JP2023042511A - Dental photocurable composition excellent in operability and storage stability - Google Patents

Abstract

To provide a dental photocurable composition which has sufficient mechanical properties and whose rheological characteristics are not deactivated even after long-term storage.SOLUTION: A dental photocurable composition comprises (A) a polymerizable monomer, (B) a photosensitizer, (D) a photopolymerization accelerator and (E) a filler. The (D) photopolymerization accelerator includes (D1) an aliphatic tertiary amine compound represented by formula (1). The (E) filler includes (E1) hydrophobized silica fine particles having an average diameter of primary particle of 1 to 40 nm (where R1 represents a substituent consisting of three or more carbon atoms having an electron-withdrawing group at α-carbon and/or β-carbon of an amine starting from N, R2 represents a substituent consisting of three or more carbon atoms, optionally having an electron-withdrawing group, R3 represents a substituent consisting of one or more carbon atoms, optionally having an electron-withdrawing group, and α-carbon of N in the formula is not an electron-withdrawing group).SELECTED DRAWING: None

Description

The present invention relates to dental photocurable compositions.

In the field of dentistry, dental photocurable compositions are used as dental adhesives, dental composite resins, dental abutment building materials, dental resin cements, dental coating materials, and 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 Document 1 proposes a dental curable composition and a dental filling and restorative kit containing an aliphatic tertiary amine as a photopolymerization initiator. In order to impart thixotropic properties, Patent Document 2 proposes the use of polyglycerol fatty acid esters, and Patent Document 3 proposes the use of hydrophobized silica fine particles.

Japanese Patent No. 5268478 Japanese Patent No. 5615720 International Publication No. 2008/068862

However, these dental photocurable compositions must satisfy all requirements of easy adjustment of rheological properties, mechanical strength suitable for dental applications, and not deactivating rheological properties even after long-term storage. was difficult.

An object of the present invention is to provide a dental photocurable composition which has sufficient mechanical properties and whose rheological properties are not lost even after long-term storage.

（式中、Ｒ_１はＮを始点としてアミンのα位炭素及び／またはβ位炭素に電子求引性基を有する３つ以上の炭素からなる置換基、Ｒ_２は電子求引性基を有してもよい３つ以上の炭素からなる置換基、Ｒ_３は電子求引性基を有してもよい１つ以上の炭素からなる置換基である。式（１）中のＮのα位炭素は電子求引性基ではない。） The dental photocurable composition of the present invention comprises (A) a polymerizable monomer, (B) a photosensitizer, (D) a photopolymerization accelerator, and (E) a filler. (D) an aliphatic tertiary amine compound represented by formula (1) (D1) as a photopolymerization accelerator, and (E) as a filler (E1) the average particle size of primary particles is a dental photocurable composition containing hydrophobized silica fine particles having a diameter of 1 to 40 nm.
[Formula (1)]

(Wherein, R ₁ is a substituent consisting of three or more carbons starting from N and having an electron-withdrawing group at the α- and / or β-position carbon of the amine, R ₂ having an electron-withdrawing group 3 or more carbon substituents, R ₃ is a one or more carbon substituents that may have an electron-withdrawing group, the α-position of N in formula (1) Carbon is not an electron-withdrawing group.)

INDUSTRIAL APPLICABILITY The present invention can provide a dental photocurable composition that has sufficient mechanical properties and whose rheological properties are not lost even after long-term storage.

In the present invention, the electron-withdrawing group for R ₁ is a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a vinyl group, an aryl group, and a halogen, or an ether bond, an ester bond, a urethane bond, or a urea bond. -OH group, -O- group, -C(O)- group, -S- group, -NH-C(O)-NH- group, -C(O)-O - group, -OC(O)- group, -OC(O)-NH- group, -NH-C(O)-O- group, aromatic hydrocarbon group, or polymerization capable of radical polymerization It can be a substituent selected from organic groups which may have a functional group.

In the present invention, (D1) the aliphatic tertiary amine compound represented by formula (1) has three or more R ₁ and R ₂ having an electron-withdrawing group at the α-position carbon and/or the β-position carbon can be an aliphatic tertiary amine compound having an aliphatic substituent consisting of carbons.

In the present invention, (D1) the aliphatic tertiary amine compound represented by formula (1) is an aliphatic tertiary amine in which R ₁ and R ₂ have an aryl group at the α-position carbon and/or the β-position carbon. It can be a compound.

In the present invention, (E1) hydrophobic silica fine particles having an average primary particle diameter of 1 to 40 nm are subjected to surface treatment with dimethylsilicone oil, or a trimethylsilyl group, a dimethylsilyl group, a methylsilyl group, and having 3 or more carbon atoms. A functional group selected from an alkylsilyl group having a linear alkyl chain of 18 or less can be hydrophobized by surface treatment by covalently bonding with fine particles.

In the present invention, 0.5 to 30 parts by mass of (E1) hydrophobized silica fine particles having an average primary particle diameter of 1 to 40 nm is included with respect to 100 parts by mass of (A) the polymerizable monomer. can.

In the present invention, the (E) filler further includes (E2) an inorganic filler having an average primary particle diameter of 0.1 to 10 μm, and the (E2) inorganic filler is combined with (E1) fine particle silica. The total amount can be 100 to 400 parts by mass per 100 parts by mass of the polymerizable monomer (A).

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

In the present invention, (C) an aryliodonium salt is further 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, and Ga. or an anion having one or more atoms and a salt of an aryliodonium cation.

In the present invention, a one-part type dental photocurable composition comprising:
(A) with respect to 100 parts by mass of the polymerizable monomer,
(B) contains 0.02 to 1 part by mass of a photosensitizer;
(D1) containing 0.1 to 10 parts by mass of an aliphatic tertiary amine compound represented by formula (1),
(E1) 0.5 to 30 parts by mass of hydrophobized fine silica particles having an average primary particle diameter of 1 to 40 nm can be included.

In the present invention, a one-part type dental photocurable composition comprising:
(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 0.1 to 10 parts by mass of a photoacid generator,
(D1) containing 0.1 to 10 parts by mass of an aliphatic tertiary amine compound represented by formula (1),
(E1) 0.5 to 30 parts by mass of hydrophobized fine silica particles having an average primary particle diameter of 1 to 40 nm can be included.

In the present invention, a two-component dental photocurable composition comprising:
consisting of a first paste and a second paste,
The first paste and the second paste have a mass ratio of 1:0.8 to 1.2,
Both the first paste and the second paste contain (E1) hydrophobized silica fine particles whose primary particles have an average particle size of 1 to 40 nm,
For a total of 200 parts by mass of the polymerizable monomer (A) contained in the first paste and the second paste,
(B) contains 0.04 to 2 parts by mass of a photosensitizer;
(D1) containing 0.2 to 20 parts by mass of an amine compound represented by formula (1),
(E1) 1 to 60 parts by mass of hydrophobized fine silica particles having an average primary particle diameter of 1 to 40 nm can be included.

In the present invention, a two-component dental photocurable composition comprising:
consisting of a first paste and a second paste,
The first paste and the second paste have a mass ratio of 1:0.8 to 1.2,
Both the first paste and the second paste contain (E1) hydrophobized silica fine particles whose primary particles have an average particle size of 1 to 40 nm,
For a total of 200 parts by mass of the polymerizable monomer (A) contained in the first paste and the second paste,
(B) contains 0.04 to 2 parts by mass of a photosensitizer;
(C) contains 0.2 to 20 parts by mass of a photoacid generator,
(D1) containing 0.2 to 20 parts by mass of an amine compound represented by formula (1),
(E1) 1 to 60 parts by mass of hydrophobized fine silica particles having an average primary particle diameter of 1 to 40 nm can be included.

In the present invention, the difference in fluidity between the fluidity of the photocurable dental composition left for one month in a thermostat set at 50° C. after production and the fluidity of the photocurable dental composition after production is 3.0 mm. can be within

In the present invention, the fluidity of the photocurable dental composition left for one month in a thermostat set at 50° C. after production and the fluidity of the photocurable dental composition after production are within 3.0 mm. can be.

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

As photopolymerization initiators used in such dental materials, photosensitizers and systems in which photosensitizers are combined with suitable photopolymerization accelerators are widely used. Acylphosphine oxide compounds and α-diketone compounds are known as photosensitizers, and α-diketone compounds in particular have the ability to initiate polymerization in the visible light wavelength region, 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 a 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.

An α-diketone compound used as a photopolymerization initiator can express good polymerization performance by combining with an aromatic tertiary amine compound represented by ethyl 4-(dimethylamino)benzoate. However, aromatic tertiary amine compounds may cause discoloration, deterioration in ambient light stability, and the like. For this reason, aliphatic tertiary amine compounds have been proposed to reduce or replace the amount of aromatic tertiary amine compounds, and are often used in dental materials.

On the other hand, dental materials need to conform to various shapes to match the complex shape of natural teeth. To manipulate the shape of the dental material as desired by the user, the dental material may contain rheology modifiers. There are two types of rheology modifiers, organic and inorganic. Polyglycerin and the like are known as organic agents, and silica fine particles are known as inorganic agents. Among these, the addition of silica fine particles to dental materials not only imparts thixotropic properties among rheological properties, but can also be expected to have effects such as improved strength and suppression of sedimentation of other fillers.

However, when a dental photocurable composition containing silica fine particles coexists with conventionally used aliphatic tertiary amine compounds such as dimethylaminoethyl methacrylate and triethanolamine, the rheological properties may be lost. was there. Although the detailed principle is unknown, the rheological properties of silica fine particles are manifested by moderate aggregation of silica fine particles in the composition due to interaction, and dispersion and reaggregation due to external stress. It is thought that the aggregate structure collapses due to the interaction of the aliphatic tertiary amine compound and the rheological properties are lost.

In order to solve the above problems, the dental photocurable composition of the present invention uses an aliphatic tertiary amine compound with a specific structure. More specifically, an aliphatic tertiary amine compound is used that has greater steric hindrance than conventionally used aliphatic tertiary amine compounds and has an electron-withdrawing group to reduce the electron density. As a result, it was found that even a dental photocurable composition containing hydrophobized silica fine particles can exhibit sufficient physical properties for dental applications without losing its rheological properties even after long-term storage, leading to the completion of 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 at least one polymerizable group and at least one acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group. Any polymerizable monomer can be used without limitation. By including a polymerizable monomer having an acidic group, it is possible to impart adhesiveness to dentin and prosthetic devices.

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

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

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

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

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

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

Preferred are 10-methacryloyloxydecyl dihydrogen phosphate and 6-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, based on the total amount of 100 parts by mass of the polymerizable monomers contained in the dental photocurable composition. A blending amount of 1 part by mass or more and 30 parts by mass or less is preferable. If the amount is less than 1 part by mass, the adhesiveness to tooth substance, metals and metal oxides may not be exhibited sufficiently, and if the amount is 30 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 a polymerizable monomer having a sulfur atom as (A) a polymerizable monomer in order to impart adhesion to noble metals. Known compounds can be used without any limitation as long as the polymerizable monomer having a sulfur atom is a polymerizable monomer having one or more sulfur atoms and a polymerizable group. Specifically, it refers to a compound having a partial structure such as -SH, -S-S-, >C=S, >C-S-C<, >P=S or resulting from tautomerism. Specific examples include 10-methacryloxydecyl-6,8-dithiooctanate, 6-methacryloxyhexyl-6,8-dithiooctanate, 6-methacryloyloxyhexyl 2-thiouracil-5-carboxylate, 2-( 11-methacryloyloxyundecylthio)-5-mercapto-1,3,4-thiadiazole and 10-(meth)acryloyloxydecyl dihydrogenthiophosphate.

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

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

The dental photocurable composition of the present invention can contain 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.

<Photoinitiator>
The dental photocurable composition of the present invention contains (B) a photosensitizer and (D) a photopolymerization accelerator as photopolymerization initiators, and may contain (C) a photoacid generator. These compounds are not particularly limited, and 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.

The amount of the photosensitizer (B) is usually preferably 0.02 to 1 part by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental photocurable composition, More preferably 0.02 to 0.5 parts by mass, still more preferably 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 it is blended in an amount of more than 1 part by mass, sufficient curability is exhibited, but the ambient light stability is shortened and yellowishness is increased.
The dental curable composition of the present invention may contain only an α-diketone compound as (B1) a photosensitizer.

[(C) Photoacid Generator]
As the (C) photoacid generator that can be 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, functional groups in which one or more of these H are substituted with F, perfluoroalkyl groups, halogens, and the like are suitable as substituents.

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

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

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

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

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

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

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

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

In the case where the dental photocurable composition of the present invention contains (C) a photoacid generator, the content of (C) photoacid generator with respect to the total amount of 100 parts by mass of (A) the total amount of polymerizable monomers 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass. If the amount of the photoacid generator is less than 0.1 part by mass, the expected polymerization accelerating ability may not be exhibited, 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 and 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 aryl iodonium 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) Photopolymerization accelerator]
The (D) photopolymerization accelerator used in the dental photocurable composition of the present invention is not particularly limited as long as it has a polymerization promoting ability, and known photopolymerization accelerators generally used in the dental field are not particularly limited. can be used. (D) As the photopolymerization accelerator, aromatic amine compounds, primary to tertiary amine compounds such as aliphatic amine compounds, organometallic compounds, phosphine compounds, and the like can be used. Among these, tertiary aliphatic amine compounds and organometallic compounds are preferred because of their good light color stability.

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

Specific examples of aromatic primary amine compounds include aniline, and specific examples of aromatic secondary amine compounds include N-phenylbenzylamine, N-benzyl-p-anisidine and N-benzyl-o-phenetidine. , N-phenylglycine ethyl, N-phenylglycine, N-protected amino acids (esters), etc. Specific examples of aromatic tertiary amine compounds include N,N-dimethylaniline, N,N-diethylaniline, N ,N-di-n-butylaniline, N,N-dibenzylaniline, pN,N-dimethyl-toluidine, mN,N-dimethyl-toluidine, pN,N-diethyl-toluidine, p- Bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid 2-butoxyethyl, p-dimethylaminobenzoic acid 2-ethylhexyl, p-dimethylaminobenzoic acid aminoester, N,N-dimethylanthrani acid methyl ester, N,N-dihydroxyethylaniline, N,N-diisopropanolaniline, pN,N-dihydroxyethyl-toluidine, pN,N-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.

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

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

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

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

The dental photocurable composition of the present invention contains (D) as a photopolymerization accelerator (D1) an aliphatic tertiary amine compound represented by formula (1).
[Formula (1)]

In the formula, R ₁ is a substituent consisting of three or more carbons starting from N and having an electron-withdrawing group at the α- and/or β-position carbon of the amine, and R ₂ has an electron-withdrawing group. 3 or more carbon substituents, R ₃ is a 1 or more carbon substituent optionally having an electron-withdrawing group. The α-position carbon of N in formula (1) is not an electron-withdrawing group.

The electron-withdrawing group in R ₁ is a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a vinyl group, an aryl group and a halogen, or an organic -OH group, -O- group, -C(O)- group, -S- group, -NH-C(O)-NH- group, -C(O)-O- group, -O -C(O)- group, -O-C(O)-NH- group, -NH-C(O)-O- group, aromatic hydrocarbon group, or having a polymerizable functional group capable of radical polymerization can be a substituent selected from organic groups that may be

Aliphatic tertiary amines such as dimethylaminoethyl methacrylate and triethanolamine are sometimes blended in conventional dental photocurable compositions for the purpose of promoting photopolymerization, improving solubility, and improving storage stability. rice field. However, when the conventional aliphatic tertiary amine and (E1) the hydrophobized silica fine particles whose primary particles have an average particle size of 1 to 40 nm are coexisted in the composition, long-term storage or long-term storage is possible. When the composition was stored in a constant temperature machine set at 50° C. for one month or longer, the rheological properties exhibited by the hydrophobized silica fine particles tended to be lost. On the other hand, electron solicitors at the p-position of N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis(2-hydroxypropyl)-p-toluidine, ethyl 4-(dimethylamino)benzoate, etc. When an aromatic tertiary amine compound having a pulling group or an aromatic tertiary amine compound having a dihydroxyalkyl group is used in combination, the rheological properties are not deactivated, but the aromatic tertiary amine reduces the environmental light stability. and loss of light color stability. In such a case, the addition of an ultraviolet absorber can be expected to improve the light color stability. A large amount of absorbent is required. When a large amount of ultraviolet absorber is blended, the mechanical properties may deteriorate. Therefore, it may not be preferable to blend only an aromatic amine compound as a photopolymerization accelerator. In order to solve these problems, attention was paid to the aliphatic tertiary amine compound (D1) represented by formula (1). (D1) By using the aliphatic tertiary amine compound represented by the formula (1) in the dental photocurable composition, rheological properties can be maintained even when stored for a long period of time. We succeeded in expressing sufficient mechanical strength for use in In addition, there was a tendency to exhibit light color stability suitable for dental applications. More preferably, (D1) the aliphatic tertiary amine compound represented by formula (1) further includes (C) a photoacid generator when the dental photocurable composition contains (B) a photosensitizer. The present inventors have found that high mechanical strength is exhibited when it is contained, and have made the invention.

In the present invention, rheological properties are evaluated using fluidity. Fluidity means that 0.05 g of a dental photocurable composition is adhered in a lump to the flat surface of a slide glass placed horizontally, and the slide glass is vertically fixed at 90° to the horizontal surface within 5 seconds. Refers to the distance traveled by the dental photocurable composition after 1 minute.

Photocurable dental compositions having various fluidities are used. For example, when used in a site with a complicated shape such as an uneven part or a constricted part, a fluidity of about 10 mm is particularly useful. 0 mm is particularly useful, and 5 mm fluidity is used when not specific to a particular use case. A change in fluidity after long-term storage means that the good operability of the dental photocurable composition is lost.

(D1) In the aliphatic tertiary amine compound represented by formula (1), R ₁ is three or more groups having an electron-withdrawing group at the α- and/or β-carbon of the amine with N as the starting point. A substituent consisting of carbon, R ₂ is a substituent consisting of 3 or more carbons which may have an electron withdrawing group, R ₃ is a substituent consisting of 1 or more carbons which may have an electron withdrawing group is a substituent. Here, each of R ₂ and R ₃ may be a carbon alicyclic compound or a heteroalicyclic compound cyclically bonded with 3 or more carbons. The α-position and/or β-position with N as the starting point means that the carbon that binds to N is the α-position carbon, and the carbon that binds to the α-position carbon is the β-position carbon. Substituents consisting of 3 or more carbons are the number including the carbons possessed by the electron-withdrawing functional group. Also, N represented by formula (1) does not bond to the electron-withdrawing group without going through a hydrocarbon group. That is, the α-position carbon itself is not an atom that constitutes an electron-withdrawing group, and (D1) the aliphatic tertiary amine compound represented by formula (1) has electron-withdrawing properties at the α-position carbon and/or the β-position carbon. functional groups are attached.

An electron-withdrawing group refers to a substituent group that easily attracts electrons from the bonding atom side. Electron-withdrawing groups include hydroxyl groups, thiol groups, nitro groups, carbonyl groups, carboxyl groups, sulfonyl groups, cyano groups, aryl groups, amino groups, halogen groups, unsaturated bonds such as vinyl groups and propargyl groups, ether bonds, and esters. Examples thereof include organic groups bonded via a bond, a urethane bond, or a urea bond.

Among the electron-withdrawing groups in formula (1), the electron-withdrawing group having the α-position carbon and/or the β-position carbon of R ₁ is a hydroxyl group, a carboxyl group, a vinyl group, an aryl group, and a halogen group. It can be a selected functional group or an organic group having an ether, ester, urethane or urea bond. The organic group includes -OH group, -O- group, -C(O)- group, -S- group, -NH-C(O)-NH- group, -C(O)-O- group, - O—C(O)— group, —O—C(O)—NH— group, —NH—C(O)—O— group, aromatic hydrocarbon group, or polymerizable functional group capable of radical polymerization may have Preferred are a hydroxyl group, a carboxyl group, an aryl group, and an organic group having an ether bond, an ester bond, a urethane bond, or a urea bond, and more preferred are aryl groups, which can be expected to have large steric hindrance or high electron-withdrawing properties. It is an organic group having a carboxyl group and an ester bond or a urethane bond, more preferably a tertiary aliphatic amine compound in which the amino group is substituted with two or more optionally substituted aryl groups.

When R ₂ and R ₃ have an electron-withdrawing group, the electron-withdrawing group is a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a vinyl group, an aryl group and a halogen, or an ether bond. , an ester bond, a urethane bond or an organic group having a urea bond. The organic group includes -OH group, -O- group, -C(O)- group, -S- group, -NH-C(O)-NH- group, -C(O)-O- group, - O—C(O)— group, —O—C(O)—NH— group, —NH—C(O)—O— group, aromatic hydrocarbon group, or polymerizable functional group capable of radical polymerization may have Preferred are a hydroxyl group, a carboxyl group, an aryl group, and an organic group having an ether bond, an ester bond, a urethane bond, or a urea bond, and more preferred are aryl groups, which can be expected to have large steric hindrance or high electron-withdrawing properties. It is an organic group having a carboxyl group and an ester bond or a urethane bond, more preferably a tertiary aliphatic amine compound in which the amino group is substituted with two or more optionally substituted aryl groups.

In formula (1), R ₁ and R ₂ are aliphatic tertiary amine compounds having an aliphatic substituent consisting of 3 or more carbons with an electron-withdrawing group at the α- and/or β-position carbon. is preferred. In this case, a high level of retention of rheological properties can be expected when the photocurable dental composition is stored. Further, a tertiary aliphatic amine compound in which the amino group is substituted by two or more optionally substituted aryl groups, i.e., having a substituent at the α- and / or β-carbon Aliphatic tertiary amine compounds having good aryl groups are preferred. Specific examples include tribenzylamine, dibenzylglycine ester compounds, and dibenzylaminoalkyl (meth)acrylates. A compound having such a structure not only stabilizes fluidity particularly when blended in a dental photocurable composition containing (E1) hydrophobic fine silica particles having an average primary particle size of 1 to 40 nm, but also , high mechanical strength can be expected.

(D1) Specific examples of the aliphatic tertiary amine compound represented by formula (1) include triisopropanolamine, 2-(dibutylamino)-1-phenyl-1-propanol, 1-[(3,3 -diphenylpropyl)(methyl)amino]-2-methyl-2-propanol, 3,3′,3″-nitrilotripropionic acid, N-benzyl-3,3′-iminodipropionic acid, 1-benzhydryl Azetidine-3-carboxylic acid, 1-benzyl-3-pyrrolidone, 1-(2-phenylethyl)-4-piperidone, 1-benzylpiperidine, 1-phenyl-2-(1-pyrrolidinyl)propan-1-ol , 2-[hydroxy(diphenyl)methyl]-1-methylpyrrolidine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, N,N,N',N'',N''- Pentakis(2-hydroxypropyl)diethylenetriamine, 2-piperidino-1,1,2-triphenylethanol, 2-[benzyl(methyl)amino]-1-phenylethanol, 2-(dibenzylamino)-3-phenyl- 1-propanol, 2,6-bis[2-(hydroxydiphenylmethyl)-1-pyrrolidinyl-methyl]-4-methylphenol, 2-benzyl-1,2,3,4-tetrahydroisoquinoline-8-carboxylic acid, 2-benzyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid, 2-(dibenzylamino)propionaldehyde, 3-(dibenzylamino)-1-propanol, 2-(dibenzylamino)- 1-propanol, 2-(N,N-dibenzylamino)-3-methylbutanol, 1-[(dibenzylamino)methyl]-2-naphthalol, 2-(dibenzylamino)-4-methyl-1- pentanol, 4-dibenzylamino-cyclohexanone, 3-dibenzylamino-2-fluoropropionic acid benzyl ester, N,N-dibenzyl-1,4-dioxaspiro[4.5]decane-8-amine, N,N -dipropyl-L-alanine, N,N-dibenzyl-2-aminoethanol, N,N-dibenzylglycine ethyl, tribenzylamine, triallylamine, 1,1'-(methylimino)dipropan-2-ol, 1- (benzyl(2-methylallyl)amino)-2-methylpropan-2-ol, 2-piperidino-1,1,2-triphenylethanol, N,N-dibenzylaminoethane Nol, N,N-dibenzylaminopropanol, 3-(N,N-dibenzylamino)propyltriethoxysilane. Furthermore, N,N-dibenzylaminoethanol, N,N-dibenzylaminopropanol, N,N-dibutylethanolamine, N,N-diisopropylaminoethanol, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine , transesterification products of tertiary amine compounds having an OH group such as N-tert-butyldiethanolamine and ester compounds containing (meth)acrylic acid esters such as methyl methacrylate and butyl methacrylate, tertiary compounds having an OH group Urethane compounds and 3,3′,3″-nitrilotri synthesized by reacting amine compounds with isocyanate-containing compounds such as 2-isocyanatoethyl (meth)acrylate and 1,1-(bisacryloyloxymethyl)ethylisocyanate Propionic acid, N-benzyl-3,3'-iminodipropionic acid, N-methyliminodiacetic acid, N-(2-hydroxyethyl)iminodiacetic acid, N-(2-carboxyethyl)iminodiacetic acid, N,N -dipropyl-L-alanine, N,N-dibenzylglycine and other amine compounds having a carboxyl group or an ester bond, transesterification products with alcohols and compounds having an OH group such as 2-hydroxyethyl methacrylate, and diisopropylamine , a urea compound synthesized by reacting a secondary amine such as dibenzylamine with a compound having an isocyanate such as 2-isocyanatoethyl (meth)acrylate or 1,1-(bisacryloyloxymethyl)ethyl isocyanate. Among them, dibenzylaminoethyl which is a transesterification product of a tertiary amine compound having an OH group such as dibenzylaminoethanol or dibenzylaminopropanol and an ester compound having a polymerizable group containing a (meth)acrylic acid ester. Urethane compounds synthesized by reaction with compounds having isocyanates such as methacrylate, dibenzylpropyl methacrylate, 2-isocyanatoethyl (meth)acrylate and 1,1-(bisacryloyloxymethyl)ethyl isocyanate, N,N-dibenzyl N-alkyldibenzylamines such as glycine ester compounds, tribenzylamine, N-methyldibenzylamine are preferred.

(D1) The amount of the aliphatic tertiary amine compound represented by formula (1) is 0.1 parts by mass per 100 parts by mass of the polymerizable monomer (A) contained in the dental photocurable composition. 10 parts by mass or less, more preferably 0.5 parts by mass or more and 5 parts by mass or less. (D1) If the amount of the aliphatic tertiary amine compound represented by formula (1) is less than 0.1 part by mass, the polymerization accelerating ability is poor and curing tends to be insufficient. If the amount is more than 10 parts by mass, sufficient curability may be exhibited, but the environmental light stability may be shortened and discoloration of the cured product may increase.

(D) The type of photopolymerization accelerator can be appropriately selected according to the type and blending amount of other components to be combined. Moreover, (D) a photopolymerization accelerator can be used individually or in combination of 2 or more types.

(D) The amount of the photopolymerization accelerator is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental photocurable composition. is 0.5 parts by mass or more and 5 parts by mass or less. If the amount of the polymerization accelerator (D) is less than 0.1 part by mass, the polymerization acceleration ability is poor and curing tends to be insufficient. If the amount is more than 10 parts by mass, sufficient curability is exhibited, but the ambient light stability is lowered, and discoloration of the cured product may increase.

The dental photocurable composition of the present invention may contain only (D) the aliphatic tertiary amine compound represented by formula (1) as (D) a photopolymerization accelerator. The dental photocurable composition of the present invention comprises (D) a photopolymerization accelerator consisting of three or more carbon atoms in which R ₁ and R ₂ have electron-withdrawing groups at the α- and/or β-position carbons. (D1), which is an aliphatic tertiary amine compound having an aliphatic substituent, may contain only the aliphatic tertiary amine compound represented by formula (1). The dental photocurable composition of the present invention is an aliphatic tertiary amine compound in which R ₁ and R ₂ have an aryl group which may have a substituent at the α- and/or β-carbon ( D1) It may contain only the aliphatic tertiary amine compound represented by formula (1).

These (B) photosensitizer, (C) photoacid generator, and (D) photopolymerization accelerator, which are polymerization initiators, may optionally be pulverized, adsorbed on a carrier, encapsulated in microcapsules, or the like. There is no problem even if secondary processing is applied. Furthermore, these various types of photopolymerization initiators can be used alone or in combination of two or more types regardless of the polymerization mode or polymerization method.

[(E) filler]
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, such as an inorganic filler, an organic filler, an organic-inorganic composite filler, or a sustained ion release glass. It is preferable to incorporate a filler of 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 preferably used. The fluoroaluminosilicate glass referred to here has a basic skeleton of silicon oxide and aluminum oxide and contains an alkali metal for non-crosslinking oxygen introduction. Further, it has alkaline earth metals including strontium and fluorine as modifier/coordinating ions. In addition, it is a composition in which a lanthanide series element is incorporated into the skeleton in order to impart further X-ray opacity. The lanthanide series elements are also incorporated into the composition as modifier/coordination ions depending on the composition range.

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

As the organic-inorganic composite filler, for example, a filler whose surface is polymerized and coated with a polymerizable monomer, a filler and a polymerizable monomer that are mixed and polymerized and pulverized to an appropriate particle size, or A product obtained by previously dispersing a filler in a polymerizable monomer and subjecting it to emulsion polymerization or suspension polymerization, a product obtained by previously dispersing a filler in a polymerizable monomer and a solvent, spray-drying it, and then polymerizing it; is dispersed in a solvent, spray-dried, impregnated with a polymerizable monomer, and then polymerized, but is not limited to these.

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

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

The solvent used for preparing the acidic polymer solution used in the reaction is not particularly problematic as long as it dissolves the acidic polymer, and examples thereof include water, ethanol, and acetone. Among these, water is particularly preferred because the acidic groups of the acidic polymer are dissociated and can react uniformly with the polysiloxane-coated sustained ion release glass. The weight average molecular weight of the polymer dissolved in the acidic polymer solution is in the range of 2000-50000, preferably in the range of 5000-40000. When treated with an acidic polymer having a weight-average molecular weight of less than 2000, no acidic polymer reaction phase is formed in the polysiloxane-coated sustained ion release glass, and as a result, the sustained ion release tends to be low. On the other hand, when treated with an acidic polymer having a weight average molecular weight exceeding 50,000, the viscosity of the acidic polymer solution increases, making it difficult to uniformly treat the polysiloxane-coated sustained ion release glass. The acidic polymer concentration in the acidic polymer solution is preferably in the range of 3 to 25% by mass, more preferably in the range of 8 to 20% by mass. If the acidic polymer concentration is less than 3% by mass, the acidic polymer reaction phase described above becomes weak, and the effect of improving the sustained release of ions cannot be obtained. Further, when the concentration of the acidic polymer exceeds 25% 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 in the range of 6 to 40% by mass, more preferably 10 to 30% by mass. In terms of this addition amount, the optimum amount of the acidic polymer and the amount of water are in the range of 1 to 7% by mass and the amount of water in the range of 10 to 25% by mass with respect to the polysiloxane-coated sustained ion release glass.

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

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

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

The dental photocurable composition of the present invention contains (E1) hydrophobized fine silica particles having an average primary particle size of 1 to 40 nm. (E1) Hydrophobized fine silica particles having an average primary particle size of 1 to 40 nm are used to impart thixotropic property among rheological properties to a dental photocurable composition. The primary particle size indicates the diameter of one particle (primary particle) that constitutes the powder. Here, the average particle size in the present invention can be an average particle size calculated based on a volume-based particle size distribution measured by, for example, a laser diffraction particle size distribution measuring device. It can be measured with a machine (Microtrac MT3300EXII: manufactured by Nikkiso Co., Ltd.). In addition, the primary particle size can be measured using dynamic light scattering particle size measurement, or electron micrographs for particles in which primary particles are strongly agglomerated to form secondary particles.

(E1) Hydrophobic fine silica particles having an average primary particle size of 1 to 40 nm are fine silica particles that have been hydrophobized by surface treatment with a silane coupling agent and/or modified silicone oil.

More specific hydrophobization methods for hydrophobized silica fine particles include surface treatment with modified silicone oil such as dimethyl silicone oil, and/or trimethylsilyl group, dimethylsilyl group, methylsilyl group, and an alkyl chain having 3 to 18 carbon atoms. and a silane coupling agent having an alkylsilyl group which may have a (meth)acryloyl group. The silane coupling agent is preferably hydrophobized via a covalent bond to the fine silica particles.

Specific examples of modified silicone oils and silane coupling agents include polydimethylsiloxane, hexamethyldisilazane, dimethylpolysiloxane, methylchlorosilane, alkyltrialkoxysilane, dialkyldialkoxysilane, alkyl groups such as octadecylalkoxysilane and octylalkoxysilane. Examples include alkoxysilanes, (meth)acryloylalkylalkoxysilanes such as 3-methacryloylpropyltrimethoxysilane and 8-methacryloyloctyltrimethoxysilane.

In order to further improve rheological properties, silica microparticles may be hydrophobized in several ways. For example, after treatment with a silane coupling agent and/or modified silicone oil, or at the same time, treatment with a surface treatment agent may be performed.

(E1) Hydrophobized fine silica particles having an average primary particle size of 1 to 40 nm include dry silica, silica aerogel, and wet silica, with dry silica being more preferred.

Among the hydrophobized silica fine particles listed above, dry silica is manufactured and marketed by Nippon Aerosil Co., Ltd. under the trade name of Aerosil, for example.例えば、Ａｅｒｏｓｉｌ Ｒ９７２、Ａｅｒｏｓｉｌ Ｒ９７４、Ａｅｒｏｓｉｌ Ｒ９７６、Ａｅｒｏｓｉｌ Ｒ９７６Ｓ、Ａｅｒｏｓｉｌ Ｒ２０２、Ａｅｒｏｓｉｌ Ｒ８１２、Ａｅｒｏｓｉｌ Ｒ８１２Ｓ、Ａｅｒｏｓｉｌ Ｒ８０５、Ａｅｒｏｓｉｌ Ｒ１０４、Ａｅｒｏｓｉｌ Ｒｌ０６、Ａｅｒｏｓｉｌ ＲＹ２００、Ａｅｒｏｓｉｌ ＲＸ２００、Ａｅｒｏｓｉｌ Ｒ７１１、Ａｅｒｏｓｉｌ ＲＹ２００Ｓ、Ａｅｒｏｓｉｌ ＲＡ２００Ｈ、Ａｅｒｏｓｉｌ Ｒ８２００、 Silica fine powder, such as Aerosil RA200HS, the surface of which has been subjected to hydrophobizing treatment may also be used.

(E1) The blending amount of the hydrophobic silica fine particles having an average primary particle diameter of 1 to 40 nm is 0.5 to 30 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the polymerizable monomer (A). part by mass. (A) If the amount is less than 0.5 parts by mass with respect to 100 parts by mass of the polymerizable monomer, the expression of rheological properties in the dental photocurable composition may not be expected, and the amount exceeds 30 parts by mass. In such a case, the photocurable dental composition may be significantly thickened, resulting in poor operability.

The dental photocurable composition of the present invention further contains (E2) an inorganic filler having an average primary particle size of 0.1 to 10 μm, and the (E2) inorganic filler is combined with (E1) fine particle silica. The total amount of (A) is preferably 100 to 400 parts by mass with respect to 100 parts by mass of the polymerizable monomer. (E2) has a larger average particle size than (E1). In general, if a large amount of particles with an average particle size of nano-order is blended, the viscosity increases significantly, resulting in a decrease in operability, so the blending amount is limited. On the other hand, since the dental photocurable composition is required to have a higher strength depending on the application, the amount of the filler compounded is preferably large within a range that does not affect the operability. In the present invention, (E1) hydrophobized silica fine particles having an average primary particle diameter of 1 to 40 nm and (E2) an inorganic filler having an average primary particle diameter of 0.1 to 10 µm are blended to obtain a suitable It can be expected that it will be a dental photocurable composition having good operability and high mechanical properties. In addition, the filler (E2) is blended for purposes other than increasing strength, such as imparting X-ray contrast properties, imparting ion release properties, imparting color tone compatibility, toning, improving adhesiveness, and improving operability. be able to.

The photocurable dental composition of the present invention preferably contains (E) a filler in an amount of 400 parts by mass or less per 100 parts by mass of the total amount of (A) polymerizable monomers. (E) If the filler exceeds 400 parts by mass, the photocurable dental composition may lack fluidity, resulting in poor operability.

The difference in fluidity between the fluidity measured after production and the fluidity measured after standing in a constant temperature machine set at 50° C. for one month is preferably within 3.0 mm. Since the dental photocurable composition has various fluidities depending on the application, a change in fluidity after long-term storage makes proper use difficult, which means a decrease in operability.

Both the fluidity measured after production and the fluidity measured after standing in a constant temperature machine set at 50° C. for one month are preferably within 3.0 mm of the dental photocurable composition of the present invention. It is preferably within 1.0 mm. A dental photocurable composition having a fluidity of 3.0 mm or less is less likely to sag, so that it can be applied to the site intended by the user. On the other hand, when the fluidity changes after long-term storage, the user is likely to feel a decrease in operability, so high property stability is required. Since the dental photocurable composition of the present invention can maintain its fluidity over a long period of time, it is particularly suitable for application to a dental photocurable composition having a fluidity of 3.0 mm or less. .

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

For the dental photocurable composition of the present invention, the exemplified organic peroxides may be used alone or in combination of two or more. Among these organic peroxides, from the viewpoint of curability, benzoyl peroxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 1,1,3,3-tetramethylbutylperoxy- 2-ethylhexanoate is preferred.

From the viewpoint of improving curability, the organic peroxide as a chemical polymerization initiator is preferably set to 0.1 to 5 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer (A). is set to 0.3 to 3 parts by mass. If the amount of the organic peroxide blended is more than 5 parts by mass, it may become difficult to ensure a sufficient operating time. strength may be insufficient.

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

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

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

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

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

Specific examples of borate compounds having one aryl group in one molecule include trialkylphenylboron, trialkyl(p-chlorophenyl)boron, trialkyl(p-fluorophenyl)boron, trialkyl(p-fluorophenyl)boron, 3,5-bistrifluoromethyl)phenylboron, trialkyl[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, trialkyl(p -nitrophenyl)boron, trialkyl(m-nitrophenyl)boron, trialkyl(p-butylphenyl)boron, trialkyl(m-butylphenyl)boron, trialkyl(p-butyloxyphenyl)boron, trialkyl( m-butyloxyphenyl)boron, trialkyl(p-octyloxyphenyl)boron and trialkyl(m-octyloxyphenyl)boron (the alkyl group consists of n-butyl group, n-octyl group and n-dodecyl group, etc. is at least one selected from the group) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, and the like. Specific examples of borate compounds having two aryl groups in one molecule include dialkyldiphenyl boron, dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron, dialkyldi(3,5-bistrifluoromethyl) Phenylboron, dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, dialkyldi(p-nitrophenyl)boron, dialkyldi(m- nitrophenyl)boron, dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron, dialkyldi(p-butyloxyphenyl)boron, dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p-octyloxyphenyl) ) Sodium salts and lithium salts of boron and dialkyldi(m-octyloxyphenyl)boron (the alkyl group is at least one selected from the group consisting of n-butyl, n-octyl, n-dodecyl, etc.) , potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt and butylquinolinium salt etc. Specific examples of borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron, monoalkyltri(p-fluorophenyl)boron, monoalkyltri( 3,5-bistrifluoromethyl)phenylboron, monoalkyltri[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, monoalkyltri (p-nitrophenyl)boron, monoalkyltri(m-nitrophenyl)boron, monoalkyltri(p-butylphenyl)boron, monoalkyltri(m-butylphenyl)boron, monoalkyltri(p-butyloxyphenyl) ) boron, monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(p-octyloxyphenyl)boron and monoalkyltri(m-octyloxyphenyl)boron (alkyl group is n-butyl group, n-octyl sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt of , butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, and the like. Specific examples of borate compounds having four aryl groups in one molecule include, for example, tetraphenylboron, tetrakis(p-chlorophenyl)boron, tetrakis(p-fluorophenyl)boron, tetrakis(3,5-bistri fluoromethyl)phenylboron, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, tetrakis(p-nitrophenyl)boron, tetrakis (m-nitrophenyl)boron, tetrakis(p-butylphenyl)boron, tetrakis(m-butylphenyl)boron, tetrakis(p-butyloxyphenyl)boron, tetrakis(m-butyloxyphenyl)boron, tetrakis(p- octyloxyphenyl)boron, tetrakis(m-octyloxyphenyl)boron, (p-fluorophenyl)triphenylboron, (3,5-bistrifluoromethyl)phenyltriphenylboron, (p-nitrophenyl)triphenylboron, sodium salts, lithium salts of (m-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron and (p-octyloxyphenyl)triphenylboron, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt and butylquinolinium salt, etc. 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.

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

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

The method for preparing the dental photocurable composition of the present invention is not particularly limited. As a general method for producing a dental photocurable composition, (A) a polymerizable monomer and (B) a photosensitizer are contained in advance, and (C) a photoacid generator and (D) photopolymerization After preparing a matrix in which an accelerator is mixed, this matrix and (E) a filler are kneaded, air bubbles are removed under vacuum, 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.

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

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

The dental photocurable composition of the present invention comprises (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, (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]
・BisGMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane ・D2.6E: 2,2-bis(4 -(Meth)acryloyloxypolyethoxyphenyl)propane・UDMA: N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)ethanol]methacrylate・NPG: neopentyl glycol dimethacrylate・TEGDMA : Triethylene glycol dimethacrylate GDMA: Glycerin dimethacrylate MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[(B) Photosensitizer]
・CQ: Camphorquinone

・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－イソプロピルフェニル）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-isopropylphenyl) 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

・Ｄ１－２：３－イソプロピル－２－メチル－７－オキソ－６，１１－ジオキソ－３，８－ジアザトリデカン－１３－イルメタクリレート

・Ｄ１－３：２－（（（２－（ジブチルアミノ）エトキシ）カルボニル）アミノ）エチルメタクリレート

・Ｄ１－４：１－［（３，３－ジフェニルプロピル）（メチル）アミノ］－２－メチル－２－プロパノール

＜Ｎを始点としてアミンのα位炭素及び／またはβ位炭素に電子求引性基を有する３つ以上の炭素からなる置換基を２つ以上有するもの＞
・Ｄ２－１：トリイソプロパノールアミン

・Ｄ２－２：ジエチルベンジルイミノジアセテート

・Ｄ２－３：１１－ベンジル－７，１５－ジオキソ－３，８，１４，１９－テトラオキソ－６，１１，１６－トリアザヘニコサン－１，２１－ジイルビス（２－メタクリレート)

＜Ｎの置換基として置換基を有しても良いアリールを２つ以上有するもの＞
・Ｄ３－１：２－ベンジル－６－オキソ－１－フェニル－５，１０－ジオキソ－２，７－ジアザドデカン－１２－イルメタクリレート

・Ｄ３－２：Ｎ，Ｎ－ジベンジルグリシンエチルエステル

・Ｄ３－３：ジベンジルアミノプロピルメタクリレート

・Ｄ３－４：（Ｓ）－（＋）－２－（ジベンジルアミノ）－３－フェニル－１－プロパノール

・Ｄ３－５：ジベンジルアミノプロパノール

・Ｄ３－６：トリベンジルアミン

・Ｄ３－７：２－（（（２－（ジベンジルアミノ）エトキシ）カルボニル）アミノ）－２－メチルプロパン－１，３－ジイルジメタクリレート

・Ｄ３－８：３－（Ｎ，Ｎ－ジベンジルアミノ）プロピルトリエトキシシラン

＜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

＜＜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

＜＜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
・ＤＥＰＴ：Ｎ，Ｎ－ジ（２－ヒドロキシエチル）－ｐ－トルイジン
[(D) Polymerization accelerator]
[(D1) Aliphatic Tertiary Amine Represented by Formula (1)]
<Those having one substituent consisting of three or more carbons and having an electron-withdrawing group at the α- and/or β-position carbon of the amine with N as the starting point>
・ D1-1: N,N-diisopropylaminoethyl methacrylate

・D1-2: 3-isopropyl-2-methyl-7-oxo-6,11-dioxo-3,8-diazatridecan-13-yl methacrylate

・ D1-3: 2-(((2-(dibutylamino)ethoxy)carbonyl)amino)ethyl methacrylate

・ D1-4: 1-[(3,3-diphenylpropyl)(methyl)amino]-2-methyl-2-propanol

<Those having two or more substituents consisting of three or more carbon atoms and having an electron-withdrawing group at the α- and/or β-position carbon of the amine with N as the starting point>
・ D2-1: Triisopropanolamine

・ D2-2: diethylbenzyliminodiacetate

・D2-3: 11-benzyl-7,15-dioxo-3,8,14,19-tetraoxo-6,11,16-triazahenicosane-1,21-diylbis(2-methacrylate)

<Those having two or more aryls which may have substituents as substituents of N>
・D3-1: 2-benzyl-6-oxo-1-phenyl-5,10-dioxo-2,7-diazadodecane-12-yl methacrylate

・ D3-2: N,N-dibenzylglycine ethyl ester

・ D3-3: dibenzylaminopropyl methacrylate

・ D3-4: (S)-(+)-2-(dibenzylamino)-3-phenyl-1-propanol

・ D3-5: dibenzylaminopropanol

・ D3-6: tribenzylamine

・ D3-7: 2-(((2-(dibenzylamino)ethoxy)carbonyl)amino)-2-methylpropane-1,3-diyl dimethacrylate

・ D3-8: 3-(N,N-dibenzylamino)propyltriethoxysilane

<Other Aliphatic Tertiary Amines>
<<Aliphatic tertiary amine compound having no primary hydroxyl group>>
・DMAEMA: N,N-dimethylaminoethyl methacrylate

<<Aliphatic tertiary amine compound having two primary hydroxyl groups>>
・MDEOA: Methyldiethanolamine

<<Aliphatic tertiary amine compound having three primary hydroxyl groups>>
・TEA: Triethanolamine

<Aromatic tertiary amine compound>
・DMBE: N,N-ethyl dimethylaminobenzoate ・DEPT: N,N-di(2-hydroxyethyl)-p-toluidine

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

<(E1) Hydrophobized fine silica particles having an average primary particle diameter of 1 to 40 nm>
<<Surface treatment with dimethyl silicone oil or surface treatment with covalent bonding with functional groups selected from trimethylsilyl groups, dimethylsilyl groups, methylsilyl groups, and straight-chain alkylsilyl groups having 3 to 18 carbon atoms. >>
· Filler E11: Aerosil R972 (manufactured by Evonik, average primary particle size: 16 nm, hydrophobization method: dimethylsilyl group)
· Filler E12: Aerosil R8200 (manufactured by Evonik, average primary particle size: 12 nm, hydrophobization method: trimethylsilyl group)
· Filler E13: Aerosil R805 (manufactured by Evonik, average primary particle size: 12 nm, hydrophobization method: octylsilyl group)
· Filler E14: Aerosil R202 (manufactured by Evonik, average primary particle size: 14 nm, hydrophobization method: dimethyl silicone)

・Filler E15
50.0 g of water, 35.0 g of ethanol, and 10.0 g of trimethoxyoctadecylsilane as a silane coupling agent are stirred at room temperature for 2 hours with respect to 100.0 g of Aerosil 200 (manufactured by Evonik, average particle size: 12 nm). The 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 E15.

<<Silica fine particles hydrophobized by a method other than dimethylsilicone oil, trimethylsilyl group, dimethylsilyl group, methylsilyl group, and linear alkylsilyl group having 3 to 18 carbon atoms>>
· Filler E21: Aerosil R7200 (manufactured by Evonik, average primary particle size: 12 nm, hydrophobization method: methacryloxysilyl group)

・Filler E22
50.0 g of water, 35.0 g of ethanol, and 10.0 g of 8-methacryloyloxyoctyltrimethoxysilane as a silane coupling agent are added to 100.0 g of Aerosil OX50 (manufactured by Evonik, average particle size of 40 nm) 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 E22.

<(E2) Inorganic filler having an average primary particle size of 0.1 to 10 μm>
・Filler E31
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 E31.

・Filler E32
Zirconium silicate filler (average particle size 0.6 μm: zirconia 85% by mass, silica 15% by mass) 100.0 g, water 50.0 g, ethanol 35.0 g, 3-methacryloyloxypropyltrimethoxy as a silane coupling agent A silane coupling treatment solution obtained by stirring 5.0 g of silane for 2 hours at room temperature was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E32.

・Filler E33
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 wt%, _{B2O3 12.3} wt%, SrO 35.7 wt%, _Na2O 2.5 wt%, F7.0 wt%). 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. (polysiloxane treatment)
4.5 g of a low condensate of silane compound "MKC Silicate MS56S" (SiO ₂ content 56.0% by mass, degree of polymerization 2 to 100, manufactured by Mitsubishi Chemical Corporation) was added to 100 g of the pulverized material obtained, Stir mixed for about 90 minutes. After mixing for a predetermined time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours, then cooled to obtain a heat treated product. The obtained heat-treated material was placed in a Henschel mixer and pulverized at 1800 rpm for 5 minutes. After pulverization, a polysiloxane-treated material having good fluidity and a surface coated with polysiloxane was obtained.

(acidic polymer treatment)
100 g of the polysiloxane-treated material was put into a Henschel mixer, and 16.0 g of an aqueous polyacrylic acid solution (polymer concentration: 13% by mass, weight average molecular weight: 20,000; manufactured by Nacalai Co., Ltd.) was sprayed from above while stirring. After spraying, the powder taken out from the mixer was heated in a hot air dryer at 100° C. for 3 hours to obtain a polysiloxane-polyacrylic acid-treated product.

(Silane treatment)
100 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent are added to 100 g of polysiloxane-polyacrylic acid-treated material for 2 hours at room temperature. The silane coupling treatment liquid obtained by stirring was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E33.

<Fillers other than (E1) and (E2)>
・Filler E34
100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent are added to 100 g of Aerosil AluC (manufactured by Evonik), which is particulate alumina. The silane coupling treatment liquid obtained by stirring at room temperature for 30 minutes was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E34.

[Chemical polymerization initiator]
・CHP: cumene hydroperoxide ・TMBH: 1,1,3,3-tetramethylbutyl hydroperoxide ・TPE: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate ・BPO: peroxide Benzoyl [chemical polymerization accelerator]
・PTU: (2-pyridyl) thiourea ・BTU: N-benzoylthiourea ・DEPT: N,N-di(2-hydroxyethyl)-p-toluidine ・COA: copper acetylacetone ・VOA: vanadyl acetylacetonate

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

<Method for producing one-component dental photocurable composition>
All except the (E) filler shown in Tables 1 and 2 were put into 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 are put into a kneader, uniformly stirred, and then defoamed under vacuum to obtain a paste-like one-component dental photocurable composition. It was filled into a beautyfill flow plus syringe container. In addition, in Tables 1 and 2, parts by mass of each component are listed in brackets after the abbreviation of each component.

<Method for producing a two-component dental photocurable composition>
All except the filler (E) shown in Tables 3 and 4 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) filler are put into a kneader and stirred uniformly, and then defoamed under vacuum to obtain pastes 1 and 2. Paste 1 is added to a double syringe (5 mL) manufactured by Mixpack. , 2 to prepare a dental photocurable composition. In Tables 3 and 4, parts by mass of each component are listed in brackets after the abbreviation of each component.

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

(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). A specimen of the one-component dental photocurable composition was immersed in water at 37° C. for 24 hours, and then subjected to a bending test. A bending test was performed on the two-part dental photocurable composition within 1 hour after light irradiation. The bending test was performed using an Instron universal testing machine (manufactured by Instron) at a distance between fulcrums of 20 mm and a crosshead speed of 1 mm/min. (A) Flexural strength of one-component dental photocurable composition and two-component dental photocurable composition containing 150 parts by mass or more of (E) filler with respect to 100 parts by mass of polymerizable monomer The thickness was judged to be good when greater than 100 MPa, applicable when between 80 and 100 MPa, and insufficient when less than 80 MPa. (A) Bending strength of one-component dental photocurable composition and two-component dental photocurable composition containing less than 150 parts by mass of (E) filler with respect to 100 parts by mass of polymerizable monomer The thickness was judged to be good when greater than 80 MPa, applicable when between 60 and 80 MPa, and insufficient when less than 60 MPa. Since the flexural strength varies depending on the amount of filler compounded, different standards were set.

(2) Fluidity 0.05 g of an initial preparation of a dental photocurable composition or an accelerated test product prepared by standing in a thermostat set at 50 ° C. for 1 month was placed horizontally on a slide glass plane. A mass is collected, and within 5 seconds, the slide glass is vertically fixed at 90 degrees to the horizontal plane, and after 1 minute, the distance traveled by the photocurable dental composition is measured. This movement distance (unit: mm) is defined as fluidity. If the fluidity was 20 mm or more, it was determined that the expected rheological properties were not exhibited. If the change is less than 1 mm between the initial adjustment and the accelerated test product, it is judged to have particularly excellent storage stability, and if it is 1 mm or more and less than 2 mm, it is judged to have good storage stability. , it was determined that the storage stability was sufficient for use. On the other hand, it was determined that the fluidity change exceeding 3 mm does not have sufficient storage stability because there is a high possibility that the operability will change after long-term storage.

(3) Light Color Stability Each of the prepared dental photocurable compositions was filled in a stainless steel mold (15φ×1 mm: disc-shaped), 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, and a2*, b2* are the color index after light exposure. be. Those with a ΔE of less than 5 were judged to be particularly good, B, those with a ΔE of 5 to less than 8 were judged to be good, and those with a ΔE of 8 to 10 were judged to be usable, and were judged to be C. On the other hand, when ΔE exceeded 10, it was judged as D as insufficient. 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 Tables 5 and 6 will be described.

It was confirmed that the compositions described in the examples have sufficient bending strength, excellent operability and storage stability.

As in Examples A1, A2, B1, and B2, (A) the amount of (E1) hydrophobized fine silica particles having an average primary particle diameter of 1 to 40 nm per 100 parts by mass of the polymerizable monomer is 1 When it is less than parts by mass, the fluidity is large, and the amount of (E1) hydrophobized silica fine particles having an average primary particle diameter of 1 to 40 nm as in Examples A5, A6, B5, and B6 is 20 parts by mass. Although there was no problem with the physical properties and storage stability when the amount was larger, the paste tended to thicken, resulting in a heavy extrusion feeling and reduced operability. This was particularly noticeable in A6 and B6, in which the amount of (E1) hydrophobized fine silica particles having an average primary particle diameter of 1 to 40 nm exceeded 30 parts by mass.

Further, as in Examples A23 to A26, (A) with respect to 100 parts by mass of the polymerizable monomer, (E1) the hydrophobized silica fine particles having an average particle diameter of the primary particles of 1 to 40 nm and (E2) the primary particles When the total amount of inorganic fillers having an average particle size of 0.1 to 10 μm was less than 100 parts by weight, bending strength tended to decrease. On the other hand, as in Example A7, (A) per 100 parts by mass of the polymerizable monomer, (E1) the hydrophobized silica fine particles having an average primary particle diameter of 1 to 40 nm and (E2) the average primary particle When the total amount of the inorganic filler having a diameter of 0.1 to 10 μm was more than 400 parts by mass, the paste tended to be thickened, resulting in a heavy push-out feeling and reduced operability.

(E1) A composition containing fine particles E21 and E22, which are fine particles hydrophobized by surface treatment with a silane coupling agent having a polymerizable group among hydrophobized silica fine particles having an average primary particle diameter of 1 to 40 nm. Examples A34, A35, B20, and B21 exhibit weaker thixotropic properties with respect to the blending amount than fine particles surface-treated with functional groups such as dimethyl silicone oil, trimethylsilyl group, dimethylsilyl group, methylsilyl group, and alkylsilyl group. , the liquidity showed a slightly high value.

Amine compounds having one substituent consisting of three or more carbon atoms and having an electron-withdrawing group at the α- and/or β-position carbon of the amine with N as the starting point, such as Examples A27 to A30 and B15 to B17 Although the composition containing was within the allowable range, the amount of change in fluidity after storage at 50 ° C. for 1 month tended to increase. In addition, as in Examples A31 to A33, B18, and B19, two substituents consisting of three or more carbon atoms having an electron-withdrawing group at the α- and/or β-position carbon of the amine with N as the starting point Compositions containing an amine compound tended to show a slightly larger amount of change in fluidity after being stored at 50°C for one month.

As in Examples A36 and B22, compositions containing (D1) an aromatic amine compound in addition to the aliphatic amine compound represented by formula (1) show little change in fluidity, but tend to be inferior in light color stability. there were. On the other hand, the composition containing an aromatic amine compound as in Examples A37 and B23 tended to suppress the decrease in light color stability by adding an ultraviolet absorber.

Compositions such as Examples A8 and B8, in which the photosensitizer (B) was less than 0.02 parts by mass relative to the polymerizable monomer (A), tended to be slightly inferior in bending strength. In addition, Examples A10, A11 and B9 containing no (C) photoacid generator tended to be slightly inferior in bending strength and light color stability. (D) Examples A21 and B13, which are compositions containing a small amount of the photopolymerization accelerator, tended to be slightly inferior in bending strength.

Examples A9, A10, A12 and B7, which contained a large amount of photosensitizer, tended to be slightly inferior in light color stability. As in Examples A8, A13, and B8, when the photoacid generator (C) is as large as 10 parts by mass or more with respect to 100 parts by mass of the polymerizable monomer (A), the light color stability tends to be slightly inferior. , Examples A12 and B10, when the content of (C) the photoacid generator was as small as 0.1 parts by mass or less, the bending strength tended to be slightly inferior. Furthermore, Examples A14 and B11, which are compositions containing at least one aryliodonium salt compound with an anion having no organic chain such as A15 to A20 and B12 or a triazine compound as a photoacid generator, are light color stable. tended to be slightly inferior. (D) A22 and B14, which contain a large amount of the photopolymerization accelerator, tended to be slightly inferior in light color stability.

Comparative Example CA1 did not cure because it did not contain (B) a photosensitizer. Since Comparative Example CA2 did not contain (D) a photopolymerization accelerator, the bending strength was remarkably low. Comparative Examples CA3 and CB1 did not contain (E1) hydrophobized fine silica particles having an average primary particle size of 1 to 40 nm, and therefore had high fluidity and did not exhibit thixotropy. Comparative Examples CA4 to CA6 and CB2 to CB4 contain (D) a photopolymerization accelerator other than the amine compound represented by (D1) formula (1), so the amount of change in fluidity after storage at 50 ° C. for 1 month is large, The rheological properties were deactivated.

The dental photocurable composition of the present invention evaluated in the examples can be used without any problem in any known dental photocurable composition. Dental photocurable compositions include dental adhesives, dental primers, dental composite resins, dental abutment building materials, dental resin cements, dental coating materials, dental pit and fissure sealing materials, and dental materials. dental manicure materials, dental room temperature polymerization resins, dental loose tooth fixing materials, dental glass ionomer cements, dental hard resins, dental cutting materials, dental 3D printer materials, and the like.

According to the present invention, it is possible to provide a dental photocurable composition which has sufficient mechanical properties and whose rheological properties are not lost even after long-term storage.

Claims (15)

A dental photocurable composition comprising (A) a polymerizable monomer, (B) a photosensitizer, (D) a photopolymerization accelerator, and (E) a filler,
(D) contains an aliphatic tertiary amine compound represented by (D1) formula (1) as a photopolymerization accelerator,
(E) A dental photocurable composition containing (E1) hydrophobic silica fine particles having an average primary particle size of 1 to 40 nm as a filler.
[Formula (1)]

(Wherein, R ₁ is a substituent consisting of three or more carbons starting from N and having an electron-withdrawing group at the α- and / or β-position carbon of the amine, R ₂ having an electron-withdrawing group 3 or more carbon substituents, R ₃ is a one or more carbon substituents that may have an electron-withdrawing group, the α-position of N in formula (1) Carbon is not an electron-withdrawing group.) The electron-withdrawing group in R ₁ is a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a vinyl group, an aryl group and a halogen, or an organic -OH group, -O- group, -C(O)- group, -S- group, -NH-C(O)-NH- group, -C(O)-O- group, -O -C(O)- group, -O-C(O)-NH- group, -NH-C(O)-O- group, aromatic hydrocarbon group, or having a polymerizable functional group capable of radical polymerization 2. A dental photocurable composition according to claim 1, which is a substituent selected from organic groups which may be (D1) The aliphatic tertiary amine compound represented by formula (1) is an aliphatic tertiary amine compound in which R ₁ and R ₂ are composed of three or more carbons and have electron-withdrawing groups at the α- and/or β-carbons. 3. The dental photocurable composition according to claim 1, which is an aliphatic tertiary amine compound having a group substituent. (D1) The aliphatic tertiary amine compound represented by formula (1) is an aliphatic tertiary amine compound in which R ₁ and R ₂ have an aryl group at the α-position carbon and/or the β-position carbon. 4. A dental photocurable composition according to any one of 1 to 3. (E1) Hydrophobic silica microparticles having an average primary particle diameter of 1 to 40 nm are surface-treated with dimethyl silicone oil, or subjected to trimethylsilyl group, dimethylsilyl group, methylsilyl group, or a linear chain having 3 to 18 carbon atoms. 5. The dental photocurable composition according to any one of claims 1 to 4, wherein the functional group selected from an alkylsilyl group having an alkyl chain of is hydrophobized by surface treatment through covalent bonding with fine particles. (A) Per 100 parts by mass of the polymerizable monomer, (E1) 0.5 to 30 parts by mass of hydrophobic silica fine particles having an average primary particle diameter of 1 to 40 nm. 6. Dental photocurable composition according to any one of 1 to 5. (E) As a filler, (E2) an inorganic filler having an average primary particle diameter of 0.1 to 10 μm is further included, and the (E2) inorganic filler is combined with (E1) fine particle silica as a total amount, ( A) The dental photocurable composition according to any one of claims 1 to 6, characterized by containing 100 to 400 parts by weight per 100 parts by weight of the polymerizable monomer. (C) further comprising an aryliodonium salt as a photoacid generator;
The aryliodonium salt according to any one of claims 1 to 7, which 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. Photocurable composition for (C) further comprising 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 8. The dental photocurable composition according to any one of items 1 to 7. A one-part dental photocurable composition comprising:
(A) with respect to 100 parts by mass of the polymerizable monomer,
(B) contains 0.02 to 1 part by mass of a photosensitizer;
(D1) containing 0.1 to 10 parts by mass of an aliphatic tertiary amine compound represented by formula (1),
(E1) The dental photocurable composition according to any one of claims 1 to 9, comprising 0.5 to 30 parts by mass of hydrophobized fine silica particles having an average primary particle size of 1 to 40 nm. A one-part dental photocurable composition comprising:
(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 0.1 to 10 parts by mass of a photoacid generator,
(D1) containing 0.1 to 10 parts by mass of an aliphatic tertiary amine compound represented by formula (1),
(E1) The dental photocurable composition according to claim 8 or 9, comprising 0.5 to 30 parts by mass of hydrophobized fine silica particles having an average primary particle diameter of 1 to 40 nm. A two-component dental photocurable composition comprising:
consisting of a first paste and a second paste,
The first paste and the second paste have a mass ratio of 1:0.8 to 1.2,
Both the first paste and the second paste contain (E1) hydrophobized silica fine particles whose primary particles have an average particle size of 1 to 40 nm,
For a total of 200 parts by mass of the polymerizable monomer (A) contained in the first paste and the second paste,
(B) contains 0.04 to 2 parts by mass of a photosensitizer;
(D1) containing 0.2 to 20 parts by mass of an amine compound represented by formula (1),
(E1) The dental photocurable composition according to any one of claims 1 to 9, comprising 1 to 60 parts by mass of hydrophobized fine silica particles having an average primary particle diameter of 1 to 40 nm. A two-component dental photocurable composition comprising:
consisting of a first paste and a second paste,
The first paste and the second paste have a mass ratio of 1:0.8 to 1.2,
Both the first paste and the second paste contain (E1) hydrophobized silica fine particles whose primary particles have an average particle size of 1 to 40 nm,
For a total of 200 parts by mass of the polymerizable monomer (A) contained in the first paste and the second paste,
(B) contains 0.04 to 2 parts by mass of a photosensitizer;
(C) contains 0.2 to 20 parts by mass of a photoacid generator,
(D1) containing 0.2 to 20 parts by mass of an amine compound represented by formula (1),
(E1) The dental photocurable composition according to claim 8 or 9, comprising 1 to 60 parts by mass of hydrophobized fine silica particles having an average primary particle diameter of 1 to 40 nm. The difference in fluidity between the fluidity of the photocurable dental composition left in a thermostat set at 50° C. for one month after production and the fluidity of the photocurable dental composition after production is within 3.0 mm. 14. The dental photocurable composition according to any one of 1 to 13. The fluidity of the photocurable dental composition left in a thermostat set at 50° C. for one month after production and the fluidity of the photocurable dental composition after production are within 3.0 mm. 15. A dental photocurable composition according to any one of 14.