JP2022139585A - Dental photocurable composition containing highly soluble photoacid generator - Google Patents

Abstract

To provide a dental photocurable composition which can exhibit excellent mechanical characteristics even after put back to the room temperature from a low temperature.SOLUTION: A dental photocurable composition comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator and (D) a photopolymerization accelerator, and the (C) photoacid generator includes (C-1) an iodonium salt-based compound with an anion having log S of -4 or less.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 adhesives, 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 dental photocurable compositions using conventional photopolymerization initiators described in Patent Documents 1 and 2 could not obtain sufficient physical properties after being stored at a low temperature.

An object of the present invention is to provide a dental photocurable composition that can exhibit excellent mechanical properties even after being cooled from a low temperature to room temperature.

The dental photocurable composition of the present invention comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, ( C) The photoacid generator is a dental photocurable composition containing (C-1) an iodonium salt compound with an anion having logS of -4 or less.

The dental photocurable composition of the present invention exhibits excellent mechanical properties even after being cooled from low temperature to room temperature.

In the present invention, (C-1) 0.5 parts by mass or more of an iodonium salt-based compound with an anion having log S of -4 or less can be included with respect to 100 parts by mass of the polymerizable monomer (A).

In the present invention, (C-1) as an iodonium salt-based compound with an anion having log S of −4 or less, has an organic group and one or more atoms of P, B, Al, S, and Ga. Aryliodonium salts with anions can be included.

In the present invention, (C-1) as the iodonium salt-based compound with an anion having logS of −4 or less, at least one or more H-substituted organic groups and P, B, Al, S, Ga aryliodonium salts having anions having any one or more atoms of

In the present invention, an aliphatic tertiary amine compound can be included as (D) a photopolymerization accelerator.

In the present invention, (D) an aliphatic tertiary amine compound that does not have two or more primary hydroxyl groups (D-1) can be included as a photopolymerization accelerator (D).

In the present invention, the one-component dental photocurable composition comprises 0.005 to 0.5 of (B) photosensitizer per 100 parts by mass of (A) polymerizable monomer. (C) 0.5 to 10.0 parts by mass of a photoacid generator, and (D) 0.01 to 20 parts by mass of a photopolymerization accelerator.

In the present invention, the two-component dental photocurable composition comprises a first paste and a second paste, and the specific gravity of the first paste and the second paste is 1:0.8-1. .2, containing 0.01 to 2.0 parts by mass of (B) a photosensitizer with respect to a total of 200 parts by mass of (A) polymerizable monomers contained in the first paste and the second paste , (C) 1.0 to 20 parts by mass of a photoacid generator, and (D) 0.02 to 40 parts by mass of a photopolymerization accelerator.

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 nail polish. It is applied as a material, adhesive for fixing loose teeth, hard resin for dentistry, material for dental cutting, and material for dental 3D printers.

In clinical dentistry, direct restoration using dental composite resins and prosthetic devices made of ceramics or hard dental resins are used for aesthetic and functional restoration of tooth defects caused by caries, fractures, etc. Indirect restorative treatment is performed with resin cement. In addition, dental adhesives for bonding dental composite resins and various dental materials and natural teeth, dental adhesives for fixing swayed teeth, hyperesthesia and living teeth after formation, external stimuli and Dental coating materials to protect against secondary caries, dental pit and fissure sealants to prevent caries by filling complex grooves such as deciduous teeth, esthetics by masking tooth discoloration A dental manicure material is used for temporarily restoring tooth decay, 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 printing materials for making prosthetic devices using 3D printers have been developed. Used. The above materials 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 having 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, the problem of poor environmental light stability arises. 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. When used as a photopolymerization initiator, it shows high sensitivity not only to irradiation light but also to ambient light, so curing progresses gradually during operations such as filling, building up, and mounting, resulting in paste 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 is a problem with the solubility of , and since it precipitates when stored at a low temperature, when a dental photocurable composition is used after being transported to a cold region, sufficient physical properties may not be exhibited.

It was found that the dental photocurable composition of the present invention exhibits excellent physical properties without precipitation when stored at a low temperature when a highly fat-soluble photoacid generator is used. Completed. More specifically, the inventors have found that the liposolubility of the anion of the aryliodonium salt greatly affects the solubility in the polymerizable monomer. A dental photocurable composition containing an aryliodonium salt with an anion having a specific value of log S (Log Solubility), which is a measure of water solubility, which is a property that contradicts fat solubility, can be refrigerated or frozen. The inventors have found that the properties are stable even under the storage conditions of , resulting in the present invention.

[(A) polymerizable monomer]
The (A) polymerizable monomer of the present invention can be used without limitation as long as it is known. 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 one or more polymerizable groups and at least one or more acidic groups 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.

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 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.

Specific examples of the polymerizable monomer having an alkoxysilyl group include (meth)acrylic compounds having one alkoxysilyl group in the molecule and (meth)acrylic compounds having multiple alkoxysilyl groups in the molecule. and 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.

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, 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 known acidic group-containing polymerizable monomer as (A) a polymerizable monomer in order to impart adhesiveness to tooth substance and prosthetic devices. Preferred are 10-methacryloyloxydecyl dihydrogen phosphate and 6-methacryloyloxyhexyl phosphonoacetate. The amount of the acidic group-containing polymerizable monomer is more preferably 1 part by mass or more based on 100 parts by mass of the total amount of polymerizable monomers contained in the photocurable dental composition from the viewpoint of imparting adhesiveness. is a compounding amount of 10 parts by mass or more.

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, and 11-methacryloxyundecyltrimethoxysilane are preferred. From the viewpoint of imparting adhesiveness, the blending amount is 1 part by mass or more, more preferably 10 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 100 parts by mass of the total amount of 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 10 parts by mass.

<Photoinitiator>
The photopolymerization initiator used in the dental photocurable composition of the present invention includes (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, which are not particularly limited. However, commonly used known compounds 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, camphorquinonecarboxylic acid, camphorquinonesulfonic acid, α-naphthyl, acetonaphthone, 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-( 4-morpholinophenyl)-butanone-1, 2-benzyl-diethylamino-1-(4-morpholinophenyl)-propanone-1 and other α-aminoacetophenones, 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 particularly camphorquinone is preferred because of its easy availability.

Usually, the amount of the photosensitizer (B) is 0.005 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. It is preferably 0.01 to 1.0 parts by mass, and still more preferably 0.05 to 1.0 parts by mass. If the amount of the photosensitizer is less than 0.005 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 will be exhibited, but the ambient light stability will be shortened and yellowishness will increase.

[(C) Photoacid Generator]
The dental photocurable composition of the present invention contains (C) an iodonium salt-based compound with an anion having logS of -4 or less as (C) a photoacid generator (C-1). In the dental photocurable composition of the present invention, (C-1) an iodonium salt-based compound with an anion having logS of -4 or less can be used together with other known photoacid generators 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 (1)].

[Formula (1)]
[(R1) ^{2I] +} _[ A] ^-

([(R1) ₂ I] ⁺ in the formula is a cation moiety, [A] ⁻ is an anion moiety, R1 shown in formula (1) represents an organic group bonded to I, and R1 is the same. 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 Represents 2-30 alkynyl groups, which are alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl. , arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups and at least one selected from the group consisting of 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; 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. Moreover, 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. / Or it most preferably has an organic group such as an aryl group. Since the iodonium salt-based compound having such an anion has high solubility in the photocurable composition, it prevents precipitation during low-temperature storage or long-term storage, and dissolves in the composition in a short time. Shortening of 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, from the viewpoint of versatility and safety, those containing P, S, B, Al, and Ga are preferable.

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 (1) improves the solubility in the photopolymerization composition, at least one or more H is an alkyl group substituted with F and / or an alkoxy Anions having organic groups such as groups and/or aryl groups are preferred. Specifically, the number of carbon atoms in the alkyl group of the [A] ⁻ anion portion of the iodonium salt compound of formula (1) 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 photocurable composition.

Further, specific examples of _alkyl groups include _{CF3 , CF3CF2} , _{( CF3} ) _{2CF , CF3CF2CF2} , _CF3CF2CF2CF2 , _{( CF3 ) 2CFCF2 ,} Linear or branched perfluoroalkyl groups such as CF ₃ CF ₂ (CF ₃ )CF and (CF ₃ ) ₃ C can be mentioned.

The number of carbon atoms in the alkoxy group of the [A] ⁻ anion portion of the iodonium salt compound of formula (1) 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. The photocurable composition may contain iodonium salts composed of anions having alkoxy groups with different ratios of hydrogen atoms and fluorine atoms.

Further, specific examples of the _alkoxy group 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 possessed by the anion portion of [A] ^- in the iodonium salt-based compound of formula (1) 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 ( _CF3C6H4 ), bis(trifluoromethyl)phenyl group _{( ( CF3} ) _2C6H3 ) _{, pentafluoroethylphenyl} group _{( CF3CF2C6H4} ), bis _{( pentafluoroethyl} ) phenyl group _{( CF3CF2} ) _2C6H3 ), _{trifluoromethylfluorophenyl} group _{( CF3C6H3F} ) _{, bistrifluoromethylfluorophenyl} group _{( ( CF3} ) _2C6H2F ), _Examples include perfluorophenyl groups such as a _{pentafluoroethylfluorophenyl} group _{( CF3CF2C6H3F} ) and a _{bispentafluoroethylfluorophenyl group ( CF3CF2} ) _2C6H2F ). Iodonium salts composed of anions having phenyl groups with different ratios of hydrogen atoms and fluorine atoms may be blended in the photocurable composition.

As specific examples of the anion moiety of [A] ^- in the iodonium salt compound of formula (1), 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 ] ^- , [( _{( CF3} ) _2CFCF2 ) _2PF4 ] ^- _, [ _{( ( CF3} ) _2CFCF2 ) _3PF3 ] ^- and the like. Anions with S _are [ _{( CF3SO2} ) _3C ] ^- _, [ _{( CF3CF2SO2} ) _3C ] ^- , [ _{( CF3CF2CF2SO2} ) _3C ] ^- , [ ₍ 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. Examples of anions having B include [B(C ₆ F ₅ ) ₄ ] ^- , [(C ₆ H ₅ )B(C ₆ F ₅ ) ₃ ] ⁻ , [(C ₆ H ₅ )B((CF ₃ ) ₂ C ₆ H ₃ )) ₃ ] ⁻ and the like. Ga-containing anions include [((CF ₃ ) ₄ Ga) ⁻ and [Ga(C ₆ F ₅ ) ₄ ] ⁻ . Examples of Al-containing anions include [((CF ₃ ) ₃ CO) ₄ Al] ^- and [((CF ₃ CF ₂ ) ₃ CO) ₄ Al] ^- .

The dental photocurable composition of the present invention contains (C) an iodonium salt-based compound with an anion having logS of -4 or less as (C) a photoacid generator (C-1).

logS is an index of the water solubility of a compound and is used to predict the water solubility of a compound. In the present invention, the calculation was performed using ChemDraw Professional ver18.1. The larger the log S value, the higher the water solubility, and the smaller the log S value, the lower the water solubility. Partition coefficients such as LogP, CLogP, AlogP, and LogD, HSP (Hansen Solubility Parameter), and tPSA (topological polar surface area) are known as indices for finding properties from the structure of such compounds. As a result of collating these indices with the experimental results, a correlation was confirmed between the aforementioned indices related to solubility and the experimental results. , that the storage stability of the photocurable dental composition is improved during low-temperature storage. It is believed that by adding a highly soluble photoacid generator to a dental photocurable composition, it does not precipitate even when stored at low temperatures, and sufficient physical properties are exhibited even when returned to room temperature. . Furthermore, it was confirmed that the storage stability was also excellent when stored at high temperatures. Such an iodonium salt has a high correlation with ClogP among the indices described above, and ClogP generally tends to decrease as the value of logS increases. When ClogP is used as an index, an iodonium salt with one or more anions showing ClogP is preferable. In the present invention, since it was possible to determine that the method can be applied to many compounds when logS is used as an index, the present invention was developed by conducting studies using logS.

Examples of anions with a logS of -4 or less include [ _{( CF3CF2} ) _3PF3 ] ^- , [ _{( CF3CF2CF2} ) _3PF3 ] ^- _, [ _{( ( CF3} ) _2CF ) 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 ] ^- , [(CF ₃ CF ₂ SO ₂ ) ₃ C] ^- , [(CF ₃ CF ₂ CF ₂ SO ₂ ) ₃ C] ^- , [ _{( CF3CF2CF2CF2SO2} ) _3C ] ^- , [B( _C6F5 ) ₄ ] ^- , [ _{( C6H5} )B _{( C6F5} ) _{3 ]} ^- _, [ _{( C 6H5} )B(( _CF3 ) _2C6H3 )) ₃ ] ^- , [(( _CF3 ) _4Ga ] ^- , [ _{Ga ( C6F5} ) ₄ ] ^- , [ _{( ( CF3} ) ₃ CO) ₄ Al] ⁻ , [((CF ₃ CF ₂ ) ₃ CO) ₄ Al] ⁻ and the like.

On the other hand, examples of anions with logS exceeding −4, that is, anions with low lipid solubility, include chloride, bromide, nitrate, perchlorate, tetrafluoroborate, hexafluoroantimonate, hexafluorophosphate, p-toluene. sulfonates, trifluoromethanesulfonates, and the like. Such anions are highly soluble in water due to their high logS values, whereas they are poorly lipid soluble due to their low ClogP values. For example, the anions shown above have a ClogP of 1 or less.

The logS of the anion in the iodonium salt compound (C-1) is -4 or less, preferably -5 or less. When 0.5 parts by mass or more of an iodonium salt with an anion having a logS exceeding −4 is added to the dental photocurable composition with respect to 100 parts by mass of the total amount of (A) polymerizable monomers, the composition can be stored under low temperature conditions. There is a possibility that it will precipitate when it is dissolved, and particularly those with low solubility may not dissolve uniformly in the dental photocurable composition. If the photoacid generator does not dissolve uniformly in the dental photocurable composition, or if there is precipitation of the photoacid generator, sufficient mechanical properties may not be exhibited, or the light color stability may be reduced. And the precipitated photo-acid generator may be observed as black spots, which may affect aesthetics.

(C-1) The iodonium salt-based compound with an anion having a logS of −4 or less is preferably contained in an amount of 0.5 parts by mass or more with respect to 100 parts by mass of the total amount of (A) the polymerizable monomer, and further Preferably, it is contained in an amount of 1.0 parts by mass or more. If it is less than 0.5 parts by mass, the bending strength may not be sufficient, and if it is 0.5 to less than 1.0 parts by mass, the bending strength tends to be lower than when it contains 1.0 parts by mass or more. It is in. On the other hand, (C-1) the iodonium salt-based compound with an anion having a logS of −4 or less is preferably 10 parts by mass or less with respect to 100 parts by mass of the total amount of (A) the polymerizable monomer, and further It is preferably 5 parts by mass or less. If the content exceeds 10 parts by mass, the stability against ambient light and the stability of light color may be deteriorated. Further, when the amount is between 5 and 10 parts by mass, it is most preferable because a significant improvement in bending strength cannot be expected by increasing the amount of the iodonium salt compound with an anion having (C-1) logS of −4 or less. The blending amount is 1.0 to 5.0 parts by mass per 100 parts by mass of the total amount of the polymerizable monomer (A). The iodonium salt compounds (C-1) can be used alone or in combination of two or more.

Incidentally, (C) the photoacid generator is not limited to the iodonium salt-based compound (C-1), and may be used in combination with (C) a photoacid generator other than the iodonium salt-based compound (C-1). can be done. In this case, in the dental photocurable composition of the present invention, the amount of (C) the photoacid generator containing the iodonium salt-based compound (C-1) is such that the total amount of (A) the polymerizable monomer is 100. It is preferably 0.5 to 10.0 parts by mass. More preferably, it is 1.0 to 5.0 parts by mass. If the blending amount is less than 0.5 parts by mass, the polymerization accelerating ability may be poor, resulting in insufficient curing. When the amount is more than 10 parts by mass, the curing property is sufficient, but the environmental light stability is shortened, and discoloration such as browning of the cured product may increase.

The dental photocurable composition of the present invention may contain only the iodonium salt compound (C-1) as (C) a photoacid generator. The dental photocurable composition of the present invention contains only an aryliodonium salt, which is a salt of an anion having an organic group and at least one atom of P, B, Al, S, Ga, and an aryliodonium cation. 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.

[(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 and organometallic compounds are preferred because of their good light color stability.

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-diisopropanol-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.

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 zirconium (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 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.

(D) Photopolymerization accelerator is preferably an aliphatic tertiary amine compound. Aromatic amine compounds have poor light color stability, so when used in prosthetic devices, restorative materials, and adhesives for areas that are likely to be exposed to light, such as anterior teeth, the color tone may change over time, which is not preferable. 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 tertiary amine compound. In addition, depending on the composition of the dental photocurable composition, when it contains an aliphatic primary amine compound and an aliphatic secondary amine compound, high storage stability and high mechanical strength can be expected. It can be used without any restrictions.

Furthermore, among aliphatic tertiary amine compounds, amine compounds having two or more primary hydroxy groups in the molecule are preferred, and amine compounds having no primary hydroxy groups in the molecule are more preferred. Specific examples of amine compounds having two or more primary hydroxyl groups in the molecule include triethanolamine and methyldiethanolamine. An amine compound having a primary hydroxyl group may cause discoloration during long-term storage of a cured product of a photocurable dental composition. Discoloration tends to increase as the number of primary hydroxy groups in the molecule increases, and is particularly noticeable when there are two or more primary hydroxy groups in the molecule. Discoloration during long-term storage of the cured product can be confirmed in a short period of time by storing it under high-temperature water conditions. Discoloration under high-temperature water conditions is small, that is, when the thermal color stability is high, discoloration is small when the cured product of the dental photocurable composition is used for a long period of time.

(D) The photopolymerization accelerator is preferably 0.01 to 20 parts by mass, more preferably 0.1 part by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental photopolymerization composition. It is preferable to contain up to 10 parts by mass. If it is less than 0.01 parts by mass, the mechanical strength may be insufficient. If the amount is more than 20 parts by mass, the curing property is sufficient, but the stability against ambient light may be shortened, and discoloration such as browning of the cured product may increase, which is not preferable.

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.

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 may contain only (D) as a photopolymerization accelerator (D-1) an aliphatic tertiary amine compound that does not have two or more primary hydroxyl groups. The dental photocurable composition of the present invention may contain (D) only an aliphatic tertiary amine compound having no primary hydroxyl group in the molecule as a photopolymerization accelerator.

[(E) filler]
The dental photopolymerizable composition of the present invention can contain (E) a filler as another component. As the (E) filler used in the present invention, 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. Fillers such as inorganic fillers, organic fillers, or organic-inorganic composite fillers are blended. preferably. They can be used not only singly but also in combination regardless of the type of filler.

The above inorganic fillers are not particularly limited in chemical composition, but specific examples include silicon dioxide, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate Acid glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boro-aluminosilicate glass, strontium boro-aluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoro Examples include aluminosilicate 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.

Further, specific examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride , polystyrene, chlorinated polyethylene, nylon, polysulfone, polyethersulfone, polycarbonate and the like.

As the organic-inorganic composite filler, for example, the surface of the filler is polymerized and coated with a polymerizable monomer, the filler and the polymerizable monomer are mixed and polymerized and then pulverized to an appropriate particle size, or Examples thereof include those obtained by previously dispersing a filler in a polymerizable monomer and subjecting the polymer to emulsion polymerization or suspension polymerization, but are not limited to these.

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. Such surface treatment materials and surface treatment methods are not particularly limited, and 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.

The shape of the filler is not particularly limited, and fillers having arbitrary shapes such as amorphous, 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. diameter.

When the (E) filler is blended in the dental photocurable composition, it is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer (A), taking into account shapeability and the like. When used, it is preferably less than 500 parts by mass. If the amount of the filler compounded is less than 10 parts by mass, the effect of improving the mechanical strength and expressing thixotropic properties when the filler is compounded may be poor. Since it becomes hard, it may be difficult to handle, but it may be contained in an amount of 1000 parts by mass or more depending on the type of filler and the surface treatment conditions of the filler. For example, it refers to a case where the filler has a high specific gravity, a case where the amount of the surface treatment agent to the filler is large, or a case where a surface treatment agent having good affinity with the polymerizable monomer is used. The composition of the present invention exerts its effects regardless of the amount of filler compounded.

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, benzoyl peroxide and cumene hydroperoxide are preferred from the viewpoint of curability. 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., and iron compounds such as 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 monomers (A). However, if it exceeds 1 part by mass, it may cause discoloration or gelation of the dental photocurable composition, which may lower 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 monomer (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, Examples include methylquinolinium salts, ethylquinolinium salts and butylquinolinium salts. 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 aryl borate 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 (D) 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.

The method for preparing 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 prepare 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, dental loose tooth fixing adhesive, dental hard resin, dental cutting material, and 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 adhesives, dental hard resins, dental cutting materials, and dental 3D printer materials, and particularly preferably for dental use. Adhesives, dental composite resins, dental abutment building materials, dental resin cements, dental coating materials, dental pit and fissure sealing materials, dental manicure materials, dental loose tooth fixing adhesives, dental hard It is preferably used in resin. 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 adhesives, dental hard resins, dental cutting materials, and dental 3D printer materials, and particularly preferably for dental use. It is preferably used for adhesives, 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 photopolymerization accelerator, ( C) The photoacid generator may contain only (C-1) an iodonium salt-based compound with an anion having logS of -4 or less. 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 2.6E: 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 ・MDP: 10-methacryloyloxydecyl dihydrogen phosphate ・MHPA: 6-methacryloxyhexylphosphonoacetate

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

[(D) Photopolymerization accelerator]
<Aliphatic tertiary amine>
<<Aliphatic tertiary amine compound having no primary hydroxyl group>>
・TBA: tribenzylamine ・DBGE: N,N-dibenzylglycine ethyl ・DEAEMA: N,N-diethylaminoethyl methacrylate ・DMAEMA: N,N-dimethylaminoethyl methacrylate <<fat having one primary hydroxyl group group tertiary amine compound >>
・DBAE: N,N-dibenzylaminoethanol <<aliphatic tertiary amine compound having two primary hydroxyl groups>>
・MDEOA: Methyldiethanolamine <<aliphatic tertiary amine compound having three primary hydroxyl groups>>
・TEA: triethanolamine <aromatic tertiary amine compound>
・DMBE: N,N-dimethylaminoethyl benzoate <organometallic compound>
・DBTL: dibutyl-tin-dilaurate

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

(Filler 1)
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, 8-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. Thereafter, heat treatment was performed at 140° C. for 15 hours to obtain Filler 1.

(Filler 2)
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, 3-methacryloyloxypropyltrimethoxysilane 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 140° C. for 15 hours to obtain filler 2 .

[Chemical polymerization initiator]
・CHP: cumene hydroperoxide ・BPO: benzoyl peroxide ・TPE: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate [chemical polymerization accelerator]
・PTU: (2-pyridyl) thiourea ・DEPT: N,N-dihydroxyethyl-p-toluidine ・DMPT: N,N-dimethyl-p-toluidine ・COA: copper acetylacetone ・VOA: vanadyl acetylacetonate

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

・Ｃ２：ジ－ｐ－トリルヨードニウムフェニルトリス(ペンタフルオロフェニル)ボレート(LogS:-11.3)

・Ｃ３：ビス（４－ｔｅｒｔ－ブチルフェニル)ヨードニウムテトラ(ノナフルオロ－ｔｅｒｔ－ブトキシ)アルミン酸塩(LogS:-14.7)

・Ｃ４:ｐ－クメニル（ｐ－トリル）ヨードニウムトリス（ペンタフルオロエタンスルホニル）メチド(LogS：－5.3)

・Ｃ５:ジフェニルヨードニウムトリス（ノナフルオロブタンスルホニル）メチド(LogS：-9.4)

・Ｃ６: 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(ClogP：-5.2)

・Ｃ７：ｐ－クメニル（ｐ－トリル）ヨードニウムトリス（ペンタフルオロエチル）トリフルオロホスフェート(ClogP：-7.2)

・Ｃ８：ｐ－クメニル（ｐ－トリル）ヨードニウムビス（トリフルオロメチル）テトラフルオロホスフェート(ClogP：-4.7)

・Ｃ９：ｐ－クメニル（ｐ－トリル)ヨードニウム（トリフルオロメチル）ペンタフルオロホスフェート(ClogP：-4.1)

＜logSが－４を超過するアニオンを含む光酸発生剤＞
・Ｃ１１：ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウム－ｐ－トルエンスルホナート(logS：-2.1)

・Ｃ１２：ジフェニルヨードニウムトリフルオロメタンスルホン酸(logS：-0.7)

・Ｃ１３：ジフェニルヨードニウムクロリド(logS：0.2)

・Ｃ１４：ビス（４－ｔｅｒｔ－ブチルフェニル)ヨードニウムヘキサフルオロホスファート(logS：-3.5)

[(C) Photoacid Generator]
The logS of the hydride of the anion of the iodonium salt was calculated using ChemDraw Professional ver18.1.
<(C-1) Iodonium salt compound with an anion having logS of −4 or less>
・ C1: bis [4-(tert-butyl) phenyl] iodonium tetra ((pentafluorophenyl) gallate (LogS: -15.1)

・C2: di-p-tolyliodonium phenyltris(pentafluorophenyl)borate (LogS: -11.3)

・C3: bis(4-tert-butylphenyl)iodonium tetra(nonafluoro-tert-butoxy)aluminate (LogS: -14.7)

・C4: p-cumenyl(p-tolyl)iodonium tris(pentafluoroethanesulfonyl)methide (LogS: -5.3)

・C5: diphenyliodonium tris(nonafluorobutanesulfonyl) methide (LogS: -9.4)

・C6: bis(4-tert-butylphenyl)iodonium tris(pentafluoropropyl)trifluorophosphate (ClogP: -5.2)

・C7: p-cumenyl (p-tolyl) iodonium tris (pentafluoroethyl) trifluorophosphate (ClogP: -7.2)

・ C8: p-cumenyl (p-tolyl) iodonium bis (trifluoromethyl) tetrafluorophosphate (ClogP: -4.7)

・ C9: p-cumenyl (p-tolyl) iodonium (trifluoromethyl) pentafluorophosphate (ClogP: -4.1)

<Photoacid generator containing an anion with logS exceeding −4>
· C11: bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate (logS: -2.1)

・C12: diphenyliodonium trifluoromethanesulfonate (logS: -0.7)

・C13: diphenyliodonium chloride (logS: 0.2)

· C14: bis (4-tert-butylphenyl) iodonium hexafluorophosphate (logS: -3.5)

<Method for producing one-component dental photocurable composition>
All except the (E) filler shown in Table 1 were placed in a wide-mouth plastic container and mixed for 48 hours at 100 rpm using a mix rotor VMRC-5 to obtain a matrix. Thereafter, the matrix and (E) the filler were charged into a kneader, uniformly stirred, and defoamed under vacuum to prepare a dental photocurable composition. In addition, in Table 1, the parts by mass of each component are listed in parentheses after the abbreviation of each component.

<Method for producing a two-component dental photocurable composition>
All except the (E) filler shown in Table 2 were placed in a wide-mouth plastic container and mixed at 100 rpm for 48 hours using a mix rotor VMRC-5 to obtain a matrix. After that, the matrix and (E) filler are put into a kneader, uniformly stirred, 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. A paste obtained by mixing pastes 1 and 2 using a mixing tip manufactured by Mixpack Co., Ltd. was used. Mixpack's mixing tip is a static mixer, and when using this, paste 1 and paste 2 can be kneaded at a volume ratio of 0.9 to 1.1:1.0, converted to a mass ratio Paste 1 and paste 2 were kneaded at a ratio of 0.8 to 1.2:1.0 before use. In addition, in Table 2, the parts by mass of each component are listed in parentheses after the abbreviation of each component.

<Accelerated test conditions>
The one-component dental photocurable composition and the two-component dental photocurable composition filled in each container were stored in a storage box set at 40 ° C (Yamato Scientific Co., Ltd.) and a storage box set at -5 ° C (KGT- 4010HC, Nippon Freezer Co., Ltd.) and stored for 6 months.

<Evaluation 1: Confirmation of Appearance>
After taking out the one-component dental photocurable composition and the two-component dental photocurable composition stored at -5°C from the storage, they were allowed to stand at room temperature of 15 to 25°C for 1 week, and 1 g was removed from the container. When the paste is discharged and no precipitates are visually confirmed at that time, A: Good, if 1 or more and 5 or less precipitates are confirmed, B: Within the allowable range, 5 or more confirmed C: Appearance was determined to be problematic.

<Evaluation 2: Confirmation of storage stability by bending strength>
After filling a stainless steel mold with a dental photocurable composition, cover glasses are placed on both sides, and pressed with a glass kneading plate. 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. [Equation 2] was used to evaluate the storage stability based on the results of the bending test. If the change is above -5% from before storage, it has high storage stability. If it is between -5% and -15%, the storage stability is rather poor. If the value was lower than -15%, it was judged that the storage stability was extremely poor.

[(Formula 2)]
(Bending strength after storage (MPa) - Bending strength before storage (MPa)) / (Bending strength before storage (MPa)) x 100 [%]

Furthermore, the bending strength before the accelerated test was separately evaluated. The bending strength of the one-component photocurable composition and the two-component photocurable composition containing 100 parts by mass or more of the filler (E) with respect to 100 parts by mass of the polymerizable monomer is preferably greater than 100 MPa. , 80 to 100 MPa is applicable, and less than 80 MPa is judged to be insufficient. The bending strength of the one-component photocurable composition and the two-component photocurable composition containing less than 100 parts by mass of the filler (E) with respect to 100 parts by mass of the polymerizable monomer is preferably greater than 90 MPa. , 60 to 90 MPa is applicable, and less than 60 MPa is judged to be insufficient. Since the flexural strength varies depending on the amount of filler compounded, different standards were set.

<Evaluation 3: Ambient Light Stability>
Using an illuminometer, the height of a dental lamp (Luna-Vue S, manufactured by Morita Seisakusho) was adjusted so that light with an illuminance of 8000±1000 lx was applied to the sample installation portion. After placing a glass slide (26×16 mm, 2 mm thick) on a glass plate covered with matte black paper, about 30 mg of sample was taken on it. After the sample was exposed for 60±5 seconds on the sample mount, the sample was removed from the sample mount and immediately another glass slide was pressed against the sample to produce a thin layer. If the state of the sample at this time did not maintain a physically uniform state, it was determined that curing had started, and the time until curing was evaluated in increments of 5 seconds. The longer this time, the better the ambient light stability. Ambient light stability was judged to be good if 90 seconds or more, acceptable if 60 seconds or more and less than 90 seconds, and insufficient if less than 60 seconds. Ambient light stability refers to the time that a photocurable dental composition can be discharged from a container and adapted to change its shape sufficiently without being cured by ambient light such as fluorescent light. Since the oral cavity is a narrow space, manipulation is not free, and the shape of natural teeth is complicated for each individual. Therefore, long environmental light stability is preferable in order to adapt to various cases.

<Evaluation 4: light 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). 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, and a2*, b2* are the color index after light exposure. be. A ΔE of less than 5 was judged to be the best, a ΔE of 5 to 10 was judged to be good, and a ΔE of more than 10 was judged to be applicable. When light color stability is good, discoloration is small when used, and high aesthetics can be maintained.

<Evaluation 5: 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, b1* are the color indices before immersion and standing, a2*, b2* are the immersion and standing It is a color quality index after standing still. Those with a ΔE of less than 5 were judged to be the best, those with a ΔE of 5 to 10 were judged to be good, and those with a ΔE of more than 10 were judged to be 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.

The results of each test shown in Tables 3 and 4 are described.

It was confirmed that the compositions described in Examples exhibit a bending strength of 80 MPa or more at the stage of preparation, and the bending strength did not significantly decrease even after long-term storage at low temperature.

Examples A8, A9, A15, A16, A23, B8, B9, B15, B16 and B17 showed slightly low values of bending strength because the amount of the photo-acid generator was slightly less. On the other hand, when the compounding amount of the photo-acid generator is slightly large as in Examples A12, A13, A14, and B14, the bending strength tends to decrease when a storage test is performed at a high temperature such as 40°C. It was confirmed that the ambient light stability was shortened and the light color stability was decreased. When the photoacid generator contains C8 or C9, which is an iodonium salt compound that is a salt of an anion and an iodonium cation whose logS is -4 to -5, and when the amount is small as in Examples A8, A9, B8, and B9 There is no problem even if it is stored at a low temperature, and in Examples A10, A11, B10, and B11 in which the compounding amount was increased and Examples A12, A13, B12, and B13 in which the amount was further increased, the storage stability tended to decrease slightly, and was stored at a low temperature. In some cases, some precipitates were observed and the light color stability tended to be slightly worse, but the change was within the range where it can be used without problems. Further, even if an iodonium salt compound, which is a salt of an iodonium cation and an anion having a logS exceeding −4, is contained as in Examples A16 and A17, about 0.1 part by mass with respect to 100 parts by mass of the polymerizable monomer. It was confirmed that a trace amount of 10% does not significantly affect the storage stability.

Examples A22 and B22 tend to have low bending strength because the amount of the photosensitizer is slightly low, and Examples A21, A47, and B21 have a slightly large amount of the photosensitizer, so the bending strength is However, it was confirmed that the ambient light stability and light color stability tended to decrease. Further, Examples A36 and B36 containing BAPO, which is an acylphosphine oxide, as a photosensitizer tended to have lower bending strength than the composition containing an α-diketone compound as a photosensitizer.

Examples A18, A48, and B18 tend to have low bending strength because the amount of the photopolymerization accelerator is slightly small, and Examples A19, A20, and B20 have a slightly large amount of the photopolymerization accelerator, so bending strength tends to be low. Although the strength was high, it was confirmed that the ambient light stability and light color stability tended to decrease.

Examples A26, A27, B26, and B27 contain dibenzylaminoethanol (DBAE) having one primary hydroxy group as a photopolymerization accelerator, and Examples A28 and B28 contain two primary hydroxy groups as a photopolymerization accelerator. Examples A29 and B29 contain triethanolamine having three primary hydroxyl groups as a photopolymerization accelerator. Comparing these, it was confirmed that as the number of primary hydroxy groups increased, the thermal color stability tended to decrease, and in particular, having two or more primary hydroxy groups significantly decreased the thermal color stability. .

Examples A30, A31, A32, B30, B31, B32 contain the aromatic amine DMBE as a photopolymerization accelerator. It was confirmed that the light color stability decreased when aromatic amines were contained. On the other hand, as in Examples A33, A34, B33, and B34, when the composition contains an aromatic amine and an ultraviolet absorber at the same time, it is possible to prevent deterioration of light color stability. However, UV absorbers increase the yellowness of the cured product, and because they themselves do not contribute to the improvement of physical properties, a large amount of UV absorbers may cause a decrease in mechanical strength, so it is more preferable not to add them.

Examples B41, B42, B44, B45 contain aromatic amines as chemical accelerators. Similar to the case of containing an aromatic amine as a photopolymerization accelerator, the light color stability tended to decrease. In addition, Examples B42, B44, and B45 containing an aromatic amine having two primary hydroxyl groups in the molecule, such as DEPT, tended to have lower heat color stability.

Since Comparative Examples CA1 and CB1 did not contain a photosensitizer, they either did not cure or their flexural strength was remarkably lowered. Since Comparative Examples CA2 and CB3 did not contain a photoacid generator, their flexural strength was significantly low. Since Comparative Examples CA3 and CB2 did not contain a photopolymerization accelerator, their flexural strengths were remarkably low. Comparative Examples CA4-CA13 and CB4-CB13 contain iodonium salt compounds that are salts of iodonium cations with anions having logS greater than -4. Comparative Examples CA4, CA5, CB5, and CB6, which contained a small amount of the photoacid generator, showed insufficient bending strength, although no decrease in storage stability was observed. When the blending amount of the photoacid generator is increased as in Comparative Examples CA6 to CA9 and Comparative Examples CB6 to CB9, although the bending strength is improved, precipitates are confirmed when stored at low temperature, and the bending strength is reduced. A trend was confirmed. Furthermore, a decrease in light color stability was also confirmed. Furthermore, in Comparative Examples CA10 to CA13 and Comparative Examples CB10 to CB13, in which the amount of the photoacid generator was increased, the bending strength was further improved, but the storage stability during low-temperature storage and high-temperature storage was reduced, and the light color was stable. decreased sex was confirmed. The solubility of the photoacid generator affects storage stability and color stability.

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 adhesives, dental glass ionomer cements, 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 that exhibits excellent mechanical properties even after returning from a low temperature to room temperature.

Claims (8)

(A) a polymerizable monomer,
(B) a photosensitizer;
(C) a photoacid generator, and
(D) contains a photopolymerization accelerator,
(C) The photoacid generator is a dental photocurable composition containing (C-1) an iodonium salt compound with an anion having logS of -4 or less. (C-1) 0.5 parts by mass or more of an iodonium salt-based compound with an anion whose logS is -4 or less (A) with respect to 100 parts by mass of the polymerizable monomer. A dental photocurable composition as described. (C-1) As an iodonium salt-based compound with an anion having log S of −4 or less, an anion having an organic group and at least one atom of P, B, Al, S, Ga, and an aryliodonium cation 3. A dental photocurable composition according to claim 1 or 2, comprising an aryliodonium salt. (C-1) As an iodonium salt-based compound with an anion having logS of −4 or less, at least one H-substituted organic group and one or more of P, B, Al, S, Ga and an aryliodonium salt consisting of an aryliodonium cation. 5. The dental photocurable composition according to any one of claims 1 to 4, comprising (D) an aliphatic tertiary amine compound as a photopolymerization accelerator. (D) The photocurable dental product according to any one of claims 1 to 4, which contains (D-1) an aliphatic tertiary amine compound having no two or more primary hydroxyl groups as a photopolymerization accelerator. Composition. A one-part dental photocurable composition comprising:
(A) with respect to 100 parts by mass of the polymerizable monomer,
(B) contains 0.005 to 1.0 parts by mass of a photosensitizer;
(C) contains 0.5 to 10.0 parts by mass of a photoacid generator, and
(D) The dental photocurable composition according to any one of claims 1 to 6, comprising 0.01 to 20 parts by mass of a photopolymerization accelerator. A two-component dental photocurable composition comprising:
consisting of a first paste and a second paste,
The first paste and the second paste have a specific gravity of 1:0.8 to 1.2,
For a total of 200 parts by mass of the polymerizable monomer (A) contained in the first paste and the second paste,
(B) contains 0.01 to 2.0 parts by mass of a photosensitizer;
(C) contains 1.0 to 20 parts by mass of a photoacid generator, and
(D) The dental photocurable composition according to any one of claims 1 to 6, comprising 0.02 to 40 parts by mass of a photopolymerization accelerator.