JP2023042484A - Dental photocurable composition - Google Patents

Abstract

To provide a dental photocurable composition having sufficient mechanical properties and excellent color tone stability.SOLUTION: A dental photocurable composition contains (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, (D) a photopolymerization accelerator. The (C) photoacid generator (C1) includes an iodonium salt compound having a structure represented by formula (1). Relative to the (A) polymerizable monomer 100 pts.mass, the content of the iodonium salt compound having the structure represented by formula (1) is 0.5 pt.mass or more. [Formula (1)] (where R1 and R2 each denote an organic group, where there may be a plurality of R1 and R2. All organic groups constituting R1 and R2 as substituents include carbon atoms of 6 more in total).SELECTED DRAWING: None

Description

The present invention relates to dental photocurable compositions.

In the field of dentistry, dental photocurable compositions are used for intraoral treatment, including dental adhesives, dental composite resins, dental abutment building materials, dental resin cements, and dental coating materials. , dental pit and fissure sealing materials, dental manicure materials, dental loose tooth fixing materials, dental glass ionomer cements, dental cutting materials, dental 3D printer materials, etc.

Patent Documents 1 and 2 propose a photopolymerization initiator comprising a photoacid generator (a triazine compound or a specific aryliodonium salt), a sensitizer and an electron donor compound. there is

Japanese Patent No. 4093974 Japanese Patent No. 4596786

However, the photocurable dental compositions using conventional photopolymerization initiators described in Patent Documents 1 and 2 have a problem in achieving both mechanical strength and color tone stability.

An object of the present invention is to provide a dental photocurable composition having excellent mechanical properties and good color stability.

（式中、Ｒ_１とＲ_２は有機基であり、複数存在しても良い。置換基である全てのＲ_１とＲ_２を構成する有機基の炭素数の合計は６以上である。） The dental photocurable composition of the present invention comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, (D) a photopolymerization accelerator, and (C) The photoacid generator contains an iodonium salt compound having a structure represented by (C1) formula (1), and (A) the structure represented by (C1) formula (1) with respect to 100 parts by mass of the polymerizable monomer A dental photocurable composition containing 0.5 parts by mass or more of an iodonium salt compound having
[Formula (1)]

(In the formula, R ₁ and R ₂ are organic groups, and a plurality of them may be present. The total number of carbon atoms of the organic groups constituting all R ₁ and R ₂ as substituents is 6 or more.)

The dental photocurable composition of the present invention exhibits excellent mechanical properties and good color stability.

In the present invention, the total number of carbon atoms of the organic groups constituting R ₁ and R ₂ in the iodonium salt compound (C1) having the structure represented by formula (1) can be 8 or more.

In the present invention, (C1) R ₁ and/or R ₂ of the iodonium salt compound having the structure represented by formula (1) can be an organic group having an alkyl chain of 8 or more carbon atoms.

In the present invention, (C1) an iodonium salt compound having a structure represented by formula (1) can be contained in an amount of 1 part by mass or more based on 100 parts by mass of the polymerizable monomer (A).

In the present invention, (C1) the anion of the iodonium salt compound having the structure represented by formula (1) can be an anion having an organic group.

In the present invention, (C1) the anion of the iodonium salt compound having the structure represented by formula (1) is an organic group in which at least one H is substituted with F, and any one of P, B, Al, S and Ga It can have one or more atoms.

In the present invention, (D) a tertiary aliphatic amine compound having no primary hydroxyl group at the α- and/or β-carbon of N can be included as (D) a photopolymerization accelerator (D1).

In the present invention, the photopolymerization accelerator (D) may be substantially free of an aromatic amine compound.

In the present invention, the photopolymerization accelerator (D) may not substantially contain a tertiary amine compound having a primary hydroxy group at the α- and/or β-position starting from an amine-derived N. .

In the present invention, it is possible to substantially contain no water or organic solvent.

In the present invention, in the dental photocurable composition, (A) with respect to 100 parts by mass of the polymerizable monomer,
(B) 0.02 to 1 part by mass of a photosensitizer (C1) 0.5 to 10 parts by mass of an iodonium salt compound having a structure represented by formula (1) (D) 0.1 of a photopolymerization accelerator ~10 parts by weight.

Each component of the photocurable dental composition of the present invention will be described in detail below.
The dental photocurable composition of the present invention can be used as a dental adhesive, a dental composite resin, a dental abutment building material, a dental resin cement, a dental coating material, a dental pit and fissure sealing material, and a dental adhesive. It is applied as a manicure material, a dental loose tooth fixing adhesive material, a dental glass ionomer cement, a dental hard resin, a dental cutting material, a dental 3D printer material, and the like.

In clinical dentistry, in order to perform aesthetic and functional restoration of tooth defects caused by caries, fractures, etc., direct restoration methods using dental adhesives and composite resins, ceramics and hard dental resins are used. Treatment by an indirect method is performed by restoring a prosthetic device consisting of dental resin cement. In addition, dental composite resin and various dental materials and dental adhesives for attaching natural teeth, dental adhesives for fixing swayed teeth, hyperesthesia and living teeth after formation Dental coatings to protect against secondary caries, dental pit and fissure sealants to prevent caries by filling deep fissures in molars, temporary esthetics by masking tooth discoloration A dental manicure material is used for restoration to the natural state, and a dental abutment building material is used for forming an abutment tooth when the crown is destroyed by caries. In recent years, composite materials such as dental cutting materials for making prosthetic devices using CAD/CAM processing, and dental 3D printer materials for making prosthetic devices using 3D printers have been developed. Used. Materials such as those described above are mixed with a resin matrix consisting of several types of polymerizable monomers, various fillers such as inorganic fillers and organic-inorganic composite fillers, and polymerization initiators according to the application, and are prepared into a uniform paste. be done. To give an example of some materials, dental filling composite resins are filled into teeth in an unhardened paste state, and after giving the anatomical shape of natural teeth with dental instruments such as instruments, It is used by irradiating light with a light irradiator or the like for curing. As the irradiation light from the light irradiator, a light source with a light intensity of about 100 to 2000 mW/cm ² in a wavelength range of about 360 to 500 nm is generally used. On the other hand, dental resin cement is used to bond a prosthetic device to a cavity or an abutment tooth, and is cured by light irradiation after the prosthetic device is attached to the cavity or the abutment tooth.

As photopolymerization initiators used in such dental materials, photosensitizers and systems in which photosensitizers are combined with suitable photopolymerization accelerators are widely used. Acylphosphine oxide compounds and α-diketone compounds are known as photosensitizers, and α-diketone compounds in particular have the ability to initiate polymerization in the visible light wavelength range, which has little effect on the human body. Tertiary amine compounds are well known as a polymerization accelerator to be combined with a photosensitizer. It is used in the field of dental materials. A dental photocurable composition containing the photopolymerization initiator exhibits excellent mechanical properties such as hardness, flexural strength, and compressive strength required for various materials.

However, when the combination of the α-diketone compound and the tertiary amine compound is used as a photopolymerization initiator, there arises a problem of poor environmental light stability. In other words, it is performed under white light (environmental light) such as a dental light that illuminates the oral cavity or a room light such as a fluorescent lamp, but only the combination of the α-diketone compound and the tertiary amine compound is used. is used as a photopolymerization initiator, it exhibits high sensitivity not only to irradiation light but also to ambient light. There was a problem that the viscosity of the liquid increased and the operation became difficult.

In order to solve the above problems, a photopolymerization initiator comprising an aryliodonium salt as a photoacid generator, a sensitizer and an electron donor compound has been proposed. There was a problem with color tone stability.

It has been found that the dental photocurable composition of the present invention exhibits excellent color tone stability when a photoacid generator having a specific structure is used. Furthermore, the inventors have found that the mechanical strength is also excellent by using a specific compounding amount of a photoacid generator, leading to the present invention.

[(A) polymerizable monomer]
As the polymerizable monomer (A) contained in the dental photocurable composition of the present invention, any known polymerizable monomer can be used without limitation. In the compound having a polymerizable monomer or a polymerizable group according to the present invention, the polymerizable group preferably exhibits radical polymerizability. Specifically, from the viewpoint of facilitating radical polymerization, the polymerizable group is ( A meth)acryl group and/or a (meth)acrylamide group are preferred. In the present specification, "(meth)acrylic" means acrylic and / or methacrylic, "(meth)acryloyl" means acryloyl and / or methacryloyl, "(meth)acrylate" means acrylate and and/or methacrylate, "(meth)acrylamide" means acrylamide and/or methacrylamide. A polymerizable monomer having a substituent at the α-position of an acrylic group and/or an acrylamide group can also be preferably used. Examples include those having one radically polymerizable group, those having two radically polymerizable groups, those having three or more radically polymerizable groups, those having an acidic group, those having an alkoxysilyl group, those having a sulfur atom, and the like.

Specific examples of polymerizable monomers having one radically polymerizable group and no acidic group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, ) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerol mono ( meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) ) acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, 3-(meth)acryloyloxypropyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, (meth)acrylamide and the like.

Specific examples of the polymerizable monomer having two radical polymerizable groups and no acidic group include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3 -(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as "Bis-GMA"), 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(4-( meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2, 2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl) -2-(4-(meth)acryloyloxydiethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyditriethoxyphenyl)propane, 2- (4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2 -bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 1,4-bis(2-(meth)acryloyloxyethyl)pyromellitate, glycerol di(meth)acrylate, 1-(acryloyloxy)-3-( methacryloyloxy)-2-propanol, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl Glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate , 1,10-decanediol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, 2,2,4- and 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane and the like.

Specific examples of the polymerizable monomer having three or more radically polymerizable groups and no acidic group include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri( meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4-trimethylhexamethylene)bis[2-(amino carboxy)propane-1,3-diol]tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane and the like.

The polymerizable monomer having an acidic group has at least one polymerizable group and at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group. Any polymerizable monomer can be used without limitation. By including a polymerizable monomer having an acidic group, it is possible to impart adhesiveness to dentin and prosthetic devices.

Specific examples of polymerizable monomers having a phosphoric acid group include 2-(meth)acryloyloxyethyl dihydrogenphosphate, 3-(meth)acryloyloxypropyl dihydrogenphosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth) acryloyloxypentyl dihydrogen phosphate, 6-(meth) acryloyloxyhexyl dihydrogen phosphate, 7-(meth) acryloyloxyheptyl dihydrogen phosphate, 8-(meth) acryloyl oxyoctyl dihydrogen phosphate, 9-(meth) acryloyloxy nonyl dihydrogen phosphate, 10-(meth) acryloyl oxydecyl dihydrogen phosphate, 11-(meth) acryloyl oxyundecyl dihydrogen phosphate, 12-( meth) acryloyl oxide decyl dihydrogen phosphate, 16-(meth) acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth) acryloyloxyicosyl dihydrogen phosphate, bis[2-(meth) acryloyloxyethyl] hydro gen phosphate, bis[4-(meth)acryloyloxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogenphosphate, bis[8-(meth)acryloyloxyoctyl]hydrogenphosphate, bis[ 9-(meth)acryloyloxynonyl]hydrogen phosphate, bis[10-(meth)acryloyloxydecyl]hydrogenphosphate, 1,3-di(meth)acryloyloxypropyl dihydrogenphosphate, 2-(meth)acryloyl Oxyethylphenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl] hydrogen phosphate; acid chlorides thereof compounds, alkali metal salts, ammonium salts; and (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond.

Specific examples of the polymerizable monomer having a pyrophosphate group include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6- (meth)acryloyloxyhexyl], bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate; acid chlorides, alkali metal salts and ammonium salts thereof; and Examples include (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

Specific examples of polymerizable monomers having a thiophosphate group include 2-(meth)acryloyloxyethyl dihydrogenthiophosphate, 3-(meth)acryloyloxypropyl dihydrogenthiophosphate, 4-(meth)acryloyl oxybutyl dihydrogenthiophosphate, 5-(meth)acryloyloxypentyl dihydrogenthiophosphate, 6-(meth)acryloyloxyhexyl dihydrogenthiophosphate, 7-(meth)acryloyloxyheptyl dihydrogenthiophosphate, 8-(meth)acryloyloxyoctyl dihydrogenthiophosphate, 9-(meth)acryloyloxynonyl dihydrogenthiophosphate, 10-(meth)acryloyloxydecyl dihydrogenthiophosphate, 11-(meth)acryloyloxyun Decyl dihydrogenthiophosphate, 12-(meth)acryloyl oxide decyl dihydrogenthiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogenthiophosphate, 20-(meth)acryloyloxyicosyl dihydrogenthiophosphate acid chlorides, alkali metal salts and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond. A polymerizable monomer having a thiophosphoric acid group is also classified as a polymerizable monomer having a sulfur atom.

Specific examples of polymerizable monomers having a phosphonic acid group include 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyl Oxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonoacetate, 10-(meth)acryloyloxy decyl-3-phosphonoacetate; acid chlorides, alkali metal salts and ammonium salts thereof; and (meth)acrylamide compounds in which the ester bond of these compounds is replaced with an amide bond.

Specific examples of polymerizable monomers having a sulfonic acid group include 2-(meth)acrylamido-2-methylpropanesulfonic acid and 2-sulfoethyl (meth)acrylate.

Polymerizable monomers having a carboxylic acid group are classified into (meth)acrylic compounds having one carboxyl group in the molecule and (meth)acrylic compounds having a plurality of carboxyl groups in the molecule. Specific examples of (meth)acrylic compounds having one carboxyl group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloyl aspartic acid, O-(meth)acryloyl Tyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4 -aminosalicylic acid, 2-(meth)acryloyloxyethylhydrogensuccinate, 2-(meth)acryloyloxyethylhydrogenphthalate, 2-(meth)acryloyloxyethylhydrogenmalate; acid halides thereof; Examples thereof include (meth)acrylamide compounds in which the ester bond of the compound is replaced with an amide bond. Specific examples of (meth)acrylic compounds having multiple carboxyl groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1- Dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydecane-1,1-dicarboxylic acid , 13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3′-(meth)acryloyloxy-2′-(3,4-dicarboxybenzoyloxy)propyl succinate acid anhydrides and acid halides thereof; and (meth)acrylamide compounds obtained by replacing the ester bond of these compounds with an amide bond.

Preferred are 10-methacryloyloxydecyl dihydrogen phosphate and 6-methacryloyloxyhexyl phosphonoacetate. From the viewpoint of imparting adhesiveness, the amount of the polymerizable monomer having an acidic group is 1 part by mass or more with respect to 100 parts by mass of the total amount of polymerizable monomers contained in the dental photocurable composition. A blending amount of 10 parts by mass or more is preferable. If the amount is less than 1 part by mass, the adhesiveness to dentin, metals and metal oxides may not be sufficiently exhibited.

Specific examples of polymerizable monomers having an alkoxysilyl group include (meth)acrylic compounds and (meth)acrylamide compounds having one alkoxysilyl group in the molecule, and multiple alkoxysilyl groups in the molecule. and (meth)acryl-based compounds and (meth)acrylamide-based compounds having 2-(meth)acryloxyethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 4- (Meth) acryloxybutyltrimethoxysilane, 5-(meth)acryloxypentyltrimethoxysilane, 6-(meth)acryloxyhexyltrimethoxysilane, 7-(meth)acryloxyheptyltrimethoxysilane, 8-(meth) ) acryloxyoctyltrimethoxysilane, 9-(meth)acryloxynonyltrimethoxysilane, 10-(meth)acryloxydecyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane. Furthermore, 3,3-dimethoxy-8,37-dioxo-2,9,36-trioxa-7,38-diaza-3-silatetracontan-40-yl (meth)acrylate as having a urethane group or an ether group , 2-((3,3-dimethoxy-8-oxo-2,9,18-trioxa-7-aza-3-silanonadecane-19-oyl)amino)-2-methylpropane-1,3-diyl di(meth ) acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,18-trioxa-7,20-diaza-3-siladocosan-22-yl (meth)acrylate, 3,3-dimethoxy-8,22 -dioxo-2,9,12,15,18,21-hexaoxa-7,23-diaza-3-silapentacosan-25-yl (meth)acrylate, 3,3-dimethoxy-8,22-dioxo-2,9 , 12,15,18,21,26-heptaoxa-7,23-diaza-3-silaoctacosan-28-yl (meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15 ,18-pentoxa-7,20-diaza-3-siladocosan-22-yl (meth)acrylate, 3,3-dimethoxy-8,19-dioxo-2,9,12,15,18,23-hexaoxa-7 , 20-diaza-3-silapentacosan-25-yl (meth)acrylate, 2-((3,3-dimethoxy-8-oxo-2,9,12,15,18-pentoxa-7-aza-3-silanonadecane -19-Oil)amino)-2-methylpropane-1,3-diyl di(meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosane-23 -yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16,21,24-tetraoxa-18-aza-4-silahexacosan-26-yl (meth)acrylate, 4,4-diethoxy-13 -oxo-3,12,17-trioxa-14-aza-4-silanonadecane-19-yl (meth)acrylate, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silicosane -20-yl (meth)acrylate, 2-methyl-2-((11-(triethoxysilyl)undecyloxy)carbonylamino)propane-1,3-diyl di(meth)acrylate.

The dental photocurable composition of the present invention can contain a polymerizable monomer having a sulfur atom as (A) a polymerizable monomer in order to impart adhesion to noble metals. Known compounds can be used without any limitation as long as the polymerizable monomer having a sulfur atom is a polymerizable monomer having one or more sulfur atoms and a polymerizable group. Specifically, it refers to a compound having a partial structure such as -SH, -S-S-, >C=S, >C-S-C<, >P=S or resulting from tautomerism. Specific examples include 10-methacryloxydecyl-6,8-dithiooctanate, 6-methacryloxyhexyl-6,8-dithiooctanate, 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate, 2-( 11-methacryloyloxyundecylthio)-5-mercapto-1,3,4-thiadiazole and 10-(meth)acryloyloxydecyl dihydrogenthiophosphate.

In addition to these polymerizable monomers, oligomers or prepolymers having at least one polymerizable group in the molecule may be used without any limitation. Moreover, there is no problem even if the same molecule has a substituent such as a fluoro group. The polymerizable monomers described above can be used singly or in combination.

The dental photocurable composition of the present invention can contain a silane coupling agent as (A) a polymerizable monomer in order to impart adhesion to glass ceramics. Any known silane coupling agent can be used without limitation, but 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 11-methacryloxyundecyltrimethoxysilane and the like are preferred. From the viewpoint of imparting adhesiveness, the blending amount is 1 part by mass or more, more preferably 5 parts by mass or more and less than 20 parts by mass, per 100 parts by mass of the total amount of polymerizable monomers in the composition. Since the silane coupling agent as a polymerizable monomer is intended to impart adhesion to glass ceramics and resin materials containing fillers made of glass ceramics, it is blended separately from surface treatment agents for fillers.

The dental photocurable composition of the present invention can contain, as (A) a polymerizable monomer, a polymerizable monomer having a sulfur atom in order to impart adhesion to noble metals. The amount of the polymerizable monomer having a sulfur atom is 0.01 parts by mass or more based on the total amount of 100 parts by mass of the polymerizable monomers contained in the photocurable dental composition from the viewpoint of imparting adhesiveness. , more preferably 0.1 parts by mass or more and less than 20 parts by mass.

The polymerizable monomer contained in the dental photocurable composition of the present invention may contain a polymerizable monomer having a cationically polymerizable functional group. It is preferred to include only mers.

<Photoinitiator>
The dental photocurable composition of the present invention contains a photoinitiator. A photopolymerization initiator is a polymerization initiator capable of initiating polymerization by irradiation with light. The photopolymerization initiator used in the dental photocurable composition of the present invention includes (B) a photosensitizer, (C) a photoacid generator, and (D) a polymerization accelerator. Known compounds for use can be used without any limitation.

[(B) Photosensitizer]
Specific examples of the (B) photosensitizer that can be used in the present invention include benzyl, camphorquinone, camphorquinone carboxylic acid, camphorquinone sulfonic acid, α-naphthyl, acetonaphthene, p,p'-dimethoxybenzyl. , p,p'-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, α-diketones such as naphthoquinone, benzoin , benzoin methyl ether, benzoin alkyl ethers such as benzoin ethyl ether, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2 , thioxanthone such as 4-diisopropylthioxanthone, benzophenone, p-chlorobenzophenone, p-methoxybenzophenone and other benzophenones, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl) (2 ,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylprop-1-yl)phosphine oxide, bis (2,6-dimethoxybenzoyl)-(1-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, Bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylprop-1-yl)phosphine oxide , bis(2,6-diethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6 -dibutoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenyl Phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis (2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoyl Acylphosphine oxides such as benzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide and 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide, bis Acylgermanium compounds such as benzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis(4-methoxybenzoyl)dimethylgermanium, and bis(4-methoxybenzoyl)diethylgermanium, 2-benzyl-dimethylamino-1-( α-aminoacetophenones such as 4-morpholinophenyl)-butanone-1, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-propanone-1, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl (2- ketals such as methoxyethyl ketal), bis(cyclopentadienyl)-bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]-titanium, bis(cyclopentadienyl)-bis(pentanefluorophenyl )-titanium, bis(cyclopentadienyl)-bis(2,3,5,6-tetrafluoro-4-disiloxyphenyl)-titanium, and the like.

(B) The photosensitizer can be appropriately selected according to the wavelength, intensity, and irradiation time of light used for polymerization, and the types and amounts of other components to be combined. Moreover, a photosensitizer can be used individually or in combination of 2 or more types. Among them, α-diketone compounds having a maximum absorption wavelength in the visible light region are preferably used, and more preferably camphorquinone compounds such as camphorquinone, camphorquinone carboxylic acid, and camphorquinone sulfonic acid. , and especially camphorquinone is preferred because of its easy availability.

The (B) photosensitizer contained in the dental photocurable composition of the present invention may be an α-diketone compound alone. When only the α-diketone compound is used, the environmental light stability and the color tone of the cured product may be excellent.

Usually, the amount of the photosensitizer (B) is 0.02 to 1.0 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental photocurable composition. Preferably, it is 0.05 to 0.5 parts by mass. (B) If the amount of the photosensitizer is less than 0.02 parts by mass, the polymerization activity against irradiation light is poor, resulting in insufficient curing. If the amount is more than 1.0 part by mass, sufficient curability may be exhibited, but environmental light stability and light color stability may be deteriorated.

[(C) Photoacid Generator]
The dental photocurable composition of the present invention contains (C) an iodonium salt compound having a structure represented by formula (1) as (C1) a photoacid generator. In the dental photocurable composition of the present invention, (C1) other known photoacid generators can be used together with the iodonium salt compound having the structure represented by formula (1) without limitation. Specific examples include triazine compounds, iodonium salt compounds, sulfonium salt compounds, sulfonic acid ester compounds, and the like. Among these, triazine compounds and iodonium salt compounds are preferred because of their high polymerizability when used in combination with a sensitizer. Iodonium salt compounds are more preferred. An iodonium salt compound is susceptible to sensitization by a photosensitizer having absorption in the visible light region.

Specific examples of triazine compounds 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-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. Among these, 2,4,6-tris(trichloromethyl)-s-triazine is preferred.

Any known iodonium salt compound can be used. As a specific example, the structural formula of the iodonium salt compound can be represented by the following [formula (2)].

[Formula (2)]
[(R1)₂I]⁺ [A]^-

([(R1) in the formula₂I]⁺is a cationic moiety, [A]^-is an anionic moiety, R1 in formula (2) represents an organic group attached to I, and R1 may be the same or different. R1 is, for example, an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms. These are alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, It may be substituted with at least one selected from the group consisting of arylsulfonyl, alkyleneoxy, amino, cyano and nitro groups and halogen. )

In the above, the aryl group having 6 to 30 carbon atoms includes a monocyclic aryl group such as a phenyl group and condensed groups such as naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone and anthraquinone. Polycyclic aryl groups are included.

Examples of heterocyclic groups having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 heteroatoms such as oxygen, nitrogen and sulfur, which may be the same or different. is a monocyclic heterocyclic group such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl; , carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl, and other condensed polycyclic heterocyclic groups.

Specific examples of alkyl groups having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl and octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and tert-pentyl. , branched alkyl groups such as isohexyl, and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Further, specific examples of alkenyl groups having 2 to 30 carbon atoms include linear groups such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl and 1-methyl-1-propenyl. or branched ones.

Furthermore, specific examples of alkynyl groups having 2 to 30 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl, 1-methyl- Linear or branched ones such as 2-propynyl are included.

The above aryl group having 6 to 30 carbon atoms, heterocyclic group having 4 to 30 carbon atoms, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms or alkynyl group having 2 to 30 carbon atoms is at least one Specific examples of substituents include straight-chain alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, octadecyl; isopropyl, isobutyl, sec-butyl, tert- branched alkyl groups having 1 to 18 carbon atoms such as butyl; cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; hydroxy groups; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy , tert-butoxy, dodecyloxy and the like linear or branched alkoxy groups having 1 to 18 carbon atoms; Linear or branched alkylcarbonyl group having a number of 2 to 18; arylcarbonyl group having 7 to 11 carbon atoms such as benzoyl and naphthoyl; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec- linear or branched alkoxycarbonyl groups having 2 to 19 carbon atoms such as butoxycarbonyl and tert-butoxycarbonyl; aryloxycarbonyl groups having 7 to 11 carbon atoms such as phenoxycarbonyl and naphthoxycarbonyl; phenylthiocarbonyl, naphthoxythiocarbonyl and the like arylthiocarbonyl group having 7 to 11 carbon atoms; straight chain or 2 to 19 carbon atoms such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octadecylcarbonyloxy Branched acyloxy group; phenylthio, biphenylylthio, methylphenylthio, chlorophenylthio, bromophenylthio, fluorophenylthio, hydroxyphenylthio, methoxyphenylthio, naphthylthio, 4-[4-(phenylthio)benzoyl]phenylthio, 4- [4-(phenylthio)phenoxy]phenylthio, 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoylphenylthio, 4-benzoyl- Arylthio groups having 6 to 20 carbon atoms such as chlorophenylthio, 4-benzoyl-methylthiophenylthio, 4-(methylthiobenzoyl)phenylthio, 4-(ptert-butylbenzoyl)phenylthio; methylthio, ethylthio, propylthio, tert-butylthio, neo Linear or branched alkylthio groups having 1 to 18 carbon atoms such as pentylthio and dodecylthio; Aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, dimethylphenyl and naphthyl; , thioxanthonyl, dibenzofuranyl and other heterocyclic groups having 4 to 20 carbon atoms; aryloxy groups having 6 to 10 carbon atoms such as phenoxy and naphthyloxy; methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, octylsulfinyl and other carbon Linear or branched alkylsulfinyl groups of number 1 to 18; arylsulfinyl groups of 6 to 10 carbon atoms such as phenylsulfinyl, tolylsulfinyl, naphthylsulfinyl; methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, octylsulfonyl A linear or branched alkylsulfonyl group having 1 to 18 carbon atoms such as; Halogens such as fluorine, chlorine, bromine and iodine are included.

Among iodonium salt compounds, aryliodonium salts are preferred because of their high stability. In addition, the aryl group preferably has a substituent in order to improve fat solubility. Specifically, straight chain alkyl groups such as methyl, propyl, octyl, decyl, undecyl, dodecyl and tridecyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl and isohexyl. Alternatively, functional groups in which one or more of these H are substituted with F, perfluoroalkyl groups, halogens, and the like are suitable as substituents.

Although the structure of the anion portion of the iodonium salt-based compound is not particularly limited, examples thereof include those having atoms such as halogen, P, S, B, Al and Ga. Although anions containing As or Sb can be used from the viewpoint of safety, they are not preferable for dental applications. In addition, the anion preferably has an organic group such as an alkyl group and/or an alkoxy group and/or an aryl group, and an alkyl group and/or an alkoxy group in which at least one or more H is substituted with F and/or an organic group such as an aryl group. Since the iodonium salt compound having such an anion is highly soluble in the dental photocurable composition, it prevents precipitation during low-temperature storage or long-term storage and dissolves in the composition in a short time. Shorter manufacturing time can be expected. In addition, an iodonium salt-based compound composed of an anion having an organic group such as an alkyl group, an alkoxy group, and/or an aryl group in which one or more H is substituted with F can be expected to have even higher solubility. Precipitation of the photo-acid generator is not preferable because it may cause deterioration in light color stability and bending strength. Such anions having organic groups such as alkyl groups and/or alkoxy groups and/or aryl groups in which at least one or more H may be substituted with F, use anions having any atoms. However, those containing P, S, B, Al, and Ga are preferable from the viewpoint of versatility and safety.

Examples of anions having no alkyl group and/or alkoxy group and/or aryl group include halogens such as chloride and bromide, perhalogen acids such as perchloric acid, aromatic sulfonic acids such as p-toluenesulfonate, and camphorsulfone. Acids, nitrates, acetates, chloroacetates, carboxylates, phenolates, tetrafluoroborates, hexafluorophosphates, hexafluoroantimonates, hexafluoroarsenates and the like. Among these, p-toluenesulfonate, camphorsulfonic acid and carboxylate are preferably used.

Since the anion portion of [A] ^- of the iodonium salt compound of formula (2) improves the solubility in the dental photocurable composition, at least one or more H is an alkyl group substituted with F and It is preferably an anion having an organic group such as/or an alkoxy group and/or an aryl group. Specifically, the number of carbon atoms in the alkyl group of the [A] ^- anion portion of the iodonium salt compound of formula (2) is preferably 1-8, preferably 1-4. Specific examples include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl sec-butyl and tert-butyl; and cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups. An alkyl group and the like can be mentioned. The ratio (F/H) of the number of hydrogen atoms to fluorine atoms in the alkyl group is 4 or more, preferably the ratio (F/H) of the number of hydrogen atoms to fluorine atoms in the alkyl group is 9 or more. More preferably, all hydrogen atoms in the hydrocarbon are substituted with fluorine. Iodonium salts composed of anions having alkyl groups with different ratios of hydrogen atoms and fluorine atoms may be blended in the dental photocurable composition.

Furthermore, specific examples of alkyl groups include CF ₃ , CF ₃ CF ₂ , (CF ₃ ) 2 CF, CF ₃ CF ₂ CF ₂ , CF ₃ CF ₂ CF _{2 CF 2} , (CF ₃ ) ₂ CFCF ₂ , Linear or branched perfluoroalkyl groups such as CF ₃ CF ₂ (CF ₃ )CF and (CF ₃ ) ₃ C are included.

The number of carbon atoms in the alkoxy group of the [A] ^- anion portion of the iodonium salt compound of formula (2) is preferably 1-8, preferably 1-4. Specific examples include linear alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentoxy and octoxy, and branched alkoxy groups such as isopropoxy, isobutoxy, sec-butoxy and tert-butoxy. The ratio (F/H) of the number of hydrogen atoms to fluorine atoms in the alkyl group is 4 or more, preferably the ratio (F/H) of the number of hydrogen atoms to fluorine atoms in the alkyl group is 9 or more. More preferably, all hydrogen atoms in the hydrocarbon are substituted with fluorine. Iodonium salts composed of anions having alkoxy groups with different ratios of hydrogen atoms and fluorine atoms may be blended in the dental photocurable composition.

Further, _specific examples of alkoxy _{groups include CF3O , CF3CF2O , CF3CF2CF2O} , ( _CF3 ) _{2CFO , CF3CF2CF2CF2O} , ( _CF3 ) _{Linear chains such as 2CFCF2O , CF3CF2 ( CF3 ) CFO , CF3CF2CF2CF2CF2O , CF3CF2CF2CF2CF2CF2CF2CF2CF2O _ _ _ _} or a branched perfluoroalkoxy group.

At least one hydrogen atom in the phenyl group of the anion portion of [A] ^- of the iodonium salt compound of formula (2) is a fluorine atom, and/or an alkyl group and/or an alkoxy group substituted with a fluorine atom. has a phenyl group substituted with The fluorine-substituted alkyl and/or alkoxy groups are preferably those described above. Specific examples of particularly preferred phenyl groups include a pentafluorophenyl group (C ₆ F ₅ ), a trifluorophenyl group (C ₆ H ₂ F ₃ ), a tetrafluorophenyl group (C ₆ HF ₄ ), a trifluoromethylphenyl group ( CF ₃ C ₆ H ₄ ), bis(trifluoromethyl)phenyl group ((CF ₃ ) ₂ C ₆ H ₃ ), pentafluoroethylphenyl group (CF ₃ CF ₂ C ₆ H ₄ ), bis(pentafluoroethyl) phenyl group (( _{CF3CF2 ) 2C6H3 )} , _{trifluoromethylfluorophenyl group ( CF3C6H3F )} , bistrifluoromethylfluorophenyl group ₍ ( _CF3 ) _2C6H2F ) , pentafluoroethylfluorophenyl group (CF ₃ CF ₂ C ₆ H ₃ F), and bispentafluoroethylfluorophenyl group ((CF ₃ CF ₂ ) ₂ C ₆ H ₂ F). Iodonium salts composed of anions having phenyl groups with different ratios of hydrogen atoms and fluorine atoms may be blended in the dental photocurable composition.

As specific examples of the anion moiety of [A] ^- in the iodonium salt compound of formula (2), the anion having P is [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₄ PF ₂ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ and the like. Anions with S are [(CF ₃ SO ₂ ) ₃ C] ⁻ , [(CF ₃ CF ₂ SO ₂ ) ₃ C] ⁻ , [(CF ₃ CF ₂ CF ₂ SO ₂ ) ₃ C] ⁻ , [( CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₃ C] ⁻ , [CF ₃ CF ₂ CF ₂ CF ₂ SO ₃ ] ⁻ , [CF ₃ CF ₂ CF ₂ SO ₃ ] ⁻ , [(CF ₃ CF ₂ SO ₂ ) ₃ C] ⁻ , [(SO ₂ CF ₃ ) ₃ N] ⁻ , [(SO ₂ CF ₂ CF ₃ ] ₂ N] ⁻ , [((CF ₃ )C ₆ H ₄ )SO ₃ ] ⁻ , [SO ₃ ((CF ₂ CF ₂ CF ₂ CF ₂ )SO ₃ ] ^2- and the like. Anions having B include [B(C ₆ F ₅ ) ₄ ] ⁻ , [(C ₆ H ₅ )B((CF ₃ ) ₂ C ₆ H ₃ ) ₃ ] ⁻ , [(C ₆ H ₅ )B(C ₆ F ₅ ) ₃ ] ⁻ , etc. An anion having Ga is [((CF ₃ ) ₄ Ga)] ^- , [Ga(C ₆ F ₅ ) ₄ ] ^- etc. Examples of Al-containing anions include [((CF ₃ ) ₃ CO) ₄ Al] ^- , [((CF ₃ CF ₂ ) ₃ CO) ₄ Al ] ^- and the like.

（式中、Ｒ_１とＲ_２は有機基であり、複数存在しても良い。置換基である全てのＲ_１とＲ_２を構成する有機基の炭素数の合計は６以上である。） The dental photocurable composition of the present invention contains (C) an iodonium salt compound having a structure represented by formula (1) as (C1) a photoacid generator.
[Formula (1)]

(In the formula, R ₁ and R ₂ are organic groups, and a plurality of them may be present. The total number of carbon atoms of the organic groups constituting all R ₁ and R ₂ as substituents is 6 or more.)

The structure of formula (1) shows the structure of a diaryliodonium cation, and the aryl group has substituents R ₁ and/or R ₂ . R ₁ and R ₂ in the structure of formula (1) are organic groups. Dental photo-curing containing 0.5 parts by mass or more of an iodonium salt compound in which the total number of carbon atoms of the organic groups constituting R ₁ and R ₂ is less than 6 with respect to 100 parts by mass of the polymerizable monomer (A) The composition tended to lose color stability. More specifically, when a product is subjected to an immersion test in high-temperature water assuming long-term use and a lightfastness test to confirm the effect of discoloration due to light, if the product undergoes significant discoloration, color unevenness, or black spots, it will improve aesthetics. tended to be damaged. On the other hand, a photo-acid generator containing an iodonium salt-based compound in which the total number of carbon atoms of the organic groups constituting R ₁ and R ₂ is 6 or more is added in an amount of 0.00 per 100 parts by mass of the polymerizable monomer (A). A dental photocurable composition containing 5 parts by mass or more can maintain aesthetics without noticeable discoloration, uneven color, or black spots when subjected to a high-temperature water immersion test and a light resistance test assuming long-term use. It was also found that good mechanical strength can be expressed.

(C1) R ₁ and R ₂ of the iodonium salt compound having the structure represented by formula (1) are organic groups. There are functional groups in which some H are replaced by F or perfluoro groups in which all H are replaced by F. Also, the organic group may have an ester group, an ether group, a urethane group and/or a urea group. (C1) The iodonium salt compound having the structure represented by formula (1) may have substituents in addition to R ₁ and R ₂ . Examples include fluoro, chloro, bromo, nitro, hydroxy, amino and the like. However, a photocurable dental composition containing an iodonium salt compound having a nitro group or an amino group as a substituent of an aryl group may exhibit a strong brownish or yellowish tinge after curing, or may exhibit light color stability or heat color stability. It is not preferred because it may lack sexuality.

The total number of carbon atoms of the organic groups constituting all the substituents R ₁ and R ₂ is 6 or more, preferably 8 or more and 26 or less. Further, the total number of carbon atoms is preferably as large as 8 to 26. As the number of carbon atoms increases, the solubility in the composition improves, so the time required to prepare the dental photocurable composition is shortened, the storage stability is improved, and the staining resistance is improved. In addition, it is expected that the compound itself will be difficult to be eluted from the composition and that the safety of the compound itself will be improved, which will lead to a reduction in toxicity to the body, such as acute toxicity, and an improvement in biosafety. On the other hand, if it is larger than 26, the reaction rate may decrease during photopolymerization. (C1) Among the iodonium salt compounds having the structure represented by formula (1), it is particularly preferred that the organic chain of R ₁ and/or R ₂ has an alkyl chain with 8 or more carbon atoms. Examples of such an alkyl chain include an octyl group, nonyl group, decyl group, octadecyl group, icosyl group, and octyloxy group. There is no problem even if there is. Such a compound can be expected to have high solubility regardless of the anionic species, and can be expected to exhibit excellent color tone stability when used in the dental photocurable composition of the present invention.

(C1) The anion of the iodonium salt-based compound having the structure represented by formula (1) is preferably an anion having an organic group, more preferably an organic group in which at least one or more H is F-substituted and P, An anion having one or more atoms selected from B, Al, S, and Ga. An iodonium salt compound having such an anion may provide good light color stability of the dental photocurable composition immediately after preparation and high storage stability.

The dental photocurable composition of the present invention may contain only the iodonium salt compound (C1) as (C) a photoacid generator. The dental photocurable composition of the present invention contains only an aryliodonium salt, which is a salt of an aryliodonium cation and an anion having an organic group and one or more atoms of P, B, Al, S and Ga. may contain. The dental photocurable composition of the present invention comprises (C) a photoacid generator comprising at least one organic group in which H is substituted with F and at least one of P, B, Al, S and Ga. with an aryliodonium cation.

The dental photocurable composition of the present invention contains 0.5 parts by mass or more, preferably 1 part by mass, of (C) a photoacid generator based on 100 parts by mass of (A) the total amount of polymerizable monomers. Above, more preferably 1 to 5 parts by mass. If the amount of the photoacid generator (C) is less than 0.5 parts by mass, sufficient mechanical strength may not be obtained. When 0.5 parts by mass or more of a photoacid generator other than (C1) is contained as the photoacid generator (C), the color stability may deteriorate. If the amount of the photoacid generator other than (C1) is less than 0.5 parts by mass, the color stability may not decrease, but (C1) and the photoacid generator other than (C1) may not be reduced. Combined use is not preferred because it is complicated.

The photoacid generator that can be used in the dental photocurable composition of the present invention is not limited to the photoacid generators shown in the specific examples, and two or more of them can be used in combination.

[(D) Photopolymerization accelerator]
The (D) photopolymerization accelerator used in the dental photocurable composition of the present invention is not particularly limited as long as it has a polymerization promoting ability, and known photopolymerization accelerators generally used in the dental field are not particularly limited. can be used. As the photopolymerization accelerator, aromatic amine compounds, primary to tertiary amine compounds such as aliphatic amine compounds, organometallic compounds, phosphine compounds, and the like can be used. Among these, tertiary aliphatic amine compounds, organometallic compounds, and phosphine compounds are preferred because of their good light color stability.

Specific examples of the above organometallic compounds include scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu ), tin (Sn), zinc (Zn) and zirconia (Zr), preferably tin (Sn), vanadium (V) and copper (Cu). Specific examples of organometallic compounds containing tin (Sn) include dibutyl-tin-diacetate, dibutyl-tin-dimaleate, dioctyl-tin-dimaleate, dioctyl-tin-dilaurate, dibutyl-tin-dilaurate, and dioctyl-tin-diversate. , dioctyl-tin-S,S'-bis-isooctylmercaptoacetate, tetramethyl-1,3-diacetoxydistannoxane, etc. Specific examples of organometallic compounds containing vanadium (V) include acetylacetone vanadium , divanadium tetroxide, vanadyl acetylacetonate, vanadium stearate oxide, vanadyl oxalate, vanadyl sulfate, oxobis(1-phenyl-1,3-butanedionate)vanadium, bis(maltrate)oxovanadium, vanadium pentoxide, Examples include sodium metavanadate, and specific examples of organometallic compounds containing copper (Cu) include copper acetylacetone, copper naphthenate, copper octylate, copper stearate, and copper acetate.

A phosphine compound refers to a compound in which the P atom is substituted with three organic groups, and an aromatic phosphine compound refers to a compound in which the P atom is substituted with a phenyl group which may have one or more substituents. Specific examples of phosphine compounds include trimethylphosphine, tributylphosphine, trihexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tri(2-thienyl)phosphine, diphenylpropylphosphine, di-tert-butyl(3-methyl -2-butenyl)phosphine, methyldiphenylphosphine, triphenylphosphine, 2-(diphenylphosphino)styrene, 3-(diphenylphosphino)styrene, 4-(diphenylphosphino)styrene, allyldiphenylphosphine, 2-(diphenyl Phosphino)benzaldehyde, 3-(diphenylphosphino)benzaldehyde, 4-(diphenylphosphino)benzaldehyde, 2-(phenylphosphino)benzoic acid, 3-(phenylphosphino)benzoic acid, 4-(phenylphosphino) Benzoic acid, tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, 2-(diphenylphosphino)biphenyl, tris(4-fluorophenyl)phosphine, tri( o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, 2-(dimethylamino)phenyldiphenylphosphine, 3-(dimethylamino)phenyldiphenylphosphine, 4-(dimethylamino)phenyldiphenyl phosphine, 2,2′-bis(diphenylphosphino)biphenyl, bis[2-(diphenylphosphino)phenyl]ether and the like. Among these, triphenylphosphine, 4-(phenylphosphino)benzoic acid, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine and tri(p-tolyl)phosphine are preferred.

An aromatic amine compound refers to a compound in which one or more Hs of ammonia (NH ₃ ) are substituted on an aromatic ring. One H of _NH3 is substituted with an aromatic ring is an aromatic primary amine compound, one H of _NH3 is substituted with an aromatic ring, and one different H is substituted with an aromatic ring or an alkyl group. Those in which one H of _NH3 is substituted by an aromatic ring and two different Hs are substituted by aromatic rings or alkyl groups are called aromatic tertiary amine compounds. can be classified.

Specific examples of aromatic primary amine compounds include aniline, and specific examples of aromatic secondary amine compounds include N-phenylbenzylamine, N-benzyl-p-anisidine and N-benzyl-o-phenetidine. , N-phenylglycine ethyl, N-phenylglycine, N-protected amino acids (esters), etc. Specific examples of aromatic tertiary amine compounds include N,N-dimethylaniline, N,N-diethylaniline, N ,N-di-n-butylaniline, N,N-dibenzylaniline, pN,N-dimethyl-toluidine, mN,N-dimethyl-toluidine, pN,N-diethyl-toluidine, p- Bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid 2-butoxyethyl, p-dimethylaminobenzoic acid 2-ethylhexyl, p-dimethylaminobenzoic acid aminoester, N,N-dimethylanthrani acid methyl ester, N,N-dihydroxyethylaniline, N,N-diisopropanolaniline, pN,N-dihydroxyethyl-toluidine, pN,N-dihydroxypropyl-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N,N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine, N,N-dimethyl-β-naphthylamine and the like. Among these, p-dimethylaminobenzoic acid ethyl ester is preferred.

An aliphatic amine compound refers to a compound in which one or more H of ammonia (NH ₃ ) is substituted with an alkyl group. In the alkyl group, CH ₃ — or —CH ₂ — is a primary alkyl group, one H of —CH ₂ — having a substituent is a secondary alkyl group, and two Hs of —CH ₂ — are substituents. are classified as tertiary alkyl groups. Aliphatic amines are aliphatic primary amine compounds in which one H in _NH3 is substituted with an alkyl group, and aliphatic secondary amine compounds in which two Hs in _NH3 are substituted with alkyl groups. Amine compounds, those in which the three Hs of _NH3 are substituted with alkyl groups, are classified as aliphatic tertiary amine compounds.

Specific examples of aliphatic primary amine compounds include amino acids or amino acid esters such as benzhydrylamine, triphenylmethylamine, and glycine, and specific examples of aliphatic secondary amine compounds include dibenzylamine, N-benzyl-1-phenylethylamine, bis(1-phenylethyl)amine, bis(4-cyanobenzyl)amine, N-benzyl-protected amino acids or N-benzyl-protected amino acid esters, and aliphatic tertiary amines. Specific examples of the compound include tributylamine, tripropylamine, triethylamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethylstearylamine, N-[3-(dimethylamino)propyl ] Acrylamide, N,N-dimethylformamide dimethylacetal, N,N-dimethylacetamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dimethylformamide dipropylacetal, N,N-dimethylformamide di-tert- Butyl acetal, 1-(2-hydroxyethyl)ethyleneimine, N,N-dimethylethanolamine, N,N-dimethylisopropanolamine, N,N-diisopropylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N- ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, N-stearyldiethanolamine, triethanolamine, triisopropanolamine, tribenzylamine, dibenzylglycine ethyl ester, N'-(2-hydroxyethyl)-N,N, N'-trimethylethylenediamine, 2-(dimethylamino)-2-methyl-1-propanol, N,N-dimethyl-2,3-dihydroxypropylamine, N,N-diethylethanolamine, 1-methyl-3-pyrrolidinol , 1-(2-hydroxyethyl)pyrrolidine, 1-isopropyl-3-pyrrolidinol, 1-piperidineethanol, 2-[2-(dimethylamino)ethoxy]ethanol, N,N-dimethylglycine, N,N-dimethylglycine methyl, N,N-diethylglycine methyl, N,N-dimethylglycine ethyl, N,N-diethylglycine sodium, 2-(dimethylamino)ethyl acetate, N-methyliminodiacetic acid, N,N-dimethylaminoethyl acrylate tris(2 -cyanoethyl)amine, N,N-dimethylallylamine, N,N-diethylallylamine, triallylamine and the like.

The dental photocurable composition of the present invention preferably contains an aliphatic amine compound. Aromatic amine compounds have poor light color stability, and when used in prosthetic devices, restorative materials, and adhesives used in areas exposed to light, their color tone may change over time, which is undesirable. In addition, it can be expected that discoloration over time due to light can be suppressed by using an ultraviolet absorber together. However, since ultraviolet absorbers are usually used as additives, improvement in mechanical properties cannot be expected by blending them, and in some cases, the yellowness of the dental photocurable composition before curing increases. It is not preferable to blend a large amount from . For these reasons, it is preferable to use an aliphatic amine compound. Furthermore, tertiary aliphatic amine compounds are preferred among primary to tertiary aliphatic amine compounds from the viewpoint of reactivity with photoacid generators. Depending on the composition of the dental photocurable composition, high storage stability and high mechanical strength can be expected when an aliphatic primary amine compound and an aliphatic secondary amine compound are used in combination. Can be used without restrictions.

Furthermore, it is preferable that (D) a photopolymerization accelerator (D1) contains a tertiary aliphatic amine compound having no primary hydroxyl group at the α-position carbon and/or the β-position carbon starting from N derived from an amine. . As used herein, the α-position carbon and the β-position carbon are referred to as the α-position carbon and the β-position carbon, respectively. Further, the amine-derived N in the tertiary amine compound is distinguished from the urethane bond, urea bond, and amide bond-derived N. When a tertiary aliphatic amine compound having a primary hydroxyl group at the α- and/or β-carbon of N is used in the dental photocurable composition of the present invention, the cured product of the dental photocurable composition may be discolored when stored for a long period of time. Therefore, it is preferable to use (D1) a tertiary aliphatic amine compound having no primary hydroxy group at the α- and/or β-carbon of N as (D) the photopolymerization accelerator.

(D1) Tributylamine, tripropylamine, triethylamine, N,N-dimethylhexylamine, N , N-dimethyldodecylamine, N,N-dimethylstearylamine, N-[3-(dimethylamino)propyl]acrylamide, N,N-dimethylisopropanolamine, triisopropanolamine, tribenzylamine, dibenzylmethylamine, di benzylglycine ethyl ester, N,N-dimethylglycine methyl, N,N-diethylglycine methyl, N,N-dimethylglycine ethyl, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N- diisopropylaminoethyl methacrylate, N,N-dibutylaminoethyl methacrylate, N,N-dibenzylaminoethyl methacrylate and the like. Among these, N,N-dimethylaminoethyl acrylate, N-diisopropylaminoethyl methacrylate, N,N-dibutylaminoethyl methacrylate, N,N-dibenzylaminoethyl methacrylate, triisopropanolamine, tribenzylamine, dibenzylmethylamine, Dibenzylglycine ethyl ester and the like are preferred.

It is preferable that the dental photocurable composition of the present invention substantially does not contain a tertiary amine compound having a primary hydroxyl group at the α- and/or β-position starting from N derived from an amine. If such a compound is contained, it may cause discoloration during long-term use of the cured product of the photocurable dental composition. Examples of such aliphatic amine compounds include N,N-dimethylethanolamine, N,N-diisopropylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-lauryldiethanolamine, N-stearyldiethanolamine, triethanolamine, N,N-diethylethanolamine and the like, and aromatic amine compounds include N,N-bis(2-hydroxyethyl)-p-toluidine.

“Not substantially contained” means (A) 0.1 parts by mass or less, preferably 0.01 parts by mass or less per 100 parts by mass of the polymerizable monomer. If the content is 0.1 parts by mass or less, it can be expected that the cured product will not undergo significant discoloration during long-term use. On the other hand, if it exceeds 0.1 part by mass, discoloration may occur when the cured product is used for a long period of time. The dental photocurable composition of the present invention can be free of tertiary amine compounds having primary hydroxyl groups at the α- and/or β-position carbons starting from amine-derived N.

Preferably, the dental photocurable composition of the present invention is substantially free of aromatic amine compounds. By including an aromatic amine compound, although further improvement in mechanical strength can be expected, deterioration in light color stability may occur. “Not substantially contained” means (A) 0.1 parts by mass or less, preferably 0.01 parts by mass or less per 100 parts by mass of the polymerizable monomer. The dental photocurable composition of the present invention can be free of aromatic amine compounds.

It is preferable that the raw material does not contain tertiary amine compounds and/or aromatic amine compounds having primary hydroxyl groups at the α- and/or β-carbons of N as impurities, but the photocurable composition for dental use This is not the case as long as it does not affect the characteristics of

(D) The photopolymerization accelerator is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental photocurable composition. It is preferably contained in an amount of 5 to 5 parts by mass. If it is less than 0.2 parts by mass, the mechanical strength may be insufficient. If the amount is more than 10 parts by mass, although the curing property is sufficient, the ambient light stability may be shortened, or discoloration such as the cured product may become brown, which is not preferable.

The dental photocurable composition of the present invention may contain only an aliphatic tertiary amine compound as (D) a photopolymerization accelerator. The dental photocurable composition of the present invention comprises (D) a photopolymerization accelerator (D1) a tertiary aliphatic amine compound having no primary hydroxyl group at the α- and/or β-carbon of N may contain only

These polymerization initiators (B) photosensitizer, (C) photoacid generator, and (D) photopolymerization accelerator can be used in two ways, such as fine pulverization, carrier adsorption, and encapsulation in microcapsules, if necessary. There is no problem even if the following processing is performed. Furthermore, these various types of photopolymerization initiators can be used alone or in combination of two or more types regardless of the polymerization mode or polymerization method.

[(E) filler]
The dental photocurable composition of the present invention can contain (E) a filler, and commonly used known fillers can be used without any limitation.

(E) The type of filler is not limited as long as it is a known filler, and a filler suitable for the application can be blended. It is preferable to add a filler such as flexible glass. The dental photocurable composition of the present invention may use the exemplified fillers alone or in combination of two or more.

Specific examples of organic fillers include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, Polymers such as polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, and polycarbonate are included.

As inorganic fillers, their chemical compositions are not particularly limited, but specific examples include silicon dioxide, alumina, titania, 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, and the like. In particular, barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, fluoroaluminosilicate glass, etc., which are used in dental glass ionomer cement, resin-reinforced glass ionomer cement, resin cement, etc., can also be preferably used. The fluoroaluminosilicate glass referred to here has a basic skeleton of silicon oxide and aluminum oxide and contains an alkali metal for non-crosslinking oxygen introduction. Further, it has alkaline earth metals including strontium and fluorine as modifier/coordinating ions. In addition, it is a composition in which a lanthanide series element is incorporated into the skeleton in order to impart further X-ray opacity. The lanthanide series elements are also incorporated into the composition as modifier/coordination ions depending on the composition range.

The inorganic filler may contain inorganic fine particles having an average primary particle size of 0.1 to 50 nm. Specific examples include alumina fine particles and silica fine particles. The hydrophobic inorganic fine particles preferably have an average particle size of 0.1 to 50 nm, and are preferably treated with a silane coupling agent and/or modified silicone oil for hydrophobization. In addition to improving bending strength, it can be expected to suppress sedimentation of inorganic fillers and impart rheological properties by blending.

Examples of the organic-inorganic composite filler include those obtained by polymerizing and coating the surface of a filler with a polymerizable monomer, those obtained by mixing and polymerizing a filler and a polymerizable monomer, and pulverizing them to an appropriate particle size, Alternatively, a filler is dispersed in a polymerizable monomer in advance and emulsion polymerization or suspension polymerization is performed, a filler is dispersed in a polymerizable monomer and a solvent in advance, spray-dried, and then polymerized, or a filler is prefilled. Examples include, but are not limited to, those obtained by dispersing an agent in a solvent, spray-drying, impregnating with a polymerizable monomer, and then polymerizing.

The sustained ion release glass is characterized by the sustained release of at least one of fluorine ions, strontium ions, borate ions, and aluminum ions. Among these ions, it is preferable that a plurality of ions are released simultaneously at the same time.

The sustained ion-releasing glass used in the present invention is any ion without any limitation as long as it contains one or more glass skeleton-forming elements that form a glass skeleton and one or more glass-modifying elements that modify the glass skeleton. Time-release glasses can also be used. These sustained ion-releasing glasses can be used not only singly but also in combination of plural sustained ion-releasing glasses. Further, in the present invention, glass amphoteric elements that play a role of either a glass skeleton-forming element or a glass-modifying element depending on the glass composition are included in the category of glass skeleton-forming elements. Specific examples of the glass skeleton-forming elements contained in the sustained ion release glass include silica, aluminum, boron, phosphorus, and the like, and these may be used singly or in combination. Specific examples of glass-modifying elements include halogen elements such as fluorine, bromine and iodine, alkali metal elements such as sodium and lithium, and alkaline earth metal elements such as calcium and strontium. can be used singly or in combination. Among these, it preferably contains silica, aluminum, and boron as glass skeleton-forming elements, and fluorine, sodium, and strontium as glass-modifying elements. Specifically, silica glass containing strontium and sodium, fluoroaluminosilicate glass, fluoroborosilicate glass, fluoroaluminoborosilicate glass, and the like. Furthermore, from the viewpoint of sustained release of fluorine ions, strontium ions, borate ions, and aluminum ions, strontium-containing fluoroaluminoborosilicate glass is more preferable. Specific examples of the glass composition range include SiO ₂ : 15 to 35% by mass, Al ₂ O ₃ : 15 to 30% by mass, B ₂ O ₃ : 5 to 20% by mass, SrO: 20 to 45% by mass, F: 5 to 15% by mass, Na ₂ O: 0 to 10% by mass. This glass composition can be confirmed by using instrumental analysis such as elemental analysis, Raman spectrum and fluorescent X-ray analysis. No problem.

The method for producing these sustained ion-releasing glasses is not particularly limited, and they can be produced by a production method such as a melting method or a sol-gel method. Among them, a method of manufacturing by a melting method using a melting furnace is preferable from the viewpoint of easiness of glass composition design including selection of raw materials. The sustained ion-releasing glass used in the present invention has an amorphous structure, but there is no problem even if it partially contains a crystalline structure. There is no problem even if it is a mixture of Whether or not the glass structure is amorphous can be confirmed by using analytical instruments such as X-ray diffraction analysis and transmission electron microscope. Among them, the sustained ion-releasing glass used in the present invention preferably has an amorphous structure, which is a homogenous structure, since various ions are slowly released depending on the equilibrium relationship with the ion concentration in the external environment.

Furthermore, in order to enhance the sustained ion release from the sustained ion release glass, it is a preferred embodiment to functionalize the glass surface by surface treatment to improve the sustained ion release. Specific examples of surface treatment agents used for surface treatment include surfactants, fatty acids, organic acids, inorganic acids, monomers, polymers, various coupling agents, silane compounds, metal alkoxide compounds and partial condensates thereof. Among these surface treatment materials, it is preferable to perform a composite surface treatment using an acidic polymer and a silane compound.

This composite surface treatment is a method in which the surface of the sustained ion release glass is coated with a silane compound and then the surface is treated with an acidic polymer, which will be described in detail below. A silane compound represented by the formula (3) is mixed with an aqueous dispersion containing a sustained ion-releasing glass pulverized to a desired average particle size (D50) by pulverization or the like, and this is added with water in the system. It is decomposed or partially hydrolyzed to form a silanol compound, which is then condensed to form polysiloxane, which is then coated on the surface of the sustained ion release glass to obtain the sustained ion release glass coated with polysiloxane.

[Formula (3)]

(Wherein, Z is RO ^- , X is halogen, Y is OH ^- , R is an organic group having 8 or less carbon atoms, n, m, and L are integers of 0 to 4, and n + m + L = 4)

Specific examples of the silane compound represented by formula (3) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraallyloxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, and trimethoxysilane. chlorosilane, triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane, diethoxydichlorosilane, tetraphenoxysilane, tetrachlorosilane, silicon hydroxide (silicon oxide hydrate) and the like, more preferably tetramethoxysilane and It is tetraethoxysilane.

Further, it is more preferably a low condensate of the silane compound represented by formula (3). For example, it is a low-condensation silane compound obtained by partially hydrolyzing and condensing tetramethoxysilane and tetraethoxysilane. These compounds can be used alone or in combination. An organosilane compound can also be added as part of the silane compound represented by formula (3) during the polysiloxane treatment.

The polysiloxane-coated sustained ion-release glass obtained in the previous step can be treated with an acidic polymer to react with an acidic polymer to obtain sustained ion-release glass. Acidic polymer treatment can be carried out using equipment commonly used in the industry as long as it is a dry fluidized agitator, such as a Henschel mixer, a super mixer, and a high speed mixer. The reaction of the acidic polymer with the sustained ion release glass on which the polysiloxane film is formed can be carried out by bringing an acidic polymer solution into contact with the glass by impregnation, spraying, or the like. For example, the polysiloxane-coated sustained ion release glass may be dry-flowed, and in the fluidized state, the acidic polymer solution may be dispersed from above and thoroughly stirred. At this time, the method for dispersing the acidic polymer solution is not particularly limited, but a dropping or spraying method that enables uniform dispersion is more preferable. Moreover, the reaction is preferably carried out at around room temperature. If the temperature rises, the reaction between the acid-reactive element and the acidic polymer will be accelerated, resulting in non-uniform formation of the cement phase.

It is preferable to remove water in the cement reaction phase by performing a post-reaction heat treatment. If moisture remains in the cement reaction phase, it is disadvantageous in terms of strength, but since the filler of the present invention is covered and strengthened by the coupling agent condensate film, the decrease in mechanical strength is suppressed. The heat treatment method after the treatment with the acidic polymer is not particularly limited, and a known general method can be used. Equipment used for the heat treatment is preferably a box-type hot air dryer or the like, or a rotary heat treatment apparatus capable of uniform heating. The heat treatment temperature is in the range of room temperature to 200°C, more preferably in the range of 40-150°C. If the temperature is lower than this range, removal of the aqueous medium is insufficient, and if it is higher than this range, the organic layer of the acidic polymer may decompose or discolor. Since the heat treatment time depends on the capacity of the dryer, etc., there is no problem as long as the time is sufficient to remove the aqueous medium. After the heat treatment, the heat-treated material can be easily crushed by applying a shearing force or an impact force, and the crushing method can be carried out using the equipment used for the above reaction.

The solvent used for preparing the acidic polymer solution used in the reaction is not particularly limited as long as it dissolves the acidic polymer, and examples thereof include water, ethanol, and acetone. Among these, water is particularly preferred because the acidic groups of the acidic polymer are dissociated and can react uniformly with the polysiloxane-coated sustained ion release glass.

The weight average molecular weight of the polymer dissolved in the acidic polymer solution is in the range of 2000-50000, preferably in the range of 5000-40000. When treated with an acidic polymer having a weight-average molecular weight of less than 2000, no acidic polymer reaction phase is formed in the polysiloxane-coated sustained ion release glass, and as a result, the sustained ion release tends to be low. On the other hand, when treated with an acidic polymer having a weight average molecular weight exceeding 50,000, the viscosity of the acidic polymer solution increases, making it difficult to uniformly treat the polysiloxane-coated sustained ion release glass. The acidic polymer concentration in the acidic polymer solution is preferably in the range of 3 to 25% by mass, more preferably in the range of 8 to 20% by mass. If the acidic polymer concentration is less than 3% by mass, the acidic polymer reaction phase described above becomes weak, and the effect of improving the sustained release of ions cannot be obtained. If the concentration of the acidic polymer exceeds 25 mass, it is difficult to diffuse the polysiloxane layer (porous) in a uniform state, and a homogeneous acidic polymer reaction phase cannot be obtained. Since the reaction occurs immediately upon contact, problems such as formation of strongly reacted agglomerates occur. The amount of the acidic polymer solution added to the polysiloxane-coated sustained ion release glass is preferably in the range of 6 to 40% by mass, more preferably 10 to 30% by mass. In terms of this addition amount, the optimum amount of the acidic polymer and the amount of water are in the range of 1 to 7% by mass and the amount of water in the range of 10 to 25% by mass with respect to the polysiloxane-coated sustained ion release glass.

Acidic polymers that can be used to form an acidic polymer reaction phase on the surface of the polysiloxane-coated sustained ion release glass by the above method include, as acidic groups, phosphoric acid residues, pyrophosphoric acid residues, and thiophosphoric acid residues. , a copolymer or a homopolymer of a polymerizable monomer having an acidic group such as a carboxylic acid residue or a sulfonic acid group can be used without any problem. Specific examples of these polymerizable monomers include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, and citracone. acid, 4-(meth)acryloyloxyethoxycarbonyl phthalic acid, 4-(meth)acryloyloxyethoxycarbonyl phthalic anhydride, 5-(meth)acryloylaminopentylcarboxylic acid, 11-(meth)acryloyloxy-1,1 -undecane dicarboxylic acid, 2-(meth) acryloyloxyethyl dihydrogen phosphate, 10-(meth) acryloyloxydecyl dihydrogen phosphate, 20-(meth) acryloyloxy eicosyl dihydrogen phosphate, 1,3-di (Meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl phosphate, 2-(meth)acryloyloxyethyl-2'-bromoethyl phosphate, (meth)acryloyloxyethylphenyl phosphonates, di(2-(meth)acryloyloxyethyl) pyrophosphate, 2-(meth)acryloyloxyethyl dihydrogendithiophosphate, 10-(meth)acryloyloxydecyldihydrogenthiophosphate and the like. Among the polymers (co)polymerized using these polymerizable monomers, the acid-base reaction with the acid-reactive element contained in the polysiloxane-coated sustained ion release glass is relatively slow, α-β It is preferable to use a homopolymer or copolymer of unsaturated carboxylic acid, and specific examples include acrylic acid polymer, acrylic acid-maleic acid copolymer, acrylic acid-itaconic acid copolymer, and the like.

The above-mentioned (E) filler is a silane coupling agent for the purpose of improving affinity with the polymerizable monomer, dispersibility in the polymerizable monomer, mechanical strength and water resistance of the cured product. It can be treated with a representative surface treatment material. The surface treatment material and the surface treatment method are not particularly limited, and include a method of spraying the surface treatment material while stirring a powdery filler, a method of dispersing and mixing the filler and the surface treatment material in a solvent. , a method of supplying a vapor or gaseous silane coupling agent to the surface of the filler, and other known methods can be employed without limitation. Silane coupling agents used for surface treatment of fillers include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(2-methoxysilane). ethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxy Octyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, hexamethyldisilazane, and the like are preferred. In addition to the silane coupling agent, the filler can be surface-treated by a method using a titanate-based coupling agent or an aluminate-based coupling agent. The treatment amount of the filler with the surface treatment material is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the filler before treatment.

(E) The shape of the filler is not particularly limited, and fillers of any shape such as spherical, needle-like, plate-like, crushed and scale-like can be used. The average particle size of the filler is preferably 0.01 μm to 50 μm, more preferably 0.01 μm to 30 μm, still more preferably 0.05 μm to 20 μm, more preferably 0.05 μm to 10 μm.

When the dental photocurable composition of the present invention contains (E) a filler, it is preferably 500 parts by mass or less per 100 parts by mass of the polymerizable monomer (A). When a filler is contained, the strength of the physical properties can be expected to be improved, and when the filler exceeds 500 parts by mass, the operability of the dental photocurable composition may deteriorate.

The dental photocurable composition of the present invention may contain a chemical polymerization initiator. Examples of organic peroxides as chemical polymerization initiators include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, peroxydicarbonates, and hydroperoxides. be. Specific examples of diacyl peroxides include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide. Peroxide etc. are mentioned. Specific examples of peroxyesters include 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-butylperoxyhexa hydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate and t-butylperoxymalelic acid. Specific examples of dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne. Specific examples of peroxyketals include 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, n-butyl 4,4-(t-butylperoxy) oxy)parerate, 1,1-di(t-amylperoxy)cyclohexane and the like. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide and cyclohexanone peroxide. Specific examples of peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, and diisopropylperoxydicarbonate. , di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate and diallyl peroxydicarbonate. Specific examples of hydroperoxides include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide and 1,1,3, 3-tetramethylbutyl hydroperoxide and the like.

As the organic peroxide, the above organic peroxides may be used alone, or two or more kinds of organic peroxides may be used in combination. Among these organic peroxides, from the viewpoint of curability, benzoyl peroxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 1,1,3,3-tetramethylbutylperoxy- 2-ethylhexanoate is preferred. From the viewpoint of improving curability, the organic peroxide as a chemical polymerization initiator is preferably set to 0.1 to 5 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer (A). is set to 0.3 to 3 parts by mass. If the amount of the organic peroxide blended is more than 5 parts by mass, it may become difficult to ensure a sufficient operating time. strength may be insufficient.

The photocurable dental composition of the present invention may further contain a chemical polymerization accelerator in order to improve curability. Examples of chemical polymerization accelerators include 4th period transition metal compounds, thiourea derivatives, aliphatic amines, aromatic amines, sulfinic acids and salts thereof, borate compounds, reducing inorganic compounds containing sulfur, and reducing compounds containing nitrogen. organic inorganic compounds, barbituric acid derivatives, triazine compounds, halogen compounds and the like. The compounding amount of the chemical polymerization accelerator is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the total amount of the polymerizable monomers.

The 4th period transition metal compound as a chemical polymerization accelerator refers to a metal compound of groups 3 to 12 of the 4th period of the periodic table, specifically scandium (Sc), titanium (Ti), vanadium (V), Metal compounds of manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu) and zinc (Zn) can be used without limitation. Each of the transition metal elements described above can have a plurality of valences, and any valence that can stably exist can be added to the dental photocurable composition of the present invention. For example, Sc (trivalent), Ti (tetravalent), V (3, 4 or 5), Cr (2, 3 or 6), Mn (2 to 7), Fe (2 or 3), They are Co (divalent or trivalent), Ni (divalent), Cu (monovalent or divalent), and Zn (divalent). Specific examples of transition metal compounds include scandium iodide (trivalent) as a scandium compound, titanium chloride (tetravalent), titanium (tetravalent) tetraisopropoxide as a titanium compound, and acetylacetone vanadium ( trivalent), divanadium tetroxide (tetravalent), vanadyl acetylacetonate (tetravalent), vanadium stearate oxide (tetravalent), vanadyl oxalate (tetravalent), vanadyl sulfate (tetravalent), oxobis (1- Phenyl-1,3-butanedionate)vanadium (tetravalent), bis(maltrate)oxovanadium (tetravalent), vanadium pentoxide (pentavalent), sodium metavanadate (pentavalent), etc., and acetic acid as a manganese compound Manganese (divalent), manganese naphthenate (divalent), etc. Iron compounds include iron acetate (divalent), iron chloride (divalent), iron acetate (trivalent), iron chloride (trivalent), etc. , Cobalt compounds such as cobalt acetate (divalent) and naphthenate (divalent), nickel compounds such as nickel chloride (divalent), and copper compounds such as copper chloride (monovalent) and copper bromide (monovalent) ), copper chloride (divalent), copper acetate (divalent) and the like, and zinc compounds such as zinc chloride (divalent) and zinc acetate (divalent).

Among these, tri- or tetravalent vanadium compounds and divalent copper compounds are preferred, tri- or tetravalent vanadium compounds having higher polymerization promoting ability are more preferred, and tetravalent vanadium compounds are most preferred. A plurality of types of these 4th period transition metal compounds may be used in combination, if necessary. The blending amount of the transition metal compound is preferably 0.0001 to 1 part by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer (A). However, if it exceeds 1 part by mass, it may cause discoloration or gelation of the dental photocurable composition, which may reduce the storage stability.

As the thiourea derivative as the chemical polymerization accelerator, any known thiourea derivative can be used without limitation. Specific examples include dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl)thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thio Urea, N-benzylthiourea, 1,3-dicyclohexylthiourea, N,N'-diphenylthiourea, 1,3-di(p-tolyl)thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea , N-benzoylthiourea, diphenylthiourea, dicyclohexylthiourea and the like. Among these, (2-pyridyl)thiourea, N-acetylthiourea, and N-benzoylthiourea are preferred. A plurality of types of these thiourea derivatives may be used in combination if necessary. The amount of the thiourea derivative is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomers (A). However, if the amount exceeds 5 parts by mass, the storage stability may deteriorate.

Sulfinic acid and its salts include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid and sodium benzenesulfinate. , potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate , 2,4,6-trimethylbenzenesulfinate lithium, 2,4,6-trimethylbenzenesulfinate calcium, 2,4,6-triethylbenzenesulfinic acid, 2,4,6-triethylbenzenesulfinate sodium, 2, 4,6-triethylbenzenesulfinate potassium, 2,4,6-triethylbenzenesulfinate lithium, 2,4,6-triethylbenzenesulfinate calcium, 2,4,6-triisopropylbenzenesulfinate, 2,4, sodium 6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate; and particularly preferred are sodium benzenesulfinate, sodium p-toluenesulfinate and sodium 2,4,6-triisopropylbenzenesulfinate.

Specific examples of borate compounds having one aryl group in one molecule include trialkylphenylboron, trialkyl(p-chlorophenyl)boron, trialkyl(p-fluorophenyl)boron, trialkyl(p-fluorophenyl)boron, 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 trialkyl(m-octyloxyphenyl)boron (the alkyl group consists of n-butyl group, n-octyl group and n-dodecyl group, etc. is at least one selected from the group) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, and the like. Specific examples of borate compounds having two aryl groups in one molecule include dialkyldiphenyl boron, dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron, dialkyldi(3,5-bistrifluoromethyl) Phenylboron, 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) ) Sodium salts and lithium salts of boron and dialkyldi(m-octyloxyphenyl)boron (the alkyl group is at least one selected from the group consisting of n-butyl, n-octyl, n-dodecyl, etc.) , potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt and butylquinolinium salt etc. Specific examples of borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron, monoalkyltri(p-fluorophenyl)boron, monoalkyltri( 3,5-bistrifluoromethyl)phenylboron, 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)boron and monoalkyltri(m-octyloxyphenyl)boron (alkyl group is n-butyl group, n-octyl sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt of , butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, and the like. Specific examples of borate compounds having four aryl groups in one molecule include, for example, tetraphenylboron, tetrakis(p-chlorophenyl)boron, tetrakis(p-fluorophenyl)boron, tetrakis(3,5-bistri fluoromethyl)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-octyloxyphenyl)boron, (p-fluorophenyl)triphenylboron, (3,5-bistrifluoromethyl)phenyltriphenylboron, (p-nitrophenyl)triphenylboron, sodium salts, lithium salts of (m-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron and (p-octyloxyphenyl)triphenylboron, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt and butylquinolinium salt, etc. are mentioned.

Among these aryl borate compounds, from the viewpoint of storage stability, it is more preferable to use borate compounds having 3 or 4 aryl groups in one molecule. Moreover, these arylborate compounds can be used singly or in combination of two or more.

Examples of reducing inorganic compounds containing sulfur include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates, and dithionites. Specific examples include sodium sulfite and potassium sulfite. , calcium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, thiobenzoic acid and the like.

The reducing inorganic compounds containing nitrogen include nitrites, and specific examples thereof include sodium nitrite, potassium nitrite, calcium nitrite, ammonium nitrite and the like.

Barbituric acid derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, and 5-ethylbarbituric acid. acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbituric acid turic 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-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5- methyl barbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octyl barbituric acid, 1-cyclohexyl-5-hexyl barbituric acid, 5-butyl-1-cyclohexyl barbituric acid, 1 -Benzyl-5-phenylbarbituric acid and salts of thiobarbituric acids (preferably alkali metals or alkaline earth metals), and specific examples of these barbituric acid salts include 5-butyl barbituric acid. sodium, sodium 1,3,5-trimethylbarbiturate and sodium 1-cyclohexyl-5-ethylbarbiturate.

Specific examples of halogen compounds include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, and dilauryldimethylammonium bromide.

The dental photocurable composition of the present invention can be free of chemical polymerization initiators and chemical polymerization accelerators. The dental photocurable composition of the present invention may not contain a polymerization initiator system other than the photopolymerization system.

<Other ingredients>
Further, the dental photocurable composition of the present invention may contain components other than the components (A) to (E) as long as they do not impair the effects of the present invention. For example, excipients represented by fumed silica, benzophenone-based, benzotriazole-based UV absorbers, hydroquinone, hydroquinone monomethyl ether, polymerization inhibitors such as 2,5-ditert-butyl-4-methylphenol, α- Mercaptan compounds such as alkylstyrene compounds, n-butylmercaptan and n-octylmercaptan; terpenoid compounds such as limonene, myrcene, α-terpinene, β-terpinene, γ-terpinene, terpinolene, β-pinene and α-pinene; Chain transfer agents, aminocarboxylic acid-based chelating agents, metal supplementary agents such as phosphonic acid-based chelating agents, discoloration inhibitors, antibacterial agents, coloring pigments, water and solvents that can be mixed with water at any ratio, and other Components such as conventionally known additives can be arbitrarily added as needed.

Preferably, the dental photocurable composition of the present invention is substantially free of water and organic solvents. Water and a highly hydrophilic organic solvent may have poor compatibility with the photoacid generator corresponding to (C1) suitable for the dental photocurable composition of the present invention. Moreover, the mechanical strength of the dental photocurable composition may be lowered by containing water or an organic solvent. “Substantially free” means 1 part by mass or less, preferably 0.1 part by mass or less per 100 parts by mass of the photocurable dental composition. For example, when an organic solvent or water is used to dissolve the raw materials to be mixed in the photocurable dental composition, it is preferable to remove the organic solvent or water through heating and/or pressure reduction steps. This does not apply if water and organic solvents are not included intentionally in the dental photocurable composition, such as when water and organic solvents are present as impurities in the raw materials, and they do not affect the physical properties. The term "organic solvent" as used herein refers to solvents such as ethanol and acetone, rather than impurities or by-products in the raw materials. The dental photocurable composition of the present invention can be free of water and organic solvents.

The method for producing the dental photocurable composition of the present invention is not particularly limited. As a general method for producing a dental photocurable composition, for example, when the dental photocurable composition contains (E), (A) a polymerizable monomer and (B) a photosensitizer are prepared in advance. and (C) a photoacid generator and (D) a photopolymerization accelerator are mixed to form a matrix, then this matrix and (E) a filler are kneaded, and air bubbles are removed under vacuum to form a uniform paste. methods of preparation. The present invention can also be produced by the above production method without any problems.

The dental photocurable composition of the present invention can be used as a dental adhesive, a dental composite resin, a dental abutment building material, a dental resin cement, a dental coating material, a dental pit and fissure sealing material, and a dental nail polish. It is applied as a dental material, a dental loose tooth fixing material, a dental hard resin, a dental cutting material, and a dental 3D printer material.

<One-component dental photocurable composition>
When the present invention is used for a one-part type dental photocurable composition, dental materials include dental adhesives, dental composite resins, dental abutment building materials, dental resin cements, dental coating materials, and dental materials. It is preferably used for pit and fissure sealing materials for dental use, dental manicure materials, dental loose tooth fixing materials, dental hard resins, dental cutting materials, and dental 3D printer materials, and particularly preferably dental adhesives. material, dental composite resin, dental abutment building material, dental resin cement, dental coating material, dental pit and fissure sealing material, dental manicure material, dental loose tooth fixation material, dental hard resin It is preferred to use In the case of a one-part type dental photocurable composition, it can be expected that there will be less technical errors and the risk of inclusion of air bubbles will be reduced.

<Two-component dental photocurable composition>
When the present invention is used for a two-part type dental photocurable composition, the dental materials include medical adhesives, dental composite resins, dental abutment building materials, dental resin cements, dental coating materials, and dental materials. It is preferably used for pit and fissure sealing materials for dental use, dental manicure materials, dental loose tooth fixing materials, dental hard resins, dental cutting materials, and dental 3D printer materials, and particularly preferably dental adhesives. It is preferably used for dental materials, dental composite resins, dental abutment building materials, and dental resin cements. The two-component dental material is used by kneading two components divided into a first paste and a second paste immediately before use. The first paste and the second paste are kneaded at a volume ratio of 0.9 to 1.1:1.0 or a mass ratio of 0.8 to 1.2:1.0, preferably at an equal volume ratio. . The kneading method can be carried out by a known method such as manual kneading using a dedicated shaking device or spatula, or automatic kneading using a static mixer. Since the components can be divided into two agents, it is possible to separately mix compounds that cannot be mixed in the same paste, so that the storage stability is excellent.

The dental photocurable composition of the present invention comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a polymerization accelerator, and (C ) The photoacid generator (C1) may contain only an iodonium salt compound having a structure represented by formula (1). Further, as components other than (A) to (D), only one or more of the above components may be included.

Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

Materials used in Examples and Comparative Examples and their abbreviations are shown below.
[(A) polymerizable monomer]
Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane D2.6E: 2,2-bis with an average number of added moles of ethoxy groups of 2.6 (4-(meth)acryloyloxypolyethoxyphenyl)propane, UDMA: N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)ethanol]methacrylate, TEGDMA: triethylene glycol dimethacrylate・NPG: neopentyl glycol dimethacrylate ・HEMA: 2-hydroxyethyl methacrylate ・GDMA: glycerol dimethacrylate ・MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[(B) Photosensitizer]
・CQ: Camphorquinone ・BAPO: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide

[(D) Photopolymerization accelerator]
<Aliphatic tertiary amine>
<<(D1) A tertiary aliphatic amine compound having no primary hydroxy group at the α- and/or β-carbon of N>>
・TBA: tribenzylamine ・DBMA: N-methyldibenzylamine ・DEAEMA: N,N-diethylaminoethyl methacrylate ・DMAEMA: N,N-dimethylaminoethyl methacrylate ・DMAPAA: N,N-dimethylaminopropylacrylamide ・TIPA: Triisopropanolamine/DBGE: N,N-dibenzylglycineethyl <<aliphatic tertiary amine compound having a primary hydroxyl group at the α- and/or β-carbon starting from the N of the amine>>
・MDEOA: methyldiethanolamine ・TEA: triethanolamine <aromatic tertiary amine compound>
<<Aromatic tertiary amine compound having no primary hydroxyl group at α-position carbon and/or β-position carbon starting from N of amine>>
・DMBE: N,N-dimethylaminoethyl benzoate ・DHPT: N,N-di(2-hydroxypropyl)-p-toluidine <<primary to α-position and/or β-position carbon starting from N of amine aromatic tertiary amine compound having a hydroxyl group >>
・DEPT: N,N-bis(2-hydroxyethyl)-p-toluidine <organometallic compound>
・DBTL: dibutyl-tin-dilaurate

[Chemical polymerization initiator]
・TMBH: 1,1,3,3-tetramethylbutyl hydroperoxide ・TPE: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate ・BPO: benzoyl peroxide [chemical polymerization accelerator ]
・PTU: (2-pyridyl)thiourea ・BTU: N-benzoylthiourea ・ATU: N-acetylthiourea ・DHPT: N,N-di(2-hydroxypropyl)-p-toluidine ・PTSA: p-toluenesulphine Sodium acid tetrahydrate COA: copper acetylacetone VOA: vanadyl acetylacetonate

[(E) filler]
The method for producing each filler used in the preparation of the dental photocurable composition is shown below.

(Filler E1)
Zirconium silicate filler (average particle size 1.2 μm: zirconia 90 wt%, silica 10 wt%) 100.0 g, water 50.0 g, ethanol 35.0 g, 3-methacryloxyoctyltrimethoxysilane 7 as a silane coupling agent A silane coupling treatment solution obtained by stirring 0.0 g of the mixture at room temperature for 2 hours was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 5 hours to obtain filler E1.

(Filler E2)
Zirconium silicate filler (average particle size 0.8 μm: zirconia 85 wt%, silica 15 wt%) 100.0 g, water 50.0 g, ethanol 35.0 g, 8-methacryloyloxyoctyltrimethoxysilane 7 as a silane coupling agent A silane coupling treatment solution obtained by stirring 0.0 g of the mixture at room temperature for 2 hours was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 5 hours to obtain filler E2.

(Filler E3)
After mixing various raw materials such as silicon dioxide, aluminum oxide, boron oxide, sodium fluoride, and strontium carbonate, the mixture was melted at 1400° C. to obtain glass A (glass composition: SiO ₂ : 22.5% by mass, Al ₂ O ₃ : 20.0% by mass, _B2O3 : 12.3% by mass, SrO: 35.7% by mass, _Na2O : 2.5% _by mass, F: 7.0% by mass). Next, the obtained glass A was pulverized using a vibration mill for 100 hours, and then pulverized using a wet bead mill for 3 hours. 4.5 g of a low condensate of silane compound "MKC Silicate MS56S" (SiO ₂ content 56.0% by mass, degree of polymerization 2 to 100, manufactured by Mitsubishi Chemical Corporation) was added to 100 g of the pulverized material obtained, Stir mixed for about 90 minutes. After mixing for a predetermined time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours, then cooled to obtain a heat treated product. The obtained heat-treated material was placed in a Henschel mixer and pulverized at 1800 rpm for 5 minutes. After pulverization, a polysiloxane-treated material having good fluidity and a surface coated with polysiloxane was obtained.
(acidic polymer treatment)
100 g of the polysiloxane-treated material was put into a Henschel mixer, and 16.0 g of an aqueous polyacrylic acid solution (polymer concentration: 13% by mass, weight average molecular weight: 20,000; manufactured by Nacalai Co., Ltd.) was sprayed from above while stirring. After spraying, the powder taken out from the mixer was heated in a hot air dryer at 100° C. for 3 hours to obtain a polysiloxane-polyacrylic acid-treated product.
(Silane treatment)
100 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 8-methacryloyloxyoctyltrimethoxysilane as a silane coupling agent were added to 100 g of the polysiloxane-polyacrylic acid treated material for 2 hours at room temperature. The silane coupling treatment liquid obtained by stirring was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E3.

(Filler E4)
100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 8-methacryloyloxyoctyltrimethoxysilane as a silane coupling agent were stirred for 2 hours at room temperature with respect to 100 g of the polysiloxane-treated product. The resulting silane coupling treatment liquid was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E4.

(Filler E5)
Filler E5 was obtained using the same material and method except that 3-methacryloyloxypropyltrimethoxysilane was used as the silane coupling agent in filler E3 instead of 8-methacryloyloxyoctyltrimethoxysilane.

(Filler E6)
Filler E6 was obtained using the same material and method except that 3-methacryloyloxypropyltrimethoxysilane was used as the silane coupling agent in filler E4 instead of 8-methacryloyloxyoctyltrimethoxysilane.

(Filler E7)
10 g of water, 20 g of ethanol, 0.001 g of phosphoric acid, and 5.0 g of 3-methacryloxyoctyltrimethoxysilane as a silane coupling agent were stirred at room temperature for 2 hours with respect to 10 g of aluminum fine particles (primary particle diameter: 13 nm). The obtained silane coupling treatment solution was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E7.

(Filler E8)
For 10 g of zirconia fine particles (primary particle diameter: 10 nm), 10 g of water, 20 g of ethanol, 0.001 g of phosphoric acid, and 5.0 g of 3-methacryloxyoctyltrimethoxysilane as a silane coupling agent can be stirred at room temperature for 2 hours. The obtained silane coupling treatment solution was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E8.

(Filler E9)
Aerosil R-8200

(Filler E10)
Aerosil R-7200

[Ultraviolet absorber]
BP: 2-hydroxy-4-(octyloxy)benzophenone BT: 2-(2-hydroxy-5-methylphenyl)benzotriazole [polymerization inhibitor]
・MeHQ: p-methoxyphenol ・BHA: 3-tert-butyl-4-hydroxyanisole ・BHT: 2,6-di-t-butyl-4-methylphenol [fluorescent agent]
・FA: diethyl 2.5-dihydroxyterephthalate

・Ｃ－２:ジフェニルヨードニウムトリス（トリフルオロメチルスルホニル）メチド

・Ｃ－３:ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムトリス（ペンタフルオロプロピル）トリフルオロホスフェート

・Ｃ－４：ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウム ノナフルオロブタンスルホン酸塩

・Ｃ－５：ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムノナフルオロブタンスルホン酸塩

・Ｃ－６：ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムビス（トリフルオロメチルスルホニル）イミド

・Ｃ－７：ｐ－（オクチロキシフェニル）フェニルヨードニウムビス（トリフルオロメチルスルホニル）イミド

・Ｃ－８：ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムテトラ（ペンタフルオロフェニル）ガレート

＜＜アニオンが有機基を有する＞＞
・Ｃ－９：ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムカンファ―スルホン酸塩

＜＜アニオンが有機基を有さない＞＞
・Ｃ－１０：ビス（３－イソプロピル－４－メトキシフェニル）ヨードニウム テトラフルオロボレート

・Ｃ－１１：ｐ－（オクチロキシフェニル）フェニルヨードニウムヘキサフルオロアンチモネート

・Ｃ－１２：ビス（４－ドデシルフェニル）ヨードニウムヘキサフルオロフォスフェート

＜全てのＲ_１とＲ_２を構成する有機基の炭素数の合計が８未満６以上＞
・Ｃ－１３：ビス（４－イソプロピルフェニル）ヨードニウム ヘキサフルオロフォスフェート

・Ｃ－１４：（４－ｔｅｒｔ－ブチルフェニル）（２，４，６－トリメトキシフェニル）ヨードニウムヘキサフルオロフォスフェート

＜その他のヨードニウム塩化合物＞
・Ｃ－２１：（４－メチルフェニル）（４－（２－メチルプロピル）フェニル）ヨードニウムヘキサフルオロフォスフェート

・Ｃ－２２：ｐ－クメニル（ｐ－トリル）ヨードニウムクロリド

・Ｃ－２３：（４－メチルフェニル）（２，４，６－トリメチルフェニル）ヨードニウムトリフルオロメタンスルホナート

[(C) Photoacid Generator]
[(C1) Iodonium salt-based compound having a structure represented by formula (1)]
<The total number of carbon atoms of the organic groups constituting all R ₁ and R ₂ is 8 or more>
<<The anion has at least one or more H-substituted organic groups and one or more atoms of P, B, Al, S, and Ga>>
· C-1: bis (4-tert-butylphenyl) iodonium tetra (nonafluoro-tert-butoxy) aluminate

・C-2: diphenyliodonium tris(trifluoromethylsulfonyl)methide

· C-3: bis (4-tert-butylphenyl) iodonium tris (pentafluoropropyl) trifluorophosphate

・ C-4: bis (4-tert-butylphenyl) iodonium nonafluorobutanesulfonate

· C-5: bis (4-tert-butylphenyl) iodonium nonafluorobutanesulfonate

· C-6: bis (4-tert-butylphenyl) iodonium bis (trifluoromethylsulfonyl) imide

· C-7: p- (octyloxyphenyl) phenyliodonium bis (trifluoromethylsulfonyl) imide

· C-8: bis (4-tert-butylphenyl) iodonium tetra (pentafluorophenyl) gallate

<<Anion has an organic group>>
・ C-9: bis (4-tert-butylphenyl) iodonium camphor-sulfonate

<<Anion does not have an organic group>>
· C-10: bis (3-isopropyl-4-methoxyphenyl) iodonium tetrafluoroborate

・C-11: p-(octyloxyphenyl)phenyliodonium hexafluoroantimonate

· C-12: bis (4-dodecylphenyl) iodonium hexafluorophosphate

<The total number of carbon atoms of the organic groups constituting all R ₁ and R ₂ is less than 8 and 6 or more>
・ C-13: bis (4-isopropylphenyl) iodonium hexafluorophosphate

· C-14: (4-tert-butylphenyl) (2,4,6-trimethoxyphenyl) iodonium hexafluorophosphate

<Other iodonium salt compounds>
· C-21: (4-methylphenyl) (4-(2-methylpropyl) phenyl) iodonium hexafluorophosphate

・ C-22: p-cumenyl (p-tolyl) iodonium chloride

· C-23: (4-methylphenyl) (2,4,6-trimethylphenyl) iodonium trifluoromethanesulfonate

<Confirmation of solubility of photoacid generator>
After weighing 60 parts by mass of Bis-GMA and 40 parts by mass of TEGDMA, they were mixed for 6 hours with a stirrer (mix rotor: VMRC-5, AS ONE) set at 50°C to obtain a uniform solution. After confirming that this solution returned to room temperature, 0.5 parts by mass of each photoacid generator was added and dissolved by stirring. The solubility was evaluated at the stirring time during which dissolution could be visually confirmed at this time. Samples with a stirring time of 6 hours or less were rated A, samples with stirring times of 24 hours or less were rated B, and samples with stirring times of 48 hours or less were rated C, indicating good solubility. Those that did not dissolve within 48 hours were additionally stirred for 6 hours with a stirrer set at 50° C., and then dissolved. Furthermore, E was assigned to those that did not dissolve even after stirring for 24 hours. Good solubility is preferred because it can be produced in a short period of time. Furthermore, it is preferable because the risk of precipitation of the photoacid generator during low-temperature storage may be low. On the other hand, a photo-acid generator with poor solubility may precipitate after long-term storage even if it is uniformly dissolved in the composition. This tends to occur when the amount is 0.5 parts by mass or more, and further 1.0 parts by mass or more. In addition, it is not preferable because the preparation of the composition takes a long time and the material needs to be exposed to high temperatures for a long time, which may cause deterioration of the material during preparation.

All of the photoacid generators C-1 to C-12 in which the total number of carbon atoms in R ₁ and R ₂ is 8 or more showed good solubility. Among them, C-4, C-7, C-11, and C-12 in which R ₁ and/or R ₂ have an alkyl chain of 8 or more carbon atoms showed particularly good solubility. Among the photoacid generators in which R ₁ and/or R ₂ do not have an alkyl chain having 8 or more carbon atoms and the total number of carbon atoms of all R ₁ and R ₂ is 8 or more, at least one anion A photoacid generator having an organic group in which H is substituted with F and at least one of P, B, Al, S and Ga atoms tends to exhibit good solubility. On the other hand, C-13 and C-14, in which the total carbon number of all R ₁ and R ₂ is 6 or more and less than 8, tended to be slightly inferior in solubility. On the other hand, C-21 to C-23 having less than 6 carbon atoms were inferior in solubility to dissolve 0.5 parts by mass or more with respect to 100 parts by mass of the polymerizable monomer (A).

<Method for producing one-component dental photocurable composition>
All except the (E) filler shown in Tables 2 and 3 were placed in a wide-mouth plastic container and mixed for 168 hours at 100 rpm using a mix rotor VMRC-5 to obtain a matrix. Thereafter, the matrix and (E) the filler were put into a kneader, and after the filler was uniformly stirred, defoaming under vacuum to prepare a dental photocurable composition. In Tables 2 and 3, parts by mass of each component are listed in brackets after the abbreviation of each component.

<Method for producing a two-component dental photocurable composition>
All except the filler (E) shown in Table 4 were placed in a wide-mouth plastic container and mixed using a mix rotor VMRC-5 at 100 rpm for 168 hours to obtain a matrix. After that, the matrix and (E) filler are put into a kneader and stirred uniformly, and then defoamed under vacuum to obtain pastes 1 and 2. Paste 1 is added to a double syringe (5 mL) manufactured by Mixpack. , 2 to prepare a dental photocurable composition. In addition, in Table 4, the parts by mass of each component are listed in parentheses after the abbreviation of each component.

The test methods employed in Examples and Comparative Examples are as follows. The one-component dental photocurable composition was used by discharging from a syringe container. For the two-component dental photocurable composition, a paste obtained by mixing pastes 1 and 2 using a mixing tip manufactured by Mixpack was used. In use, a paste obtained by mixing pastes 1 and 2 using a mixing tip manufactured by Mixpack was used. A Mixpak mixing tip can be mixed through a static mixer and when used, Paste 1 and Paste 2 are in a volume ratio of 0.9 to 1.1:1.0, ideally equal. It can be kneaded by volume. When converted to mass ratio, Paste 1 and Paste 2 were kneaded and used so that the ratio would be 0.8 to 1.2:1.0.

<Evaluation 1: Bending strength>
After filling a stainless steel mold with a dental photocurable composition, cover glasses are placed on both sides, and after pressing with a glass kneading plate, a photopolymerization irradiator (Blue Shot: manufactured by Shofu) is used for 10 seconds at 5 locations. Light irradiation was performed one by one to cure. After curing, the cured product was taken out from the mold, and the back surface was similarly irradiated with light to obtain a test piece (25×2×2 mm: cuboid type). After the specimen was immersed in water at 37° C. for 24 hours, a bending test was performed. The two-part photocurable composition was subjected to a bending test within 1 hour after light irradiation. The bending test was performed using an Instron universal testing machine (manufactured by Instron) at a distance between fulcrums of 20 mm and a crosshead speed of 1 mm/min. The bending strength was judged to be good when 100 MPa or more, normal when 90 to less than 100 MPa, slightly bad when 80 to less than 90 MPa, and insufficient when less than 80 MPa. High flexural strength indicates excellent mechanical strength of the dental photocurable composition.

<Evaluation 2: Thermal color stability>
After each of the prepared dental photocurable compositions was filled in a stainless steel mold (15φ×1 mm: disc-shaped), a cover glass was placed from above and pressed with a glass plate. Using a photopolymerization irradiator (Griplight II: manufactured by Shofu) from above the cover glass, light irradiation is performed for 1 minute to cure, the cured product is removed from the mold, the cover glass is removed, and the color tone of this test piece is measured. Colorimetric. For colorimetry, place the specimen on the background of a standard white plate (D65/10° X = 81.07, Y = 86.15, Z = 93.38) and use a spectrocolorimeter (manufactured by BYK-Chemie) (light source: C, viewing angle: 2°, measurement area: 11 mm). After that, after immersing the test specimen in a container containing 10 mL of water in a constant temperature chamber set at 70 ° C. and allowing it to stand for one week, the color tone of the test specimen was measured again, and the difference in discoloration was calculated by the following formula. ΔE calculated from

ΔE = {(ΔL*) ² + (Δa*) ² + (Δb*) ² } ^1/2
ΔL*＝L1*−L2*
Δa* = a1* - a2*
Δb* = b1* - b2*

where L1* is the lightness index before immersion and standing, L2* is the lightness index after immersion and standing, a1* and b1* are the color indices before immersion and standing, a2* and b2* are the immersion・It is the color quality index after standing still. ΔE of less than 5 is the best, ΔE of 5 to less than 7 is good, ΔE of 7 to less than 10 is slightly poor, and ΔE of 10 or more or significant color unevenness is visually observed. It was determined that the case is N and not applicable. When the dental material has good thermal stability, it is less discolored when used in the oral cavity for a long period of time, and can maintain a highly aesthetic state over a long period of time.

<Evaluation 3: light color stability>
After filling a stainless steel mold (15φ×1 mm: disk shape) with the prepared dental photocurable composition, a cover glass was placed from above and pressure-welded using a glass plate. Using a photopolymerization irradiator (Griplight II: manufactured by Shofu) from above the cover glass, light irradiation is performed for 1 minute to cure, the cured product is removed from the mold, the cover glass is removed, and the color tone of this test piece is measured. Colorimetric. For colorimetry, place the specimen on the background of a standard white plate (D65/10° X = 81.07, Y = 86.15, Z = 93.38) and use a spectrocolorimeter (manufactured by BYK-Chemie) (light source: C, viewing angle: 2°, measurement area: 11 mm). Then, after exposing the specimen to light for 24 hours using a xenon lamp light exposure tester (Suntest CPS+), the color tone of the specimen was measured again, and the difference in color change was expressed as ΔE calculated from the following formula. .

ΔE = {(ΔL*) ² + (Δa*) ² + (Δb*) ² } ^1/2
ΔL*＝L1*−L2*
Δa* = a1* - a2*
Δb* = b1* - b2*

where L1* is the lightness index before light exposure, L2* is the lightness index after light exposure, a1*, b1* are the color index before light exposure, a2*, b2* are the color index after light exposure is. ΔE of less than 5 is the best, ΔE of less than 5 to 7 is good, ΔE of 7 to less than 10 is slightly poor, ΔE of 10 or more, or 5 when the appearance is visually confirmed. When one or more black spots were confirmed, it was judged as N and not applicable. When light color stability is good, discoloration is small when used, and high aesthetics can be maintained.

The results of each test shown in Tables 5 and 6 are discussed.

It was confirmed that the compositions described in the Examples exhibited a bending strength of 80 MPa or more in the preparation stage, and the light color stability and heat color stability did not deteriorate significantly.

(C) Examples 10, 12 to 16, 26, 35 to 37, and 39 in which the amount of the iodonium salt compound (C1) having the structure represented by formula (1) in the photoacid generator is 0.5 parts by mass. , 40 tended to be slightly low in bending strength. Moreover, Example 17, in which the amount of the photoacid generator was more than 10 parts by mass, tended to slightly lower the light color stability. In addition, Example 17, in which the compounding amount of camphorquinone as a photosensitizer was 0.02 parts by mass or less, tended to have slightly low bending strength. Moreover, Example 18, in which the compounding amount of camphorquinone as a sensitizer exceeded 1 part by mass, tended to slightly lower the light color stability. In Example 18, in which the amount of the photopolymerization accelerator was less than 0.2 parts by mass, the bending strength tended to be slightly low. Moreover, Example 19, in which the amount of the photopolymerization accelerator was more than 10 parts by mass, tended to slightly lower the light color stability.

Examples 15 and 16 containing C-13 and C-14, which are iodonium salt compounds having a structure represented by formula (1) (C1) in which the anion does not have an organic group as a photoacid generator, are slightly The light color stability tended to be inferior. Further, in Examples 10 and 11 containing a C-9 photoacid generator having an anion having an organic group, Example 11 containing 1 part by mass of C-9 tended to be slightly inferior in light color stability. On the other hand, even if the anion is a photoacid generator that does not have an organic group, it is favorable if R ₁ and / or R ₂ in formula (1) is a photoacid generator having an alkyl group having 8 or more carbon atoms. showed excellent light color stability.

Triethanolamine (TEA), methyldiethanolamine (MDEOA), N,N-bis(2 -Hydroxyethyl)-p-toluidine (DEPT), Examples 31, 32, 36, 37, 39, 41, 42 tended to have lower heat color stability.

Among Examples 33 to 42 containing aromatic amines such as DMBE and DEPT, Examples 38 to 41 containing an ultraviolet absorber tended to exhibit excellent light color stability.

Example 43, which did not contain a tertiary aliphatic amine compound as a photopolymerization accelerator, tended to have slightly low bending strength. In addition, Example 44, which does not contain an α-diketone compound as a photosensitizer, tended to have slightly low bending strength.

Examples 101 to 109 of the 2-paste type dental photocurable composition showed good physical properties like the 1-paste type dental photocurable composition.

(C1) Comparative Examples 1 to 4 and Comparative Example 9, which do not contain an iodonium salt compound having a structure represented by formula (1) and contain 0.5 parts by mass or more of a photoacid generator, have thermal color stability and light After the color stability test, it was confirmed that color unevenness and black spots were generated, and the aesthetic appearance was remarkably inferior. (C1) Comparative Examples 5 to 8, in which the amount of the iodonium salt compound having the structure represented by formula (1) was less than 0.5 parts by mass, were significantly inferior in bending strength. (D) Comparative Example 10 containing no photopolymerization accelerator had a remarkably low bending strength, and (B) Comparative Example 11 containing no photosensitizer was not sufficiently cured.

The dental photocurable composition of the present invention evaluated in the examples can be used without any problem in any known dental photocurable composition. Dental light-curing compositions include dental adhesives, dental composite resins, dental abutment building materials, dental resin cements, dental coating materials, dental pit and fissure sealing materials, dental manicure materials, and dental materials. sway tooth fixing materials for dental use, dental glass ionomer cement, dental hard resins, dental cutting materials, dental 3D printer materials, and the like.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a dental photocurable composition having excellent mechanical properties and good color stability.

Claims (11)

(A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator,
(C) the photoacid generator (C1) contains an iodonium salt compound having a structure represented by formula (1),
(A) with respect to 100 parts by mass of the polymerizable monomer,
(C1) A dental photocurable composition containing 0.5 parts by mass or more of an iodonium salt compound having a structure represented by formula (1).
[Formula (1)]

(In the formula, R ₁ and R ₂ are organic groups, and a plurality of them may be present. The total number of carbon atoms of the organic groups constituting all R ₁ and R ₂ as substituents is 6 or more.) (C1) The dental photocurable composition according to claim 1, wherein the total number of carbon atoms of the organic groups constituting R ₁ and R ₂ of the iodonium salt compound having the structure represented by formula (1) is 8 or more. . (C1) The dental photocuring agent according to claim 1 or 2, wherein R ₁ and/or R ₂ of the iodonium salt compound having the structure represented by formula (1) is an organic group having an alkyl chain of 8 or more carbon atoms. sex composition. (C1) 1 part by mass or more of an iodonium salt compound having a structure represented by formula (1) with respect to 100 parts by mass of the polymerizable monomer (A). The dental photocurable composition according to . (C1) The dental photocurable composition according to any one of claims 1 to 4, wherein the anion of the iodonium salt compound having the structure represented by formula (1) is an anion having an organic group. (C1) the anion of the iodonium salt compound having the structure represented by formula (1) is an organic group in which at least one H is substituted with F and one or more atoms of P, B, Al, S and Ga The dental photocurable composition according to any one of claims 1 to 5. (D) as a photopolymerization accelerator (D1) a tertiary aliphatic amine compound having no primary hydroxyl group at the α- and/or β-carbon of N according to any one of claims 1 to 6. dental photocurable composition. The dental photocurable composition according to any one of claims 1 to 7, which does not substantially contain (D) an aromatic amine compound as a photopolymerization accelerator. 2. The dental product according to claim 1, wherein the photopolymerization accelerator (D) does not substantially contain an amine-derived N-based tertiary amine compound having primary hydroxyl groups at the α- and/or β-position carbons. Photocurable composition. 2. A dental photocurable composition according to claim 1, which is substantially free of water and organic solvents. For a dental photocurable composition (A) 100 parts by mass of a polymerizable monomer,
(B) 0.02 to 1 part by mass of a photosensitizer (C1) 0.5 to 10 parts by mass of an iodonium salt compound having a structure represented by formula (1) (D) 0.1 of a photopolymerization accelerator The dental photocurable composition of claim 1, comprising ~10 parts by weight.