JP2011190254A - Dental curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dental curable composition and a composite resin, satisfying the both of morphological retention of the paste and extrusion properties from a vessel such as a syringe, and having good handleability. <P>SOLUTION: There is provided a dental curable composition comprising a polymerizable monomer (A), a filler (B), a polyglycerol fatty acid ester (C) and a polymerization initiator (D), wherein, the average molecular weight of the polyglycerol fatty acid ester (C) is 2,000-4,000; and a composite resin using the dental curable composition is provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a dental curable composition that can be suitably used as a dental material that can replace a part or the whole of a natural tooth, particularly a dental composite resin, in the field of dentistry.

  A dental curable composition composed of a polymerizable monomer, an inorganic filler, a polymerization initiator, and the like is called a composite resin, and it is most frequently used today as a material for repairing tooth defects and dental caries. It is a dental material. Such a dental curable composition is required to have the following characteristics. That is, in the cured product after polymerization and curing, there are sufficient mechanical strength that can be replaced with natural teeth, hardness, abrasion resistance against engagement in the oral cavity, surface smoothness, and the like.

  Furthermore, in the paste state before polymerization and curing, it has moderate fluidity and shapeability, does not adhere to dental instruments, does not stick, and does not drip too much, making it easy for clinicians and dental technicians to handle ( High handleability) is desired. The composition can exhibit a favorable effect as a dental material with respect to the above characteristics by using a specific blending component or adjusting a blending component ratio.

  In particular, with regard to the paste handling property before polymerization curing required for a dental curable composition, when the paste is built up in and out of the oral cavity to restore the tooth form, there is an appropriate form retainability (formability). Necessary. When the form retention is insufficient, the paste drips and it is difficult to restore the tooth form. Therefore, in order to obtain an appropriate form retaining property, the paste may be hardened by increasing the amount of the inorganic filler in the paste, but on the other hand, the fluidity of the paste is lowered. When the paste is made using a paste having low fluidity, cutting or separation occurs when the paste is stretched, and it becomes difficult to entrap bubbles or obtain a smooth surface. Even in a paste having a high fluidity called a flowable composite, if the fluidity is too high, it will sag from the cavity and it will be difficult to restore the shape of the teeth. In particular, in recent years, the use of sub-micron sized pulverized inorganic fillers has made it possible to achieve both surface smoothness and mechanical strength, but on the other hand, good paste handling properties can be obtained. It became difficult.

  Patent Document 1 discloses a composition comprising a component i) that is a hydrogen-bondable compound that is a polymer having a molecular weight greater than about 10,000, and a component ii) that is a hydrogen-bondable crosslinking compound. One of component i) and component ii) includes two or more hydrogen bond donor sites per compound and component i) or component ii) the other includes two or more hydrogen bond acceptor sites per compound. And a method for improving and controlling the rheology of dental materials, particularly dental composite materials, utilizing hydrogen bonding between a material acting as a hydrogen bond acceptor and a material acting as a hydrogen bond donor. ing.

Special Table 2002-544214

  In the dental material described in Patent Document 1, if the polymerizable monomer blended with the polymer having a molecular weight of more than about 10,000 is not a hydrogen bond donor or a hydrogen bond acceptor, a sufficient form is obtained. It was not a material that could exhibit retention. Moreover, when hydrogen bonding is inadequate, shape retention can also be expressed by increasing the amount of the polymer, but since it does not have polymerization curability, the mechanical properties of the cured product are lowered.

  The present invention has been made to solve the above-described problems of the prior art, and the object of the present invention is good handling properties that achieve both paste form retention and extrudability from a container such as a syringe. And providing a dental curable composition. Another object of the present invention is to provide a composite resin having good handleability that satisfies both the form retention of paste and the extrudability from a container such as a syringe.

That is, the gist of the present invention is as follows.
[1] A dental curable composition containing a polymerizable monomer (A), a filler (B), a polyglycerol fatty acid ester (C) and a polymerization initiator (D), wherein the polyglycerol fatty acid ester ( C) an average molecular weight of 2000 to 4000; and [2] a composite resin using the dental curable composition according to [1]. .

  ADVANTAGE OF THE INVENTION According to this invention, the dental curable composition with favorable handleability which compatible the form retention of paste and the extrudability from containers, such as a syringe, is obtained. The dental curable composition of the present invention can be suitably used particularly as a composite resin, and the composite resin is a composite having good handleability that satisfies both paste form retention and extrudability from a container such as a syringe. Become a resin.

Polymerizable monomer (A)
As the polymerizable monomer (A) used in the present invention, a known polymerizable monomer used in a dental composition is used without any limitation. In general, a radical polymerizable monomer is preferably used. Used. Specific examples of the radical polymerizable monomer in the polymerizable monomer (A) include α-cyanoacrylic acid, (meth) acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid. Examples include esters of acids, organic acids such as itaconic acid, (meth) acrylamides, (meth) acrylamide derivatives, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives, and the like. In these, (meth) acrylic acid ester is preferable. In the present invention, the notation of (meth) acryl is used to include both methacryl and acryl.

Examples of (meth) acrylic acid ester-based polymerizable monomers are shown below.
(I) monofunctional (meth) acrylate methyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerin mono (meta) ) Acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N- (dihydroxyethyl) (meth) acrylamide, (meth) acryloyloxy Examples include sidodecylpyridinium bromide, (meth) acryloyloxide decylpyridinium chloride, (meth) acryloyloxyhexadecylpyridinium chloride, and (meth) acryloyloxydecylammonium chloride.

(II) Bifunctional (meth) acrylates Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, 1,10-decandiol di (meth) acrylate, bisphenol A diglycidyl (meth) acrylate (2,2-bis [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] Propane, commonly known as BisGMA), 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 2,2-bis [4 -[3-((Meth) acrylo Ruoxy-2-hydroxypropoxy] phenyl] propane, 1,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy] ethane, pentaerythritol di (meth) acrylate, [2,2,4-trimethylhexamethylene Bis (2-carbamoyloxyethyl)] dimethacrylate (commonly known as UDMA).

(III) Trifunctional or higher (meth) acrylates Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, N, N ′-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diacryloyloxy-2 2,6,6-tetraacryloyloxymethyl-4-oxyheptane and the like.

  Any of the polymerizable monomers can be used alone or in admixture of two or more.

  In addition, when improving the adhesiveness with respect to a tooth substance, a metal, ceramics, etc., the functional monomer which provides the adhesiveness with respect to these adherends is used as a polymerizable monomer in the dental curable composition of the present invention. It may be preferable to make it contain.

  Examples of functional monomers include phosphate groups such as 2- (meth) acryloyloxyethyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, and the like. And monomers having a carboxylic acid group such as 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid and 4- (meth) acryloyloxyethoxycarbonylphthalic acid are excellent for dental substances and base metals. It is preferable because it exhibits excellent adhesion.

  Further, as functional monomers, for example, 10-mercaptodecyl (meth) acrylate, 6- (4-vinylbenzyl-n-propyl) amino-1,3,5-triazine-2,4-dithione, A thiouracil derivative described in Japanese Patent No. 1473 and a compound having a sulfur element described in Japanese Patent Application Laid-Open No. 11-92461 are preferable because they exhibit excellent adhesion to noble metals.

  Furthermore, as a functional monomer, for example, a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane is effective for adhesion to ceramics, porcelain, and dental composite resins.

  However, if the dental curable composition of the present invention contains a functional monomer that imparts adhesiveness to the tooth as a polymerizable monomer, the paste becomes hard and the extrusion property from the syringe container decreases. There is a trend. Examples of functional monomers that impart adhesiveness to teeth include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl Monomers having a phosphate group such as hydrogen phosphate, and monomers having a carboxylic acid group such as 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic acid It is done.

  The content of the polymerizable monomer (A) is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the filler (B) from the viewpoint of the handleability of the composition and the mechanical strength of the cured product. 8 to 60 parts by weight is more preferable.

Filler (B)
As the filler (B) used in the present invention, a material used for a known filler used for dental use, preferably an inorganic filler can be used. The filler (B) is a non-aggregated inorganic filler (B) having an average particle diameter of 0.1 to 1 μm because the mechanical strength, abrasiveness, and operability of the paste can be easily obtained. -I) is preferred. From the viewpoint of suppressing stickiness of the paste and ensuring the mechanical strength of the cured product, the average particle diameter is preferably 0.1 μm or more, and from the viewpoint of ensuring the abrasiveness of the cured product, the average particle diameter is 1 μm or less. Preferably there is. From the viewpoint of the mechanical strength of the cured product, abrasiveness, and operability of the paste, the average particle size of the inorganic filler (BI) is more preferably 0.2 to 0.7 μm, and 0.2 to 0.4 μm Is more preferable.

  The amount of the non-aggregated inorganic filler (BI) is not particularly limited as long as a predetermined effect is obtained. For example, the inorganic filler (BI) is 10 to 100 of the inorganic filler (B). It is preferable to occupy 40% by weight, more preferably 40 to 100% by weight, and still more preferably 60 to 100% by weight.

  The inorganic filler (BI) can be used without any limitation as long as it is a non-aggregated inorganic filler having an average particle diameter of 0.1 to 1 μm. Examples of the inorganic filler include various glasses [having silica as a main component and, if necessary, containing an oxide such as heavy metal, boron, and aluminum]. For example, fused silica, quartz, soda lime silica glass, E glass, strontium boroaluminosilicate glass (GM27884, 8235, manufactured by Schott Corp .; Ray-SorbE2000, Ray-SorbE3000, Specialty Glass Corp.), strontium borosilicate glass (Ray) -Dental glass powders such as SorbE4000, Specialty Glass, lanthanum glass ceramics (GM31684, Schott) are applicable. In addition to the above various glasses, various ceramics, composite oxides such as silica-titania and silica-zirconia, kaolin, clay mineral (montmorillonite, etc.), mica, ytterbium fluoride, yttrium fluoride, calcium phosphate, barium sulfate, Zirconium dioxide, titanium dioxide, hydroxyapatite and the like are also included in the inorganic filler (BI). However, ion-eluting fillers are not preferred because of a decrease in strength over time. These can be used alone or in admixture of two or more.

  The filler (B) contains an inorganic filler other than the inorganic filler (B-I) described above in order to give a better paste handling property while having sufficient abrasiveness and mechanical properties. You can leave. As the said inorganic filler, the well-known inorganic filler used for a dental curable composition is used without a restriction | limiting at all. Agglomerated particles are preferable, for example, particles obtained by aggregating silica sol (Snowtex series; manufactured by Nissan Chemical Co., Ltd., Cataloid series; manufactured by JGC Catalysts & Chemicals Co., Ltd.), zirconia sol (Nano Youth Series; manufactured by Nissan Chemical Industries) Etc.

  Since the filler (B) is used in a dental composition in combination with a polymerizable monomer, the affinity between the filler and the polymerizable monomer is improved, or the filler and the polymerizable monomer are used. In order to improve the chemical bondability with the body and improve the mechanical strength of the cured product, it is desirable to perform surface treatment with a surface treatment agent in advance. When surface treatment is performed, the average particle size after the surface treatment is the measurement target as the average particle size of the filler (B).

  As such a surface treating agent, at least one organometallic compound selected from the group consisting of an organosilicon compound, an organotitanium compound, an organozirconium compound, and an organoaluminum compound can be used. When two or more kinds of organometallic compounds are used, a surface treatment layer of a mixture of two or more kinds of metal compounds may be used, or a surface treatment layer having a multilayer structure in which a plurality of organometallic compound layers are laminated.

Examples of the organosilicon compound include compounds represented by R ¹ _n SiX _4-n (wherein R ¹ is a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and X is the number of carbon atoms. 1 to 4 represents an alkoxy group, a hydroxyl group, a halogen atom or a hydrogen atom, and n is an integer of 0 to 3. When there are a plurality of R ¹ and X, they may be the same or different.

  Specifically, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol , Methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethylbromosilane, diethyl Silane, vinyltriacetoxysilane, ω- (meth) acryloxyalkyltrimethoxysilane (carbon number between (meth) acryloxy group and silicon atom: 3 to 12, for example, γ-methacryloxypropyltrimethoxysilane) , Ω- (meth) acryloxyalkyltriethoxysilane (the number of carbons between the (meth) acryloxy group and the silicon atom: 3 to 12, for example, γ-methacryloxypropyltriethoxysilane) and the like.

  Among these, a coupling agent having a functional group capable of copolymerizing with the polymerizable monomer (A), such as ω- (meth) acryloxyalkyltrimethoxysilane (carbon between the (meth) acryloxy group and the silicon atom). Number: 3 to 12), ω- (meth) acryloxyalkyltriethoxysilane (carbon number between (meth) acryloxy group and silicon atom: 3 to 12), vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Triacetoxysilane, γ-glycidoxypropyltrimethoxysilane and the like are particularly preferably used.

  Examples of the organic titanium compound include tetramethyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, butyl titanate dimer, and tetra (2-ethylhexyl) titanate.

  Examples of the organic zirconium compound include zirconium isopropoxide, zirconium n-butoxide, zirconium acetylacetonate, zirconyl acetate and the like.

  Examples of the organic aluminum compound include aluminum acetylacetonate and aluminum organic acid salt chelate compound.

Polyglycerin fatty acid ester (C)
As the polyglycerol fatty acid ester (C) used in the present invention, a known one having an average molecular weight of 2000 to 4000 is used. With respect to the average molecular weight of the polyglycerol fatty acid ester (C), those having a molecular weight of 2000 to 3800 are preferred. As such polyglycerol fatty acid ester (C), those having an average degree of polymerization of glycerol of 2 to 10 are preferable. Furthermore, that whose carbon number of the fatty acid of polyglycerol fatty acid ester (C) is 8-22 is preferable. Furthermore, the esterification degree of the polyglycerol fatty acid ester (C) is preferably 50% or more. Specific examples of preferable polyglyceryl fatty acid esters used in the present invention include decaglyceryl pentaoleate, decaglyceryl pentastearate, decaglyceryl pentalinoleate, decaglyceryl pentaricinoleate, decaglyceryl pentaercaate, decaglyceryl heptalaurate , Decaglyceryl heptamyristate, Decaglyceryl heptapalmitate, Decaglyceryl heptastearate, Decaglyceryl heptaoleate, Decaglyceryl heptalinolate, Decaglyceryl heptarisinol, Decaglyceryl heptaercate, Decaglyceryl octaerca Glyceryl, decalaurate decaglyceryl, decamyristate decaglyceryl, decapalmitate decaglyceryl, decastearic acid Kaguriseriru, Dekaorein decaglyceryl, deca linoleic acid decaglyceryl Dekarishinoru decaglyceryl, polyglycerol fatty acid esters and the like. The said polyglycerol fatty acid ester (C) can be used individually or in mixture of 2 or more types.

  The content of the polyglycerin fatty acid ester (C) is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the filler (B) from the viewpoint of paste form retention and extrudability from the container, 0.5-2.0 weight part is more preferable, and 0.5-1.5 weight part is further more preferable.

Polymerization initiator (D)
The polymerization initiator (D) used in the present invention can be selected from polymerization initiators used in the general industry, and among them, polymerization initiators used for dental use are preferably used. In particular, polymerization initiators for photopolymerization and chemical polymerization are used singly or in appropriate combination of two or more.

  Photopolymerization initiators include (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyls Examples include ether compounds and α-aminoketone compounds.

  Among the (bis) acylphosphine oxides used as the photopolymerization initiator, acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2, 6-dichlorobenzoyldiphenylphosphine 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. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, and the like (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide.

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

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

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

  Examples of thioxanthones or quaternary ammonium salts of thioxanthones used as the photopolymerization initiator include thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3- (9-oxy-9H- Thioxanthen-4-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (1-methyl-9-oxy-9H-thioxanthen-4-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- ( 3,4-Dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trime Ru-1-propaneaminium chloride, 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, 2-hydroxy -3- (1,3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride and the like can be used.

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

  Examples of ketals used as the photopolymerization initiator include benzyl dimethyl ketal and benzyl diethyl ketal.

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

  Examples of the coumarin compound used as the photopolymerization initiator include 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin, and 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, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3′-carbonylbiscoumarin, 3-benzoyl-7-dimethyl Aminocoumarin, 3-benzoylbenzo [f] coumarin, 3-carboxyc Phosphorus, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo [f] coumarin, 7-methoxy-3- (p-nitro Benzoyl) coumarin, 3- (p-nitrobenzoyl) coumarin, 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-methoxy Coumarin, 3- (4-dimethylaminocinnamoyl) coumarin, 3- (4-diphenylaminocinnamoyl) coumarin, 3-[(3-dimethylbenzothiazol-2-ylidene) acetyl] coumarin, 3-[(1- Methylnaphtho [1,2-d] thiazol-2-ylidene) acetyl] coumarin, 3,3′-carbonylbis (6-methoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin), 3,3 ′ -Carbonylbis (7-dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2 -Benzimidazolyl) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dioctylamino) c Marine, 3-acetyl-7- (dimethylamino) coumarin, 3,3′-carbonylbis (7-dibutylaminocoumarin), 3,3′-carbonyl-7-diethylaminocoumarin-7′-bis (butoxyethyl) amino Coumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] Benzopyrano [6,7,8-ij] quinolizin-11-one, 10- (2-benzothiazoyl) -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl 1H , 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one and the like, and compounds described in JP-A-9-3109 and JP-A-10-245525. It is.

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

  Examples of the anthraquinones used as the photopolymerization initiator include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1 -Hydroxyanthraquinone and the like.

  Examples of benzoin alkyl ethers used as the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

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

  Among these photopolymerization initiators, it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides and salts thereof, α-diketones, and coumarin compounds. As a result, 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 initiator (D) used in the present invention, an organic peroxide is preferably used as the chemical polymerization initiator. The organic peroxide used for said chemical polymerization initiator is not specifically limited, A well-known thing can be used. Typical organic peroxides include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, peroxydicarbonate, and the like.

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

  Examples of the hydroperoxide used as the chemical polymerization initiator include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1, 1,3,3-tetramethylbutyl hydroperoxide and the like.

  Examples of the diacyl peroxide used as the chemical polymerization initiator include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, and 2,4-dichlorobenzoyl. Examples thereof include peroxide and lauroyl peroxide.

  Examples of the dialkyl peroxide used as the chemical polymerization initiator include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxide). Oxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne and the like.

  Examples of the peroxyketal used as the chemical polymerization initiator include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 4,4-bis (t-butylperoxy) valeric acid-n-butyl ester, etc. Can be mentioned.

  Peroxyesters used as the chemical polymerization initiator include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentyl. Peroxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t- Examples include butyl peroxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, and t-butylperoxymaleic acid. It is done.

  Examples of the peroxydicarbonate used as the chemical polymerization initiator include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and diisopropyl. Examples include peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate.

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

  The content of the polymerization initiator (D) used in the present invention is not particularly limited, but from the viewpoint of curability and the like of the resulting composition, the polymerization is started with respect to 100 parts by weight of the total amount of polymerizable monomer components. The agent (D) is preferably contained in an amount of 0.001 to 30 parts by weight. From the viewpoint of sufficiently proceeding the polymerization and ensuring sufficient adhesive strength, the content of the polymerization initiator (D) is preferably 0.001 part by weight or more, more preferably 0.05 part by weight or more, and further preferably. Is 0.1 parts by weight or more. On the other hand, the content of the polymerization initiator (D) is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably, from the viewpoint of suppressing precipitation from the composition and ensuring sufficient adhesive strength. Is 15 parts by weight or less, and most preferably 10 parts by weight or less.

  As the total content of the polymerizable monomer (A), the filler (B), the polyglycerin fatty acid ester (C) and the polymerization initiator (D) in the dental curable composition, For example, 85-100 weight% is preferable and 90-100 weight% is more preferable.

Polymerization accelerator (E)
The composition of the present invention preferably contains a polymerization accelerator (E). The polymerization accelerator (E) used in the present invention includes amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiols. Compound, sulfite, bisulfite, thiourea compound and the like can be mentioned.

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

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

  Examples of the sulfinic acid and salts thereof used as the polymerization accelerator (E) include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, p-toluenesulfin. Acid calcium, benzenesulfinic acid, 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-triethylben Sulfinic acid, sodium 2,4,6-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, 2,4,6-triisopropylbenzenesulfinic acid Examples include lithium, calcium 2,4,6-triisopropylbenzenesulfinate, and sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferable. .

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

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

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

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

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

  Examples of the barbituric acid derivative used as the polymerization accelerator (E) include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, and 5-butyl. Barbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric 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-cyclohexyl barbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl -1-ethyl barbituric acid, 1-benzyl-5-phenyl barbituric acid, 5-methyl barbituric acid, 5-propyl barbituric acid, 1,5-diethyl barbituric acid, 1-ethyl-5-methylbarbi Tool acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1 -Cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, and these (Especially alkali metals or alkaline earth metals are preferred) The salt of Luo barbiturates, e.g., sodium 5-butyl barbituric acid, 1,3,5-trimethyl barbituric acid sodium and 1-cyclohexyl-5-ethyl barbituric sodium tools acids and the like.

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

  Examples of the triazine compound used as the polymerization accelerator (E) 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- Lyazine, 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-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) -s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, and the like.

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

  As the copper compound used as the polymerization accelerator (E), for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.

  Examples of the tin compound used as the polymerization accelerator (E) include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. It is done. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

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

  Examples of the halogen compound used as the polymerization accelerator (E) include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide and the like. Are preferably used.

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

  Examples of the thiol compound used as the polymerization accelerator (E) include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

  Examples of the sulfite used as the polymerization accelerator (E) include sodium sulfite, potassium sulfite, calcium sulfite, and ammonium sulfite.

  Examples of the bisulfite used as the polymerization accelerator (E) include sodium bisulfite and potassium bisulfite.

  As the thiourea compound used as the polymerization accelerator (E), 1- (2-pyridyl) -2-thiourea, thiourea, methylthiourea, ethylthiourea, N, N′-dimethylthiourea, N, N′— Diethylthiourea, N, N′-di-n-propylthiourea, N, N′-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthio Examples include urea, tetra-n-propylthiourea, tetracyclohexylthiourea and the like.

  Although content of the polymerization accelerator (E) used for this invention is not specifically limited, From viewpoints, such as sclerosis | hardenability of the composition obtained, superposition | polymerization acceleration | stimulation is performed with respect to 100 weight part of whole quantity of a polymerizable monomer component. It is preferable to contain 0.001-30 weight part of agents (E). The content of the polymerization accelerator (E) is preferably 0.001 part by weight or more, more preferably 0.05 part by weight or more, and still more preferably 0, from the viewpoint of sufficiently proceeding the polymerization and ensuring adhesive strength. .1 part by weight or more. On the other hand, from the viewpoint of suppressing precipitation from the composition and ensuring sufficient adhesive strength, the content of the polymerization accelerator (E) is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably. Is 10 parts by weight or less.

Method for preparing dental curable composition The method for preparing the dental curable composition of the present invention is the same as the method for preparing a conventional dental curable composition, for example, each component is mixed in a predetermined manner. It is possible to employ a method of vacuum defoaming a mixture that is mixed and kneaded in an amount.

Composite Resin The composite resin of the present invention is obtained by using the above-described dental curable composition of the present invention.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples. The test methods, materials, etc. used in the examples are summarized below.

(Measurement of average particle size of filler particles)
A laser diffraction particle size distribution analyzer (SALD-2100: manufactured by Shimadzu Corporation) was used for measurement of the particle size and average particle size of the produced powder containing the non-aggregated inorganic filler (BI). A 0.2% sodium hexametaphosphate aqueous solution was used as the dispersion medium.

[Measurement of average molecular weight of polyglycerol fatty acid ester]
A GPC analyzer (GPC101: Shodex) was used to measure the average molecular weight of the polyglycerol fatty acid ester. The analysis conditions are as follows: columns: KF802.5 and KF801 (Shodex), column oven temperature: 40 ° C., mobile phase: THF, flow rate: 1.0 mL / min, detector: RI, sample concentration: 0.1%, injection amount : 100 μL.

[Form retention (sagging)]
The prepared paste-like dental curable composition (about 50 mg) was placed on a slide glass, and then left standing in a vertical direction (90 °) in a 37 ° C. incubator. The distance the paste moved after 1 minute was measured. A moving distance of 5 mm or less is suitable.

[Extrudability (extrusion force)]
The manufactured paste-like dental curable composition (3 g) was filled into a Majesty LV syringe container manufactured by Kuraray Medical. The paste was pushed out of the syringe by pushing the piston into the syringe at a crosshead speed of 4 mm / min using a universal testing machine (manufactured by Instron), and the force applied to the piston, ie, the pushing force was measured. . The extrusion force is preferably 60 N or less, particularly preferably 50 N or less.

[Bending strength of cured product]
A test piece (2 mm × 2 mm × 30 mm) made of a cured product of the produced dental curable composition was prepared. The test piece is immersed in water at 37 ° C. for 24 hours, using a universal testing machine (Instron), setting the crosshead speed to 1 mm / min, and using a three-point bending test method with a distance between fulcrums of 20 mm. The bending strength was measured. A bending strength of 80 MPa or more is suitable.

[Polymerizable monomer composition A-1]
2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane (average number of moles of ethoxy group: 2.6) (referred to as D2.6E), triethylene glycol dimethacrylate (TEGDMA) 30 parts by weight) is mixed, 0.5 part by weight of α-camphorquinone as a polymerization initiator, and 1.0 part by weight of ethyl N, N-dimethylaminobenzoate as a polymerization accelerator are dissolved, and polymerized. A monomer composition (A-1) was prepared.

[Polymerizable monomer composition A-2]
40 parts by weight of 10- (meth) acryloyloxydecyl dihydrogen phosphate (referred to as MDP) and 2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane (average number of moles of ethoxy group added: 2 .6) 40 parts by weight (referred to as D2.6E) and 20 parts by weight of triethylene glycol dimethacrylate (referred to as TEGDMA) are mixed, 0.5 parts by weight of α-camphorquinone as a polymerization initiator, and a polymerization accelerator As a solution, 1.0 part by weight of ethyl N, N-dimethylaminobenzoate was dissolved to prepare a polymerizable monomer composition (A-2).

[Inorganic filler (B-1)]
Surface treatment is performed with 13.5 parts by weight of γ-methacryloxypropyltrimethoxysilane to 100 parts by weight of barium glass (manufactured by Schott, GM27884NF180) to obtain an inorganic filler B-1 having an average particle size of 0.18 μm. It was. The inorganic filler B-1 corresponds to a non-aggregated inorganic filler (BI).

[Inorganic filler (B-2)]
Nissan Chemical's silica sol, Snowtex ST-20 (average particle size 10-20 nm) 1000 g was spread on a hollow enamel vat, dried in a hot air dryer set at 90 ° C. until constant weight, and then set at 400 ° C. Firing in an oven for 1 hour gave 200 g of calcined solid. The obtained fired solid was pulverized for 90 minutes with a vibration ball mill, and then surface-treated with 20 parts by weight of γ-methacryloxypropyltrimethoxysilane (KBE503, manufactured by Shin-Etsu Chemical Co., Ltd.) with respect to 100 parts by weight of the obtained powder. An inorganic filler B-2 having an average particle diameter of 5.6 μm was obtained.

[Examples 1, 4 to 6]
The polymerizable monomer composition A-1, the inorganic filler, and decaglyceryl octaerucate (C-1; average molecular weight 3315) prepared above were mixed and kneaded in the blending amounts (parts by weight) shown in Tables 1 and 2. The uniformed and defoamed product was vacuum defoamed to obtain paste-like dental curable compositions of Examples 1 and 4-6.

[Example 2]
The polymerizable monomer composition A-1, the inorganic filler, and decaglyceryl heptamyristate (C-2; average molecular weight 2226) produced above were mixed and kneaded in the amount (parts by weight) shown in Table 1. Then, the uniformed product was vacuum degassed to obtain a paste-like dental curable composition of Example 2.

Example 3
The polymerizable monomer composition A-1, the inorganic filler, and decaglyceryl dekaoleate (C-3; average molecular weight 3395) produced above were mixed and kneaded in the blending amounts (parts by weight) shown in Table 1. Then, the mixture was vacuum degassed to obtain a paste-like dental curable composition of Example 3.

Example 7
The polymerizable monomer composition A-2 produced above, the inorganic filler, and decaglyceryl octaerucate (C-1; average molecular weight 3315) were mixed and kneaded in the blending amounts (parts by weight) shown in Table 2. The homogenized product was vacuum degassed to obtain a paste-like dental curable composition of Example 7.

[Comparative Example 1]
The polymerizable monomer composition A-1, the inorganic filler, and tetraglyceryl pentaoleate (C-4; average molecular weight 1822) produced above were mixed and kneaded in the blending amounts (parts by weight) shown in Table 1. Then, the uniformed product was vacuum degassed to obtain a paste-like dental curable composition of Comparative Example 1.

[Comparative Example 2]
The polymerizable monomer composition A-1, the inorganic filler, and the hexaglyceryl condensed ricinoleate (C-5; average molecular weight 4250) produced above were mixed and kneaded in the amount (parts by weight) shown in Table 1. Then, the uniformed product was vacuum degassed to obtain a paste-like dental curable composition of Comparative Example 2.

[Comparative Example 3]
The polymerizable monomer composition A-1 produced above and the inorganic filler were mixed and kneaded with the blending amounts (parts by weight) shown in Table 2 to make them uniform, and vacuum degassed. A paste-like dental curable composition was obtained.

[Comparative Examples 4 and 5]
The above-prepared polymerizable monomer composition A-1, inorganic filler, and polyvinylpyrrolidone (average molecular weight 55,000) were mixed and kneaded with the blending amounts (parts by weight) shown in Table 2 to be uniform. The product was vacuum degassed to obtain paste-like dental curable compositions of Comparative Examples 4 and 5.

  The characteristics of these dental curable compositions were evaluated by the method described above. The results are shown in Tables 1 and 2.

In addition, the value of each component in a table | surface is a weight part.
In all of the compositions of Examples 1 to 7, good shape retention (sagging) and extrudability were achieved. Furthermore, the bending strength was also good.

  Since the molecular weight of the polyglycerin fatty acid ester C-4 of Comparative Example 1 was smaller than the molecular weight defined in the present invention, the sagging property was large and the shape retention was not improved. In particular, when Example 2 and Comparative Example 1 were compared, it was found that the shape retention was remarkably different in spite of only a difference of about 200 from the average molecular weight of 2000. Since the molecular weight of the polyglycerin fatty acid ester C-5 of Comparative Example 2 was larger than the molecular weight defined in the present invention, the extrusion force was large and the handleability was lowered. In particular, from Examples 1 and 3 and Comparative Example 2, it was found that when the average molecular weight exceeded 4000, the extrusion force tended to increase rapidly. Since the comparative example 3 did not mix | blend polyglycerol fatty acid ester, there was no form retainability. In Comparative Examples 4 and 5, when polyvinylpyrrolidone was used instead of polyglycerin fatty acid ester, when the blending amount was small, the shape retention was not exhibited, and when the blending amount was large, the extrusion force increased and the bending strength also decreased. .

  The dental curable composition of the present invention is suitably used as a dental material, particularly a dental composite resin.

Claims (6)

  A dental curable composition comprising a polymerizable monomer (A), a filler (B), a polyglycerin fatty acid ester (C) and a polymerization initiator (D), wherein the polyglycerin fatty acid ester (C) A dental curable composition having an average molecular weight of 2000 to 4000.   The dental curable composition according to claim 1, comprising 0.1 to 5 parts by weight of the polyglycerin fatty acid ester (C) with respect to 100 parts by weight of the filler (B).   The dental curable composition according to claim 1 or 2, comprising 5 to 100 parts by weight of the polymerizable monomer (A) with respect to 100 parts by weight of the filler (B).   The dental material according to any one of claims 1 to 3, wherein the filler (B) contains 10 to 100% by weight of a non-aggregated inorganic filler (BI) having an average particle diameter of 0.1 to 1 µm. Curable composition.   The total content of the polymerizable monomer (A), the filler (B), the polyglycerin fatty acid ester (C), and the polymerization initiator (D) in the dental curable composition is 85. The dental curable composition according to any one of claims 1 to 4, which is -100% by weight.   The composite resin using the dental curable composition in any one of Claims 1-5.