JP2021080196A - Dental composition - Google Patents

Abstract

To provide a dental composition having excellent transparency, curing depth, and mechanical strength.SOLUTION: A dental composition has a fluorine-containing monomer (A) with a refractive index of less than 1.460, a fluorine-free monomer (B), an inorganic filler (C) with a refractive index of 1.450 or more and 1.500 or less, and a polymerization initiator (D), where the content of an inorganic filler (E) with a refractive index of less than 1.450 is less than 10 mass%.SELECTED DRAWING: None

Description

The present invention relates to dental compositions.

In the treatment of dental caries and associated defects, restoration treatment using a dental composition such as a dental adhesive, a dental composite resin, and a dental cement has been generally performed. As an example of treatment, in restoration treatment using a dental adhesive and a dental composite resin, the work is generally performed by the following procedure. First, the carious portion is scraped to form a cavity, and then a dental adhesive is applied to the cavity, and then the portion to which the adhesive is applied is irradiated with visible light to be cured. Next, the dental composite resin is filled on the cured adhesive layer, and the finally filled dental composite resin is irradiated with visible light to be cured.

In tooth restoration treatment with a dental composition, not only the occlusion is restored, but also operability, mechanical strength, and the like, as well as good aesthetics to make the tooth look natural are required. For that purpose, it is required to have transparency as close as possible to natural dentin. For example, dental composite resins generally contain monomers, inorganic fillers, and polymerization catalysts, but in order to ensure the transparency of the cured product, the organic matrix formed by curing the monomers The refractive index and the refractive index of the inorganic filler need to be approximately equal. However, while amorphous silica, which is highly versatile as an inorganic filler, has a wide variety of types, and has high mechanical strength, has a low refractive index, the monomer has a benzene skeleton from the viewpoint of mechanical strength. The refractive index of the cured product is generally high, such as when a considerable amount of is blended. Therefore, when amorphous silica is used as it is as a filler in a dental composition, a considerable difference occurs between the refractive index of the organic matrix and the refractive index of amorphous silica, and the produced dental composition is produced. Transparency is significantly reduced and aesthetics are inferior.

In order to obtain good aesthetics, for example, as in Patent Document 1, as a dental composition that produces the same specific light scattering phenomenon (opal effect) as the mineral opal, which is similar to the enamel of natural dentin, it is simply used. Spherical silica-based particles having a polymer and an average particle size in the range of 0.1 to 0.5 μm and a standard deviation value of the particle size distribution within 1.30, and these silica-based particles are dispersed in an organic matrix. It contains an organic-inorganic composite filler and a polymerization initiator, and the difference in refractive index between the spherical silica-based particles and the polymer of the polymerizable monomer is 0.1 or less, and is polymerizable with the organic-inorganic composite filler. A dental composition having a refractive index difference of 0.1 or less from a monomer polymer is disclosed.

Patent Document 2 contains, as a dental composition having excellent aesthetic properties, a monomer component, a spherical filler having an average particle size in the range of 260 nm to 1000 nm, and a polymerization initiator, and has a thickness. The brightness (V) of the color measurement value by the Munsell color system of the colored light under the black background, which was measured using a color difference meter in the state where the 1 mm cured product was formed, was less than 5, and the saturation (C). ) Is 0.05 or more, and the brightness (V) of the color measurement value of the colored light under the white background by the Munsell color system is 6 or more, and the saturation (C) is less than 2. The thing is disclosed.

Patent Document 3 describes a monomer having a refractive index <1.45 (for example, a fluorine-containing monomer) as a dental composition having high aesthetics, adjustable translucency, and high opalescence. Or at least selected from the group consisting of a monomer mixture, a milky filler having a refractive index <1.45, another conventional filler or filler mixture, and a polymerization initiator, stabilizer and colorant. A curable dental material containing one type, the difference in refractive index between the monomer and the opalescent filler is ≤0.04, and the average particle size of the opalescent filler is 230 nm +/- 50 nm. Discloses dental materials.

International Publication No. 2011/158742 International Publication No. 2017/069274 Special Table 2007-532518

In the conventional dental composition, there is a considerable difference between the refractive index of amorphous silica and the refractive index of the monomer, so that there is room for further improvement in terms of aesthetics. Further, the opal effect of the dental compositions described in Patent Documents 1 and 2 is generally suitable for repairing the enamel portion of natural dentin because it exhibits a bluish color tone, but dentin such as the cervical region. It is not always suitable for reproducing the color tone of a part. Therefore, it was still difficult to reproduce the transparency and color tone of various restoration sites of natural dentin. Further, in the dental composition described in Patent Document 3, the refractive index of the opalescent filler is limited to less than 1.450, but in general, when the refractive index is low, a reddish color tone is exhibited. It is suitable for repairing dentin parts such as the cervical part of natural dentin, but not necessarily for reproducing the color tone of enamel parts. Therefore, it was difficult to reproduce the transparency and color tone of various restoration sites of natural dentin. Further, in Patent Documents 1 to 3, the mechanical strength and surface hardness of the cured product have not been examined.

Therefore, an object of the present invention is to provide a dental composition having excellent transparency, curing depth, surface hardness and mechanical strength.

As a result of diligent studies to achieve the above object, the present inventors have made a fluorine-containing monomer having a specific range of refractive index, a monomer without fluorine, and an inorganic filler having a specific range of refractive index. , And a combination of a polymerization initiator results in a dental composition having excellent transparency, curing depth, surface hardness and mechanical strength, and based on this finding, further studies have been carried out to complete the present invention. ..

That is, the present invention relates to the following.
[1] A fluorine-containing monomer (A) having a refractive index of less than 1.460, a monomer (B) having no fluorine, and an inorganic filler (C) having a refractive index of 1.450 or more and 1.500 or less. , And the content of the inorganic filler (E) containing the polymerization initiator (D) and having a refractive index of less than 1.450 is less than 10% by mass;
[2] The dental composition according to [1], wherein the inorganic filler (C) is an amorphous inorganic oxide.
[3] The dental composition according to [1] or [2], wherein the inorganic filler (C) has an average particle size of 0.0001 to 50 μm;
[4] The dentistry according to any one of [1] to [3], further comprising an X-ray opaque inorganic filler (F) having a refractive index of more than 1.500 and an average particle size of 200 nm or less. Composition;
[5] The X-ray opaque element of the X-ray opaque inorganic filler (F) contains at least one selected from the group consisting of Yb, Ba, Zr, Sr, and La, according to [4]. Dental composition;
[6] The dental composition according to [4], wherein the X-ray opaque element of the X-ray opaque inorganic filler (F) contains at least one selected from the group consisting of Yb, Ba, and Zr. Stuff;
[7] The dental composition according to any one of [1] to [6], wherein the inorganic filler (C) has a spherical grain shape;
[8] The dental composition according to any one of [1] to [7], wherein the fluorine-containing monomer (A) has one polymerizable group;
[9] The dental composition according to any one of [1] to [8], wherein the content of the fluorine-containing monomer (A) is 1 to 70 parts by mass in 100 parts by mass of all the monomers. ;
[10] The dental composition according to any one of [1] to [9], wherein the fluorine-free monomer (B) contains a monomer (B-1) having an acidic group;
[11] The fluorine-free monomer (B) contains a polyfunctional (meth) acrylamide (B-5) having no acidic group and having two or more polymerizable groups [1]. The dental composition according to any one of [10];
[12] A dental composite resin comprising the dental composition according to any one of [1] to [11];
[13] A self-adhesive dental composite resin comprising the dental composition according to any one of [1] to [11];
[14] A dental cement comprising the dental composition according to any one of [1] to [11].

According to the present invention, there is provided a dental composition having excellent transparency, curing depth, surface hardness and mechanical strength. Further, according to the present invention, there is provided a dental composition capable of easily reproducing the color tone of natural dentin. Further, according to the present invention, since the surface hardness of the cured product is high, it is easy to polish the cured product, and there is provided a dental composition capable of obtaining a cured product having good smoothing durability.

The dental composition of the present invention has a refractive index of less than 1.460, a fluorine-containing monomer (A), a fluorine-free monomer (B), and a refractive index of 1.450 or more and 1.500 or less. The content of the inorganic filler (E) containing a certain inorganic filler (C) and the polymerization initiator (D) and having a refractive index of less than 1.450 is less than 10% by mass. With this structure, a dental composition having excellent transparency, curing depth, and mechanical strength can be obtained.

Hereinafter, each component used in the dental composition of the present invention will be described.

-Fluorine-containing monomer (A) having a refractive index of less than 1.460
The dental composition of the present invention is excellent in mechanical strength and surface hardness of the cured product while exhibiting high transparency and high curing depth when combined with the fluorine-free monomer (B). It contains a fluorine-containing monomer (A) having a refractive index of less than 1.460 (hereinafter, also simply referred to as “fluorine-containing monomer (A)”). Further, by using the fluorine-containing monomer (A) in combination with other components, good color tone reproducibility close to that of the surrounding natural dentin filled with the hardening of the dental composition can be easily obtained. The fluorine-containing monomer (A) includes, for example, a polymerizable monomer having at least one fluorine atom and at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group, and a styrene group. Fluorine-containing (meth) acrylic acid esters, fluorine-containing (meth) acrylamide and other fluorine-containing (meth) acrylic monomers are preferable, fluorine-containing (meth) acrylic acid esters are more preferable, and fluorine-containing methacrylic acid. Esters are even more preferred. In addition, in this specification, the notation "(meth) acrylic" is used in the meaning which includes both methacrylic and acrylic.

The number of polymerizable groups of the fluorine-containing monomer (A) is not particularly limited as long as it is one or more, but one is preferable from the viewpoint of the elastic modulus of the cured product.

The monomer contained in the dental composition of the present invention is generally a monomer mixture in which a plurality of types of monomers are mixed in order to adjust physical properties such as mechanical strength and adhesion to dentin. However, from the viewpoint of transparency and opal effect, it is preferable to set the type and blending ratio of the monomer so that the refractive index of the monomer mixture is higher than the refractive index of the filler. At this time, since the refractive index of the monomer mixture can be easily prepared, the refractive index of the fluorine-containing monomer (A) is preferably 1.459 or less, more preferably 1.400 or less. It is preferably 1.380 or less, more preferably 1.370 or less, and particularly preferably 1.370 or less. The lower limit is not particularly limited, but may be 1.350 or more, for example. In the present specification, the refractive index of the polymerizable monomer refers to a value measured in a constant temperature room at 25 ° C. using an Abbe refractive index meter (manufactured by Atago Co., Ltd.).

As the fluorine-containing monomer (A), a monomer having 3 or more fluorine atoms is preferable, a monomer having 4 or more fluorine atoms is more preferable, and a monomer having 4 or more fluorine atoms is contained in the molecule. A monomer having an alkyl group or an alkylene group having 2 to 15 carbon atoms as the main chain is more preferable.

As the fluorine-containing monomer (A), one type may be used alone, or two or more types may be used in combination. Specific examples of the fluorine-containing (meth) acrylic monomer that can be preferably used as the fluorine-containing monomer (A) are shown below.

Examples of the fluorine-containing monomer (A) include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (perfluoro). Butyl) ethyl (meth) acrylate, 3- (perfluorobutyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) ) Acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate , 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate and the like. Among these, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H- Dodecafluoroheptyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate is preferred, 1H, 1H, 5H-octafluoropentyl (Meta) acrylates, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylates are more preferred.

The content of the fluorine-containing monomer (A) is not particularly limited, but the dental composition of the present invention has improved curability and adhesiveness, and the mechanical strength of the obtained cured product is improved. In 100 parts by mass of all the monomers contained in, it is preferably 1 part by mass or more, more preferably 10 parts by mass or more, further preferably 20 parts by mass or more, and 70 parts by mass or less. It is preferably 60 parts by mass or less, more preferably 50 parts by mass or less.

-Fluorine-free monomer (B)
The monomer (B) having no fluorine includes, for example, a polymerizable monomer having no fluorine atom and having at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group, and a styrene group. Fluorine-free (meth) acrylic acid esters, fluorine-free (meth) acrylamide and other fluorine-free (meth) acrylic monomers are preferable, and fluorine-free (meth) acrylic acid esters. Is more preferable, and a methacrylic acid ester having no fluorine is further preferable. As the monomer (B) having no fluorine, one type may be used alone, or two or more types may be used in combination.

Examples of the fluorine-free monomer (B) include (i) a monomer having an acidic group (B-1) and (ii) an aromatic bifunctional (ii) having no acidic group. Meta) acrylic acid ester (B-2) (hereinafter, also simply referred to as "aromatic bifunctional (meth) acrylic acid ester (B-2)"), (iii) aliphatic having no acidic group. Bifunctional (meth) acrylic acid ester of the system (B-3) (hereinafter, also simply referred to as "aliphatic bifunctional (meth) acrylic acid ester (B-3)"), (iv). Trifunctional or higher (meth) acrylic acid ester (B-4) having no acidic group (hereinafter, also simply referred to as “trifunctional or higher (meth) acrylic acid ester (B-4)”), (v. ) Polyfunctional (meth) acrylamide (B-5) having no acidic group and having two or more polymerizable groups, (vi) Hydrophilic monofunctional polymerizable monomer having no acidic group (B-6) (hereinafter, also simply referred to as “hydrophilic monofunctional polymerizable monomer (B-6)”) and the like can be mentioned.

(I) Monomer having an acidic group (B-1)
The dental composition of the present invention has an acidic group for the purpose of promoting decalcification of the dentin and improving the adhesiveness to the dentin as well as promoting chemical polymerization at the adhesive interface. It may contain a monomer (B-1).

The monomer (B-1) having an acidic group is, for example, polymerizable having at least one acidic group and at least one polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group, or a styrene group. Examples thereof include (meth) acrylic acid esters having an acidic group, (meth) acrylic monomers having an acidic group such as (meth) acrylamide having an acidic group, and preferred (meth) acrylic monomers having an acidic group (meth). ) Acryloyl ester is more preferable, and a methacrylate ester having an acidic group is further preferable.

Examples of the acidic group include a phosphoric acid group, a pyrophosphate group, a thiophosphate group, a phosphonic acid group, a carboxylic acid group, a sulfonic acid group, and the like. It may have only one of them, or it may have two or more of them.

As the monomer (B-1) having an acidic group, one type may be used alone, or two or more types may be used in combination. Specific examples of the (meth) acrylic monomer having various acidic groups, which can be preferably used as the monomer having an acidic group (B-1), are shown below.

Examples of the (meth) acrylic monomer having a phosphoric acid group include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, and 4- (meth) acryloyl. Oxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) ) Acryloyloxyoctyldihydrogenphosphate, 9- (meth) acryloyloxynonyldihydrogenphosphate, 10- (meth) acryloyloxydecyldihydrogenphosphate, 11- (meth) acryloyloxyundecyldihydrogenphosphate, 12 -(Meta) acryloyl oxide decyldihydrogen phosphate, 16- (meth) acryloyloxyhexadecyldihydrogen phosphate, 20- (meth) acryloyloxyeicosildihydrogen phosphate, 2- (meth) acryloyloxyethylphenylhydro Genphosphate, 2- (meth) acryloyloxyethyl-2-bromoethylhydrogenphosphate, 2- (meth) acryloyloxyethyl (4-methoxyphenyl) hydrogenphosphate, 2- (meth) acryloyloxypropyl (4-methoxy) Monofunctional (meth) acrylic monomers having a phosphoric acid group such as phenyl) hydrogen phosphate, and their acid anhydrides, acid halides (acidides, etc.), alkali metal salts, ammonium salts; bis [2- (Meta) acryloyloxyethyl] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- (meth) ) Acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyloxynonyl] hydrogen phosphate, bis [10- (meth) acryloyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl Dihydrogen phosphate, bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethi Le] Polyfunctional (meth) acrylic monomers having a phosphate group such as hydrogen phosphate, and their acid anhydrides, acid halides (acid chlorides, etc.), alkali metal salts, ammonium salts, etc. Can be mentioned.

Examples of the (meth) acrylic monomer having a pyrophosphate group include bis pyrophosphate [2- (meth) acryloyloxyethyl], bis pyrophosphate [4- (meth) acryloyloxybutyl], and bis pyrophosphate [ 6- (meth) acryloyloxyhexyl], bis pyrophosphate [8- (meth) acryloyloxyoctyl], bis pyrophosphate [10- (meth) acryloyloxydecyl], and their acid anhydrides, acid halides (acids). Chloride, etc.), alkali metal salts, ammonium salts, etc. can be mentioned.

Examples of the (meth) acrylic monomer having a thiophosphate group include 2- (meth) acryloyloxyethyl dihydrogenthiophosphate, 3- (meth) acryloyloxypropyl dihydrogenthiophosphate, and 4- (meth). ) Acryloyloxybutyl dihydrogenthiophosphate, 5- (meth) acryloyloxypentyl dihydrogenthiophosphate, 6- (meth) acryloyloxyhexyl dihydrogenthiophosphate, 7- (meth) acryloyloxyheptyl dihydrogenthio Phosphate, 8- (meth) acryloyloxyoctyldihydrogenthiophosphate, 9- (meth) acryloyloxynonyldihydrogenthiophosphate, 10- (meth) acryloyloxydecyldihydrogenthiophosphate, 11- (meth) acryloyl Oxyundecyldihydrogenthiophosphate, 12- (meth) acryloyl oxide decyldihydrogenthiophosphate, 16- (meth) acryloyloxyhexadecyldihydrogenthiophosphate, 20- (meth) acryloyloxyeicosildihydrogen Examples thereof include thiophosphate, acid anhydrides thereof, acid halides (acidides, etc.), alkali metal salts, ammonium salts and the like.

Examples of the (meth) acrylic monomer having a phosphonic acid group include 2- (meth) acryloyloxyethylphenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, and 6- (meth). ) Acryloyloxyhexyl-3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexylphosphonoacetate, 10- (meth) acryloyloxydecyl Phosphonoacetates and their acid anhydrides, acid halides (acidides, etc.), alkali metal salts, ammonium salts and the like can be mentioned.

Examples of the (meth) acrylic monomer having a carboxylic acid group include a polymerizable monomer having one carboxyl group in the molecule and a polymerizable monomer having a plurality of carboxyl groups in the molecule.

Examples of the polymerizable monomer having one carboxyl group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloyl aspartic acid, and 2- (meth) acryloyloxyethyl. Hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogenphthalate, 2- (meth) acryloyloxyethyl hydrogenmalate, O- (meth) acryloyl tyrosine, N- (meth) acryloyl tyrosine, N- (meth) Acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4 -(Meta) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, and their acid anhydrides, acid halides (acidides, etc.), Examples thereof include alkali metal salts and ammonium salts.

Examples of the polymerizable monomer having a plurality of carboxyl groups in the molecule include 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid and 9- (meth) acryloyloxynonane-1,1-dicarboxylic acid. 10- (meth) acryloyloxydecane-1,1-dicarboxylic acid, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 12- (meth) acryloyloxidedecane-1,1-dicarboxylic acid, 13- (Meta) acryloyloxytridecane-1,1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimerite, 4- (meth) acryloyloxybutyl trimerite, 4- (meth) acryloyloxyhexyl trimerite , 4- (meth) acryloyloxydecyl trimerite, 2- (meth) acryloyloxyethyl-3'-(meth) acryloyloxy-2'-(3,4-dicarboxybenzoyloxy) propylsuccinate, 6- (Meta) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid, 6- (meth) acryloyloxyethylnaphthalene-2,3,6-tricarboxylic acid, 4- (meth) acryloyloxyethylcarbonylpropionoyl-1 , 8-Naphthalic acid, 4- (meth) acryloyloxyethylnaphthalene-1,8-tricarboxylic acid, and acid anhydrides thereof, acid halides (acetates, etc.), alkali metal salts, ammonium salts and the like. ..

Examples of the (meth) acrylic monomer having a sulfonic acid group include 2- (meth) acrylamide-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, and their acid anhydrides and acid halides. (Acrylate, etc.), alkali metal salts, ammonium salts, etc. can be mentioned.

Among the above-mentioned monomers having an acidic group (B-1), a (meth) acrylic single having a phosphoric acid group has improved adhesiveness when used as a self-adhesive dental composite resin or the like. A (meth) acrylic monomer having a weight and / or a carboxylic acid group is preferable, 2-methacryloyloxyethyl dihydrogen phosphate, 10- (meth) acryloyloxydecyldihydrogen phosphate, bis (2-methacryloyloxy). Acid anhydrides of ethyl) hydrogen phosphate, 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 4- (meth) acryloyloxyethyl trimerite, 4- (meth) acryloyloxyethyl trimerite More preferably, 10-methacryloyloxydecyldihydrogen phosphate is even more preferred. As the monomer (B-1) having an acidic group, a (meth) acrylic monomer having a phosphoric acid group is particularly preferable.

The content of the monomer (B-1) having an acidic group is not particularly limited, but the curability and adhesiveness are improved, and the mechanical strength of the obtained cured product is improved. It is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 5 parts by mass or more with respect to 100 parts by mass of all the monomers contained in the dental composition. Further, it is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 20 parts by mass or less.

(Ii) Aromatic bifunctional (meth) acrylic acid ester having no acidic group (B-2)
Examples of the aromatic bifunctional (meth) acrylic acid ester (B-2) include 2,2-bis ((meth) acryloyloxyphenyl) propane and 2,2-bis [4- (3- (3-) 3-). Acryloyloxy-2-hydroxypropoxy) Phenyl] propane, 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (commonly known as Bis-GMA), 2,2-bis (4-) (Meta) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane (for example, those with an average additional molar number of ethoxy groups of 2.6), 2,2 -Bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytetraethoxy) Phenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4-( Meta) acryloyloxydipropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4-( Meta) acryloyloxyethoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2- (4- (meth) acryloyloxy) Dipropoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane and the like, among which 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] Propane (commonly known as Bis-GMA) and 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (with an average number of moles of ethoxy groups of 2.6 (commonly known as D-2.6E)) are preferable. ..

(Iii) Aliphatic bifunctional (meth) acrylic acid ester having no acidic group (B-3)
Examples of the aliphatic bifunctional (meth) acrylic acid ester (B-3) include glycerol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di. Acrylate, triethylene glycol dimethacrylate (commonly known as TEGDMA), propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl 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, 2,2,4-trimethylhexamethylenebis (2-carbamoyl) Oxyethyl) diacrylate, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (commonly known as UDMA), 1,2-bis (3- (meth) acryloyloxy-2-hydroxypropoxy) Examples thereof include ethane, and among these, glycerol di (meth) acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate (commonly known as TEGDMA), neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di. (Meta) acrylate, 1,10-decanediol di (meth) acrylate, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (commonly known as UDMA), 1,2-bis (3-) Methacryloyloxy-2-hydroxypropoxy) ethane is preferred.

(Iv) Trifunctional or higher (meth) acrylic acid ester having no acidic group (B-4)
Examples of the trifunctional or higher (meth) acrylic acid ester (B-4) include trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolmethane tri (meth) acrylate, and pentaerythritol. Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N'-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propan-1 , 3-diol] Tetra (meth) acrylate, 1,7-di (meth) acryloyloxy-2,2,6,6-tetra (meth) acryloyloxymethyl-4-oxaheptan, etc. , N, N'-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate is preferred.

The above-mentioned aromatic bifunctional (meth) acrylic acid ester (B-2), aliphatic bifunctional (meth) acrylic acid ester (B-3), and trifunctional or higher (meth). As the acrylic acid ester (B-4), one type may be used alone, or two or more types may be used in combination. Among these, aromatic bifunctional (meth) acrylic acid ester (B-2) and aliphatic bifunctional (meth) acrylates are available because they are easier to handle and the mechanical strength of the obtained cured product is improved. Bifunctional (meth) acrylic acid ester (B-3) is preferred, 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (commonly known as Bis-GMA), 2, 2-Bis (4-methacryloyloxypolyethoxyphenyl) propane (with an average number of moles of ethoxy groups of 2.6; commonly known as D-2.6E), triethylene glycol dimethacrylate (commonly known as TEGDMA), 2, 2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (commonly known as UDMA) is more preferable, and triethylene glycol dimethacrylate (TEGDMA), 2,2,4-trimethylhexamethylenebis (2-carbamoyloxy). Ethyl) dimethacrylate (UDM) is more preferred.

In the dental composition of the present invention, the above-mentioned aromatic bifunctional (meth) acrylic acid ester (B-2) and aliphatic bifunctional (meth) acrylic acid ester (B-3). The total content of the trifunctional or higher (meth) acrylic acid ester (B-4) is not particularly limited, but the curability, permeability to the dentin and adhesion are improved, and the obtained cured product is obtained. 10 parts by mass or more, preferably 20 parts by mass or more, based on 100 parts by mass of all the monomers contained in the dental composition of the present invention, because the mechanical strength of the above is improved. More preferably, it is more preferably 30 parts by mass or more, particularly preferably 40 parts by mass or more, and more preferably 95 parts by mass or less, further preferably 90 parts by mass or less, and 85 parts by mass. It is more preferably parts or less, particularly preferably 80 parts by mass or less, and most preferably 75 parts by mass or less.

(V) Polyfunctional (meth) acrylamide (B-5) having no acidic group and having two or more polymerizable groups
As another example of the fluorine-free monomer (B), a polyfunctional (meth) acrylamide (B-5) having no acidic group and having two or more polymerizable groups (hereinafter, simply " It is also referred to as "polyfunctional (meth) acrylamide (B-5)"). In the polyfunctional (meth) acrylamide (B-5), the two or more polymerizable groups possessed by the polyfunctional (meth) acrylamide may be all (meth) acrylamide groups, or some of them may be (meth) acrylamide groups. ) It may be a polymerizable group other than the (meth) acrylamide group such as an acryloyloxy group, a vinyl group and a styrene group. Further, the polyfunctional (meth) acrylamide (B-5) preferably has at least one amide proton. Since the polyfunctional (meth) acrylamide (B-5) has at least one (meth) acrylamide group (preferably an amide proton), it has high hydrophilicity and easily penetrates into the collagen layer of dentin. In addition, because it has a plurality of polymerizable groups in the molecule, it exhibits extremely high curability together with other components of the dental composite resin of the present invention, and has a higher adhesive force to dentin. Will be obtained.

Examples of the polyfunctional (meth) acrylamide (B-5) include a compound represented by the following general formula (1), a compound represented by the following general formula (2), and a compound represented by the following general formula (3). Examples thereof include compounds to be used.

In the above general formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is an alkylene group having 1 to 8 carbon atoms which may have a substituent (may be linear or branched). And p is an integer of 1-6. However, a plurality of R ¹ and R ² may be the same or different from each other.

In the above general formula (2), R ³ is a hydrogen atom or a methyl group, and R ⁴ is an alkylene group having 1 to 8 carbon atoms which may have a substituent (may be linear or branched). And q is 2 or 3. However, a plurality of R ³ and R ⁴ may be the same or different from each other.

In the above general formula (3), R ⁵ has an aliphatic group having 1 to 8 carbon atoms (which may be linear, branched or cyclic) or a substituent which may have a substituent. It is an aromatic group that may be used. However, the aliphatic groups are -O-, -S-, -CO-, -CO-O- *, -O-CO- *, -NR ^6- , -CO-NR ^6- *, -NR ⁶ It may be interrupted by at least one binding group selected from the group consisting of −CO− *, −O−CONR ⁶⁻ *, −NR ⁶ CO−O− * and −NR ⁶ −CO−NR ^6−. .. Here, * indicates the side and R ⁵ nitrogen atom to which R ⁵ is attached directly out of the side of the oxygen atom attached directly, which is the side of the oxygen atom. Further, R ⁶ is a hydrogen atom or have a substituent which may C1-8 aliphatic group (which may be cyclic or be linear or branched), R ⁶ there are a plurality, each other It may be the same or different.

In the above general formulas (1) and (2), R ¹ and R ³ are preferably hydrogen atoms from the viewpoint of adhesiveness to the dentin and curability.

In the above general formulas (1) and (2), R ² and R ⁴ are alkylene groups having 1 to 8 carbon atoms, respectively, preferably alkylene groups having 2 to 8 carbon atoms, and have 2 to 8 carbon atoms. It is more preferably an alkylene group of 4, and even more preferably an alkylene group having 2 or 3 carbon atoms. Further, in the alkylene group, one or two or more hydrogen atoms thereof may be substituted with a substituent, but it is preferable that the alkylene group is not substituted with a substituent.

In the above general formulas (1) and (2), as R ² and R ⁴ , for example, methylene group, methyl methylene group, ethylene group, 1-methylethylene group, trimethylene group, 1-ethylethylene group, 1, 2 -Dimethylethylene group, 1,1-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, tetramethylene group, 1-propylethylene group, 2-propylethylene group, 1-ethyl-1-methyl Ethylene group, 1-ethyl-2-methylethylene group, 1,1,2-trimethylethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 1,2- Dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, pentamethylene group, 1-butylethylene group, 1-methyl-1-propylethylene group, 1- Methylene-2-propylethylene group, 1,1-diethylethylene group, 1,2-diethylethylene group, 1-ethyl-1,2-dimethylethylene group, 1-ethyl-2,2-dimethylethylene group, 1- Examples thereof include a methylpentamethylene group, a 2-methylpentamethylene group, a 3-methylpentamethylene group, and a hexamethylene group.

In the above general formula (1), p is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, further preferably 1 or 2, and particularly preferably 2. .. Further, in the above general formula (2), q is preferably 3.

In the above general formula (3), the aliphatic group having 1 to 8 carbon atoms which may have a substituent represented by ^{R 5 is a saturated aliphatic group (alkylene group, cycloalkylene group (1,4).} -It may be either a cyclohexylene group (etc.)) or an unsaturated aliphatic group (alkenylene group, alkynylene group, etc.), and from the viewpoint of availability, ease of production, chemical stability, etc., saturated fat It is preferably a group group, more preferably an alkylene group. Specific examples of the alkylene group include the same as those described above in the description ^{of R 2} and R ^{4 in the general formulas (1) and (2).} From the viewpoint of adhesiveness to the dentin and curability, R ⁵ is preferably an aliphatic group having 1 to 4 carbon atoms which may have a substituent, and may have a substituent. More preferably, it is an aliphatic group of several 2 to 4.

In the above general formula (3), the aliphatic group having 1 to 8 carbon atoms which may have a substituent represented by ^{R 5 may be interrupted by at least one of the above-mentioned binding groups.} That is, at least one of the above-mentioned binding groups may be inserted into the aliphatic group. When the aliphatic group is interrupted by the binding group, the number of binding groups is not particularly limited and can be about 1 to 10, preferably 1 to 3, and more preferably 1. Or two. It is preferable that the aliphatic group is not interrupted by the continuous binding group. That is, it is preferable that the binding groups are not adjacent to each other.

In the above general formula (3), the aliphatic group having 1 to 8 carbon atoms which may have a substituent represented ^{by R 6 which constitutes a part of the binding group is a saturated aliphatic group (alkyl).} It may be any of a group, a cycloalkylene group (cyclohexyl group, etc.) and an unsaturated aliphatic group (alkenyl group, alkynyl group, etc.) from the viewpoints of availability, ease of production, chemical stability, and the like. , Saturated aliphatic group is preferable, and alkyl group is more preferable. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group and n-. Examples thereof include a hexyl group, an n-heptyl group, a 2-methylhexyl group, and an n-octyl group. R ⁶ is preferably an alkyl group having 1 to 4 carbon atoms which may have a hydrogen atom or a substituent, and an alkyl group having 1 to 3 carbon atoms which may have a hydrogen atom or a substituent. Is more preferable.

Examples of the binding group include -O-, -S-, -CO-, -CO-O- *, -O-CO- *, -NH-, -CO-NH- *, -NH-CO- *, At least one selected from the group consisting of -O-CONH- *, -NHCO-O- * and -NH-CO-NH- is preferable, and -O-, -S-, -CO-, -NH-,- At least one selected from the group consisting of CO-NH- * and -NH-CO- * is more preferable.

In the above general formula (3) ^{, examples of the aromatic group which may have a substituent represented by R 5} include an aryl group and an aromatic heterocyclic group, and an aryl group is preferable. A phenyl group is more preferred. The heterocycle of an aromatic heterocyclic group is generally unsaturated, eg, furan group, thiophene group, pyrazole group, oxazole group, isoxazole group, thiazole group, isothiazole group, imidazole group, pyrazole group, frazane. Examples thereof include a group, a triazole group, a pyran group, a pyridine group, a pyridazine group, a pyrimidine group, a pyrazine group, and a 1,3,5-triazine group. The aromatic heterocycle is preferably a 5-membered ring or a 6-membered ring.

In the above general formulas (1), (2) and (3) ^{, examples of the substituent that R 2} , R ⁴ and R ⁵ may have include a halogen atom (chlorine atom, bromine atom, iodine atom). , Carboxy group, hydroxyl group, amino group, amino group mono- or di-substituted with an alkyl group having 1 to 8 carbon atoms, an acyl group, an acyloxy group, an amide group, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carbon number of carbon atoms. Examples thereof include an alkoxy group having 1 to 8 and an alkylthio group having 1 to 8 carbon atoms, and a halogen atom is preferable. The number of substituents is not particularly limited and may be about 1 to 8, preferably 1 to 3.

Specific examples of the compound represented by the general formula (1) include those shown below.

Among these, from the viewpoint of adhesiveness to dentin and curability, the compound represented by the formula (1-1), the compound represented by the formula (1-3), and the compound represented by the formula (1-5) are represented. The compound, the compound represented by the formula (1-7), is preferable, the compound represented by the formula (1-1), and the compound represented by the formula (1-5) are more preferable, and the compound represented by the formula (1-5) is more preferable. From the viewpoint of high hydrophilicity involved in permeation, the compound represented by the formula (1-5) is more preferable.

Specific examples of the compound represented by the general formula (2) include those shown below.

Among these, from the viewpoint of adhesiveness to dentin and curability, the compound represented by the formula (2-1), the compound represented by the formula (2-3), and the compound represented by the formula (2-5) are represented. The compound, the compound represented by the formula (2-7), is preferable, the compound represented by the formula (2-1), and the compound represented by the formula (2-3) are more preferable, and the compound represented by the formula (2-3) is more preferable. From the viewpoint of high hydrophilicity involved in permeation, the compound represented by the formula (2-1) is more preferable.

Specific examples of the compound represented by the general formula (3) include those shown below.

Among these, from the viewpoint of adhesiveness to dentin and curability, the compound represented by the formula (3-1), the compound represented by the formula (3-3), and the compound represented by the formula (3-4) are represented. A compound, a compound represented by the formula (3-9), and a compound represented by the formula (3-10) are preferable, and from the viewpoint of high hydrophilicity involved in the penetration of dentin into the collagen layer, the formula (3) The compound represented by -1) and the compound represented by the formula (3-4) are more preferable, and the compound represented by the formula (3-1) is further preferable.

The polyfunctional (meth) acrylamide (B-5) may be used alone or in combination of two or more. In particular, when at least one selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2) is used in combination with the compound represented by the formula (3), the effect of the present invention is obtained. Is preferable because it is played more prominently.

The content of the polyfunctional (meth) acrylamide (B-5) in the dental composition of the present invention is not particularly limited, but the curability and adhesiveness are improved, and the obtained cured product is mechanically obtained. From the viewpoint of improving the strength, the amount is preferably 0.5 parts by mass or more, and more preferably 2 parts by mass or more, based on 100 parts by mass of all the monomers contained in the dental composition of the present invention. Preferably, it is more preferably 3 parts by mass or more, particularly preferably 5 parts by mass or more, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and 15 parts by mass. The following is more preferable.

(Vi) Hydrophilic, monofunctional polymerizable monomer (B-6)
Yet another example of the fluorine-free monomer (B) is a hydrophilic monofunctional polymerizable monomer (B-6). The hydrophilic, monofunctional polymerizable monomer (B-6) typically has no acidic group and has a polymerizable group such as an acryloyl group, a methacryloyl group, a vinyl group, or a styrene group. Has only one. The hydrophilic monofunctional polymerizable monomer (B-6) preferably has a solubility in water (pure water) at 25 ° C. of 5% by mass or more, and has a solubility of 10% by mass or more. It is more preferable that the solubility is 15% by mass or more. When the dental composition of the present invention contains the hydrophilic monofunctional polymerizable monomer (B-6), higher adhesive force to dentin can be obtained.

The hydrophilic monofunctional polymerizable monomer (B-6) has a hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxyproprene group and an amide group. Examples of the hydrophilic monofunctional polymerizable monomer (B-6) include hydrophilic monofunctional (meth) acrylic acid esters and hydrophilic monofunctional (meth) acrylamides. Monofunctional (meth) acrylic monomers are preferred.

Examples of the hydrophilic monofunctional (meth) acrylic acid ester include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 1,3-dihydroxy. Examples thereof include -2-propyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, and 2- (meth) acryloyloxyethyltrimethylammonium chloride.

Examples of the hydrophilic monofunctional (meth) acrylamide include compounds represented by the following general formula (4), N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-bis. (Hydroxyethyl) (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, 4- (meth) acryloylmorpholin, N-tri (hydroxymethyl) methyl- Examples thereof include N-methyl (meth) acrylamide.

In the above general formula (4), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, an isopropyl group, etc.). However, R ⁸ existing in plural numbers may be different may be identical or different.

Among these hydrophilic monofunctional polymerizable monomers (B-6), 2-hydroxyethyl (meth) acrylate and 2,3-dihydroxypropyl (meth) acrylate are used from the viewpoint of adhesion to dentin. , The compound represented by the general formula (4), diacetone (meth) acrylamide is preferable, 2-hydroxyethyl (meth) acrylate, and the compound represented by the general formula (4) are more preferable, 2-hydroxyethyl methacrylate, N. , N-diethylacrylamide is more preferred.

As the hydrophilic monofunctional polymerizable monomer (B-6), one type may be used alone, or two or more types may be used in combination.

The content of the hydrophilic monofunctional polymerizable monomer (B-6) in the dental composition of the present invention is not particularly limited, but the curability and adhesiveness are improved, and the obtained curing is improved. From the viewpoint of improving the mechanical strength of the product, the amount is preferably 1 part by mass or more and 2 parts by mass or more with respect to 100 parts by mass of all the monomers contained in the dental composite resin of the present invention. Is more preferably 5 parts by mass or more, particularly preferably 7 parts by mass or more, preferably 30 parts by mass or less, more preferably 28 parts by mass or less, and 25 parts by mass. It is more preferably parts by mass or less, particularly preferably 20 parts by mass or less, and most preferably 12 parts by mass or less.

Examples of the fluorine-free monomer (B) include the above-mentioned monomer having an acidic group (B-1), aromatic bifunctional (meth) acrylic acid ester (B-2), and aliphatic. Bifunctional (meth) acrylic acid ester (B-3), trifunctional or higher (meth) acrylic acid ester (B-4), polyfunctional (meth) acrylamide (B-5), hydrophilic It may further contain a polymerizable monomer other than the monofunctional polymerizable monomer (B-6). Since the effect of the present invention is more prominently exhibited in the fluorine-free monomer (B), the above-mentioned aromatic bifunctional (meth) acrylate (B-2) and fat At least one selected from the group consisting of a trifunctional (meth) acrylic acid ester (B-3) and a trifunctional or higher (meth) acrylic acid ester (B-4), the above-mentioned polyfunctionality. It is preferable to contain both (meth) acrylamide (B-5).

The content of the monomer (B) having no fluorine is not particularly limited, but the curability and adhesiveness are improved, and the mechanical strength of the obtained cured product is improved. Therefore, the dental product of the present invention is used. It is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, further preferably 80 parts by mass or more, and more preferably 80 parts by mass or more, based on 100 parts by mass of all the monomers contained in the composition. It is preferably 99 parts by mass or less, more preferably 98 parts by mass or less, and further preferably 95 parts by mass or less.

The refractive index of the fluorine-free monomer (B) is not particularly limited, and is 1.450 because it exhibits good color reproducibility close to that of the surrounding natural dentin filled with the hardening of the dental composition. It is preferably 1.600 or more, more preferably 1.455 or more and 1.590 or less, and further preferably 1.460 or more and 1.570 or less. Monomer having an acidic group (B-1), aromatic bifunctional (meth) acrylic acid ester (B-2), aliphatic bifunctional (meth) acrylic acid ester (B-) 3), trifunctional or higher (meth) acrylic acid ester (B-4), polyfunctional (meth) acrylamide (B-5) having no acidic group and having two or more polymerizable groups, and It is preferable that the refractive index of the hydrophilic monofunctional polymerizable monomer (B-6) is in the above numerical range. In one preferred embodiment, the fluorine-free monomer (B) comprises a polyfunctional (meth) acrylamide (B-5) having no acidic group and having two or more polymerizable groups. , Dental compositions in which the refractive index of the polyfunctional (meth) acrylamide (B-5) is in the above numerical range. In another preferred embodiment, the fluorine-free monomer (B) comprises an aliphatic bifunctional (meth) acrylic acid ester (B-3) and is aliphatic bifunctional. A dental composition in which the refractive index of the (meth) acrylic acid ester (B-3) is in the above numerical range can be mentioned. Further, in another preferred embodiment, the fluorine-free monomer (B) does not have an aliphatic bifunctional (meth) acrylic acid ester (B-3) and an acidic group 2 Contains polyfunctional (meth) acrylamide (B-5) with one or more polymerizable groups, free of aliphatic bifunctional (meth) acrylic acid ester (B-3) and acidic groups Examples thereof include dental compositions in which the refractive index of polyfunctional (meth) acrylamide (B-5) having two or more polymerizable groups is in the above numerical range. Further, as another preferred embodiment, in any of the preferred embodiments described above, the fluorine-free monomer (B) further contains a monomer (B-1) having an acidic group and is acidic. Examples thereof include dental compositions in which the refractive index of the monomer (B-1) having a group is in the above numerical range.

-Inorganic filler (C) having a refractive index of 1.450 or more and 1.500 or less.
The inorganic filler (C) having a refractive index of 1.450 or more and 1.500 or less (hereinafter, also simply referred to as "inorganic filler (C)") improves the mechanical strength of the cured product of the dental composition. And the operability of the dental composition can be improved. As the inorganic filler (C), a known inorganic filler having a refractive index of 1.450 or more and 1.500 or less used in the dental composition can be used without any limitation. In addition, by using the inorganic filler (C) in combination with other components such as the fluorine-containing monomer (A), a good color tone reproduction close to that of the surrounding natural tooth substance filled with the hardening of the dental composition is reproduced. Sex is easily obtained. As the inorganic filler (C), one type may be used alone, or two or more types may be used in combination. Examples of the case where two or more kinds are used in combination include a case where a filler having different inorganic materials, particle size distribution, morphology, etc. is used in combination. As the inorganic filler (C), a commercially available product can be used, and an amorphous inorganic oxide is preferable.

As the inorganic filler (C), a known filler can be used without any limitation as long as the refractive index is in the range of 1.450 or more and 1.500 or less. A refractive index of 1.450 or higher is preferable because the effect and the refractive index can be easily prepared, and 1.453 or higher is more preferable, and 1.455 or higher is further preferable. The refractive index is preferably 1.500 or less, more preferably 1.490 or less, and even more preferably 1.480 or less. In the present specification, the refractive index of various fillers refers to a value measured in a thermostatic chamber at 25 ° C. using an Abbe refractive index meter (manufactured by Atago Co., Ltd.).

Examples of the inorganic material used for the inorganic filler (C) include silica, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, and 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 Etc., and silica is preferable.

The shape of the inorganic filler (C) is not particularly limited and may be appropriately selected according to the characteristics to be enhanced as a dental composition, and specifically, it can be used as a powder of amorphous or spherical particles. When the amorphous inorganic filler (C) is used, the mechanical strength and abrasion resistance of the obtained cured product are improved, and when the spherical inorganic filler (C) is used, the obtained cured product is polished. A spherical shape is preferable because it improves smoothness and durability. In the present specification, the spherical shape of the filler means that the particles observed in the unit field of view of the filler taken by taking a picture of the filler with a scanning electron microscope (SEM) are rounded and orthogonal to the maximum diameter thereof. It means that the average uniformity obtained by dividing the particle diameter in the direction to be formed by the maximum diameter is 0.6 or more.

The average particle size of the inorganic filler (C) is preferably 0.0001 to 50 μm, preferably 0.001 to 50 μm, from the viewpoint of operability of the obtained dental composition and mechanical strength of the obtained cured product. It is more preferably 10 μm, further preferably 0.003 to 5 μm, and particularly preferably 0.005 to 1 μm. In the present specification, the average particle size of the inorganic filler (C) means the average particle size (average primary particle size) of the primary particles of the inorganic filler (C). As the average particle size of the inorganic filler (C), the inorganic filler (C) is dispersed in a dispersion medium consisting of at least one selected from alcohol and water, and "SALD-2300" manufactured by Shimadzu Corporation, etc. The median value (median diameter: d50) of the volumetric particle size distribution when measured with the laser diffraction type particle size distribution measuring device of the above can be adopted. If the average particle size of the inorganic filler (C) is small and falls below the lower limit of measurement (for example, 0.10 μm) in the laser diffraction type particle size distribution measuring device, “SU3500” or “SU9000” manufactured by Hitachi, Ltd. An electron micrograph is taken using a scanning electron microscope such as the above, and an average value obtained from the particle size of 20 randomly selected particles can be adopted. When the particles are non-spherical, the particle size may be the arithmetic mean of the longest and shortest lengths of the particles.

The inorganic filler (C) may be agglomerated particles formed by agglomerating particles. Normally, commercially available inorganic fillers exist as aggregates, but 10 mg of inorganic filler powder is added to 300 mL of water (dispersion medium) to which water or a surfactant such as sodium hexametaphosphate of 5% by mass or less is added. However, when the dispersion treatment is performed for 30 minutes with an ultrasonic intensity of 40 W and a frequency of 39 KHz, it has only a weak cohesive force to disperse to the particle size indicated by the manufacturer. However, the agglomerated particles are particles in which particles that are hardly dispersed even under such conditions are strongly agglomerated.

As a method of producing agglomerated particles in which particles are strongly agglomerated from commercially available agglomerates of an inorganic filler, the particles are heated to near the temperature immediately before the inorganic filler melts, and the particles of the inorganic filler that come into contact with each other are few. A method of heating to the extent that the particles are fused to the surface is preferably adopted. Further, in this case, in order to control the shape of the agglomerated particles, the agglomerated form may be set before heating. Examples of the method include a method in which an inorganic filler is placed in an appropriate container and pressurized, and a method in which the solvent is once dispersed in a solvent and then the solvent is removed by a method such as spray drying.

Further, as another suitable method for producing agglomerated particles, a sol such as a silica sol produced by a wet method is used, which is dried by a method such as freeze-drying or spray drying, and heat-treated if necessary. There is a way to do it. Specific examples of the sol include Nippon Shokubai Co., Ltd., product name "Sea Hoster", JGC Catalysts and Chemicals Co., Ltd., product name "OSCAL", "QUEEN TITANIC", Nissan Chemical Industries, Ltd., product name "Snowtex". , "Aluminasol", "Celnax", "Nanouse" and the like.

The inorganic filler (C) improves the affinity with the monomer contained in the dental composition of the present invention, or enhances the chemical bond with the monomer to improve the mechanical strength of the cured product. It is preferable to perform surface treatment with a surface treatment agent in advance in order to prevent the surface treatment. Examples of the surface treatment agent include organosilicon compounds, organotitanium compounds, organozirconium compounds, and organoaluminum compounds. These surface treatment agents may be used alone or in combination of two or more. When two or more kinds of surface treatment agents are used in combination, the surface treatment layer resulting from the use may be a surface treatment layer of a mixture of two or more kinds of surface treatment agents, or the surface treatment layer may be a stack of a plurality of surface treatment layers. It may be a surface-treated layer having a multi-layer structure. As the surface treatment method, a known method can be used without particular limitation.

Examples of the organic silicon compound include compounds represented by R ⁹ _n SiX _4-n (in the formula, R ⁹ is a substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms, and X is a carbon number of carbon atoms. It represents an alkoxy group, an acetoxy group, a hydroxyl group, a halogen atom or a hydrogen atom of 1 to 4, and n is an integer of 0 to 3. However, ^{when a plurality of R 9} and X are present, they are the same. Can be different).

Specific examples of the organic silicon compound include, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, and isobutyl. Trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloyloxy Propylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) γ-aminopropyltrimethoxysilane, N- ( β-Aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethyl Cyranol, methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethylbromosilane, diethylsilane, vinyltriacetoxysilane, ω- (meth) acryloyloxyalkyltri Methoxysilane (carbon number between (meth) acryloyloxy group and silicon atom: 3-12, eg γ-methacryloyloxypropyltrimethoxysilane, etc.), ω- (meth) acryloyloxyalkyltriethoxysilane ((meth) ) Carbon number between acryloyloxy group and silicon atom: 3-12, eg γ-methacryloyloxypropyltriethoxysilane, etc.), organosilazane (hexaethyl disilazane, hexan-propyl disilazane, hexaisopropyl disilazane, etc.) , 1,1,2,2-tetramethyl-3,3-diethyldisilazane, 1,1,3,3-tetramethyldisilazan, 1,1 , 1,3,3,3-hexamethyldisilazane, 1,1,1,3,3-pentamethyldisilazane, etc.).

Among these, an organosilicon compound having a functional group capable of copolymerizing with the monomer contained in the dental composition of the present invention is preferable. Preferred specific examples of organosilicon compounds are ω- (meth) acryloyloxyalkyl trimethoxysilane (carbon number between (meth) acryloyloxy group and silicon atom: 3 to 12), ω- (meth) acryloyloxyalkyl. Triethoxysilane (number of carbon atoms between (meth) acryloyloxy group and silicon atom: 3-12), vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, With organosilazane (1,1,3,3-tetramethyldisilazan, 1,1,1,3,3,3-hexamethyldisilazan, 1,1,1,3,3-pentamethyldisilazan, etc.) is there.

Examples of the organic titanium compound include tetramethyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate and the like.

Examples of the organic zirconium compound include zirconium isopropoxide, zirconium n-butoxide, zirconium acetylacetonate, zirconium acetate and the like.

Examples of the organoaluminum compound include aluminum acetylacetoneate and an aluminum organolate chelate compound.

The content of the inorganic filler (C) is not particularly limited, but the total mass contained in the dental composition of the present invention is considered from the viewpoint of operability of the obtained dental composition and mechanical strength of the cured product. It is preferably 100 parts by mass or more, more preferably 120 parts by mass or more, further preferably 140 parts by mass or more, and 900 parts by mass or less with respect to 100 parts by mass of the body. It is more preferably 600 parts by mass or less, further preferably 450 parts by mass or less, and particularly preferably 200 parts by mass or less.

-Inorganic filler (E) having a refractive index of less than 1.450
The inorganic filler (E) having a refractive index of less than 1.450 (hereinafter, also simply referred to as “inorganic filler (E)”) has a refractive index of less than 1.450 used in dental compositions. A known inorganic filler (E) can be used without any limitation. As the inorganic filler (E), one type may be used alone, or two or more types may be used in combination. Examples of the case where two or more kinds are used in combination include a case where a filler having different inorganic materials, particle size distribution, morphology, etc. is used in combination. As the inorganic filler (E), a commercially available product can be used.

The shape of the inorganic filler (E) is not particularly limited and may be appropriately selected according to the characteristics to be enhanced as a dental composition, and specifically, it can be used as a powder of amorphous or spherical particles. When the amorphous inorganic filler (E) is used, the mechanical strength and abrasion resistance of the obtained cured product are improved, and when the spherical inorganic filler (E) is used, the obtained cured product is polished. A spherical shape is preferable because it improves smoothness and durability.

The average particle size of the inorganic filler (E) is preferably 0.0001 to 50 μm, preferably 0.001 to 50 μm, from the viewpoint of operability of the obtained dental composition and mechanical strength of the obtained cured product. It is more preferably 30 μm, further preferably 0.003 to 10 μm, and particularly preferably 0.005 to 5 μm. In the present specification, the average particle size of the inorganic filler (E) means the average particle size (average primary particle size) of the primary particles of the inorganic filler (E). The method for measuring the average particle size of the inorganic filler (E) is the same as the method for measuring the inorganic filler (C).

The inorganic filler (E) may be agglomerated particles formed by agglomerating particles. Normally, commercially available inorganic fillers exist as aggregates, but 10 mg of inorganic filler powder is added to 300 mL of water (dispersion medium) to which water or a surfactant such as sodium hexametaphosphate of 5% by mass or less is added. However, when the dispersion treatment is performed for 30 minutes with an ultrasonic intensity of 40 W and a frequency of 39 KHz, it has only a weak cohesive force to disperse to the particle size indicated by the manufacturer. However, the agglomerated particles are particles in which particles that are hardly dispersed even under such conditions are strongly agglomerated.

As a method of producing agglomerated particles in which particles are strongly agglomerated from commercially available agglomerates of an inorganic filler, the particles are heated to near the temperature immediately before the inorganic filler melts, and the particles of the inorganic filler that come into contact with each other are few. A method of heating to the extent that the particles are fused to the surface is preferably adopted. Further, in this case, in order to control the shape of the agglomerated particles, the agglomerated form may be set before heating. Examples of the method include a method in which an inorganic filler is placed in an appropriate container and pressurized, and a method in which the solvent is once dispersed in a solvent and then the solvent is removed by a method such as spray drying.

Further, as another suitable method for producing agglomerated particles, a sol such as silica sol produced by a wet method is used, which is dried by a method such as freeze-drying or spray drying, and heat-treated if necessary. The method can be mentioned. Specific examples of the sol include Nippon Shokubai Co., Ltd., product name "Sea Hoster", JGC Catalysts and Chemicals Co., Ltd., product name "OSCAL", "QUEEN TITANIC", Nissan Chemical Industries, Ltd., product name "Snowtex". , "Aluminasol", "Celnax", "Nanouse" and the like.

Like the inorganic filler (C), the inorganic filler (E) improves the affinity with the monomer contained in the dental composition of the present invention and enhances the chemical bondability with the monomer. In order to improve the mechanical strength of the cured product, it is preferable to perform surface treatment with a surface treatment agent in advance. Examples of the surface treatment agent include organosilicon compounds, organotitanium compounds, organozirconium compounds, and organoaluminum compounds. These surface treatment agents may be used alone or in combination of two or more. When two or more kinds of surface treatment agents are used in combination, the surface treatment layer resulting from the use may be a surface treatment layer of a mixture of two or more kinds of surface treatment agents, or a multi-layer structure in which a plurality of surface treatment layers are laminated. It may be a surface treatment layer. As the surface treatment method, a known method can be used without particular limitation as in the case of the inorganic filler (C).

The content of the inorganic filler (E) is less than 10% by mass with respect to 100 parts by mass of the dental composition of the present invention from the viewpoint of operability of the obtained dental composition and mechanical strength of the cured product. It is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 1% by mass or less, and may be 0% by mass. When the content is 10% by mass or more, a reddish color tone is strongly exhibited, which is suitable for reproducing the color tone of the dentin portion of the natural dentin, but it is difficult to reproduce the color tone of the enamel portion.

-Polymerization initiator (D)
The polymerization initiator promotes the polymerization curing of the dental composition. As the polymerization initiator (D), a polymerization initiator used in the general industry can be used, and in particular, a polymerization initiator used for dental applications can be preferably used. As the polymerization initiator (D), for example, at least one selected from the group consisting of the photopolymerization initiator (D-1) and the chemical polymerization initiator (D-2) can be used, and the photopolymerization initiator (D) can be used. D-1) is preferable. As the polymerization initiator (D), one type may be used alone, or two or more types may be used in combination.

Examples of the photopolymerization initiator (D-1) include (bis) acylphosphine oxides (including salts), thioxanthones (including salts such as quaternary ammonium salts), ketals, α-diketones, and the like. Examples thereof include coumarins, anthraquinones, benzoin alkyl ethers and α-aminoketones.

Among these photopolymerization initiators (D-1), at least one selected from the group consisting of (bis) acylphosphine oxides (including salts), α-diketones and coumarins is preferable. As a result, a dental composition having excellent photocurability in the visible light region and the near-ultraviolet region and exhibiting sufficient photocurability using any light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp can be obtained. Be done.

Among the (bis) acylphosphine oxides, examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine oxide. Oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi (2,6-dimethyl) Phosphine) phosphonate and the like.

Among the (bis) acylphosphine oxides, examples of the bisacylphosphine oxides include bis (2,6-dichlorobenzoyl) phenylphosphine oxide and bis (2,6-dichlorobenzoyl) -2,5-dimethylphenyl. Phosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) Examples thereof include phenylphosphine oxide and bis (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide.

The (bis) acylphosphine oxides may be water-soluble (bis) acylphosphine oxides. Examples of the water-soluble acylphosphine oxides include salts of (bis) acylphosphine oxides as exemplified above. Examples of the salt include alkali metal salts such as sodium salt, potassium salt and lithium salt; alkaline earth metal salt; pyridinium salt; ammonium salt and the like. Water-soluble (bis) acylphosphine oxides can be synthesized, for example, by the methods disclosed in European Patent No. 0009348, JP-A-57-197289 and the like.

Among these (bis) acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide The sodium salt of oxide, 2,4,6-trimethylbenzoylphenylphosphine oxide is preferable, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide are more preferable.

Examples of the α-diketones include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4'-oxybenzyl, acenaphthenquinone and the like. Be done. Among these, camphorquinone is preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.

Examples of the coumarins include 3,3'-carbonylbis (7-diethylamino kumarin), 3- (4-methoxybenzoyl) coumarin, 3-thienyl coumarin, 3-benzoyl-5,7-dimethoxy kumarin, 3-. Benzoyl-7-methoxykumarin, 3-benzoyl-6-methoxykumarin, 3-benzoyl-8-methoxykumarin, 3-benzoyl kumarin, 7-methoxy-3- (p-nitrobenzoyl) kumarin, 3- (p-nitro) Benzoyl) coumarin, 3,5-carbonylbis (7-methoxykumarin), 3-benzoyl-6-bromokumarin, 3,3'-carbonylbis coumarin, 3-benzoyl-7-dimethylaminocumarin, 3-benzoylbenzo [ f] Kumarin, 3-carboxykumarin, 3-carboxy-7-methoxykumarin, 3-ethoxycarbonyl-6-methoxykumarin, 3-ethoxycarbonyl-8-methoxykumarin, 3-acetylbenzo [f] kumarin, 3-benzoyl -6-Nitrokumarin, 3-benzoyl-7-diethylaminokumarin, 7-dimethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3-3 (4-Diethylamino) coumarin, 7-methoxy-3- (4-methoxybenzoyl) coumarin, 3- (4-nitrobenzoyl) benzo [f] coumarin, 3- (4-ethoxycinnamoyl) -7-methoxycoumarin, 3- (4-Dimethylaminocinnamoyle) coumarin, 3- (4-diphenylaminocinnamoyle) coumarin, 3-[(3-dimethylbenzothiazole-2-ylidene) acetyl] coumarin, 3-[(1-methylnaphtho] 1,2-d] thiazole-2-ylidene) acetyl] coumarin, 3,3'-carbonylbis (6-methoxycumarin), 3,3'-carbonylbis (7-acetoxycmarin), 3,3'-carbonyl Bis (7-dimethylaminocoumarin), 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (dibutylamino) coumarin, 3- (2-benzoimidazolyl) -7- (Diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (dioctylamino) coumarin, 3-acetyl-7- (dimethylamino) coumarin, 3,3'-carbonylbis (7-dibutylaminocoumarin), 3, 3'- Carbonyl-7-diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7- Tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine-11-one, 10- (2-benzothiazolyl) -2,3 Examples thereof include 6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidine-11-one. Among these, 3,3'-carbonylbis (7-diethylaminocoumarin) and 3,3'-carbonylbis (7-dibutylaminocoumarin) are preferable.

Examples of the chemical polymerization initiator (D-2) include organic peroxides such as ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, and peroxydicarbonate.

The content of the polymerization initiator (D) is not particularly limited, but all the monomers contained in the dental composition of the present invention can be obtained because a dental composition having excellent adhesiveness and curability can be obtained. It is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, further preferably 0.05 part by mass or more, and 0.1 part by mass or more with respect to the mass part. Is particularly preferable. Further, since a dental composition having excellent adhesiveness can be obtained and precipitation from the dental composition can be suppressed, the content of the polymerization initiator (D) is determined by the dental composition of the present invention. It is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, further preferably 10 parts by mass or less, and 5 parts by mass or less with respect to 100 parts by mass of all the monomers contained in. Is particularly preferable.

The total content of the above-mentioned fluorine-containing monomer (A), fluorine-free monomer (B), inorganic filler (C), and polymerization initiator (D) in the dental composition of the present invention. Can be appropriately changed according to the usage pattern and purpose of the dental composition of the present invention, but is preferably 50% by mass or more because the effect of the present invention is more prominently exhibited. , 80% by mass or more, more preferably 95% by mass or more, and may be 98% by mass or more, 99% by mass or more, and further 100% by mass.

-Optional Ingredients The dental composition of the present invention consists only of the above-mentioned fluorine-containing monomer (A), fluorine-free monomer (B), inorganic filler (C), and polymerization initiator (D). Although it may be configured, it may further contain one or more of any other optional components. Examples of the optional component include an X-ray opaque inorganic filler (F) having a refractive index of more than 1.500 and an average particle size of 200 nm or less, a polymerization accelerator, a polymerization inhibitor, a pH adjuster, and ultraviolet rays. Examples include absorbents, thickeners, antibacterial agents, and fragrances. The dental composition of the present invention may contain known dyes and pigments as colorants.

X-ray opaque inorganic filler (F) having a refractive index of more than 1.500 and an average particle size of 200 nm or less.
The dental composition of the present invention has a refractive index of more than 1.500 and average particles for the purpose of imparting X-ray impermeableness to the dental composition or improving the strength or operability of a cured product. It is preferable to further contain an X-ray impermeable inorganic filler (F) having a diameter of 200 nm or less (hereinafter, also simply referred to as “X-ray impermeable inorganic filler (F)”). The "X-ray opaque" represents the property of a substance that cannot transmit X-rays, and the X-ray opaque region on the X-ray photograph looks white. As used herein, the ability to distinguish between natural dentin and hardened dental compositions using standard dental X-ray equipment in a conventional manner is described. Dental compositions that are X-ray opaque are advantageous in certain cases where X-rays are used to diagnose tooth condition. As the X-ray opaque inorganic filler (F), a known filler used in a dental composition can be used without any limitation. As the X-ray opaque inorganic filler (F), one type may be used alone, or two or more types may be used in combination. Examples of the case where two or more kinds are used in combination include a case where a filler having different inorganic materials, particle size distribution, morphology, etc. is used in combination. As the X-ray opaque inorganic filler (F), a commercially available product can be used.

The surface of the X-ray permeable inorganic filler (F) is coated with, for example, barium glass, strontium borosilicate glass, dental glass powder such as lanthanum glass ceramics, composite oxides such as silica-zirconia, and silica. Examples thereof include itterbium fluoride having a core-shell structure, barium sulfate having a core-shell structure whose surface is coated with silica, and zirconium dioxide having a core-shell structure whose surface is coated with silica. Each of these may be used alone or in combination of two or more, and the X-ray opaque element is at least selected from the group consisting of Yb, Ba, Zr, Sr, and La. It is preferable to contain one kind, and it is more preferable to contain at least one kind selected from the group consisting of Yb, Ba, and Zr.

The shape of the X-ray opaque inorganic filler (F) is not particularly limited and may be appropriately selected according to the characteristics desired to be enhanced as a dental composition. Specifically, as a powder of amorphous or spherical particles. Can be used. When the amorphous X-ray impermeable inorganic filler (F) is used, the mechanical strength and abrasion resistance of the obtained cured product are improved, and the spherical X-ray impermeable inorganic filler (F) is used. Is used to improve the polishing smoothness and smoothness durability of the obtained cured product.

The average particle size of the X-ray impermeable inorganic filler (F) is 0.0001 to 200 nm from the viewpoint of operability of the obtained dental composition, transparency of the obtained cured product, mechanical strength, and the like. It is preferably 0.001 to 180 nm, more preferably 0.003 to 160 nm, and particularly preferably 0.005 to 150 nm. In the present specification, the average particle size of the X-ray impermeable inorganic filler (F) means the average particle size (average primary particle size) of the primary particles of the X-ray impermeable inorganic filler (F). To do. The method for measuring the average particle size of the X-ray opaque inorganic filler (F) is the same as the method for measuring the inorganic filler (C).

The X-ray impermeable inorganic filler (F) may be agglomerated particles formed by agglomeration of particles. Normally, commercially available inorganic fillers exist as aggregates, but 10 mg of inorganic filler powder is added to 300 mL of water (dispersion medium) to which water or a surfactant such as sodium hexametaphosphate of 5% by mass or less is added. However, when the dispersion treatment is performed for 30 minutes with an ultrasonic intensity of 40 W and a frequency of 39 KHz, it has only a weak cohesive force to disperse to the particle size indicated by the manufacturer. However, the agglomerated particles are particles in which particles that are hardly dispersed even under such conditions are strongly agglomerated.

As a method of producing agglomerated particles in which particles are strongly agglomerated from commercially available agglomerates of an inorganic filler, the particles are heated to near the temperature immediately before the inorganic filler melts, and the particles of the inorganic filler that come into contact with each other are few. A method of heating to the extent that the particles are fused to is preferably adopted. Further, in this case, in order to control the shape of the agglomerated particles, the agglomerated form may be set before heating. Examples of the method include a method in which an inorganic filler is placed in an appropriate container and pressurized, and a method in which the solvent is once dispersed in a solvent and then the solvent is removed by a method such as spray drying.

Similar to the inorganic filler (C), the X-ray opaque inorganic filler (F) improves the affinity with the monomer contained in the dental composition of the present invention, and can be used with the monomer. In order to enhance the chemical bondability and improve the mechanical strength of the cured product, it is preferable to perform surface treatment with a surface treatment agent in advance. Examples of the surface treatment agent include organosilicon compounds, organotitanium compounds, organozirconium compounds, and organoaluminum compounds. These surface treatment agents may be used alone or in combination of two or more. When two or more kinds of surface treatment agents are used in combination, the surface treatment layer resulting from the use may be a surface treatment layer of a mixture of two or more kinds of surface treatment agents, or a multi-layer structure in which a plurality of surface treatment layers are laminated. It may be a surface treatment layer. As the surface treatment method, a known method can be used without particular limitation as in the case of the inorganic filler (C).

The content of the X-ray opaque inorganic filler (F) is not particularly limited, but the dental composition of the present invention can be used from the viewpoint of operability of the obtained dental composition and mechanical strength of the cured product. It is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and 120 parts by mass or less with respect to 100 parts by mass of all the contained monomers. It is preferably 90 parts by mass or less, more preferably 60 parts by mass or less, and particularly preferably 30 parts by mass or less.

The dental composition of the present invention may further contain an organic-inorganic composite filler in order to obtain a higher opal effect. The organic-inorganic composite filler is not particularly limited, but a material having a refractive index of more than 1.500 may be used, or a material having a refractive index of 1.500 or less may be used. In certain embodiments, the refractive index of the organic-inorganic composite filler may be 1.510 or more and 1.590 or less, or 1.530 or more and 1.580 or less. Further, in some other embodiments, the refractive index of the organic-inorganic composite filler may be 1.400 or more and 1.500 or less, or 1.440 or more and 1.490 or less. As the monomer used for the organic-inorganic composite filler, the above-mentioned monomer (B) having no fluorine can be used. As the inorganic material used for the organic-inorganic composite filler, the same one as the inorganic filler (C) can be used.

-Polymerization accelerator The polymerization accelerator can promote the polymerization curing of the dental composition together with the polymerization initiator (D) and the like. As the polymerization accelerator, known polymerization accelerators can be used, and for example, amines, sulfinic acids (including salts), borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, halogen compounds, etc. Examples thereof include aldehydes, thiol compounds, sulfites, hydrogen sulfites, thiourea compounds, and amines are preferable. As the polymerization accelerator, one type may be used alone, or two or more types may be used in combination.

The amines are divided into aliphatic amines and aromatic amines. Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; and secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine. N-Methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethylmethacrylate, N-methyldiethanolaminedimethacrylate, N-ethyldiethanolaminedimethacrylate, triethanolamine mono Examples thereof include tertiary aliphatic amines such as methacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine and tributylamine. Among these, from the viewpoint of curability and storage stability of the dental composition, a tertiary aliphatic amine is preferable, and N-methyldiethanolamine and triethanolamine are more preferable.

Examples of the aromatic amine include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis ( 2-Hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N -Bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-diisopropylaniline, N, N-bis (2-hydroxyethyl) -3,5 -Di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl -3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl-4 -T-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, ethyl 4- (N, N-dimethylamino) benzoate, methyl 4- (N, N-dimethylamino) benzoate , 4- (N, N-dimethylamino) propyl benzoate, 4- (N, N-dimethylamino) n-butoxyethyl benzoate, 4- (N, N-dimethylamino) 2- (methacryloyloxy) benzoate Examples thereof include ethyl, 4- (N, N-dimethylamino) benzophenone, and 4- (N, N-dimethylamino) butyl benzoate. Among these, ethyl N, N-bis (2-hydroxyethyl) -p-toluidine and 4- (N, N-dimethylamino) ethyl benzoate can impart excellent curability to the dental composition. , 4- (N, N-dimethylamino) benzoate n-butoxyethyl, 4- (N, N-dimethylamino) benzophenone is preferred, and 4- (N, N-dimethylamino) benzoate ethyl is more preferred.

Specific examples of the sulfinic acids (including salts), borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, halogen compounds, aldehydes, thiol compounds, sulfites, hydrogen sulfites, and thiourea compounds include For example, those described in International Publication No. 2008/08977.

Although the content of the polymerization accelerator is not particularly limited, 100 parts by mass of all the monomers contained in the dental composition of the present invention can be obtained because a dental composition having excellent adhesiveness and curability can be obtained. On the other hand, it is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, further preferably 0.05 part by mass or more, and 0.1 part by mass or more. Is particularly preferable. In addition, the content of the polymerization accelerator is included in the dental composition of the present invention because a dental composition having excellent adhesiveness can be obtained and precipitation from the dental composition can be suppressed. It is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, and 5 parts by mass or less with respect to 100 parts by mass of all the monomers. Is particularly preferable.

-Polymerization inhibitor Examples of the polymerization inhibitor include 3,5-di-t-butyl-4-hydroxytoluene, hydroquinone, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, hydroquinone monomethyl ether, and 2,6-di-t-butylphenol. And so on. As the polymerization inhibitor, one type may be used alone, or two or more types may be used in combination.

Although the content of the polymerization inhibitor is not particularly limited, it is 0.001 part by mass or more with respect to 100 parts by mass of all the monomers contained in the dental composition of the present invention because a desired effect can be obtained. It is preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, particularly preferably 0.05 part by mass or more, and 10 parts by mass. It is preferably less than or equal to, more preferably 5 parts by mass or less, further preferably 1 part by mass or less, and particularly preferably 0.5 parts by mass or less.

-Form of dental composition The dental composition of the present invention can be used, for example, as a dental composite resin, a dental cement, a pit fissure filling material, a swaying tooth fixing material, an orthodontic adhesive, and the like. Among them, it is used as a dental composite resin or a dental cement. At this time, the form is not particularly limited, and the components of the dental composition of the present invention may be used as a two-agent type (two-paste type, two-component type) divided into two. Hereinafter, specific embodiments when the dental composition is applied will be shown.

<Dental composite resin>
It is one of the preferred embodiments that the dental composition of the present invention is used as a dental composite resin (particularly, a self-adhesive dental composite resin). In particular, in recent years, self-adhesive dental composite resins having adhesiveness to dental composite resins have been developed, and the process is further simplified as compared with the conventional adhesive system using dental adhesives. Great merit in use. When the dental composition of the present invention is used as a self-adhesive dental composite resin, a fluorine-containing monomer (A), a fluorine-free monomer (B), an inorganic filler (C), and a polymerization initiator ( It is preferable that the monomer (B) containing D) and the X-ray permeable inorganic filler (F) and having no fluorine contains a monomer (B-1) having an acidic group, and further contains fluorine. It is more preferable that the non-containing monomer (B) contains a polyfunctional (meth) acrylamide (B-5), and it is further preferable that the monomer (B) contains a polymerization accelerator in addition to the polyfunctional (meth) acrylamide (B-5).

The content of each component in the self-adhesive dental composite resin is 1 to 70 parts by mass of the fluorine-containing monomer (A) and the fluorine-free monomer (B) 10 in 100 parts by mass of all the monomers. The monomer (B) containing ~ 95 parts by mass and having no fluorine contains 1 to 40 parts by mass of the monomer (B-1) having an acidic group, and is inorganic with respect to 100 parts by mass of all the monomers. It is preferable to contain 100 to 900 parts by mass of the filler (C), 0.001 to 20 parts by mass of the polymerization initiator (D), and 1 to 120 parts by mass of the X-ray permeable inorganic filler (F). A monomer (B) containing 10 to 60 parts by mass of a fluorine-containing monomer (A) and 20 to 90 parts by mass of a fluorine-free monomer (B) in 100 parts by mass of the weight. Contains 2 to 30 parts by mass of a monomer (B-1) having an acidic group and 2 to 30 parts by mass of a polyfunctional (meth) acrylamide (B-5), based on 100 parts by mass of all the monomers. , 120 to 600 parts by mass of the inorganic filler (C), 0.01 to 10 parts by mass of the polymerization initiator (D), and 3 to 90 parts by mass of the X-ray impermeable inorganic filler (F). , 20 to 50 parts by mass of the fluorine-containing monomer (A) and 30 to 85 parts by mass of the fluorine-free monomer (B) in 100 parts by mass of all the monomers. (B) contains 5 to 20 parts by mass of the monomer (B-1) having an acidic group and 3 to 15 parts by mass of the polyfunctional (meth) acrylamide (B-5), and 100 parts by mass of the total monomer. The part contains 140 to 450 parts by mass of the inorganic filler (C), 0.05 to 5 parts by mass of the polymerization initiator (D), and 5 to 60 parts by mass of the X-ray impermeable inorganic filler (F). Is even more preferable. Further, in any of the above embodiments, the self-adhesive dental composite resin further contains a polymerization accelerator, and the content of the polymerization accelerator is 0.001 to 30 with respect to 100 parts by mass of all the monomers. It is preferably parts by mass, more preferably 0.01 to 20 parts by mass, and even more preferably 0.05 to 10 parts by mass.

<Dental cement>
It is also one of the preferred embodiments to use the dental composition of the present invention as a dental cement. As the dental cement, resin cement, glass ionomer cement, resin reinforced glass ionomer cement and the like are exemplified as suitable ones. As the dental cement, a dental adhesive, a self-etching primer, or the like may be used as a pretreatment material. When the dental composition of the present invention is used as a dental cement, a fluorine-containing monomer (A), a fluorine-free monomer (B), an inorganic filler (C), and a polymerization initiator (D), It is preferable that the X-ray permeable inorganic filler (F) is contained, and it is more preferable that the monomer (B) having no fluorine contains a monomer (B-1) having an acidic group, and more preferably. It is even more preferable to include functional (meth) acrylamide (B-5), and even more preferably to include a polymerization accelerator. Further, it is preferable that the polymerization initiator (D) contains a chemical polymerization initiator (D-2).

The content of each component in the dental cement is 1 to 70 parts by mass of the fluorine-containing monomer (A) and 10 to 95 parts by mass of the fluorine-free monomer (B) in 100 parts by mass of all the monomers. The inorganic filler (C) is contained in an amount of 1 to 40 parts by mass of the monomer (B-1) having an acidic group, and the monomer (B) having no fluorine is 100 parts by mass of the total monomer. ) 100 to 900 parts by mass, 0.001 to 20 parts by mass of the polymerization initiator (D), and 1 to 120 parts by mass of the X-ray impermeable inorganic filler (F), and 100 parts by mass of the total monomer. In parts, the fluorine-containing monomer (A) contains 10 to 60 parts by mass, and the fluorine-free monomer (B) contains 20 to 90 parts by mass, and the fluorine-free monomer (B) is an acidic group. Contains 2 to 30 parts by mass of the monomer (B-1) and 2 to 30 parts by mass of the polyfunctional (meth) acrylamide (B-5), and is inorganic with respect to 100 parts by mass of all the monomers. It is more preferable to contain 120 to 600 parts by mass of the filler (C), 0.01 to 10 parts by mass of the polymerization initiator (D), and 3 to 90 parts by mass of the X-ray impermeable inorganic filler (F). In 100 parts by mass of all the monomers, 20 to 50 parts by mass of the fluorine-containing monomer (A) and 30 to 85 parts by mass of the fluorine-free monomer (B) are contained, and the monomer having no fluorine ( B) contains 5 to 20 parts by mass of the monomer (B-1) having an acidic group and 3 to 15 parts by mass of the polyfunctional (meth) acrylamide (B-5), and 100 parts by mass of all the monomers. It contains 140 to 450 parts by mass of the inorganic filler (C), 0.05 to 5 parts by mass of the polymerization initiator (D), and 5 to 60 parts by mass of the X-ray permeable inorganic filler (F). Is even more preferable. Further, in any of the above embodiments, the dental cement further contains a polymerization accelerator, the polymerization initiator (D) contains a chemical polymerization initiator (D-2), and the total amount of the monomer is 100 parts by mass. On the other hand, the content of the chemical polymerization initiator (D-2) is preferably 0.001 to 20 parts by mass, and the content of the polymerization accelerator is 0.001 to 30 parts by mass, and the chemical polymerization initiation is started. It is more preferable that the content of the agent (D-2) is 0.01 to 10 parts by mass and the content of the polymerization accelerator is 0.01 to 20 parts by mass, and the content of the chemical polymerization initiator (D-2) is more preferable. ) Is 0.05 to 5 parts by mass, and the content of the polymerization initiator is 0.05 to 10 parts by mass. Further, in any of the above embodiments, when a dual cure type dental cement is used, the dental cement further contains a polymerization accelerator, and the polymerization initiator (D) becomes a chemical polymerization initiator (D-2). In addition, it contains a photopolymerization initiator (D-1), and the content of the photopolymerization initiator (D-1) is 0.001 to 20 parts by mass with respect to 100 parts by mass of all the monomers. The content of the polymerization accelerator is preferably 0.001 to 30 parts by mass, the content of the photopolymerization initiator (D-1) is 0.01 to 10 parts by mass, and the content of the polymerization accelerator. Is more preferably 0.01 to 20 parts by mass, the content of the photopolymerization initiator (D-1) is 0.05 to 5 parts by mass, and the content of the polymerization accelerator is 0.05 to to 0.05 parts. It is more preferably 10 parts by mass.

[Preparation method]
The method for preparing the dental composition of the present invention is not particularly limited, and can be obtained by blending each of the above-mentioned components. The order of blending is not particularly limited, and each component may be blended at once, or may be blended in two or more portions.

In any of the preferred embodiments of the dental composite resin and the dental cement described above, the content of each component can be appropriately changed based on the description in the above specification, and any component can be added or deleted. Etc. can be changed.

The present invention includes embodiments in which the above configurations are variously combined within the scope of the technical idea of the present invention as long as the effects of the present invention are exhibited.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. Also, not all combinations of features described in the examples are essential to the solution of the present invention. The components used in the following examples and comparative examples, their abbreviations, structures, and test methods are as follows.

[Fluorine-containing monomer (A) having a refractive index of less than 1.460]
8FMA: 1H, 1H, 5H-octafluoropentyl methacrylate (refractive index 1.360)

[Fluorine-free monomer (B)]
-Monomer having an acidic group (B-1)
MDP: 10-methacryloyloxydecyldihydrogen phosphate (refractive index 1.460)

Aliphatic bifunctional (meth) acrylic acid ester (B-3)
UDMA: 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate (refractive index 1.480)
TEGDMA: Triethylene glycol dimethacrylate (refractive index 1.460)
DD: 1,10-decanediol dimethacrylate (refractive index 1.460)

-Multifunctional (meth) acrylamide (B-5)
MAEA: N-methacryloyloxyethyl acrylamide (Compound (3-1)) (refractive index 1.460)

[Inorganic filler (C) having a refractive index of 1.450 or more and 1.500 or less]
SC2500-SMJ: Spherical fine particle silica (manufactured by Admatex Co., Ltd., Admafine SC2500-SMJ, average particle size 0.4-0.6 μm, amorphous, refractive index 1.460)
YC100C-SM1: Spherical fine particle silica (manufactured by Admatex Co., Ltd., Admanano YC100C-SM1, average particle size 0.1 μm, amorphous, refractive index 1.460)
SO-C5: Spherical fine particle silica (manufactured by Admatex Co., Ltd., Admafine SO-C5, average particle size 1.3-1.7 μm, amorphous, refractive index 1.460)
Sciqas: Spherical fine particle silica (manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.4 μm, amorphous, refractive index 1.470)

[Polymerization initiator (D)]
CQ: dl-camphorquinone

[X-ray opaque inorganic filler (F) having a refractive index of more than 1.500 and an average particle size of 200 nm or less]
YbF-20-AV330: Ytterbium fluoride particles (manufactured by MATHYM, average particle size 20-40 nm, refractive index 1.520)
YBF100: Silica-coated ytterbium fluoride particles (manufactured by SG JAPAN Co., Ltd., average particle size 110 nm, spherical, trade name "SG-YBF100", refractive index 1.530)
Varifine BF-40: Ultrafine barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., average particle size 10 nm, refractive index 1.640)
Varifine BF-1L: Ultrafine barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., average particle size 100 nm, refractive index 1.640)
Nano zirconia TZ-0: Zirconia powder (manufactured by Tosoh Corporation, average particle size 20-30 nm, trade name "TZ-0", refractive index 2.130)

[Inorganic filler having a refractive index of more than 1.500 and an average particle size of more than 200 nm]
Inorganic filler 1: Silane-treated silica stone powder Silica stone powder (manufactured by Nitchitsu Co., Ltd., trade name: high silica) was pulverized with a ball mill to obtain crushed silica stone powder. The average particle size of the obtained pulverized siliceous powder was measured using a laser diffraction type particle size distribution measuring device (manufactured by Shimadzu Corporation, model "SALD-2300") and found to be 2.2 μm (refractive index 1). .560). 100 parts by mass of this crushed silica stone powder was surface-treated with 4 parts by mass of γ-methacryloyloxypropyltrimethoxysilane by a conventional method to obtain a silane-treated silica stone powder.
Inorganic filler 2: Silane-treated barium boroaluminosilicate glass Barium boroaluminosilicate glass (manufactured by SCHOTT, GM27884 UF0.7 grade, average particle size: 0.7 μm, refractive index 1.550) 100 g, γ-methacryloyloxypropyltri 6 g of methoxysilane and 200 mL of a 0.3 mass% acetic acid aqueous solution were placed in a three-necked flask and stirred for 2 hours at room temperature. After water was removed by freeze-drying, heat treatment was performed at 80 ° C. for 5 hours to obtain a silane-treated barium boroaluminosilicate glass.

[Polymerization accelerator]
DABE: 4- (N, N-dimethylamino) ethyl benzoate [polymerization inhibitor]
BHT: 3,5-di-t-butyl-4-hydroxytoluene [Example 1 and Comparative Example 1 Application of dental composition to dental composite resin]
<Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-4>
By mixing and kneading each component shown in Tables 1 and 2 at room temperature using the above-mentioned components, the dental composites of Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-4 The resin was prepared. Then, using these dental composite resins, the transparency, curing depth, bending strength, surface hardness, and color tone reproducibility of the cured product were measured according to the methods described below. Tables 1 and 2 show the compounding ratios (parts by mass) and test results of the dental composite resins of each Example and Comparative Example.

[Transparency of cured product]
A cover glass and a circular stainless steel mold having a diameter of 20 mm and a thickness of 1 mm are set on the slide glass, and the dental compositions obtained in each Example and Comparative Example are placed in the mold. It was filled to the extent that it overflowed a little. Further, another cover glass and then a slide glass were put on it, and a force was applied from above so as to push out the excess dental composition from the mold. This was cured by irradiating it with an LED polymerizer "α Light V" (manufactured by Morita Co., Ltd.) for 2 minutes each on the front and back, and the cover glass, slide glass, and mold were removed to obtain a sample of the cured product. ..

Transparency was evaluated using a spectrophotometer (CM-3610d, (JIS Z 8722: 2009, compliant with condition c) manufactured by Konica Minolta Japan Co., Ltd.). Specifically, the brightness (L1) representing the brightness index L * in the L * a * b * color system of JIS Z 8781-4: 2013 when a standard white plate is placed behind the sample and the chromaticity is measured. , When the standard blackboard is placed behind the same sample and the chromaticity is measured, the brightness (L2) representing the brightness index L * in the L * a * b * color system is measured, and the difference between the two (ΔL = L1- L2) was calculated and used as an index of transparency (N = 1). The larger the value of ΔL, the higher the transparency.

[Curing depth]
The curing depth was evaluated according to JIS T 6514: 2015 (composite resin for dental restoration). Specifically, it was done as follows. The produced dental composition was filled in a stainless steel mold (thickness 12 mm, diameter 4 mm). The upper and lower surfaces are laminated and pressure-welded in the order of film and slide glass, and the film pressure-welded surface with the glass plate removed from one side is irradiated with light for 10 seconds with the dental visible light irradiator "Pencure 2000" (manufactured by Morita Co., Ltd.) It was cured. After removing the cured product from the mold, wipe off the uncured part, measure the curing depth from the light irradiation surface using a micrometer (manufactured by Mitutoyo Co., Ltd.), and set half of the measured value as the curing depth (N). = 5), the average value was calculated.

[Bending physical properties]
Strength was evaluated by bending test according to ISO4049: 2009. Specifically, it is as follows. The dental composition was filled in a SUS mold (length 2 mm × width 25 mm × thickness 2 mm), and the upper and lower sides (2 mm × 25 mm surface) of the dental composition (paste) were pressure-welded with a slide glass. Next, the dental composition was cured by irradiating the front and back of the paste with light through a slide glass at 5 locations on each side for 10 seconds with a dental visible light irradiator "Pencure 2000" (manufactured by Morita Co., Ltd.). The obtained cured product was subjected to a bending test at a crosshead speed of 1 mm / min using a universal testing machine "Autograph AG-I 100 kN" (manufactured by Shimadzu Corporation), and the bending strength was measured (N). = 5), the average value was calculated.

[surface hardness]
An appropriate amount of the paste of the dental composition prepared in each Example and Comparative Example was placed on a slide glass, and the upper and lower surfaces were pressed with the slide glass using a 1 mm gauge (manufactured by Mitutoyo Co., Ltd.), and dentistry was performed only from above. A disk having a diameter of 10 mm and a thickness of 1 mm was prepared by irradiating with light for 10 seconds with a visible light irradiator "Pencure 2000" (manufactured by Morita Co., Ltd.) for curing. A clean smooth surface was polished with # 1500 abrasive paper under dry conditions, and finally mirror-polished with diamond paste. The sample prepared here was loaded with 200 g for 10 seconds using a micro-hardness tester (HM-221, manufactured by Mitutoyo Co., Ltd.), and the Vickers hardness (Hv) was measured (N = 5) and averaged. The value was calculated.

[Evaluation of color reproducibility]
The color reproducibility of the I-class and IV-class cavities was evaluated using the paste of the dental composition prepared in each Example and Comparative Example containing an appropriate amount of pigment. Specifically, as a class I cavity, a Box-shaped cavity (approximately 4 mm in width and approximately 3 mm in length) is used in the center of the occlusal surface using the first molar with a color tone of M32A3 of Enduraposterio (manufactured by Matsukaze Co., Ltd.). (Depth about 2 mm) is prepared, filled with the adjusted dental composition, and after molding, it is irradiated with light for 10 seconds with the dental visible light irradiator "Pencure 2000" (manufactured by Morita Co., Ltd.). Hardened and polished.

In addition, as a class IV cavity, a sample with a color tone of A3 in the shade guide of VITAPAN classical (manufactured by VITA) was used to prepare a mesial box-shaped cavity (width about 3 mm, length about 4 mm). The prepared dental composition was filled, molded, and then irradiated with light for 10 seconds with a dental visible light irradiator "Pencure 2000" (manufactured by Morita Co., Ltd.) to cure and polish. The reproducibility of the color tone of the repaired part was visually evaluated according to the following criteria.
<Color compatibility with restored teeth>
A: In both class I and class IV cavities, the color tone of the dental composition matches well with the surrounding area.
B: In both class I and class IV cavities, the color tone of the dental composition matches the surrounding area, but the repair site is visible.
C: In both class I and class IV cavities, the color tone of the dental composition is clearly darker than the surrounding area and does not match.

As shown in Table 1, the dental composite resin (Examples 1-1 to 1-11) according to the present invention has a cured product having a transparency of 13.0 or more and a curing of 3.0 mm or more. Since the depth was expressed, it was confirmed that it showed high transparency and curing depth. It was also confirmed that the dental composite resin according to the present invention exhibits good color reproducibility. Furthermore, it was confirmed that the dental composite resin according to the present invention has a surface hardness of 28 or more. On the other hand, as shown in Table 2, the inorganic filler (C) which does not contain the fluorine-containing monomer (A) having a refractive index of less than 1.460 or has a refractive index of 1.450 or more and 1.500 or less. ) Is not included in the dental composite resins (Comparative Examples 1-1 to 1-4), each of which has a transparency of less than 13.0 and a curing depth of less than 3.0 mm, and it has been confirmed that the transparency is not sufficient. It was confirmed that the color reproducibility was not sufficient. Further, in Comparative Examples 1-1 and 1-2, the surface hardness was 26 or less.

According to the present invention, the dental composition according to the present invention is suitably used as a dental composite resin and a dental cement in the field of dentistry.

Claims (14)

A fluorine-containing monomer (A) having a refractive index of less than 1.460, a monomer (B) having no fluorine, an inorganic filler (C) having a refractive index of 1.450 or more and 1.500 or less, and A dental composition containing the polymerization initiator (D) and having a refractive index of less than 1.450 and an inorganic filler (E) having a content of less than 10% by mass. The dental composition according to claim 1, wherein the inorganic filler (C) is an amorphous inorganic oxide. The dental composition according to claim 1 or 2, wherein the inorganic filler (C) has an average particle size of 0.0001 to 50 μm. The dental composition according to any one of claims 1 to 3, further comprising an X-ray opaque inorganic filler (F) having a refractive index of more than 1.500 and an average particle size of 200 nm or less. .. The dental use according to claim 4, wherein the X-ray opaque element of the X-ray opaque inorganic filler (F) contains at least one selected from the group consisting of Yb, Ba, Zr, Sr, and La. Composition. The dental composition according to claim 4, wherein the X-ray opaque element of the X-ray opaque inorganic filler (F) contains at least one selected from the group consisting of Yb, Ba, and Zr. The dental composition according to any one of claims 1 to 6, wherein the inorganic filler (C) has a spherical grain shape. The dental composition according to any one of claims 1 to 7, wherein the fluorine-containing monomer (A) has one polymerizable group. The dental composition according to any one of claims 1 to 8, wherein the content of the fluorine-containing monomer (A) is 1 to 70 parts by mass in 100 parts by mass of all the monomers. The dental composition according to any one of claims 1 to 9, wherein the fluorine-free monomer (B) contains a monomer (B-1) having an acidic group. Claims 1 to 10, wherein the fluorine-free monomer (B) contains a polyfunctional (meth) acrylamide (B-5) having no acidic group and having two or more polymerizable groups. The dental composition according to any one of the following items. A dental composite resin comprising the dental composition according to any one of claims 1 to 11. A self-adhesive dental composite resin comprising the dental composition according to any one of claims 1 to 11. A dental cement comprising the dental composition according to any one of claims 1 to 11.