JP2011016775A - Composition for dentistry - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for dentistry, exhibiting little change in a curing rate and adhesiveness to dentine even after long-term preservation, and having excellent preservation stability, and to provide a cement for the dentistry, comprising the composition.SOLUTION: The composition for the dentistry includes a polymerizable monomer (a), a filler (b), an oxidizing agent (c), a reducing agent (d) and a polymerization accelerator (e), wherein the filler (b) contains a filler (b') surface-treated with a surface-treating agent containing an organic compound (p) having a basic functional group.

Description

  The present invention relates to a dental composition. More specifically, the present invention relates to a dental composition having a small curing rate and a change in adhesiveness to a tooth even after long-term storage and excellent in storage stability, and a dental cement comprising the composition.

  A dental composition is generally a blend of a polymerizable monomer, a filler such as an inorganic compound, and a polymerization initiator, and is used as a material for filling a tooth defect or caries or as a metal called an inlay or crown. It is used as an adhesive for fixing dental restoration materials for dental crowns and ceramics to teeth. Such a dental composition is required to have an appropriate curing time that is easy to use as a dental material and an adhesive property that prevents the filler from dropping off. In addition, since these dental materials are used in the oral cavity, they are required to have high aesthetics after treatment. As one of means for satisfying these performances, compositions containing various polymerization initiators have been developed so far.

  For example, Patent Document 1 discloses a dental in which color stability before polymerization and color stability of a cured product are improved by using a reducing agent such as an organic peroxide, a tertiary amine, and an aromatic sulfinic acid in combination. A composition for use is described. Patent Document 2 reports an example in which the operable time and adhesion durability are improved in the same composition as Patent Document 1.

International Publication No. 1998/056332 Pamphlet International Publication No. 2008/090784 Pamphlet

  In Patent Document 1, although the color tone stability of the polymerizable composition before and after curing can be improved, there is room for improvement in the storage stability of the composition, which is important when these are marketed as products. It remained.

  Further, in Patent Document 2, although the operable time and the adhesion durability have been improved, there remains room for improvement in the storage stability of the composition as in the invention described in Patent Document 1.

  The present invention has been made to solve the above-described problems of the prior art, and the object of the present invention is to provide a small change in curing rate and adhesiveness to the tooth even after long-term storage. An object of the present invention is to provide a dental composition having excellent stability and a dental cement comprising the composition.

The present invention
[1] A dental composition comprising a polymerizable monomer (a), a filler (b), an oxidizing agent (c), a reducing agent (d) and a polymerization accelerator (e), wherein the filler (B) a dental composition comprising a filler (b ′) surface-treated with a surface treating agent containing an organic compound (p) having a basic functional group, and [2] the above-mentioned [1] It is related with the dental cement which consists of a dental composition.

  The dental composition of the present invention has the effect that the change in the curing rate and the adhesiveness to the tooth is small and the storage stability is excellent even after long-term storage.

  The dental composition of the present invention is a composition containing a polymerizable monomer (a), a filler (b), an oxidizing agent (c), a reducing agent (d) and a polymerization accelerator (e), The filler (b) has a great feature in that it contains a filler (b ′) surface-treated with a surface treatment agent containing an organic compound (p) having a basic functional group.

The present invention is described in detail below.
The polymerizable monomer (a) constituting the dental composition of the present invention is preferably a radical polymerizable monomer having a polymerizable group. From the viewpoint of easy radical polymerization, the polymerizable group is (meth). Acrylic groups and / or (meth) acrylamide groups are preferred. Although the dental composition of the present invention is used in the oral cavity, the oral cavity is a moist environment, and there is a possibility that the polymerizable group may be detached due to hydrolysis or the like. In consideration of irritation, the polymerizable group is preferably a methacryl group and / or a methacrylamide group. In the present specification, “(meth) acryl” means acryl or methacryl, and “(meth) acryloyl” means acryloyl or methacryloyl.

  In the present invention, examples of the polymerizable monomer (a) include a polyfunctional monomer having a plurality of the polymerizable groups and a monofunctional monomer having one polymerizable group.

  Examples of the polyfunctional monomer include aromatic compound-based bifunctional polymerizable monomers, aliphatic compound-based bifunctional polymerizable monomers, and trifunctional or higher functional polymerizable monomers. It is done.

  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 “Bis-GMA”), 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- (Meth) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphene) ) 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. Among these, 2,2-bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl] propane and 2,2-bis are preferred in that the mechanical strength of the resulting dental composition is large. (4- (Meth) acryloyloxypolyethoxyphenyl) propane is preferred. Among 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, a compound having an average addition mole number of ethoxy groups of 2.6 (commonly referred to as “D2.6E”) is preferable.

  Examples of aliphatic compound-based bifunctional polymerizable monomers include glycerol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene Glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,5-pentanediol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, 2, 2 4- trimethylhexamethylene bis (2-carbamoyloxyethyl) dimethacrylate (commonly known as "UDMA"), 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane and the like. Among these, glycerol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,2,4-trimethyl are preferred because of the excellent handling properties of the resulting dental composition. Hexamethylene bis (2-carbamoyloxyethyl) dimethacrylate and 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane are preferred.

  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 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane and the like. Among these, N, N- (2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] is used because the mechanical strength of the obtained dental composition is large. Tetramethacrylate is preferred.

  Examples of monofunctional monomers include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxy Decyl (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, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) ) Acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 3- (meth) acryloyloxypropyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane , (Meth) acrylamide and the like. Among these, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glycerol mono (meta) is high in that the obtained dental composition has high affinity with the tooth substance and high adhesion strength. ) Acrylate and erythritol mono (meth) acrylate are preferred.

  In addition, the dental composition of the present invention may contain an acidic group-containing polymerizable monomer as the polymerizable monomer (a) from the viewpoint of good adhesion strength to a tooth or a dental prosthesis. Good. Such an acidic group-containing polymerizable monomer has at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group, and is polymerized. And radically polymerizable monomers having a functional group.

  Examples of the polymerizable monomer having a phosphoric acid group include, for example, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxy. Butyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) Acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth ) Acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxy hexadecyl dihydrogen phosphate, 20- (meth) acryloyloxy icosyl dihydrogen phosphate Bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- (Meth) acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyloxynonyl] hydrogen phosphate, bis [10- (meth) acryl Yloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl Examples thereof include hydrogen phosphate, bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl] hydrogen phosphate, and acid chlorides, alkali metal salts, ammonium salts and the like thereof.

  Examples of polymerizable monomers having a pyrophosphate group include, for example, bis [2- (meth) acryloyloxyethyl pyrophosphate], bis [4- (meth) acryloyloxybutyl pyrophosphate], bis [6 pyrophosphate] [6 -(Meth) acryloyloxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate, and their acid chlorides, alkali metal salts, ammonium salts Etc. are exemplified.

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

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

  Examples of the polymerizable monomer having a sulfonic acid group include 2- (meth) acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, 2-sulfoethyl (meth) acrylate and the like.

  Examples of the polymerizable monomer having a carboxylic acid group include a polymerizable monomer having one carboxyl group in the molecule and a polymerizable monomer having a plurality of carboxyl groups in the molecule.

  Examples of the polymerizable monomer having one carboxyl group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, N- (meth) acryloyl-5-amino. Salicylic acid, O- (meth) acryloyl tyrosine, N- (meth) acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid Acid, p-vinylbenzoic acid, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid and acid halides thereof It is shown.

  Examples of the polymerizable monomer having a plurality of carboxyl groups in the molecule include 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, and 2- (meth) acryloyloxyethyl. Hydrogenmalate, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 9- (meth) acryloyloxynonane-1,1-dicarboxylic acid, 10- (meth) acryloyloxydecane-1,1-dicarboxylic acid Acid, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 12- (meth) acryloyl oxide decane-1,1-dicarboxylic acid, 13- (meth) acryloyloxytridecane-1,1-dicarboxylic acid , 4- (Meth) acryloyloxyethyl trime Tate, 4- (meth) acryloyloxybutyl trimellitate, 4- (meth) acryloyloxyhexyl trimellitate, 4- (meth) acryloyloxydecyl trimellitate, 2- (meth) acryloyloxyethyl-3′- Examples include (meth) acryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) propyl succinate and acid anhydrides or acid halides thereof.

  Among the above acidic group-containing polymerizable monomers, from the viewpoint of good adhesive strength of the dental composition, the acidic group-containing polymerizable monomer preferably has a phosphate group or a phosphonic acid group, It is more preferable to have a phosphate group. Among them, it is preferable to have an alkyl group or alkylene group having 6 to 20 carbon atoms in the molecule, and the main chain has 8 carbon atoms in the molecule such as 10- (meth) acryloyloxydecyl dihydrogen phosphate. More preferably, it has ˜12 alkylene groups.

  The polymerizable monomer (a) may be used alone, but from the viewpoint of mechanical strength, handleability, adhesive strength and curability of the dental composition, an aromatic compound-based bifunctional Preferably, the polymerizable polymerizable monomer and the aliphatic compound-based bifunctional polymerizable monomer and / or monofunctional monomer are used in combination, and the aromatic compound-based bifunctional polymerizable monomer and It is more preferable to use an aliphatic compound-based bifunctional polymerizable monomer in combination. The ratio in the case of using them together is not particularly limited, but when the total amount of the polymerizable monomer (a) is 100% by weight, the blending amount of the aromatic compound-based bifunctional polymerizable monomer is 30. It is preferably -90% by weight, more preferably 40-85% by weight, and still more preferably 45-80% by weight. In the present specification, the “total amount of the polymerizable monomer (a)” means the total amount of the polymerizable monomer contained in the entire composition, for example, the composition of the present invention When taking the form of two-agent type, it means the sum of the weights of polymerizable monomers contained in each agent.

  The amount of the acidic group-containing polymerizable monomer is not particularly limited, but is preferably 1 to 60% by weight when the total amount of the polymerizable monomer (a) is 100% by weight, More preferably, it is 50 weight%, and it is further more preferable that it is 5-40 weight%. When the blending amount of the acidic group-containing polymerizable monomer is 1% by weight or more, good adhesive strength is obtained, and the blending amount of the acidic group-containing polymerizable monomer is 60% by weight or less. The polymerizability of the dental composition is moderate and the adhesive strength is also kept good.

  The filler (b) is necessary for enhancing the storage stability of the dental composition. The filler (b) in the present invention contains a filler (b ′) surface-treated with a surface treatment agent containing an organic compound (p) having a basic functional group, but is covered with the organic compound (p). The filler (b ′), which has become basic due to the above, is dispersed in the composition, but the detailed mechanism is unknown, but the composition becomes basic and the polymerization accelerator (e) is decomposed. It is presumed that the effect of improving the storage stability of the composition by suppressing the above can be exhibited. In the present specification, the filler (b ′) is also referred to as “basic filler”.

  Examples of the core filler that is surface-treated in the filler (b ′) include an inorganic filler and an organic-inorganic composite filler.

  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 be used alone or in admixture of two or more. The shape of the inorganic filler is not particularly limited, and an amorphous filler and a spherical filler can be appropriately selected and used.

  The organic-inorganic composite filler is obtained by adding a polymerizable monomer in advance to the above-mentioned inorganic filler, forming a paste, polymerizing and pulverizing, for example, TMPT filler (trimethylolpropane). And those obtained by mixing and polymerizing methacrylate and silica filler and then pulverizing them. 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.

  The organic compound (p) having a basic functional group is preferably an alkylsilane compound having an amino group. The alkylsilane compound having an amino group is not particularly limited as long as the alkyl group bonded to the silicon atom is substituted with an amino group, and examples thereof include aminoalkylsilane compounds and ureidoalkylsilane compounds. In addition, as an alkyl group substituted by an amino group, Preferably it is C1-C16, More preferably, a C2-C10 alkyl group is mentioned. Moreover, the carbon atom substituted with an amino group is not particularly limited, but the carbon atom that is furthest from the silicon atom is preferable. The silicon substituent other than the alkyl group is not particularly limited, and examples thereof include an unsubstituted or substituted alkyl group other than an amino group, and an unsubstituted or substituted alkoxy group. Among these, from the viewpoint of reactivity to the nuclear filler, an alkoxy group is preferable, and a methoxy group, an ethoxy group, a propyl group, and the like are more preferable. The substituent for the alkoxy group is not particularly limited, and may be an amino group.

  Examples of aminoalkylsilane compounds include 3-aminopropyldimethylethoxysilane, 3-aminopropyl (diethoxy) methylsilane, 3-aminopropyltriethoxysilane, (N, N′-dimethylaminopropyl) trimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3- [ 2- (2-aminoethylamino) ethylamino] propyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane It is done.

  Examples of ureidoalkylsilane compounds include 3- (ureido) propyltriethoxysilane and 3- (ureido) propyltrimethoxysilane.

  These organic compounds (p) having a basic functional group can be used alone or in admixture of two or more. In the present invention, from the viewpoint of the storage stability of the composition, among these, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3 -It is preferably at least one selected from the group consisting of aminopropyltrimethoxysilane and 3- (ureido) propyltriethoxysilane.

  The organic compound (p) having a basic functional group can be synthesized according to a known method. For example, a ureidoalkylsilane compound can be obtained by reacting a silylalkyl isocyanate compound and an alkyldiamine compound as raw materials according to a known method.

  Examples of the silylalkyl isocyanate include 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropyltrimethoxysilane.

  Examples of the alkyldiamine compound include 1,2-ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,3-pentanediamine, 1,6-hexanediamine, 1,2-cyclohexanediamine, 1,8 -Octanediamine, 1,6- (2-ethylhexane) diamine, 1,9-nonanediamine, N, N'-dimethylethylenediamine, N, N-dimethylethylenediamine, N-ethylethylenediamine, 3- (methylamino) propylamine N-methyl-1,3 diaminopropane and the like.

  The reaction temperature is preferably 10 to 80 ° C., and the reaction time is preferably 0.5 to 5 hours.

  Moreover, a commercial item may be used for the organic compound (p) which has a basic functional group. Specifically, “KBE-903” (manufactured by Shin-Etsu Silicone) is used as 3-aminopropyltriethoxysilane, and “KBM-603” (as N-2- (aminoethyl) -3-aminopropyltrimethoxysilane) ( Shin-Etsu Silicone), “KBM-573” (manufactured by Shin-Etsu Silicone) as N-phenyl-3-aminopropyltrimethoxysilane, and “KBE-585” (Shin-Etsu Silicone) as 3- (ureido) propyltriethoxysilane Etc.) are preferably used.

  In this invention, in order to adjust the fluidity | liquidity of a composition, you may surface-treat together with well-known surface treatment compounds other than the organic compound (p) which has the said basic functional group as needed. Examples of the surface treatment compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, 3-methacryloyloxypropyltrimethoxysilane, and 11-methacryloyloxyundecyltrimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like. The content of the organic compound (p) having a basic functional group is preferably 20% by weight or more, more preferably 40% by weight or more, and still more preferably substantially, in the surface treatment agent, from the viewpoint of not impairing storage stability. 100% by weight.

  As a surface treatment method using a surface treatment agent, a known method can be used without particular limitation. For example, a method of spraying the surface treatment agent while vigorously stirring the inorganic filler, a method of removing the solvent after dispersing or dissolving the inorganic filler and the surface treatment agent in an appropriate solvent, or the above in an aqueous solution There is a method of removing the water after hydrolyzing the alkoxy group of the surface treatment agent with an acid catalyst to convert it to a silanol group and attaching it to the surface of the inorganic filler in the aqueous solution. By heating in the range of -150 degreeC, reaction with the surface of an inorganic filler and the said surface treating agent is completed, and surface treatment can be performed. In addition, when making a surface treating agent react on the surface of an inorganic filler, you may surface-treat an inorganic filler by reaction over two steps. Specifically, for example, when performing surface treatment with a ureidoalkylsilane compound, first, the silylalkyl isocyanate compound is allowed to react with the inorganic filler surface, and then the alkyldiamine compound can be reacted.

  The amount of treatment with the organic compound (p) having a basic functional group in the basic filler is preferably 0.01 to 10 parts by weight, and 0.05 to 5 parts by weight with respect to 100 parts by weight of the core filler before the treatment. More preferred.

  The average particle size of the basic filler is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm, from the viewpoints of handleability and mechanical strength of the obtained dental composition. In the present specification, the average particle diameter of the filler can be measured by any method known to those skilled in the art, and can be easily measured by, for example, a laser diffraction particle size distribution measuring apparatus described in the following examples.

  In addition, the dental composition of the present invention can be blended with fillers other than the above basic fillers for the purpose of improving mechanical strength and paste properties. Examples of the filler other than the basic filler include inorganic fillers, organic-inorganic composite fillers, and organic fillers that are surface-treated only with the aforementioned surface treatment compound other than the organic compound (p) having a basic functional group. These can be used alone or as a mixture of two or more.

  Examples of the inorganic filler and the organic-inorganic composite filler are the same as the core filler used in the basic filler.

  Organic fillers include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, polystyrene, and chloroprene rubber. , Nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and other organic fillers. It can be used as a mixture of the above. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used.

  The content of the filler (b ′) (basic filler) in the filler (b) is preferably 20% by weight or more, more preferably 30% by weight or more, and further preferably 40% by weight from the viewpoint of making the composition basic. % Or more. Moreover, from a reactive viewpoint with a chemical polymerization initiator, Preferably it is 100 weight% or less, More preferably, it is 90 weight% or less, More preferably, it is 80 weight% or less. Therefore, it is preferably 20 to 100% by weight, more preferably 30 to 100% by weight, further preferably 40 to 100% by weight, further preferably 40 to 90% by weight, and further preferably 40 to 80% by weight.

  Although the compounding quantity of a filler (b) is not specifically limited, From a viewpoint of the handleability of the dental composition obtained and a storage stability, 50-900 weight with respect to 100 weight part of total amounts of a polymerizable monomer (a). Parts, preferably 60 to 600 parts by weight, more preferably 75 to 400 parts by weight. When the content of the filler (b) is 50 parts by weight or more, the storage stability of the paste is good, and when it is 900 parts by weight or less, the flowability of the dental composition is good and sufficient mixing is achieved. There is no fear that the curing time will be delayed.

  Examples of the oxidizing agent (c) include organic peroxides, azo compounds, and inorganic peroxides. Examples of the organic peroxide include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, and hydroperoxides. Specific examples of diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, and the like. Specific examples of peroxyesters include t-butyl peroxybenzoate, bis-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy -2-ethylhexanoate, t-butyl peroxyisopropyl carbonate and the like. Specific examples of dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide and lauroyl peroxide. Specific examples of peroxyketals include 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (T-hexylperoxy) cyclohexane and the like. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide, and the like. Specific examples of hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, p-diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide and the like. Examples of the azo compound include azobisisobutyronitrile and azobisisobutylvaleronitrile. Examples of inorganic peroxides include sodium persulfate, potassium persulfate, aluminum persulfate, and ammonium persulfate.

  Examples of the reducing agent (d) include aromatic amines, thioureas, and ascorbic acid that do not have an electron withdrawing group in the aromatic ring. The oxidizing agent (c) and the reducing agent (d) are also collectively referred to as a chemical polymerization initiator in the present invention.

  As an aromatic amine having no electron withdrawing group in the aromatic ring, the hydrogen atom of the aromatic ring of the aromatic amine is not substituted with an electron withdrawing group such as a carboxylic acid group, a carboxylic acid ester group, a nitrile group, or a halogen group. Specific examples include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, 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 and the like can be mentioned. As for the aromatic amine which does not have an electron withdrawing group in the aromatic ring mentioned above, all may be used alone or in combination of two or more.

  Examples of thioureas include thiourea, methylthiourea, ethylthiourea, N, N′-dimethylthiourea, N, N′-diethylthiourea, N, N′-di-n-propylthiourea, dicyclohexylthiourea, trimethylthiourea. , Triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, tetracyclohexylthiourea and the like. Any of the above-described thioureas may be used alone or in combination.

  When the total amount of the oxidizing agent (c) and the reducing agent (d) is 0.001 part by weight or more with respect to 100 parts by weight of the total amount of the polymerizable monomer (a), the curing rate is not delayed. The adhesive strength is not lowered, and is preferably 0.01 parts by weight or more, and more preferably 0.1 parts by weight or more. Further, if it is 20 parts by weight or less, the curing time is not too fast and there is no fear that the working time cannot be secured, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less. . Therefore, from the above viewpoint, the total amount of the oxidizing agent (c) and the reducing agent (d) is preferably 0.001 to 20 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer (a). 0.01-10 weight part is more preferable, and 0.1-5 weight part is further more preferable.

  The polymerization accelerator (e) used in the present invention contains an aliphatic amine, an aromatic tertiary amine having an electron withdrawing group, sulfinic acid and / or a salt thereof, a sulfur-containing reducing inorganic compound, and nitrogen. Reducing inorganic compounds, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, and the like.

  Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine and dibutylamine; N-methyldiethanolamine, N- Ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl (meth) acrylate, N-methyldiethanolamine di (meth) acrylate, N-ethyldiethanolamine di (meth) acrylate, triethanolamine Tertiary fats such as mono (meth) acrylate, triethanolamine di (meth) acrylate, triethanolamine tri (meth) acrylate, triethanolamine, trimethylamine, triethylamine, tributylamine Family amines are exemplified. 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 preferable.

  As an aromatic tertiary amine having an electron withdrawing group, an aromatic ring hydrogen atom of an aromatic tertiary amine is substituted with an electron withdrawing group such as a carboxylic acid group, a carboxylic acid ester group, a nitrile group, or a halogen group. Specific examples include 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, 4-N, N-dimethylaminobenzoic acid propyl ester. 4-N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid 2-[(meth) acryloyloxy] ethyl ester, 4-N, N-dimethylaminobenzophenone, etc. Can be mentioned. Among these, from the viewpoint of curability of the composition, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, 4-N, N-dimethylaminobenzoic acid n -Butoxyethyl ester and 4-N, N-dimethylaminobenzophenone are preferred.

  Specific examples of the sulfinic acid and / or salt thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, and benzene. Sulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfate, 2,4, Potassium 6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate, 2, Sodium 6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6 -Triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, 2,4,6 Examples include calcium 6-triisopropylbenzenesulfinate.

  Examples of the reducing inorganic compound containing sulfur include sulfite, bisulfite, pyrosulfite, thiosulfate, thionate, dithionite, etc. Specific examples include sodium sulfite and potassium sulfite. , Calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite and the like.

  The reducing inorganic compound containing nitrogen includes nitrite, and specific examples include sodium nitrite, potassium nitrite, calcium nitrite, ammonium nitrite and the like.

  As the borate compound, an aryl borate compound is preferable. 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 (wherein the alkyl group is at least one selected from the group consisting of n-butyl, n-octyl and n-dodecyl) And salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt) , Ethyl quinolinium salt, butyl quinolinium salt, etc.).

  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 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 and the like) and salts thereof (sodium salt, lithium salt) Salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium Salt).

  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 at least one selected from the group consisting of n-butyl group, n-octyl group, n-dodecyl group, etc.) And their salts (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium Salt, ethylquinolinium salt, butylquinolinium salt, etc.).

  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, and their salts (sodium, lithium, potassium, magnesium, tetra Butylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc.).

  Examples of barbituric acid derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, and 5-ethylbarbituric acid. Acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbi Tool 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, 1-cyclohexyl-1-ethylbarbituric acid, Benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutyl Barbituric acid, 1,3-diethyl-5-butyl barbituric 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 salts thereof (alkali metal or alkaline earth metal) Examples of salts of these barbituric acids include If, sodium 5-butyl barbituric acid, 1,3,5-trimethyl barbituric acid sodium and 1-cyclohexyl-5-ethyl barbituric sodium tools acids and the like.

  Examples of the triazine compound 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 (trichloromethyl) -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- Methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-trimethoxyphenyl) 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} ethoxy] -4,6-bis (trichloromethyl)- Examples include s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, and the like.

  As the copper compound, for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.

  Examples of the tin compound include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. Among these, suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

  The vanadium compound is preferably an IV valent and / or V valent vanadium compound. 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.

  As the halogen compound, for example, dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide and the like are preferably used.

  Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like.

  Examples of the thiol compound include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

  These polymerization accelerators (e) may be used alone or in combination of two or more. However, in terms of excellent storage stability, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, 4-N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzophenone, sodium benzenesulfinate, sodium p-toluenesulfinate, 2,4 1,6-trimethylbenzenesulfinate sodium, 2,4,6-triisopropylbenzenesulfinate sodium, sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite, and potassium bisulfite at least 1 Preferably it is a seed.

  The blending amount of the polymerization accelerator (e) is not particularly limited, but when it is 0.001 part by weight or more with respect to 100 parts by weight of the total amount of the polymerizable monomer (a), the curing rate increases and the adhesive strength. Is preferable, more preferably 0.01 parts by weight or more, and even more preferably 0.1 parts by weight or more. Further, when the amount is 20 parts by weight or less, a decrease in adhesive strength is not recognized, and the color tone of the composition is maintained, which is preferably 15 parts by weight or less, and more preferably 10 parts by weight or less. More preferably, it is 5 parts by weight or less. Therefore, from the above viewpoint, the blending amount of the polymerization accelerator (e) is preferably 0.001 to 20 parts by weight, and 0.01 to 15 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer (a). Part is more preferable, 0.1 to 10 parts by weight is further preferable, and 0.1 to 5 parts by weight is further preferable.

  Moreover, in order to start superposition | polymerization by light irradiation, the dental composition of this invention may further contain a photoinitiator (f). Examples of the photopolymerization initiator (f) include α-diketones.

  Examples of α-diketones include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, acenaphthenequinone, and the like. Can be mentioned. Among these, camphorquinone is preferable because it is excellent in photocurability in the visible and near-ultraviolet regions and exhibits sufficient photocurability using any light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp.

  The blending amount of the photopolymerization initiator (f) is not particularly limited, but from the viewpoint of photocurability, 0.01 to 10 parts by weight is preferable with respect to 100 parts by weight of the total amount of the polymerizable monomer (a). 0.10 to 3 parts by weight is more preferable.

  Moreover, a well-known additive can be mix | blended with the dental composition of this invention in the range which does not reduce performance. Examples of such additives include polymerization inhibitors, antioxidants, pigments, dyes, ultraviolet absorbers, organic solvents, thickeners and the like.

  Examples of the polymerization inhibitor include 2,6-di-butylhydroxytoluene, hydroquinone, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, 2,6-t-butylphenol, 2,6-di-t-butyl-4-methylphenol. Is mentioned. The content of the polymerization inhibitor is preferably 0.001 to 1.0 part by weight with respect to 100 parts by weight of the total amount of the polymerizable monomer (a).

  The dental composition of the present invention is particularly limited as long as it contains the polymerizable monomer (a), filler (b), oxidizing agent (c), reducing agent (d) and polymerization accelerator (e). However, it can be easily produced as a resin cement by a method known to those skilled in the art.

  In the present invention, since the redox polymerization initiator comprising the oxidizing agent (c) and the reducing agent (d) is used as the chemical polymerization initiator, from the viewpoint of storage stability, the oxidizing agent (c) and The reducing agent (d) is stored in a separate container. That is, in an embodiment, the dental composition of the present invention is provided as including at least a first agent containing an oxidizing agent (c) and a second agent containing a reducing agent (d). Examples of the agent other than the first agent and the second agent include a third agent containing a polymerization accelerator and the like. Moreover, in a preferable aspect, it is provided as a kit used in the form of a two-component type consisting of the first agent and the second agent, and in a more preferable embodiment, the two agents are both pasty. It is provided as a kit used in the form of When used in the form of a two-paste type, each paste is stored in a state where the pastes are isolated from each other, and the two pastes are kneaded immediately before use to advance chemical polymerization, and further contains a photopolymerization initiator. In some cases, it is preferable to proceed by chemical progress and photopolymerization and cure.

  When the dental composition of the present invention is used as a resin cement (dental cement), the dental composition comprises a polymerizable monomer (a), a filler (b), an oxidizing agent (c), a reducing agent (d), A composition containing a polymerization accelerator (e) and a photopolymerization initiator (f) is preferred. In the case of the two-paste type product form, the above-mentioned two pastes, that is, the first agent paste containing the oxidizing agent (c) and the second agent paste containing the reducing agent (d) are respectively the first paste. When referred to as the paste (A paste) and the second paste (B paste), the A and B pastes contain a polymerizable monomer (a) in addition to the oxidizing agent (c) or the reducing agent (d), respectively. It is preferable. Moreover, it is preferable that any one or both of A and B paste contain filler (b ') (basic filler) among fillers (b). Moreover, it is desirable that at least one of the A and B pastes, preferably the A paste contains the photopolymerization initiator (f). Furthermore, it is preferable that at least one of the A and B pastes contains a polymerization accelerator (e). From the viewpoint of storage stability of the composition, the paste containing the filler (b ′) contains the polymerization accelerator (e). It is more preferable to contain. In addition, when the polymerizable monomer (a) contains an acidic group-containing polymerizable monomer, the acidic group-containing polymerizable monomer is preferably contained in one of the A and B pastes. Is more preferably contained on the paste side containing the oxidizing agent (c) so as not to react with the reducing agent (d) and the polymerization accelerator (e).

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited at all by these Examples. The abbreviations used below are as follows.

[Polymerizable monomer (a)]
D-2.6E: 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane NPG: neopentyl glycol dimethacrylate # 801: 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[Filler (b)]
Basic fillers (b′-1) to (b′-5) are obtained according to the following production method. In addition, in the following manufacturing methods, room temperature shows 25 degreeC.

Basic filler (b′-1): 3-aminopropyltriethoxysilane-treated barium glass powder Barium glass (“Raysorb E-3000” manufactured by STEC Co.) was pulverized with a vibration ball mill to obtain barium glass powder. 100 g of the obtained barium glass powder, 0.5 g of 3-aminopropyltriethoxysilane (“KBE-903” manufactured by Shin-Etsu Silicone Co., Ltd.) (0.5 parts by weight with respect to 100 parts by weight of the core filler) and 200 mL of toluene were added to 500 mL. The mixture was placed in a one-necked eggplant flask and stirred at room temperature for 2 hours. Subsequently, toluene was distilled off under reduced pressure, followed by vacuum drying at 40 ° C. for 16 hours, and further vacuum drying at 90 ° C. for 3 hours, and 3-aminopropyltriethoxysilane-treated barium glass powder [basic filler (b′- 1)] was obtained. It was 2.4 micrometers when the average particle diameter of the basic filler (b'-1) was measured using the laser diffraction type particle size distribution measuring apparatus (Shimadzu Corporation model "SALD-2100").

Basic filler (b′-2): N-2- (aminoethyl) -3-aminopropyltrimethoxysilane-treated barium glass powder 3-aminopropyltriethoxysilane was treated with N-2- (aminoethyl) -3- N-2- (aminoethyl) -3-aminopropyltri was treated in the same manner as the basic filler (b′-1) except that it was changed to aminopropyltrimethoxysilane (“KBM-603” manufactured by Shin-Etsu Silicone). A methoxysilane-treated barium glass powder [basic filler (b′-2)] was obtained. When the average particle diameter of the basic filler (b′-2) was measured in the same manner as the basic filler (b′-1), it was 2.5 μm.

Basic filler (b′-3): N-phenyl-3-aminopropyltrimethoxysilane-treated barium glass powder 3-aminopropyltriethoxysilane was replaced with N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone). N-phenyl-3-aminopropyltrimethoxysilane-treated barium glass powder [basic filler (b′-3) was treated in the same manner as the basic filler (b′-1) except that it was changed to “KBM-573”). )]. When the average particle diameter of the basic filler (b′-3) was measured in the same manner as the basic filler (b′-1), it was 2.6 μm.

Basic filler (b′-4): 3-aminopropyltriethoxysilane-treated silica powder Barium glass (“Raysorb E-3000” manufactured by STEC Co.) was changed to silica powder (“KE-P250” manufactured by Nippon Shokubai Co., Ltd.) Otherwise, the same treatment as in the basic filler (b′-1) was performed to obtain 3-aminopropyltriethoxysilane-treated silica powder [basic filler (b′-4)]. It was 2.5 micrometers when the average particle diameter of the basic filler (b'-4) was measured similarly to the basic filler (b'-1).

Basic filler (b′-5): 3-isocyanatopropyltriethoxysilane / ethylenediamine-treated silica powder [3- (ureido) propyltriethoxysilane-treated silica powder]
100 g of silica powder (“KE-P250” manufactured by Nippon Shokubai Co., Ltd.), 0.5 g of 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Silicone Co., Ltd.) and 200 mL of toluene are placed in a 500 mL one-necked eggplant flask, and at room temperature. Stir for 2 hours. Subsequently, toluene was distilled off under reduced pressure, followed by vacuum drying at 40 ° C. for 16 hours and further vacuum drying at 90 ° C. for 3 hours to obtain 3-isocyanatopropyltriethoxysilane-treated silica powder. Next, 200 mL of toluene and 0.5 g of 1,2-ethylenediamine were added to a 500 mL single-necked eggplant flask containing the silica powder obtained and stirred at room temperature for 2 hours. Subsequently, toluene was distilled off under reduced pressure, followed by vacuum drying at 40 ° C. for 16 hours, and further vacuum drying at 90 ° C. for 3 hours to obtain 3-isocyanatopropyltriethoxysilane / ethylenediamine-treated silica powder [3- (ureido) propyl Triethoxysilane-treated silica powder, basic filler (b′-5)] was obtained. When the average particle diameter of the basic filler (b′-5) was measured in the same manner as the basic filler (b′-1), it was 2.6 μm. The treatment amount with the surface treatment agent was 0.5 parts by weight with respect to 100 parts by weight of the core filler.

Filler 1: Silica powder treated with 3-methacryloyloxypropyltrimethoxysilane Barium glass (“Raysorb E-3000” manufactured by ESTEC), silica (“KE-P250” manufactured by Nippon Shokubai Co., Ltd.), and 3-aminopropyltriethoxysilane Except having changed to 3-methacryloyloxypropyltrimethoxysilane, it processed like the basic filler (b'-1), and obtained the 3-methacryloyloxypropyltrimethoxysilane processing silica powder (filler 1). When the average particle diameter of the filler 1 was measured similarly to the basic filler (b′-1), it was 2.5 μm.

Filler 2: Silane-treated colloidal silica powder Barium glass ("Raysorb E-3000" manufactured by ESTEC) is colloidal silica ("Aerosil OX50" manufactured by Nippon Aerosil Co., Ltd.), and 3-aminopropyltriethoxysilane is added to 3-methacryloyloxypropyltri A 3-methacryloyloxypropyltrimethoxysilane-treated colloidal silica powder (filler 2) was obtained in the same manner as the basic filler (b′-1) except that the methoxysilane was used.

[Chemical polymerization initiator: oxidizing agent (c)]
BPO: Benzoyl peroxide

[Chemical polymerization initiator: reducing agent (d)]
DEPT: N, N-di (2-hydroxyethyl) -p-toluidine

[Polymerization accelerator (e)]
TPBSS: sodium 2,4,6-triisopropylbenzenesulfinate BSS: sodium benzenesulfinate DBB: 4-N, N-dimethylaminobenzoic acid n-butoxyethyl ester sodium sulfite

[Photoinitiator (f)]
CQ: dl-camphorquinone

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

Examples 1-9 and Comparative Examples 1-2 (Preparation of resin cement)
The raw materials shown in Table 1 or 2 are mixed at room temperature (25 ° C.) to prepare A paste and B paste, and after storage at 4 ° C. for 1 day and 3 years, the properties are measured according to the methods of Test Examples 1 and 2 below. Examined. The results are shown in Tables 1 and 2.

Test example 1 (operation possible time)
About each Example and Comparative Example After mixing equal amounts of A paste and B paste collected on dental kneaded paper at room temperature with a dental kneading rod for 20 seconds, about 30 mg of the kneaded material obtained was used for a microscope. Placed on a glass slide. After a predetermined time from the start of kneading, another microscope slide glass was pressed so that a shearing force was applied to the kneaded product, and the kneaded product was visually inspected for unevenness. . This inspection was performed by extending the time from the start of kneading until the shearing force was applied to the kneaded product by 10 seconds, and was repeated until a nonuniform portion was generated. Since the time when the non-uniform portion was generated was the time when the curing started, the time from the start of kneading until the non-uniform portion was generated was defined as the operable time. Using the operable time obtained for each sample after storage, the change rate (%) of the operable time was calculated from the following equation. The absolute value of the calculated value was used as the change rate (%).
Percent change in operable time (%) = [(time after 1 day storage−time after 3 year storage) / time after 1 day storage] × 100
When the operable time is from 300 seconds to 500 seconds, the operation allowance time is sufficient and excellent in curability, and when the change rate is 10% or less, it can be determined that the change is small.

Test Example 2 (Tensile bond strength to bovine dentin)
The lip surface of bovine mandibular anterior teeth was polished with silicon carbide paper under running water to expose the flat surface of dentin. The exposed flat surface was further polished with # 1000 silicon carbide paper under running water. After polishing, the surface water was dried by air blowing. A 150 μm thick adhesive tape having a 3 mm diameter round hole was affixed to the smooth surface after drying to define the adhesion area. Next, “ED primer II” solution A and solution B (manufactured by Kuraray Medical Co., Ltd.) were collected in equal amounts in a dental mixing dish and mixed. The obtained mixed solution was applied to a smooth surface of a round hole having a diameter of 3 mm, and after 20 seconds, the volatile matter on the surface was blown to dry. Subsequently, A paste and B paste collected in equal amounts on dental kneaded paper were mixed with a dental kneading rod for 20 seconds. ) On one end face (circular cross section), and the end face on the side on which the kneaded material is placed so that the center of the round hole and the center of the stainless steel cylindrical rod substantially coincide with each other. And a stainless steel cylindrical rod was pressed and bonded perpendicularly to the smooth surface to obtain a sample. Five samples were prepared. After removing the excess kneaded material protruding from the periphery of the stainless steel cylindrical rod when pressed, the sample was allowed to stand at room temperature for 1 hour and immersed in distilled water for 24 hours. The sample immersed in distilled water was allowed to stand in an incubator for 24 hours, and then the tensile bond strength was measured at a crosshead speed of 2 mm / min with a universal testing machine (manufactured by Shimadzu Corporation). The value (average bond strength) was determined. Moreover, the change rate (%) of tensile adhesive strength was computed from the following formula | equation using the average adhesive strength obtained about the sample after each preservation | save. The absolute value of the calculated value was used as the rate of change (%).
Tensile bond strength change rate (%) = [(average adhesive strength after 1 day storage−average adhesive strength after 3 years storage) / average adhesive strength after 1 day storage] × 100
When the tensile bond strength is 7.0 MPa or more, the adhesiveness is excellent, and when the change rate is 15% or less, it can be determined that the change is small.

  From the results of Tables 1 and 2, the resin cements of the examples containing basic fillers were able to be operated after being stored at 4 ° C for 1 day and bovine teeth compared to the resin cements of comparative examples not containing basic fillers. It can be seen that the difference between the tensile bond strength to the dentin and the operable time after storage at 4 ° C. for 3 years and the tensile bond strength to the bovine dentin are small, that is, excellent in storage stability.

  The dental composition of the present invention is suitably used in the field of dentistry when adhering a dentine and a restoration for a crown.

Claims (8)

  A dental composition comprising a polymerizable monomer (a), a filler (b), an oxidizing agent (c), a reducing agent (d) and a polymerization accelerator (e), wherein the filler (b) A dental composition comprising a filler (b ′) surface-treated with a surface treatment agent comprising an organic compound (p) having a basic functional group.   The dental composition according to claim 1, wherein the organic compound (p) having a basic functional group is an alkylsilane compound having an amino group.   Alkylsilane compounds having an amino group include 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 3- The dental composition according to claim 2, which is at least one selected from the group consisting of (ureido) propyltriethoxysilane.   A dental composition comprising a first agent containing an oxidizing agent (c) and a second agent containing a reducing agent (d), wherein the first agent and the second agent are polymerizable monomers ( The dental composition according to any one of claims 1 to 3, comprising a), and either or both of the first agent and the second agent contain a filler (b ').   The dental composition of Claim 4 in which the agent containing a filler (b ') contains a polymerization accelerator (e) among 1st agent and 2nd agent.   Furthermore, the dental composition in any one of Claims 1-5 formed by containing a photoinitiator (f).   Polymerization accelerator (e) is 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, 4-N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4 -N, N-dimethylaminobenzophenone, sodium benzenesulfinate, sodium p-toluenesulfinate, sodium 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate, sodium sulfite, sulfurous acid The dental composition according to any one of claims 1 to 6, which is at least one selected from the group consisting of potassium, calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, and potassium hydrogen sulfite.   A dental cement comprising the dental composition according to claim 1.