JP2023042485A - Dental photocurable composition excellent in color tone stability - Google Patents

Abstract

To provide a dental photocurable composition having sufficient mechanical strength while having excellent color tone stability after curing.SOLUTION: A dental photocurable composition comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, which is (D1) a tertiary amine compound represented by formula (1) (where each R1 is an ether bond, an ester bond, a urethane bond, an unsaturated double bond, an aromatic ring, an organic group optionally having a halogen, or H, which may be the same as or different from each other; R2 is an organic group optionally having a hydroxy group, or an aromatic ring optionally having a substituent; the compound represented by formula (1) does not have a primary hydroxy group at α-carbon and/or β-carbon of N).SELECTED DRAWING: None

Description

The present invention relates to dental photocurable compositions.

In the field of dentistry, dental photocurable compositions are used and are used as dental adhesives, dental composite resins, dental abutment building materials, dental resin cements, dental coating materials, dental pits and fissures. It is applied to sealing materials, dental manicure materials, dental loose tooth fixing adhesives, dental glass ionomer cements, dental hard resins, 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 as a photopolymerization initiator, Patent Document 3 proposes a resin composition containing N,N-di(2-hydroxypropyl)-p-toluidine, which is superior to conventional tertiary amines because of its lower colorability after curing.

Japanese Patent No. 4093974 Japanese Patent No. 4596786 JP-A-1-031706

However, these compositions have a problem in achieving both sufficient mechanical strength and color tone stability after curing.

An object of the present invention is to provide a dental photocurable composition that can achieve both sufficient mechanical strength and color tone stability after curing.

（式中、Ｒ_１はエーテル結合、エステル結合、ウレタン結合、不飽和二重結合、芳香環、ハロゲンを有して良い有機基、またはHであり、互いに同一でも異なっていてもよい。Ｒ_２はヒドロキシ基を有しても良い有機基、または置換基を有しても良い芳香環である。式（１）で示される化合物はＮのα位炭素及び／またはβ位炭素に１級ヒドロキシ基を有さない。） The present invention provides (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a tertiary amine represented by formula (1) as (D1) a polymerization accelerator. Kind Code: A1 A dental photocurable composition comprising a compound is provided.
[Formula (1)]

(In the formula, R ₁ is an ether bond, an ester bond, a urethane bond, an unsaturated double bond, an aromatic ring, an organic group which may have a halogen, or H, and may be the same or different. R ₂ is an organic group which may have a hydroxy group, or an aromatic ring which may have a substituent.The compound represented by formula (1) has a primary hydroxy at the α- and/or β-carbon of N. does not have a group.)

The dental photocurable composition of the present invention can achieve both sufficient mechanical strength and color tone stability after curing.

In the present invention, (D1) the tertiary amine compound represented by formula (1) can be a tertiary aliphatic amine compound represented by (D11) formula (1).

In the present invention, (C) an aryliodonium salt is included as a photoacid generator, and the aryliodonium salt includes an anion having an organic group and at least one atom of P, B, Al, S, Ga, and an aryl It can be a salt with an iodonium cation.

In the present invention, (C) an aryliodonium salt is included as a photoacid generator, and the aryliodonium salt includes at least one or more H-substituted organic groups and any of P, B, Al, S, Ga It can be a salt of an aryliodonium cation with an anion having one or more atoms.

In the present invention, (D12) a tertiary aromatic amine compound and a tertiary aliphatic amine compound represented by formula (1) can be included.

In the present invention,
(A) with respect to 100 parts by mass of the polymerizable monomer,
(B) contains 0.02 to 1 part by mass of a photosensitizer;
(C) contains 0.02 to 10 parts by mass of a photoacid generator,
(D11) It can contain 0.2 to 10 parts by mass of a tertiary aliphatic amine compound represented by formula (1).

In the present invention,
(A) with respect to 100 parts by mass of the polymerizable monomer,
(B) contains 0.02 to 1 part by mass of a photosensitizer;
(C) contains 0.02 to 10 parts by mass of a photoacid generator,
(D) contains 0.2 to 10 parts by mass of a polymerization accelerator,
(D) As a polymerization accelerator, (D12) 0.02 to 1 part by mass of a tertiary aromatic amine compound represented by formula (1) can be included.

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

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

As photopolymerization initiators used in 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. Photoacid generators and tertiary amine compounds are well known as compounds to be combined with photosensitizers. A combination of an α-diketone compound, a photoacid generator and a tertiary amine compound has high polymerization activity with respect to irradiation light, and is therefore 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.

Amine compounds having a primary hydroxyl group, such as methyldiethanolamine, triethanolamine and p-tolylethanolamine, are known as typical tertiary amine compounds used as such photopolymerization initiators. However, when an amine compound having a primary hydroxyl group is incorporated into a composition in combination with a photoacid generator, there is a problem of discoloration of the cured product after long-term use. Although the detailed principle is unknown, discoloration tends to occur when containing an acidic compound such as a polymerizable monomer having an acidic group, not limited to a photoacid generator, so a photoacid generator was generated. It is speculated that the coexistence of an acid and an amine compound having a primary hydroxyl group causes the discoloration.

We have found that the above problems can be solved by incorporating a tertiary amine compound having a specific structure into the dental photocurable composition. More specifically, the inventors have found that the above problems can be overcome by using a tertiary amine compound having two or more secondary and/or tertiary hydroxy groups, and have completed the present invention. rice field.

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

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

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

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

The polymerizable monomer having an acidic group has 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. By including a polymerizable monomer having an acidic group, it is possible to impart adhesiveness to dentin and prosthetic devices.

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

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

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

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

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

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

Preferred are 10-methacryloyloxydecyl dihydrogen phosphate and 6-methacryloxyhexyl phosphonoacetate. From the viewpoint of imparting adhesiveness, the amount of the polymerizable monomer having an acidic group is 1 part by mass or more relative to the total amount of 100 parts by mass of the polymerizable monomer contained in the dental photocurable composition. A blending amount of 10 parts by mass or more and 50 parts by mass or less is preferable. If the amount is less than 1 part by mass, sufficient adhesion to tooth substance, metals and metal oxides may not be exhibited, and if the amount is 50 parts by mass or more, storage stability may be lowered.

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

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

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

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

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

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

<Photoinitiator>
The dental photocurable composition of the present invention contains a photoinitiator. A photopolymerization initiator is a polymerization initiator capable of initiating polymerization by irradiation with light. The photopolymerization initiator contained in the dental photocurable composition of the present invention includes (B) a photosensitizer, (C) a photoacid generator, and (D) a polymerization accelerator. 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, camphorquinone carboxylic acid, camphorquinone sulfonic acid, α-naphthyl, acetonaphthene, p,p'-dimethoxybenzyl. , p,p'-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, α-diketones such as naphthoquinone, benzoin , benzoin methyl ether, benzoin alkyl ethers such as benzoin ethyl ether, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2 , thioxanthone such as 4-diisopropylthioxanthone, benzophenone, p-chlorobenzophenone, p-methoxybenzophenone and other benzophenones, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl) (2 ,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylprop-1-yl)phosphine oxide, bis (2,6-dimethoxybenzoyl)-(1-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, Bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylprop-1-yl)phosphine oxide , bis(2,6-diethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6 -dibutoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenyl Phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis (2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoyl Acylphosphine oxides such as benzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide and 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide, bis Acylgermanium compounds such as benzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis(4-methoxybenzoyl)dimethylgermanium, and bis(4-methoxybenzoyl)diethylgermanium, 2-benzyl-dimethylamino-1-( 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 especially camphorquinone is preferred because of its easy availability.

Usually, the amount of the photosensitizer (B) is 0.02 to 1.0 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental photocurable composition. Preferably, it is 0.05 to 0.5 parts by mass. (B) If the amount of the photosensitizer is less than 0.02 parts by mass, the polymerization activity against irradiation light may be 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.
The dental photocurable composition of the present invention may contain only an α-diketone compound as (B) a photosensitizer.

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

Specific examples of triazine compounds include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis (trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p -methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)- 4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6 -bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s -triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2- [2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)- s-triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4, 6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(1- naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis (2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis( trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,6-bis(trichloromethyl) -s-triazine, 2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine. Among these, 2,4,6-tris(trichloromethyl)-s-triazine is preferred.

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

[Formula (2)]
[(R1)₂I]⁺ [A]^-

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

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

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

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

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

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

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

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

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

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

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

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

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

Further, _specific examples of alkoxy _{groups include CF3O , CF3CF2O} , _CF3CF2CF2O , ( _CF3 ) _{2CFO , CF3CF2CF2CF2O} , _{( CF3} ) _{Linear chains such as 2CFCF2O , CF3CF2 ( CF3 ) CFO , CF3CF2CF2CF2CF2O , CF3CF2CF2CF2CF2CF2CF2CF2CF2O _ _ _ _} or a branched perfluoroalkoxy group.

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

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

The dental photocurable composition of the present invention preferably contains 0.02 to 10 parts by mass of (C) a photoacid generator with respect to 100 parts by mass of the total amount of (A) polymerizable monomers, and more It is preferably 0.2 to 5 parts by mass. If the amount of the photoacid generator is less than 0.02 part by mass, the polymerization accelerating ability may be poor, resulting in insufficient curing. If the amount is more than 10 parts by mass, sufficient curability is exhibited, but the ambient light stability may be reduced, the operating time may be shortened, or discoloration such as the cured product may become brownish.

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

The dental photocurable composition of the present invention comprises (C) an anion having an organic group and at least one atom selected from P, B, Al, S and Ga as a photoacid generator, and an aryliodonium cation. may contain only aryliodonium salts that are salts of 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) Polymerization accelerator]
The (D) polymerization accelerator used in the dental photocurable composition of the present invention is not particularly limited as long as it has the ability to accelerate polymerization, and known polymerization accelerators generally used in the dental field can be used without any limitation. be able to. (D) Polymerization accelerators include aromatic amine compounds, primary to tertiary amine compounds such as aliphatic amine compounds, phosphine compounds, organometallic compounds, 4th period transition metal compounds, thiourea derivatives, sulfinic acids and their Salts, borate compounds, sulfur-containing reducing inorganic compounds, nitrogen-containing reducing inorganic compounds, barbituric acid derivatives, triazine compounds, halogen compounds, and the like can be used.

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

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

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.

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.

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. These 4th period transition metal compounds may be used in combination of a plurality of types, 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, 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 the like; 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. is mentioned.

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

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

The reducing inorganic compound containing nitrogen includes 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.

（式中、Ｒ_１はエーテル結合、エステル結合、ウレタン結合、不飽和二重結合、芳香環、ハロゲンを有して良い有機基、またＨであり、互いに同一でも異なっていてもよい。Ｒ_２はヒドロキシ基を有しても良い有機基、または置換基を有しても良い芳香環である。式（１）で示される化合物はＮのα位炭素及び／またはβ位炭素に１級ヒドロキシ基を有さない。） The dental photocurable composition of the present invention contains (D) a tertiary amine compound represented by formula (1) as (D1) a polymerization accelerator.
[Formula (1)]

(In the formula, R ₁ is an ether bond, an ester bond, a urethane bond, an unsaturated double bond, an aromatic ring, an organic group which may have a halogen, or H, and may be the same or different. R ₂ is an organic group which may have a hydroxy group, or an aromatic ring which may have a substituent.The compound represented by formula (1) has a primary hydroxy at the α- and/or β-carbon of N. does not have a group.)

Tertiary amine compounds having a primary hydroxyl group, such as methyldiethanolamine, triethanolamine and p-tolyldiethanolamine, have been used in conventional dental photocurable compositions. Amine compounds with a primary hydroxyl group may have less unpleasant odor peculiar to amines than conventionally used amine compounds such as dimethylaminoethyl methacrylate and dimethyl-p-toluidine, and are suitable for dental materials. there is However, the cured product of the dental photocurable composition containing (B) a photosensitizer and (C) a photopolymerization initiator obtained by combining a photoacid generator and an amine compound having a primary hydroxyl group discolors over time. tended to be large. This discoloration over time can be inferred from an accelerated test. For example, a test of immersion in water at a high temperature of 50 to 70° C. is used as an accelerated test for predicting discoloration after long-term use, and is used as an index for predicting discoloration after long-term use. For this reason, (B) a photosensitizer, (C) a photopolymerization initiator containing a photoacid generator and an amine compound having a primary hydroxy group, after curing the dental photocurable composition, Discoloration occurs, which is undesirable from the aesthetic point of view. Therefore, as a result of investigation by the inventors, when the amine compound represented by the structure of formula (1) is used in the photopolymerization accelerator dental photocurable composition, immediately after curing the dental photocurable composition It was found that the color difference of the cured product after a long period of time was small, and the degree of discoloration was reduced.

(B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization initiator consisting of an amine compound having a primary hydroxyl group as a photopolymerization accelerator. It tends to occur remarkably when containing a compound having two or more hydroxy groups. More specifically, it is an amine compound having two or more primary hydroxyl groups at the α- and/or β-position starting from N derived from amine. Here, the α-position carbon and the β-position carbon refer to the first carbon adjacent to the N derived from the amine as the α-position carbon, and the second carbon next thereto as the β-carbon. If the primary hydroxy group starts at N and binds to a carbon other than the α- and/or β-position carbon, it does not cause discoloration. In the present invention, N derived from amine refers to the case where the one bonded to N is hydrogen or a hydrocarbon group. For example, N derived from an amide bond, a urethane bond, a urea bond, and an azo group is distinguished.

A composition using a photopolymerization initiator containing an amine compound having a primary hydroxyl group is not limited to (C) a photoacid generator, but when it has an acidic compound such as a polymerizable monomer having an acidic group, curing after curing When stored for a long period of time, the body tends to undergo large discoloration. Therefore, similar effects can be expected when the tertiary amine compound represented by formula (1) (D1) is used as the photopolymerization initiator for the composition containing an acidic compound. Among acidic compounds, especially when (C) a photoacid generator is included, there is a tendency to cause a large discoloration. Therefore, (C) a photoacid generator and (D1) a tertiary amine compound represented by formula (1) are combined. is useful.

(D1) A known tertiary amine compound represented by formula (1) can be used. can be synthesized using (D1) As a synthesis example of the tertiary amine compound represented by formula (1), when synthesizing an aliphatic tertiary amine corresponding to the tertiary amine compound represented by (D1) formula (1), ammonia It can be synthesized by reacting with an epoxide in a molar ratio of 3 times the amount of the primary aliphatic amine compound, or by reacting the primary aliphatic amine compound with an epoxide in an amount of 2 times the molar ratio. (D1) The aromatic tertiary amine corresponding to the tertiary amine compound represented by formula (1) is obtained by reacting the epoxide with a primary aromatic amine such as p-methyltoluidine in a molar ratio of two times. can be synthesized with

(D1) Specific examples of epoxides that can be used to synthesize the tertiary amine compound represented by formula (1) include propylene oxide, butadiene monoepoxide, isobutylene oxide, butylene oxide, pentylene oxide, decylene oxide and glycidyl methyl ether. , ethyl glycidyl ether, glycidyl trityl ether, benzyl glycidyl ether, glycidyl phenyl ether, allyl glycidyl ether, glycidyl isopropyl ether, butyl glycidyl ether, t-butyl glycidyl ether, glycidyl phenyl ether, epichlorohydrin, 2-(chloromethyl) -1,2-propylene oxide, epibromohydrin, styrene oxide, glycidyl acrylate, glycidyl methacrylate and the like.

(D1) The tertiary amine compound represented by formula (1) comprises (D11) the tertiary aliphatic amine compound represented by formula (1) and (D12) the tertiary aromatic amine represented by formula (1). Divided into compounds.

(D11) Specific examples of the tertiary aliphatic amine compound represented by formula (1) include triisopropanolamine, N-methyl-N,N-bis(2-hydroxypropyl)amine, 3,3′-( butanezandiyl)bis(1-butoxypropan-2-ol), 1,1′-((3-chlorobenzyl)azanediyl)bis(propan-2-ol), 1,1′-(cyclohexylazanediyl)bis (propan-2-ol), N,N-bis(2-hydroxypropyl)ethanolamine, and the like. Among these, triisopropanolamine is preferred.

(D12) Specific examples of the tertiary aromatic amine compound represented by formula (1) include N,N-bis(2-hydroxypropyl)-p-toluidine and N,N-bis(2-hydroxypropyl) Aniline, 2-[(2-hydroxy-2-phenyl-ethyl)-p-tolyl-amino]-1-phenyl-ethanol and the like can be mentioned. Among these, N,N-bis(2-hydroxypropyl)-p-toluidine is particularly preferred.

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.

(D) The photopolymerization accelerator is preferably 0.2 to 10 parts by mass, more preferably 0.2 to 10 parts by mass based on 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental photocurable composition. It is preferably contained in an amount of 2 to 5 parts by mass. If it is less than 0.2 parts by mass, the mechanical strength may be insufficient. When the amount is more than 10 parts by mass, the curing property is sufficient, but the stability against ambient light is shortened, and discoloration such as brown or yellowishness of the cured product may increase, which is not preferable.

(D1) Among the tertiary amine compounds represented by formula (1), (D11) a tertiary aliphatic amine compound represented by formula (1), (B) a photosensitizer, and (C) a photoacid generator A photopolymerization initiator consisting of a photopolymerization agent is preferable in terms of light color stability. It is preferable because the photostability is improved and the operating margin time is extended in some cases. In this case, (D11) the tertiary aliphatic amine compound represented by formula (1) is preferably 0.2 to 10 parts by mass, more preferably It is preferably contained in an amount of 0.2 to 5 parts by mass. If it is less than 0.2 parts by mass, the mechanical strength may be insufficient. When the amount is more than 10 parts by mass, the curing property is sufficient, but the stability against ambient light is shortened, and discoloration such as brown or yellowishness of the cured product may increase, which is not preferable.

In addition, (B) a photosensitizer, (C) a photoacid generator, and (D) a tertiary aliphatic amine compound as a polymerization accelerator and (D1) a tertiary amine compound represented by formula (1) Among them, (D12) a composition containing a tertiary aromatic amine compound represented by formula (1) is also preferable. (B) a photosensitizer, (C) a photoacid generator, and a tertiary aliphatic amine compound combined with a tertiary aromatic amine compound having a primary hydroxyl group such as p-tolyldiethanolamine In this case, it can be expected that the environmental light stability will be improved and the operating margin time will be longer than when the tertiary aromatic amine compound having a primary hydroxyl group is not contained. However, when a tertiary aromatic amine compound having a primary hydroxyl group is used, it is aesthetically unfavorable due to significant discoloration over time after curing. Therefore, by using (D) a tertiary aromatic amine compound represented by formula (1) together with a tertiary aliphatic amine compound (D12) as a polymerization accelerator (D), environmental light stability can be improved and good It is preferable because it can be expected to exhibit both color tone stability and good mechanical strength. In this case, the tertiary aliphatic amine compound to be mixed together is preferably a tertiary amine compound having no primary hydroxyl group. Among tertiary aliphatic amine compounds, compounds that can be preferably used in combination are preferably compounds having a dibenzylamino group structure such as tribenzylamine, and aliphatic tertiary amine compounds such as dimethylamino methacrylate having a dialkylamino group. In addition, there is no problem even if a tertiary aromatic amine compound such as ethyl dimethylaminobenzoate, which is a dialkylaminobenzoic acid ester compound, is added separately. On the other hand, when the tertiary aromatic amine containing the tertiary aromatic amine compound represented by formula (1) (D12) is used, it is particularly good against long-term discoloration when it is not exposed to strong light. However, it is preferable to incorporate an ultraviolet absorber because the light color stability may deteriorate when exposed to strong light. (D12) When the tertiary aromatic amine compound represented by formula (1) is blended, it is preferably 0.02 to 1 part by mass, more preferably 0.02 to 1 part by mass based on 100 parts by mass of the total amount of the polymerizable monomers (A). is preferably contained in an amount of 0.05 to 0.5 parts. If the amount is less than 0.02 part by mass, the environmental light stability may not be sufficiently improved, and if the amount is more than 1 part by mass, the light color stability may be significantly reduced or the cured product may be brown. Discoloration such as tinge of taste and yellowness may increase, which is not preferable.

[(E) filler]
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. It is preferable to add a filler such as flexible glass. The dental photocurable composition of the present invention may use the exemplified fillers alone or in combination of two or more.

As inorganic fillers, their chemical compositions are not particularly limited, but specific examples include silicon dioxide, alumina, titania, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, Borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium-calcium fluoroaluminosilicate glass, and the like. In particular, barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, fluoroaluminosilicate glass, etc., which are used in dental glass ionomer cement, resin-reinforced glass ionomer cement, resin cement, etc., can also be suitably 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.

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

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

Examples of the organic-inorganic composite filler include those obtained by polymerizing and coating the surface of a filler with a polymerizable monomer, those obtained by mixing and polymerizing a filler and a polymerizable monomer, and pulverizing them to an appropriate particle size, Alternatively, one obtained by previously dispersing a filler in a polymerizable monomer and subjecting it to emulsion polymerization or suspension polymerization, one obtained by previously dispersing a filler in a polymerizable monomer and a solvent, spray-drying it, and then polymerizing it, or pre-filling Examples include, but are not limited to, those obtained by dispersing an agent in a solvent, spray-drying, impregnating with a polymerizable monomer, and then polymerizing.

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

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

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

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

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

[Formula (3)]

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

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

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

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

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

The solvent used for preparing the acidic polymer solution used in the reaction is not particularly problematic as long as it dissolves the acidic polymer, examples of which include water, ethanol, ethanol, and acetone. Especially preferred among these is water, which dissociates the acidic groups of the acidic polymer and can uniformly react with the surface of the core basic filler.

The weight average molecular weight of the polymer dissolved in the acidic polymer solution is in the range of 2000-50000, preferably in the range of 5000-40000. When treated with an acidic polymer having a weight-average molecular weight of less than 2000, no acidic polymer reaction phase is formed in the polysiloxane-coated sustained ion release glass, and as a result, the sustained ion release tends to be low. On the other hand, when treated with an acidic polymer having a weight average molecular weight exceeding 50,000, the viscosity of the acidic polymer solution increases, making it difficult to uniformly treat the polysiloxane-coated sustained ion release glass. The acidic polymer concentration in 100 parts by mass of the acidic polymer solution is preferably in the range of 3 to 25 parts by mass, more preferably in the range of 8 to 20 parts by mass. If the concentration of the acidic polymer is less than 3 parts by mass, the acidic polymer reaction phase described above becomes weak, and the effect of improving the sustained release of ions cannot be obtained. On the other hand, if the acidic polymer concentration exceeds 25 parts by mass, the polysiloxane layer (porous) is difficult to diffuse in a uniform state, and a homogeneous acidic polymer reaction phase cannot be obtained. Since the reaction occurs immediately upon contact with , problems such as formation of strongly reacted agglomerates occur. The amount of the acidic polymer solution added to the polysiloxane-coated sustained ion release glass is preferably 6 to 40 parts by mass, more preferably 10 to 30 parts by mass. In terms of this addition amount, the optimum amount of the acidic polymer and the amount of water for the polysiloxane-coated sustained ion release glass are in the range of 1 to 7 parts by mass and the amount of water in the range of 10 to 25 parts by mass.

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

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

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

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

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

The method for producing the dental photocurable composition of the present invention is not particularly limited. As a general method for producing a dental photocurable composition, (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator and (D) a polymerization accelerator are mixed in advance. After preparing the matrix, the matrix and (E) the filler are kneaded, air bubbles are removed under reduced pressure, and a uniform paste is prepared. 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. materials, adhesives for fixing loose teeth, dental hard resins, materials for dental cutting, and materials for dental 3D printers.

The dental photocurable composition of the present invention can be used as a dental adhesive, a dental composite resin, a dental abutment building material, a dental resin cement, a dental coating material, a dental pit and fissure sealing material, and a dental adhesive. It is preferably used for manicure materials, dental loose tooth fixing adhesives, dental cutting materials, and dental 3D printer materials, particularly preferably dental adhesives, dental composite resins, dental abutment construction materials, It is preferably used in dental resin cements, dental coatings, dental pit and fissure sealants, dental manicures, and dental loose tooth fixatives.

The dental photocurable composition of the present invention comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, (D) a photopolymerization accelerator, and (E) It may contain only fillers. As components other than (A) to (E), only one or more of the above components may be included.

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

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

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

・Ｃ２：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

・Ｃ３：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

・Ｃ４：ビス（４－ｎ－ドデシルフェニル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート

・Ｃ５：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

・Ｃ６：ビス［４－（ｔｅｒｔ－ブチル）フェニル］ヨードニウムテトラ(ペンタフルオロフェニル)ガレート

＜有機基及びＰ、Ｂ、Ａｌ、Ｓ、Ｇａのいずれか１つ以上の原子を有するアニオンと、アリールヨードニウムカチオンとの塩＞
・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

＜有機基及びＰ、Ｂ、Ａｌ、Ｓ、Ｇａのいずれか１つ以上の原子を有するアニオンと、アリールヨードニウムカチオンとの塩ではない光酸発生剤＞
・Ｃ２１：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

・Ｃ２２：２，４，６，－トリス（トリクロロメチル）－１，３，５－トリアジン

・Ｃ２３：ジフェニルヨードニウム－２－カルボキシラート一水和物

[(C) Photoacid Generator]
<A salt of an anion having at least one or more H-substituted organic groups and one or more atoms selected from P, B, Al, S, and Ga, and an aryliodonium cation>
· C1: bis (4-tert-butylphenyl) iodonium nonafluorobutanesulfonate

· C2: bis (4-tert-butylphenyl) iodonium tris (pentafluoropropyl) trifluorophosphate

・C3: p-cumenyl (p-tolyl) iodonium tris (pentafluoroethyl) trifluorophosphate

・C4: bis (4-n-dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate

・ C5: bis [4-(tert-butyl) phenyl] iodonium tetra (nonafluoro-tert-butoxy) aluminate

・ C6: bis [4-(tert-butyl) phenyl] iodonium tetra (pentafluorophenyl) gallate

<Salt of Anion Having Organic Group and One or More Atoms of P, B, Al, S, Ga, and Aryliodonium Cation>
· C11: bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate

<Photoacid generator that is not a salt of an anion having an organic group and at least one atom of P, B, Al, S, Ga, and an aryliodonium cation>
· C21: bis (4-tert-butylphenyl) iodonium hexafluorophosphate

・C22: 2,4,6,-tris(trichloromethyl)-1,3,5-triazine

・C23: diphenyliodonium-2-carboxylate monohydrate

・Ｄ１１－２：Ｎ‐メチル－Ｎ，Ｎ－ビス（２―ヒドロキシプロピル）アミン

・Ｄ１１－３：３，３′－（ブタンアザンジイル）ビス（１－ブトキシプロパン－２－オール）

・Ｄ１１－４：１，１′－（（３－クロロベンジル）アザンジイル）ビス（プロパン－２－オール）

・Ｄ１１－５：１，１′－（シクロヘキシルアザンジイル）ビス（プロパン－２－オール）

［（Ｄ１２）式（１）で示される第３級芳香族アミン］
・Ｄ１２－１：Ｎ，Ｎ－ビス（２－ヒドロキシプロピル）―ｐ―トルイジン

・Ｄ１２－２：Ｎ，Ｎ－ビス（２－ヒドロキシプロピル）アニリン

＜他の脂肪族第３級アミン＞
＜＜１級のヒドロキシル基を有さない脂肪族第３級アミン化合物＞＞
・ＤＭＡＥＭＡ：Ｎ，Ｎ－ジメチルアミノエチルメタクリレート
・ＤＩＡＥＭＡ：Ｎ，Ｎ－ジイソプロピルアミノエチルメタクリレート
・ＴＢＡ：トリベンジルアミン
・ＤＢＭＡ：ジベンジルメチルアミン
＜＜２つの１級のヒドロキシル基を有する脂肪族第３級アミン化合物＞＞
・ＭＤＥＯＡ：メチルジエタノールアミン
・ＤＥＩＰＡ：Ｎ，Ｎ－ビス（２－ヒドロキシエチル）イソプロパノールアミン
＜＜２つの１級のヒドロキシル基を有する芳香族第３級アミン化合物＞＞
・ＤＥＰＴ：Ｎ，Ｎ－ジヒドロキシエチル－ｐ－トルイジン
＜＜３つの１級のヒドロキシル基を有する脂肪族第３級アミン化合物＞＞
・ＴＥＡ：トリエタノールアミン

＜芳香族第３級アミン化合物＞
・ＤＭＢＥ：Ｎ，Ｎ－ジメチルアミノ安息香酸エチル
[(D) Polymerization accelerator]
[(D1) Tertiary Amine Represented by Formula (1)]
[(D11) Tertiary Aliphatic Amine Represented by Formula (1)]
・ D11-1: Triisopropanolamine

・ D11-2: N-methyl-N,N-bis(2-hydroxypropyl)amine

・D11-3: 3,3′-(butanezandiyl)bis(1-butoxypropan-2-ol)

・ D11-4: 1,1′-((3-chlorobenzyl)azanediyl)bis(propan-2-ol)

・D11-5: 1,1′-(cyclohexylazanediyl)bis(propan-2-ol)

[(D12) Tertiary Aromatic Amine Represented by Formula (1)]
・ D12-1: N,N-bis(2-hydroxypropyl)-p-toluidine

・ D12-2: N,N-bis(2-hydroxypropyl)aniline

<Other Aliphatic Tertiary Amines>
<<Aliphatic tertiary amine compound having no primary hydroxyl group>>
DMAEMA: N,N-dimethylaminoethyl methacrylate DIAEMA: N,N-diisopropylaminoethyl methacrylate TBA: tribenzylamine DBMA: dibenzylmethylamine <<aliphatic tertiary with two primary hydroxyl groups class amine compound >>
・MDEOA: methyldiethanolamine ・DEIPA: N,N-bis(2-hydroxyethyl)isopropanolamine <<aromatic tertiary amine compound having two primary hydroxyl groups>>
・DEPT: N,N-dihydroxyethyl-p-toluidine <<aliphatic tertiary amine compound having three primary hydroxyl groups>>
・TEA: Triethanolamine

<Aromatic tertiary amine compound>
・DMBE: ethyl N,N-dimethylaminobenzoate

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

(Filler E1)
50.0 g of water, 35.0 g of ethanol, and 3.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were added to 100.0 g of fluoroaluminosilicate glass (average particle size: 1.1 μm) for 2 hours at room temperature. The silane coupling treatment liquid obtained by stirring was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E1.

(Filler E2)
Zirconium silicate filler (average particle size 0.8 μm: zirconia 85 wt%, silica 15 wt%) 100.0 g, water 50.0 g, ethanol 35.0 g, 3-methacryloyloxypropyltrimethoxysilane 5 as a silane coupling agent A silane coupling treatment solution obtained by stirring 0.0 g of the mixture at room temperature for 2 hours was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E2.

(Filler E3)
After mixing various raw materials such as silicon dioxide, aluminum oxide, boron oxide, sodium fluoride, and strontium carbonate, the mixture was melted at 1400° C. to obtain glass A (glass composition: SiO ₂ : 22.5% by mass, Al ₂ O ₃ : 20.0% by mass, _B2O3 : 12.3% by mass, SrO: 35.7% by mass, _Na2O : 2.5% _by mass, F: 7.0% by mass). Next, the obtained glass A was pulverized using a vibration mill for 100 hours, and then pulverized using a wet bead mill for 3 hours. 4.5 g of a low condensate of silane compound "MKC Silicate MS56S" (SiO ₂ content 56.0% by mass, degree of polymerization 2 to 100, manufactured by Mitsubishi Chemical Corporation) was added to 100 g of the pulverized material obtained, Stir mixed for about 90 minutes. After mixing for a predetermined time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours, then cooled to obtain a heat treated product. The obtained heat-treated material was placed in a Henschel mixer and pulverized at 1800 rpm for 5 minutes. After pulverization, a polysiloxane-treated material with good fluidity was obtained.
(acidic polymer treatment)
100 g of the polysiloxane-treated material was put into a Henschel mixer, and 16.0 g of an aqueous polyacrylic acid solution (polymer concentration: 13% by mass, weight average molecular weight: 20,000; manufactured by Nacalai Co., Ltd.) was sprayed from above while stirring. After spraying, the powder taken out from the mixer was heated in a hot air dryer at 100° C. for 3 hours to obtain a polysiloxane-polyacrylic acid-treated product.
(Silane treatment)
Polysiloxane-polyacrylic acid treated material: 100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 8-methacryloyloxypropyltrimethoxysilane as a silane coupling agent for 100 g at room temperature for 2 hours. The silane coupling treatment liquid obtained by stirring in was added, and the mixture was stirred and mixed for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E3.

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

(Filler E5)
Aerosil R-711

[Ultraviolet absorber]
BT: 2-(2-hydroxy-5-methylphenyl)benzotriazole [polymerization inhibitor]
・ MeHQ: p-methoxyphenol [fluorescent agent]
・FA: diethyl 2.5-dihydroxyterephthalate

<Method for producing 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. After that, the matrix and (E) the filler were put into a rotation-revolution kneader, uniformly stirred, and then defoamed under vacuum to obtain a paste. A curable composition was prepared. In addition, in Table 1, the parts by mass of each component are listed in parentheses after the abbreviation of each component.

(1) Bending strength After filling a stainless steel mold with the prepared dental photocurable composition, cover glasses were placed on both sides and pressed with a glass kneading plate. ) was used, light irradiation was performed for 10 seconds at each of 5 locations, and cured. 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 bending test was performed using an Instron universal testing machine (manufactured by Instron) at a distance between fulcrums of 20 mm and a crosshead speed of 1 mm/min. The bending strength of the dental photocurable composition was judged to be good when 100 MPa or more, acceptable when 90 to less than 100 MPa, slightly low when 80 to less than 90 MPa, and insufficient when less than 80 MPa.

(2) 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 8,000±1,000 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 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. A longer time is preferable because it takes longer to take the composition out of the light-shielding container and apply it. Ambient light stability was judged to be particularly good at 150 seconds or more, good at 100 seconds to less than 150 seconds, adaptable at 80 seconds to less than 100 seconds, slightly poor at 60 seconds to less than 80 seconds, and insufficient at less than 60 seconds. .

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

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

where L1* is the lightness index before immersion and standing, L2* is the lightness index after immersion and standing, a1* and b1* are the color indices before immersion and standing, a2* and b2* are the immersion・It is the color quality index after standing still. A is good if ΔE is less than 5, B is applicable if ΔE is less than 5 to 8, C is slightly bad if ΔE is less than 8 to 10, and ΔE is 10. The above case was judged to be D because it was insufficient. Thermal color stability is performed to predict color tone change when the cured product is used for a long period of time.

(4) Light Color Stability A stainless steel mold (15φ×1 mm: disk shape) was filled with the prepared dental photocurable composition, and then 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, a2*, b2* are the color index after light exposure is. If ΔE is less than 5, A is considered good, B is applicable if ΔE is 5 to less than 8, C is acceptable if ΔE is 8 to less than 10, and is inappropriate if ΔE is 10 or more. decided enough. Light color stability is used to predict color tone changes when a cured product is used for a long period of time in a location exposed to light. .

The results of Table 2 are described.

It was confirmed that the compositions described in Examples had sufficient bending strength and color stability.

Example 2 in which the amount of camphorquinone as a photosensitizer is small, Example 4 in which the amount of photoacid generator is small, and Example 9 in which the amount of photopolymerization accelerator is small tend to have a slightly low bending strength. was in Example 4, which contained a large amount of photosensitizer, Example 3, which contained a relatively large amount, and Example 2, which contained a large amount of photoacid generator, tended to exhibit low light color stability. (D1) Example 10, which contained a large amount of the tertiary amine compound represented by formula (1), tended to have low thermal color stability.

Example 33 containing BAPO as a photosensitizer had good bending strength, but had low ambient light stability and tended to have low light color stability.

Does not contain a salt of an aryliodonium cation and an anion having at least one or more H-substituted organic groups and one or more atoms of P, B, Al, S, Ga as a photoacid generator Among the examples, Example 5 containing a C11 photoacid generator that is a salt of an anion having an organic group and one or more atoms of P, B, Al, S, Ga, and an aryl iodonium cation is The light color stability was slightly lowered, and Examples 6 to 8 containing other photoacid generators tended to have even lower light color stability.

(D12) Examples 18 to 24 containing the tertiary aromatic amine compound represented by formula (1) exhibited particularly good ambient light stability. Examples 26 to 30 containing DMBE, which is another tertiary aromatic amine compound, tended to deteriorate in ambient light stability. Aromatic amine compounds such as DMBE, which have a dialkylamino group and an electron-withdrawing group at the p-position, can be expected to exhibit good curability when used in combination with camphorquinone. Loss of color stability may occur. Among Examples 26 to 30, Examples 27 and 30 containing the tertiary aromatic amine compound represented by the formula (1) (D12) tended to have slightly improved ambient light stability. Examples 26 and 27 containing an ultraviolet absorber tended to improve the light color stability although they contained an aromatic amine compound.

Since Example 31 does not contain a filler, the flexural strength tends to be slightly low. In Example 32, although there were no problems with the physical properties, the operability was somewhat poor due to the large amount of filler blended.

Comparative Examples 1 and 2, which did not contain a photosensitizer or a photoacid generator, tended to have low bending strength. Comparative Examples 4 to 7 containing amine compounds having two or more primary hydroxy groups tended to have low thermal color stability. Comparative Example 8 had sufficient flexural strength, but had insufficient ambient light stability due to the relatively large amount of DMBE contained.

According to the present invention, it is possible to provide a dental photocurable composition that achieves both sufficient mechanical strength and color tone stability after curing.

Claims (7)

(A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a tertiary amine compound represented by (D1) formula (1) as a polymerization accelerator. Photocurable composition for
[Formula (1)]

(In the formula, R ₁ is an ether bond, an ester bond, a urethane bond, an unsaturated double bond, an aromatic ring, an organic group which may have a halogen, or H, and may be the same or different. R ₂ is an organic group which may have a hydroxy group, or an aromatic ring which may have a substituent.The compound represented by formula (1) has a primary hydroxy at the α- and/or β-carbon of N. does not have a group.) (D1) The tertiary amine compound represented by formula (1) is (D11) a tertiary aliphatic amine compound represented by formula (1). sex composition. (C) contains an aryliodonium salt as a photoacid generator,
3. The dental photocuring agent according to claim 1 or 2, wherein the aryliodonium salt is a salt of an aryliodonium cation and an anion having an organic group and at least one atom of P, B, Al, S and Ga. sex composition. (C) contains an aryliodonium salt as a photoacid generator,
The aryliodonium salt is a salt of an aryliodonium cation and an anion having at least one or more H-substituted organic groups and one or more atoms of P, B, Al, S and Ga. Item 3. The dental photocurable composition according to Item 1 or 2. (D12) The dental photocurable composition according to any one of claims 1 to 4, comprising a tertiary aromatic amine compound represented by formula (1) and a tertiary aliphatic amine compound. (A) with respect to 100 parts by mass of the polymerizable monomer,
(B) contains 0.02 to 1 part by mass of a photosensitizer;
(C) contains 0.02 to 10 parts by mass of a photoacid generator,
(D11) containing 0.2 to 10 parts by mass of a tertiary aliphatic amine compound represented by formula (1),
3. A dental photocurable composition according to claim 2. (A) with respect to 100 parts by mass of the polymerizable monomer,
(B) contains 0.02 to 1 part by mass of a photosensitizer;
(C) contains 0.02 to 10 parts by mass of a photoacid generator,
(D) contains 0.2 to 10 parts by mass of a polymerization accelerator,
(D) containing 0.02 to 1 part by mass of a tertiary aromatic amine compound represented by (D12) formula (1) as a polymerization accelerator,
A dental photocurable composition according to claim 5 .