JP2018172332A - Method for producing silane coupling agent having radical polymerizable group requiring urethanization reaction and dental curable composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for synthesizing a silane coupling agent using a urethanization reaction without using an organic tin compound to solve the problem of yellowing of a silane coupling agent itself or yellowing with time of a cured product of a dental curable composition containing an organic filler treated with the silane coupling agent since an inorganic filler blended in a dental curable composition is surface-modified with the silane coupling agent in order to improve mechanical strength or wettability and a soluble organic tin compound has been conventionally used in the silane coupling agent requiring a urethanization reaction.SOLUTION: There is provided a method for synthesizing a silane coupling agent in which no organic tin compound is contained in the silane coupling agent synthesized using a heterogeneous tertiary amine-supported catalyst without using a soluble organic tin compound in the urethanization reaction in synthesizing a silane coupling agent.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a silane coupling agent having a radical polymerizable group and a dental curable composition containing an inorganic filler surface-modified with the silane coupling agent.

Silane coupling agents having radically polymerizable groups are widely used in the industrial and medical / dental fields. Their purpose is to increase the affinity between the radical polymerizable monomer and the filler and to improve the mechanical strength of the material.

As prior art aimed at improving the durability of materials and the filling rate of inorganic fillers, a method using a silane coupling agent having a long alkyl chain (Patent Documents 1 and 2) and a silane coupling agent having a fluoroalkylene group are used. A method (Patent Document 3) and a method using a silane coupling agent having many polymerizable groups (Patent Document 4) have been proposed.

JP-A-2015-196682 JP-A-2015-196684 JP 2015-196685 JP-A-2015-196686 JP 6-33290

However, the soluble tin catalyst remains in the silane coupling agent having a radical polymerizable group described in Patent Documents 1 to 4. Therefore, the dental curable composition containing the synthesized silane coupling agent and the inorganic filler surface-modified using the silane coupling agent has a problem of yellowing with time. Further, the purification of the silane coupling agent by thin film distillation in Patent Document 5 has a limit in the molecular weight that can be distilled. Even if the molecular weight is distillable, a large amount of energy is required for thin-film distillation, which increases the manufacturing cost.

The present invention relates to a production method of synthesizing a silane coupling agent having a radical polymerizable group without using a soluble tin catalyst for urethanization, and a silane coupling agent having the radical polymerizable group. The present invention relates to a dental curable composition comprising a surface-modified inorganic filler.

As a result of intensive studies by the inventors, no soluble tin catalyst is included by using a tertiary amine supported catalyst that is a heterogeneous catalyst without using a soluble tin catalyst during the urethanization reaction in the synthesis of a silane coupling agent. It was possible to synthesize a silane coupling agent that did not turn yellow over time.

By using a heterogeneous catalyst tertiary amine supported catalyst without using a soluble tin catalyst during the urethanization reaction in the synthesis of a silane coupling agent, it does not contain a soluble tin catalyst in the synthesis process, and over time It became possible to synthesize silane coupling agents that did not turn yellow. The tertiary amine-supported catalyst, which is a heterogeneous catalyst, can be easily isolated from the silane coupling agent after synthesis by filtration or centrifugation.

More specifically, since the tertiary amine-supported catalyst that is a heterogeneous catalyst can be easily isolated by filtration or centrifugation after synthesis, the synthesized silane coupling agent does not contain a soluble tin catalyst. This made it possible to synthesize a silane coupling agent that did not turn yellow over time. In addition, by modifying the surface of the inorganic filler using the silane coupling agent, it became possible to produce a dental curable composition that does not yellow over time.

Furthermore, the intramolecular structure includes -NH-, -S-, -NH-C (O) -O-, -NH-C (O) -S-, -NH-C (O) -NH-, -C ( By using a silane coupling agent having a polar connecting group such as O) -S-, -CH (OH) -CH ₂ -S-, -CH (OH) -CH ₂ -O- High mechanical strength and durability were obtained when used in dental curable compositions. That is, since the inorganic filler surface-modified with the silane coupling agent having the above-described chemical structure has high affinity and high hydrophobicity for the radical polymerizable monomer, the cured body of the produced dental curable composition High mechanical strength and durability were obtained.

The method for producing a silane coupling agent having a radically polymerizable group in the present invention is characterized by using a tertiary amine-supported catalyst which is a heterogeneous catalyst. Specifically, when synthesizing a silane coupling agent having a radical polymerizable group, first, depending on the structure of the target silane coupling agent, a radical polymerizable group and an unsaturated double bond can be obtained by any synthesis method. Is synthesized at both ends. Thereafter, a hydrosilane reaction is performed on the compound having a radical polymerizable group and an unsaturated double bond at both ends by using a silane compound to synthesize a silane coupling agent. In the case of synthesizing a compound having a radical polymerizable group and an unsaturated double bond at both ends before synthesizing via a urethanization reaction before the hydrosilylation reaction, the third invention is a heterogeneous catalyst. It is characterized by using a secondary amine supported catalyst.

The urethanization reaction is preferably performed in a column, reaction vessel, or microreactor in which a tertiary amine supported catalyst is enclosed. Moreover, it is preferable to finally remove the tertiary amine-supported catalyst by filtration and / or centrifugation.

In the present invention, a solvent may be added when the urethanization reaction is performed and when the hydrosilylation reaction is performed. When the viscosity of the product is high, it is preferable to use a solvent. However, any solvent may be used as long as it has no reactivity with the substrate and dissolves the raw material and the product.

In the present invention, a carrier that preferably supports a tertiary amine, which is a heterogeneous catalyst used in the urethanization reaction in the synthesis of a silane coupling agent having a radical polymerizable group, includes silica, alumina, soda glass, activated carbon, and the like. More preferred are silica, alumina, and soda glass, and more preferred are silica and soda glass. Moreover, those shapes are not particularly limited, and may be either crushed or spherical. Furthermore, their diameter is preferably 10 nm to 1 mm, more preferably 20 nm to 0.5 mm, and even more preferably 30 nm to 0.3 mm.

The supported tertiary amine skeleton includes 2-((λ ³ methyl) imino) -N, N-dimethylethane-1-amine group, 3-((λ ³ -methyl) imino) -N, N- Dimethylpropan-1-amine group, 4-((λ ³ -methyl) imino) -N, N-dimethylbutane-1-amine group, 2-((λ ³ -methyl) imino) -N, N-diethylethane -1-amine group, 2-((λ ³ -methyl) imino) -N, N-diethylethane-1-amine group, 4-((λ ³ -methyl) imino) -N, N-diethylbutane-1 -Amine group, N- (2-((λ ³ -methyl) imino) ethyl) -N-propylpropan-1-amine group, 3-((λ ³ -methyl) imino) -N, N-dipropylpropane -1-amine group, 4-((λ ³ -methyl) imino) -N, N-dipropylbutan-1-amine group, N- (2-((λ ³ -methyl) imino) ethyl) -N- Isopropylpropan-2-amine group, 3-((λ ³ -methyl) imino) -N, N-diisopropylpropan-1-amine group, 4-((λ ³ -methyl) imino) -N, N-diisopropylbutane -1-A Down group, 2 - ((λ ³ - methyl) imino) -N- ethyl -N- methylethane-1-amine, ³ - ((λ 3 - methyl) imino) -N- ethyl -N- methylpropan -1 -Amine group, 4-((λ ³ -methyl) imino) -N-ethyl-N-methylbutan-1-amine group, 4-(((λ ³ -methyl) imino) methyl) -N, N-dimethylaniline Group, 4- (2-((λ ³ -methyl) imino) ethyl) -N, N-dimethylaniline group, 4- (3-((λ ³ -methyl) imino) propyl) -N, N-dimethylaniline Group, 4- (3-((λ ³ -methyl) imino) propyl) -N, N-dimethylaniline group, 4- (4-((λ ³ -methyl) imino) butyl) -N, N-dimethylaniline Group, 4- (λ ³ -methyl) -N, N-dimethylaniline group, 3- (λ ³ -methyl) -N, N-dimethylaniline group, 2- (λ ³ -methyl) -N, N-dimethyl Aniline group, N, N-diethyl-4- (λ ³ -methyl) aniline group, 4- (λ ³ -methyl) -N, N-dipropylaniline group, N, N-diisopropyl-4- (λ ^3- Methyl) aniline group, N-ethyl-4- (λ ³ -methyl) -N-methylaniline group, N-isopropyl-4- (λ ³ -methyl) -N-methylaniline group, 4- (λ ³ -methyl) -N-methyl-N-propylaniline group N, N-diethyl-3- (λ ³ -methyl) aniline group, 3- (λ ³ -methyl) -N, N-dipropylaniline group, N, N-diisopropyl-3- (λ ³ -methyl) Aniline group, N-ethyl-3- (λ ³ -methyl) -N-methylaniline group, N-isopropyl-3- (λ ³ -methyl) -N-methylaniline group, 3- (λ ³ -methyl)- N-methyl-N-propylaniline group, N, N-diethyl-2- (λ ³ -methyl) aniline group, 2- (λ ³ -methyl) -N, N-dipropylaniline group, N, N-diisopropyl -2- (λ ³ -methyl) aniline group, N-ethyl-2- (λ ³ -methyl) -N-methylaniline group, N-isopropyl-2- (λ ³ -methyl) -N-methylaniline group, It is preferable that at least one selected from 2- (λ ³ -methyl) -N-methyl-N-propylaniline groups is supported.

The addition amount of the tertiary amine-supported catalyst in the present invention is arbitrary, but it is preferable that the tertiary amine corresponding to 100 ppm to 1% in molar equivalent is supported on the substrate to be reacted.

The molecular structure of the silane coupling agent having a radical polymerizable group produced by the production method of the present invention is shown in [Chemical Formula 1]. Specifically, A represents H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ − group (C ₆ H ₄ represents a phenylene group). B represents -C (O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH-, -NH-C (O ) -S-, represents -NH-C (O) -O- group, Z is a straight-chain or branched alkylene group of C ₁ -C _30, Y is, -NH-C (O) - O—, —NH—C (O) —S— group, wherein R ² is a C _{7 to} C ₃₀ linear or branched alkylene group, —S—, —NH—, —NR ⁴ — ( R ⁴ represents an alkylene group), —CH ₂ —C ₆ H ₄ — (C ₆ H ₄ represents a phenylene group), —C (O) —O—, —O— group, and R ³ represents C _{1 to} C _{6 represents} a linear or branched alkyl group, R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group, a phenyl group or a halogen atom, and when n is 0, at least 1 The above halogen atoms are bonded to Si. Here, a is 1 to 6, and n is 0 to 3.

The chemical structures of typical compounds are described below.

The inorganic filler surface-treated with the silane coupling agent produced by the production method of the present invention is not particularly limited, and specific examples include silicon dioxide, alumina, silica-titania, silica-titania-barium oxide, silica- Zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate Glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. It is.

In particular, fluoroaluminosilicate barium glass, fluoroaluminosilicate strontium glass, fluoroaluminosilicate glass, and the like used for dental glass ionomer cement, resin reinforced glass ionomer cement, and resin cement can be preferably used. The fluoroaluminosilicate glass mentioned here has silicon oxide and aluminum oxide as a basic skeleton, and contains an alkali metal for introducing non-crosslinkable oxygen. Furthermore, it has an alkaline earth metal containing strontium and fluorine as a modification / coordination ion.

Furthermore, lanthanoid series elements can be incorporated into the skeleton in order to impart radiopacity. This lanthanoid series element can also act as a modifying / coordinating ion depending on the composition range. These inorganic fillers may be used alone or in combination. The average particle size of the inorganic filler is preferably 0.001 to 100 μm, more preferably 0.001 to 10 μm. Furthermore, the shape of the inorganic filler may be either spherical or indefinite. Further, regarding the treatment concentration of the silane coupling agent having a radical polymerizable group produced by the production method of the present invention, although it depends on the silanol group density (mol / g) of the inorganic filler, It is preferably from 1 to 10 times the density. If the treatment is lower than 1X, the silane coupling agent cannot be introduced sufficiently, and if it exceeds 10 times, a condensate of only the silane coupling agent is generated, which affects the mechanical strength. . The filling amount of the inorganic filler treated with the silane coupling agent produced by the production method of the present invention is not particularly limited, but is preferably in the range of 25 to 90% by weight. When it is less than 25% by weight, the cured product has a low mechanical (physical) strength, which is not preferable. On the other hand, when the content exceeds 90% by weight, the prepared paste is too high in viscosity, and clinical operability is poor, which is not preferable.

As the radical polymerizable monomer used in the dental curable composition of the present invention, any of those used in the dental field can be used without any limitation, but preferably has a urethane bond in its molecular skeleton. This is because the urethane bond (—NH—C (O) —O—) effectively forms a hydrogen bond with the silane coupling agent produced by the production method of the present invention.

Specifically, 7,7,9-trimethyl-4,13-dioxo-3, 14 synthesized by urethane reaction of 2,2,4-trimethylhexamethylene diisocyanate and 2-hydroxyethyl methacrylate (HEMA). -Dioxa-5, 12-diazahexadecane-1, 16-diyl dimethacrylate (UDMA) or HEMA or HEA with 2,4-toluylene diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate or hexamethylene diisocyanate Radically polymerizable monomers synthesized by urethane reaction, urethane diacrylates obtained by reaction of aliphatic and / or aromatic diisocyanates with glycerol (meth) acrylate and 3-methacrylol-2-hydroxypropyl ester, 1,3-bis (2-isocyanate, 2-propyl) benzene and hydro Urethane reaction product of a compound having a sheet group. More specifically, 2,7,7,9,15-pentamethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyl diacrylate, 2,7, 7,9,15-Pentamethyl-4,13-18-trioxo-3,14,17-trioxa-5,12-diazaicos-19-enyl methacrylate, 2,8,10,10,15-pentamethyl-4,13 , 18-trioxo-3,14,17-trioxa-5,12-diazaicos-19-enyl methacrylate, 2,7,7,9,15-pentamethyl-4,13-dioxo-3,14-dioxa-5, 12-diazahexadecane-1,16-diylbis (2-methylacrylate), 2,2 '-(cyclohexane-1,2-diylbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis ( Propane-2,1-diyl) diacrylate, 2-((2-(((1- (acryloyloxy) propan-2-yloxy) carbonylamino) methyl) cyclohexyl) methylcarbamoyloxy Propyl methacrylate, 2,2 '-(cyclohexane-1,2-diylbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) bis (2-methylacrylate) 2,2 '-(bicyclo [4.1.0] heptane-3,4-diylbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) diacrylate, 2-((4-(((1- (acryloyloxy) propan-2-yloxy) carbonylamino) methyl) bicyclo [4.1.0] heptan-3-yl) methylcarbamoyloxy) propyl methacrylate, 2,2'- (Bicyclo [4.1.0] heptane-3,4-diylbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) bis (2-methylacrylate), 7 , 7,9-trime -4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyl diacrylate, 7,7,9-trimethyl-4,13,18-trioxo-3,14, 17-trioxa-5,12-diazaikos-19-enyl methacrylate, 8,10,10-trimethyl-4,13,18-trioxo-3,14,17-trioxa-5,12-diazaikos-19-enyl methacrylate, 7 , 7,9-Trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diylbis (2-methyl acrylate), 4,13-dioxo-3,14-dioxa -5,12-diazahexadecane-1,16-diyl diacrylate, 4,13,18-trioxo-3,14,17-trioxa-5,12-diazaicos-19-enyl methacrylate, 4,13-dioxo- 3,14-dioxa-5,12-diazahexadecane-1,16-diylbis (2-methyl acrylate), 2- (1- (2-((2- (acryloyloxy) ethoxy) carbonylamino) -4,4 -Dimethylcyclohexyl) Tylcarbamoyloxy) ethyl methacrylate, 2- (1- (2-((2- (acryloyloxy) ethoxy) carbonylamino) ethyl) -5,5-dimethylcyclohexylcarbamoyloxy) ethyl methacrylate, 2- (2- ( ((1- (methacryloyloxy) propan-2-yloxy) carbonylamino) methyl) -2,5,5-trimethylcyclohexylcarbamoyloxy) propane-1,3-diylbis (2-methyl acrylate), 2- ( 2-((((1- (methacryloyloxy) propan-2-yloxy) carbonylamino) methyl) -2,5,5-trimethylcyclohexylcarbamoyloxy) propane-1,3-diyl diacrylate, 2- (2 -((((1- (acryloyloxy) propan-2-yloxy) carbonylamino) methyl) -2,5,5-trimethylcyclohexylcarbamoyloxy) propane-1,3-diylbis (2 -Methyl acrylate), 3- (15- (2- (acryloyloxy) ethyl) -3,12,19-trioxo-2,13,18-trioxa-4,11-diazahenicos-20-enyl) pentane-1,5 -Diyl diacrylate, 3- (15- (2- (acryloyloxy) ethyl) -3,12,19-trioxo-2,13,18-trioxa-4,11-diazahenicos-20-enyl) pentane-1,5 -Diylbis (2-methylacrylate), 2,2 '-(cyclhexane-1,2-diylbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) Diacrylate, 2-((2-(((2- (acryloyloxy) ethoxy) carbonylamino) methyl) cyclohexyl) methylcarbamoyloxy) ethyl methacrylate, 2,2 '-(cyclixane-1,2-diylbis (methylene )) Bis (azanediyl) bis (oxomethylene) bis ( Xyl) bis (ethane-2,1-diyl) bis (2-methylacrylate), 2,15-bis (cyclohexyloxymethyl) -4,13-dioxo-3,14-dioxa-5,12-diazahexadecane -1,16-diyldiacrylate, 2,15-bis (cyclohexyloxymethyl) -4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diylbis (2-methylacrylate) ), 2,15-bis (cyclohexyloxymethyl) -4,13,18-trioxo-3,14,17-trioxa-5,12-diazicos-19-enyl methacrylate, 1,18-bis (cyclohexyloxy)- 5,14-Dioxo-4,15-dioxa-6,13-diazaoctadecane-2,17-diyl diacrylate, 1- (cyclohexyloxy) -17- (cyclohexyloxymethyl) -5,14,19-trioxo -4,15,18-trioxa-6,13-diazahenicos-20-en-2-yl methacrylate, 1,18-bis (cyclohexyl) Xy) -5,14-dioxo-4,15-dioxa-6,13-diazaoctadecane-2,17-diylbis (2-methylacrylate), 7,7,9-trimethyl-4,13-dioxo-3 , 14-Dioxa-5,12-diazahexadecane-1,16-diylbis (2-methyl acrylate), 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-dia The hexadecane-1,16-diyl diacrylate, 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) Bis (2-methacrylate), 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) diacrylate, 2 -(3-(((2- (acryloyloxy) ethoxy) carbonylamino) methyl) benzylcarbamoyloxy) ethyl methacrylate, 2 , 2 '-(1,3-phenylenebis (methylene)) bis (methylazanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) bis (2-methacrylate), 2,2 '-(1,3-phenylenebis (methylene)) bis (methylazanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) diacrylate, 2-((3-((( (2- (acryloyloxy) ethoxy) carbonyl) (methyl) amino) methyl) benzyl) (methyl) carbamoyloxy) ethyl methacrylate, 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxo Methylene) bis (oxy) bis (propane-2,1-diyl) bis (2-methylacrylate), 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (Oxy) Bis (propane-2,1-diyl) diacrylate, 2- (3-(((2- (acryloyloxy) ethoxy) carbonylamino) methyl) benzylcarbamoyloxy) propyl methacrylate, 2- (3-(((1 -(Acryloyloxy) propan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) ethyl methacrylate, 4,4 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bisoxomethylene) bis (oxy ) Bis (4,1-phenylene) bis (2-methylacrylate), 4,4 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bisoxomethylene) bis (oxy) bis (4,1 -Phenylene) diacrylate, 4- (3-(((4- (acryloxy) phenoxy) carbonylamino) methyl) benzylcarbamoyloxy) phenyl methacrylate 4,4 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (butane-4,1-diyl) bis (2-methylacrylate), 4 , 4 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (butane-4,1-diyl) diacrylate, 4- (3-(((4 -(Acryloyloxy) butoxy) carbonylamino) methyl) benzylcarbamoyloxy) butyl methacrylate, 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis ( 3-phenoxypropane-2,1-diyl) bis (2-methylacrylate), 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis ( 3-phenoxy Lopan-2,1-diyl) diacrylate, 2- (3-(((1- (acryloyloxy) -3-phenoxypropan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) -3-phenoxypropyl methacrylate 2-2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (phenylamino) propane-2,1-diyl) bis (2- Methyl acrylate), 2-2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (phenylamino) propane-2,1-diyl) di Acrylate, 2- (3-(((1- (acryloyloxy) -3- (phenylamino) propan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) -3- (phenylamino) propyl meta Relate, 2,2 '-(1,3phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (phenylthio) propane-2,1-diyl) bis (2-methyl Acrylate), 2,2 '-(1,3 phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (phenylthio) propane-2,1-diyl) diacrylate, 2 -(3-(((1- (Acryloxy) -3- (phenylthio) propan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) -3- (phenylthio) propyl methacrylate, 2,2 '-(1 , 3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (benzyloxy) propane-2,1-diyl) bis (2-methylacrylate), 2,2 ' -(1,3-fe Renbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (benzyloxy) propane-2,1-diyl) diacrylate, 2- (3-(((1- (acryloyloxy) -3- (Benzyloxy) propan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) -3- (benzyloxy) propyl methacrylate, 2,2 '-(1,3-phenylenebis (methylene)) bis (Azandiyl) bis (oxomethylene) bis (oxy) bis (3- (methacryloyloxy) propane-2,1-diyl) dibenzoate, 2,2 '-(1,3-phenylenebis (methylene)) bis (Azandiyl) bis (oxomethylene) bis (oxy) bis (3- (acryloyloxy) propane-2,1-diyl) dibenzoate, 2,2 '-(1,3-phenylenebis (methylene)) bis ( Zandiyl) bis (oxomethylene) bis (oxy) bis (3- (2-phenylacetoxy) propane-2,1-diyl) bis (2-methylacrylate), 2,2 '-(1,3-phenylenebis ( Methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (2-phenylacetoxy) propane-2,1-diyl) diacrylate, 2- (3-(((1- (acryloyloxy) -3- (2-phenylacetoxy) propan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) -3- (2-phenylacetoxy) propyl methacrylate 2, 2 '-(2, 2'-(1, 3-phenylene) bis (propane-2.2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) bis (2-methacrylate), 2, 2'- (2,2 '-(1,3-phenylene) bis (prop -2. 2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) diacrylate, 2- (2- (3- (2-((2- ( Acryloyloxy) ethoxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) ethyl methacrylate, 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2) , 2-diyl)) bis (methylazanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) bis (2-methacrylate), 2, 2 '-(2,2'-( 1,3-phenylene) bis (propane-2,2-diyl)) bis (methylazanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) diacrylate, 2-((2 -(3- (2-(((2- (acryloyloxy) ethoxy) carbonyl) (methyl) amino) prop -2-yl) phenyl) propan-2-yl) (methyl) carbamoyloxy) ethyl methacrylate, 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl) ) Bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) bis (2-methylacrylate), 2,2 '-(2,2'-(1,3-phenylene) Bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) diacrylate, 2- (2- (3- (2-(( 2- (acryloyloxy) ethoxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) propyl methacrylate, 2- (2- (3- (2-((1- (acryloyloxy) propane-2) -Yloxy) carbonylamino) propan-2-ylcarbamoyloxy) ethyl meta Relate, 4,4 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (4,1- Phenylene) bis (2-methylacrylate), 4,4 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis ( Oxy) bis (4,1-phenylene) diacrylate, 4- (2- (3- (2-((4- (acryloyloxy) phenoxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyl Xyl) phenyl methacrylate, 4,4 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (butane) -4,1-diyl) bis (2-methacrylate), 4,4 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (a Ndiyl) bis (oxomethylene) bis (oxy) bis (butane-4,1-diyl) diacrylate, 4- (2- (3- (2-((4-acryloyloxy) butoxy) carbonylamino) propane-2- Yl) phenyl) propan-2-ylcarbamoyloxy) butyl methacrylate, 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis ( Oxomethylene) bis (oxy) bis (3-phenoxypropane-2,1-diyl) bis (2-methacrylate), 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2 , 2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3-phenoxypropane-2,1-diyl) diacrylate, 2- (2- (3- (2-((1- (Acryloyloxy) -3-phenoxypropan-2-yloxy) carbonylamino) propan-2-yl) Phenyl) propan-2-ylcarbamoyloxy) -3-phenoxypropyl methacrylate, 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) Bis (oxomethylene) bis (oxy) bis (3- (phenylamino) propane-2,1-diyl) bis (2-methacrylate), 2,2 '-(2,2'-(1,3-phenylene) Bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (phenylamino) propane-2,1-diyl) diacrylate, 2- (2- (3 -(2-((1- (acryloyloxy) -3- (phenylamino) propan-2-yloxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) -3- (phenylamino ) Propyl methacrylate, 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2 , 2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (phenylthio) propane-2,1-diyl) bis (2-methylacrylate), 2,2 '-(2, 2 '-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (phenylthio) propane-2,1-diyl) di Acrylate, 2- (2- (3- (2-((1- (acryloyloxy) -3- (phenylthio) propan-2-yloxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoy Roxy) -3- (phenylthio) propyl methacrylate, 2-2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (3- (Benzyloxy) propane-2,1-diyl) bis (2-methylacrylate) 2-2 ′-(2,2 ′-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (3- (benzyloxy) propane-2, 1-diyl) diacrylate, 2- (2- (3- (2-((1- (acryloyloxy) -3- (benzyloxy) propan-2-yloxy) carbonylamino) propan-2-yl) phenyl) propane -2-ylcarbamoyloxy) -3- (benzyloxy) propyl methacrylate, 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) ) Bis (oxomethylene) bis (oxy) bis (3- (methacryloyloxy) propane-2,1-diyl) dibenzoate, 2,2 '-(2,2'-(1,3-phenylene) bis ( Propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (acryloyloxy) propyl Lopan-2,1-diyl) dibenzoate, 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (Oxy) bis (3- (2-phenylacetoxy) propane-2,1-diyl) bis (2-methacrylate), 2,2 '-(2,2'-(1,3-phenylene) bis (propane- 2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (2-phenylacetoxy) propane-2,1-diyl) diacrylate, 2- (2- (3- ( 2-((1- (acryloyloxy) -3- (2-phenylacetoxy) propan-2-yloxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) -3- (2- And phenylacetoxy) propyl methacrylate.

As the polymerization initiator contained in the dental curable composition of the present invention, a polymerization initiator used in the industry can be selected and used, and among them, a polymerization initiator used for dental use is preferably used. . In particular, polymerization initiators for photopolymerization and chemical polymerization are used alone or in combination of two or more. Specifically, among the polymerization initiators contained in the dental curable composition of the present invention, as the photopolymerization initiator, (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or thioxanthones Quaternary ammonium salts, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, α-amino ketone compounds, and the like. Further, the proportion thereof is preferably 0.5 wt% to 5 wt% with respect to the radical polymerizable monomer. If the concentration is lower than 0.5 wt%, the amount of unpolymerized radically polymerizable monomer increases, so the mechanical strength decreases. In addition, when the concentration is higher than 5 wt%, the degree of polymerization decreases and the mechanical strength decreases.

Specific examples of acylphosphine oxides used as photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenyl. Phosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6 -Dimethylphenyl) phosphonate and the like. 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) phenylphosphine oxide, (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine Examples include oxides.

Specific examples of thioxanthones or quaternary ammonium salts of thioxanthones used as photopolymerization initiators include, for example, 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-propaneaminium 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-propanaminium chloride, 2-hydroxy-3- (3,4-dimethyl -9H-thioxanthen-2-yloxy) -N, N , N-trimethyl-1-propaneaminium chloride, 2-hydroxy-3- (1,3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1 -Propanaminium chloride and the like.

Specific examples of α-diketones used as photopolymerization initiators include, for example, diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4, 4'-oxybenzyl, acenaphthenequinone, etc. are mentioned.

Specific examples of the coumarin compound used as the photopolymerization initiator 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, 3-benzoylbenzo [f] coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbo Nyl-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-nitrobenzoyl) benzo [f] coumarin, 3- ( 4-Ethoxycinnamoyl) -7-methoxycoumarin, 3- (4-dimethylaminocinnamoyl) coumarin, 3- (4-diphenylaminocinnamoyl) coumarin, 3-[(3-dimethylbenzothiazo -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-benzothia Zoyl) -7- (dibutylamino) coumarin, 3- (2-benzimidazoloyl) -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-benzo Thiazoyl) -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one Compound etc. are mentioned.

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

Specific examples of anthraquinones used as photopolymerization initiators include, for example, anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethyl Anthraquinone, 1-hydroxyanthraquinone and the like can be mentioned.

Specific examples of benzoin alkyl ethers used as photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Specific examples of the α-amino ketones used as the photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

Among 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, a composition having excellent photocurability in the visible and near-ultraviolet regions and having sufficient photocurability can be obtained using any light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp.

Of the polymerization initiators contained in the dental curable composition of 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.

Specific examples of the ketone peroxide used as the chemical polymerization initiator include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.

Specific examples of hydroperoxides used as chemical polymerization initiators include, for example, 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydro gen. Examples thereof include peroxide and 1,1,3,3-tetramethylbutyl hydroperoxide.

Specific examples of diacyl peroxides used as chemical polymerization initiators include, for example, acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2 1,4-dichlorobenzoyl peroxide and lauroyl peroxide.

Specific examples of dialkyl peroxides used as chemical polymerization initiators include, for example, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di- (T-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne .

Specific examples of peroxyketals used as chemical polymerization initiators include, for example, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butyl) Peroxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane and 4,4-bis (t-butylperoxy) valeric acid-n -Butyl ester.

Specific examples of peroxyesters used as chemical polymerization initiators include, for example, α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2 , 4-Trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate , Di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-tilperoxyacetate, t-butylperoxybenzoate and t-butylperoxymaleate Rick acid etc. are mentioned.

Specific examples of peroxydicarbonates used as chemical polymerization initiators include, for example, di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxide. Examples thereof include oxydicarbonate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate and diallyl peroxydicarbonate.

Among 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.

Specific examples of the polymerization accelerator include amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, and the like. Is mentioned.

Amines used as polymerization accelerators are classified into aliphatic amines and aromatic amines. Specific examples of aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary fats such as diisopropylamine, dibutylamine and N-methyldiethanolamine. N-methylethanolamine, N-ethyldiethanolamine, N-n-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, tri Tertiary aliphatic amines such as ethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine And the like. Among these, tertiary aliphatic amines are preferable from the viewpoint of curability and storage stability of the composition, and among these, N-methyldiethanolamine and triethanolamine are more preferably used.

Specific examples of aromatic amines 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, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylaminobenzoic acid methyl ester, N, N-dimethylaminobenzoic acid-n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid-2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone, 4-dimethylaminobenzoic acid Examples include butyl acid. Among these, from the viewpoint of imparting excellent curability to the composition, N, N-di (2-hydroxyethyl) -p-toluidine, 4-N, N-dimethylaminobenzoic acid ethyl ester, N, N- Examples thereof include dimethylaminobenzoic acid-n-butoxyethyl ester and 4-N, N-dimethylaminobenzophenone.

Specific examples of sulfinic acid and its salts used as polymerization accelerators include, for example, p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, p-toluene. Calcium sulfinate, benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfinate , Potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate, 2, 4,6-triethylbenzenesulfinate sodium Lithium, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinate, Sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinate Examples thereof include calcium and the like, and sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferable.

Specific examples of the borate compound used as the polymerization accelerator include a borate compound having one aryl group in one molecule. For example, trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p -Fluorophenyl) 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- Butyloxyphenyl) boron, trialkyl (m-butyloxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron and Sodium salt, lithium salt, potassium salt of alkyl (m-octyloxyphenyl) boron (the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, n-dodecyl group, etc.) , Magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt and butylquinolinium salt It is done.

Further, specific examples of borate compounds having two aryl groups in one molecule include, for example, dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, and dialkyldi (3,5 -Bistrifluoromethyl) phenyl boron, dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron , Dialkyldi (m-nitrophenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi ( p-octyloxyphenyl) boron and dialkyldi (m-octyloxyphenyl) phospho Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium of urine (the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group and n-dodecyl group) Examples thereof include salts, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt and butylquinolinium salt.

Furthermore, specific examples of the borate compound having three aryl groups in one molecule include, for example, monoalkyltriphenyl boron, 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, monoalkyltri (p-octyloxyphenyl) Sodium salt and lithium salt of potassium and monoalkyltri (m-octyloxyphenyl) boron (alkyl group is one selected from n-butyl group, n-octyl group, n-dodecyl group, etc.) Salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc. Can be mentioned.

Further specific examples of the borate compound having four aryl groups in one molecule include, for example, tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5- Bistrifluoromethyl) phenyl boron, 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-octyloxyphenyl) boron, (p-fluorophenyl) tri Phenyl boron, (3,5-bistrifluoromethyl) phenyl triphenyl boron, (p-nitrophenyl) triphenyl boron, (m-butyloxyphenyl) triphenyl boron, (p-butyloxyphenyl) triphenyl boron, ( sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt of m-octyloxyphenyl) triphenylboron and (p-octyloxyphenyl) triphenylboron , 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.

Specific examples of the babituric acid derivative used as a polymerization accelerator include, for example, 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-trimethyl barbituric acid, 1,3-dimethyl-5-ethyl barbituric 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, 1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methyl Barbituric acid, 5- Lopyrbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric 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- Examples thereof include cyclohexyl barbituric acid, 1-benzyl-5-phenyl barbituric acid and thiobarbituric acid, and salts thereof (especially, alkali metal or alkaline earth metal is preferable). For example, sodium 5-butyl barbiturate, sodium 1,3,5-trimethylbarbiturate and sodium 1-cyclohexyl-5-ethylbarbiturate It is below.

Specific examples of particularly suitable barbituric acid derivatives include, for example, 5-butyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5 -Phenyl barbituric acid and sodium salts of these barbituric acids.

Specific examples of the triazine compound used as the polymerization accelerator 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-dimethoxyphenyl) 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 -Bi (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, Examples thereof include 6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine.

Among the triazine compounds exemplified above, 2,4,6-tris (trichloromethyl) -s-triazine is particularly preferable in terms of polymerization activity, and 2-phenyl-4 in terms 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.

Specific examples of the copper compound used as the polymerization accelerator include acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like.

Specific examples of tin compounds used as polymerization accelerators include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. Can be mentioned. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

The vanadium compound used as a polymerization accelerator is preferably an IV and / or V vanadium compound. Specific examples of the IV-valent and / or V-valent vanadium compounds include, for example, divanadium tetroxide (IV), vanadium acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), Oxobis (1-phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammon metavanadate (V), etc. Is mentioned.

Specific examples of halogen compounds used as polymerization accelerators include, for example, dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide. Etc.

Specific examples of aldehydes used as polymerization accelerators 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.

Specific examples of the thiol compound used as the polymerization accelerator include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, thiobenzoic acid and the like.

Hereinafter, a method for producing a silane coupling agent according to the present invention, the color stability of the obtained silane coupling agent, and a dental curable composition containing an inorganic filler surface-modified with those silane coupling agents. Preparation methods and physical characteristics will be described in detail, but the present invention is not limited to these descriptions.

Synthesis of tertiary amine supported catalyst (1)
A flanged four-necked flask (100 mL volume) equipped with a stirring blade, thermometer, dropping funnel and calcium chloride tube was charged with 30 mL of anhydrous ethanol, 5.0 g of anhydrous sodium sulfate and 7.46 g (0.05 mol) of 4- (dimethylamino) benzaldehyde. Further, the mixture was sufficiently stirred and dissolved at 25 ° C. Next, 3- (trimethoxysilyl) propan-1-amine: 8.97 g (0.05 mol) was weighed in the dropping funnel. While maintaining the four-necked flask at 25 ° C, 3- (trimethoxysilyl) propan-1-amine was added dropwise with stirring so that the internal temperature did not exceed 30 ° C. After completion of the dropping, stirring was continued for 24 hours for aging. After completion of aging, anhydrous sodium sulfate was removed by filtration, and the solvent was removed with an evaporator. The obtained synthesized product was a yellowish oily product, and the synthesized product was subjected to HPLC and FT-IR measurement. Analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by ATR method. As a result of HPLC measurement, the peaks of raw materials 4- (dimethylamino) benzaldehyde and 3- (trimethoxysilyl) propan-1-amine disappeared, and a new peak: N, N-dimethyl-4-((((3 -(Trimethoxysilyl) propyl) imino) methyl) aniline (molecular weight 310.5) was confirmed. Further, as a result of FT-IR measurement, it was confirmed that primary amine absorption and aldehyde absorption disappeared. The structural formula of the synthesized N, N-dimethyl-4-(((3- (trimethoxysilyl) propyl) imino) methyl) aniline is shown in [Chemical Formula 4].
Next, 1.0 g of N, N-dimethyl-4-(((3- (trimethoxysilyl) propyl) imino) methyl) aniline synthesized in a 100 mL eggplant flask equipped with a magnetic stir bar, 50 mL of toluene and silica gel (median particles) 10 g of a particle having a diameter of 100 μm) was added, and the mixture was refluxed with stirring in an oil bath for 24 hours, and N, N-dimethyl-4-(((3- (trimethoxysilyl) propyl) imino) methyl) aniline was supported on silica. Then, it returned to room temperature, the tertiary amine carrying | support catalyst was isolated by filtration, and it dried under reduced pressure. The structural formula of the synthesized tertiary amine supported catalyst is shown in [Chemical Formula 5]. In the structural formula, S represents silica of the support.

Synthesis of tertiary amine supported catalyst (2)
To a flanged four-necked flask (100 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser tube with calcium chloride tube, 30 mL of toluene, dibutyltin (IV) dilaurate: 18.5 mg (equivalent to 1000 ppm) and 2- (4- (Dimethylamino) phenyl) ethane-1-ol: 8.26 g (0.05 mol) was added and dissolved by stirring at 70 ° C. Next, (27) (3-isocyanatopropyl) trimethoxysilane: 10.27 g (0.05 mol) was weighed in the dropping funnel. While maintaining the four-necked flask at 70 ° C, (3-isocyanatopropyl) trimethoxysilane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropping, stirring was continued for 24 hours for aging. After completion of aging, the solvent was removed with an evaporator. The obtained synthesized product was an oily oil with very pale yellow color, and HPLC and FT-IR measurement of the synthesized product were performed. Analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by ATR method. As a result of HPLC measurement, the peaks of 2- (4- (dimethylamino) phenyl) ethan-1-ol and (3-isocyanatopropyl) trimethoxysilane as raw materials disappeared, and a new peak: 4- (dimethylamino ) Phenethyl (3- (trimethoxysilyl) propyl) carbamate (molecular weight 370.5) was confirmed. Further, as a result of FT-IR measurement, disappearance of hydroxyl group and isocyanate group absorption was confirmed. The structural formula of the synthesized 4- (dimethylamino) phenethyl (3- (trimethoxysilyl) propyl) carbamate is shown in [Chemical Formula 6].
Next, 4- (dimethylamino) phenethyl (3- (trimethoxysilyl) propyl) carbamate: 1.0 g, 50 mL of toluene and 10 g of alumina gel (median particle size 100 μm) were synthesized in a 100 mL eggplant flask equipped with a magnetic stir bar. In addition, the mixture was refluxed with stirring in an oil bath for 24 hours, and 4- (dimethylamino) phenethyl (3- (trimethoxysilyl) propyl) carbamate was supported on alumina. Then, after returning to room temperature and repeating washing and filtration with dry toluene, the tertiary amine-supported catalyst was isolated and dried under reduced pressure. The structural formula of the synthesized tertiary amine supported catalyst is shown in [Chemical Formula 7]. In the structural formula, S represents the support alumina.

Synthesis of tertiary amine supported catalyst (3)
A flanged four-necked flask (100 mL volume) equipped with a stirring blade, thermometer, dropping funnel and calcium chloride tube was charged with 30 mL of anhydrous ethanol, 5.0 g of anhydrous sodium sulfate and 5.76 g (0.05 mol) of 4- (dimethylamino) butanal. Further, the mixture was sufficiently stirred and dissolved at 25 ° C. Next, 3- (trimethoxysilyl) propan-1-amine: 8.97 g (0.05 mol) was weighed in the dropping funnel. While maintaining the four-necked flask at 25 ° C, 3- (trimethoxysilyl) propan-1-amine was added dropwise with stirring so that the internal temperature did not exceed 30 ° C. After completion of the dropping, stirring was continued for 24 hours for aging. After completion of aging, anhydrous sodium sulfate was removed by filtration, and the solvent was removed with an evaporator. The obtained synthesized product was a yellowish oily product, and the synthesized product was subjected to HPLC and FT-IR measurement. Analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by ATR method. As a result of HPLC measurement, the peaks of raw materials 4- (dimethylamino) butanal and 3- (trimethoxysilyl) propan-1-amine disappeared, and a new peak: (E) -N, N-dimethyl-4- ((3- (Trimethoxysilyl) propyl) imino) butan-1-amine (molecular weight 276.5) was confirmed. Further, as a result of FT-IR measurement, it was confirmed that primary amine absorption and aldehyde absorption disappeared. The structural formula of the synthesized (E) -N, N-dimethyl-4-((3- (trimethoxysilyl) propyl) imino) butan-1-amine is shown in [Chemical Formula 8].
Next, (E) -N, N-dimethyl-4-((3- (trimethoxysilyl) propyl) imino) butan-1-amine 1.0 g synthesized in a 100 mL eggplant flask equipped with a magnetic stir bar, toluene 50 mL And 10 g of soda glass beads (median particle size 100 μm) were added, and the mixture was stirred and refluxed in an oil bath for 24 hours. (E) -N, N-dimethyl-4-((3- (trimethoxysilyl) propyl) imino) butane -1-amine was supported on glass. Then, it returned to room temperature, the tertiary amine carrying | support catalyst was isolated by filtration, and it dried under reduced pressure. The structural formula of the synthesized tertiary amine-supported catalyst is shown in [Chemical 9]. In the structural formula, S represents the glass of the support.

(Synthesis Example 1) Synthesis of a silane coupling agent having a radical polymerizable group 10-Undecen-1-ol: 17.0 g in a four-necked flask (100 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser (0.10 mol), heterogeneous catalyst synthesized in synthesis of tertiary amine supported catalyst (1): 5.0 g and p-methoxyphenol: 16.3 mg (corresponding to 500 ppm) were added and dissolved. Next, 2-isocyanate ethyl methacrylate: 15.5 g (0.10 mol) was weighed in the dropping funnel. The four-necked flask was immersed in an oil bath heated to 75 ° C, and 2-isocyanatoethyl methacrylate was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropping, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, the four-necked flask was removed from the oil bath, the reaction product was returned to room temperature, the tertiary amine-supported catalyst was removed by centrifugation, and HPLC and FT-IR measurements were performed. Analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by ATR method. As a result of HPLC measurement, the peaks of 10-undecen-1-ol and 2-isocyanatoethyl methacrylate, which are raw materials, disappeared, and a new peak: 2-((Undec-10-enyloxy) carbonylamino) ethyl methacrylate (molecular weight 325.5) was confirmed. Further, as a result of FT-IR measurement, it was confirmed that isocyanate group absorption and hydroxy group absorption disappeared. Next, Siliacat ^@ Pt ⁰ (SILICYCLE), a platinum-supported heterogeneous catalyst, was added to 32.6 g of 2-((Undec-10-enyloxy) carbonylamino) ethyl methacrylate synthesized in the above procedure in a four-necked flask (300 mL volume). 5.0 g and 100 mL of toluene were added and sufficiently stirred and dispersed. Separately, 16.4 g of triethoxysilane was weighed in a dropping funnel. While stirring the four-necked flask at room temperature, triethoxysilane was added dropwise so that the internal temperature did not exceed 35 ° C. After completion of the dropwise addition, the reaction was continued for 12 hours for aging. After completion of ripening, the platinum-supported heterogeneous catalyst was removed by centrifugation, and the solvent was removed by an evaporator, followed by HPLC and FT-IR measurement. As a result of HPLC measurement, peaks of 2-((Undec-10-enyloxy) carbonylamino) ethyl methacrylate and triethoxysilane, which are raw materials, disappeared, and a new peak: 4,4-diethoxy-17-oxo-3, 16-dioxa-18-aza-4-silicosan-20-yl methacrylate (molecular weight 489.7) was confirmed. Further, as a result of FT-IR measurement, it was confirmed that silane group absorption at 2190 cm ⁻¹ disappeared. The chemical structural formula of the compound synthesized in this synthesis example is shown in [Chemical Formula 10].

(Synthesis Example 2) Synthesis of Silane Coupling Agent Having Radical Polymerizable Group 10-Undecen-1-ol: 17.0 g in a four-necked flask (100 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser (0.10 mol), the heterogeneous catalyst synthesized in the synthesis of the tertiary amine supported catalyst (2): 5.0 g and p-methoxyphenol: 15.6 mg (corresponding to 500 ppm) were added and dissolved. Next, 14.1 g (0.10 mol) of 2-isocyanate ethyl methacrylate was weighed into the dropping funnel. The four-necked flask was immersed in an oil bath heated to 75 ° C, and 2-isocyanatoethyl methacrylate was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropping, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, the four-necked flask was removed from the oil bath, the reaction product was returned to room temperature, the tertiary amine-supported catalyst was removed by centrifugation, and HPLC and FT-IR measurements were performed. Analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by ATR method. As a result of HPLC measurement, the peaks of the raw materials 10-undecen-1-ol and 2-isocyanatoethyl methacrylate disappeared, and a new peak: 2-((Undec-10-enyloxy) carbonylamino) ethyl acrylate (molecular weight 311.4 )It was confirmed. Further, as a result of FT-IR measurement, it was confirmed that isocyanate group absorption and hydroxy group absorption disappeared. Next, 2-((Undec-10-enyloxy) carbonylamino) ethyl acrylate synthesized in the above procedure in a four-necked flask (300 mL volume): 31.1 g and platinum-supported heterogeneous catalyst Siliacat ^@ Pt ⁰ (SILICYCLE 5.0 g and 100 mL of toluene were added and sufficiently stirred and dispersed. Separately, 16.4 g of triethoxysilane was weighed in a dropping funnel. While stirring the four-necked flask at room temperature, triethoxysilane was added dropwise so that the internal temperature did not exceed 35 ° C. After completion of the dropwise addition, the reaction was continued for 12 hours for aging. After completion of ripening, the platinum-supported heterogeneous catalyst was removed by centrifugation, and the solvent was removed by an evaporator, followed by HPLC and FT-IR measurement. As a result of HPLC measurement, peaks of 2-((Undec-10-enyloxy) carbonylamino) ethyl acrylate and triethoxysilane as raw materials disappeared, and a new peak: 4,4-diethoxy-17-oxo-3,16 -Dioxa-18-aza-4-silicosan-20-yl methacrylate (molecular weight 475.7) was confirmed. Further, as a result of FT-IR measurement, it was confirmed that silane group absorption at 2190 cm ⁻¹ disappeared. The chemical structural formula of the compound synthesized in this synthesis example is shown in Chemical Formula 11.

(Synthesis Example 3) Synthesis of a silane coupling agent having a radical polymerizable group 10-undecen-1-ol: 17.0 g in a four-necked flask (100 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser (0.10 mol), the heterogeneous catalyst synthesized in the synthesis of tertiary amine supported catalyst (3): 5.0 g and p-methoxyphenol: 20.5 mg (corresponding to 500 ppm) were added and dissolved. Next, 2-isocyanate-2-methylpropane-1,3-diyl diacrylate: 23.9 g (0.10 mol) was weighed in the dropping funnel. The four-necked flask was immersed in an oil bath heated to 75 ° C., and 2-isocyanato-2-methylpropane-1,3-diyl diacrylate was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropping, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, the four-necked flask was removed from the oil bath, the reaction product was returned to room temperature, the tertiary amine-supported catalyst was removed by centrifugation, and HPLC and FT-IR measurements were performed. Analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by ATR method. As a result of HPLC measurement, the peaks of the raw materials 10-undecen-1-ol and 2-isocyanato-2-methylpropane-1,3-diyldiacrylate disappeared, and a new peak: 2-methyl-2- ( (Undec-10-enyloxy) carbonylamino) propane-1,3-diyl diacrylate (molecular weight 409.5) was confirmed. Further, as a result of FT-IR measurement, it was confirmed that isocyanate group absorption and hydroxy group absorption disappeared. Next, 2-methyl-2-((undec-10-enyloxy) carbonylamino) propane-1,3-diyldiacrylate synthesized in the above procedure in a four-necked flask (300 mL volume): 41.0 g of platinum supported heterogeneous catalysts in which Siliacat ^@ Pt ⁰ (SILICYCLE Co.): 5.0 g, toluene was added 100mL then sufficiently stirred and dispersed. Separately, 16.4 g of triethoxysilane was weighed in a dropping funnel. While stirring the four-necked flask at room temperature, triethoxysilane was added dropwise so that the internal temperature did not exceed 35 ° C. After completion of the dropwise addition, the reaction was continued for 12 hours for aging. After completion of ripening, the platinum-supported heterogeneous catalyst was removed by centrifugation, and the solvent was removed by an evaporator, followed by HPLC and FT-IR measurement. As a result of HPLC measurement, the peaks of 2-methyl-2-((undec-10-enyloxy) carbonylamino) propane-1,3-diyldiacrylate and triethoxysilane, which are raw materials, disappeared, and a new peak: 2- Methyl-2-((11- (triethoxysilyl) undecyloxy) carbonylamino) propane-1,3-diyl diacrylate (molecular weight 573.8) was confirmed. Further, as a result of FT-IR measurement, it was confirmed that silane group absorption at 2190 cm ⁻¹ disappeared. The chemical structural formula of the compound synthesized in this example is shown in Chemical Formula 12.

(Comparative Synthesis Example 1) Synthesis of silane coupling agent having radical polymerizable group 10-Undecen-1-ol in a four-necked flask (100 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser g (0.10 mol), dibutyltin (IV) dilaurate: 32.5 mg (equivalent to 1000 ppm) and p-methoxyphenol: 16.3 mg (equivalent to 500 ppm) were added and dissolved. Next, 2-isocyanate ethyl methacrylate: 15.5 g (0.10 mol) was weighed in the dropping funnel. The four-necked flask was immersed in an oil bath heated to 75 ° C, and 2-isocyanatoethyl methacrylate was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropping, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, the four-necked flask was removed from the oil bath, the reaction product was returned to room temperature, and HPLC and FT-IR measurements were performed. Analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by ATR method. As a result of HPLC measurement, the peaks of 10-undecen-1-ol and 2-isocyanatoethyl methacrylate, which are raw materials, disappeared, and a new peak: 2-((Undec-10-enyloxy) carbonylamino) ethyl methacrylate (molecular weight 325.5) was confirmed. Further, as a result of FT-IR measurement, it was confirmed that isocyanate group absorption and hydroxy group absorption disappeared. Next, Siliacat ^@ Pt ⁰ (SILICYCLE), a platinum-supported heterogeneous catalyst, was added to 32.6 g of 2-((Undec-10-enyloxy) carbonylamino) ethyl methacrylate synthesized in the above procedure in a four-necked flask (300 mL volume). 5.0 g and 100 mL of toluene were added and sufficiently stirred and dispersed. Separately, 16.4 g of triethoxysilane was weighed in a dropping funnel. While stirring the four-necked flask at room temperature, triethoxysilane was added dropwise so that the internal temperature did not exceed 35 ° C. After completion of the dropwise addition, the reaction was continued for 12 hours for aging. After completion of ripening, the platinum-supported heterogeneous catalyst was removed by centrifugation, and the solvent was removed by an evaporator, followed by HPLC and FT-IR measurement. As a result of HPLC measurement, peaks of 2-((Undec-10-enyloxy) carbonylamino) ethyl methacrylate and triethoxysilane, which are raw materials, disappeared, and a new peak: 4,4-diethoxy-17-oxo-3, 16-dioxa-18-aza-4-silicosan-20-yl methacrylate (molecular weight 489.7) was confirmed. As a result of FT-IR measurement, the disappearance of silane group absorption was confirmed. The chemical structural formula of the compound synthesized in this comparative synthesis example is shown in Chemical formula 13.

(Comparative Synthesis Example 2) Synthesis of silane coupling agent having radical polymerizable group 10-Undecen-1-ol: 17.0 g (0.10 mol), dibutyltin (IV) dilaurate: 31.1 mg (equivalent to 1000 ppm) and p-methoxyphenol: 15.6 mg (equivalent to 500 ppm) were added and dissolved. Next, 14.1 g (0.10 mol) of 2-isocyanate ethyl methacrylate was weighed into the dropping funnel. The four-necked flask was immersed in an oil bath heated to 75 ° C, and 2-isocyanatoethyl methacrylate was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropping, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, the four-necked flask was removed from the oil bath, the reaction product was returned to room temperature, and HPLC and FT-IR measurements were performed. Analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by ATR method. As a result of HPLC measurement, the peaks of the raw materials 10-undecen-1-ol and 2-isocyanatoethyl methacrylate disappeared, and a new peak: 2-((Undec-10-enyloxy) carbonylamino) ethyl acrylate (molecular weight 311.4 )It was confirmed. Further, as a result of FT-IR measurement, it was confirmed that isocyanate group absorption and hydroxy group absorption disappeared. Next, 2-((Undec-10-enyloxy) carbonylamino) ethyl acrylate synthesized in the above procedure in a four-necked flask (300 mL volume): 31.1 g and platinum-supported heterogeneous catalyst Siliacat ^@ Pt ⁰ (SILICYCLE 5.0 g and 100 mL of toluene were added and sufficiently stirred and dispersed. Separately, 16.4 g of triethoxysilane was weighed in a dropping funnel. While stirring the four-necked flask at room temperature, triethoxysilane was added dropwise so that the internal temperature did not exceed 35 ° C. After completion of the dropwise addition, the reaction was continued for 12 hours for aging. After completion of ripening, the platinum-supported heterogeneous catalyst was removed by centrifugation, and the solvent was removed by an evaporator, followed by HPLC and FT-IR measurement. As a result of HPLC measurement, peaks of 2-((Undec-10-enyloxy) carbonylamino) ethyl acrylate and triethoxysilane as raw materials disappeared, and a new peak: 4,4-diethoxy-17-oxo-3,16 -Dioxa-18-aza-4-silicosan-20-yl methacrylate (molecular weight 475.7) was confirmed. As a result of FT-IR measurement, the disappearance of silane group absorption was confirmed. The chemical structural formula of the compound synthesized in this comparative synthesis example is shown in Chemical formula 14.

(Comparative Synthesis Example 3) Synthesis of Silane Coupling Agent Having Radical Polymerizable Group 10-Undecen-1-ol: 17.0 in a four-necked flask (100 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser g (0.10 mol), dibutyltin (IV) dilaurate: 40.9 mg (equivalent to 1000 ppm) and p-methoxyphenol: 20.5 mg (equivalent to 500 ppm) were added and dissolved. Next, 2-isocyanate-2-methylpropane-1,3-diyl diacrylate: 23.9 g (0.10 mol) was weighed in the dropping funnel. The four-necked flask was immersed in an oil bath heated to 75 ° C., and 2-isocyanato-2-methylpropane-1,3-diyl diacrylate was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropping, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, the four-necked flask was removed from the oil bath, the reaction product was returned to room temperature, and HPLC and FT-IR measurements were performed. Analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by ATR method. As a result of HPLC measurement, the peaks of the raw materials 10-undecen-1-ol and 2-isocyanato-2-methylpropane-1,3-diyldiacrylate disappeared, and a new peak: 2-methyl-2- ( (Undec-10-enyloxy) carbonylamino) propane-1,3-diyl diacrylate (molecular weight 409.5) was confirmed. Further, as a result of FT-IR measurement, it was confirmed that isocyanate group absorption and hydroxy group absorption disappeared. Next, 2-methyl-2-((undec-10-enyloxy) carbonylamino) propane-1,3-diyldiacrylate synthesized in the above procedure in a four-necked flask (300 mL volume): 41.0 g of platinum supported heterogeneous catalysts in which Siliacat ^@ Pt ⁰ (SILICYCLE Co.): 5.0 g, toluene was added 100mL then sufficiently stirred and dispersed. Separately, 16.4 g of triethoxysilane was weighed in a dropping funnel. While stirring the four-necked flask at room temperature, triethoxysilane was added dropwise so that the internal temperature did not exceed 35 ° C. After completion of the dropwise addition, the reaction was continued for 12 hours for aging. After completion of ripening, the platinum-supported heterogeneous catalyst was removed by centrifugation, and the solvent was removed by an evaporator, followed by HPLC and FT-IR measurement. As a result of HPLC measurement, the peaks of 2-methyl-2-((undec-10-enyloxy) carbonylamino) propane-1,3-diyldiacrylate and triethoxysilane, which are raw materials, disappeared, and a new peak: 2- Methyl-2-((11- (triethoxysilyl) undecyloxy) carbonylamino) propane-1,3-diyl diacrylate (molecular weight 573.8) was confirmed. As a result of FT-IR measurement, the disappearance of silane group absorption was confirmed. The chemical structural formula of the compound synthesized in this comparative synthesis example is shown in Chemical formula 15.

Color Stability Test of Synthetic Products 9.0 mL of the polymerizable silane coupling agent synthesized in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 3 was transferred to a 10 mL volume colorless transparent glass vial, and the Hazen color number was measured. In addition, the Hazen color number was measured after the same sample was stored in a 50 ° C. incubator for 1 month in the dark.

Examples 1-1 to 1-3, Comparative Examples 1-1 to 1-3 (filling rate 70 wt%)
Surface modification and dental use of OX-50 (Nippon Aerosil Co., Ltd.) and Fuselex (manufactured by Tatsumori Co., Ltd.) using the polymerizable silane coupling agents synthesized in Synthesis Examples 1-3 and Comparative Synthesis Examples 1-3 A composite resin was prepared. A specific surface modification method is described below. The amount of polymerizable silane coupling agent described in Table 1-1 was dissolved in 300 mL of ethanol and added to a 500 mL eggplant flask containing OX-50: 15.0 g and Fuselex: 45.0 g. Thereafter, an electromagnetic stir bar was added and the mixture was stirred for 10 minutes, and further dispersed for 5 minutes with an ultrasonic disperser of 28 KHz-150 W. After the completion of dispersion, 2.4 g of distilled water and 1.2 g of 1 wt% phosphoric acid aqueous solution were added with stirring, and the flask was immersed in a boiling water bath and refluxed for 5 hours. After completion of the reflux, the internal temperature was returned to room temperature, and the binder liquid (UDMA, 2G) and photopolymerization initiator shown in Table 1 were added under light shielding. After stirring uniformly, ethanol was distilled off with an evaporator. Thereafter, the solvent was completely removed under a condition of 1000 rpm-5 KPa-15 min using a Thinky Planetary Vacuum mixer ARV-310 to obtain a dental composite resin. The dental composite resin thus obtained was cured according to ISO 4049, and the bending strength was determined using an Instron universal testing machine (Instron 5567, manufactured by Instron). In addition, a circular disk with a diameter of 15mmφ-thickness of 1.0mm was prepared using the same curing procedure, and the color stability of the cured product was adjusted to a light resistance tester (Atlas Suntest CPS +, manufactured by Toyo Seiki Co., Ltd.) according to ISO4049. Asked. The photopolymerization was performed by light irradiation for 30 seconds with Griplight II manufactured by Matsukaze Co., Ltd.

Examples 2-1 to 2-3, Comparative Examples 2-1 to 2-3 (filling rate 85 wt%)
Surface modification and dental use of OX-50 (Nippon Aerosil Co., Ltd.) and Fuselex (manufactured by Tatsumori Co., Ltd.) using the polymerizable silane coupling agents synthesized in Synthesis Examples 1-3 and Comparative Synthesis Examples 1-3 A composite resin was prepared. A specific surface modification method is described below. The amount of polymerizable silane coupling agent described in Table 1-2 was dissolved in 300 mL of ethanol and added to a 500 mL eggplant flask containing OX-50: 15.0 g and Fuselex: 45.0 g. Thereafter, an electromagnetic stir bar was added and the mixture was stirred for 10 minutes, and further dispersed for 5 minutes with an ultrasonic disperser of 28 KHz-150 W. After the completion of dispersion, 2.4 g of distilled water and 1.2 g of 1 wt% phosphoric acid aqueous solution were added with stirring, and the flask was immersed in a boiling water bath and refluxed for 5 hours. After completion of the reflux, the internal temperature was returned to room temperature, and the binder liquid (UDMA, 2G) and photopolymerization initiator shown in Table 2 were added under light shielding. After stirring uniformly, ethanol was distilled off with an evaporator. Thereafter, the solvent was completely removed under a condition of 1000 rpm-5 KPa-15 min using a Thinky Planetary Vacuum mixer ARV-310 to obtain a dental composite resin. The dental composite resin thus obtained was cured according to ISO 4049, and the bending strength was determined using an Instron universal testing machine (Instron 5567, manufactured by Instron). In addition, a circular disk with a diameter of 15mmφ-thickness of 1.0mm was prepared using the same curing procedure, and the color stability of the cured product was adjusted to a light resistance tester (Atlas Suntest CPS +, manufactured by Toyo Seiki Co., Ltd.) according to ISO4049. Asked. The photopolymerization was performed by light irradiation for 30 seconds with Griplight II manufactured by Matsukaze Co., Ltd.

Evaluation Results Table 2-1 shows the measurement results of the Hazen color number obtained in the color stability test of the composite. As is clear from these measurement results, the Hazen color number of the polymerizable silane coupling agent containing no organotin compound synthesized in Synthesis Examples 1 to 3 is not significantly different from that immediately after synthesis and after storage at 50 ° C. for 1 month after shading. I was not able to admit. In contrast, the Hazen color number of the polymerizable silane coupling agent containing the organotin compound synthesized in Comparative Synthesis Examples 1 to 3 was significantly different from that immediately after synthesis and after light-shielded storage at 50 ° C. for 1 month. This large color change is considered to be due to the remaining organotin compound. Next, the measurement results regarding the color tone stability of the cured product are shown in Table 2-2. As is clear from these measurement results, the dental curability containing an inorganic filler subjected to surface modification using a polymerizable silane coupling agent containing no organotin compound synthesized in Synthesis Examples 1 to 3 There was no significant difference in the color change of the cured composition. On the other hand, a cured dental curable composition containing an inorganic filler subjected to surface modification using a polymerizable silane coupling agent containing an organotin compound synthesized in Comparative Synthesis Examples 1 to 3 There was a big difference in color change and yellowing was remarkable. Table 2-3 shows the bending strength test results of the dental composite resin (dental curable composition) prepared based on the examples. Table 2-4 also shows the bending test specimens by thermal cycling (after bending the specimen for 1 minute in cold water at 4 ° C and then immersing it for 1 minute in hot water at 60 ° C for 3000 minutes). The result of having evaluated water resistance is shown. As is clear from these results, the cured body of the dental curable composition containing the inorganic filler surface-modified with the silane coupling agent synthesized according to the present invention uses an organic tin compound that is an existing technology. It can be seen that the cured product of the dental curable composition containing the inorganic filler surface-modified with the synthesized silane coupling agent is completely inferior and has high bending strength characteristics and water resistance.

That is, by surface-modifying the inorganic filler with the silane coupling agent produced by the production method of the present invention, high affinity for the radical polymerizable monomer is exhibited while having high color stability, and as a result As a result, the dental material was given high mechanical strength and durability. In addition, the high affinity makes it possible to fill the surface-modified inorganic filler at a high concentration. This high mechanical strength and durability is due to the structure of silane coupling agent: -NH-, -S-, -NH-C (O) -S-, -NH-C (O) -O-, -NH-C Due to the presence of polar connecting groups such as (O) -NH-, -C (O) -S-, -CH (OH) -CH ₂ -S-, -CH (OH) -CH ₂ -O- groups I think to do. That is, the inorganic filler surface-modified with the silane coupling agent produced by the production method of the present invention has -NH-, -S-, -NH-C (O) -S-, -NH- C (O) -O-, -NH-C (O) -NH-, -C (O) -S-, -CH (OH) -CH ₂ -S-, -CH (OH) -CH ₂ -O -A group is introduced, which is considered to express a markedly high affinity for radically polymerizable monomers having a urethane group. According to the present invention, it is possible to increase the filling of the inorganic filler while having high color tone stability, and as a result, it is possible to achieve high mechanical strength. As is clear from the above evaluation results, it has become possible to provide dental materials having high color stability and high mechanical strength that could not be achieved by the prior art.

(Meth) acrylic acid derivative monomers such as methyl methacrylate, triethylene glycol dimethacrylate, and urethane dimethacrylate are used in medical and dental adhesives and composite resins. In free radical polymerization (hereinafter referred to as radical polymerization) of vinyl monomers such as these (meth) acrylic acid derivative monomers, a polymer is formed and cured by breaking the carbon-carbon double bond into a single bond. . In addition to the vinyl monomer, an inorganic filler is added to the composite resin for the purpose of improving mechanical strength. In general, these inorganic fillers are surface-modified with a silane coupling agent having a polymerizable group to improve wettability and mechanical strength. Conventionally, γ-methacryloxypropyltrimethoxysilane (KBM-503) has been widely used as this silane coupling agent. When particles whose surface has been modified with the compound are used, there is a problem that hydrolysis tends to proceed due to low hydrophobicity, and durability of the material is low. In addition, due to its low hydrophobicity, the filling rate of the inorganic filler is also low, and there is a disadvantage that sufficient mechanical strength cannot be obtained. In order to solve the problem, various silane coupling agents have been synthesized and applied. However, since urethanation reaction using soluble organotin compounds has been used for their synthesis, yellowing of the silane coupling agent itself, and inorganic filling with surface modification using the silane coupling agent There existed a problem that the hardened | cured material of a dental curable composition containing a material yellowed with time. The silane coupling agent according to the present invention overcomes all of these problems and does not contain an organotin compound that is a urethanization catalyst. Therefore, the silane coupling agent is particularly excellent in color tone stability and has great industrial applicability. .

Claims (10)

A method for producing a silane coupling agent having a radical polymerizable group, wherein a soluble tin catalyst is not used in the process of synthesizing a silane coupling agent having a radical polymerizable group that requires a urethanization reaction.
A method for producing a silane coupling agent having a radical polymerizable group, characterized in that a tertiary amine-supported catalyst is used in a method for synthesizing a silane coupling agent having a radical polymerizable group that requires a urethanization reaction.

3. The silane coupling having a radical polymerizable group according to claim 1, wherein the support of the tertiary amine-supported catalyst is at least one selected from silica, alumina, soda glass, and activated carbon. Manufacturing method.
4. The radical polymerization according to claim 1, wherein the urethanization reaction is performed in a heterogeneous system using a tertiary amine-supported catalyst, and finally the tertiary amine-supported catalyst is removed by filtration and / or centrifugation. A method for producing a silane coupling agent having a functional group.
The method for producing a silane coupling agent having a radical polymerizable group according to claim 1, wherein the tertiary amine-supported catalyst has the following chemical structure.
In the formula, Z represents a C _{1 to} C ₃₀ linear or branched alkylene group -NH-, -O-, -S-, -NH-C (O) -O-, -NH-C ( O) -S-, -NH-C (O) -NH-, -C (O) -S-, -C (O) -O-, -CH (OH) -CH ₂ -S-, -CH ( OH) —CH ₂ —O—, —N═CH— groups may be included. n is 0-5. R ₁ and R ₂ each independently represent a C _{1 to} C ₁₀ linear or branched alkylene group. In the formula, S represents a carrier.

The method for producing a silane coupling agent having a radical polymerizable group according to claim 1, wherein the tertiary amine-supported catalyst has the following chemical structure. In the formula, Z represents a C _{1 to} C ₃₀ linear or branched alkylene group -NH-, -O-, -S-, -NH-C (O) -O-, -NH-C ( O) -S-, -NH-C (O) -NH-, -C (O) -S-, -C (O) -O-, -CH (OH) -CH ₂ -S-, -CH ( OH) —CH ₂ —O—, —N═CH— group. R ₁ and R ₂ each independently represent a C _{1 to} C ₁₀ linear or branched alkylene group. In the formula, S represents a carrier.
7. The method for producing a silane coupling agent having a radical polymerizable group according to claim 1, wherein the structural formula of the silane coupling agent having a radical polymerizable group is represented by the following formula.

A represents H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ − group (C ₆ H ₄ represents a phenylene group), and B represents -C (O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH-, -NH-C (O) -S-,- represents NH-C (O) -O- group, Z is a straight-chain or branched alkylene group of C ₁ -C _30, Y is, -NH-C (O) -O- , -NH- Represents a C (O) —S— group, R ² represents a C _{7 to} C ₃₀ linear or branched alkylene group, —S—, —NH—, —NR ⁴ — (R ⁴ represents an alkylene group) ), —CH ₂ —C ₆ H ₄ — (C ₆ H ₄ represents a phenylene group), —C (O) —O—, —O— group, and R ³ is C _{1 to} C ₆ . Represents a linear or branched alkyl group, and R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group, a phenyl group, or a halogen atom, and when n is 0, at least one or more halogen atoms in Si Join. Here, a is 1 to 6, and n is 0 to 3.
The dental curable composition containing the inorganic filler surface-modified by the silane coupling agent which has the radically polymerizable group manufactured with the manufacturing method of Claims 1-7.
A silane coupling agent having a radically polymerizable group, characterized by not containing a soluble tin catalyst in a silane coupling agent having a radically polymerizable group that requires a urethanization reaction.
A dental curable composition comprising an inorganic filler surface-modified with a silane coupling agent having a radical polymerizable group according to claim 9.