manner as in Example 1 except that 3 parts by weight of “ErMA” was used. The adhesive strength with bovine enamel and bovine ivory The adhesive strength with the quality was measured. The obtained results are summarized in Table 1.

  From Table 1, 5 to 95 parts by weight of a polymerizable monomer (a) having a carboxylic acid group, two or more polymerizable groups and a primary hydroxyl group with respect to 100 parts by weight of the total amount of polymerizable monomer components. In Examples 1 and 2 using a composition comprising 5 to 95 parts by weight of the polymerizable monomer (b) having 2 or more and 1 to 1000 parts by weight of the filler (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. On the other hand, in Comparative Example 4 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 1 to 1 in which the polymerizable monomer (b) was not used. 3, Comparative Example 5 in which the content of the polymerizable monomer (a) was 3 parts by weight, and Comparative Example 6 in which the content of the polymerizable monomer (b) was 3 parts by weight, The adhesive strength between the enamel and the adhesive strength between the composite resin and dentin were both inferior.

[Preparation of cement composition]
(Example 3)
The following components were mixed at room temperature to prepare A paste and B paste. Next, these were mixed to prepare a dental cement composition, and the adhesive strength between bovine enamel and bovine dentin was measured.
A paste:
4-META 45 parts by weight ErMA 30 parts by weight 3G 25 parts by weight BPO 3 parts by weight BHT 0.05 parts by weight Inorganic filler 1 15 parts by weight Inorganic filler 2 220 parts by weight

B paste:
ErMA 30 parts by weight 3G 70 parts by weight DEPT 1 part by weight TPBSS 2 parts by weight BHT 0.05 parts by weight Inorganic filler 1 15 parts by weight Inorganic filler 2 220 parts by weight

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

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

  The cement composition obtained by kneading the prepared A paste and B paste at a weight ratio of 1: 1 was built on one end face (circular cross section) of a stainless steel cylindrical rod (diameter 7 mm, length 2.5 cm). The end face on which the cement composition was built up was placed in the round hole and pressed so that the center of the round hole and the center of the stainless steel cylindrical rod coincided, and the stainless steel was perpendicular to the tooth surface. A cylindrical rod made of plant was planted.

  After planting, the excess cement composition that appeared around the stainless steel cylindrical rod was removed with an instrument, and 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 for 24 hours in a thermostat maintained at 37 ° C., thereby preparing a 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 adhesive strength with bovine enamel was 12 MPa, and the adhesive strength with bovine dentin was 8 MPa. The obtained results are summarized in Table 2.

Example 4
In Example 3, instead of using 45 parts by weight of “4-META” which is the polymerizable monomer (a), A paste was prepared using 45 parts by weight of “MAC-10”. Similarly, A paste and B paste were kneaded at a weight ratio of 1: 1 to prepare a cement composition, 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 3, instead of using 30 parts by weight of “ErMA” which is the polymerizable monomer (b), the same as in Example 3 except that A paste and B paste were prepared using 30 parts by weight of “GDMA”. A paste and B paste were kneaded at a weight ratio of 1: 1 to prepare a cement composition, 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 3, instead of using 30 parts by weight of “ErMA” which is the polymerizable monomer (b), A paste and B paste were prepared using 30 parts by weight of “# 801”. Similarly, A paste and B paste were kneaded at a weight ratio of 1: 1 to prepare a cement composition, 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 3, instead of using 45 parts by weight of “4-META” which is the polymerizable monomer (a), A paste was prepared using 45 parts by weight of “AMPS”. A paste and B paste were kneaded at a weight ratio of 1: 1 to prepare a cement composition, 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 3, instead of using 30 parts by weight of the polymerizable monomer (b) “ErMA”, the same as Example 3 except that 30 parts by weight of “DPEPA” was used to prepare the A paste and the B paste. A paste and B paste were kneaded at a weight ratio of 1: 1 to prepare a cement composition, 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 3, instead of using 45 parts by weight of “4-META” which is the polymerizable monomer (a), 6 parts by weight of “4-META” is used and the polymerizable monomer (d) is used. Instead of using 25 parts by weight of “3G”, A paste and B paste were kneaded at a weight ratio of 1: 1 in the same manner as in Example 3 except that 44 parts by weight of “3G” was used to prepare A paste. A cement 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 12)
In Example 3, instead of using 30 parts by weight of “ErMA” as the polymerizable monomer (b), 3 parts by weight of “ErMA” was used, and “3G” as the polymerizable monomer (d) was used. Instead of using 25 parts by weight, prepare A paste using 52 parts by weight of “3G”, and then using “ErMA” as the polymerizable monomer (b), instead of 30 parts by weight of “ErMA”. In the same manner as in Example 3, except that 3 parts by weight of the polymerizable monomer (d) “3G” and 70 parts by weight of “3G” were used, and B paste was prepared using 97 parts by weight of “3G”. A cement paste was prepared by kneading A paste and B paste at a weight ratio of 1: 1, and the adhesive strength with bovine enamel and the adhesive strength with bovine dentin were measured. The obtained results are summarized in Table 2.

  From Table 2, 5 to 95 parts by weight of a polymerizable monomer (a) having a carboxylic acid group, two or more polymerizable groups and a primary hydroxyl group with respect to 100 parts by weight of the total amount of polymerizable monomer components. In Examples 3 and 4 using a composition comprising 5 to 95 parts by weight of the polymerizable monomer (b) having 2 or more and 1 to 1000 parts by weight of the filler (c), the cement composition It can be seen that the adhesive strength between the cement and the enamel and the adhesive strength between the cement composition and the dentin are both good and useful as a dental composition. In contrast, Comparative Example 9 in which the polymerizable monomer (a) was not used, Comparative Example 11 in which the content of the polymerizable monomer (a) was 3 parts by weight, the polymerizable monomer (a) In Comparative Example 12 in which the content of the polymerizable monomer (b) was 3 parts by weight, the adhesive strength between the cement composition and the dentin was greatly inferior, and the polymerizable monomer (b) was not used. In Comparative Examples 7, 8, and 10, the adhesive strength between the cement composition and the enamel was inferior, and the adhesive strength between the cement composition and the dentin was greatly inferior.

Claims (11)

At least one polymerizable monomer selected from the group consisting of a polymerizable monomer (a) having a carboxylic acid group, pentaerythritol di (meth) acrylate, and dipentaerythritol di, tri, and tetra (meth) acrylate A composition comprising a monomer (b) and a filler (c), wherein the polymerizable monomer (a) is added in an amount of 5 to 95 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer components. A composition comprising 5 to 95 parts by weight of the polymerizable monomer (b) and 1 to 1000 parts by weight of the filler (c).   The composition according to claim 1, further comprising 1 to 90 parts by weight of a polymerizable monomer (d) other than (a) and (b) with respect to 100 parts by weight of the total amount of the polymerizable monomer components. .   The polymerizable monomer (a) is at least one selected from the group consisting of 4-methacryloyloxyethyl trimellitic anhydride, 4-methacryloyloxyethyl trimellitic acid and 11-methacryloyloxyundecane-1,1-dicarboxylic acid. The composition according to claim 1 or 2, which is a seed. The composition according to any one of claims 1 to 3 , comprising 0.001 to 30 parts by weight of the polymerization initiator (e) 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 4 , comprising 0.001 to 30 parts by weight of a polymerization accelerator (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 5 , comprising 1 to 2000 parts by weight of the solvent (g) with respect to 100 parts by weight of the total amount of the polymerizable monomer components. The composition according to claim 6 , wherein the solvent (g) is a water-soluble solvent. Dental composition comprising a composition according to any one of claims 1-7. A composite resin comprising the dental composition according to claim 8 . A cement comprising the dental composition according to claim 8 . A bonding material comprising the dental composition according to claim 8 .