JP2023042510A - Dental curable composition excellent in storage stability - Google Patents

Abstract

To provide a dental curable composition having sufficient mechanical properties and excellent storage stability before and after curing.SOLUTION: A dental curable composition contains (A) a polymerizable monomer, (BC) polymerization initiators, (D) a polymerization accelerator, and (E) a filler. The (BC) polymerization initiators include (B) a photopolymerization initiator and/or (C) a chemical polymerization initiator. The (B) photopolymerization initiator includes (B1) a photosensitizer and (B2) a photoacid generator. The (C) chemical polymerization initiator includes (C1) organic peroxide. The (E) filler includes (E1) surface-treated basic filler. The (E1) surface-treated basic filler is surface-treated with a surface treatment agent represented by the following formula and/or a condensate thereof (where each M is a metal atom selected from Si, Ti, Zr, and Al; each X is H, OH, or a hydrolyzable group, which may be the same as or different from each other; if M is Si, Ti, or Zr, n is 4, or if M is Al, n is 3).SELECTED DRAWING: None

Description

The present invention relates to dental hardenable compositions.

In the field of dentistry, dental hardenable compositions are used, such as dental adhesives, dental composite resins, dental abutment building materials, dental resin cements, dental coating materials, and dental pit and fissure sealants. materials, dental manicure materials, dental loose tooth fixing adhesives, dental glass ionomer cements, dental hard resins, dental cutting materials, dental 3D printer materials, etc.

Patent Document 1 discloses a dental composition containing sodium fluoride surface-treated with polysiloxane in order to realize sustained release of fluorine, dental compositions containing inorganic fine particles that have been surface-treated with polysiloxane to achieve a lustrous gloss, and also basic core materials coated with an inorganic shell containing metal oxides as in US Pat. A dental composition has been proposed.

International publication WO2006/106838 Japanese Patent Application Laid-Open No. 2001-139843 Japanese Patent Publication No. 2020-500879

Dental curable compositions are required to have both better storage stability and better physical properties than existing dental curable compositions.

An object of the present invention is to provide a dental curable composition having good mechanical properties and good storage stability before and after curing.

（式中、ＭはＳｉ、Ｔｉ、Ｚｒ、Ａｌから選ばれる金属原子、ＸはＨ、ＯＨ、加水分解性基であり、互いに同一でも異なっても良い。ＭがＳｉ、Ｔｉ、Ｚｒである場合にｎは４であり、ＭがＡｌである場合にｎは３である。） The dental curable composition of the present invention is
A dental curable composition comprising (A) a polymerizable monomer, (BC) a polymerization initiator, (D) a polymerization accelerator, and (E) a filler,
(BC) the polymerization initiator comprises (B) a photoinitiator and/or (C) a chemical polymerization initiator;
(B) the photoinitiator comprises (B1) a photosensitizer and (B2) a photoacid generator;
(C) the chemical polymerization initiator comprises (C1) an organic peroxide;
(E) the filler comprises (E1) a surface-treated basic filler;
(E1) A dental curable composition in which the surface-treated basic filler is (F1) a surface-treated basic filler surface-treated with a surface-treating agent represented by formula (1) and/or a condensate thereof be.
[Formula (1)]

(In the formula, M is a metal atom selected from Si, Ti, Zr and Al, X is H, OH, a hydrolyzable group, which may be the same or different. When M is Si, Ti, Zr where n is 4, and n is 3 when M is Al.)

The dental curable composition of the present invention has high storage stability and good mechanical properties.

In the present invention, (F1) the surface treatment agent represented by formula (1) and/or its condensate is a partial condensate of 2 to 100 molecules of tetraalkoxysilane or a partial condensate of 2 to 100 molecules of tetraalkoxysilane. All or part of the alkoxy groups of is a polysiloxane substituted with OH groups.

In the present invention, (E1) the surface-treated basic filler is (F1) a surface-treating agent represented by formula (1) and/or a condensate thereof, which is prepared by a wet method and under heat treatment conditions of 130°C to 400°C. A curable dental composition surface-treated by heating at the following temperature for 1 hour or longer can be obtained.

In the present invention, (E1) the surface-treated basic filler is (F1) a surface treatment agent represented by formula (1) and/or a condensate thereof, in addition to surface treatment with a silane coupling agent having a polymerizable group. and/or a dental curable composition surface-treated with an acidic polymer.

In the present invention, (E1) 1.0 g of the surface-treated basic filler is added to a mixed solution of 40 g of distilled water and 10 g of ethanol, and stirred for 1 hour. It can be a dental hardenable composition.

In the present invention, (E1) the surface-treated basic filler is one or more of fluorosilicate glass containing strontium and/or calcium ions, fluoroaluminosilicate glass, and fluoroaluminoborosilicate glass. can be

In the present invention, the composition range of (E1) the surface-treated basic filler is SiO ₂ : 15 to 35% by mass, Al ₂ O ₃ : 15 to 30% by mass, SrO: 20 to 45% by mass, P ₂ O ₅ : 0 to 15% by mass, F: 5 to 15% by mass, Na ₂ O: 0 to 10% by mass, B ₂ O ₃ : 0 to 20% by mass, CaO: 0 to 10% by mass. It can be a composition.

In the present invention, (B2) contains an aryliodonium salt as a photoacid generator,
An aryliodonium salt can be a dental curable composition that is a salt of an aryliodonium cation with an anion having an organic group and one or more atoms of P, B, Al, S, Ga.

In the present invention, (B2) contains an aryliodonium salt as a photoacid generator, and the aryliodonium salt includes at least one or more H-substituted organic groups and any one of P, B, Al, S, and Ga. A dental curable composition can be a salt of an anion having one or more atoms and an aryliodonium cation.

In the present invention, (D) the polymerization accelerator may be a dental curable composition containing an aliphatic tertiary amine compound.

In the present invention, the dental curable composition contains 1 to 30 parts by mass of the (A1) polymerizable monomer having an acidic group out of 100 parts by mass of the (A) polymerizable monomer contained in the dental curable composition. It can be a sexual composition.

In the present invention, a one-component dental curable composition containing (B) a photopolymerization initiator,
With respect to 100 parts by mass of the polymerizable monomer (A) contained in the dental curable composition,
(B1) contains 0.02 to 1.0 parts by mass of a photosensitizer,
(B2) contains 0.1 to 10 parts by mass of a photoacid generator,
(D) contains 0.2 to 10 parts by mass of a polymerization accelerator,
(E1) A dental curable composition containing 10 to 500 parts by mass of a surface-treated basic filler.

In the present invention, a two-component dental curable composition containing (B) a photopolymerization initiator,
consisting of a first paste and a second paste,
The first paste and the second paste have a mass ratio of 1:0.8 to 1.2,
For a total of 200 parts by mass of the polymerizable monomer (A) contained in the first paste and the second paste,
(B1) contains 0.04 to 2.0 parts by mass of a photosensitizer,
(B2) contains 0.2 to 20 parts by mass of a photoacid generator,
(D) contains 0.4 to 20 parts by mass of a polymerization accelerator,
(E1) A dental curable composition containing 10 to 500 parts by mass of a surface-treated basic filler.

In the present invention, a two-component dental curable composition containing (C) a chemical polymerization initiator,
consisting of a first paste and a second paste,
The first paste and the second paste have a mass ratio of 1:0.8 to 1.2,
For a total of 200 parts by mass of the polymerizable monomer (A) contained in the first paste and the second paste,
(C1) contains 0.2 to 10 parts by mass of an organic peroxide,
(D) contains 0.4 to 20 parts by mass of a polymerization accelerator,
(E1) A dental curable composition containing 10 to 400 parts by mass of a surface-treated basic filler.

In the present invention, a two-component dental curable composition containing (C) a chemical polymerization initiator,
consisting of a first paste and a second paste,
The first paste and the second paste have a mass ratio of 1:0.8 to 1.2,
For a total of 200 parts by mass of the polymerizable monomer (A) contained in the first paste and the second paste,
(C1) contains 0.2 to 10 parts by mass of an organic peroxide,
(D) contains 0.4 to 20 parts by mass of a polymerization accelerator,
(E1) 10 to 400 parts by mass of a surface-treated basic filler,
Furthermore, a dental curable composition can be prepared in which (A1) a polymerizable monomer having an acidic group accounts for 2 to 60 parts by mass of the total 200 parts by mass of the polymerizable monomers (A).

In the present invention, a dental curable composition having a diameter of 15 mm and a thickness of 1 mm is immersed in 5 mL of an aqueous lactic acid solution having a pH of 4.0 for 24 hours. It can be a composition.

In the present invention, a dental curable composition that does not substantially contain water can be obtained.

Each component of the dental hardenable composition of the present invention will be described in detail below.
The curable dental composition of the present invention includes a dental adhesive, a dental composite resin, a dental abutment building material, a dental resin cement, a dental coating, a dental pit and fissure sealing material, and a dental manicure. , dental loose tooth fixing material, dental cutting material, dental 3D printer material, etc.

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

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

However, when the combination of the α-diketone compound and the tertiary amine compound is used as a photopolymerization initiator, the problem of poor environmental light stability arises. For this reason, a photopolymerization initiator comprising a specific aryliodonium salt photoacid generator, a sensitizer and an electron donor compound has been proposed. While dental materials containing photoacid generators have high stability against ambient light, they exhibit high sensitivity to irradiation light. It exhibits curability.

On the other hand, chemical polymerization initiators are sometimes used for dental materials used in areas where light does not reach sufficiently, in order to eliminate the operation of light irradiation. As a chemical polymerization initiator, a system in which an organic peroxide represented by benzoyl peroxide and a tertiary aromatic amine compound are combined is known. Usually, the organic peroxide and the tertiary aromatic amine compound react when they are in the same package, so they are divided into two or more agents for use. At the time of use, it is possible to cure without light irradiation by mixing the two agents before applying to the application site, so it is suitable for materials that are suitable for areas where light irradiation cannot be performed sufficiently. be able to. In addition, the rate of polymerization can be further increased by further performing light irradiation.

Dental materials may contain ion releasing basic fillers as well as polymerization initiators and polymerizable monomers. Examples of basic fillers include fluoroaluminosilicates and calcium silicates. By adding basic fillers to dental materials, we prepare several oral environments such as neutralization of acidic components around dental materials and release of ions that can be expected to contribute to remineralization such as calcium. expected to be effective. However, the photoacid generators and organic peroxides described above tended to deteriorate storage stability when they coexisted with untreated or insufficiently surface-treated basic fillers. There is also a method of crystallizing a basic filler by heat-treating it at a high temperature for a long period of time to change the properties of the filler, but in this case, the acid-neutralizing ability and ion-releasing ability tended to be poor.

In addition, when the composition contains an acidic compound such as a photoacid generator or an acidic group-containing polymerizable monomer, the physical properties of the cured product tend to deteriorate. Although the detailed principle is unknown, it is believed that the hydrolysis is promoted by the acid in the composition.

In order to solve the above problems, the basic filler contained in the dental curable composition of the present invention is a surface-treated basic filler with a specific surface treatment agent and a photoacid generator and/or a polymerization initiator. Alternatively, the inventors have found that the above problems can be solved by using an organic peroxide, and have completed the present invention.

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

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

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

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

[(A1) Polymerizable monomer having acidic group]
The dental curable composition of the present invention can contain (A1) a polymerizable monomer having an acidic group. (A1) The polymerizable monomer having an acidic group has at least one polymerizable group and at least an acidic group such as a phosphoric acid group, a pyrophosphoric acid group, a thiophosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group. Any polymerizable monomer having one or more can be used without limitation. By including (A1) a polymerizable monomer having an acidic group, it is possible to impart adhesiveness to dentin and prosthetic devices. Furthermore, when the dental curable composition contains a basic filler, it is expected that the stability of the cured product of the dental curable composition will be improved.

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

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

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

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

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

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

The amount of the (A1) acidic group-containing polymerizable monomer in the dental curable composition of the present invention is 100 mass of the polymerizable monomer contained in the dental curable composition from the viewpoint of imparting adhesiveness. 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 20 parts by mass or less. If the amount is less than 1 part by mass, sufficient adhesion to tooth substance, metals and metal oxides may not be exhibited, and if the amount is 30 parts by mass or more, storage stability may be lowered.

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

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

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

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

The dental curable composition of the present invention can contain a polymerizable monomer having a sulfur atom as (A) a polymerizable monomer in order to impart adhesion to noble metals. The amount of the polymerizable monomer having a sulfur atom is 0.01 parts by mass or more based on the total amount of 100 parts by mass of the polymerizable monomers contained in the curable dental composition from the viewpoint of imparting adhesiveness. More preferably, the blending amount is 0.1 parts by mass or more and less than 10 parts by mass.

<(BC) polymerization initiator>
The (BC) polymerization initiator used in the dental curable composition of the present invention includes (B) a photopolymerization initiator and/or (C) a chemical polymerization initiator. (B) The photopolymerization initiator is a polymerization initiator capable of initiating polymerization by irradiating the dental curable composition with light using a light irradiator or the like. (C) A chemical polymerization initiator is a polymerization initiator capable of initiating polymerization when an oxidizing agent and a reducing agent that are divided into two or more agents are mixed. (B) A photopolymerization initiator and (C) a chemical polymerization initiator are used in combination with (D) a polymerization accelerator to remarkably enhance curability.

<(B) Photoinitiator>
The dental curable composition of the present invention contains (B) a photopolymerization initiator containing (B1) a photosensitizer and (B2) a photoacid generator when (C1) does not contain an organic peroxide. Further, even when (C1) an organic peroxide is contained, (B) a photopolymerization initiator containing (B1) a photosensitizer and (B2) a photoacid generator can be contained. The (B) photopolymerization accelerator contained in the dental curable composition of the present invention is not particularly limited, and commonly used known compounds can be used without any limitation.

[(B1) photosensitizer]
Specific examples of the (B1) photosensitizer that can be used in the present invention include benzyl, camphorquinone, camphorquinone carboxylic acid, camphorquinone sulfonic acid, α-naphthyl, acetonafthene, p,p'-dimethoxybenzyl. , p,p'-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, α-diketones such as naphthoquinone, benzoin , benzoin methyl ether, benzoin alkyl ethers such as benzoin ethyl ether, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2 , thioxanthone such as 4-diisopropylthioxanthone, benzophenone, p-chlorobenzophenone, p-methoxybenzophenone and other benzophenones, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl) (2 ,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylprop-1-yl)phosphine oxide, bis (2,6-dimethoxybenzoyl)-(1-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, Bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylprop-1-yl)phosphine oxide , bis(2,6-diethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6 -dibutoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzyl phosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, Bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxy acylphosphine oxides such as benzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide and 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide; Acylgermanium compounds such as bisbenzoyldiethylgermanium, bisbenzoyldimethylgermanium, bisbenzoyldibutylgermanium, bis(4-methoxybenzoyl)dimethylgermanium, and bis(4-methoxybenzoyl)diethylgermanium, 2-benzyl-dimethylamino-1- α-Aminoacetophenones such as (4-morpholinophenyl)-butanone-1,2-benzyl-diethylamino-1-(4-morpholinophenyl)-propanone-1, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl (2 -methoxyethyl ketal), bis(cyclopentadienyl)-bis[2,6-difluoro-3-(1-pyrrolyl)phenyl]-titanium, bis(cyclopentadienyl)-bis(pentanefluoro phenyl)-titanium, bis(cyclopentadienyl)-bis(2,3,5,6-tetrafluoro-4-disiloxyphenyl)-titanium, and the like.

(B1) The photosensitizer can be appropriately selected according to the wavelength, intensity, and light irradiation time of light used for polymerization, and the types and amounts of other components to be combined. Moreover, a photosensitizer can be used individually or in combination of 2 or more types. Among them, α-diketone compounds having a maximum absorption wavelength in the visible light region are preferably used, and more preferably camphorquinone compounds such as camphorquinone, camphorquinone carboxylic acid, and camphorquinone sulfonic acid. , and especially camphorquinone is preferred because of its easy availability.

Usually, the amount of the photosensitizer (B1) to be blended is usually 0.02 to 1.0 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental curable composition. is preferred, and more preferably 0.05 to 0.5 parts by mass. (B1) If the amount of the photosensitizer is less than 0.02 parts by mass, the polymerization activity against irradiation light may be poor, resulting in insufficient curing. If the amount is more than 1.0 part by mass, sufficient curability will be exhibited, but the ambient light stability will be shortened and yellowishness will increase. The dental curable composition of the present invention may contain only an α-diketone compound as (B1) a photosensitizer.

[(B2) Photoacid Generator]
As the photoacid generator (B2) used in the dental curable composition of the present invention, known compounds can be used without limitation. Specific examples include triazine compounds, iodonium salt compounds, sulfonium salt compounds, sulfonic acid ester compounds, and the like. Among these, triazine compounds and iodonium salt compounds are preferred because of their high polymerizability when used in combination with a sensitizer. Iodonium salt compounds are more preferred. An iodonium salt compound is susceptible to sensitization by a photosensitizer having absorption in the visible light region.

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

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

[Formula (2)]
[(R1)₂I]⁺ [A]^-

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The dental curable composition of the present invention preferably contains 0.1 to 10 parts by mass of (B2) a photoacid generator with respect to 100 parts by mass of the total amount of (A) polymerizable monomers, more preferably. is 0.2 to 5 parts by mass. If the amount of the photoacid generator is less than 0.1 parts by mass, the expected polymerization accelerating ability may not be exhibited, resulting in insufficient curing. If the amount is more than 10 parts by mass, sufficient curability is exhibited, but the ambient light stability may be shortened and the operating time may be shortened, or discoloration such as the cured product may become brownish.

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

The dental curable composition of the present invention comprises (B2) an anion having an organic group and at least one atom of P, B, Al, S and Ga as a photoacid generator, and an aryliodonium cation. It may contain only an aryliodonium salt that is a salt. The dental curable composition of the present invention comprises (B2) a photoacid generator containing at least one or more H-substituted organic groups and one or more of P, B, Al, S and Ga. It may contain only salts of anions having atoms and aryliodonium cations.

<(C) Chemical polymerization initiator>
When the dental curable composition of the present invention does not contain (B) a photopolymerization initiator (B1) a photosensitizer and (B2) a photoacid generator, (C) a chemical polymerization initiator (C1) Contains organic peroxides. In addition, even when (B) a photopolymerization initiator (B1) photosensitizer and (B2) a photoacid generator are included, (C) the chemical polymerization initiator includes (C1) an organic peroxide. be able to. (C) The chemical polymerization initiator is not particularly limited, and commonly used known compounds can be used without any limitation.

<(C1) Organic Peroxide>
The (C1) organic peroxide used as the (C) chemical polymerization initiator used in the dental curable composition of the present invention includes diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, Examples include 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. peroxide and the like. Specific examples of peroxyesters include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2 -ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexa hydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate and t-butylperoxymalelic acid. Specific examples of dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne. Specific examples of peroxyketals include 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, n-butyl 4,4-(t-butylperoxy) oxy)parerate, 1,1-di(t-amylperoxy)cyclohexane and the like. Specific examples of ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide and cyclohexanone peroxide. Specific examples of peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, and diisopropylperoxydicarbonate. , di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate and diallyl peroxydicarbonate. Specific examples of hydroperoxides include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide and 1,1,3, 3-tetramethylbutyl hydroperoxide and the like.

The curable dental composition of the present invention may use the exemplified organic peroxides alone or in combination of two or more. Among these organic peroxides, diacyl peroxides, peroxyesters, and hydroperoxides are preferred from the viewpoint of curability, such as benzoyl peroxide, cumene hydroperoxide, and 1,1,3,3-tetramethylbutyl. Hydroperoxide, t-butylperoxy-3,3,5-trimethylhexanoate is preferred. From the viewpoint of improving curability, the organic peroxide as a chemical polymerization initiator is preferably set to 0.1 to 5 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer (A). is set to 0.3 to 3 parts by mass. If the amount of the organic peroxide blended is more than 5 parts by mass, it may be difficult to ensure a sufficient operating time. May lack mechanical strength.

[(D) Polymerization accelerator]
The (D) polymerization accelerator used in the dental curable composition of the present invention is not particularly limited as long as it has the ability to accelerate polymerization, and known polymerization accelerators generally used in the dental field may be used without any restrictions. can be done. (D) Polymerization accelerators include aromatic amine compounds, primary to tertiary amine compounds such as aliphatic amine compounds, phosphine compounds, organometallic compounds, 4th period transition metal compounds, thiourea derivatives, sulfinic acid and A salt thereof, a borate compound, a reducing inorganic compound containing sulfur, a reducing inorganic compound containing nitrogen, a barbituric acid derivative, a triazine compound, a halogen compound, or the like is used as a photopolymerization accelerator and/or a chemical polymerization accelerator. be able to. Each compound can be used as an accelerator for photopolymerization and chemical polymerization, and amine compounds, phosphine compounds, sulfinic acids and salts thereof, and organometallic compounds that can be particularly used as photopolymerization accelerators, especially chemical polymerization accelerators. Agents that can be used include aromatic amine compounds, phosphine compounds, organometallic compounds, 4th period transition metal compounds, thiourea derivatives, sulfinic acid and its salts, borate compounds, reducing inorganic compounds containing sulfur, and nitrogen-containing compounds. They can be classified as reducing inorganic compounds, barbituric acid derivatives, triazine compounds, and halogen compounds contained.

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

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

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

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

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

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

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

Specific examples of thiourea derivatives include dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl)thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea, N-allyl-N'-(2- hydroxyethyl)thiourea, N-benzylthiourea, 1,3-dicyclohexylthiourea, N,N'-diphenylthiourea, 1,3-di(p-tolyl)thiourea, 1-methyl-3-phenylthiourea, Examples include N-acetylthiourea, N-benzoylthiourea, diphenylthiourea and dicyclohexylthiourea. Among these, (2-pyridyl)thiourea, N-acetylthiourea, and N-benzoylthiourea are preferred. A plurality of types of these thiourea derivatives may be used in combination if necessary. The amount of the thiourea derivative is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer (A). However, if the amount exceeds 5 parts by mass, the storage stability may deteriorate.

Specific 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, and benzene. sodium sulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzene potassium sulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate , 2,4,6-triethylbenzenesulfinate potassium, 2,4,6-triethylbenzenesulfinate lithium, 2,4,6-triethylbenzenesulfinate calcium, 2,4,6-triisopropylbenzenesulfinate, 2 , Sodium 4,6-triisopropylbenzenesulfinate, Potassium 2,4,6-triisopropylbenzenesulfinate, Lithium 2,4,6-triisopropylbenzenesulfinate, Calcium 2,4,6-triisopropylbenzenesulfinate etc., and sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferred.

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

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

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

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

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

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

(D) The polymerization accelerator is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 100 parts by mass based on 100 parts by mass of the total amount of the polymerizable monomer (A) contained in the dental curable composition. It is preferable to contain 5 parts by mass. If it is less than 0.2 parts by mass, the mechanical strength may be insufficient. When the amount is more than 10 parts by mass, the curing property is sufficient, but the stability against ambient light is shortened, and discoloration such as brown or yellowishness of the cured product may increase, which is not preferable.

These (B1) photosensitizer, (B2) photoacid generator, (C1) organic peroxide, and (D) polymerization accelerator are finely pulverized, adsorbed on a carrier, encapsulated in microcapsules, or the like, if necessary. There is no problem even if the secondary processing is performed. Furthermore, these various types of photopolymerization initiators may be used alone or in combination of two or more types regardless of the polymerization mode or polymerization method.

[(E) filler]
As the (E) filler used in the present invention, commonly used known fillers can be used without any limitation.

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

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

Among inorganic fillers, inorganic fine particles having an average primary particle diameter of 0.1 to 50 nm can be included. Specific examples include alumina fine particles and silica fine particles. When mixed with such inorganic fine particles, improvement in mechanical properties and expression of rheological properties can be expected. Further, it is preferably hydrophobized with a silane coupling agent or the like. The primary particle size indicates the diameter of one particle (primary particle) that constitutes the powder. Here, the average particle size in the present invention can be an average particle size calculated based on a volume-based particle size distribution measured by, for example, a laser diffraction particle size distribution measuring device. It can be measured with a machine (Microtrac MT3300EXII: manufactured by Nikkiso Co., Ltd.). In addition, the primary particle size can be measured using dynamic light scattering particle size measurement, or electron micrographs for particles in which primary particles are strongly agglomerated to form secondary particles.

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

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

<(E1) Surface-treated basic filler>
As the (E1) surface-treated basic filler that can be used in the present invention, a known filler that is generally used in dental composite materials can be used. 1.0 g of a filler is added and stirred for 1 hour, and the pH of the dispersion is 7.5 or more, preferably 7.5 to 10.0, more preferably 7.5 to 10.0. is 7.7 to 9.0, more preferably pH is 8.0 to 9.0.

The curable dental composition of the present invention is expected to have improved storage stability when it contains (E1) a surface-treated basic filler. When the compound used as the polymerization initiator and the basic filler coexist for a long period of time, there is a problem of storage stability. By treating the surface of with a surface treatment agent, the storage stability when coexisting with the polymerization initiator is improved. Among polymerization initiators, particularly high storage stability is exhibited when coexisting with a compound such as a photoacid generator or an organic peroxide. In addition, since the (E1) surface-treated basic filler has moderate basicity, it is expected to neutralize the acid derived from the photoacid generator or the polymerizable monomer having an acidic group, for example, after long-term storage. It is thought that good storage stability can be expected by suppressing hydrolysis of the composition. Good storage stability can be expected in both pre-cured and post-cured forms. Furthermore, when the surroundings of the cured product of the dental curable composition are under acidic conditions, it can be expected to develop an acid-neutralizing ability capable of neutralizing acid. Since demineralization of dentin composed of enamel and dentin proceeds under acidic conditions, neutralization of acid is expected to have an effect of suppressing demineralization.

Types of basic fillers include inorganic fillers, organic fillers, organic-inorganic composite fillers, etc. They can be used not only singly, but also in combination regardless of the type of filler. can be done.

Fillers that can be used as basic fillers are not particularly limited, but are preferably oxides or hydroxides, fluorides, carbonates, silicic acids containing metal elements of groups 2 to 13 of the periodic table. A compound selected from at least one of salts or mixtures thereof, polyvalent metal alkoxides, polyvalent metal hydrides, and alkyl polyvalent metals. The valence of the polyvalent metal compound is not particularly limited as long as it is divalent or higher.

Specific examples of typical basic fillers include oxides such as alumina, calcia, and magnesia; hydroxides such as calcium hydroxide, magnesium hydroxide, and strontium hydroxide; and fluorides. As magnesium fluoride, calcium fluoride, barium fluoride, strontium fluoride, aluminum fluoride, titanium fluoride, lanthanum fluoride, zirconium fluoride, zinc fluoride, etc., as carbonates, magnesium carbonate, strontium carbonate, etc. Calcium carbonate, barium carbonate, aluminum carbonate, lanthanum carbonate, yttrium carbonate, zirconium carbonate, zinc carbonate, etc. Silicates include calcium silicate, aluminum silicate, fluoroaluminosilicate glass, fluoroaluminoborosilicate glass, and other silicate glasses. mentioned. Among them, fluoroaluminosilicate glass containing strontium and/or calcium ions, and fluoroaluminoborosilicate glass containing strontium and/or calcium ions are preferable, and the composition range thereof is SiO ₂ : 15 to 35% by mass and Al ₂ O ₃ : 15 to 30% by mass, SrO: 20 to 45% by mass, P ₂ O ₅ : 0 to 15% by mass, F: 5 to 15% by mass, Na ₂ O: 0 to 10% by mass, B ₂ O ₃ : 0 to 20% by mass % and CaO: 0 to 10% by mass are preferable from the viewpoint of storage stability. Particularly preferably, the total content of Al ₂ O ₃ and SrO is 40 to 60 mass % in the above composition range. If the total amount of Al ₂ O ₃ and SrO is less than 40% by mass, the high basicity may not be maintained and the color tone stability may be low, and the total amount of Al ₂ O ₃ and SrO is 60% by mass. If it is larger, the filler may become too basic.

The organic group in the polyvalent metal alkoxide is not particularly limited, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, octyl and the like. An alkyl group having 4 or less carbon atoms is preferred. The alkyl group in the alkyl polyvalent metal is not particularly limited, and examples thereof include alkyl groups having 1 to 20 carbon atoms. In addition, these may be used individually by 1 type, and may use 2 or more types together.

Specific compounds of the polyvalent metal alkoxide include, for example, magnesium diethoxide, calcium diisopropoxide, barium diisopropoxide, aluminum triethoxide, aluminum triisopropoxide, gallium triethoxide, scandium triethoxide, isopropoxide, lanthanum triisopropoxide, ytterbium triisopropoxide, yttrium tetraisopropoxide, cerium tetraisopropoxide, samarium tetraisopropoxide, titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, zirconium tetraisopropoxide, hafnium tetraisopropoxide, tantalum (V) ethoxide, chromium (III) isopropoxide, molybdenum (V) ethoxide, tungsten (VI) isopropoxide, iron (III) ethoxide, copper (II) ethoxide, zinc (II) ethoxide and the like.

Specific compounds of the polyvalent metal hydride include, for example, calcium hydride, aluminum hydride, zirconium hydride, etc. Specific compounds of the alkyl polyvalent metal include, for example, diethylmagnesium, trimethylaluminum and the like.

The shape of the basic filler is not particularly limited, and amorphous and spherical fillers can be used. The average particle size of the basic filler is preferably 0.01 μm to 50 μm, more preferably 0.1 μm to 30 μm, still more preferably 0.5 μm to 20 μm, more preferably 0.5 μm to 10 μm. It has an average particle size.

A basic filler having an average particle size of 0.01 μm to 50 μm can be obtained by wet pulverizing inorganic particles as a raw material of the basic filler. Wet pulverization does not require a special method and can be carried out by adopting a method generally used in the industry. For example, the raw material inorganic particles can be pulverized using a container driven medium mill such as a ball mill or a vibration mill, or a pulverizing medium stirring mill such as an attritor, sand grinder, aniler mill or tower mill. As the medium, water or a mixed solvent of water and a water-soluble organic solvent can be used. Water-soluble organic solvents include alcohols, ketones such as acetone, and ethers. When these water-soluble organic solvents are used, the cohesive force of the solidified product after drying may be weakened, making it easier to pulverize. Wet pulverization conditions vary depending on the size and hardness of the raw material inorganic particles, the amount charged, the amount of water or aqueous medium added, the type of pulverizer, etc., but the pulverization operation time varies depending on the average particle size of the inorganic fine particles required. can be selected as appropriate.

The amount of filler (E) in the dental curable composition is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the total amount of polymerizable monomers (A). It is preferably less than 400 parts by mass. If the amount of the filler is less than 10 parts by mass, the effect of improving the mechanical strength and developing thixotropic properties may be poor. Since it becomes hard, it may be difficult to handle, but it may be contained in an amount of 1000 parts by mass or more depending on the type of filler and the surface treatment conditions of the filler. For example, it refers to a case where the filler has a high specific gravity, a case where the amount of the surface treatment agent to the filler is large, or a case where a surface treatment agent having good affinity with the polymerizable monomer is used. The effect of the composition of the present invention is exhibited regardless of the amount of filler compounded. In addition, in the case of a dental curable composition packaged in a plurality of two or more agents, since a mixing operation is required, (A) 10 to 400 parts by mass per 100 parts by mass of the total amount of polymerizable monomers part is preferred.

The amount of the (E1) surface-treated basic filler in the dental curable composition of the present invention is preferably 10 to 500 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the total amount of the polymerizable monomers (A). It is preferably less than parts by mass. If the content is less than 10 parts by mass, the effect of improving storage stability may not be exhibited. If the amount is more than 500 parts by mass, the composition may become hard and difficult to handle. In the case of a dental curable composition divided into two or more parts, since a mixing operation is required, (A) 10 to 500 parts by weight per 200 parts by weight of the total amount of polymerizable monomers, More preferably 10 to 400 parts by mass.

<(F) Surface treatment agent>
(E) The filler is a surfactant, polymer, or silane cup for the purpose of improving affinity with the polymerizable monomer, dispersibility in the polymerizable monomer, mechanical strength and water resistance of the cured product. It can be treated with (F) a surface treatment material typified by a ring material. The surface treatment material and surface treatment method are not particularly limited, and known methods can be employed without limitation.

Silane coupling agents used for surface treatment of fillers include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris(2-methoxysilane). ethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 8-(meth)acryloxy Octyltrimethoxysilane, 11-(meth)acryloxyundecyltrimethoxysilane, 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silaicosan-20-yl (meth)acrylate, 2-methyl-2-((((11-(triethoxysilyl)undecyl)oxy)carbonyl)amino)propane-1,3-diyl di(meth)acrylate, 4,4-diethoxy-17-oxo-3,16 , 21-trioxa-18-aza-4-silatricosan-23-yl (meth)acrylate or hexamethyldisilazane are preferred. In addition to the silane coupling agent, the filler can be surface-treated by a method using a titanate-based coupling agent or an aluminate-based coupling agent.

The silane coupling agent used as the surface treatment of the filler and the silane coupling agent as (A) the polymerizable monomer are used separately. The silane coupling agent with a polymerizable group used for the surface treatment of the filler reacts with the filler and cannot be expected to exhibit adhesion to glass ceramics. When a silane coupling agent (A) is added as a polymerizable monomer for imparting, it is blended separately from the surface treatment agent.

The acidic polymer that can be used for the surface treatment of the filler is a polymerizable unit having an acidic group such as a phosphoric acid residue, a pyrophosphoric acid residue, a thiophosphoric acid residue, a carboxylic acid residue, and a sulfonic acid group. are copolymers or homopolymers of the monomers. Examples of polymerizable monomers having these acidic groups include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, 4-(meth)acryloyloxyethoxycarbonyl phthalic acid, 4-(meth)acryloyloxyethoxycarbonyl phthalic anhydride, 5-(meth)acryloylaminopentylcarboxylic acid, 11-(meth)acryloyloxy-1, 1-undecanedicarboxylic acid, 2-(meth)acryloyloxyethyl dihydrogenphosphate, 10-(meth)acryloyloxydecyldihydrogenphosphate, 20-(meth)acryloyloxyeicosyldihydrogenphosphate, 1,3- Di(meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl phosphate, 2-(meth)acryloyloxyethyl-2'-bromoethyl phosphate, (meth)acryloyloxyethyl phosphate phenyl phosphonate, di(2-(meth)acryloyloxyethyl) pyrophosphate, 2-(meth)acryloyloxyethyl dihydrogendithiophosphate, 10-(meth)acryloyloxydecyldihydrogenthiophosphate and the like.

The treatment amount of the surface treatment material with respect to the filler is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass, per 100 parts by mass of the filler before treatment. If the amount is less than 0.1 part by mass, the improvement in mechanical properties and paste properties expected of the surface treatment agent may not be remarkable, and if it exceeds 40 parts by mass, the amount of the surface treatment agent to the filler Because of the large amount of

<(F1) surface treatment agent represented by formula (1) and/or condensate thereof>
The above-mentioned (E1) surface-treated basic filler is surface-treated with (F1) a surface-treating agent represented by formula (1) and/or a condensate thereof.

（式中、ＭはＳｉ、Ｔｉ、Ｚｒ、Ａｌから選ばれる金属原子、ＸはＨ、ＯＨ、加水分解性基であり、互いに同一でも異なっても良い。ＭがＳｉ、Ｔｉ、Ｚｒである場合にｎは４であり、ＭがＡｌである場合にｎは３である。） That is, the dental curable composition of the present invention contains (F1) a surface-treated basic filler surface-treated with a surface-treating agent represented by formula (1) and/or a condensate thereof (E1).
[Formula (1)]

(In the formula, M is a metal atom selected from Si, Ti, Zr and Al, X is H, OH, a hydrolyzable group, which may be the same or different. When M is Si, Ti, Zr where n is 4, and n is 3 when M is Al.)

(F1) The hydrolyzable group in the surface treatment agent represented by formula (1) and/or its condensate refers to an alkoxy group or a halogen group, specifically a methoxy group, an ethoxy group, an isopropoxy group, n-butoxy group, t-butoxy group, and chloro group can be mentioned, and from the viewpoint of handling, an alkoxy group is preferable, and a methoxy group or an ethoxy group is more preferable. (F1) When used in a dental curable composition by using (E1) a surface-treated basic filler surface-treated with a surface-treating agent represented by formula (1) and/or a condensate thereof storage stability is improved.

(F1) The surface treatment agent represented by formula (1) and/or its condensate is preferably heated to 130°C or higher during the surface treatment process for the filler. An improvement in storage stability can be expected by setting the temperature to 130° C. or higher. It is considered that this is because the reaction between the basic filler and the surface treatment agent progresses easily. On the other hand, if the temperature is less than 130°C, the improvement in storage stability may not be sufficient. Even if the temperature is less than 100°C, it can be expected to improve the storage stability when it is blended in a dental curable composition by exposing it to a temperature for a long time of several days, but it requires a long period of time for production. I don't like it.

(F1) The surface treatment agent represented by formula (1) and/or its condensate is preferably calcined at 400°C or less during the surface treatment of the filler. If the temperature exceeds 400° C., the acid-neutralizing ability may not be sufficiently exhibited when the cured product of the dental curable composition is immersed in an acidic aqueous solution. When the oral cavity environment is under acidic conditions for a long period of time, demineralization of tooth substance progresses. In particular, it is remarkable in the restoration part of the tooth, and secondary caries etc. may occur in such a case. The acid-neutralizing ability of the curable dental composition refers to the ability to increase the pH of the surroundings of the curable dental composition when the pH is under acidic conditions. To give a specific example of the method for measuring the acid neutralization ability, the pH of a hardened dental curable composition having a diameter of 15 mm and a thickness of 1 mm was immersed in 5 mL of an aqueous lactic acid solution having a pH of 4.0 for 24 hours. is 4.5 or more, more preferably 5.0 or more. Suppression of tooth demineralization can be expected by using a dental curable composition having an acid-neutralizing ability.

(F1) The surface treating agent represented by formula (1) and/or its condensate does not have a polymerizable group. In the case where a polymerizable group is contained, long-term exposure to high heat of 130° C. or higher causes coloring of the filler or impurities that adversely affect the properties of the dental curable composition, and therefore does not result in good storage stability. There is This tendency is remarkable in those having a polymerizable group among organic groups. Moreover, when a plurality of organic groups having steric hindrance such as polymerizable groups are contained, the surface of the filler may not be uniformly surface-treated. On the other hand, a hydrolyzable group containing an organic group is removed as a volatile component before remaining on the surface of the filler, or can be washed as a free component, so there is no problem.

(F1) surface treating agent represented by formula (1) and/or a condensate thereof that corresponds to formula (1) used for producing (E1) the surface-treated basic filler of the present invention Examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, tetraphenoxysilane, tetrachlorosilane, silicon hydroxide (silicon oxide hydrate), zirconium tetra -n-butoxide, zirconium tetra-t-butoxide, zirconium tetrapropoxide, tetraethyl orthotitanate, tetraisopropyl orthotitanate, dichlorotitanium diisopropoxide, tetrabutyl orthotitanate, tetraisobutyl orthotitanate, tetrakis orthotitanate (2-ethylhexyl), aluminum ethoxide, aluminum isopropoxide, aluminum-sec-butoxide, aluminum-tert-butoxide, etc., and more preferably tetramethoxysilane and tetraethoxysilane.

Furthermore, (F1) is a partial condensate obtained by partially hydrolyzing and condensing tetramethoxysilane or tetraethoxysilane among the surface treating agent represented by formula (1) and/or its condensate. Specific examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, trimethoxychlorosilane, triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane, diethoxysilane. chlorosilane, tetraphenoxysilane, tetrachlorosilane, silicon hydroxide (silicon oxide hydrate), zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium tetrapropoxide, tetraethyl orthotitanate, tetraisopropyl orthotitanate, Dichlorotitanium diisopropoxide, tetrabutyl orthotitanate, tetraisobutyl orthotitanate, tetrakis(2-ethylhexyl) orthotitanate, aluminum ethoxide, aluminum isopropoxide, aluminum-sec-butoxide, aluminum-tert-butoxide, etc. Partial condensates can be exemplified, and these compounds can be condensed singly or in combination. The partial condensate is a condensate formed by hydrolysis and / or dehydration condensation of the surface treatment agent represented by formula (1), not all of the bonds possessed by the surface treatment agent form covalent bonds. , refers to a state in which a hydrolyzable group, an OH group, or H that can be sufficiently bonded is present due to a partial condensation reaction. Furthermore, the condensate may have OH groups for all or part of the functional groups that bind to the metal atoms. If the condensate does not have hydrolyzable groups, the generation of volatile substances can be reduced.

Furthermore, these coupling agents may be used together with the surface treatment agent represented by formula (1) (F1) and/or its condensate during film formation, and an organosilane compound having no polymerizable group may also be added. can. Specific examples of organosilane compounds include methyltrimethoxysilane, ethyltrimethoxysilane, methoxytripropylsilane, propyltriethoxysilane, and methyltrichlorosilane. Particularly preferred are methyltrimethoxysilane and ethyltrimethoxysilane. These compounds can be used alone or in combination. However, since organic groups are present in the coating of the coupling agent condensate, they may be subjected to strain during the formation of the coating of the coupling agent condensate, which may cause problems in mechanical strength. In addition, when forming the coating of the condensate of the coupling agent (F1), in combination with the surface treatment agent represented by the formula (1) and/or the condensate thereof, alkoxide compounds, halides, hydrated oxides and nitrates of other metals , carbonates can also be added.

By treating the surface of the basic filler with the above compound, a film is formed on the surface of the basic filler by condensation of the coupling agent. The surface treatment method is performed, for example, as follows. (F1) A surface treatment agent represented by formula (1) and/or a condensate thereof is added to the resulting aqueous dispersion of basic filler after pulverization or pulverization to a desired average particle size. They are mixed, hydrolyzed or partially hydrolyzed and then condensed or dispersed in the system. In the film forming method described above, the hydrolysis and condensation of the coupling agent and the film formation on the surface of the basic filler proceed simultaneously in the same system. A film-forming method in which a low-condensation coupling agent is produced in a system and mixed with an aqueous dispersion of a basic filler obtained in a wet pulverization process or a wet dispersion process is more efficient than the basic filler surface. It is possible to form a film on More preferred is a film-forming method in which a commercially available low-condensation coupling agent is used and mixed without undergoing a low-condensation formation process. The reason why this method is preferable is that when a monomeric coupling agent is used, a large amount of water is present in the film formation process, so condensation occurs three-dimensionally, self-condensation proceeds predominantly, and uniform It is believed that a film cannot be formed on the basic filler surface.

On the other hand, when a low-condensation coupling agent is used, it is considered possible to uniformly form a film on the surface of the basic filler in unit units having a main chain of a certain length. The shape of the low-condensation coupling agent is not particularly limited, but a straight-chain shape is preferable to a three-dimensional one. The degree of polymerization is preferably in the range of 2 to 100 because formation of a coupling agent condensate film on the surface is poor. Specifically, (F1) the surface treatment agent represented by formula (1) and/or its condensate is a partial condensate of 2 to 100 molecules of tetraalkoxysilane or a partial condensation of 2 to 100 molecules of tetraalkoxysilane. It is preferably a polysiloxane in which all or part of the alkoxy groups in the body are substituted with OH groups. A partial condensate of 2 to 10 molecules is more preferable, and the molecular weight thereof is in the range of 500 to 1,000. In addition, when preparing a linear low-condensation coupling agent in another system, it is necessary to use a small amount of water so that the hydrolysis and condensation of the coupling agent can partially proceed. Alternatively, it is possible by using a catalyst used in other sol-gel methods. As a result, the system becomes finely dispersed without association of the basic filler having an average particle size of 0.01 to 10 μm in the aqueous medium in which the coupling agent condensate is dispersed.

The hydrolysis or partial hydrolysis of the coupling agent in the aqueous dispersion is carried out under relatively slow stirring conditions at a temperature in the range of room temperature to 100°C, more preferably in the range of room temperature to 50°C for a stirring time. It is usually carried out for several minutes to several tens of hours, more preferably 30 minutes to 4 hours. Stirring does not require a special method, and can be carried out using equipment commonly used in the general industry. For example, an agitator capable of agitating a slurry such as a universal mixing agitator or a planetary mixer can be used. There is no problem if the stirring temperature is below the boiling point of the aqueous medium. The stirring time depends on the type and amount of coupling agent or low-condensation coupling agent added, the type of inorganic fine particles, the particle size and its proportion in the aqueous dispersion, the type of aqueous medium and the proportion in the aqueous dispersion, and condensation The rate of gel formation is affected and must be adjusted and until a gel is formed. If the stirring speed is too high, the gel structure will collapse and a uniform film will not be formed. As used herein, the term "gel" refers to a creamy or jelly-like swelling caused by growth of condensation and absorption of an aqueous medium. For the purpose of increasing the gelation rate, addition of a sol-gel catalyst such as an acid, an alkali, an organometallic compound, a metal alkoxide, or a metal chelate compound is a preferred mode in terms of increasing the gelation rate. Examples of specific catalysts include inorganic acids such as hydrochloric acid, acetic acid, nitric acid, formic acid, sulfuric acid, and phosphoric acid; organic acids such as paratoluenesulfonic acid, benzoic acid, phthalic acid, and maleic acid; potassium hydroxide; sodium hydroxide; Basic catalysts such as ammonia can be mentioned. The acid or alkali used as a catalyst not only adjusts the gelation speed but also plays a major role in charging the surface of the inorganic fine particles as a pH adjuster, thereby forming a uniform film. However, since acids or bases affect the material of the inorganic fine particles, it is necessary to select their use as appropriate. Also, by adding alcohol in this step, there is a significant effect of reducing the agglomeration of the inorganic fine particles in the drying step and further improving the pulverization property. Preferred alcohols are alcohols having 2 to 10 carbon atoms, but the addition of alcohols having 10 or more carbon atoms has a high boiling point and requires a long time to dry and remove the solvent. Specific alcohols include ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, iso-butyl alcohol, n-pentyl alcohol, iso-amyl alcohol, n-hexyl alcohol n-heptyl alcohol, n-octyl alcohol and n-dodecyl alcohol, more preferably alcohols having 2 to 4 carbon atoms such as ethyl alcohol, n-propyl alcohol and iso-propyl alcohol. The amount of alcohol added is 5 to 100% by mass, preferably 5 to 20% by mass, based on water. This addition amount is the addition amount including the amount of alcohol contained in the wet pulverization process or the wet dispersion process. If the amount added is 100% by mass or more, problems such as a complicated drying process occur. The basic filler content is in the range of 25 to 100% by mass, preferably 30 to 75% by mass, relative to the aqueous medium. If the content exceeds 100% by mass, the speed of gelation due to condensation is high, making it difficult to form a uniform film. phase separation occurs. The amount of the coupling agent added depends on the particle size of the basic filler, but is in the range of 0.1 to 10% by mass, preferably 0.1 to 4%, in terms of SiO ₂ with respect to the basic filler. % by mass. If the amount added is 0.1% by mass or less, there is no effect of forming a film, and the primary particles cannot be crushed and aggregated. cannot be crushed.

The system in such a gel state is then dried and solidified by removing the aqueous medium. Drying consists of two stages, aging and baking, the former aiming to grow the gel structure and remove the aqueous medium, and the latter to strengthen the gel structure. The former does not distort the gel structure and removes the aqueous medium, so it must be left standing, and equipment such as a box-type hot air dryer is preferable. The aging temperature is in the range of room temperature to 100°C, more preferably in the range of 40-80°C. If the temperature is lower than this range, the removal of the aqueous medium is insufficient, and if it is higher than this range, it may volatilize rapidly, causing defects in the gel structure or exfoliation from the surface of the basic filler. . Since the aging time depends on the capacity of the dryer, etc., there is no problem as long as the time is enough to remove the aqueous medium. On the other hand, the firing process is divided into temperature rise and mooring. In the former, it is better to gradually raise the temperature to the target temperature over a long period of time. may occur. The latter is calcination at a constant temperature for a period of 1 hour to 100 hours, preferably 2 hours to 75 hours, more preferably 5 hours to 50 hours. The longer this time is, the more effective it is, but the effect is not recognized after a certain period of time. The firing temperature is in the range of 100-500°C, preferably 100-450°C, more preferably 130-400°C. This temperature must be selected appropriately so as not to affect the raw material of the basic filler and to the extent that the porous gel structure is not made non-porous. As described above, the aqueous medium is removed from the gel by drying to obtain a shrunk solid. Although the solidified product is in the state of agglomeration of the basic filler, it is not a mere agglomeration of the basic filler, and a film formed by condensation is interposed at the interface between individual fine particles. Therefore, in the next step, this solidified product is pulverized to a level equivalent to that of the basic filler before film formation, to obtain individual inorganic fine particles coated on the surface, ie, the inorganic filler of the present invention. Here, "crushing equivalent to the basic filler before film formation" means crushing to the basic filler. is covered with However, secondary agglomerates may be included as long as there is no problem. The solidified material can be easily pulverized by applying a shearing force or an impact force, and the pulverization method can be performed using, for example, a Henschel mixer, a cross rotary mixer, a super mixer, or the like.

The basic filler is (F1) surface-treated with a surface-treating agent represented by formula (1) and/or a condensate thereof, and then surface-treated with a silane coupling agent having a polymerizable group and/or an acidic polymer. treatment is preferred. By surface-treating with a silane coupling agent having a polymerizable group, it is possible to copolymerize with a polymerizable monomer, so improvement in mechanical strength can be expected. In addition, surface treatment with an acidic polymer increases the amount of ions released, thereby improving the acid-neutralizing ability.

(E1) By treating the surface-treated basic filler with a silane coupling agent having a polymerizable group, affinity for the polymerizable monomer, dispersibility in the polymerizable monomer, mechanical properties of the cured product, The effect of improving strength and water resistance is also exhibited. A silane coupling agent having a polymerizable group forms a silanol bond with a silanol group on the surface of the filler. A coating of the coupling agent condensate is formed on the surface of the filler by performing surface treatment on the body. In particular, when the surface treatment agent represented by formula (1) and/or its condensate (F1) is a silane coupling agent, a large number of silanol groups are introduced as reaction sites of the silane coupling agent having a polymerizable group. It is Therefore, since the silane coupling agent having more polymerizable groups can be reacted with the surface of the filler, the wettability of the basic filler to the polymerizable monomer is improved, and the curable composition for dental use It becomes possible to incorporate more (E1) surface-treated basic filler, which improves the mechanical strength of the dental curable composition.

The surface treatment method of the silane coupling agent having a polymerizable group is not particularly limited, and known methods can be employed without limitation. The amount of treatment with the surface treatment material in the basic filler is preferably 0.01 to 30 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the filler before treatment from the viewpoint of not reducing basicity. more preferred.

When the basic filler contains an acid-reactive element, surface treatment with an acidic polymer causes the acid-reactive element contained in the basic filler to undergo a cement reaction with the acidic polymer, resulting in A cement reaction phase can also be formed. A coating layer of the coupling agent condensate exists on the surface of the basic filler, and since this coupling agent condensate coating layer has a porous gel structure, the acidic polymer permeates the coupling agent condensate coating. and reaches the surface of the basic filler while diffusing. Acidic polymers that reach the filler surface undergo an acid-base reaction to form a cement layer. The presence of this cement layer is expected to increase the amount of ions released from the basic filler, which in turn improves the acid neutralization ability and captures ions when there is a large amount of ions around the basic filler. can.

More preferred acid-reactive elements are metal elements belonging to Groups I, II and III of the periodic table, and particularly preferred are sodium, potassium, calcium, strontium, lanthanum and aluminum. Specific examples of these basic fillers include aluminum silicate, aluminum oxide, various glasses (including melting glass, gas phase reaction glass, sol-gel synthetic glass, etc.), strontium fluoride, Calcium carbonate, kaolin, mica, aluminum sulfate, calcium sulfate, barium sulfate, calcium phosphate, calcium hydroxide, strontium hydroxide, zeolite, hydroxyapatite, aluminum nitride and the like. Glasses are particularly preferred. Glass is lower in hardness than silica compounds, has excellent optical transparency, and can contain elements that block X-rays and fluorine. preferable. Most preferred are alumina silicate glass, borosilicate, alumina borate and boro-alumina silicate glass containing heavy metals such as strontium, barium and lanthanum and fluorine.

If the acid-base reaction is too fast, the formation of the cementitious phase will be non-uniform. Homopolymers or copolymers of unsaturated carboxylic acids are preferred. Acrylic acid polymers, acrylic acid-maleic acid copolymers, and acrylic acid-itaconic acid copolymers are more preferred.

When the basic filler of the present invention contains fluorine, the dental curable composition can be endowed with fluorine sustained release performance. Examples of fluorine-containing basic fillers include sodium fluoride, strontium fluoride, lanthanum fluoride, ytterbium fluoride, yttrium fluoride, and calcium-containing fluoroaluminasilicate. In addition, in order for the inorganic filler of the present invention to have X-ray contrast performance, the core basic filler must contain a heavy metal. Lanthanum oxide, ytterbium fluoride, yttrium fluoride, lanthanum-containing fluoroaluminasilicate, and strontium-containing fluoroaluminasilicate are used.

For the acidic polymer used for the surface treatment of the basic filler, in addition to the polymerizable monomer having an acidic group, a polymerizable monomer that does not contain an acidic group is used to form a cement reaction phase with the basic filler. It may be included as long as it does not cause any trouble.

For the method of reacting the basic filler with the acidic polymer, equipment commonly used in the industry can be used as long as it is a dry fluidized agitator, and examples thereof include Henschel mixers, super mixers, and high-speed mixers. . The reaction of the acidic polymer with the basic filler containing the acid-reactive element coated with the coupling agent condensate can be carried out by simply contacting the basic filler with the acidic polymer solution, such as by impregnation. For example, a basic filler coated with a condensate of a coupling agent is dry-fluidized, and the acidic polymer solution is dispersed from above in the fluidized state, followed by thorough stirring. At this time, the method for dispersing the acidic polymer solution is not particularly limited, but a dropping or spraying method that enables uniform dispersion is more preferable. Moreover, the reaction is preferably carried out at around room temperature. If the temperature rises, the reaction between the acid-reactive element and the acidic polymer will be accelerated, resulting in non-uniform formation of the cement phase.

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

The solvent used for preparing the acidic polymer solution used in the reaction is not particularly problematic as long as it dissolves the acidic polymer, and examples thereof include water, ethanol, and acetone. Especially preferred among these is water, which dissociates the acidic groups of the acidic polymer and can uniformly react with the surface of the core basic filler. On the other hand, other solvents react insufficiently with the surface of the basic filler, which is the core, and have residual unreacted acidic groups. Inhibition of polymerization of the polymerizable monomer and water absorption of the cured product cause deterioration of the material.

The weight average molecular weight of the polymer dissolved in the acidic polymer solution is in the range of 2000-50000, more preferably in the range of 5000-40000. Acidic polymers having a weight-average molecular weight of less than 2000 tend to lower the strength of the cement reaction phase and reduce material strength. Acidic polymers having a weight-average molecular weight exceeding 50,000 tend to increase the viscosity of the acidic polymer solution, making it difficult to diffuse in the coating (porous) of the coupling agent condensate, leaving residual unreacted acidic groups and having an adverse effect. The acidic polymer concentration in 100 parts by mass of the acidic polymer solution is preferably in the range of 3 to 25 parts by mass, more preferably in the range of 8 to 20 parts by mass. When the concentration of the acidic polymer is less than 3 parts by mass, the strength of the cement phase described above is weakened, and the fluidity of the surface-treated basic filler deteriorates due to the influence of water, and a uniform cement reaction phase is not formed. If the concentration of the acidic polymer exceeds 25 parts by mass, it becomes difficult to diffuse the coupling agent condensate film (porous), but on the other hand, when it comes into contact with the basic filler in the core, the acid-base reaction is rapid, and curing begins during the reaction. Problems such as aggregation occur. The amount of the acidic polymer solution added to the surface-treated basic filler is preferably 6 to 40 parts by mass, more preferably 10 to 30 parts by mass. In terms of this addition amount, the optimum amount of the acidic polymer is 1 to 7 parts by weight and the amount of water is 10 to 25 parts by weight with respect to the basic filler coated with the condensate of the coupling agent.

This reaction is affected by the surface area of the basic filler in the core, with a small surface area resulting in a slow acid-base reaction and a large surface area resulting in a fast reaction. In other words, the particle size distribution is important, and a basic filler with a monodisperse particle size distribution may cause the cement reaction phase to occur simultaneously. It is thought that the cement reaction phase can be formed efficiently and uniformly. In addition, due to the presence of the outermost coating of the coupling agent condensate, the acidic polymer reaches the surface of the coupling agent condensate, diffuses through the porous surface, and reaches the surface of the core of the basic filler. It controls the time until the cement reaction phase, which enables the formation of a uniform cement reaction phase. In the absence of the coupling agent condensate film, the reaction starts as soon as the acidic polymer comes into contact with the surface of the basic filler, causing bridging between particles, but this is also prevented.

The amount of the surface-treated basic filler (E1) in the paste is preferably 10 to 400 parts by mass, more preferably 50 to 400 parts by mass, more preferably 50 to 400 parts by mass based on 100 parts by mass of the polymerizable monomer (A). 100 to 400 parts by mass. If the amount of the basic filler is less than 10 parts by mass, the storage stability may not be improved, and if it is more than 400 parts by mass, the composition may become hard and difficult to handle. However, for example, when the filler is surface-treated with a large amount of surface-treating agent, good paste properties can be obtained even when 400 parts by mass or more of the filler is blended.

A basic filler that satisfies the above definition may be used alone, or two or more kinds of basic fillers may be used in combination. A non-basic filler may also be added to the dental curable composition of the present invention.

In the present invention, the non-basic filler refers to a dispersion having a pH of less than 7.5 based on the above definition of the preferable basic filler. , organic fillers, organic-inorganic composite fillers, etc., and they can be used not only singly but also in combination regardless of the type of filler. Examples include inorganic compounds containing silica as a main component, such as silica and silica-zirconia, and trifluoroytterbium.

As with basic fillers, non-basic fillers also aim to improve affinity with polymerizable monomers, dispersibility in polymerizable monomers, and mechanical strength and water resistance of cured products. It can be treated with a surface treatment agent typified by a silane coupling agent.

The shape of the non-basic filler is not particularly limited, and amorphous and spherical fillers can be used. Preferably, the non-basic filler has an average particle size in the range of 0.01 μm to 50 μm.

The dental hardenable composition of the present invention can be substantially free of water. When water is included, deterioration of storage stability and strength may occur. “Substantially containing water” means that water is intentionally added to the dental curable composition, excluding cases where it is contained as impurities or by-products in the raw materials, or where it is unintentionally contained during the manufacturing process. Refers to when The dental hardenable composition of the present invention can contain water for the purpose of dissolving raw materials, but even in such a case water is not preferably contained in the dental hardenable composition. On the other hand, if water can be removed from the final composition by heating, pressure reduction, or the like during the manufacturing process, it can be expected that the strength of the dental hardenable composition will not be affected. In the present invention, "substantially free of water" means that the amount of water contained in 100 parts by mass of the curable dental composition is less than 1 part by mass, preferably less than 0.1 part by mass.

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

The method for preparing the dental curable composition of the present invention is not particularly limited. As a general method for producing a dental curable composition, a matrix is prepared in advance by mixing (A) a polymerizable monomer and (BC) a polymerization initiator, and then this matrix and (E) a filler are kneaded. and a method of preparing a uniform paste by removing air bubbles under vacuum. The present invention can also be produced by the above production method without any problems.

The curable dental composition of the present invention includes a dental adhesive, a dental composite resin, a dental abutment building material, a dental resin cement, a dental coating, a dental pit and fissure sealing material, and a dental manicure. , dental loose tooth fixing adhesives, dental hard resins, dental cutting materials, and dental 3D printer materials.

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

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

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

Materials used in Examples and Comparative Examples and their abbreviations are shown below.
[(A) polymerizable monomer]
<(A1) Polymerizable monomer not corresponding to polymerizable monomer having acidic group>
Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane 2.6E: 2,2-bis with an average number of added moles of ethoxy groups of 2.6 (4-(meth)acryloyloxypolyethoxyphenyl)propane, UDMA: N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)ethanol]methacrylate, TEGDMA: triethylene glycol dimethacrylate・GDMA: glycerin dimethacrylate ・HEMA: 2-hydroxyethyl methacrylate ・NPG: neopentyl glycol dimethacrylate ・MOTMS: 8-methacryloxyoctyltrimethoxysilane ・MPTMS: 3-methacryloxypropyltrimethoxysilane ・MDDT: 10-methacrylate Roxydecyl-6,8-dithiooctanate

<(A1) Polymerizable Monomer Having Acidic Group>
・MDP: 10-methacryloyloxydecyl dihydrogen phosphate ・MHPA: 6-methacryloxyhexylphosphonoacetate ・MET: 4-methacryloyloxyethyl trimellitate ・META: 4-methacryloyloxyethyl trimellitate anhydride ・AET: 4-Acryloyloxyethyl Trimellitate

[(B) Photoinitiator]
<(B1) Photosensitizer>
・CQ: camphorquinone ・MAPO: diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide ・BAPO: phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide

・Ｂ２－２：ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウムトリス（ペンタフルオロプロピル）トリフルオロホスフェート

・Ｂ２－３：ｐ－クメニル（ｐ－トリル）ヨードニウムトリス（ペンタフルオロエチル）トリフルオロホスフェート

・Ｂ２－４： ビス（４－ｎ－ドデシルフェニル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボレート

・Ｂ２－５：ビス［４－（ｔｅｒｔ－ブチル）フェニル］ヨードニウムテトラ（ノナフルオロ－ｔｅｒｔ－ブトキシ）アルミン酸塩

・Ｂ２－６：ビス（4－イソプロピルフェニル）ヨードニウムテトラ(ペンタフルオロフェニル)ガレート

・Ｂ２－７： ４－クメニル（４－トリル）ヨードニウムテトラキス（ペンタフルオロフェニル）ボラート

＜＜有機基及びＰ、Ｂ、Ａｌ、Ｓ、Ｇａのいずれか１つ以上の原子を有するアニオンと、アリールヨードニウムカチオンとの塩＞＞
・Ｂ２－１１：ビス（４－ｔｅｒｔ－ブチルフェニル）ヨードニウム－ｐ－トルエンスルホナート

＜＜有機基及びＰ、Ｂ、Ａｌ、Ｓ、Ｇａのいずれか１つ以上の原子を有するアニオンと、アリールヨードニウムカチオンとの塩ではない光酸発生剤＞＞
・Ｂ２－１２：ビス（４－ｔｅｒｔ－ブチルフェニル)ヨードニウムヘキサフルオロホスファート

・Ｂ２－１３：２，４，６，－トリス（トリクロロメチル）－１，３，５－トリアジン

・Ｂ２－１４：ジフェニルヨードニウム－２－カルボキシラート一水和物

<(B2) Photoacid generator>
<<A salt of an anion having an organic group in which at least one or more H is substituted with F and one or more atoms of P, B, Al, S, Ga, and an aryliodonium cation>>
· B2-1: bis (4-tert-butylphenyl) iodonium nonafluorobutanesulfonate

· B2-2: bis (4-tert-butylphenyl) iodonium tris (pentafluoropropyl) trifluorophosphate

· B2-3: p-cumenyl (p-tolyl) iodonium tris (pentafluoroethyl) trifluorophosphate

・B2-4: bis (4-n-dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate

· B2-5: bis [4-(tert-butyl) phenyl] iodonium tetra (nonafluoro-tert-butoxy) aluminate

・ B2-6: Bis (4-isopropylphenyl) iodonium tetra (pentafluorophenyl) gallate

- B2-7: 4-cumenyl (4-tolyl) iodonium tetrakis (pentafluorophenyl) borate

<<A salt of an anion having an organic group and one or more atoms of P, B, Al, S, and Ga, and an aryliodonium cation>>
· B2-11: bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate

<<Anion having an organic group and at least one atom of P, B, Al, S, Ga, and a photoacid generator that is not a salt of an aryliodonium cation>>
· B2-12: bis (4-tert-butylphenyl) iodonium hexafluorophosphate

・B2-13: 2,4,6,-tris(trichloromethyl)-1,3,5-triazine

- B2-14: diphenyliodonium-2-carboxylate monohydrate

[(C) chemical polymerization initiator]
<(C1) Organic Peroxide>
・CHP: cumene hydroperoxide ・TMBH: 1,1,3,3-tetramethylbutyl hydroperoxide ・TPE: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate ・BPO: peroxide Benzoyl

[(D) Polymerization accelerator]
<Aliphatic tertiary amine compound>
・MDEOA: methyldiethanolamine ・TEA: triethanolamine ・TIPA: triisopropanolamine ・DMAEMA: N,N-dimethylaminoethyl methacrylate ・DIAEMA: N,N-diisopropylaminoethyl methacrylate ・TBA: tribenzylamine ・DBGE: N, N-dibenzylglycine ethyl DBAE: dibenzylaminoethanol DBMA: dibenzylmethylamine <aromatic tertiary amine compound>
・DMBE: N,N-dimethylaminoethyl benzoate ・DEPT: N,N-di(2-hydroxyethyl)-p-toluidine ・DHPT: N,N-di(2-hydroxypropyl)-p-toluidine <organic Metal compound>
・SnL: Dioctyl-tin-dilaurate ・CAA: Copper acetylacetone ・VOA: Vanadyl acetylacetonate <Other polymerization accelerators>
・BTU: N-benzoylthiourea ・PTU: 2-pyridylthiourea ・PTSA: sodium p-toluenesulfinate ・TMBA: trimethylbarbituric acid sodium salt ・KPS: potassium peroxodisulfate

[Ultraviolet absorber]
・BT: 2-(2-hydroxy-5-methylphenyl)benzotriazole

[Polymerization inhibitor]
・BHT: 2,6-di-t-butyl-4-methylphenol ・MeHQ: p-methoxyphenol

[Fluorescent agent]
・FA: diethyl 2,5-dihydroxyterephthalate

[(E) filler]
The method for producing each filler used in the preparation of the dental curable composition is shown below.
Raw material glasses (G1 to G7) in Table 1 were used for the production of fillers. The pH of the raw glass was measured by adding 1.0 g of a filler to a mixed solution of 40 g of distilled water and 10 g of ethanol and stirring the mixture for 1 hour.

[Preparation of filler E1]
(polysiloxane treatment)
Raw material glass G1: 100.0 g was added with 1.5 g of a low condensate of silane compound "MKC Silicate MS56S" (SiO ₂ content: 56.0% by mass, degree of polymerization: 2 to 100, manufactured by Mitsubishi Chemical Corporation). was stirred and mixed for about 90 minutes. After mixing for a predetermined time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours, then cooled to obtain a heat treated product. The obtained heat-treated material was placed in a Henschel mixer and pulverized at 1800 rpm for 5 minutes. After pulverization, a polysiloxane-treated material having a surface coated with polysiloxane and having good fluidity was obtained.
(Silane treatment)
100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 5.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were mixed with 100.0 g of polysiloxane-treated material and stirred at room temperature for 2 hours. The resulting silane coupling treatment liquid was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E1.

[Preparation of filler E2]
(Silane treatment)
Filler E5 explained below: 100.0 g, water 100.0 g, ethanol 80.0 g, phosphoric acid 0.003 g, 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent 9.0 g for 2 hours The silane coupling treatment liquid obtained by stirring at room temperature was added, and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E2.

[Preparation of filler E3]
(acidic polymer treatment)
100.0 g of filler E5 described below was put into a Henschel mixer, and while stirring, 12.0 g of an aqueous polyacrylic acid solution (polymer concentration: 13% by mass, weight average molecular weight: 20,000; manufactured by Nacalai Co., Ltd.) was added from above. was sprayed. After spraying, the powder taken out from the mixer was heated at 100° C. for 3 hours in a hot air dryer to obtain a polysiloxane-polyacrylic acid-treated product.
(Silane treatment)
100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 9.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent to 100.0 g of polysiloxane-polyacrylic acid treated product for 2 hours. The silane coupling treatment liquid obtained by stirring at room temperature was added, and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E3.

[Preparation of filler E4]
(acidic polymer treatment)
After obtaining a polysiloxane-treated product by the same procedure as for filler E1, 100.0 g of the polysiloxane-treated product was put into a Henschel mixer, and while stirring, an aqueous polyacrylic acid solution (polymer concentration: 13% by mass, Weight average molecular weight 20,000: Nacalai Co., Ltd.) 23.0 g was sprayed. After the spraying, the powder taken out from the mixer was heated in a hot air dryer at 100° C. for 3 hours to obtain a polysiloxane-polyacrylic acid-treated filler E4.

[Preparation of filler E5]
(polysiloxane treatment)
To raw glass G2: 100.0 g, 3.5 g of a low condensate of silane compound "MKC Silicate MS56S" (SiO ₂ content: 56.0% by mass, degree of polymerization: 2 to 100, manufactured by Mitsubishi Chemical Corporation) was added. was stirred and mixed for about 90 minutes. After mixing for a predetermined time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours, then cooled to obtain a heat treated product. The obtained heat-treated material was placed in a Henschel mixer and pulverized at 1800 rpm for 5 minutes. A polysiloxane-treated filler E5 having a surface coated with polysiloxane and having good fluidity after pulverization was obtained.

[Preparation of filler E6]
(polysiloxane treatment)
4.5 g of a low condensate of a silane compound "MKC Silicate MS56S" (SiO ₂ content: 56.0% by mass, degree of polymerization: 2 to 100, manufactured by Mitsubishi Chemical Corporation) was added to raw glass G3: 100.0 g. was stirred and mixed for about 90 minutes. After mixing for a predetermined time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours, then cooled to obtain a heat treated product. The obtained heat-treated material was placed in a Henschel mixer and pulverized at 1800 rpm for 5 minutes. After pulverization, a polysiloxane-treated material having a surface coated with polysiloxane and having good fluidity was obtained.
(acidic polymer treatment)
100.0 g of polysiloxane-treated material was put into a Henschel mixer, and 16.0 g of an aqueous polyacrylic acid solution (polymer concentration: 13% by mass, weight average molecular weight: 20,000; manufactured by Nacalai Co., Ltd.) was sprayed from above while stirring. After spraying, the powder taken out from the mixer was heated in a hot air dryer at 100° C. for 3 hours to obtain a polysiloxane-polyacrylic acid-treated product.
(Silane treatment)
100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 12.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent for 100.0 g of polysiloxane-polyacrylic acid treated product for 2 hours. The silane coupling treatment liquid obtained by stirring at room temperature was added, and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E6.

[Preparation of filler E7]
(polysiloxane treatment)
To raw glass G7: 100.0 g, 1.0 g of a low condensate of silane compound "MKC Silicate MS56S" (SiO ₂ content: 56.0% by mass, degree of polymerization: 2 to 100, manufactured by Mitsubishi Chemical Corporation) was added. was stirred and mixed for about 90 minutes. After mixing for a predetermined time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours, then cooled to obtain a heat treated product. The obtained heat-treated material was placed in a Henschel mixer and pulverized at 1800 rpm for 5 minutes. After pulverization, a polysiloxane-treated material having a surface coated with polysiloxane and having good fluidity was obtained.
(Silane treatment)
100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 3.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were mixed with 100.0 g of polysiloxane-treated material and stirred at room temperature for 2 hours. The resulting silane coupling treatment liquid was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E7.

[Preparation of filler E8]
The heat treatment conditions in the polysiloxane treatment were the same as for filler E2 except that after aging at 50 ° C. for 40 hours in a hot air dryer, the temperature was raised to 450 ° C. and kept for 6 hours. The preparation yielded filler E8.

[Preparation of Filler E9]
(polysiloxane treatment)
0.5 g of a low condensate of a silane compound "MKC Silicate MS56S" (SiO ₂ content: 56.0% by mass, degree of polymerization: 2 to 100, manufactured by Mitsubishi Chemical Corporation) was added to 100.0 g of raw material glass G4. was stirred and mixed for about 90 minutes. After mixing for a predetermined time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours, then cooled to obtain a heat treated product. The obtained heat-treated material was placed in a Henschel mixer and pulverized at 1800 rpm for 5 minutes. After pulverization, a polysiloxane-treated material having a surface coated with polysiloxane and having good fluidity was obtained.
(Silane treatment)
100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 1.5 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were mixed with 100.0 g of the polysiloxane-treated material and stirred at room temperature for 2 hours. The resulting silane coupling treatment liquid was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E9.

[Preparation of filler E10]
The heat treatment conditions in the polysiloxane treatment were the same as for filler E1, except that after aging at 50 ° C. for 40 hours in a hot air dryer, the temperature was raised to 400 ° C. and the conditions were kept for 6 hours. The preparation yielded filler E10.

[Preparation of filler E11]
Filler E11 was obtained under the same conditions as filler E1, except that the silane coupling agent used in the silane treatment was changed to 7.0 g of 8-methacryloyloxyoctyltrimethoxysilane.

[Preparation of filler E12]
(Silane treatment)
After obtaining a polysiloxane-treated product by the same procedure as for filler E6, 100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and as a silane coupling agent are added to 100.0 g of the polysiloxane-treated product. The silane coupling treatment liquid obtained by stirring 15.0 g of 8-methacryloyloxyoctyltrimethoxysilane for 2 hours at room temperature was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler E12.

[Preparation of filler E13]
Filler E13 was obtained by manufacturing under the same conditions as for filler E2, except that the silane coupling agent used in the silane treatment was changed to SC1: 12.0 g.

SC1: 4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-silaicosan-20-yl methacrylate

[Preparation of filler E14]
Filler E14 was obtained by manufacturing under the same conditions as for filler E2, except that the silane coupling agent used in the silane treatment was changed to SC2: 12.0 g.

SC2: 4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosan-23-yl methacrylate

[Preparation of filler E15]
Filler E15 was obtained under the same conditions as for filler E6 except that the silane coupling agent used in the silane treatment was changed to 15.0 g of 8-methacryloyloxyoctyltrimethoxysilane.

[Preparation of filler E16]
The heat treatment conditions in the polysiloxane treatment were the same as for filler E2 except that after aging at 50 ° C. for 40 hours in a hot air dryer, the temperature was raised to 100 ° C. and kept for 6 hours. The preparation yielded filler E16.

[Preparation of filler EC1]
Filler EC1 was obtained by manufacturing under the same conditions as for filler E1, except that the raw material glass was changed from G1 to G5.

[Preparation of filler EC2]
(Silane treatment)
100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 5.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred for 2 hours at room temperature with respect to 100.0 g of raw glass G5. The silane coupling treatment liquid was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler EC2.

[Preparation of filler EC3]
(Silane treatment)
100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 8.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were mixed with 100.0 g of filler EC9 and stirred at room temperature for 2 hours. The resulting silane coupling treatment liquid was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler EC3.

[Preparation of filler EC4]
Raw material glass G1 which was not treated at all was used as filler EC4.

[Preparation of filler EC5]
Raw material glass G2 which was not treated at all was used as filler EC5.

[Preparation of filler EC6]
(polysiloxane treatment)
3.0 g of a low condensate of silane compound "MKC Silicate MS56S" (SiO ₂ content: 56.0% by mass, degree of polymerization: 2 to 100, manufactured by Mitsubishi Chemical Corporation) was added to raw glass G6: 100.0 g. was stirred and mixed for about 90 minutes. After mixing for a predetermined time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours, then cooled to obtain a heat treated product. The obtained heat-treated material was placed in a Henschel mixer and pulverized at 1800 rpm for 5 minutes. After pulverization, a polysiloxane-treated material having a surface coated with polysiloxane and having good fluidity was obtained.
(acidic polymer treatment)
100.0 g of polysiloxane-treated material was put into a Henschel mixer, and 10.0 g of an aqueous polyacrylic acid solution (polymer concentration: 13% by mass, weight average molecular weight: 20,000; manufactured by Nacalai Co., Ltd.) was sprayed from above while stirring. After spraying, the powder taken out from the mixer was heated in a hot air dryer at 100° C. for 3 hours to obtain a polysiloxane-polyacrylic acid-treated product.
(Silane treatment)
100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 8.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent to 100.0 g of polysiloxane-polyacrylic acid treated product for 2 hours. The silane coupling treatment liquid obtained by stirring at room temperature was added, and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler EC6.

[Preparation of filler EC7]
(Silane treatment)
Raw material glass G2: 100.0 g was mixed with 100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 9.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent at room temperature for 2 hours. The resulting silane coupling treatment liquid was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler EC7.

[Preparation of filler EC8]
(acidic polymer treatment)
Raw material glass G2: 100.0 g was put into a Henschel mixer, and 12.0 g of polyacrylic acid aqueous solution (polymer concentration: 13% by mass, weight average molecular weight: 20,000; manufactured by Nacalai Co., Ltd.) was sprayed from above while stirring. After spraying, the powder taken out from the mixer was heated at 100° C. for 3 hours in a hot air dryer to obtain a polysiloxane-polyacrylic acid-treated product.
(Silane treatment)
100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 9.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent are mixed with 100.0 g of polyacrylic acid-treated product and stirred at room temperature for 2 hours. The obtained silane coupling treatment solution was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler EC8.

[Preparation of filler EC9]
(polysiloxane treatment)
3.0 g of a low condensate of silane compound "MKC Silicate MS56S" (SiO ₂ content: 56.0% by mass, degree of polymerization: 2 to 100, manufactured by Mitsubishi Chemical Corporation) was added to raw glass G6: 100.0 g. was stirred and mixed for about 90 minutes. After mixing for a predetermined time, the resulting treated slurry was aged in a hot air dryer at 50°C for 40 hours, then heated to 150°C and held for 6 hours, then cooled to obtain a heat treated product. The obtained heat-treated material was placed in a Henschel mixer and pulverized at 1800 rpm for 5 minutes. A polysiloxane-treated filler EC9 having a surface coated with polysiloxane and having good fluidity after pulverization was obtained.

[Preparation of filler EC10]
(Silane treatment)
100.0 g of water, 80.0 g of ethanol, 0.003 g of phosphoric acid, and 3.0 g of 3-methacryloyloxypropyltrimethoxysilane as a silane coupling agent were stirred for 2 hours at room temperature with respect to 100.0 g of raw material glass G7. The silane coupling treatment liquid was added and mixed with stirring for 30 minutes. After that, heat treatment was performed at 100° C. for 15 hours to obtain filler EC10.

[pH measurement]
pH measurements were performed to determine the acid-base level of the surface-treated fillers. For pH measurement, 1.0 g of filler was added to a mixed solution of 40 g of distilled water and 10 g of ethanol, and the mixture was stirred for 1 hour to measure the pH of the dispersion. Fillers with a pH between 7.5 and 10.0 were considered basic fillers, and those with a pH greater than 10.0 were considered non-basic fillers. Also, fillers with a pH less than 7.5 were classified as non-basic fillers. Table 2 shows the classification results.

<Method for producing one-component dental curable composition>
All except the (E) filler shown in Tables 3 and 4 were put into a wide-mouth plastic container and mixed for 48 hours at 100 rpm using a mix rotor VMRC-5 to obtain a matrix. After that, the matrix and (E) filler were put into a kneader, uniformly stirred, and degassed under vacuum to prepare dental curable compositions of Examples A1 to A49 and Comparative Examples CA1 to CA17. .

<Method for producing a two-component dental curable composition>
All except the (E) filler shown in Tables 5 and 6 and Tables 7 and 8 were placed in a wide-mouth plastic container and mixed for 48 hours at 100 rpm using a mix rotor VMRC-5 to obtain a matrix. rice field. After that, the matrix and the filler (E) are put into a kneader, stirred uniformly, deaerated under vacuum to obtain pastes 1 and 2, and then filled into a double syringe (5 mL) manufactured by Mixpack. The dental curable compositions of Examples B1-B28 and Examples D1-D39 and Comparative Examples CB1-CB7 and Comparative Examples CD1-CD6 were prepared.

<Accelerated test conditions>
The one-component dental curable composition or the two-component dental curable composition filled in each container was allowed to stand in a storage cabinet (Yamato Scientific Co., Ltd.) set at 40° C. for 6 months.

<Evaluation 1-1: Bending strength (photopolymerization)>
After filling the dental curable composition into a stainless steel mold, cover glasses were placed on both sides and pressed with a glass kneading plate. Light irradiation was performed and cured. After curing, the cured product was taken out from the mold, and the back surface was similarly irradiated with light to obtain a test piece (25×2×2 mm: cuboid type). After the specimen was immersed in water at 37° C. for 24 hours, a bending test was performed. As for the composition containing the chemical polymerization initiator, the measurement was performed within 2 hours after the end of light irradiation. The bending test was performed using an Instron universal testing machine (manufactured by Instron) at a distance between fulcrums of 20 mm and a crosshead speed of 1 mm/min. The bending strength test results show excellent bending strength when 100 MPa or more, sufficient bending strength when 90 to less than 100 MPa, slightly inferior bending strength when 80 to less than 90 MPa, and less than 80 MPa. determined to be insufficient. In addition, the one-component dental curable composition and the two-component dental curable composition in which the amount of the (E) filler is less than 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer is 80 MPa or more. Excellent bending strength was judged to be good, less than 70 to 80 MPa was sufficient, less than 60 to less than 70 MPa was slightly inferior, and less than 60 MPa was insufficient.

<Evaluation 1-2: Bending strength (chemical polymerization)>
After the curable dental composition was filled in a stainless steel mold, cover glasses were placed on both sides and pressed with a glass kneading plate, followed by standing in a constant temperature machine set at 37° C. for 1 hour. After removing the cured product from the mold, the specimen was immersed in water at 37° C. for 24 hours, and then subjected to a bending test. The bending test was performed using an Instron universal testing machine (manufactured by Instron) at a distance between fulcrums of 20 mm and a crosshead speed of 1 mm/min. The bending strength test results show excellent bending strength when 100 MPa or more, sufficient bending strength when 90 to less than 100 MPa, slightly inferior bending strength when 80 to less than 90 MPa, and less than 80 MPa. determined to be insufficient. In addition, the curable composition in which the amount of (E) filler is less than 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer has excellent bending strength when it is 80 MPa or more, and 70 to 80 MPa is sufficient. A bending strength of less than 60 to 70 MPa was judged to be slightly inferior, and a bending strength of less than 60 MPa was judged to be insufficient.

<Evaluation 2: Bending strength of composition before curing after accelerated test>
<Evaluation 1-1: Bending strength (photopolymerization)> or <Evaluation 1-2: Bending strength (Chemical Polymerization)>, bending strength was measured. Comparison with the flexural strength of the composition before storage was performed using formula (3). If the change is -5% or more compared to before storage in a storage box set at 40 ° C, it has high storage stability, and if it is between -5% and -10%, it has sufficient storage stability. If it is less than -10% to -15%, the storage stability is rather poor. When it was less than -20%, it was judged that the storage stability was remarkably poor and unsatisfactory.

[(Formula 3)]
(Bending strength after storage (MPa) - Bending strength before storage (MPa)) / (Bending strength before storage (MPa)) x 100 [%]

<Evaluation 3: Bending strength of cured composition after accelerated test>
<Evaluation 1-1: Bending strength (photopolymerization)> or <Evaluation 1-2: Bending strength (chemical polymerization)> Test specimens prepared according to the method are stored in a storage cabinet set at 40 ° C. (Yamato Scientific Co., Ltd.) After standing for 6 months, the bending strength was compared with the bending strength of the composition before storage in a storage cabinet set at 40° C. in which a bending test was performed using the formula (4). If the change is -10% or more than before storage, it has high storage stability, if it is less than -10% to -20%, it has sufficient storage stability, and if it is less than -20% to -30% If there is, the storage stability is slightly poor. When it was less than -30%, it was judged that the storage stability was extremely poor and insufficient.
[(Formula 4)]
(Bending strength after storage (MPa) - Bending strength before storage (MPa)) / (Bending strength before storage (MPa)) x 100 [%]

<Evaluation 4: acid neutralization ability>
A stainless steel mold (15φ×1 mm: disk shape) was filled with each of the prepared dental curable compositions, and then a cover glass was placed from above and pressed with a glass plate. Using a photopolymerization irradiator (Blue Shot: manufactured by Shofu) for 1 minute from the cover glass to cure by light irradiation, remove the cured product from the mold, remove the cover glass, and water-resistant abrasive paper (#600) polished the surface with After removing the polishing dust, it was placed in a PP container containing 5 mL of an aqueous lactic acid solution adjusted to pH 4.0, and placed in a thermostat set at 37° C. for 48 hours. After 48 hours, the cured product was removed from the PP container, and the pH was measured using a pH meter (electrode: 9618S-10D, main body: D-74, Horiba, Ltd.). When the pH at this time was less than 4.5, the acid-neutralizing ability was considered to be insufficient, and was rated as D. When the pH is 4.5 or more and less than 5.0, C is considered to have a certain acid neutralization ability, and when the pH is 5.0 or more and less than 5.5, B is regarded as having sufficient acid neutralization ability. When the pH was 5.5 or more, it was rated as A because it had excellent acid-neutralizing ability. When the dental curable composition has an acid-neutralizing ability, it can be expected to neutralize the surrounding acid even in the oral cavity, so that an effect such as inhibition of demineralization of tooth substance can be expected.

<Evaluation 5: light color stability>
A stainless steel mold (15φ×1 mm: disk shape) was filled with each of the prepared dental curable compositions, and then a cover glass was placed from above and pressed with a glass plate. Using a photopolymerization irradiator (Griplight II: manufactured by Shofu) from above the cover glass, light irradiation is performed for 1 minute to cure, the cured product is removed from the mold, the cover glass is removed, and the color tone of this test piece is measured. Colorimetric. For colorimetry, place the specimen on the background of a standard white plate (D65/10° X = 81.07, Y = 86.15, Z = 93.38) and use a spectrocolorimeter (manufactured by BYK-Chemie) (light source: C, viewing angle: 2°, measurement area: 11 mm). Then, after exposing the specimen to light for 24 hours using a xenon lamp light exposure tester (Suntest CPS+), the color tone of the specimen was measured again, and the difference in color change was expressed as ΔE calculated from the following formula. .
ΔE = {(ΔL*) ² + (Δa*) ² + (Δb*) ² } ^1/2
ΔL*＝L1*−L2*
Δa* = a1* - a2*
Δb* = b1* - b2*

where L1* is the lightness index before light exposure, L2* is the lightness index after light exposure, a1*, b1* are the color index before light exposure, a2*, b2* are the color index after light exposure is. Those with a ΔE of less than 5 were judged as good, those with a ΔE of 5 to less than 8 were usable, those with a ΔE of 8 to less than 10 were judged to be bad, and those with a ΔE of more than 10 were judged unusable.

<Evaluation 6: Adhesion strength to tooth substance>
A test piece of bovine anterior tooth embedded in epoxy resin was polished with #600 water-resistant abrasive paper to scrape out the enamel or dentin plane. After that, a perforated tape with a diameter of 4 mm was applied to the adherend surface to define the adhesion area. On the other hand, the adhering surface of a stainless steel rod (φ4.5 mm) was sandblasted (0.2 MPa, 1 second) with alumina (50 μm) → washed with water and dried, and a metal adhesive primer (Metal Link, manufactured by Shofu). was applied. An appropriate amount of the curable dental composition of the example or comparative example was applied to the attachment surface of a stainless steel rod, and the cattle was embedded in epoxy resin to expose the enamel or dentin plane so that it fits in the frame of the perforated double-sided tape. The specimen of the anterior tooth and the stainless steel rod were luted. A load of 200 N was applied from the vertical direction of the stainless steel rod, and excess cement was wiped off with a cloth. After that, light was irradiated for 10 seconds with an LED light irradiator for dental polymerization (Blue Shot, manufactured by Shofu), and the adhesion test specimen prepared after removing the load was immersed in water at 37 ° C. for 24 hours. Co.) was used to measure the tensile bond strength at a crosshead speed of 1 mm/min. When the adhesive strength was 10 MPa or more, it was judged to have excellent adhesive strength. On the other hand, when it was less than 5 Mpa, it was judged that the adhesive strength was low.
The adhesive strength to tooth substance was tested only for Examples D23 to D39 and Comparative Examples CD1, CD2, and CD3 to CD6. In Examples D23 to D39, a polymerizable monomer having an acidic group was blended for the purpose of imparting adhesiveness to tooth substance.

It was confirmed that the compositions described in Examples have sufficient bending strength, storage stability, and acid-neutralizing ability.

(E1) Example A3, Example A4, Example B14, etc. containing fillers E3, E4, E6, and E15 containing a surface-treated basic filler and treated with an acidic polymer are good There was a tendency to exhibit a high acid-neutralizing ability. In addition, Example A1, Example A2, etc. containing fillers E1, E2, E3, E6, E7, E8, E9, E11, E12, E13, E14, and E15 treated with a silane coupling agent tended to exhibit good bending strength. Examples A4 and B3, which contain only fillers that have not been treated with a silane coupling agent, have slightly low flexural strength, and are implemented by blending filler E5 that has not been treated with a silane coupling agent and not treated with an acidic polymer. Example A5 and the like tended to have slightly low bending strength and slightly low acid-neutralizing ability.

(E1) Among the surface-treated basic fillers, Examples A15, B6, and D6 containing only the highly basic filler E7 had slightly low storage stability of the composition before curing. In Examples A37, A46, B23, and D11 containing only filler E8, which was heat-treated at a temperature of 450° C., the storage stability of the cured composition was slightly low, and the acid neutralization ability tended to be low. rice field. Example A39, Example B24, Example D13, Example D34 with filler E10, where the heat treatment was carried out at a temperature of 400° C., also showed a moderate but post-curing reduction compared to the example with only filler E8. The storage stability of the composition tended to be slightly low. On the other hand, Example D33 containing filler E1 and filler E3 while containing filler E8 showed good acid-neutralizing ability. Example A49 containing filler E16, in which the heat treatment temperature was as low as 90°C, had slightly low storage stability of the composition before curing. (E1) In Examples A16, B10, D9, and D25, which contained a small amount of the surface-treated basic filler, the storage stability of the cured composition tended to be low, and the acid-neutralizing ability tended to be low.

A19 and B11 containing a small amount of the photosensitizer tended to have slightly low flexural strength, while A20 and B12 containing a large amount of the photosensitizer tended to slightly lower the light color stability. Example D19, which contained a small amount of organic peroxide, tended to have slightly low bending strength. Examples A23, B15, and D20, which contained a small amount of the polymerization accelerator, tended to have slightly low bending strength. In Examples A24 and B16, which contained a large amount of the polymerization accelerator, the storage stability of the composition before curing tended to decrease slightly.

Examples A20 and B12, in which the amount of the photo-acid generator was small, tended to be slightly low in bending strength. In Examples A21 and B11, which contained a large amount of the photoacid generator, the storage stability of the cured composition tended to be slightly low. In addition, as a photoacid generator, an anion having at least one or more H-substituted organic groups and one or more atoms of P, B, Al, S, Ga, and a salt other than a salt of an aryliodonium cation Examples A30 to 33, A35, and B19 to 21, in which the above was blended, tended to slightly decrease in light color stability. Example D27, which contains a small amount of the polymerizable monomer having an acid group, has a slightly low adhesive strength to dentin. The storage stability of the subsequent composition tended to be slightly low. Examples A28 and B17, which did not contain a camphorquinone-based photosensitizer as a photopolymerization initiator, tended to have slightly low bending strength.

Example A26 containing an aromatic amine such as DMBE or DEPT as a polymerization accelerator tended to have a lower light color stability. No loss of color stability was observed.

Comparative Examples CA1, CA2, CA15, CA16, CA17, CB1, CB2, CB7, CD1 and CD2 did not contain a portion of the polymerization initiator or polymerization accelerator, and therefore had low flexural strength or did not cure.
Comparative Examples CA3, CA4, CA5, CA8, CA11, CB5, CB6, CD4, CD5, and CD6, which contain basic fillers that are not treated with polysiloxane, have good flexural properties after storage of the paste before curing. It showed a tendency to decrease remarkably compared to before. In Comparative Examples CA6, CA7, CA9, CA10, CA12, CA13, CA14, CB3, CB4, and CD6, which contain only non-basic fillers, the bending properties after storage of the cured products are all compared to those before storage. decreased markedly.

According to the present invention, it is possible to provide a dental curable composition having high storage stability and good mechanical properties.

Claims (17)

A dental curable composition comprising (A) a polymerizable monomer, (BC) a polymerization initiator, (D) a polymerization accelerator, and (E) a filler,
(BC) the polymerization initiator comprises (B) a photoinitiator and/or (C) a chemical polymerization initiator;
(B) the photoinitiator comprises (B1) a photosensitizer and (B2) a photoacid generator;
(C) the chemical polymerization initiator comprises (C1) an organic peroxide;
(E) the filler comprises (E1) a surface-treated basic filler;
(E1) A dental curable composition, wherein the surface-treated basic filler is surface-treated with a surface-treated basic filler represented by (F1) formula (1) and/or a condensate thereof.
[Formula (1)]

(In the formula, M is a metal atom selected from Si, Ti, Zr and Al, X is H, OH, a hydrolyzable group, which may be the same or different. When M is Si, Ti, Zr where n is 4, and n is 3 when M is Al.) (F1) All of the alkoxy groups of the surface-treating agent represented by formula (1) and/or the condensate of 2 to 100 molecules of partial condensate of tetraalkoxysilane or the partial condensate of 2 to 100 molecules of tetraalkoxysilane 2. The dental curable composition according to claim 1, which is polysiloxane partially substituted with OH groups. (E1) The surface-treated basic filler is obtained by using a surface-treating agent represented by (F1) formula (1) and/or a condensate thereof, using a wet method and a heat treatment condition of 130° C. or more and 400° C. or less. 3. The dental curable composition according to claim 1 or 2, which is surface-treated by heating for at least one hour. (E1) Surface-treated basic filler is (F1) In addition to surface treatment with a surface treatment agent represented by formula (1) and/or a condensate thereof, a silane coupling agent having a polymerizable group and/or an acidic polymer The dental curable composition according to any one of claims 1 to 3, which is surface-treated with. (E1) 1.0 g of the surface-treated basic filler is added to a mixed solution of 40 g of distilled water and 10 g of ethanol, and the mixture is stirred for 1 hour, and the resulting dispersion has a pH of 7.5 to 10.0. The dental curable composition according to any one of claims 1 to 4. (E1) The surface-treated basic filler is one or more of fluorosilicate glass containing strontium and/or calcium ions, fluoroaluminosilicate glass, and fluoroaluminoborosilicate glass according to any one of claims 1 to 5. A dental curable composition. (E1) The composition range of the surface-treated basic filler is SiO ₂ : 15-35% by mass, Al ₂ O ₃ : 15-30% by mass, SrO: 20-45% by mass, P ₂ O ₅ : 0-15. % by mass, F: 5 to 15 mass %, Na ₂ O: 0 to 10 mass %, B ₂ O ₃ : 0 to 20 mass %, CaO: 0 to 10 mass %. 7. A dental curable composition according to any one of 6. (B2) contains an aryliodonium salt as a photoacid generator,
The aryliodonium salt according to any one of claims 1 to 7, which is a salt of an aryliodonium cation and an anion having an organic group and at least one atom of P, B, Al, S and Ga. curable composition for (B2) contains an aryliodonium salt as a photoacid generator,
The aryliodonium salt is a salt of an aryliodonium cation and an anion having at least one or more H-substituted organic groups and one or more atoms of P, B, Al, S and Ga. Item 8. The dental curable composition according to any one of items 1 to 7. 10. The dental curable composition according to claim 8 or 9, wherein (D) the polymerization accelerator contains an aliphatic tertiary amine compound. Any one of claims 1 to 10, wherein (A1) the polymerizable monomer having an acidic group is 1 to 30 parts by mass out of 100 parts by mass of the polymerizable monomer (A) contained in the dental curable composition. The dental curable composition according to . (B) A one-component dental curable composition containing a photopolymerization initiator,
With respect to 100 parts by mass of the polymerizable monomer (A) contained in the dental curable composition,
(B1) contains 0.02 to 1.0 parts by mass of a photosensitizer,
(B2) contains 0.1 to 10 parts by mass of a photoacid generator,
(D) contains 0.2 to 10 parts by mass of a polymerization accelerator,
(E1) The dental curable composition according to any one of claims 1 to 11, comprising 10 to 500 parts by mass of a surface-treated basic filler. (B) A two-component dental curable composition containing a photopolymerization initiator,
consisting of a first paste and a second paste,
The first paste and the second paste have a mass ratio of 1:0.8 to 1.2,
For a total of 200 parts by mass of the polymerizable monomer (A) contained in the first paste and the second paste,
(B1) contains 0.04 to 2.0 parts by mass of a photosensitizer,
(B2) contains 0.2 to 20 parts by mass of a photoacid generator,
(D) contains 0.4 to 20 parts by mass of a polymerization accelerator,
(E1) 10 to 500 parts by mass of a surface-treated basic filler,
A dental curable composition according to any one of claims 1 to 11. (C) a two-component dental curable composition containing a chemical polymerization initiator,
consisting of a first paste and a second paste,
The first paste and the second paste have a mass ratio of 1:0.8 to 1.2,
For a total of 200 parts by mass of the polymerizable monomer (A) contained in the first paste and the second paste,
(C1) contains 0.2 to 10 parts by mass of an organic peroxide,
(D) contains 0.4 to 20 parts by mass of a polymerization accelerator,
(E1) 10 to 400 parts by mass of a surface-treated basic filler,
A dental curable composition according to any one of claims 1 to 11. (C) a two-component dental curable composition containing a chemical polymerization initiator,
consisting of a first paste and a second paste,
The first paste and the second paste have a mass ratio of 1:0.8 to 1.2,
For a total of 200 parts by mass of the polymerizable monomer (A) contained in the first paste and the second paste,
(C1) contains 0.2 to 10 parts by mass of an organic peroxide,
(D) contains 0.4 to 20 parts by mass of a polymerization accelerator,
(E1) 10 to 400 parts by mass of a surface-treated basic filler,
The dental curing agent according to any one of claims 1 to 11, further comprising 2 to 60 parts by mass of (A1) a polymerizable monomer having an acidic group in a total of 200 parts by mass of (A) polymerizable monomers. sex composition. Claims 1 to 4, characterized in that a hardened dental composition having a diameter of 15 mm and a thickness of 1 mm is immersed in 5 mL of an aqueous solution of lactic acid having a pH of 4.0 for 24 hours and has a pH of 4.5 or higher. 16. A dental curable composition according to any one of 15. A dental curable composition according to any one of claims 1 to 16, which is substantially free of water.