1. A dental photocurable composition comprising (A) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, (D) a photopolymerization accelerator, and (E) a filler, wherein,

as the (B) photosensitizer, comprises (B-1) alpha-diketone compounds,

the composition contains 0.15 parts by mass or less of (B-1) an alpha-diketone compound, 0.5 parts by mass or more of (C) a photoacid generator, and 100 parts by mass or more of (E) a filler, per 100 parts by mass of (A) a polymerizable monomer.

2. The dental photocurable composition according to claim 1, wherein,

(B-1) the α -diketones are camphorquinone compounds.

3. The dental photocurable composition according to claim 1 or 2, wherein,

the photoacid generator (C) comprises an aryl iodonium salt,

the aryl iodonium salt is a salt of an anion having an organic group and at least one atom selected from the group consisting of P, B, Al, S and Ga and an aryl iodonium cation.

4. The dental photocurable composition according to claim 1 or 2, wherein,

the photoacid generator (C) comprises an aryl iodonium salt,

the aryl iodonium salt is a salt of an anion having at least one H substituted by F and at least one atom selected from P, B, Al, S and Ga and an aryl iodonium cation.

5. The dental photocurable composition according to any one of claims 1 to 4, wherein,

the photopolymerization accelerator (D) contains (D-1) an aliphatic tertiary amine compound having no two or more primary hydroxyl groups.

6. The dental photocurable composition according to any one of claims 1 to 5, wherein,

the composition contains 1 part by mass or more of (C) a photoacid generator and 0.5 part by mass or more of (D) a photopolymerization accelerator per 100 parts by mass of (A) a polymerizable monomer.

7. The dental photocurable composition according to any one of claims 1 to 6, wherein,

when the dental photocurable composition contains a pigment, the difference between b before curing, in which the color tone in L a b space is measured on a white background under a condition of a thickness of 1mm, and b before curing, in which the color tone in L a b space is measured on a white background under a condition of a thickness of 1mm, of the dental photocurable composition is 5 or less.

8. The dental photocurable composition according to any one of claims 1 to 7, wherein,

which is a one-pack type dental photocurable composition,

the composition contains (B-1) an alpha-diketone compound 0.005-0.15 parts by mass, a photoacid generator (C) 0.5-10 parts by mass, a photopolymerization accelerator (D) 0.1-10.0 parts by mass, and a filler (E) 150-1000 parts by mass, based on 100 parts by mass of the polymerizable monomer (A).

9. The dental photocurable composition according to any one of claims 1 to 7, wherein,

which is a two-part dental photocurable composition comprising a first paste and a second paste,

the first paste comprises a first base containing (A) a polymerizable monomer, (B-1) an alpha-diketone compound, (C) a photoacid generator, (D) a photopolymerization accelerator, and (E) a filler,

the second paste comprises a second base containing (A) a polymerizable monomer, (B-1) an alpha-diketone compound, (C) a photoacid generator, (D) a photopolymerization accelerator, and (E) a filler,

the specific gravity of the first paste and the second paste is 1: 0.8 to 1.2 parts by weight,

the composition contains 0.01-0.3 parts by mass of (B-1) an alpha-diketone compound, 1.0-20.0 parts by mass of (C) a photoacid generator, 0.2-20.0 parts by mass of (D) a photopolymerization accelerator, and 200-800 parts by mass of (E) a filler, based on 200 parts by mass of the total of (A) polymerizable monomers contained in the first substrate and the second substrate.

10. The dental photocurable composition according to any one of claims 1 to 9, wherein,

the dental kit is used in combination with a dental composition for confirmation of color tone.

Background

In the Dental field, there are used Dental photocurable compositions which are applied to Dental adhesives, Dental composite resins, Dental abutment building materials, Dental resin cements, Dental coating materials, Dental pit and fissure sealants, Dental cosmetic materials (Dental cosmetic materials), Dental loose tooth-fixing adhesives, Dental glass ionomer cements, Dental hard resins, Dental cutting materials, Dental 3D printing materials, and the like.

Japanese patent No. 4093974 and japanese patent No. 4596786 propose photopolymerization initiators containing a photoacid generator (triazine compound or specific aryl iodonium salt), a sensitizer, and an electron donor compound as photopolymerization initiators.

Japanese patent No. 5114498 proposes a two-part dental cement in which the amount of alpha-diketones is limited.

Disclosure of Invention

However, these dental photocurable compositions have a large difference in color tone before and after curing, and it is difficult to select an appropriate color tone according to the color tone of the dental photocurable composition before curing, and it is difficult to express sufficient mechanical properties when the amount of the photosensitizer to be added is reduced in order to reduce the difference in color tone before and after curing.

The invention aims to provide a dental photocurable composition which has sufficient mechanical physical properties, small color difference before and after curing and excellent color tone selectivity.

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) a filler, wherein the photosensitizer (B) comprises (B-1) an α -diketone compound, and contains, per 100 parts by mass of the polymerizable monomer (A), 0.15 parts by mass or less of the α -diketone compound (B-1), 0.5 parts by mass or more of the photoacid generator (C), and 100 parts by mass or more of the filler (E).

The dental photocurable composition of the present invention has sufficient mechanical properties, and also has a small color difference before and after curing and excellent color tone selectivity.

Detailed Description

In the present invention, (B-1) the α -diketones can be camphorquinones.

In the present invention, the photoacid generator (C) includes an aryliodonium salt, and the aryliodonium salt may be a salt of an anion having an organic group and any one or more atoms selected from P, B, Al, S, and Ga and an aryliodonium cation.

In the present invention, the photoacid generator (C) includes an aryliodonium salt, and the aryliodonium salt may be a salt of an anion having at least one H substituted by F and at least one atom selected from P, B, Al, S, and Ga and an aryliodonium cation.

In the present invention, (D-1) an aliphatic tertiary amine compound having no two or more primary hydroxyl groups can be contained as the photopolymerization accelerator (D).

In the present invention, the photoacid generator (C) may be contained by 1 part by mass or more and the photopolymerization accelerator (D) may be contained by 0.5 part by mass or more with respect to 100 parts by mass of the polymerizable monomer (a).

In the present invention, the difference between b before curing in which the color tone in L x a b space is measured on a white background under a condition of a thickness of 1mm in a dental photocurable composition (in a case where the dental photocurable composition contains a pigment, the dental photocurable composition excluding the pigment) and b before curing in which the color tone in L a b space is measured on a white background under a condition of a thickness of 1mm in a cured body of the dental photocurable composition can be 5 or less.

The present invention can be a one-part dental photocurable composition comprising (A) 100 parts by mass of a polymerizable monomer, (B-1) 0.005 to 0.15 parts by mass of an alpha-diketone compound, (C) 0.5 to 10 parts by mass of a photoacid generator, (D) 0.1 to 10.0 parts by mass of a photopolymerization accelerator, and (E) 150 to 1000 parts by mass of a filler.

The present invention can be a two-pack type dental photocurable composition comprising a first paste and a second paste, the first paste comprising a first base containing (a) a polymerizable monomer, (B-1) an α -diketone compound, (C) a photoacid generator, (D) a photopolymerization accelerator, and (E) a filler, the second paste comprising a second base containing (a) a polymerizable monomer, (B-1) an α -diketone compound, (C) a photoacid generator, (D) a photopolymerization accelerator, and (E) a filler, the specific gravity of the first paste and the second paste being 1: 0.8 to 1.2, 0.01 to 0.3 parts by mass of (B-1) an alpha-diketone compound, 1.0 to 20.0 parts by mass of (C) a photoacid generator, 0.2 to 20.0 parts by mass of (D) a photopolymerization accelerator, and 200 to 800 parts by mass of (E) a filler, based on 200 parts by mass of the total of the polymerizable monomers (A) contained in the first substrate and the second substrate.

The dental photocurable composition of the present invention is used in combination with a dental composition for confirmation of color tone to constitute a dental kit.

The components of the dental photocurable composition of the present invention will be described in detail below. The dental photocurable composition of the present invention is useful as a dental adhesive material, a dental composite resin, a dental abutment building material, a dental resin cement, a dental coating material, a dental pit crack sealer, a dental cosmetic material, a dental loose tooth fixture adhesive material, a dental glass ionomer cement, a dental hard resin, a dental cutting material, a dental 3D printing material, and the like.

In the dental clinic, in order to restore the aesthetic and functional defects of teeth caused by caries, breakage, or the like, a treatment is performed in which a prosthetic device made of ceramic or a dental hard resin is directly restored with a dental composite resin or indirectly restored with a dental resin cement. In addition, a dental adhesive material for bonding a dental composite resin to various dental materials and natural teeth, a dental loose tooth fixing adhesive material for fixing loose teeth, a dental coating material for protecting hypersensitive or formed living pulp teeth from external stimulus or secondary caries, a dental pit crack sealer for preventing caries by filling up a complicated groove such as a deciduous tooth, a dental cosmetic material for temporarily restoring aesthetic quality by masking tooth discoloration, and a dental abutment restorative material for forming an abutment when a crown portion of a tooth is collapsed by caries. In recent years, new composite materials such as dental cutting materials for producing prosthetic devices by CAD/CAM processing and dental 3D printing materials for producing prosthetic devices by 3D printing have been developed, and various dental materials are used for treatment. The above-mentioned material is prepared into a uniform paste by mixing a resin matrix composed of several polymerizable monomers, various fillers such as inorganic fillers or organic-inorganic composite fillers, and a polymerization initiator according to the use thereof. Some materials are used as examples, and the dental filling composite resin is filled into a tooth in an uncured paste stateIn the method, after the anatomical shape of natural teeth is imparted using a dental instrument such as a device, the natural teeth are irradiated with light using a dental light irradiator or the like to be cured. The irradiation light from the light irradiator is generally used in a range of 100 to 2000mW/cm in light intensity in a wavelength range of about 360 to 500nm²Left and right output light sources. On the other hand, a dental resin cement is used when adhering a prosthetic device to a cavity or an abutment, and light irradiation and curing are performed after the prosthetic device is attached to the cavity or the abutment.

As a photopolymerization initiator used for such dental materials, a photosensitizer or a system in which an appropriate photopolymerization accelerator is combined with a photosensitizer is widely used. As the photosensitizer, an acylphosphine oxide compound or an α -diketone compound, particularly an α -diketone compound, is known to have polymerization initiation energy in a visible light wavelength region which has little influence on the human body. Further, the α -diketone compound has a photobleaching ability, and the yellow color as an original color tone disappears after light irradiation, and thus, there is an advantage that the affinity of the color tone to white dentin is particularly high.

As a polymerization accelerator combined with a photosensitizer, a tertiary amine compound is well known, and since the combination of an α -diketone compound and a tertiary amine compound has high polymerization activity against light, it is used in the field of dental materials. The dental photocurable composition containing the photopolymerization initiator exhibits excellent mechanical properties such as hardness, flexural strength, and compressive strength required for various materials.

However, the photopolymerization initiator used in the past has a problem that the color tone is different before and after curing because the amount of the photosensitizer added is large. For example, when filling a composite resin, since it is difficult to imagine the color tone after curing, there is a risk that the color tone selection by an operator is wrong, or when the curing of the dental photocurable composition filled deep into the cavity is uneven, the color tone uniformity is insufficient.

In addition, the dental cement can be used in combination with a try-on paste in cases where high aesthetic quality is required, such as cases where prosthetic devices or laminate veneers made of ceramics are used. The color tone selection of the prosthetic device or dental cement for end use is performed by use during the fitting (trial) phase. Since the trial plaster is used to confirm the final adhesion state of the prosthetic device, it can be produced in the same color tone as that of the dental photocurable composition after curing. Therefore, when the color tone of the dental photocurable composition before curing is different from the color tone after curing, the color tone of the dental photocurable composition is different from that of the try-on paste, and thus the operator may erroneously recognize that the color tone has been selected incorrectly.

Thus, for example, in a conventional photopolymerization initiator system, a change in color tone before and after curing can be reduced by reducing the amount of a photosensitizer to be added, but in this case, curing does not proceed sufficiently, and it is difficult to express sufficient mechanical strength for use in dental materials.

In order to solve the above problems, the present inventors have found that a photocurable dental composition of the present invention can reduce the amount of α -diketones as a photosensitizer to a smaller amount than conventional compositions and can obtain good mechanical properties by using a combination of a photoacid generator and a photopolymerization accelerator, thereby completing the present invention. That is, when the dental photocurable composition of the present invention is used, the operator can easily imagine the color tone after curing from the stage before light irradiation, and can expect to express excellent color tone consistency to the tooth. Since the color tone of the dental photocurable composition before and after curing is the same as that of the try-on paste, it is expected that the dental cement kit combining these components will reduce the color tone selection error of the operator.

The polymerizable monomer (a) of the present invention can be used without limitation as long as it is a known monomer. Among the polymerizable monomers or compounds having a polymerizable group described in the present invention, a polymerizable group exhibiting radical polymerizability is preferable, and specifically, from the viewpoint of easy radical polymerization, the polymerizable group is preferably a (meth) acrylic group and/or a (meth) acrylamide group. In the present specification, "(meth) acrylic acid" means acrylic acid and/or methacrylic acid, "(meth) acryloyl group" means acryloyl group and/or methacryloyl group, "(meth) acrylate" means acrylate and/or methacrylate, and "(meth) acrylamide" means acrylamide and/or methacrylamide. It is also possible to use a polymerizable monomer having a substituent at the α -position of the acrylic group and/or the acrylamide group. There are a substance having one radical polymerizable group, a substance having two radical polymerizable groups, a substance having three or more radical polymerizable groups, a substance having an acidic group, a substance having an alkoxysilyl group, a substance having a sulfur atom, and the like.

Specific examples of the polymerizable monomer having one radical polymerizable group and no acidic group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) 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- (dihydroxyethyl) (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and the like, 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 radically polymerizable groups and no acidic group include 2, 2-Bis ((meth) acryloyloxyphenyl) propane, 2-Bis [4- (3- (meth) acryloyloxy) -2-hydroxypropoxyphenyl ] propane (commonly known as "Bis-GMA"), 2-Bis (4- (meth) acryloyloxyphenyl) propane, 2-Bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2-Bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2-Bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2-Bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2, 2-bis (4- (meth) acryloyloxydipropylphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxydiethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropylphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2-bis (4- (meth) acryloyloxypropylphenyl) propane, 2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane, a salt thereof, a hydrate thereof, a crystalline solid thereof, and a crystalline solid thereof, 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, butanediol 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, ethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, ethylene glycol (2-acrylate, propylene glycol (2-acrylate, ethylene glycol (meth) acrylate, ethylene glycol (2-acrylate, ethylene glycol (2-acrylate, propylene glycol (2-acrylate, and propylene glycol (2-acrylate, ethylene glycol (2-acrylate, and propylene glycol (2-acrylate, and propylene glycol (2-acrylate, and propylene glycol (2-acrylate), and propylene glycol (2-2, 2,2, 4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (commonly known as "UDMA"), 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 tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N- (2,2, 4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1, 3-diol ] tetramethylacrylate, 1, 7-diacryloyloxy-2, 2,6, 6-tetraacryloxymethyl-4-oxyheptane, and the like.

The polymerizable monomer having an acidic group can be used without limitation as long as it 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, or a carboxylic acid group.

Specific examples of the polymerizable monomer having a phosphoric acid group include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxydecyl undecyl dihydrogen phosphate, 12- (meth) acryloyloxydodecyl dihydrogen phosphate, 16- (meth) acryloyloxycetanyl dihydrogen phosphate, and mixtures thereof, 20- (meth) acryloyloxyeicosyl dihydrogen phosphate, bis [2- (meth) acryloyloxyethyl ] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl ] hydrogen phosphate, bis [ 6- (meth) acryloyloxyhexyl ] hydrogen phosphate, bis [ 8- (meth) acryloyloxyoctyl ] hydrogen phosphate, bis [ 9- (meth) acryloyloxynonyl ] hydrogen phosphate, bis [ 10- (meth) acryloyloxydecyl ] hydrogen phosphate, 1, 3-bis (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl ] hydrogen phosphate; acid chlorides, alkali metal salts, ammonium salts of these compounds; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds.

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 pyrophosphate ], bis [ 8- (meth) acryloyloxyoctyl pyrophosphate ], bis [ 10- (meth) acryloyldecyl pyrophosphate ]; acid chlorides, alkali metal salts, ammonium salts of these compounds; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds.

Specific examples of the polymerizable monomer having a thiophosphoric acid group include 2- (meth) acryloyloxyethyl dihydrogen thiophosphate, 3- (meth) acryloyloxypropyl dihydrogen thiophosphate, 4- (meth) acryloyloxybutyl dihydrogen thiophosphate, 5- (meth) acryloyloxypentyl dihydrogen thiophosphate, 6- (meth) acryloyloxyhexyl dihydrogen thiophosphate, 7- (meth) acryloyloxyheptyl dihydrogen thiophosphate, 8- (meth) acryloyloxyoctyl dihydrogen thiophosphate, 9- (meth) acryloyloxynonyl dihydrogen thiophosphate, 10- (meth) acryloyloxydecyl dihydrogen thiophosphate, 11- (meth) acryloyloxydecyl hydrogen thiophosphate, 12- (meth) acryloyloxydodecyl hydrogen thiophosphate, 2- (meth) acryloyloxy hydrogen sulfide, 3- (meth) acryloyloxybutyl hydrogen thiophosphate, 5- (meth) acryloyloxy butyl hydrogen sulfide, 5- (meth) acryloyloxy-butyl) thiophosphate, 2- (meth) acryloyloxy-butyl hydrogen sulfide, 2- (meth) alkyl hydrogen sulfide, 2- (meth) acryloyloxy-butyl) thio-phosphate, 2-phosphate, and (meth) acryloyloxy-butyl-hydrogen sulfide, 16- (meth) acryloyloxycetaxalkyl thiophosphate dihydrogen ester, 20- (meth) acryloyloxyeicosyl thiophosphate dihydrogen ester; acid chlorides, alkali metal salts, ammonium salts of these compounds; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds. The polymerizable monomer having a thiophosphoric group may be classified as a polymerizable monomer having a sulfur atom.

Specific examples of the polymerizable monomer having a phosphonic acid group include 2- (meth) acryloyloxyethylphenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonoacetate, 10- (meth) acryloyloxydecyl-3-phosphonoacetate; acid chlorides, alkali metal salts, ammonium salts of these compounds; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds.

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

Polymerizable monomers having a carboxylic acid group are classified into (meth) acrylic compounds having one carboxylic acid group in the molecule and (meth) acrylic compounds having a plurality of carboxylic acid groups in the molecule. Specific examples of the (meth) acrylic compound having one carboxyl group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, O- (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, N- (meth) acryloylaspartic acid, N- (meth) acryloyltyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloylp-aminobenzoic acid, N- (meth) acryloylbenzoic acid, N- (meth) acryloylL-4-aminosalicylic acid, N- (meth) acryloylaspartic acid, N- (meth) acryloylL-4-aminosalicylic acid, N- (meth) acryloylaspartic acid, N-4-aminosalicylic acid, N- (meth) acryloylbenzoic acid, N- (meth) acryloylaspartic acid, N-p-4-aminobenzoic acid, N-4-acryloylbenzoic acid, N-4-aminobenzoic acid, N-4-aminobenzoic acid, N-4-acryloylbenzoic acid, or N-4-aminobenzoic acid, N-acryloylbenzoic acid, N-4-amino-4-amino-benzoic acid, or N-4-amino-4-amino-benzoic acid, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydrogen malate; acid halides of these compounds; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds. Specific examples of the (meth) acrylic compound having a plurality of 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) acryloyloxydodecane-1, 1-dicarboxylic acid, 13- (meth) acryloyloxytridecane-1, 1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxybutyl trimellitate, 4- (meth) acryloyloxyhexyl trimellitate, and, 4- (meth) acryloyloxydecyl trimellitate, 2- (meth) acryloyloxyethyl-3 '- (meth) acryloyloxy-2' - (3, 4-dicarboxybenzoyloxy) propyl succinate; acid anhydrides and acid halides of these compounds; and (meth) acrylamide compounds in which ester bonds of these compounds are substituted with amide bonds.

Specific examples of the polymerizable monomer having an alkoxysilyl group include a (meth) acrylic compound having one alkoxysilyl group in the molecule and a (meth) acrylic compound having a plurality of alkoxysilyl groups in the molecule. Examples thereof include 2- (meth) acryloyloxyethyltrimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 4- (meth) acryloyloxybutyltrimethoxysilane, 5- (meth) acryloyloxypentyltrimethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 7- (meth) acryloyloxyheptyltrimethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 9- (meth) acryloyloxynonyltrimethoxysilane, 10- (meth) acryloyloxydecyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane.

As long as the polymerizable monomer having a sulfur atom is a polymerizable monomer having one or more sulfur atoms and a polymerizable group, a known compound can be used without any limitation. Specifically, the compound has a partial structure such as-SH, -S-, > C ═ S, > C-S-C <, > P ═ S, or the like, or the above structure is produced by tautomerism. Specific examples thereof include 10-methacryloyloxydecyl-6, 8-dithiooctanoate, 6-methacryloyloxyhexyl-2-thiouracil-5-carboxylate, 2- (11-methacryloyloxyundecylthio) -5-mercapto-1, 3, 4-thiadiazole, and 10- (meth) acryloyloxydecyl thiophosphate.

There is no limitation to use an oligomer or prepolymer having at least one polymerizable group in the molecule other than the polymerizable monomers. Further, there is no problem even if a substituent such as a fluorine group is present in the same molecule. The polymerizable monomers described above can be used not only alone but also in combination of a plurality of types.

The dental photocurable composition of the present invention can contain a known polymerizable monomer having an acid group as the polymerizable monomer (a) to impart adhesiveness to dentin and a prosthetic device. Preferably 10-methacryloyloxydecyl dihydrogen phosphate or 6-methacryloyloxyhexyl phosphoryl acetate. From the viewpoint of imparting adhesiveness, the amount of the acidic group-containing polymerizable monomer is 1 part by mass or more, and more preferably 10 parts by mass or more, relative to 100 parts by mass of the total amount of the polymerizable monomers contained in the dental photocurable composition.

The dental photocurable composition of the present invention can contain a silane coupling agent as the polymerizable monomer (a) in order to impart adhesiveness to the glass ceramic. Any known silane coupling agent can be used without limitation, but 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, and 11-methacryloxyundecyltrimethoxysilane are preferable. From the viewpoint of imparting adhesiveness, the amount of the polymerizable monomer is 1 part by mass or more, and more preferably 10 parts by mass or more and less than 20 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomers in the composition. Since the silane coupling agent as a polymerizable monomer is intended to impart adhesiveness to a resin material or the like containing a glass ceramic or a filler made of a glass ceramic, it is necessary to mix the silane coupling agent separately from a surface treatment agent for the filler.

The dental photocurable composition of the present invention can contain a polymerizable monomer having a sulfur atom as the polymerizable monomer (a) in order to impart adhesion to a noble metal. From the viewpoint of imparting adhesiveness, the amount of the polymerizable monomer having a sulfur atom to be blended is 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more and less than 10 parts by mass, relative to 100 parts by mass of the total amount of the polymerizable monomers contained in the dental photocurable composition.

< photopolymerization initiator >

The photopolymerization initiator used in the dental photocurable composition of the present invention includes (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator, and these are not particularly limited, and commonly used known compounds can be used without any limitation.

[ (B) photosensitizer ]

Specific examples of the photosensitizer (B) that can be used in the present invention include benzyl, camphorquinone carboxylic acid, camphorquinone sulfonic acid, α -naphthyl, naphthone, p '-dimethoxybenzyl, p' -dichlorobenzylacetyl, pentanedione, 1, 2-phenanthrenequinone, 1, 4-phenanthrenequinone, α -diketones such as 3, 4-phenanthrenequinone, 9, 10-phenanthrenequinone, and naphthoquinone, benzoin alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2, 4-diethylthioxanthone and 2, 4-diisopropylthioxanthone; benzophenones such as benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone; 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-methylpropan-1-yl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) - (1-methylpropan-1-yl) phosphine oxide, bis (2, 6-dimethoxybenzoyl) -tert-butylphosphine oxide, bis (2, 6-dimethoxybenzoyl) cyclohexylphosphine oxide, bis (2, 6-dimethoxybenzoyl) octylphosphine oxide, bis (2-methoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2-methoxybenzoyl) phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) octylphosphine oxide, bis (2-dimethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2-dimethoxybenzoyl) phosphine oxide, bis (2-methylpropan-1-yl) phosphine oxide, bis (2-methyl-ethyl) phosphine oxide, bis (2, 2-methyl-ethyl) phosphine oxide, 2-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-phenyl-methyl-ethyl-phenyl-methyl-ethyl-methyl-ethyl-methyl-phenyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl, Bis (2-methoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2, 6-diethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2, 6-diethoxybenzoyl) (1-methylpropan-1-yl) phosphine oxide, bis (2, 6-dibutoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2, 4-dimethoxybenzoyl) (2-methylpropan-1-yl) phosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) (2, 4-dipentyloxyphenyl) phosphine 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-dimethoxybenzoylbenzyloctylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) isobutylphosphine oxide and 2, 6-dimethoxybenzoyl-2, acylphosphine oxides such as 4, 6-trimethylbenzoyl-n-butylphosphine oxide, acylgermanium compounds such as bisbenzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis (4-methoxybenzoyl) dimethylgermanium and bis (4-methoxybenzoyl) diethylgermanium, α -aminophenylethanones such as 2-benzyl-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholinylphenyl) -acetone-1, benzyldimethylketal, benzyldiethylketal, ketals such as benzyl (2-methoxyethylketal), bis (cyclopentadienyl) -bis [2, 6-difluoro-3- (1-pyrrolyl) phenyl ] -titanium, and mixtures thereof, Metallocenes such as bis (cyclopentadienyl) -bis (pentafluorophenyl) -titanium, bis (cyclopentadienyl) -bis (2, 3,5, 6-tetrafluoro-4-disiloxyphenyl) -titanium and the like.

(B) The photosensitizer can be appropriately selected depending on the wavelength, intensity, light irradiation time, and kind or blending amount of other components to be combined of the light used for polymerization. In addition, the photosensitizer can be used alone or in combination of two or more.

[ (B-1) alpha-diketones ]

The dental photopolymerizable composition of the invention comprises (B-1) an α -diketone compound as (B) a photosensitizer. By using (B-1) an alpha-diketone compound in combination with (C) a photoacid generator and (D) a photopolymerization accelerator, radical polymerization is carried out upon irradiation with light. In this case, when the amount of the α -diketone compound (B-1) is as low as 0.15 parts by mass or less based on 100 parts by mass of the total amount of polymerizable monomers contained in the dental photocurable composition, the photoacid generator (C) is added in an amount of 0.5 parts by mass or more and the photopolymerization accelerator (D) is simultaneously added, and radical polymerization is carried out, and it is found that sufficient mechanical strength for withstanding dental use is expressed. Further, the dental photocurable composition has a yellow color tone before curing by blending (B-1) α -diketone compound, but the dental photocurable composition of the present invention has a reduced yellowness before curing because the amount of (B-1) α -diketone compound blended is smaller than that of the conventional one. Therefore, even when the color tone of the (B-1) α -diketone compound changes after the radical polymerization, the color difference is reduced because the amount blended is small. Therefore, an operator who discharges a paste or the like can easily imagine a color tone after curing, and can expect a reduction in the risk of error in selecting a color tone, and since the amount of the (B-1) α -diketone compound to be added is necessarily minimized, even if the dental photocurable composition to be filled in the deep cavity has curing unevenness, the color difference before and after curing is small, and high color tone consistency can be expected. Further, since the amount of the (B-1) α -diketone compound which causes deterioration of light color stability is small, it can be expected that high light color stability can be obtained without adding a large amount of an ultraviolet absorber.

Examples of the α -diketones include benzyl, camphorquinone carboxylic acid, camphorquinone sulfonic acid, α -naphthyl, naphthone, p '-dimethoxybenzyl, p' -dichlorobenzylacetyl, pentanedione, 1, 2-phenanthrenequinone, 1, 4-phenanthrenequinone, 3, 4-phenanthrenequinone, 9, 10-phenanthrenequinone, and naphthoquinone. Of these, camphorquinone compounds such as camphorquinone, camphorquinone carboxylic acid and camphorquinone sulfonic acid are preferable, and camphorquinone is particularly preferable.

The dental photocurable composition of the present invention contains 0.15 parts by mass or less of (B-1) an alpha-diketone compound per 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the composition. Preferably 0.005 to 0.15 parts by mass, more preferably 0.01 to 0.15 parts by mass, and still more preferably 0.05 to 0.12 parts by mass. When the amount is more than 0.15 part by mass, the color difference before and after curing becomes large. When it is 0.005 parts by mass or more, sufficient mechanical properties can be reliably expressed. In addition, a plurality of (B-1) α -diketones may be used in combination.

The dental photocurable composition of the present invention may contain only (B-1) an α -diketone compound as the (B) photosensitizer. When the photosensitizer (B) is contained in addition to the alpha-diketone compound (B-1), the amount thereof is preferably 0.001 to 1.0 part by mass based on 100 parts by mass of the total amount of the polymerizable monomer (A). Since the photosensitizer (B) having strong absorption at a light source wavelength of 400 to 500nm, which is widely used for dental purposes, has a strong yellow hue in many cases, it is more preferably 0.001 to 0.2 parts by mass. On the other hand, the photosensitizer (B) having no strong absorption at 400 to 500nm is often weak yellow, and therefore, it is more preferably 0.001 to 0.5 parts by mass. In addition, in the (B) photosensitizer, there is a case where no photobleaching ability is present. In this case, even when the amount of the photosensitizer (B) is added is large, the difference in color tone (difference in B ″) between before and after curing does not increase, but the yellowness of the composition before and after curing increases, and therefore, when the composition is applied to a repair site, which is particularly preferably white, the color tone uniformity may deteriorate or the ambient light stability may decrease. In the (B) photosensitizer having a strong absorption between 400 and 500nm, the yellowing tends to be remarkably increased. The (B-1) alpha-diketones represented by camphorquinone are preferable because they have a good photobleaching ability because of a reduced color tone derived from the (B-1) alpha-diketones, and are also preferable because they have a high sensitizing effect on photoacid generators as compared with (B) photosensitizers other than the (B-1) alpha-diketones.

[ (C) photoacid generators ]

The photoacid generator (C) used in the dental photocurable composition of the present invention can be a known compound without limitation. Specific examples thereof include triazine compounds, iodonium salt compounds, sulfonium salt compounds, sulfonate compounds, and the like. Among them, triazine compounds and iodonium salt compounds are preferable because of high polymerizability when used in combination with a sensitizer. More preferably an iodonium salt compound. Iodonium salt compounds are susceptible to sensitization by photosensitizers that absorb in the visible region.

Specific examples of the triazine compound 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- (p-trichloromethyl) -s-triazine, and the like, 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- (. alpha.,. beta. -trichloroethyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-styryl-4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (p-methoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (o-methoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (p-butoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3, 4, 5-trimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-biphenyl) -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 them, 2,4, 6-tris (trichloromethyl) -s-triazine is preferable.

Any known iodonium salt compound can be used as long as it is known. Specifically, the structural formula of the iodonium salt compound can be represented by the following formula (1).

[(R1)₂I]⁺[A]^-Formula (1)

(in the formula [ (R1)₂I]⁺Is a cationic moiety, [ A ]]^-Is an anionic moiety, R1 represented by formula (1) represents an organic group bonded to I, and R1 are the same or different. For example, R1 represents 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, and these groups may be substituted with at least one member selected from the group consisting of an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkyleneoxy group, an amino group, a cyano group, a nitro group and the like, and a halogen. )

Examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl groups and condensed polycyclic aryl groups such as naphthyl, anthryl, phenanthryl, pyrenyl, chrysenyl (chrysenyl), naphthacenyl, benzanthryl, anthraquinonyl, fluorenyl, naphthoquinone, and anthraquinone.

Examples of the heterocyclic group having 4 to 30 carbon atoms include cyclic substances containing 1 to 3 heteroatoms such as oxygen, nitrogen and sulfur, and these heteroatoms may be the same or different, and specific examples thereof include monocyclic heterocyclic groups such as thienyl, furyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidinyl and pyrazinyl, and condensed heterocyclic groups such as indolyl, benzofuryl, isobenzofuryl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalyl, quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, Xanthenyl (Xanthenyl), Thianthrenyl, phenoxazinyl, phenoxathinyl, chromanyl, isobenzodihydropyranyl, dibenzothienyl, xanthonyl (thioxanthyl), thioxanthyl (thioxanthyl) and dibenzofuranyl.

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

Specific examples of the alkenyl group having 2 to 30 carbon atoms include a straight-chain or branched alkenyl group such as a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and a 1-methyl-1-propenyl group.

Specific examples of the alkynyl group having 2 to 30 carbon atoms include straight-chain or branched alkynyl groups such as an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-methyl-1-propynyl group, and a 1-methyl-2-propynyl group.

The above-mentioned 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 may or may not have at least one substituent, and specific examples of the substituent include straight-chain alkyl group having 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, octadecyl group and the like; branched alkyl groups having 1 to 18 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like; cycloalkyl groups having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; a hydroxyl group; a linear or branched alkoxy group having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, or a dodecyloxy group; a linear or branched alkylcarbonyl group having 2 to 18 carbon atoms such as an acetyl group, a propionyl group, a butyryl group, a 2-methylpropionyl group, a heptanoyl group, a 2-methylbutyryl group, a 3-methylbutyryl group, and an octanoyl group; arylcarbonyl groups having 7 to 11 carbon atoms such as benzoyl and naphthoyl; a linear or branched alkoxycarbonyl group having 2 to 19 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, or the like; aryloxycarbonyl groups having 7 to 11 carbon atoms such as a phenoxycarbonyl group and a naphthoxycarbonyl group; arylthiocarbonyl groups having 7 to 11 carbon atoms such as phenylthiocarbonyl group and naphthyloxysulfuryl group; a linear or branched acyloxy group having 2 to 19 carbon atoms such as an acetoxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isobutylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, an octadecylcarbonyloxy group; arylthio groups having 6 to 20 carbon atoms such as phenylthio, biphenylthio, 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-chlorophenylthio, 4-benzoyl-methylthiophenylthio, 4- (methylthiobenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio and the like; straight-chain or branched alkylthio groups having 1 to 18 carbon atoms such as a methylthio group, an ethylthio group, a propylthio group, a tert-butylthio group, a neopentylthio group, a dodecylthio group and the like; aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, xylyl, naphthyl, and the like; a heterocyclic group having 4 to 20 carbon atoms such as thienyl, furyl, pyranyl, xanthenyl, chromanyl, isochromanyl, xanthenone, thioxanthone, dibenzofuranyl, etc.; aryloxy groups having 6 to 10 carbon atoms such as phenoxy groups and naphthoxy groups; linear or branched alkylsulfinyl groups having 1 to 18 carbon atoms such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, and octylsulfinyl; arylsulfinyl groups having 6 to 10 carbon atoms such as phenylsulfinyl, tolylsulfinyl, and naphthylsulfinyl; a linear or branched alkylsulfonyl group having 1 to 18 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, or an octylsulfonyl group; arylsulfonyl groups having 6 to 10 carbon atoms such as phenylsulfonyl group, tolylsulfonyl group (tosyl group), and naphthylsulfonyl group; an alkyleneoxy group; a cyano group; a nitro group; halogen such as fluorine, chlorine, bromine, and iodine.

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

The structure of the anion portion of the iodonium salt compound is not particularly limited, and examples thereof include structures having atoms such as halogen, P, S, B, Al, and Ga. From the viewpoint of safety, anions having As or Sb can be used, but are not preferable in dental applications. The anion preferably has an organic group such as an alkyl group and/or an alkoxy group and/or an aryl group, and most preferably has an organic group such as an alkyl group and/or an alkoxy group and/or an aryl group in which at least one or more H is substituted with F. Since the iodonium salt compound having such an anion has high solubility in the photocurable composition, it is expected that the production time can be shortened by preventing precipitation during low-temperature storage or long-term storage, or dissolving the iodonium salt compound in the composition in a short time. Further, iodonium salt compounds composed of anions having organic groups such as alkyl groups and/or alkoxy groups and/or aryl groups in which one or more H groups are substituted with F can be expected to have higher solubility. When the photoacid generator precipitates, the light color stability may be lowered or the bending strength may be lowered, which is not preferable. As the anion having an organic group such as an alkyl group and/or an alkoxy group and/or an aryl group, in which at least one H may be substituted with F, an anion having an arbitrary atom can be used, but from the viewpoint of general versatility and safety, an anion having P, S, B, Al, or Ga is preferable.

Examples of the anion having no alkyl group and/or alkoxy group and/or aryl group include halogen such as chloride and bromide, high-halogen acid such as perchloric acid, aromatic sulfonic acid such as p-toluenesulfonate, camphorsulfonic acid, nitrate, acetate, chloroacetate, carboxylate, phenoxide, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, and the like. Among them, p-toluenesulfonate, camphorsulfonic acid and carboxylate are preferably used.

Due to [ A ] of the iodonium salt-based compound of the formula (1)]^-The anionic moiety has improved solubility in the photopolymerizable composition, and therefore, an anion having an organic group such as an alkyl group and/or an alkoxy group and/or an aryl group in which at least one or more H is substituted with F is preferable. Specifically, the iodonium salt compound of the formula (1) [ A ]]^-The preferred number of carbon atoms of the alkyl group of the anionic moiety is 1 to 8, preferably 1 to 4. Specific examples thereof 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; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The number ratio (F/H) of hydrogen atoms to fluorine atoms in the alkyl group is preferably 4 or more, and the number ratio (F/H) of hydrogen atoms to fluorine atoms in the alkyl group is preferably 9 or more. It is further preferred that all hydrogen atoms of the hydrocarbon are substituted by fluorine. An iodonium salt composed of anions having alkyl groups with different ratios of hydrogen atoms to fluorine atoms may be blended in the photocurable composition.

Specific examples of the alkyl group include CF₃、CF₃CF₂、(CF₃)₂CF、CF₃CF₂CF₂、CF₃CF₂CF₂CF₂、(CF₃)₂CFCF₂、CF₃CF₂(CF₃)CF、(CF₃)₃C, and the like linear or branched perfluoroalkyl group.

[ A ] of an iodonium salt compound of the formula (1)]^-The preferred number of carbon atoms of the alkoxy group of the anionic moiety is 1 to 8, preferably 1 to 4. Specific examples thereof include a linear alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and an octyloxy group, and a branched alkoxy group such as an isopropoxy group, an isobutoxy group, a sec-butoxy group and a tert-butoxy group. The number ratio of hydrogen atoms to fluorine atoms (F/H) in the alkyl group is 4 or more, and the number ratio of hydrogen atoms to fluorine atoms (F/H) in the alkyl group is preferably 9 or more. It is further preferred that all hydrogen atoms of the hydrocarbon are substituted by fluorine. An iodonium salt composed of anions having alkoxy groups with different ratios of hydrogen atoms to fluorine atoms may be blended in the photocurable composition.

Specific examples of the alkoxy group include CF₃O、CF₃CF₂O、CF₃CF₂CF₂O、(CF₃)₂CFO、CF₃CF₂CF₂CF₂O、(CF₃)₂CFCF₂O、CF₃CF₂(CF₃)CFO、CF₃CF₂CF₂CF₂CF₂O、CF₃CF₂CF₂CF₂CF₂CF₂CF₂CF₂CF₂O, etc., linear or branched perfluoroalkoxy.

In [ A ] of the iodonium salt-based compound of the formula (1)]^-The anionic moiety has a phenyl group in which at least one or more hydrogen atoms are substituted with a fluorine atom, and/or an alkyl group and/or an alkoxy group substituted with a fluorine atom. The alkyl group and/or alkoxy group substituted with a fluorine atom is preferably the above-mentioned group. As a particularly preferred example of the phenyl group, there may be mentionedMention may be made of pentafluorophenyl (C)₆F₅) Trifluorophenyl (C)₆H₂F₃) Tetrafluorophenyl (C)₆HF₄) Trifluoromethyl phenyl (CF)₃C₆H₄) Bis (trifluoromethyl) phenyl ((CF)₃)₂C₆H₃) Pentafluoroethylphenyl (CF)₃CF₂C₆H₄) Bis (pentafluoroethyl) phenyl ((CF)₃CF₂)₂C₆H₃) Trifluoromethyl fluorophenyl (CF)₃C₆H₃F) Bis-trifluoromethylfluorophenyl ((CF)₃)₂C₆H₂F) Pentafluoroethyl fluorophenyl (CF)₃CF₂C₆H₃F) Bis-pentafluoroethyl-fluorophenyl ((CF)₃CF₂)₂C₆H₂F) And the like perfluorophenyl groups. An iodonium salt composed of anions having phenyl groups with different ratios of hydrogen atoms to fluorine atoms may be blended in the photocurable composition.

[ A ] as an iodonium salt-based compound of the formula (1)]^-Specific examples of the anionic moiety include anions having P, and [ (CF)₃CF₂)₃PF₃]^-、[(CF₃CF₂CF₂)₃PF₃]^-、[((CF₃)₂CF)₂PF₄]^-、[((CF₃)₂CF)₃PF₃]^-、[((CF₃)₂CF)₄PF₂]^-、[((CF₃)₂CFCF₂)₂PF₄]^-、[((CF₃)₂CFCF₂)₃PF₃]^-And the like. Examples of the anion having S include [ (CF)₃SO₂)₃C]^-、[(CF₃CF₂SO₂)₃C]^-、[(CF₃CF₂CF₂SO₂)₃C]^-、[(CF₃CF₂CF₂CF₂SO₂)₃C]^-、[CF₃CF₂CF₂CF₂SO₃]^-、[CF₃CF₂CF₂SO₃]^-、[(CF₃CF₂SO₂)₃C]^-、[(SO₂CF₃)₃N]^-、[(SO₂CF₂CF₃)₂N]^-、[((CF₃)C₆H₄)SO₃]^-、[SO₃((CF₂CF₂CF₂CF₂)SO₃]^2-And the like. Examples of the anion having B include [ B (C)₆F₅)₄]^-、[(C₆H₅)B(C₆F₅)₃]^-、[(C₆H₅)B((CF₃)₂C₆H₃))₃]^-And the like. As the anion having Ga, there may be mentioned [ ((CF)₃)₄Ga)^-、[Ga(C₆F₅)₄]^-And the like. Examples of the anion having Al include [ ((CF)₃)₃CO)₄Al]^-、[((CF₃CF₂)₃CO)₄Al]^-And the like.

The dental photocurable composition of the present invention may contain only an aryl iodonium salt as the photoacid generator (C). The dental photocurable composition of the present invention may contain, as the photoacid generator (C), only an aryl iodonium salt which is a salt of an anion having an organic group and at least one atom selected from P, B, Al, S, and Ga and an aryl iodonium cation. The dental photocurable composition of the present invention may contain, as the photoacid generator (C), only a salt of an anion having at least one or more H substituted by F and at least one atom selected from P, B, Al, S, and Ga and an aryliodonium cation.

The dental photocurable composition of the present invention contains 0.5 parts by mass or more of (C) a photoacid generator per 100 parts by mass of the total amount of the polymerizable monomers (a). The amount is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass. In the case where the compounding amount of the photoacid generator is less than 0.5 parts by mass, polymerization accelerating ability may be lacking and curing may be insufficient. When the amount is more than 10 parts by mass, the curing property is sufficient, but the stability to ambient light is shortened, and the discoloration of the cured product such as brown or yellow is increased, which is not preferable.

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 kinds can be used in combination.

[ (D) photopolymerization Accelerator ]

The photopolymerization accelerator (D) used in the dental photocurable composition of the present invention is not particularly limited as long as it is a photopolymerization accelerator having a polymerization accelerating ability, and a known photopolymerization accelerator generally used in the dental field can be used without any limitation. As the photopolymerization accelerator, a primary to tertiary amine compound such as an aromatic amine compound or an aliphatic amine compound, an organic metal compound, a phosphine compound, or the like can be used. Among them, aliphatic tertiary amine compounds and organometallic compounds are preferable because of their excellent color stability.

The aromatic amine compound is ammonia (NH)₃) And (3) a compound in which 1 or more of H in (1) is substituted with an aromatic ring. Can react NH with₃The compound in which 1H is substituted with an aromatic ring is classified into an aromatic primary amine compound, NH₃The compound in which 1H is substituted with an aromatic ring and 1H which is different from the above is substituted with an aromatic ring or an alkyl group is classified as an aromatic secondary amine compound, and NH₃The compounds in which 1H of (a) is substituted with an aromatic ring and different 2H are substituted with an aromatic ring or an alkyl group are classified as aromatic tertiary amine compounds.

Specific examples of the aromatic primary amine compound include aniline, specific examples of the aromatic secondary amine compound include N-protected amino acids (esters) such as N-phenylbenzylamine, N-benzyl-p-anisidine, N-benzyl-o-phenetole, N-phenylglycine ethyl ester, and N-phenylglycine, and specific examples of the aromatic tertiary amine compound include N, N-dimethylaniline, N-diethylaniline, N-di-N-butylaniline, N-dimethyl-p-toluidine, N-dimethyl-m-toluidine, N-diethyl-p-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-methylaniline, Ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-butoxyethyl p-dimethylaminobenzoate, 2-ethylhexyl p-dimethylaminobenzoate, amino p-dimethylaminobenzoate, methyl N, N-dimethyl anthranilate, N-dihydroxyethylaniline, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N-dimethyl-3, 5-dimethylaniline, 4-dimethylaminopyridine, N-dimethyl-alpha-naphthylamine, N-dimethyl-beta-naphthylamine, and the like.

Specifically, the organometallic compound includes organometallic compounds containing scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), tin (Sn), zinc (Zn), and zirconium (Zr), and preferably organometallic compounds containing tin (Sn), vanadium (V), and copper (Cu). Specific examples of the organic metal compound containing tin (Sn) include dibutyltin diacetate, dibutyltin dimaleate, dioctyltin dilaurate, dibutyltin dilaurate, dioctyltin di-tert-carbonate, dioctyltin S, S' -diisooctylmercaptoacetate, tetramethyl-1, 3-diacetoxyditaxodistannoxane and the like, specific examples of the organic metal compound containing vanadium (V) include vanadium acetylacetonate, vanadium tetraoxide, vanadyl acetylacetonate, vanadyl stearate, vanadyl oxalate, vanadium sulfate, bis (1-phenyl-1, 3-butanedione) oxovanadium, bis (maltitol) vanadyl, vanadium pentoxide, sodium metavanadate and the like, and specific examples of the organic metal compound containing copper (Cu) include copper acetylacetonate, copper naphthenate, copper, Copper octoate, copper stearate, copper acetate.

The phosphine compound is a compound in which an organic group is trisubstituted at a P atom, and the aromatic phosphine compound is a phenyl-substituted compound having or not having 1 or more substituents at the P atom. Specific examples of the phosphine compound include trimethylphosphine, tributylphosphine, trihexylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tris (2-thienyl) phosphine, diphenylpropylphosphine, di-t-butyl (3-methyl-2-butenyl) phosphine, methyldiphenylphosphine, triphenylphosphine, 2- (diphenylphosphino) styrene, 3- (diphenylphosphino) styrene, 4- (diphenylphosphino) styrene, allyldiphenylphosphine, 2- (diphenylphosphino) 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, trihexylphosphine, tri (2-octylphosphine), tricyclohexylphosphine, tris (2-thienyl) phosphine, diphenylphosphine, 3- (diphenylphosphino) styrene, 4- (diphenylphosphino) benzaldehyde, 2- (diphenylphosphino) benzoic acid, tris (2-methoxyphenyl) phosphine, tris (3-methoxyphenyl) phosphine, tris (2-methyl-phenyl) phosphine, tris (2-phenyl) benzoate, tris (phenyl) phosphine, tris (phenyl) benzoate, tris (phenyl) phosphine, tris (phenyl) benzoate, tris (phenyl) phosphonium, tris (phenyl) phosphonium, tris (2-phenyl) phosphonium, tris (2-phenyl) phosphonium, tris (tris) phosphonium), tris (2-phenyl) phosphonium), tris (tris) phosphonium), or (tris) phosphonium), tris (tris) phosphonium), tris (, Tris (4-methoxyphenyl) phosphine, 2- (diphenylphosphino) biphenyl, tris (4-fluorophenyl) phosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine, tris (p-tolyl) phosphine, 2- (dimethylamino) phenyldiphenylphosphine, 3- (dimethylamino) phenyldiphenylphosphine, 4- (dimethylamino) phenyldiphenylphosphine, 2' -bis (diphenylphosphino) biphenyl, bis [2- (diphenylphosphino) phenyl ] ether, and the like. Among them, triphenylphosphine, 4- (phenylphosphino) benzoic acid, tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, and tri (p-tolyl) phosphine are preferable.

The aliphatic amine compound means ammonia (NH)₃) And (3) a compound in which 1 or more of H in (b) is substituted with an alkyl group. For alkyl, the reaction product of CH₃-or-CH₂Classification as primary alkyl, of-CH₂Alkyl in which 1H of-has a substituent is classified as secondary alkyl, and-CH₂The alkyl group in which 2H's in-are substituted is classified as a tertiary alkyl group. For aliphatic amines, NH is₃Aliphatic amines in which 1H is substituted with an alkyl group are classified as primary aliphatic amines, NH₃Aliphatic amines in which 2H's are substituted with alkyl groups are classified as secondary aliphatic amine compounds, NH₃Aliphatic amines in which 3H's are substituted with alkyl groups are classified as aliphatic tertiary amine compounds.

Specific examples of the aliphatic primary amine compound include amino acids or amino acid esters such as benzhydrylamine, triphenylmethylamine, and glycine, specific examples of the aliphatic secondary amine compound include dibenzylamine, N-benzyl-1-phenylethylamine, bis (1-phenylethyl) amine, bis (4-cyanobenzyl) amine, N-benzyl protected amino acid, and N-benzyl protected amino acid ester, and specific examples of the aliphatic tertiary amine compound include tributylamine, tripropylamine, triethylamine, N-dimethylhexylamine, N-dimethyldodecylamine, N-dimethylstearylamine, N- [3- (dimethylamino) propyl ] acrylamide, N-dimethylformamide dimethyl acetal, N-dimethylacetamide dimethyl acetal, and the like, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, 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-butyldiethanolamine, N-lauryldiethanolamine, N-stearyldiethanolamine, triethanolamine, tribenzylamine, dibenzylglycine ethyl ester, N '- (2-hydroxyethyl) -N, N, N' -trimethylethylenediamine, 2- (dimethylamino) -2-methyl-1-propanol, N, N-dimethylformamide di-tert-butyl acetal, N, N-dimethyl-2, 3-dihydroxypropylamine, N-diethylethanolamine, 1-methyl-3-pyrrolidinol, 1- (2-hydroxyethyl) pyrrolidine, 1-isopropyl-3-pyrrolidinol, 1-piperidineethanol, 2- [2- (dimethylamino) ethoxy ] ethanol, N-dimethylglycine, N-dimethylglycine methyl ester, N-diethylglycine methyl ester, N-dimethylglycine ethyl ester, N-diethylglycine sodium salt, 2- (dimethylamino) ethyl acetate, N-methyliminodiacetic acid, N-dimethylaminoethylacrylate, N-diethylaminoethylmethacrylate, N-diethylcarbamoylethanolamine, N-diethylcarbamoylethanolamine, 1-methyl-3-pyrrolidinol, 1- (2-hydroxyethyl) pyrrolidine, 1-isopropyl-3-pyrrolidinol, 1-piperidineethanol, 2- [2- (dimethylamino) ethoxy ] ethanol, N-dimethylcarbamoylglycine methyl-ethyl-glycolate, N-dimethylaminoethyl-methylglycine, N-dimethylaminoethyl-acrylate, N-dimethylaminoethyl methacrylate, N-diethylaminoethylcarbamoylglycine, N-methyl-ethyl-1-piperidinol, N-dimethylaminoethyl-1-4-methyl-3-pyrrolidinol, N-dimethylaminoethyl-methyl-ethyl-methyl-3-methyl-glycine, N-methyl-glycine methyl-glycine, N-methyl-glycine methyl-ethyl acrylate, N-ethyl acrylate, N-ethyl acrylate, N-ethyl acrylate, N-ethyl acrylate, N-ethyl acrylate, N-ethyl, N-ethyl acrylate, N-ethyl, N-N, N-N, n, N-dibutylaminoethyl methacrylate, N-dibenzylaminoethyl methacrylate, 3-dimethylaminopropionitrile, tris (2-cyanoethyl) amine, N-dimethylallylamine, N-diethylallylamine, triallylamine, and the like.

(D) The photopolymerization accelerator particularly preferably uses an aliphatic tertiary amine compound. Since the aromatic amine compound has poor light color stability, if it is used for prosthetic devices, prosthetic materials, and adhesives in a site such as anterior teeth where light is likely to be irradiated, the color tone may change with time, which is not preferable. Further, by using an ultraviolet absorber in combination, suppression of temporal discoloration due to light can be expected. However, since the ultraviolet absorber is used as a general additive, it cannot be expected to improve mechanical properties by blending, and further, the yellow tone of the dental photocurable composition before curing may be increased, so that it is not preferable to blend a large amount. For these reasons, it is preferable to use an aliphatic tertiary amine compound. In addition, depending on the composition of the dental photocurable composition, when the composition contains an aliphatic primary amine compound and an aliphatic secondary amine compound, high storage stability and high mechanical strength can be expected, and therefore, known substances can be used without any limitation.

Further, among the aliphatic tertiary amine compounds, (D-1) is preferably not an aliphatic tertiary amine compound having two or more primary hydroxyl groups in the molecule, that is, (D-1) is an aliphatic tertiary amine compound having no two or more primary hydroxyl groups, and more preferably an aliphatic tertiary amine compound having no primary hydroxyl groups in the molecule. Specific examples of the aliphatic tertiary amine compound having two or more primary hydroxyl groups in the molecule include triethanolamine and methyldiethanolamine. Specific examples of the aliphatic tertiary amine compound having no two or more primary hydroxyl groups in (D-1) include N, N-dimethylethanolamine, N-diethylethanolamine, N-dibenzylethanolamine, and the like. In the specific example described above, N-dibenzylethanolamine is preferable because a large amount of a low-boiling compound such as N, N-dimethylethanolamine or N, N-diethylethanolamine generates odor peculiar to an amine. Specific examples of the aliphatic tertiary amine compound having no primary hydroxyl group in the molecule include tribenzylamine, ethyl N, N-dibenzylglycinate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like. When a cured product of a dental photocurable composition is stored for a long period of time, an amine compound having a primary hydroxyl group may cause discoloration. The discoloration tends to increase as the number of primary hydroxyl groups in the molecule increases, and the discoloration becomes particularly significant when two or more primary hydroxyl groups are present in the molecule. Discoloration can be confirmed in a short time when the cured product is stored for a long period of time by storing the cured product in high-temperature water. The cured product of the dental photocurable composition is less discolored under high-temperature water conditions, that is, when the thermal color stability is high, the cured product is less discolored when used for a long period of time.

The dental photocurable composition of the present invention may contain only an aliphatic tertiary amine compound as the photopolymerization accelerator (D). The dental photocurable composition of the present invention may contain, as the photopolymerization accelerator (D), only (D-1) an aliphatic tertiary amine compound having no two or more primary hydroxyl groups. The dental photocurable composition of the present invention may contain, as the photopolymerization accelerator (D), only an aliphatic tertiary amine compound having no primary hydroxyl group in the molecule.

The photopolymerization accelerator (D) is preferably contained in an amount of 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and most preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental photopolymerizable composition. If the amount is less than 0.1 part by mass, the mechanical strength may be insufficient. When the amount is more than 20 parts by mass, the curing property is sufficient, but the stability to ambient light is shortened, and the discoloration of the cured product such as brown or yellow is increased, which is not preferable.

If necessary, the polymerization initiator (B) is a photosensitizer, (C) is a photoacid generator, and (D) is a photopolymerization accelerator, and the secondary treatment such as pulverization, carrier adsorption, and encapsulation in a microcapsule is not problematic. Further, these various photopolymerization initiators can be used alone or in combination of two or more, regardless of the polymerization method or polymerization method.

[ (E) Filler ]

The filler (E) used in the present invention can be any commonly used known filler without limitation.

The type of the filler (E) is not limited as long as it is a known filler, and a filler may be blended according to the use thereof, and preferably a filler such as an inorganic filler, an organic filler, or an organic-inorganic composite filler is blended. These fillers can be used not only alone, but also in combination of a plurality of types regardless of the kind of the filler.

The chemical composition of the inorganic filler is not particularly limited, and specific examples thereof include silica, alumina, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramics, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, aluminum fluorosilicate glass, calcium aluminum fluorosilicate glass, strontium aluminum fluorosilicate glass, barium aluminum fluorosilicate glass, strontium calcium aluminum fluorosilicate glass, and strontium calcium aluminum fluorosilicate glass. In particular, barium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, and fluoroaluminosilicate glass used for dental glass ionomer cement, resin-reinforced glass ionomer cement, resin cement, and the like can also be preferably used. The fluoroaluminosilicate glass described herein has a basic skeleton of silica and alumina, and contains an alkali metal for introducing non-crosslinkable oxygen. Further, the metal material has an alkaline earth metal as a modifying/coordinating ion including strontium and fluorine. In addition, in order to further impart X-ray opacity, it is a composition in which a lanthanoid element is incorporated into a skeleton. The lanthanide element also incorporates as a modification/coordination ion into the composition depending on the composition domain.

Specific examples of the organic filler include polymers such as polymethyl methacrylate, polyethyl methacrylate, a methyl methacrylate-ethyl methacrylate copolymer, an ethyl methacrylate-butyl methacrylate copolymer, a methyl methacrylate-trimethylolpropane methacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone, polyether sulfone, and polycarbonate.

Examples of the organic-inorganic composite filler include a composite filler in which the surface of a filler is polymerized and coated with a polymerizable monomer, a composite filler in which a filler and a polymerizable monomer are mixed and polymerized and then pulverized into an appropriate particle size, and a composite filler in which a filler is dispersed in a polymerizable monomer in advance and then emulsion polymerized or suspension polymerized, but are not limited to these composite fillers.

The filler (E) can be treated with a surface treatment material represented by a silane coupling agent for the purpose of improving affinity with a polymerizable monomer, dispersibility in a polymerizable monomer, mechanical strength of a cured product, and water resistance. The surface treatment material and the surface treatment method are not particularly limited, and a known method can be used without limitation. As the silane coupling agent used for the surface treatment of the filler, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane, hexamethyldisilazane or the like is preferable. In addition to the silane coupling agent, the surface treatment of the filler can be performed by a method using a titanate-based coupling agent or an aluminate-based coupling agent. The amount of the surface treatment material to be treated in the filler is preferably 0.01 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the filler before treatment.

The shape of the filler is not particularly limited, and fillers having any shape such as an amorphous shape, a spherical shape, a needle shape, a plate shape, a crushed shape, and a flake shape can be used. The average particle size of the filler is preferably in the range of 0.2 to 50 μm, more preferably 0.2 to 30 μm, still more preferably 0.2 to 20 μm, and yet more preferably 0.2 to 10 μm.

The dental photocurable composition of the present invention contains 100 parts by mass or more of (E) a filler per 100 parts by mass of the total amount of the polymerizable monomers (a). (E) When the amount of the filler is less than 100 parts by mass, the ratio of the α -diketone compound (B) in the dental photocurable composition is increased as compared with the case where the amount of the filler (E) is 100 parts by mass or more, and thus the change in color difference between before and after curing may be increased. When the dental photocurable composition is in a one-pack form, the amount of the filler (E) is 150 parts by mass or more, preferably 1000 parts by mass or less. When the amount is more than 1000 parts by mass, the paste state of the composition becomes hard, and therefore, the treatment may be difficult, but 1000 parts by mass or more may be included depending on the kind of the filler or the surface treatment condition of the filler. For example, the case where the specific gravity of the filler is high, the case where the amount of the surface treatment agent to the filler is large, the case where the surface treatment agent having good affinity with the polymerizable monomer is used, and the like are mentioned. When the dental photocurable composition is a two-part type, the filler (E) is preferably 200 parts by mass or more and 800 parts by mass or less, based on 200 parts by mass of the total of the polymerizable monomers (a) contained in the first matrix constituting the first paste and the polymerizable monomers (E) contained in the second matrix constituting the second paste.

The dental photocurable composition of the present invention may contain a chemical polymerization initiator. Examples of the organic peroxide as the chemical polymerization initiator include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, peroxydicarbonates, and hydroperoxides. 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. Specific examples of the peroxyesters include α -cumyl peroxyneodecanoate, t-butyl peroxypivalate, 2, 4-trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxy isophthalate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3, 3, 5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, t-butylperoxymaleate, and the like. Specific examples of the dialkyl peroxides include di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, 1, 3-bis (tert-butylperoxyisopropyl) benzene, and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) -3-hexyne. Specific examples of the peroxyketals include 1, 1-bis (t-butylperoxy) cyclohexane, 2-bis (t-butylperoxy) butane, n-butyl-4, 4- (t-butylperoxy) valerate, 1-bis (t-amylperoxy) cyclohexane, and the like. Specific examples of the ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide. Specific examples of the peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate. Specific examples of the hydroperoxides include 2, 5-dimethylhexane-2, 5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, and 1, 1,3, 3-tetramethylbutyl hydroperoxide.

The organic peroxide may be used alone or in combination with 2 or more kinds thereof. Among these organic peroxides, benzoyl peroxide and cumene hydroperoxide are preferable from the viewpoint of curability. From the viewpoint of improving curability, the amount of the organic peroxide as the chemical polymerization initiator is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomer (a). On the other hand, if the amount of the organic peroxide is less than 0.1 part by mass, the mechanical strength may be insufficient.

In order to improve curability, a chemical polymerization accelerator may be added to the dental photocurable composition of the present invention. Examples of the chemical polymerization accelerator include a4 th-cycle transition metal compound, a thiourea derivative, an aliphatic amine, an aromatic amine, sulfinic acid and a salt thereof, a borate compound, a sulfur-containing reductive inorganic compound, a nitrogen-containing reductive inorganic compound, a barbituric acid derivative, a triazine compound, a halogen compound, and the like. The amount of the chemical polymerization accelerator is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total amount of the polymerizable monomers.

The 4 th period transition metal compound as the chemical polymerization accelerator means a metal compound of groups 3 to 12 of the 4 th period of the periodic table, and specifically, any metal compound of scandium (Sc), titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn) can be used without limitation. The above-mentioned transition metal elements may have a plurality of valences, and may be added to the dental photocurable composition of the present invention as long as the valences are stable. For example, Sc (3-valent), Ti (4-valent), V (3-, 4-or 5-valent), Cr (2-, 3-or 6-valent), Mn (2-to 7-valent), Fe (2-or 3-valent), Co (2-or 3-valent), Ni (2-valent), Cu (1-or 2-valent), and Zn (2-valent). Specific examples of the transition metal compound include scandium iodide (3 valent), titanium chloride (4 valent), titanium tetraisopropoxide (4 valent), etc., as the titanium compound, vanadium acetylacetonate (3 valent), vanadium tetraoxide (4 valent), vanadyl acetylacetonate (4 valent), vanadyl stearate (4 valent), vanadyl oxalate (4 valent), vanadium sulfate (4 valent), bis (1-phenyl-1, 3-butanedione) oxovanadium (4 valent), bis (maltol) oxovanadium (4 valent), vanadyl pentavanadate (5 valent), sodium metavanadate (5 valent), etc., as the manganese compound, manganese acetate (2 valent), manganese naphthenate (2 valent), etc., as the iron compound, iron acetate (2 valent), iron chloride (2 valent), iron oxide (3 valent), iron chloride (3 valent), etc., examples of the cobalt compound include cobalt acetate (2-valent) and cobalt naphthenate (2-valent), examples of the nickel compound include nickel chloride (2-valent) and the like, examples of the copper compound include copper chloride (1-valent), copper bromide (1-valent), copper chloride (2-valent) and copper acetate (2-valent) and examples of the zinc compound include zinc chloride (2-valent) and zinc acetate (2-valent).

Among them, a vanadium compound having a valence of 3 or 4, a copper compound having a valence of 2 are preferable, among them, a vanadium compound having a valence of 3 or 4 having a higher polymerization-promoting ability is more preferable, and a vanadium compound having a valence of 4 is most preferable. These transition metal compounds of the 4 th cycle may be used in combination in plural numbers as required. The amount of the transition metal compound to be blended is preferably 0.0001 to 1 part by mass based on 100 parts by mass of the total amount of the polymerizable monomer (a), and when the amount is less than 0.0001 part by mass, the polymerization acceleration effect may be insufficient, and when the amount is more than 1 part by mass, discoloration or gelation of the dental photocurable composition may occur, resulting in a decrease in storage stability.

The thiourea derivative as the chemical polymerization accelerator can be used without limitation as long as it is a known thiourea derivative. Specific examples thereof include dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl) thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N '- (2-hydroxyethyl) thiourea, N-benzylthiourea, 1, 3-dicyclohexylthiourea, N' -diphenylthiourea, 1, 3-di (p-tolyl) thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea and dicyclohexylthiourea. Among them, (2-pyridyl) thiourea, N-acetylthiourea and N-benzoylthiourea are preferable. These thiourea derivatives may be used in combination in plural numbers as required. The amount of the thiourea derivative blended is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the total amount of the polymerizable monomer (a), and when less than 0.1 part by mass, the polymerization accelerating ability may be insufficient, and when more than 5 parts by mass, the storage stability may be lowered.

Examples of sulfinic acids and salts thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4, 6-trimethylbenzenesulfinic acid, sodium 2,4, 6-trimethylbenzenesulfinate, potassium 2,4, 6-trimethylbenzenesulfinate, lithium 2,4, 6-trimethylbenzenesulfinate, calcium 2,4, 6-trimethylbenzenesulfinate, 2,4, 6-triethylbenzenesulfinic acid, sodium 2,4, 6-triethylbenzenesulfinate, potassium 2,4, 6-triethylbenzenesulfinate, lithium 2,4, 6-triethylbenzenesulfinate, calcium 2,4, 6-triethylbenzenesulfinate, 2,4, 6-triisopropylbenzenesulfinic acid, Sodium 2,4, 6-triisopropylsulfinate, potassium 2,4, 6-triisopropylsulfinate, lithium 2,4, 6-triisopropylsulfinate, calcium 2,4, 6-triisopropylsulfinate, and the like, and sodium benzenesulfonate, sodium p-toluenesulfinate, and sodium 2,4, 6-triisopropylsulfinate are particularly preferable.

Specific examples of the borate compound having 1 aryl group in the molecule include trialkylphenylboron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluorophenyl) boron, trialkyl (3, 5-bistrifluoromethyl) phenylboron, trialkyl [3, 5-bis (1, 1, 1,3, 3, 3-hexafluoro-2-methoxy-2-propyl) phenyl ] boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl (p-butoxyphenyl) boron, trialkyl (m-butoxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (alkyl is at least one member selected from the group consisting of n-butyl, n-octyl and n-dodecyl groups), sodium salts thereof, Lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, picolinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, and the like. Specific examples of the borate compound having 2 aryl groups in 1 molecule include sodium salts of dialkyldiphenylboron, dialkylbis (p-chlorophenyl) boron, dialkylbis (p-fluorophenyl) boron, dialkylbis (3, 5-bistrifluoromethyl) phenylboron, dialkylbis [3, 5-bis (1, 1, 1,3, 3, 3-hexafluoro-2-methoxy-2-propyl) phenyl ] boron, dialkylbis (p-nitrophenyl) boron, dialkylbis (m-nitrophenyl) boron, dialkylbis (p-butylphenyl) boron, dialkylbis (m-butylphenyl) boron, dialkylbis (p-butoxyphenyl) boron, dialkylbis (m-butoxyphenyl) boron, dialkylbis (p-octyloxyphenyl) boron and dialkylbis (m-octyloxyphenyl) boron (alkyl group is at least one selected from the group consisting of n-butyl, n-octyl and n-dodecyl), sodium salts of these, sodium salts, and sodium salts of these, Lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, picolinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, and the like. Specific examples of the borate compound having 3 aryl groups in 1 molecule include sodium salts of 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-butoxyphenyl) boron, monoalkyltri (m-butoxyphenyl) boron, monoalkyltri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (alkyl is 1 selected from n-butyl, n-octyl or n-dodecyl, etc.), sodium salts of monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (p-nitrophenyl) boron, monoalkyltri (m-octyloxyphenyl) boron, monoalkyltri (n-dodecyl, etc.), Lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, picolinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, and the like. Specific examples of the borate compound include borate compounds having 4 aryl groups in 1 molecule, and examples thereof include tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3, 5-bistrifluoromethyl) phenylboron, tetrakis [3, 5-bis (1, 1, 1,3, 3, 3-hexafluoro-2-methoxy-2-propyl) phenyl ] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m-nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butoxyphenyl) boron, tetrakis (m-butoxyphenyl) boron, tetrakis (p-octyloxyphenyl) boron, tetrakis (m-octyloxyphenyl) boron, (p-fluorophenyl) triphenylboron, (3, 5-bistrifluoromethyl) phenyltriphenylboron, (p-nitrophenyl) triphenylboron, (m-butoxyphenyl) triphenylboron, Sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, picolinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, and butylquinolinium salts of (p-butoxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron and (p-octyloxyphenyl) triphenylboron.

Among these aryl borate compounds, from the viewpoint of storage stability, it is more preferable to use a borate compound having 3 or 4 aryl groups in 1 molecule. These aryl borate compounds may be used in 1 kind or in combination of 2 or more kinds.

Examples of the sulfur-containing reducing inorganic compound include sulfite, bisulfite, pyrosulfite, thiosulfate, thiosulfonate (thionate), and dithionite, and specific examples thereof include sodium sulfite, potassium sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decylthiol, and thiobenzoic acid.

Examples of the nitrogen-containing reducing inorganic compound include nitrites, and specific examples thereof include sodium nitrite, potassium nitrite, calcium nitrite, and ammonium nitrite.

Examples of the barbituric acid derivatives include barbituric acid, 1, 3-dimethylbarbituric acid, 1, 3-diphenylbarbituric acid, 1, 5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3, 5-trimethylbarbituric acid, 1, 3-dimethyl-5-ethylbarbituric acid, 1, 3-dimethyl-n-butylbarbituric acid, 1, 3-dimethyl-5-isobutylbarbituric acid, 1, 3-dimethylbarbituric acid, 1, 3-dimethyl-5-cyclopentylbarbituric acid, 1, 3-dimethyl-5-cyclohexylbarbituric acid, 1, 3-dimethyl-5-phenylbarbituric acid, Salts of 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-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acid (preferably alkali metal or alkaline earth metal based salts thereof ) Specific examples of the barbituric acid salts include sodium 5-butylbarbiturate, sodium 1,3, 5-trimethylbarbiturate, and sodium 1-cyclohexyl-5-ethylbarbiturate.

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

The dental photocurable composition of the present invention can contain no chemical polymerization initiator or chemical polymerization accelerator. The photocurable composition of the present invention can contain no polymerization initiator system for a polymerization system other than the photopolymerization system.

< other ingredients >

The dental photocurable composition of the present invention may contain components other than the components (a) to (D) as long as the effects of the present invention are not inhibited. For example, a polymerization inhibitor such as a benzophenone-based or benzotriazole-based ultraviolet absorber, hydroquinone monomethyl ether, or 2, 5-di-t-butyl-4-methylphenol; thiol compounds such as α -alkylstyrene compounds, n-butylmercaptan, and n-octylmercaptan; chain transfer agents such as terpenoid compounds such as limonene, myrcene, alpha-terpinene, beta-terpinene, gamma-terpinene, beta-pinene, and alpha-pinene; metal-capturing materials such as aminocarboxylic acid-based chelating agents and phosphonic acid-based chelating agents; a discoloration inhibitor, an antibacterial agent, a coloring pigment, water, a solvent which can be mixed with water at an arbitrary ratio, and other conventionally known additives.

In the case where the dental photocurable composition of the present invention contains a colorant such as a pigment, the change in color tone before and after curing may be reduced in appearance as compared with the case where the composition does not contain a colorant, but in any case, the change in color tone before and after curing is small as compared with the conventional photopolymerization initiator, and therefore, it can be expected that sufficient mechanical properties can be expressed in dental applications.

The method for producing the dental photocurable composition of the present invention is not particularly limited. A general method for producing a dental photocurable composition includes a method of preparing a matrix in which (a) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, and (D) a photopolymerization accelerator are mixed in advance, kneading the matrix with (E) a filler, and removing bubbles under vacuum to prepare a uniform paste. In the present invention, the above-described production method can be used for production without any problem.

The dental photocurable composition of the present invention is useful as a dental adhesive material, a dental composite resin, a dental abutment building material, a dental resin cement, a dental coating material, a dental pit crack sealer, a dental cosmetic material, a dental loose tooth fixture adhesive material, a dental hard resin, a dental cutting material, and a dental 3D printing material.

The present invention provides a dental photocurable composition, wherein the difference between b before curing, in which the color tone in L a b space is measured on a white background under a condition of a thickness of 1mm in a dental photocurable composition (in a case where the dental photocurable composition contains a pigment, the dental photocurable composition excluding the pigment), and b before curing, in which the color tone in L a b space is measured on a white background under a condition of a thickness of 1mm in a cured body of the dental photocurable composition is preferably less than 4. In the present invention, after filling a mold (15. phi. times.1 mm: disk-shaped) made of stainless steel with the dental photocurable composition, a colorless and transparent cover glass having a thickness of 170 μm or less was placed from above and pressure-bonded using a glass plate, and after confirming that the dental photocurable composition was in a uniform state without bubbles, color measurement of the color tone before curing was performed. Then, the cured product was removed from the mold by irradiating the cover glass with light for 1 minute using a photopolymerization irradiator (Griplight II (グリップライト II): pine air system), and the color tone of the test piece was measured as the color tone after curing. The test piece was placed on a background of a standard white plate (D65/10 ° X: 81.07, Y: 86.15, and Z: 93.38), and color measurement was performed under predetermined conditions (light source: C, viewing angle: 2 °, measurement area: 11mm) using a spectrocolorimeter (manufactured by byk chemical corporation, ビックケミー).

< one-part type dental photocurable composition >

When the present invention is applied to a one-part dental photocurable composition, the dental material is preferably used as a dental adhesive material, a dental composite resin, a dental abutment setting material, a dental resin cement, a dental coating material, a dental pit and fissure sealant, a dental cosmetic material, a dental loose tooth fixing adhesive material, a dental hard resin, a dental cutting material, or a dental 3D printing material, and is particularly preferably used as a dental adhesive material, a dental composite resin, a dental abutment setting material, a dental resin cement, a dental coating material, a dental pit and fissure sealant, a dental cosmetic material, a dental loose tooth fixing adhesive material, or a dental hard resin. In the case of a one-pack type dental photocurable composition, it can be expected that the technical errors are less and the risk of air bubble inclusion is reduced.

< two-part dental photocurable composition >

When the present invention is applied to a two-part dental photocurable composition, the composition is preferably used as a dental material, in particular, as a dental adhesive material, a dental composite resin, a dental abutment building material, a dental resin cement, a dental coating material, a dental pit and fissure sealant, a dental cosmetic material, a dental loose tooth fixing adhesive material, a dental hard resin, a dental cutting material, a dental 3D printing material, and particularly, as a dental adhesive material, a dental composite resin, a dental abutment building material, or a dental resin cement. The two-part type dental material is used by kneading two agents divided into a first paste and a second paste immediately before use. And (3) mixing the first paste and the second paste in a ratio of 0.9-1.1: 1.0 or 0.8 to 1.2: the kneading is carried out at a mass ratio of 1.0, preferably at an equal volume ratio. The kneading method can be carried out by a known method such as a dedicated shaking device, manual kneading using a scraper or the like, automatic kneading using a static mixer, or the like. Since the components can be divided into two components and a compound which cannot be mixed in the same paste can be mixed separately, the storage stability is excellent.

The dental photocurable composition of the present invention may contain only (a) a polymerizable monomer, (B) a photosensitizer, (C) a photoacid generator, (D) a photopolymerization accelerator, and (E) a filler. In addition, as the components other than (a) to (E), only one or more of the above components may be contained.

[ examples ]

The following specifically describes examples of the present invention, but the present invention is not limited to these examples.

The materials used in the examples and comparative examples and their abbreviations are as follows.

[ (A) polymerizable monomer ]

Bis-GMA: 2, 2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl ] propane.

D2.6E: 2, 2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane having an average molar number of addition of ethoxy groups of 2.6.

UDMA: n, N- (2,2, 4-trimethylhexamethylene) bis [2- (aminocarboxy) ethanol ] methacrylate.

TEGDMA: triethylene glycol dimethacrylate.

NPG: neopentyl glycol dimethacrylate.

MDP: 10-methacryloyloxydecyl dihydrogen phosphate.

MHPA: 6-methacryloyloxyhexylphosphonoacetate.

[ photosensitizers (B) other than (B-1) alpha-diketones ]

BAPO: phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide.

[ (B-1) alpha-diketones ]

CQ: camphorquinone.

CQ-COOH: camphorquinone carboxylic acid.

[ (C) photoacid generators ]

< salts of anions having an organic group and at least one atom selected from the group consisting of P, B, Al, S and Ga with aryliodonium cations >

C1: bis (4-tert-butylphenyl) iodonium p-toluenesulfonate.

C2: bis (4-tert-butylphenyl) iodonium camphorsulfonate.

< salts of anions having one or more H-substituted organic groups and one or more atoms selected from P, B, Al, S and Ga with aryliodonium cations >)

C3: bis (4-tert-butylphenyl) iodonium nonafluorobutane sulfonate.

C4: bis (4-tert-butylphenyl) iodonium tris (pentafluoropropyl) trifluorophosphate.

C5: p-cumenyl (p-tolyl) iodonium tris (pentafluoroethyl) trifluorophosphate.

C6: bis (4-tert-butylphenyl) iodonium tetrakis (nonafluoro-tert-butoxy) aluminate.

C7: di-p-tolyliodonium phenyltris (pentafluorophenyl) borate.

C8: bis (4-tert-butylphenyl) iodonium tris (trifluoromethanesulfonyl) methide.

C9: bis (4-tert-butylphenyl) iodonium-o-trifluoromethylbenzenesulfonate.

C10: bis (4-tert-butylphenyl) iodonium) octafluorobutane disulfonate.

C11: bis [4- (tert-butyl) phenyl ] iodonium tetrakis (pentafluorophenyl) gallate.

C12: bis (4-n-dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate.

Photoacid generators which are not salts of anions having organic groups with aryliodonium cations > C13: bis (4-tert-butylphenyl) iodonium hexafluorophosphate.

C14: 2,4, 6-tris (trichloromethyl) -1,3, 5-triazine.

C15: diphenyliodonium-2-carboxylate monohydrate.

[ (D) photopolymerization Accelerator ]

< aliphatic tertiary amine >

< aliphatic tertiary amine compound having no primary hydroxyl group >)

TBA: tribenzylamine.

DBGE: n, N-dibenzylglycine ethyl.

DEAEMA: n, N-diethylaminoethyl methacrylate.

DMAEMA: n, N-dimethylaminoethyl methacrylate.

[ aliphatic tertiary amine compound having one primary hydroxyl group ]

DBAE: n, N-dibenzylaminoethanol.

[ aliphatic tertiary amine Compound having two Primary hydroxyl groups ]

MDEOA: methyldiethanolamine.

[ aliphatic tertiary amine Compound having three Primary hydroxyl groups ]

TEA: triethanolamine.

< aromatic tertiary amine Compound >

DMBE: ethyl N, N-dimethylaminobenzoate.

DEPT: n, N-dihydroxyethyl-p-toluidine.

DMPT: n, N-dimethyl-p-toluidine.

< organometallic Compound >

DBTL: dibutyltin dilaurate.

[ (E) Filler ]

The production methods of the respective fillers used for the preparation of the dental photocurable composition are as follows.

(Filler 1)

A silane coupling treatment solution, which was obtained by stirring 50.0g of water, 35.0g of ethanol, and 3.0g of 3-methacryloxypropyltrimethoxysilane as a silane coupling agent at room temperature for 2 hours, was added to 100.0g of fluoroaluminosilicate glass (average particle diameter 0.9 μm), and the mixture was stirred and mixed for 30 minutes. Thereafter, heat treatment was performed at 100 ℃ for 15 hours to obtain filler 1.

(Filler 2)

100.0g of a zirconium silicate filler (average particle diameter: 0.8 μm: 85 wt% of zirconium oxide, 15 wt% of silicon dioxide) was added with a silane coupling treatment solution obtained by stirring 50.0g of water, 35.0g of ethanol, and 5.0g of 3-methacryloxypropyltrimethoxysilane as a silane coupling agent at room temperature for 2 hours, and the mixture was stirred and mixed for 30 minutes. Thereafter, heat treatment was performed at 100 ℃ for 15 hours to obtain filler 2.

[ chemical polymerization initiator ]

CHP: cumene hydroperoxide.

BPO: benzoyl peroxide.

[ chemical polymerization Accelerator ]

PTU: (2-pyridyl) thiourea.

DEPT: n, N-dihydroxyethyl-p-toluidine.

DMPT: n, N-dimethyl-p-toluidine.

COA: copper acetylacetonate.

VOA: vanadyl acetylacetonate.

[ ultraviolet absorbers ]

BT: 2- (2-hydroxy-5-methylphenyl) benzotriazole.

[ polymerization inhibitor ]

BHT: 2, 6-di-tert-butyl-4-methylphenol.

MeHQ: p-methoxyphenol.

[ fluorescent Agents ]

FA: 2.5-Dihydroxyterephthalic acid diethyl ester.

< method for producing single-dose dental photocurable composition >

All the ingredients shown in table 1 except for (E) filler were charged into a wide-mouth plastic container and mixed for 48 hours at 100rpm using a mixing rotor VMRC-5 to obtain a base. Thereafter, the base and (E) filler were put into a kneader, uniformly stirred, and then defoamed under vacuum to prepare a dental photocurable composition. The contents (parts by mass) of the respective components in the table are indicated by the numerical values in parentheses after the abbreviations of the respective components.

[ Table 1]

< method for producing two-part dental photocurable composition >

All the ingredients shown in Table 2 except for (E) filler were charged into a wide-mouth plastic container and mixed for 48 hours at 100rpm using a mixing rotor VMRC-5 to obtain a base. Thereafter, the base and the filler (E) were put into a kneader, and after uniformly stirring and defoaming in vacuum, pastes 1 and 2 were obtained, and then a double syringe (5mL) manufactured by hybrid packaging company (ミックスパック) was filled with the first paste and the second paste to prepare a dental photocurable composition. When used, a paste obtained by mixing the first paste and the second paste with a mixing tip (mixing tip) manufactured by mixing packaging corporation was used. The mixing head manufactured by mixing packaging company can be mixed by a static mixer, and when the mixing head is used, the first paste and the second paste can be mixed in a ratio of 0.9-1.1: kneading at a volume ratio of 1.00, and ideally at an equal volume. The first paste and the second paste are 0.8-1.2: 1.0 was kneaded and used. The contents (parts by mass) of the respective components in the table are indicated by the numerical values in parentheses after the abbreviations of the respective components.

[ Table 2]

The test methods used in examples and comparative examples are as follows. The single-component dental photocurable composition was collected as it was, and the two-component dental photocurable composition was obtained by mixing the first paste and the second paste using a mixing head manufactured by mixing packaging company (ミックスパック).

(1) Bending strength

After the prepared dental photocurable composition was filled in a stainless steel mold, cover glass was placed on both sides and pressure-bonded using a glass plate, and then light irradiation was performed at 5 spots for 10 seconds each using a photopolymerization irradiator (Pen Bright (ペンブライト): pine wind system) to cure. After curing, the cured product was taken out of the mold, and then the back surface was irradiated with light again in the same manner to prepare a test piece (25X 2 mm: rectangular parallelepiped shape). The one-pack type dental photocurable composition was subjected to a bending test after immersing a test piece in water at 37 ℃ for 24 hours. The two-part dental photocurable composition is subjected to a bending test within 1 hour of irradiation of a bending test piece with light. A bending test was carried out using an Instron universal tester (available from Instron corporation) at an inter-fulcrum distance of 20mm and a crosshead speed of 1 mm/min. The bending strength of the one-pack dental photocurable composition and the two-pack dental photocurable composition was good when judged at 100MPa or more, applicable when judged at 80 to less than 100MPa, and insufficient when judged at less than 80 MPa.

(2) Difference in hue before and after photocuring

After each of the dental photocurable compositions prepared was filled in a stainless steel mold (15. phi. times.1 mm: disk shape), a colorless and transparent cover glass having a thickness of 170 μm or less was placed from the top and pressure-bonded using a glass plate. After confirming that the dental photocurable composition was in a uniform state without bubbles, the color tone before curing was measured. Then, the test piece was cured by irradiation with light for 1 minute using a photopolymerization irradiator (Griplight II: air blown) from the cover glass, and the color tone of the test piece was measured after the cured product was taken out from the mold. The test piece was placed on a background of a standard white plate (D65/10 ° X: 81.07, Y: 86.15, and Z: 93.38), and color measurement was performed under predetermined conditions (light source: C, viewing angle: 2 °, measurement area: 11mm) using a spectrocolorimeter (manufactured by byk chemical corporation, ビックケミー). From the results of color measurement, the difference in color tone before and after photocuring was evaluated from the values of b before and after curing. b corresponds to blue to yellow, and a higher b indicates a higher degree of yellow. Generally, the light source of 400-500 nm, especially 450-490 nm is used for the dental material, and the photosensitizer has absorption at 400-500 nm, so the increase of b is proportional to the amount of the photosensitizer. On the other hand, in the case where the color tone of the photosensitizer disappears after polymerization, b decreases. In addition, since discoloration is often yellow or reddish brown in dental materials, a change in color tone can be evaluated from a change in b ×. In the present invention, it is judged that Δ b, which is a change value of b before and after curing, is good when Δ b is less than 4, it is judged that Δ b is applicable when Δ b is 4 to 5, and it is judged that Δ b exceeds 5. When Δ b exceeds 5, it is determined that the change in color tone before and after curing is large, and the color tone after curing cannot be predicted from before curing. On the other hand, when Δ b is 5 or less, it is determined that the change in color tone before and after curing is small, and the color tone after curing can be predicted from before curing. After curing, b may be less than 7, preferably less than 6. When b after curing is less than 7, the resin composition can be used in cases where it is applied to teeth with low yellowness, and in particular, it can be preferably used in a white dental material in which a white pigment such as titanium oxide is additionally blended.

(3) Light color stability

The prepared dental photocurable composition was filled in a stainless steel mold (15. phi. times.1 mm: disk shape), and then a cover glass was placed from the top and pressure-bonded using a glass plate. The test piece was cured by irradiation with light for 1 minute using a photopolymerization irradiator (Griplight II: air) from the cover glass, and after the cured product was taken out from the mold, the cover glass was removed and the color tone of the test piece was measured. The test piece was placed on a background of a standard white plate (D65/10 ° X: 81.07, Y: 86.15, and Z: 93.38), and color measurement was performed under predetermined conditions (light source: C, viewing angle: 2 °, measurement area: 11mm) using a spectrocolorimeter (manufactured by byk chemical corporation, ビックケミー). After that, the test piece was exposed to light for 24 hours using a xenon lamp exposure tester (SUNTEST CPS +), and then the color tone of the test piece was measured again, and the difference in the color change was represented by Δ E calculated by the following formula.

ΔE＝{(ΔL*)²+(Δa*)²+(Δb*)²}^1/2

ΔL*＝L1*-L2*

Δa*＝a1*-a2*

Δb*＝b1*-b2*

Here, L1 denotes the luminance index before exposure, L2 denotes the luminance index after exposure, a1 and b1 denote the color quality indexes before exposure, and a2 and b2 denote the color quality indexes after exposure. When the delta E is less than 5, the test is the most excellent, when the delta E is 5 to 10, the test is excellent, and when the delta E exceeds 10, the test is applicable. When the optical color stability is good, when the dental material is used in the oral cavity for a long period of time, the dental material is less discolored during use and can maintain a high aesthetic quality.

(4) Thermal color stability

The prepared dental photocurable composition was filled in a stainless steel mold (15. phi. times.1 mm: disk shape), and then a cover glass was placed from the top and pressure-bonded using a glass plate. The test piece was cured by irradiation with light for 1 minute using a photopolymerization irradiator (Griplight II: air) from the cover glass, and after the cured product was taken out from the mold, the cover glass was removed and the color tone of the test piece was measured. The test piece was placed on a background of a standard white plate (D65/10 ° X: 81.07, Y: 86.15, and Z: 93.38), and color measurement was performed under predetermined conditions (light source: C, viewing angle: 2 °, measurement area: 11mm) using a spectrocolorimeter (manufactured by byk chemical corporation, ビックケミー). Thereafter, the test piece was immersed in a container containing 10mL of water in a thermostat set at 70 ℃ and then allowed to stand for one week, and the color tone of the test piece was measured again, and the difference in the discoloration was represented by Δ E calculated by the following formula.

ΔE＝{(ΔL*)²+(Δa*)²+(Δb*)²}^1/2

ΔL*＝L1*-L2*

Δa*＝a1*-a2*

Δb*＝b1*-b2*

Here, L1 is the brightness index before immersion and standing, L2 is the brightness index after immersion and standing, a1 and b1 are the color quality indexes before immersion and standing, and a2 and b2 are the color quality indexes after immersion and standing. When the delta E is less than 5, the test is the most excellent, when the delta E is 5 to 10, the test is excellent, and when the delta E exceeds 10, the test is applicable. When the thermal stability is good, the dental material can be used in the oral cavity for a long period of time, and the dental material is less discolored and can maintain a high aesthetic state for a long period of time.

The results shown in tables 3 and 4 are described.

[ Table 3]

[ Table 4]

Since the compositions described in examples have Δ b of less than 5 and a flexural strength of 80MPa or more, the change in color tone before and after curing is sufficiently small, and the compositions have sufficient mechanical strength suitable for dental materials.

Examples a1, a60, a66 and B1 tend to have low flexural strength because the amount of the α -diketone compound added is small. On the other hand, in examples A8, a19, a50, a51, B5 and B15, B before and after curing tends to increase because the amount of α -diketone compound added is large.

Examples a9, a60, a66, and B6 tend to have low flexural strength because the amount of the photoacid generator added is small. On the other hand, in examples a13, a19, a51, a61 and B10, since the amount of the photoacid generator added was large, the cured products tended to have poor color stability and increased B after curing, although the flexural strength was high.

Examples a29 to a34 and B24 to B29 each contain, as a photoacid generator, an aryl iodonium salt, which is a composition containing a compound other than a salt of an anion having an organic group and one or more atoms selected from P, B, Al, S and Ga and an aryl iodonium cation. Examples A29 to A31 and B24 to B26, in which the amount of the photoacid generator blended was relatively small, tended to have low bending strength and slightly deteriorated color stability. Examples a32 to a34 and B27 to B29, in which the amount of the photoacid generator blended was large, tended to further deteriorate the color stability of light and also tended to increase B after curing. Examples 69 and 70, in which the aryl iodonium salt contained as the photoacid generator is a salt of an anion having an organic group and one or more atoms selected from P, B, Al, S, and Ga and an aryl iodonium cation, tend to suppress deterioration in light color stability or increase in B ×.

Examples a35 to a38 and B31 to B34 are compositions containing aryl iodonium salts as photoacid generators, which are salts of an anion having an organic group in which not more than one H is substituted with F and at least one atom selected from P, B, Al, S and Ga, and an aryl iodonium cation. Examples A35, A36, B31 and B32, in which the amount of the photoacid generator blended was relatively small, tended to have low flexural strength. Examples A37, A38, B33 and B34, in which the amount of the photoacid generator blended was relatively large, tended to have poor color stability. The aryl iodonium salts contained as the photoacid generators are the salts of the aryl iodonium cations and anions having an organic group and one or more atoms selected from P, B, Al, S, and Ga, and tend to suppress deterioration in light color stability in examples 69 and 70.

Examples a14, a48, a66 and B11 tend to have low flexural strength because of a small amount of photopolymerization accelerator. On the other hand, in examples a18, a67, and B14, since the amount of the photopolymerization accelerator added was large, the color stability of the light tended to be poor, and B after curing also tended to be large.

Examples A20 to A23, A43 to A46, A52, A53, A59, A65, and B34 to B37 contained aromatic amines as photopolymerization promoters. For example, examples a20, a21, B34, B35 have a tendency to lack color stability of light. On the other hand, when an ultraviolet absorber is blended at the same time as in examples a22 and a23, the deterioration of the light color stability tends to be suppressed. However, when a large amount of the ultraviolet absorber is blended, the blending amount may be increased b or the mechanical strength may be decreased, and therefore, it is preferable that the blending amount is not large. In addition, example a65, which contained only a trace amount of 0.01 part by mass of aromatic amine, exhibited good color stability.

Examples A24 to A26, A39 to A43, B16 to B18, and B41 to B44 contained aliphatic amines having a primary hydroxyl group. Examples a24 and B16 containing DBAE having one primary hydroxyl group in the molecule tended to be slightly inferior in thermal color stability, but were still in a particularly good range, and examples a25, a26, a39 to a43, B17, B18, and B41 to B44 containing MDEOA having two primary hydroxyl groups in the molecule and TEA having three primary hydroxyl groups in the molecule tended to be significantly poor in thermal color stability. Examples a45, a46, B36 and B37 containing DEPT having two primary hydroxyl groups in the molecule also tended to lack thermal color stability. This also applies to examples B45, B46, and B48 which were blended as chemical polymerization accelerators, and even when blended as chemical polymerization accelerators, they may act as photopolymerization accelerators.

Comparative examples CA1 and CB1, which did not contain an α -diketone compound, did not show sufficient curability. Comparative example CA11, which contained BAPO as a photosensitizer instead of α -diketones, had insufficient flexural strength. Comparative examples CA2 to CA4 and comparative examples CB2 to CB4, in which the amount of α -diketones added was large, were insufficient because Δ b before and after curing exceeded 5. Comparative examples CA5 and CB5 in which the amount of the photoacid generator added was small and comparative examples CA6 and CB6 in which no photopolymerization accelerator was included were insufficient in flexural strength. Comparative examples CA7 to CA10, CB7 and CB8 in which the amount of the filler was small or not blended had no problem in curability because the flexural strength was sufficiently high, but Δ b before and after curing exceeded 5 and was not sufficient.

The dental photocurable compositions of the present invention evaluated in the examples can be used without any problem in all known dental photocurable compositions. The dental photocurable composition is 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 sealer, a dental cosmetic material, a dental loose tooth fixture adhesive, a dental glass cement, a dental hard resin, a dental cutting material, a dental 3D printing material, or the like.

In the present specification, when a constituent element of the invention is described as either a singular or a plural, or when it is not described as being limited to a singular or a plural, the constituent element may be either a singular or a plural, unless otherwise clear from the context.

Although the present invention has been described with reference to the detailed embodiments, it should be understood that various changes and modifications can be made by those skilled in the art based on the matters disclosed in the present specification. Therefore, the scope of the embodiments of the present invention is intended to include any alterations or modifications.

According to the present invention, a dental photocurable composition having sufficient mechanical properties, small color difference before and after curing, and excellent color tone selectivity can be provided.