Dental hardenable composition with good color match

Abstract

To provide a dental hardenable composition that enables highly aesthetic restorations that blend in with the surroundings to the extent that they are indistinguishable from natural teeth, and that has a single composition and exhibits good color matching with natural teeth of a wide range of colors, particularly for cases where a cavity bottom exists, such as Class I, Class II, or Class V. The dental curable composition includes a polymerizable monomer (A), a filler (B), a polymerization initiator (C), and a colorant (D), and when a 1.0 mm thick cured product of the dental curable composition is measured against a white background using a spectrocolorimeter, the ratio R of the spectral reflectance at wavelengths of 650 nm, 700 nm, and 750 nm to the spectral reflectance at a wavelength of 600 nm is 650 / 600 , R 700 / 600 , and R 750 / 600 The dental hardenable composition is provided, in which the values ​​of the above are all within the range of 97% to 103%.

Description

[Technical Field]

[0001] The present invention relates to a dental hardenable composition that can be suitably used in the field of dentistry as a dental material capable of substituting part or all of natural teeth, particularly as a dental composite resin. [Background technology]

[0002] Before the advent of dental hardenable compositions, especially dental composite resins, amalgams and gold alloys were used for filling dental caries. In contrast, dental composite resins have rapidly become popular because they are inexpensive and can relatively easily achieve a color similar to that of natural teeth. In recent years, improvements in the mechanical strength and adhesive strength of dental filling and restorative materials have led to their use not only in anterior teeth but also in molars, which are subject to high occlusal pressure. Currently, most filling treatments are performed using dental filling and restorative materials.

[0003] Various studies have been conducted to improve the appearance of dental composite resins to resemble natural teeth. For example, Patent Document 1 proposes a dental composite material that uses a base filler with a refractive index similar to that of the cured product of a polymerizable monomer. This composite material further incorporates a different filler with a different refractive index than the cured product of the polymerizable monomer and an average particle size of 1 μm or greater to adequately scatter light entering the cured product of the composition containing the filler and the polymerizable monomer. Such dental composite materials have a specific degree of transmitted light diffusion, similar to that of natural teeth, allowing for highly aesthetic restorations. However, even with these properties approximating those of natural teeth, various problems remain in clinical applications. For example, the color of natural teeth varies from person to person, and even within the same individual's teeth, the color varies depending on the region. To achieve highly aesthetic restorations using the dental composite resin proposed in Patent Document 1, it is necessary to prepare multiple dental composite resins with different shades and select the one that best matches the color of the actual tooth. Selecting the best shade in this way requires skill, and it is not possible to match the shade easily. Furthermore, dentists must stock dental composite resins in multiple shades, which is a cost disadvantage. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 9-255516 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made to solve the problems associated with the prior art, and aims to provide a dental hardenable composition that enables highly aesthetic restorations that blend in with the surroundings to the point that they are indistinguishable from natural teeth, and that has a single composition and exhibits good color matching with natural teeth of a wide range of shades. Another aim of the present invention is to provide a dental hardenable composition that has a single composition and exhibits good color matching with natural teeth of a wide range of shades, particularly for cases where a cavity floor exists, such as Class I, Class II, or Class V. [Means for solving the problem]

[0006] As a result of extensive research to achieve the above object, the present inventors have found that when a cured product of a dental curable composition is measured against a white background using a spectrocolorimeter, the spectral reflectance is nearly constant within a certain range of wavelengths, and therefore the dental curable composition exhibits good color matching with natural teeth having a wide range of color tones.

[0007] That is, the present invention includes the following inventions. [1] A dental curable composition comprising a polymerizable monomer (A), a filler (B), a polymerization initiator (C), and a colorant (D), The ratio R of the spectral reflectance at wavelengths of 650 nm, 700 nm, and 750 nm to the spectral reflectance at a wavelength of 600 nm when a 1.0 mm thick cured product of the dental curable composition is measured using a spectrocolorimeter against a white background. 650 / 600 , R 700 / 600 , and R 750 / 600 The dental hardenable composition, wherein each of the following is within the range of 97% to 103%: [2] The dental curable composition according to [1], wherein a contrast ratio defined by the following formula (1) in a cured product having a thickness of 1.0 mm satisfies 0.35 to 0.65. Contrast ratio = Y b / Y w (1) (where Y b represents the Y value of the XYZ color system measured against a black background, and Y wrepresents the Y value of the XYZ color system measured against a white background.) [3] The dental curable composition according to [1] or [2], wherein the optical diffusion index LD of a cured product having a thickness of 0.25 mm, as defined by the following formula (2), is 0.0001 to 0.99: LD=(I5 / cos5°) / I0(2) (Here, I represents the luminous intensity of light transmitted through the cured product, and I0 and I5 represent the luminous intensity of transmitted light at angles of 0 degrees and 5 degrees, respectively, relative to the direction perpendicular to the sample plate (the direction of incident light).) [4] The dental curable composition according to any one of [1] to [3], wherein a chromaticity index a* / w in the L*a*b* color system of a 1.0 mm thick cured product is -3.0 to 2.0 when measured with a standard white plate placed behind the cured product. [5] The dental curable composition according to any one of [1] to [4], wherein the filler (B) contains inorganic fine particles (BF-1) having an average particle size of 0.05 to 1 μm. [6] The dental curable composition according to any one of [1] to [5], wherein the filler (B) contains inorganic agglomerated particles (BF-2) formed by agglomeration of inorganic primary particles (x), and the inorganic primary particles (x) have an average particle size of 0.001 to 1 μm. [7] The dental curable composition according to [6], wherein the inorganic agglomerated particles (BF-2) contain light-diffusing inorganic agglomerated particles (BF-2d), and the refractive index of the light-diffusing inorganic agglomerated particles (BF-2d) satisfies the following formula (3): 0.03<|nP-nF BF-2d |<1.0 (3) (where nP is the refractive index of the polymer obtained by polymerizing the polymerizable monomer (A), and nF BF-2d represents the refractive index of the light-diffusing inorganic agglomerated particles (BF-2d). [8] The dental curable composition according to any one of [1] to [7], wherein the filler (B) comprises an organic-inorganic composite filler (BC) containing inorganic primary particles (x), and the inorganic primary particles (x) have an average particle size of 0.001 to 1 μm. [9] The dental curable composition according to [8], wherein the organic-inorganic composite filler (BC) contains a light-diffusing organic-inorganic composite filler (BC-d), and the refractive index of the light-diffusing organic-inorganic composite filler (BC-d) satisfies the following formula (7): 0.03<|nP-nF BC-d |<1.0 (7) (where nP is the refractive index of the polymer obtained by polymerizing the polymerizable monomer (A), and nF BC-d represents the refractive index of the light-diffusing organic-inorganic composite filler (BC-d). [Effects of the Invention]

[0008] According to the present invention, a dental hardenable composition can be provided that enables highly aesthetic restorations that blend in with the surroundings to the point that they are indistinguishable from natural teeth, and that exhibits good color matching with a wide range of natural tooth shades using a single dental hardenable composition. Furthermore, according to the present invention, a dental hardenable composition can be provided that exhibits good color matching with a wide range of natural tooth shades using a single dental hardenable composition, particularly for cases where a cavity floor is present, such as Class I, Class II, or Class V. Furthermore, the dental hardenable composition of the present invention can be suitably used for dental composite resins. Furthermore, according to the present invention, a dental hardenable composition can be provided that produces a cured product that is easily polished and has excellent smoothness durability. Furthermore, according to the present invention, a dental hardenable composition that is excellent in operability can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below. The dental hardenable composition of the present invention is a dental hardenable composition comprising a polymerizable monomer (A), a filler (B), a polymerization initiator (C), and a colorant (D), and when a 1.0 mm thick cured product of the dental hardenable composition is measured against a white background using a spectrophotometer, the ratios R of the reflectance at wavelengths of 650, 700, and 750 nm to the spectral reflectance at a wavelength of 600 nm are all within the range of 97% to 103%. This configuration enables highly aesthetic restorations that blend in with the surroundings to the point that they are indistinguishable from natural teeth. In particular, for cases where a cavity floor is present, such as Class I, Class II, or Class V, the dental hardenable composition has a single composition and exhibits good color matching with a wide range of natural tooth shades.

[0010] The dental hardenable composition of the present invention has a spectral reflectance (r 600 ) at wavelengths of 650, 700, and 750 nm (r 650 , r 700 and r 750 ) ratio (respectively, R 650 / 600 =r 650 / r 600 ×100, R 700 / 600 =r 700 / r 600 ×100, and R 750 / 600 =r 750 / r 600 × 100) is in the range of 97.0% to 103.0%. 650 / 600 , R 700 / 600 , and R 750 / 600are preferably in the range of 97.5% to 102.5%, more preferably in the range of 97.8% to 102.2%, and even more preferably in the range of 98.0% to 102.0%. By being in the above ranges, when a cavity in a natural tooth is filled and restored with the dental hardenable composition, the color tone of the cavity floor of the natural tooth is easily reflected in the filling portion of the tooth filled with the dental hardenable composition. This effect makes it possible to provide a highly aesthetic restoration method for natural teeth of a wide range of color tones using a dental hardenable composition of one type, without the need to prepare multiple types of dental hardenable compositions of different color tones. In a preferred embodiment, the spectral reflectance (r 650 ) at wavelengths of 700 and 750 nm (r 700 and r 750 ) ratio (respectively, R 700 / 650 =r 700 / r 650 ×100, and R 750 / 650 =r 750 / r 650 × 100) is preferably in the range of 97.0% to 103.0%, more preferably in the range of 97.5% to 102.5%, even more preferably in the range of 97.8% to 102.2%, and particularly preferably in the range of 98.0% to 102.0%.

[0011] The above spectral reflectance ratio within a preferred range means that the spectral reflectance is substantially constant in the wavelength range of 600 to 750 nm, i.e., the spectral reflectance curve plateaus in that range. In this measurement system, incident light passes through a plate of the cured product, reflects off a white background, and then passes through the plate of the cured product again (measurement light), and the resulting measurement is used. The spectral reflectance curve plateaus in that range means that the measurement light is constant in that range. This constant measurement light means that when light reflected off a white background passes through the cured product, the light absorbed by the cured product is constant regardless of wavelength, meaning that the color of the background can be reflected directly on the surface. The cured product of the dental curable composition of the present invention exhibits constant reflected light in the wavelength range of 600 to 750 nm, which is the yellow to red color tone of natural teeth, and therefore reflects the background very well in this range of colors, i.e., it is able to pick up the background color well. This feature is clinically very effective, especially in cases where a cavity floor (cavity floor) exists, such as in Black's Class I, Class II, and Class V classifications. Black's classification refers to a classification of cavity types, and includes Class I, Class II, Class III, Class IV, and Class V cavities. Class I cavities are created for caries originating in pits and fissures of molars. Class II cavities originate on the approximal surfaces of molars. Class III cavities originate on the approximal surfaces of anterior teeth and canines and do not include the incisal corners. Class IV cavities originate on the approximal surfaces of anterior teeth and canines and include the incisal corners. Class V cavities are located on the labial (buccal) or lingual (palatal) side of the crown, on the gingival third. When the dental hardenable composition of the present invention is used to restore such cases, the hardened product closely reflects the color of the cavity floor of the natural tooth, enabling highly aesthetic restorations that blend in with the surrounding area.Furthermore, a dental hardenable composition with a single composition exhibits good color matching with a wide range of natural tooth colors.

[0012] The spectral reflectance can be measured using a spectrophotometer capable of measuring reflected light. The spectrophotometer can be a commercially available product such as the SE7700 or SE6000 spectrophotometer manufactured by Nippon Denshoku Industries Co., Ltd. A calibrated standard white plate is used as the white background. The XYZ tristimulus values, measured using a C / 2 light source and the 0°-45° method of JIS Z 8722, satisfy the following ranges: 90≦X≦96, 92≦Y≦98, and 100≦Z≦116. The standard white plate is placed in close contact with the cured plate of the dental curable composition to be measured. The spectral reflectance of the cured product of the dental curable composition of the present invention can be measured specifically by the method described in the Examples below.

[0013] The spectral reflectance can be adjusted by varying the type and compounding ratio of the filler (B) and colorant (D), which will be described later. Specifically, an uncolored curable composition is first prepared using the polymerizable monomer (A), filler (B), and polymerization initiator (C), and the spectral reflectance is measured. At this point, it is preferable that the spectral reflectance curve in the wavelength range of 600 to 750 nm shows a slight increasing trend or plateaus. This can be controlled by varying the type and compounding ratio of the polymerizable monomer (A) and filler (B). Subsequently, by adding a colorant (D), particularly a yellow or red pigment, the spectral reflectance curve in this wavelength range can be adjusted to a plateau.

[0014] The dental hardenable composition of the present invention exhibits excellent color matching with natural teeth even without strict control of various color-related parameters (e.g., contrast ratio, saturation, etc.) to approximate those of natural teeth in order to reproduce the color tone of natural teeth. Meanwhile, to further improve aesthetics, the contrast ratio of a 1.0 mm thick cured product of the dental hardenable composition of the present invention is preferably 0.35 or more, more preferably 0.40 or more, even more preferably 0.43 or more, and particularly preferably 0.45 or more. Furthermore, the contrast ratio is preferably 0.65 or less, more preferably 0.60 or less, even more preferably 0.57 or less, and particularly preferably 0.55 or less. By being equal to or greater than the above lower limit, the impression of a dark, sunken impression in a tooth filled with the dental hardenable composition can be effectively prevented. By being equal to or less than the above upper limit, the color tone of the cavity floor can be effectively reflected in the filling portion filled with the dental hardenable composition. In the present invention, the contrast ratio is a value calculated based on the following formula (1). Furthermore, in formula (1), Y b is the Y value of the XYZ color system measured against a black background using a color difference meter. w and represent the Y value of the XYZ color system measured on a white background using a color difference meter. Contrast ratio = Y b / Y w (1) The contrast ratio is an index of transparency, with values ​​closer to 1 representing a more opaque material and values ​​closer to 0 representing a more transparent material.

[0015] The contrast ratio can be measured using the above-mentioned spectrocolorimeter or the like. A standard white plate is used as the white background, and the measurement is performed by bringing it into close contact with the cured plate of the dental curable composition to be measured. A matte dark box is used as the black background. The contrast ratio of the cured product of the dental curable composition of the present invention can be measured specifically by the method described in the Examples below.

[0016] The contrast ratio can be adjusted by adding a colorant (D) or by increasing or decreasing its blending ratio, etc. Adjustment by the blending amount of a white pigment such as zinc oxide or titanium oxide is preferred because it has little effect on other color factors, such as hue and saturation.

[0017] The dental curable composition of the present invention preferably further has light diffusibility. Light diffusibility can be measured using a goniophotometer or goniophotometer. That is, light is incident perpendicularly to the cured product, and the luminous intensities of the specularly transmitted light and the diffused transmitted light of the portion other than the specularly transmitted light are measured. The degree of light diffusibility can be measured by determining the luminous intensities of the diffused transmitted light relative to the specular transmitted light. Having a certain degree of light diffusibility in the dental curable composition of the present invention can blur the boundary between the natural tooth and the filling when filling and restoring a natural tooth cavity with the dental curable composition of the present invention. This effect allows the natural tooth and the filling to blend in color, making the filling less noticeable, thereby providing a highly aesthetic restoration method. This effect is particularly effective in cases where cavities that penetrate from the labial side to the lingual side are restored, such as Black's Class III or IV. In such cases, if a dental curable composition with a low contrast ratio (high transparency) is used for restoration, the restored area will usually have a dark, colorless appearance. Therefore, aesthetics can be improved by using a dental curable composition with a higher contrast ratio (lower transparency) by increasing the amount of pigment such as titanium oxide. However, a dental curable composition with light diffusing properties can impart a natural and highly aesthetic appearance even to a composition with a relatively low contrast ratio (high transparency).

[0018] Regarding the dental curable composition of the present invention, the light diffusivity LD of a 0.25 mm thick cured product, as defined by the following formula (2), is preferably 0.0001 or more, more preferably 0.001 or more, and even more preferably 0.0015 or more. Furthermore, the light diffusivity LD is preferably 0.99 or less, more preferably 0.97 or less, and even more preferably 0.95 or less. Here, the light diffusivity LD is defined by the following formula (2). LD=(I5 / cos5°) / I0(2) (Here, I represents the luminous intensity of light transmitted through the cured product, and I0 and I5 represent the luminous intensity of transmitted light at angles of 0 degrees and 5 degrees, respectively, relative to the direction perpendicular to the sample plate (the direction of incident light).)

[0019] In equation (2), the luminous intensity value at 5 degrees is divided by the cosine of that angle to make it correspond to a scale that can be perceived by the human eye. In other words, based on the definition of illuminance, luminous intensity can be converted to illuminance by dividing it by the cosine of the measurement angle. Therefore, the closer the LD value is to 1, the stronger the light diffusion.

[0020] By being equal to or greater than the lower limit, it is possible to effectively prevent the impression of the filled portion being dark and sunken, and to blur the boundary between the filled portion and the natural tooth. By being equal to or less than the upper limit, it is possible to effectively reflect the color tone of the cavity floor in the filled portion. The light diffusion index LD can be measured by the method described in the Examples below.

[0021] The light diffusibility can be adjusted by adjusting the blending amount of a light diffusive filler, which will be described later.

[0022] The dental hardenable composition of the present invention achieves a good color match to natural teeth even without strict control of various color parameters (contrast ratio, saturation, etc.) to approximate those of natural teeth in order to reproduce the color tone of natural teeth. To further improve aesthetics, the dental hardenable composition of the present invention, for a 1.0 mm thick cured product thereof, exhibits a red chromaticity index a* / w in the L*a*b* color system against a white background of preferably -3.0 or greater, more preferably -2.5 or greater, even more preferably -2.0 or greater, and particularly preferably -1.8 or greater. Furthermore, a* / w is preferably 2.0 or less, more preferably 1.5 or less, even more preferably 1.0 or less, and particularly preferably 0.5 or less. By ensuring that a* / w is within the above range, the color tone of the cavity floor can be effectively reflected in the filling portion.

[0023] The a* / w can be measured using the above-mentioned spectrocolorimeter or the like. A standard white plate is used as the white background, and measurement can be performed by bringing it into close contact with the cured plate of the dental curable composition to be measured. Specifically, the a* / w of the cured product of the dental curable composition of the present invention can be measured by the method described in the Examples below.

[0024] The a* / w ratio can be adjusted by adding pigments or by increasing or decreasing the blending ratio of the pigments. In particular, it is preferable to adjust the blending amount of red pigments such as red iron oxide.

[0025] In order to further improve the aesthetics of the dental curable composition of the present invention, for a 1.0 mm thick cured product of the dental curable composition of the present invention, the L* / w in the L*a*b* color system on a white background is preferably 60.0 or more, more preferably 65.0 or more, even more preferably 68.0 or more, and particularly preferably 70.0 or more. Furthermore, L* / w is preferably 90.0 or less, more preferably 88.0 or less, even more preferably 85.0 or less, and particularly preferably 82.0 or less.

[0026] In order to further improve the aesthetics of the dental curable composition of the present invention, for a 1.0 mm thick cured product of the dental curable composition of the present invention, the b* / w ratio in the L*a*b* color system on a white background is preferably 0.0 or more, more preferably 1.0 or more, even more preferably 2.0 or more, and particularly preferably 3.0 or more. Furthermore, the b* / w ratio is preferably 50.0 or less, more preferably 45.0 or less, even more preferably 40.0 or less, and particularly preferably 35.0 or less.

[0027] Each component of the dental hardenable composition of the present invention will be described below.

[0028] [Polymerizable monomer (A)] The polymerizable monomer (A) in the dental curable composition of the present invention may be any polymerizable monomer known for use in dental curable compositions, with radically polymerizable monomers being particularly preferred. Examples of such radically polymerizable monomers include esters of unsaturated carboxylic acids such as α-cyanoacrylic acid, (meth)acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid; (meth)acrylamide; (meth)acrylamide derivatives; vinyl esters; vinyl ethers; mono-N-vinyl derivatives; and styrene derivatives. The polymerizable monomer (A) may be used alone or in combination of two or more. Among these, esters of unsaturated carboxylic acids and (meth)acrylamide derivatives are preferred, with (meth)acrylic acid esters and (meth)acrylamide derivatives being more preferred, and (meth)acrylic acid esters being even more preferred. In this specification, the term "(meth)acrylic" is used to encompass both methacrylic and acrylic. The term "(meth)acrylic monomer" is used to encompass both (meth)acrylic acid esters and (meth)acrylamide derivatives. Examples of (meth)acrylic acid esters and (meth)acrylamide derivatives are shown below.

[0029] (i) Monofunctional (meth)acrylic acid ester and (meth)acrylamide derivatives For example, methyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, dodecyl (meth)acrylate, 2-(N,N-dimethylamino)ethyl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, 3-(meth)acryloyloxypropyltrimethoxysilane, 11-(meth)acryloyloxyundecyltrimethoxysilane, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate , 10-hydroxydecyl (meth)acrylate, propylene glycol mono(meth)acrylate, glycerin mono(meth)acrylate, erythritol mono(meth)acrylate, phenoxyethylene glycol (meth)acrylate, isobornyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate, N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N,N-bis(hydroxyethyl) (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-di-n-propyl(meth)acrylamide, N-ethyl-N-methyl(meth)acrylamide, (meth)acryloylmorpholine, (meth)acryloyloxydodecylpyridinium bromide, (meth)acryloyloxydodecylpyridinium chloride, (meth)acryloyloxyhexadecylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, ethoxylated-o-phenylphenol (meth)acrylate, ethoxylated-m-phenylphenol (meth)acrylate, ethoxylated-p-phenylphenol (meth) Examples of suitable acrylates include propoxylated o-phenylphenol (meth)acrylate, propoxylated m-phenylphenol (meth)acrylate, propoxylated p-phenylphenol (meth)acrylate, o-phenoxybenzyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate, p-phenoxybenzyl (meth)acrylate, 2-(o-phenoxyphenyl)ethyl (meth)acrylate, 2-(m-phenoxyphenyl)ethyl (meth)acrylate, and 2-(p-phenoxyphenyl)ethyl (meth)acrylate. Among these, ethoxylated o-phenylphenol (meth)acrylate and m-phenoxybenzyl (meth)acrylate are most preferred, as the resulting dental hardenable composition has good paste handling properties and excellent mechanical strength after hardening.

[0030] (ii) Difunctional (meth)acrylic acid ester For example, aromatic bifunctional (meth)acrylic esters, aliphatic bifunctional (meth)acrylic esters, and the like can be mentioned.

[0031] Examples of aromatic bifunctional (meth)acrylic acid esters include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(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-(meth)acryloyloxypolyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2- Examples of such silane include bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-(meth)acryloyloxypolyethoxy)phenyl]fluorene, diphenylbis[3-(meth)acryloyloxypropyl]silane, and methylphenylbis[3-(meth)acryloyloxypropyl]silane.

[0032] Examples of the aliphatic difunctional (meth)acrylic acid esters include glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate (commonly known as 3G), 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-hexane ... tert-acrylate, 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,2-bis(3-(meth)acryloyloxy-2-hydroxypropyloxy)ethane, tricyclodecane dimethanol di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)diacrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate (commonly known as UDMA), dicyclohexylbis[3-(meth)acryloyloxypropyl]silane, and the like.

[0033] Among the above-mentioned bifunctional (meth)acrylic acid esters, 2,2-bis[4-(3-acryloyloxy-2-hydroxypropoxy)phenyl]propane, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (Bis-GMA), 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 1 to 30), thiazolinone, ... Triethylene glycol diacrylate, triethylene glycol dimethacrylate (3G), 1,10-decanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,2-bis(3-(meth)acryloyloxy-2-hydroxypropyloxy)ethane, tricyclodecane dimethanol di(meth)acrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)diacrylate, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxy) More preferred are 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (Bis-GMA), 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 1 to 30), triethylene glycol dimethacrylate (3G), 1,10-decanediol dimethacrylate, 1,12-dodecanediol dimethacrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)phenyl]dimethacrylate (UDMA), and more ..., and 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)phenyl]dimethacrylate. More preferred are 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (Bis-GMA), 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 2.6), and triethylene glycol dimethacrylate (3G).

[0034] (iii) Tri- or higher functional (meth)acrylic acid esters Examples thereof include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N'-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetra(meth)acrylate, and 1,7-di(meth)acryloyloxy-2,2,6,6-tetra(meth)acryloyloxymethyl-4-oxaheptane.

[0035] In addition, as the polymerizable monomer (A), oligomers and polymers having a radically polymerizable group such as a (meth)acrylic acid ester group can also be suitably used. For example, the polymerizable prepolymers described in JP-A-50-42696, the unsaturated urethane oligomers described in JP-A-2011-144121, the polyfunctional acrylate compounds described in JP-A-2006-510583, and the prepolymers described in WO2020 / 122192 can be used.

[0036] In addition, since the polymerizable monomer (A) results in a dental curable composition with excellent adhesive properties to teeth, metals, ceramics, etc., it may be preferable in some cases for the polymerizable monomer (A) to contain a functional monomer that can impart adhesive properties to these adherends.

[0037] Examples of such functional monomers, which exhibit excellent adhesion to teeth and base metals, include polymerizable monomers having a phosphate group, such as 2-(meth)acryloyloxyethyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, and 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate; and polymerizable monomers having a carboxylic acid group, such as 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid and 4-(meth)acryloyloxyethoxycarbonyl phthalic acid. Furthermore, in terms of exhibiting excellent adhesion to precious metals, examples thereof include 10-mercaptodecyl(meth)acrylate, 6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4-dithione, thiouracil derivatives described in JP-A-10-1473, and compounds containing sulfur element described in JP-A-11-92461. Furthermore, in terms of being effective in adhering to ceramics, porcelain, and other dental curable compositions, examples thereof include silane coupling agents such as γ-(meth)acryloyloxypropyltrimethoxysilane.

[0038] The content of the polymerizable monomer (A) in the dental curable composition of the present invention is not particularly limited, but from the viewpoints of the operability of the resulting dental curable composition and the mechanical strength of the cured product, it is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 5% by mass or more, or may be 8% by mass or more, or even 15% by mass or more, and is preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less, based on the total mass of the dental curable composition.

[0039] [Filler (B)] The dental hardenable composition of the present invention contains a filler (B).

[0040] The overall shape of the filler (B) particles is not particularly limited, and they can be used as either an amorphous or spherical powder. Using an amorphous filler (B) allows for the production of a dental curable composition with particularly excellent mechanical strength, smoothness durability, and abrasion resistance in the cured product. Using a spherical filler (B) allows for the production of a dental curable composition with smooth paste properties, good spreadability, and excellent workability. The superior mechanical strength of an amorphous filler compared to a spherical filler is believed to be due to the interlocking of filler particles within the cured product. The superior smoothness durability and abrasion resistance of an amorphous filler compared to a spherical filler is believed to be due to the filler particles being less likely to shed from the surface of the cured product, preventing the formation of blemishes and the resulting increase in surface roughness of the cured product. The superior workability of a spherical filler compared to an amorphous filler is believed to be due to the smaller specific surface area of ​​spherical particles, resulting in a smaller contact area with the polymerizable monomer (A). The overall shape of the filler (B) may be appropriately selected depending on the purpose of the dental curable composition, but it is preferable to use an irregularly shaped filler (B) because it has excellent mechanical strength and smoothness durability.

[0041] The filler (B) in the present invention is roughly classified into inorganic fillers (BF), organic-inorganic composite fillers (BC), and organic fillers (BP).

[0042] The inorganic filler (BF) is preferably a glass of various kinds (mainly composed of silica, and optionally containing oxides of heavy metals, boron, aluminum, etc.). Examples of the glass powder include fused silica, quartz, soda-lime silica glass, E-glass, C-glass, and borosilicate glass (Pyrex (registered trademark) glass) with a general composition; barium glass (GM27884, 8235, manufactured by Schott; E-2000, E-3000, manufactured by ESSTECH); strontium borosilicate glass (E-4000, manufactured by ESSTECH); lanthanum glass ceramics (GM31684, manufactured by Schott); and fluoroaluminosilicate glass (GM35429, G018-091, G0 Examples of suitable fillers include dental glass powders such as 18-117 (manufactured by Schott), various ceramics, composite oxides such as alumina, silica-titania, silica-zirconia, and silica-ytterbia, diatomaceous earth, kaolin, clay minerals (such as montmorillonite), activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, yttrium fluoride, calcium phosphate, barium sulfate, zirconium oxide, titanium oxide, and hydroxyapatite. These may be used alone or in combination. Among these, fillers containing silica as the main component (containing 5% or more by mass of silica, preferably 10% or more by mass) are preferred. Among these, inorganic fillers containing metal elements such as barium, zirconium, aluminum, and ytterbium, which have high X-ray contrast properties (such as barium glass, alumina, silica-titania, silica-zirconia, and silica-ytterbia), and ytterbium fluoride are preferred.

[0043] The inorganic filler (BF) may be amorphous, crystalline, or a mixture of both, but preferably contains at least an amorphous portion. A high proportion of the amorphous portion in the inorganic filler (BF) improves transparency.

[0044] The inorganic filler (BF) in the present invention preferably contains inorganic fine particles (BF-1) having an average particle size of 0.05 to 1 μm, more preferably 0.08 to 0.9 μm, and even more preferably 0.1 to 0.8 μm. When the average particle size of the inorganic fine particles (BF-1) is equal to or greater than the above-mentioned lower limit, the stickiness and stringiness of the resulting dental curable composition can be more effectively suppressed, improving operability. Furthermore, when the average particle size of the inorganic fine particles (BF-1) is equal to or less than the above-mentioned upper limit, the cured product of the resulting dental curable composition has improved polishability and smoothness durability. Furthermore, a filling and restoration with high color matching can be provided, as it is easy to achieve a gloss equivalent to that of natural teeth.

[0045] The average particle size of the inorganic microparticles (BF-1) can be determined by laser diffraction scattering or electron microscope observation of the particles. Laser diffraction scattering can be performed, for example, using a laser diffraction particle size distribution analyzer (such as the SALD-2300 manufactured by Shimadzu Corporation) to measure the particle size on a volume basis using ethanol or a 0.2% aqueous solution of sodium hexametaphosphate as a dispersion medium. Laser diffraction scattering is particularly convenient for measuring the particle size of particles 0.1 μm or larger. For electron microscope observation, a scanning electron microscope (such as the SU3500, SU3800, or S-4000 manufactured by Hitachi High-Technologies Corporation) can be used. Specifically, electron microscope observation can be performed by taking an electron microscope photograph of the particles and measuring the particle sizes of 200 or more particles observed within a unit field of view of the photograph using image analysis particle size distribution measurement software (Mac-View manufactured by Mountec Co., Ltd.). In this case, the particle diameter is determined as the arithmetic mean value of the longest and shortest lengths of the particles, and the average particle diameter is calculated from the number of particles and their particle diameters. More specifically, the average particle diameter of the inorganic fine particles (BF-1) can be measured by the method described in the Examples. In this specification, when the inorganic filler (BF) has been surface-treated, the average particle diameter of the inorganic filler (BF) means the average particle diameter before the surface treatment.

[0046] Although there is no particular limitation on the refractive index of the inorganic fine particles (BF-1), by making the refractive index similar to that of the components other than the inorganic fine particles (BF-1) in the cured product of the dental curable composition, it is easy to increase the transparency of the obtained cured product. For this reason, the refractive index of the inorganic fine particles (BF-1) is preferably 1.40 or more, more preferably 1.45 or more, even more preferably 1.50 or more, and preferably 1.63 or less, more preferably 1.60 or less, even more preferably 1.58 or less. The refractive index of the inorganic fine particles (BF-1) can be controlled by adjusting the type and ratio of the metal elements contained therein.

[0047] The inorganic filler (BF) in the dental curable composition of the present invention preferably contains inorganic agglomerated particles (BF-2) formed by agglomeration of inorganic primary particles (x). The average particle size of the inorganic primary particles (x) is preferably 0.001 to 1 μm, more preferably 0.005 to 0.8 μm, and even more preferably 0.01 to 0.5 μm. By having the average particle size of the inorganic primary particles (x) at or above the above-mentioned lower limit, the specific surface area of ​​the inorganic agglomerated particles (BF-2) can be prevented from increasing more than necessary, thereby more effectively suppressing stickiness and stringiness of the dental curable composition and improving operability. Furthermore, by having the average particle size of the inorganic primary particles (x) at or below the above-mentioned upper limit, the resulting cured product of the dental curable composition has improved polishability and smooth durability. Furthermore, a filling and restoration with high color matching can be provided, as it is easy to achieve a gloss equivalent to that of natural teeth. The average particle size of the inorganic primary particles (x) can be determined by the laser diffraction / scattering method or electron microscope observation method.

[0048] In the present invention, the inorganic agglomerated particles (BF-2) are in the form of agglomerated particles formed by the aggregation of inorganic primary particles (x). Commercially available inorganic fillers typically exist as agglomerates, but they have such weak cohesion that when 10 mg of inorganic filler powder is added to 300 mL of a dispersion medium such as water, water containing 5% or less by mass of a surfactant such as sodium hexametaphosphate, or ethanol, and dispersed for 30 minutes with an ultrasonic intensity of 40 W and 39 kHz, the particles are dispersed to the particle size indicated by the manufacturer. However, the inorganic agglomerated particles (BF-2) in the present invention are strongly agglomerated particles that are barely dispersed even under such conditions.

[0049] A suitable method for producing agglomerated particles in which particles are firmly agglomerated from commercially available agglomerated particles of an inorganic filler is to heat the inorganic filler to a temperature close to just before it melts, so that the contacting inorganic filler particles are slightly fused together, in order to further increase the agglomeration force. In this case, the agglomerated form may be formed before heating in order to control the shape of the agglomerated particles. Examples of methods for this include placing the inorganic filler in a suitable container and applying pressure, or dispersing it in a solvent and then removing the solvent by a method such as spray drying.

[0050] Another suitable method for producing inorganic agglomerated particles (BF-2) in which inorganic filler particles are firmly agglomerated to one another is to use a sol such as silica sol, alumina sol, titania sol, or zirconia sol produced by a wet method, dry it by freeze drying, spray drying, or the like, and optionally heat treat it. By this method, inorganic agglomerated particles (BF-2) in which particles are firmly agglomerated to one another can be easily obtained. Specific examples of sols include spherical silica particles (trade name "Seahoster (registered trademark)" (KE series, surface-treated type, etc.; all manufactured by Nippon Shokubai Co., Ltd.)), silica organosol (trade name "OSCAL (registered trademark)"; manufactured by JGC Catalysts and Chemicals Co., Ltd.), titania sol (trade name "QUEEN TITANIC" series; manufactured by Nissan Chemical Industries, Ltd.), silica sol (trade name "Snowtex (registered trademark)"; manufactured by Nissan Chemical Industries, Ltd.), alumina sol (trade names "Alumina Sol-100," "Alumina Sol-200," and "Alumina Sol-520"; all manufactured by Nissan Chemical Industries, Ltd.), and zirconia sol (trade name "Nanouse (registered trademark) ZR" series; manufactured by Nissan Chemical Industries, Ltd.). The shape of the inorganic agglomerated particles (BF-2) is not particularly limited, and an appropriate shape may be selected and used.

[0051] The conditions for the heat treatment in the method for producing inorganic agglomerated particles (BF-2) cannot be generally specified because the optimal treatment conditions (temperature, time) vary depending on the composition of the inorganic primary particles (x), etc., but for many compositions, the heat treatment temperature (baking temperature) is preferably within the range of 500 to 1,200° C. If the heat treatment temperature is too low, the mechanical strength of the cured product of the dental curable composition obtained as a final product is likely to decrease, while if the heat treatment temperature is too high, the inorganic primary particles (x) will fuse together excessively, and the polishing properties and smoothness durability of the cured product of the dental curable composition obtained as a final product are likely to decrease.

[0052] To determine the detailed conditions for the heat treatment, for example, inorganic agglomerated particles (BF-2) are produced as secondary particles (agglomerated particles) by firing under several conditions within the heat treatment temperature range described above, and then the particles are subjected to powder X-ray diffraction analysis to determine conditions under which the crystalline structure cannot be confirmed. Alternatively, after producing the inorganic agglomerated particles (BF-2) as described above, dental curable compositions may be produced using the particles, and the bending strength of the cured product formed therefrom and the smoothness of the polished surface of the cured product may be measured and determined. In many cases, insufficient heat treatment tends to result in insufficient bending strength of the cured product. Conversely, excessive heat treatment not only results in an unnaturally opaque appearance of the cured product, but also tends to reduce the smoothness of the polished surface of the cured product. This is thought to be because excessive heating causes some of the constituent components to begin to crystallize, which increases the refractive index of the inorganic agglomerated particles (BF-2), causing the cured product formed from the dental hardenable composition using them to exhibit an unnatural whiteness that differs from that of natural teeth; and because the hardness of the inorganic agglomerated particles (BF-2) increases, the cured product formed from the dental hardenable composition becomes difficult to grind, leading to a decrease in polishing ability.

[0053] In the present invention, the specific surface area of ​​the inorganic agglomerated particles (BF-2) is 10 m 2 / g or more is preferable, and 15m 2 / g or more is preferable, and 18m 2 / g or more is more preferable, and 20m 2 / g or more is more preferable, and 2 / g or less, and 250m 2 / g or less, and 2 / g or less is more preferable, and 190m 2 / g or less is more preferable, and 170m 2 / g or less, and even 150m 2 / g or less. When the specific surface area of ​​the inorganic agglomerated particles (BF-2) is equal to or greater than the above lower limit, the polishability of the cured product of the dental curable composition obtained is improved, and the color compatibility is also improved. When the specific surface area of ​​the inorganic agglomerated particles (BF-2) is equal to or less than the above upper limit, the amount of the inorganic agglomerated particles (BF-2) can be increased, and the mechanical strength of the cured product obtained is improved. Note that the specific surface area of ​​the inorganic agglomerated particles (BF-2) means the specific surface area of ​​the agglomerated particles (secondary particles).

[0054] The specific surface area of ​​the inorganic agglomerated particles (BF-2) can be determined by the BET method. Specifically, it can be measured using a specific surface area measuring device (such as the "BELSORP-mini" series manufactured by Microtrack-Bell Corporation). More specifically, the specific surface area of ​​the inorganic agglomerated particles (BF-2) can be measured by the method described in the Examples.

[0055] The average particle size of the inorganic agglomerated particles (BF-2) in the present invention is preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 1.5 μm or more, and particularly preferably 2 μm or more. It is also preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. When the average particle size of the inorganic agglomerated particles (BF-2) is equal to or greater than the above-mentioned lower limit, the resulting dental curable composition can be more effectively prevented from becoming sticky or stringy, thereby improving operability. When the average particle size of the inorganic agglomerated particles (BF-2) is equal to or less than the above-mentioned upper limit, the resulting dental curable composition can be more effectively prevented from becoming rough or sagging, thereby also improving operability. The average particle size of the inorganic agglomerated particles (BF-2) refers to the average particle size of the agglomerated particles (secondary particles). The average particle size of the inorganic agglomerated particles (BF-2) can be determined by the laser diffraction scattering method or electron microscope observation described above. The average particle size of the inorganic agglomerated particles (BF-2) can be measured in the same manner as that of the inorganic fine particles (BF-1), specifically, by the method described in the Examples below.

[0056] The inorganic agglomerated particles (BF-2) in the dental curable composition of the present invention preferably include light-diffusing inorganic agglomerated particles (BF-2d). The light-diffusing inorganic agglomerated particles (BF-2d) are formed by agglomeration of inorganic primary particles (x), as described for the inorganic agglomerated particles (BF-2). The light-diffusing inorganic agglomerated particles (BF-2d) have a refractive index that satisfies the following formula (3), preferably the following formula (4), more preferably the following formula (5), and even more preferably the following formula (6). The refractive index of the light-diffusing inorganic agglomerated particles (BF-2d) can be measured by the method described in the Examples below. 0.03<|nP-nF BF-2d |<1.0 (3) 0.04<|nP-nF BF-2d |<0.6 (4) 0.05<|nP-nF BF-2d |<0.4 (5) 0.06<|nP-nF BF-2d |<0.2 (6) (where nP is the refractive index of the polymer obtained by polymerizing the polymerizable monomer (A), and nF BF-2d represents the refractive index of the light-diffusing inorganic agglomerated particles (BF-2d).

[0057] By having the refractive index of the light-diffusing inorganic aggregate particles (BF-2d) equal to or greater than the lower limit of the formula (3), sufficient light diffusibility can be imparted to the resulting dental hardenable composition. By imparting sufficient light diffusibility, when a natural tooth cavity is repaired with the resulting dental hardenable composition, the margin (boundary) between the natural tooth and the filling becomes blurred, making the filling less noticeable, thereby providing a highly aesthetic restoration method. Furthermore, by having the refractive index equal to or less than the upper limit of the formula, a certain level of transparency can be imparted to the resulting dental hardenable composition. By imparting a certain level of transparency, when a natural tooth cavity is repaired with the resulting dental hardenable composition, the color tone of the cavity floor of the natural tooth can be reflected in the filling. This effect allows a highly aesthetic restoration method to be provided for natural teeth of a wide range of colors using a dental hardenable composition of a single composition, without the need to prepare multiple dental hardenable compositions with different colors.

[0058] In the present invention, the refractive index nP of a polymer obtained by polymerizing polymerizable monomer (A) refers to the value measured using an Abbe refractometer on a 1.0 mm thick polymer obtained by casting a mixture of polymerizable monomer (A) and all components (e.g., polymerization initiator (C)) other than filler (B) and colorant (D) under specified conditions, as shown in the Examples described below. When polymerizable monomer (A) is a single type, the refractive index refers to the refractive index of a mixture containing a homopolymer of that polymerizable monomer. When polymerizable monomer (A) contains multiple types of polymerizable monomers, the refractive index refers to the refractive index of a mixture containing a random copolymer of those multiple types of polymerizable monomers. Unless otherwise specified, the "refractive index" refers to the value at 25°C.

[0059] The inorganic primary particles (x) of the light-diffusing inorganic agglomerated particles (BF-2d) can be any of the raw materials listed as usable for the inorganic filler (BF) without any limitations, but in order to control the refractive index so as to satisfy the above formula, various glass powders with common compositions such as fused silica, quartz, soda lime silica glass, E glass, C glass, and borosilicate glass (Pyrex (registered trademark) glass), ceramics, alumina, and composite oxides such as silica-titania, silica-zirconia, and silica-ytterbia can be particularly preferably used. These may be used alone or in combination of two or more.

[0060] The average particle size of the light-diffusing inorganic agglomerated particles (BF-2d) can be suitably within the range of average particle sizes listed above as suitable for use with the inorganic agglomerated particles (BF-2). When the average particle size of the light-diffusing inorganic agglomerated particles (BF-2d) is equal to or greater than the lower limit, the resulting dental curable composition can be more effectively prevented from becoming sticky or stringy, improving operability, and can also be imparted with white light diffusibility similar to that of natural teeth. When the average particle size is equal to or less than the lower limit, the bluish scattered light becomes stronger, resulting in a poor color match with natural teeth. Furthermore, when the average particle size of the light-diffusing inorganic agglomerated particles (BF-2d) is equal to or less than the upper limit, the resulting dental curable composition can be more effectively prevented from becoming rough or sagging, again improving operability.

[0061] The inorganic agglomerated particles (BF-2) may contain inorganic agglomerated particles (BF-2e) other than the light-diffusing inorganic agglomerated particles (BF-2d) (hereinafter simply referred to as "other inorganic agglomerated particles (BF-2e)"). As with the light-diffusing inorganic agglomerated particles (BF-2d), the average particle diameter of the other inorganic agglomerated particles (BF-2e) can be suitably within the range of average particle diameters listed as suitable for use in the inorganic agglomerated particles (BF-2). The other inorganic agglomerated particles (BF-2e) can be produced by the method described for the inorganic agglomerated particles (BF-2). The inorganic primary particles (x) of the other inorganic agglomerated particles (BF-2e) can be any of the raw materials listed as suitable for use in the inorganic filler (BF) without any restrictions.

[0062] The inorganic filler (BF) may contain inorganic particles (BF-3) other than the inorganic fine particles (BF-1) and the inorganic aggregated particles (BF-2) (hereinafter simply referred to as "other inorganic particles (BF-3)"). The average particle diameter of the other inorganic particles (BF-3) is preferably greater than 1 μm and less than 30 μm, more preferably greater than 1 μm and less than 20 μm, and even more preferably greater than 1 μm and less than 10 μm. The average particle diameter of the other inorganic particles (BF-3) can be determined by laser diffraction scattering or electron microscope observation of the particles. The laser diffraction scattering method can be used, for example, to measure the particle size on a volume basis using a laser diffraction particle size distribution analyzer (such as the "SALD-2300" manufactured by Shimadzu Corporation) using ethanol or a 0.2% aqueous solution of sodium hexametaphosphate as a dispersion medium.

[0063] The organic-inorganic composite filler (BC) in the present invention refers to a filler containing the inorganic filler (BF) and a polymer of the polymerizable monomer (A').

[0064] The average particle size of the organic-inorganic composite filler (BC) is preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 1.5 μm or more, and particularly preferably 2 μm or more. It is also preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and particularly preferably 20 μm or less. When the average particle size of the organic-inorganic composite filler (BC) is at or above the lower limit, the resulting dental curable composition can be more effectively inhibited from becoming sticky or stringy, improving operability. When the average particle size of the organic-inorganic composite filler (BC) is at or below the upper limit, the resulting dental curable composition can be more effectively inhibited from becoming rough or sagging, improving operability. The average particle size of the organic-inorganic composite filler (BC) can be determined by the laser diffraction / scattering method or electron microscope observation.

[0065] The method for producing the organic-inorganic composite filler (BC) of the present invention is not particularly limited. For example, the organic-inorganic composite filler (BC) may be produced by adding the polymerizable monomer (A') and a known polymerization initiator to the inorganic filler (BF) in advance to form a paste, polymerizing the paste by solution polymerization, suspension polymerization, emulsion polymerization, or bulk polymerization, and pulverizing the paste.

[0066] The content of the inorganic filler (BF) in the organic-inorganic composite filler (BC) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, and particularly preferably 40 parts by mass or more, relative to 100 parts by mass of the total of the inorganic filler (BF) and the polymerizable monomer (A') in the organic-inorganic composite filler (BC). By ensuring that the content is above the lower limit, the mechanical strength of the resulting dental curable composition is improved. There is no particular upper limit, but because the viscosity of the paste increases during production, the content is preferably 99 parts by mass or less, more preferably 95 parts by mass or less.

[0067] As the polymerizable monomer (A'), the polymerizable monomers listed as the polymerizable monomer (A) usable in the dental curable composition of the present invention are preferably used. Among them, the absolute value of the difference between the refractive index of the polymerizable monomer (A') when cured and the refractive index of the inorganic filler (BF) in the organic-inorganic composite filler (BC) is preferably 0.30 or less, more preferably 0.20 or less. By setting it below the above upper limit, the transparency of the organic-inorganic composite filler (BC) itself is improved, and a dental curable composition with high aesthetic appeal can be provided.

[0068] As the inorganic filler (BF) in the organic-inorganic composite filler (BC), the inorganic primary particles (x) are preferably used from the viewpoint of ease of polishing and the like.

[0069] The organic-inorganic composite filler (BC) in the dental curable composition of the present invention preferably includes a light-diffusing organic-inorganic composite filler (BC-d). The light-diffusing organic-inorganic composite filler (BC-d), like the organic-inorganic composite filler (BC), includes the inorganic filler (BF) and a polymer of the polymerizable monomer (A'). The refractive index of the light-diffusing organic-inorganic composite filler (BC-d) satisfies the following formula (7), preferably formula (8), more preferably formula (9), and even more preferably formula (10). The refractive index of the light-diffusing organic-inorganic composite filler (BC-d) can be measured by the method described in the Examples below. 0.03<|nP-nF BC-d |<1.0 (7) 0.04<|nP-nF BC-d |<0.6 (8) 0.05<|nP-nF BC-d |<0.4 (9) 0.06<|nP-nF BC-d |<0.2 (10) (where nP is the refractive index of the polymer obtained by polymerizing the polymerizable monomer (A), and nF BC-d represents the refractive index of the light-diffusing organic-inorganic composite filler (BC-d).

[0070] By having the refractive index of the light-diffusing organic-inorganic composite filler (BC-d) at or above the lower limit of the above formula, sufficient light diffusibility can be imparted to the resulting dental hardenable composition. By imparting sufficient light diffusibility, when a natural tooth cavity is restored with the resulting dental hardenable composition, the margin (boundary) between the natural tooth and the filling becomes blurred, making the filled area less noticeable, thereby providing a highly aesthetic restoration method. Furthermore, by having the refractive index at or below the upper limit of the above formula, a certain level of transparency can be imparted to the resulting dental hardenable composition. By imparting a certain level of transparency, when a natural tooth cavity is restored with the resulting dental hardenable composition, the color of the cavity floor of the natural tooth can be reflected in the filled area. This effect allows a highly aesthetic restoration method to be provided for natural teeth of a wide range of colors using a dental hardenable composition of a single composition, without the need to prepare multiple dental hardenable compositions with different colors.

[0071] The inorganic filler (BF) in the light-diffusing organic-inorganic composite filler (BC-d) can preferably be the inorganic primary particles (x). The raw materials listed as being usable for the inorganic filler (BF) can be used as the inorganic primary particles (x) without any limitations. However, in order to control the refractive index so as to satisfy the above formula, various glass powders with common compositions, such as fused silica, quartz, soda-lime silica glass, E-glass, C-glass, and borosilicate glass (Pyrex (registered trademark) glass), ceramics, and composite oxides such as alumina, silica-titania, silica-zirconia, and silica-ytterbia, can be particularly preferably used. These may be used alone or in combination of two or more.

[0072] The light-diffusing organic-inorganic composite filler (BC-d) can be suitably used within the average particle size ranges listed above as suitable for use with the inorganic agglomerated particles (BF-2). When the average particle size of the light-diffusing organic-inorganic composite filler (BC-d) is at or above the lower limit, the resulting dental curable composition can be more effectively prevented from becoming sticky or stringy, improving operability and imparting white light diffusion properties similar to those of natural teeth. When the average particle size is below the lower limit, the bluish scattered light becomes stronger, reducing color matching with natural teeth. Furthermore, when the average particle size of the light-diffusing organic-inorganic composite filler (BC-d) is at or below the upper limit, the resulting dental curable composition can be more effectively prevented from becoming rough or sagging, again improving operability. The average particle size of the light-diffusing organic-inorganic composite filler (BC-d) can be measured in the same manner as the inorganic agglomerated particles (BF-2), as with the inorganic fine particles (BF-1), specifically, by the method described in the Examples below.

[0073] The inorganic filler (BF) and the organic-inorganic composite filler (BC) do not need to be surface-treated, but are preferably surface-treated because the surfaces of the inorganic filler (BF) and the organic-inorganic composite filler (BC) are rendered hydrophobic, improving their affinity with the polymerizable monomer (A), thereby allowing for a larger blending amount of the inorganic filler (BF) and the organic-inorganic composite filler (BC). The surface treatment can be carried out using a surface treatment agent. The type of surface treatment agent is not particularly limited, and known surface treatment agents can be used, such as silane coupling agents, organotitanium coupling agents, organozirconium coupling agents, and organoaluminum coupling agents. One type of surface treatment agent may be used alone, or two or more types may be used in combination. Among these, silane coupling agents are preferred from the viewpoints of the affinity between the polymerizable monomer (A) and the inorganic filler (BF) and the organic-inorganic composite filler (BC) and their availability.

[0074] There is no particular limitation on the type of silane coupling agent, but it is preferably a compound represented by the following general formula (11). H2C=CR 4 -CO-R 5 -(CH2) q -SiR 6 p R 7 (3-p) (11) (In the formula, R 4 is a hydrogen atom or a methyl group, and R 5 is an oxygen atom, a sulfur atom, or -NR 8 - where R 8 is a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms (which may be linear, branched, or cyclic), and R 6 is a hydrolyzable group, and R 7 is a hydrocarbon group having 1 to 6 carbon atoms, p is an integer of 1 to 3, q ​​is an integer of 1 to 13, and there are a plurality of R 6 and R 7 may be the same or different from each other.)

[0075] In the above general formula (11), R 4is a hydrogen atom or a methyl group, and is preferably a methyl group. 5 is an oxygen atom, a sulfur atom, or -NR 8 -, and is preferably an oxygen atom. 8 is a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms (which may be linear, branched, or cyclic), and the R 8 The aliphatic group having 1 to 8 carbon atoms represented by the formula (R) may be either a saturated aliphatic group (such as an alkyl group or a cycloalkylene group (e.g., a cyclohexyl group)) or an unsaturated aliphatic group (such as an alkenyl group or an alkynyl group). From the viewpoints of availability, ease of production, chemical stability, etc., a saturated aliphatic group is preferred, and an alkyl group is more preferred. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an n-heptyl group, a 2-methylhexyl group, and an n-octyl group. 8 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and even more preferably a hydrogen atom.

[0076] In the above general formula (11), R 6 Examples of the hydrolyzable group represented by R include alkoxy groups such as methoxy, ethoxy, and butoxy; halogen atoms such as chlorine and bromine; and isocyanate groups. 6 If there are multiple R 6 may be the same or different. 6 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group, and even more preferably a methoxy group.

[0077] In the above general formula (11), R 7Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by the formula (R) include an alkyl group having 1 to 6 carbon atoms (which may be cyclic), an alkenyl group having 2 to 6 carbon atoms (which may be cyclic), and an alkynyl group having 2 to 6 carbon atoms. 7 If there are multiple R 7 may be the same or different from each other.

[0078] Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an n-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0079] Examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, a 1-methylvinyl group, a 1-propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.

[0080] Examples of the alkynyl group having 2 to 6 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 1-ethyl-2-propynyl, 2-pentynyl, 3-pentynyl, 1-methyl-2-butynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-hexynyl, 2-hexynyl, 1-ethyl-2-butynyl, 3-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 4-methyl-1-pentynyl, 3-methyl-1-pentynyl, 5-hexynyl, and 1-ethyl-3-butynyl.

[0081] In the above general formula (11), p is an integer of 1 to 3, preferably 2 or 3, and more preferably 3. Furthermore, in the above general formula (11), q is an integer of 1 to 13, preferably an integer of 2 to 12, and more preferably an integer of 3 to 11.

[0082] Specific examples of the silane coupling agent represented by the general formula (11) include methacryloyloxymethyltrimethoxysilane, 2-methacryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 4-methacryloyloxybutyltrimethoxysilane, 5-methacryloyloxypentyltrimethoxysilane, 6-methacryloyloxyhexyltrimethoxysilane, 7-methacryloyloxyheptyltrimethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, Examples of the silane coupling agent include methacryloyloxysilane, 9-methacryloyloxynonyltrimethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, 12-methacryloyloxydodecyltrimethoxysilane, 13-methacryloyloxytridecyltrimethoxysilane, 11-methacryloyloxyundecyldichloromethylsilane, 11-methacryloyloxyundecyltrichlorosilane, and 12-methacryloyloxydodecyldimethoxymethylsilane. One type of silane coupling agent may be used alone, or two or more types may be used in combination. Among these, from the viewpoint of availability, 3-methacryloyloxypropyltrimethoxysilane is preferred, and from the viewpoint of further increasing the affinity between the polymerizable monomer (A) and the inorganic filler (BF) and the organic-inorganic composite filler (BC), 8-methacryloyloxyoctyltrimethoxysilane, 9-methacryloyloxynonyltrimethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, and 11-methacryloyloxyundecyltrimethoxysilane are preferred.

[0083] The surface treatment method is not particularly limited, and any known method can be applied.

[0084] Although there are no particular restrictions on the amount of surface treatment agent used, the amount of surface treatment agent used can be, for example, 1 part by mass or more relative to 100 parts by mass of the filler before surface treatment, and the amount used is preferably 5 parts by mass or more, more preferably 6 parts by mass or more, even more preferably 8 parts by mass or more, particularly preferably 10 parts by mass or more, most preferably 20 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less. When the amount used is at least the above lower limit, the mechanical strength of the resulting cured product is more likely to be improved, and when the amount used is at most the above upper limit, a decrease in the mechanical strength of the resulting cured product due to excess surface treatment agent can be suppressed.

[0085] Examples of the organic filler (BP) in the present invention include acrylic polymers such as polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, and polyamide; polyvinyl chloride, polystyrene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, and acrylonitrile-styrene-butadiene copolymer. These may be used alone or in combination of two or more. The shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected. From the viewpoints of the handleability and mechanical strength of the resulting dental curable composition, the average particle size of the organic filler (BP) is preferably 0.001 to 50 μm, more preferably 0.001 to 10 μm.

[0086] The content of filler (B) in the dental curable composition of the present invention (or the content of filler (B) after surface treatment if surface-treated) is not particularly limited, but from the viewpoints of the operability of the resulting dental curable composition and the mechanical strength of the cured product, the content of filler (B) in the dental curable composition of the present invention is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, particularly preferably 65 parts by mass or more, and preferably 97 parts by mass or less, more preferably 96 parts by mass or less, even more preferably 95 parts by mass or less, particularly preferably 90 parts by mass or less, per 100 parts by mass of the total of polymerizable monomer (A) and filler (B). When the content of filler (B) is equal to or greater than the above-mentioned lower limit, the mechanical strength of the cured product is improved, and stickiness and stringiness of the dental curable composition are more effectively suppressed, improving the operability. Furthermore, by ensuring that the content of the filler (B) is equal to or less than the upper limit, the resulting dental curable composition can be prevented from becoming excessively hard, and the operability is improved.

[0087] In the dental curable composition of the present invention, the content of inorganic fine particles (BF-1) (if surface-treated, the content of inorganic fine particles (BF-1) after surface treatment) is not particularly limited. However, from the viewpoint of the ease of handling of the resulting dental curable composition and the mechanical strength of the cured product, the content of inorganic fine particles (BF-1) in the dental curable composition of the present invention is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, particularly preferably 10 parts by mass or more, and preferably 95 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 80 parts by mass or less, particularly preferably 70 parts by mass or less, per 100 parts by mass of the total of the polymerizable monomer (A) and the filler (B). By having the content of inorganic fine particles (BF-1) at or above the lower limit, the mechanical strength of the cured product is improved, and the polishability of the cured product of the resulting dental curable composition is improved, as well as the color compatibility. Furthermore, by ensuring that the content of the inorganic fine particles (BF-1) is equal to or less than the upper limit, the resulting dental curable composition can be prevented from becoming excessively hard, and the operability is improved.

[0088] The dental curable composition of the present invention preferably contains inorganic agglomerated particles (BF-2) and / or an organic-inorganic composite filler (BC). The total content of the inorganic agglomerated particles (BF-2) and the organic-inorganic composite filler (BC) (the content of the inorganic agglomerated particles (BF-2) and the organic-inorganic composite filler (BC) after surface treatment, if any, is not particularly limited. However, from the viewpoints of the ease of handling of the resulting dental curable composition and the mechanical strength of the cured product, the total content of the inorganic agglomerated particles (BF-2) and the organic-inorganic composite filler (BC) in the dental curable composition of the present invention is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and particularly preferably 4 parts by mass or more, and is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less, per 100 parts by mass of the total of the polymerizable monomer (A) and the filler (B). When the total content of the inorganic agglomerated particles (BF-2) and the organic-inorganic composite filler (BC) is equal to or greater than the lower limit, stickiness and stringiness are more effectively suppressed, improving the operability. When the total content of the inorganic agglomerated particles (BF-2) and the organic-inorganic composite filler (BC) is equal to or less than the upper limit, roughness and sagging of the dental curable composition obtained can be more effectively suppressed, also improving the operability.

[0089] The dental curable composition of the present invention preferably contains either or both of light-diffusing inorganic aggregate particles (BF-2d) and light-diffusing organic-inorganic composite filler (BC-d). The total content of the light-diffusing inorganic agglomerated particles (BF-2d) and the light-diffusing organic-inorganic composite filler (BC-d) (if the filler has been surface-treated, the content of the light-diffusing inorganic agglomerated particles (BF-2d) and the light-diffusing organic-inorganic composite filler (BC-d) after the surface treatment) is not particularly limited. However, from the viewpoints of the operability of the resulting dental curable composition, the mechanical strength of the cured product, and the aesthetic quality of the filling, the total content of the light-diffusing inorganic agglomerated particles (BF-2d) and the light-diffusing organic-inorganic composite filler (BC-d) in the dental curable composition of the present invention is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, and particularly preferably 3 parts by mass or more, per 100 parts by mass of the total of the polymerizable monomer (A) and the filler (B), and is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 35 parts by mass or less. When the total content of the light-diffusing inorganic agglomerated particles (BF-2d) and the light-diffusing organic-inorganic composite filler (BC-d) is at least the above-mentioned lower limit, stickiness and stringiness are more effectively suppressed, improving operability, and sufficient light diffusibility is imparted to the resulting dental curable composition, thereby providing a highly aesthetic restoration method as described above. Furthermore, when the total content of the light-diffusing inorganic agglomerated particles (BF-2d) and the light-diffusing organic-inorganic composite filler (BC-d) is at most the above-mentioned upper limit, roughness and sagging of the resulting dental curable composition are more effectively suppressed, and a certain level of transparency is imparted, thereby providing a highly aesthetic restoration method for natural teeth of a wide range of shades using a dental curable composition of a single composition as described above.

[0090] The content of the organic filler (BP) in the dental curable composition of the present invention is not particularly limited, and it does not necessarily have to be present. Dental curable compositions containing an organic filler (BP) have reduced polymerization shrinkage during curing. However, the mechanical strength of the cured product is likely to decrease. Therefore, the content of the organic filler (BP) in the dental curable composition of the present invention is preferably 10 parts by mass or less, but may also be 5 parts by mass or less, 3 parts by mass or less, or none at all, per 100 parts by mass of the total of the polymerizable monomer (A) and the inorganic filler (BF).

[0091] [Polymerization initiator (C)] The dental curable composition of the present invention contains a polymerization initiator (C). The polymerization initiator (C) can be selected from polymerization initiators used in general industry, and polymerization initiators used in dental applications are preferably used. Photopolymerization initiators and chemical polymerization initiators are particularly preferably used. The polymerization initiator (C) may be used alone or in appropriate combination of two or more.

[0092] Examples of the photopolymerization initiator include (bis)acylphosphine oxides, ketals, α-diketones, and coumarins.

[0093] Among the (bis)acylphosphine oxides, examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi(2,6-dimethylphenyl)phosphonate, and salts thereof (such as sodium salts, potassium salts, and ammonium salts). Examples of bisacylphosphine oxides include bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine 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)phenylphosphine oxide, bis(2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, and salts thereof (sodium salts, potassium salts, ammonium salts, etc.).

[0094] Among these (bis)acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are preferred.

[0095] Examples of ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

[0096] Examples of α-diketones include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, acenaphthenequinone, etc. Among these, camphorquinone is preferred because it has a maximum absorption wavelength in the visible light region.

[0097] Examples of the coumarin compounds include 3,3'-carbonylbis(7-diethylaminocoumarin), 3-(4-methoxybenzoyl)coumarin, 3-thienoylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3-(p-nitrobenzoyl)coumarin, 3-(p-nitrobenzoyl)coumarin, 3,5-carbonylbis(7-methoxycoumarin), 3-benzoyl-6-bromo Coumarin, 3,3'-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo[f]coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo[f]coumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin, 7-dimethylamino-3-(4-methoxybenzoyl)coumarin, 7-diethylamino-3-(4-methoxybenzoyl) )coumarin, 7-diethylamino-3-(4-diethylamino)coumarin, 7-methoxy-3-(4-methoxybenzoyl)coumarin, 3-(4-nitrobenzoyl)benzo[f]coumarin, 3-(4-ethoxycinnamoyl)-7-methoxycoumarin, 3-(4-dimethylaminocinnamoyl)coumarin, 3-(4-diphenylaminocinnamoyl)coumarin, 3-[(3-dimethylbenzothiazol-2-ylidene)acetyl]coumarin, 3-[(1-methylnaphtho[1,2-d]thiazol-2-ylidene)acetyl]coumarin, 3,3'-carbo Nylbis(6-methoxycoumarin), 3,3'-carbonylbis(7-acetoxycoumarin), 3,3'-carbonylbis(7-dimethylaminocoumarin), 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dibutylamino)coumarin, 3-(2-benzimidazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dioctylamino)coumarin, 3-acetyl-7-(dimethylamino)coumarin, 3,3'-carbonylbis(7-dibutylaminocoumarin), 3,Examples of compounds include those described in JP-A-9-3109 and JP-A-10-245525, such as 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]quinolizin-11-one, and 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizin-11-one.

[0098] Among the coumarin compounds, 3,3'-carbonylbis(7-diethylaminocoumarin) and 3,3'-carbonylbis(7-dibutylaminocoumarin) are particularly suitable.

[0099] By using at least one photopolymerization initiator selected from the group consisting of (bis)acylphosphine oxides, α-diketones, and coumarin compounds, a dental curable composition can be obtained that exhibits excellent photocurability in the visible and near-ultraviolet regions and sufficient photocurability whether using a halogen lamp, light-emitting diode (LED), or xenon lamp. Furthermore, from the viewpoint of obtaining a dental curable composition with even more excellent smoothness durability, it is preferable to use a (bis)acylphosphine oxide in combination with an α-diketone. This is because the surface hardness of the cured product is improved, although the mechanism is not necessarily clear.

[0100] As the chemical polymerization initiator, an organic peroxide is preferably used. The organic peroxide used as the chemical polymerization initiator is not particularly limited, and known organic peroxides can be used. Typical organic peroxides include ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxydicarbonates.

[0101] Examples of the ketone peroxide include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.

[0102] Examples of hydroperoxides include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0103] Examples of diacyl peroxides include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide.

[0104] Examples of dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne.

[0105] Examples of peroxyketals include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, and 4,4-bis(t-butylperoxy)valeric acid-n-butyl ester.

[0106] Examples of peroxyesters include α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butyl peroxymaleic acid.

[0107] Examples of peroxydicarbonates include di-3-methoxyperoxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, and diallylperoxydicarbonate.

[0108] Among organic peroxides, diacyl peroxides are preferably used in view of the overall balance of safety, storage stability, and radical generating ability, and among these, benzoyl peroxide is more preferably used.

[0109] The content of the polymerization initiator (C) in the dental curable composition of the present invention is not particularly limited, but from the viewpoint of the curability of the resulting dental curable composition, it is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, even more preferably 0.02 part by mass or more, and particularly preferably 0.1 part by mass or more, relative to 100 parts by mass of the total polymerizable monomers (A). Furthermore, since an excessively high content of the polymerization initiator (C) may cause precipitation from the dental curable composition, the content is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less, or may be 5 parts by mass or less, or 2 parts by mass or less, relative to 100 parts by mass of the total polymerizable monomers (A).

[0110] [Colorant (D)] The dental curable composition of the present invention contains a colorant (D). The type of colorant (D) is not particularly limited, and either inorganic or organic pigments can be used without restriction depending on the desired color tone of the dental curable composition. The shape of the colorant particles is not particularly limited, and any particle shape, such as spherical, needle-like, plate-like, crushed, or scaly, can be used without restriction. Specific examples of inorganic pigments include chromates such as yellow lead, zinc yellow, and barium yellow; ferrocyanides such as Prussian blue; sulfides such as vermilion, cadmium yellow, zinc sulfide, and cadmium red; sulfates such as barium sulfate, zinc sulfate, and strontium sulfate; oxides such as zinc white, titanium white, antimony white, red iron oxide, iron black, and chromium oxide; hydroxides such as aluminum hydroxide; silicates such as calcium silicate and ultramarine; and carbon such as carbon black and graphite. Specific examples of organic pigments include nitroso pigments such as Naphthol Green B and Naphthol Green Y; nitro pigments such as Naphthol Yellow S and Lithol Fast Yellow 2G; insoluble azo pigments such as Permanent Red 4R, Brilliant Fast Scarlet, Hansa Yellow, and Benzidine Yellow; sparingly soluble azo pigments such as Lithol Red, Lake Red C, and Lake Red D; soluble azo pigments such as Brilliant Carmine 6B, Permanent Red F5R, Pigment Scarlet 3B, and Bordeaux 10B; phthalocyanine pigments such as Phthalocyanine Blue, Phthalocyanine Green, and Sky Blue; basic dye pigments such as Rhodamine Lake, Malachite Green Lake, and Methyl Violet Lake; and acid dye pigments such as Peacock Blue Lake, Eosin Lake, Quinoline Yellow Lake, and Aluminum Lake. These colorants (D) may be used alone or in combination of two or more. Among these colorants (D), inorganic pigments such as titanium white, red iron oxide, iron black, and yellow iron oxide are preferred because they are superior in heat resistance and light resistance to organic pigments.

[0111] The content of the colorant (D) in the dental curable composition of the present invention is not limited as long as the effects of the present invention are achieved. However, from the viewpoint of aesthetics, it is preferably 0.0005 parts by mass or more, more preferably 0.002 parts by mass or more, even more preferably 0.004 parts by mass or more, and particularly preferably 0.006 parts by mass or more, per 100 parts by mass of the polymerizable monomer (A). By being above the lower limit, the impression of the filled portion being dark and sunken can be effectively suppressed. Furthermore, it is preferably 0.5 parts by mass or less, more preferably 0.4 parts by mass or less, and even more preferably 0.3 parts by mass or less. By being below the upper limit, the color tone of the cavity floor can be effectively reflected in the filled portion. Furthermore, the content of the colorant (D) is preferably 0.00001 parts by mass or more, more preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and particularly preferably 0.001 parts by mass or more, per 100 parts by mass of the dental curable composition. The content of the colorant (D) is preferably 0.3 parts by mass or less, more preferably 0.1 parts by mass or less, and even more preferably 0.07 parts by mass or less.

[0112] [Polymerization accelerator (E)] The dental curable composition of the present invention may further contain a polymerization accelerator (E). Examples of the polymerization accelerator include amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, hydrogen sulfites, and thiourea compounds. The polymerization accelerator (E) may be used alone or in combination of two or more.

[0113] Amines are divided into aliphatic amines and aromatic amines. Examples of aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine, and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine, and N-methylethanolamine; and tertiary aliphatic amines such as N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, and tributylamine. Among these, tertiary aliphatic amines are preferred from the viewpoint of the curability and storage stability of the dental curable composition, and N-methyldiethanolamine and triethanolamine are more preferred.

[0114] Examples of aromatic amines 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-di-isopropylaniline, N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, and N,N-dimethyl-m-toluidine. aniline, 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, 2-butoxyethyl 4-(N,N-dimethylamino)benzoate, 2-(methacryloyloxy)ethyl 4-(N,N-dimethylamino)benzoate, 4-(N,N-dimethylamino)benzophenone, and butyl 4-(N,N-dimethylamino)benzoate. Among these, from the viewpoint of imparting excellent hardenability to the dental hardenable composition, at least one selected from the group consisting of N,N-bis(2-hydroxyethyl)-p-toluidine, ethyl 4-(N,N-dimethylamino)benzoate, 2-butoxyethyl 4-(N,N-dimethylamino)benzoate, and 4-(N,N-dimethylamino)benzophenone is preferably used.

[0115] Examples of sulfinic acids and salts thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, and 2,4,6-triethylbenzenesulfinic acid. , sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, calcium 2,4,6-triisopropylbenzenesulfinate, and the like, with sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate being preferred.

[0116] The borate compound is preferably an aryl borate compound, such as a borate compound having one aryl group per molecule, a borate compound having two aryl groups per molecule, a borate compound having three aryl groups per molecule, or a borate compound having four aryl groups per molecule, and from the viewpoint of storage stability, a borate compound having three or four aryl groups per molecule is preferred.

[0117] Examples of borate compounds having one aryl group per molecule include trialkylphenylboron, trialkyl(p-chlorophenyl)boron, trialkyl(p-fluorophenyl)boron, trialkyl[3,5-bis(trifluoromethyl)phenyl]boron, trialkyl[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, trialkyl(p-nitrophenyl)boron, trialkyl(m-nitrophenyl)boron, trialkyl(p-butylphenyl)boron, trialkyl(m-butylphenyl)boron, and trialkyl(p-butyloxyphenyl)boron. Examples thereof include boron, trialkyl(m-butyloxyphenyl)boron, trialkyl(p-octyloxyphenyl)boron, and trialkyl(m-octyloxyphenyl)boron (wherein the alkyl group is at least one selected from the group consisting of an n-butyl group, an n-octyl group, an n-dodecyl group, and the like), and salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, and the like).

[0118] Examples of borate compounds having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi(p-chlorophenyl)boron, dialkyldi(p-fluorophenyl)boron, dialkyldi[3,5-bis(trifluoromethyl)phenyl]boron, dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, dialkyldi(p-nitrophenyl)boron, dialkyldi(m-nitrophenyl)boron, dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron, and dialkyldi(p-butyloxophenyl). dialkyldi(m-butyloxyphenyl)boron, dialkyldi(p-octyloxyphenyl)boron, dialkyldi(m-octyloxyphenyl)boron (the alkyl group in each of the above examples is an n-butyl group, an n-octyl group, an n-dodecyl group, or the like), and salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, or the like).

[0119] Examples of borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron, monoalkyltri(p-fluorophenyl)boron, monoalkyltri[3,5-bis(trifluoromethyl)phenyl]boron, monoalkyltri[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, monoalkyltri(p-nitrophenyl)boron, monoalkyltri(m-nitrophenyl)boron, monoalkyltri(p-butylphenyl)boron, monoalkyltri(m-butylphenyl)boron, monoalkyltri(p

[0033] Examples of the alkyl group include monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(m-butyloxyphenyl)boron, monoalkyltri(p-octyloxyphenyl)boron, and monoalkyltri(m-octyloxyphenyl)boron (wherein the alkyl group is one selected from an n-butyl group, an n-octyl group, an n-dodecyl group, etc.), and salts thereof (sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc.).

[0120] Examples of borate compounds having four aryl groups in one molecule include tetraphenylboron, tetrakis(p-chlorophenyl)boron, tetrakis(p-fluorophenyl)boron, tetrakis[3,5-bis(trifluoromethyl)phenyl]boron, tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron, tetrakis(p-nitrophenyl)boron, tetrakis(m-nitrophenyl)boron, tetrakis(p-butylphenyl)boron, tetrakis(m-butylphenyl)boron, tetrakis(p-butyloxyphenyl)boron, tetrakis(m-butyloxyphenyl)boron, tetrakis(p-octyloxyphenyl)boron, and tetrakis(m-octyloxyphenyl).

[0033] Examples of suitable hydroxyphenyls include (p-nitrophenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron, and (p-octyloxyphenyl)triphenylboron, as well as salts thereof (sodium salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, etc.).

[0121] Barbituric acid derivatives include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-5-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-1-ethylbarbituric acid, Examples thereof include 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and thiobarbituric acids, as well as salts thereof (particularly preferred are those derived from alkali metals or alkaline earth metals). Particularly suitable barbituric acid derivatives include 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, and sodium salts thereof.

[0122] Examples of the triazine compound include 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine. 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine s(trichloromethyl)-s-triazine, 2-[2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4, 6-bis(trichloromethyl)-s-triazine, 2-(1-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N,N-bis(2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,Examples include 6-bis(trichloromethyl)-s-triazine and 2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triazine.

[0123] Among the triazine compounds exemplified above, 2,4,6-tris(trichloromethyl)-s-triazine is preferred in terms of polymerization activity, and 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine are preferred in terms of storage stability. The above triazine compounds may be used alone or in combination of two or more.

[0124] Suitable copper compounds include, for example, copper acetylacetonate, copper (II) acetate, copper oleate, copper (II) chloride, and copper (II) bromide.

[0125] Examples of tin compounds include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, di-n-butyltin dilaurate, etc. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

[0126] The vanadium compound is preferably a tetravalent and / or pentavalent vanadium compound. Examples of the tetravalent and / or pentavalent vanadium compound include divanadium(IV) tetroxide, vanadium oxide acetylacetonate(IV), vanadyl oxalate(IV), vanadyl sulfate(IV), oxobis(1-phenyl-1,3-butanedionato)vanadium(IV), bis(maltolato)oxovanadium(IV), vanadium(V) pentoxide, sodium metavanadate(V), and ammonium metavanadate(V), as described in JP 2003-96122 A.

[0127] Suitable examples of halogen compounds include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, and dilauryldimethylammonium bromide.

[0128] Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, and pn-octyloxybenzaldehyde. Among these, pn-octyloxybenzaldehyde is preferably used from the viewpoint of curability.

[0129] Examples of the thiol compound include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

[0130] Examples of sulfites include sodium sulfite, potassium sulfite, calcium sulfite, and ammonium sulfite.

[0131] Examples of bisulfites include sodium bisulfite and potassium bisulfite.

[0132] Examples of the thiourea compound include 1-(2-pyridyl)-2-thiourea, thiourea, methylthiourea, ethylthiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-di-n-propylthiourea, N,N'-dicyclohexylthiourea, trimethylthiourea, triethylthiourea, tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea, tetraethylthiourea, tetra-n-propylthiourea, and tetracyclohexylthiourea.

[0133] When the dental curable composition of the present invention contains a polymerization accelerator (E), its content is not particularly limited, but from the viewpoint of the curability of the resulting dental curable composition, it is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, even more preferably 0.02 part by mass or more, or may be 0.03 part by mass or more, 0.05 part by mass or more, or even 0.1 part by mass or more, relative to 100 parts by mass of the total polymerizable monomers (A). Furthermore, since too much polymerization accelerator (E) may cause precipitation in the dental curable composition, the content of the polymerization accelerator (E) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, particularly preferably 5 parts by mass or less, or may be 2 parts by mass or less, 1 part by mass or less, or even 0.5 parts by mass or less, relative to 100 parts by mass of the total polymerizable monomers (A).

[0134] [Additive (F)] In addition to the above-mentioned polymerizable monomer (A), filler (B), polymerization initiator (C), colorant (D), and polymerization accelerator (E), the dental curable composition of the present invention may further contain, as necessary, additives (F) such as polymerization inhibitors, chain transfer agents, ultraviolet absorbers, antioxidants, antibacterial agents, dispersants, pH adjusters, etc. The additives (F) may be used alone or in combination of two or more.

[0135] Examples of polymerization inhibitors include 3,5-di-t-butyl-4-hydroxytoluene, hydroquinone, dibutyl hydroquinone, dibutyl hydroquinone monomethyl ether, hydroquinone monomethyl ether, and 2,6-di-t-butylphenol. These may be used alone or in combination of two or more. Examples of ultraviolet absorbers include benzotriazole compounds such as 2-(2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-ethylphenyl)benzotriazole, 2-(2-hydroxy-5-propylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, and 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chloro-2H-benzotriazole (Tinuvin 326), and benzimidazole compounds. These may be used alone or in combination of two or more.

[0136] As described above, the dental hardenable composition of the present invention is suitable for cases where a cavity floor is present, such as Class I, Class II, or Class V cavities, and not only does it exhibit good color matching with a wide range of natural tooth shades with a single dental hardenable composition, but the cured product also exhibits excellent polishability and smoothness durability. Furthermore, within the scope of the present specification, an embodiment that particularly emphasizes smoothness durability may be selected. For example, in view of particularly emphasizing smoothness durability, an embodiment (Y-1) may be a dental hardenable composition in which the color match to Class I cavities (ΔE* represented by the following formula) is 6.0 or less for both shades A1 and A4 of the shade guide (product name "Vita Classical Shade Guide," manufactured by VITA Zahnfabrik, Germany) and the smoothness durability is 40% or more. ΔE*=((L*1-L*0) 2 +(a*1-a*0) 2 +(b*1-b*0) 2 ) 1 / 2 (In the formula, the symbols are as described in the Examples below.)

[0137] In addition, in the embodiment (Y-1), the method for measuring the color compatibility with a Class I cavity and the method for measuring the smoothness durability are as described in the Examples below.

[0138] As described above, the dental hardenable composition of the present invention exhibits excellent color matching with a wide range of natural tooth shades, even with only one composition, without any change in composition. Therefore, in one embodiment, the dental hardenable composition exhibits excellent color matching (ΔE*) with both the A1 and A4 shade guides in cases where a Class I cavity is present.

[0139] The dental curable composition in embodiment (Y-1) can be appropriately modified based on the description in this specification.

[0140] The dental hardenable composition of embodiment (Y-1) is not particularly limited in composition, as long as the color match for Class I cavities and the smoothness durability are within predetermined ranges. For example, the dental hardenable composition of embodiment (Y-1) preferably contains a polymerizable monomer (A). The dental hardenable composition of embodiment (Y-1) preferably contains a filler (B). The dental hardenable composition of embodiment (Y-1) preferably contains a polymerization initiator (C). Furthermore, the dental hardenable composition of embodiment (Y-1) preferably contains a colorant (D). The dental hardenable composition of embodiment (Y-1) does not necessarily contain the colorant (D). For example, even in a dental curable composition that does not contain a colorant (D), the spectral reflectance ratio R can be increased by appropriately combining the type of polymerization initiator (C) (for example, the combined use of (bis)acylphosphine oxides and α-diketones as photopolymerization initiators), the type of filler (B), the size such as the average particle diameter, the shape (for example, an irregular filler), the production method (for example, surface treatment with a surface treatment agent, heat treatment, etc.), etc. 650 / 600 , R 700 / 600 , and R 750 / 600The dental hardenable composition of the present invention also includes compositions that exhibit good color matching with a wide range of natural tooth colors and excellent smoothness durability, without changing the composition, using only one type of composition, as long as all of the above are within the specified ranges.

[0141] In addition, in embodiment (Y-1), the smoothness durability is preferably 55% or more, more preferably 60% or more, and even more preferably 65% ​​or more.

[0142] Furthermore, in embodiment (Y-1), the color compatibility (ΔE*) for Class I cavities is preferably 5.5 or less, more preferably 5.0 or less, and even more preferably 4.5 or less for both shades A1 and A4 of the shade guide (product name "Vita Classical Shade Guide", manufactured by VITA Zahnfabrik, Germany).

[0143] <<Method for producing dental hardenable composition>> There is no particular limitation on the method for preparing the dental curable composition of the present invention, and it can be obtained by blending the respective components in the prescribed blending amounts. There is no particular limitation on the blending order, and the respective components may be blended all at once or in two or more batches. Furthermore, the components may be mixed or kneaded, or may be subjected to a degassing treatment such as vacuum degassing, as needed. The obtained dental curable composition can be filled into a single container (such as a syringe) to form a one-component (one-paste) dental curable composition.

[0144] 《Application》 The dental curable composition of the present invention may be used for any purpose, including various dental materials, such as dental composite resins (e.g., caries cavity filling composite resins, core buildup composite resins, crown composite resins, and self-adhesive composite resins), denture base resins, denture base lining materials, impression materials, luting materials (e.g., resin cements and resin-modified glass ionomer cements), dental adhesives (e.g., orthodontic adhesives and cavity application adhesives), fissure sealants, CAD / CAM resin blocks, temporary crowns, and artificial tooth materials. Among these, the dental curable composition of the present invention is particularly preferably used as a dental composite resin and a CAD / CAM resin block because of its high aesthetic appeal and excellent mechanical strength.

[0145] The present invention includes embodiments in which the above-described configurations are combined in various ways within the scope of the technical concept of the present invention, as long as the effects of the present invention are achieved. [Example]

[0146] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Test methods, materials, etc. used in the examples are summarized below.

[0147] Test Method [Average particle size of filler] The average particle size of the following fillers was measured on a volume basis using ethanol as a dispersion medium with a laser diffraction particle size analyzer (SALD-2300, manufactured by Shimadzu Corporation) (particularly for measuring the particle size of particles 0.1 μm or larger), or with a scanning electron microscope (SU3500, manufactured by Hitachi High-Technologies Corporation) (n=1).

[0148] [Refractive index of filler] For the following fillers, a certain amount (0.1 g / mL) of each filler was dispersed in an organic solvent with a known refractive index (adjusted to various refractive indices by mixing two or more organic solvents selected from the group consisting of 1-bromonaphthalene, methyl salicylate, dimethylformamide, and 1-pentanol). The refractive index (nD25) of the organic solvent that maximized the dispersion's optical transmittance at 589 nm was determined, and this refractive index was used as the refractive index of the filler. Depending on the type of filler whose refractive index is to be measured, the type of organic solvent with a known refractive index can be selected based on the expected refractive index. The refractive index of the organic solvent was measured using an Abbe refractometer (manufactured by Atago Co., Ltd., product name: NAR-1T LIQUID) with an Na-D light source. The optical transmittance of the dispersion was measured in a quartz cell with a 10 mm optical path length using a UV-visible spectrophotometer (manufactured by Shimadzu Corporation, product name: UV-2400).

[0149] [Refractive index of polymer] The refractive index of the polymer of the polymerizable monomer was measured using the Abbe refractometer in a thermostatic chamber at 25°C. Specifically, for each example and comparative example in Table 1, a homogeneous polymerizable monomer mixture containing the polymerizable monomer (A), polymerization initiator (C), polymerization accelerator (E), and additive (F) in the ratios listed in Table 1 was placed in a mold with a φ10 mm x 1.0 mm hole, and glass slides were pressed onto both sides. The mixture was then cured by irradiating both sides with light using an LED photopolymerizer (α Light V, manufactured by Morita Seisakusho Co., Ltd., wavelengths: 400-408 nm, 465-475 nm) for 45 seconds each. The mixture was then removed from the mold to produce a cured product of the polymerizable monomer mixture. When placing the cured product in the Abbe refractometer, a solvent (1-bromonaphthalene) with a higher refractive index than the sample but without dissolving it was added dropwise to the sample to ensure close contact between the cured product and the measurement surface.

[0150] [Specific surface area of ​​inorganic filler] The inorganic fillers obtained in each of the following production examples were subjected to vacuum degassing at 100°C for 2 hours, and then their specific surface areas were measured (n=1) using a specific surface area measuring device (Microtrac-Bell Corporation's "BELSORP-mini II") based on the BET method under the conditions of adsorption gas: nitrogen, measurement temperature: 77K. Note that in this measurement, analysis was performed using the BET multipoint method, using five points on the adsorption isotherm where the ratio (P / P0) of the adsorption equilibrium pressure P (kPa) to the saturated vapor pressure P0 (kPa) was in the range of 0.05 to 0.3.

[0151] [Spectral reflectance ratio (R 650 / 600 , R 700 / 600 , R 750 / 600 ) The spectral reflectance ratio of the cured product was evaluated using a spectrophotometer (SE6000, manufactured by Nippon Denshoku Industries Co., Ltd., light source: D65 / 2, measurement window: φ6 mm). Specifically, the dental curable composition was filled into a stainless steel mold (φ10 mm x thickness: 1 mm), sandwiched between cover glasses on the top and bottom, and pressed together. The composition was then cured by irradiating both sides with light using an LED photopolymerizer (α Light V, manufactured by Morita Seisakusho Co., Ltd., wavelengths: 400-408 nm, 465-475 nm) for 45 seconds each. The cured plate was removed from the mold, and the spectral reflectance for wavelengths of 380-780 nm was measured (n=1) with a standard white plate (X=93.94, Y=95.90, Z=112.92) placed behind the cured plate. The spectral reflectance ratio (R 650 / 600 , R 700 / 600 , R 750 / 600 ) was calculated.

[0152] [Contrast ratio] The contrast ratio of the cured product was evaluated using the above-mentioned spectrocolorimeter. Specifically, a cured plate measuring φ10 mm and thickness 1 mm was prepared in the same manner as above, and the tristimulus Y value was measured on a black background and a white background. A standard white plate was used for the white background, and a matte dark box for the black background. The contrast ratio was calculated based on the above-mentioned formula (n=1).

[0153] [Light Diffusion Degree LD] The light diffusion coefficient (LD) of the cured product was evaluated using a goniophotometer (GP-200, Murakami Color Research Laboratory Co., Ltd.). Specifically, the dental curable composition was sandwiched between cover glasses and pressed together using a 0.25 mm thick stainless steel spacer. The composition was then cured by irradiating both sides with light for 45 seconds each using an LED photopolymerization device (α Light V, Morita Manufacturing Co., Ltd., wavelengths: 400-408 nm, 465-475 nm) to produce a cured plate measuring φ30 mm and 0.25 mm thick. The luminous intensity distribution of the transmitted light from -90° to +90° at an incident light angle of 0° was measured using the goniophotometer, and the light diffusion coefficient (LD) was calculated according to the previously described formula (2) (n=1).

[0154] [Lightness (L* / w), chromaticity index (a* / w, b* / w)] The brightness and chromaticity of the cured product were evaluated using the above-mentioned spectral color difference meter (SE6000, manufactured by Nippon Denshoku Industries Co., Ltd., light source: D65 / 2, measurement window: φ6 mm) used to measure the ratio of spectral reflectance. Specifically, a cured plate with a diameter of φ10 mm and a thickness of 1 mm was prepared in the same manner as above, and a standard white plate was placed behind the cured plate, and the L * a * b * The lightness (L* / w) and chromaticity index (a* / w, b* / w) in the color system were measured (n=1).

[0155] [Evaluation of operability] A plastic simulated cavity (a hole simulating a Class 5 cavity, 3 mm in diameter and 2 mm deep) was filled with the composition using a metal filling tool at 25°C, and the ease of filling was evaluated. Specifically, when the dental curable composition was clay-like, the dental curable composition of each Example and Comparative Example was filled into the simulated cavity using a metal dental filling tool (Yoshida Co., Ltd., kneading filling tools #4 and #5), and the stickiness felt during this process was evaluated according to the following criteria. When the dental curable composition was liquid, the dental curable composition was filled into a syringe container (Kuraray Noritake Dental Co., Ltd., Clearfil Majesty ES Flow syringe container), and the dental curable composition was extruded from the syringe container equipped with an attached needle tip to fill the simulated cavity. The stringiness of the dental curable composition during this process was evaluated according to the following criteria. 〇: No stickiness or stringiness △: Slightly sticky or slightly stringy ×: Severe stickiness or stringiness

[0156] [Color compatibility for Class I cavities] The color compatibility of the dental curable composition to a molar tooth was evaluated by filling and restoring a cavity formed in an artificial tooth and measuring the color of the cavity using a dental colorimeter. Specifically, an artificial tooth No. 6 molar (Zen Opal molar, size: PL16, shades: A1, A3, and A4, manufactured by GC Corporation) was first photographed using a dental colorimeter (Crystaleye Spectrophotometer, manufactured by Olympus Corporation). The artificial tooth was measured in a dark box (checkbox wear cover) attached to the dental colorimeter. Next, a Class I cavity measuring 4 mm in diameter and 2 mm deep was formed in the center of the artificial tooth, and the cavity surface was etched using a dental etching agent (K Etchant GEL, manufactured by Kuraray Noritake Dental Co., Ltd.) using the method recommended by the manufacturer (described in the attached document). Next, a dental adhesive (Clearfil Universal Bond QuickER, manufactured by Kuraray Noritake Dental Co., Ltd.) was used to bond the cavity surface according to the manufacturer's recommended method, and the cavity was then irradiated for 10 seconds using a dental visible light irradiator (PenCure 2000, manufactured by Morita Seisakusho Co., Ltd.) in normal mode. The cavity was then filled with a dental curable composition, and pressed against a mold for the artificial tooth previously made with a silicone impression material (Memosil 2, manufactured by Heraeus-Kulzer Japan Co., Ltd.) to create the surface shape of the artificial tooth. Using a dental unit (PortaCare 21, manufactured by Morita Seisakusho Co., Ltd.), the filled area was polished for 30 seconds under water using a dental rubber polishing material (Compomaster CA, 13S, manufactured by Matsufuku Co., Ltd.) at a rotation speed of approximately 10,000 rpm. Finally, using the dental visible light irradiator described above, the mold was irradiated with light in normal mode for 10 seconds. The mold was then removed, and light was irradiated in normal mode for 10 seconds to harden the dental curable composition, producing a filled sample. The prepared sample was photographed using the same method as the initial photograph. The lightness (L*1) and chromaticity (a*1, b*1) of the filled area in the photographed image of the filled sample were measured using the software provided with the dental colorimeter. Furthermore, the lightness (L*0) and chromaticity (a*0, b*0) of the same areas measured in the image of the untreated artificial tooth photographed initially were also measured. The color difference ΔE* was calculated using the following formula and used as an index of color compatibility (n=1). ΔE*=((L*1-L*0) 2 +(a*1-a*0) 2 +(b*1-b*0) 2 ) 1 / 2 For the artificial teeth A1, A3, and A4, each ΔE* is preferably 6.0 or less, more preferably 5.5 or less, and even more preferably 5.0 or less.

[0157] [Color compatibility for Class IV cavities] The color match of dental curable compositions to anterior teeth was evaluated by filling and restoring a cavity formed in a shade guide and measuring the color of the resulting cavity using a dental colorimeter. Specifically, a shade guide (Vita Classical Shade Guide, shades A1, A3, and A4, manufactured by VITA Zahnfabrik, Germany) was first photographed using the same method as described above. Next, a 4mm diameter quadrant-shaped Class IV cavity was formed in the incisal portion of the shade guide, penetrating from the lingual side to the labial side. A filling sample was then prepared using the same method as described above. The color difference ΔE* was calculated using the same method as described above and used as an index of color match (n=1). For the A1, A3, and A4 shade guides, ΔE* is preferably 7.0 or less, more preferably 6.0 or less, and even more preferably 5.0 or less, and it is particularly preferable that all ΔE* values ​​are 6.0 or less for the A1, A3, and A4 shade guides.

[0158] [Easy sanding of the cured product] A polytetrafluoroethylene mold (φ10 mm × thickness 2.0 mm) was filled with the dental curable composition and irradiated with light for 10 seconds using a dental visible light irradiator (Pencure 2000, Morita Seisakusho Co., Ltd.). The cured product was removed from the mold and used as a test specimen. The smooth surface of this test specimen was polished with #600 abrasive paper under dry conditions. Next, using a dental unit (Portacare 21, Morita Seisakusho Co., Ltd.) and a dental rubber abrasive (Compomaster CA, 13S, Matsufuku Co., Ltd.) under water, the specimen was polished at a rotation speed of approximately 10,000 rpm for 10 seconds. The gloss of the polished surface was then measured using a glossmeter (VG2000, Nippon Denshoku Industries Co., Ltd., measurement angle: 60°, compliant with JIS Z 8741:1997). The gloss (ratio of gloss to a mirror, taken as 100%) was calculated, and this was used as an index of the polishability of the cured product (n=3). The average values ​​of the measured values ​​are shown in Table 2. The gloss level is preferably 20% or more, more preferably 25% or more, and even more preferably 30% or more.

[0159] [Smoothness durability of cured product] The smoothness durability was evaluated based on the change in gloss before and after the abrasion resistance test. Specifically, the procedure is as follows: The dental curable composition (paste) was filled into a stainless steel mold (30 mm long x 20 mm wide x 2 mm thick), and the top and bottom of the paste (30 mm x 20 mm surfaces) were pressed against glass slides. The paste was then cured by irradiating the front and back of the paste through the glass slide with a dental laboratory visible light irradiator (α Light V, manufactured by Morita Corporation) for 180 seconds each. The resulting cured product was used as a test specimen, and its surface was polished with 1500-grit waterproof abrasive paper to create a polished surface. The polished surface was then buffed for 20 seconds at 3000 rpm using a laboratory polishing box (EWL80, manufactured by KaVo). The buffed test specimen was then subjected to the abrasion resistance test. A dental abrasive (trade name: PORCENY HYDON, manufactured by Tokyo Dental Materials Co., Ltd.) was used for buffing. The gloss (G1) of the test specimens before the abrasion test was measured using a glossmeter (VG2000, manufactured by Nippon Denshoku Industries Co., Ltd., in accordance with JIS Z 8741:1997) as a percentage of the mirror, with the measurement angle set at 60°. The test specimens were subjected to an abrasion test under a load of 250 g for 40,000 cycles using a toothbrush abrasion tester (manufactured by Daiei Scientific Instruments Manufacturing Co., Ltd.) with a dentifrice suspension and a commercially available toothbrush (Bitoine, regular size, medium hardness, manufactured by Lion Corporation). The dentifrice suspension was prepared using commercially available dentifrice (Denta Clear Max, manufactured by Lion Corporation) at a dentifrice / distilled water mass ratio of 10 / 90. The gloss (G2) of the test specimens' surfaces after the abrasion test was measured in the same manner as before the abrasion test. The smoothness durability (%) was calculated from the surface gloss of the test piece before and after the abrasion resistance test as {(G2) × 100} / (G1). The smoothness durability is preferably 40% or more, more preferably 45% or more, even more preferably 50% or more, and particularly preferably 55% or more, 60% or more, or 65% or more.

[0160] "material" (Polymerizable Monomer (A)) Bis-GMA: 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane D2.6E: 2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane (average number of moles of ethyleneoxy groups added: 2.6) UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate DD: 1,10-decanediol dimethacrylate 3G: Triethylene glycol dimethacrylate POBMA: m-phenoxybenzyl methacrylate

[0161] (Filling material (B)) The fillers used were those obtained in the following production examples. Commercially available products were also used as they were.

[0162] [Manufacturing Example 1] Manufacturing of inorganic fine particles (BF-1-1) 100 parts by weight of commercially available barium glass (8235 UF0.7, manufactured by Schott, average particle size 0.7 μm, refractive index: 1.55), 2 parts by weight of 3-methacryloyloxypropyltrimethoxysilane, and 170 parts by weight of toluene were placed in a three-neck flask and stirred at room temperature for 2 hours. After the toluene was distilled off under reduced pressure, the mixture was vacuum dried at 40°C for 16 hours and then heated at 90°C for 3 hours to obtain inorganic microparticles (BF-1-1) with a surface treatment layer. The average particle size of the resulting inorganic microparticles (BF-1-1) was 0.7 μm.

[0163] [Manufacturing Example 2] - Manufacturing of inorganic fine particles (BF-1-2) 100 parts by weight of commercially available barium glass (GM27884 NanoFine180, manufactured by Schott, average particle size 0.2 μm, refractive index: 1.53), 11 parts by weight of 3-methacryloyloxypropyltrimethoxysilane, and 170 parts by weight of toluene were placed in a three-neck flask and stirred at room temperature for 2 hours. After the toluene was distilled off under reduced pressure, the mixture was vacuum dried at 40°C for 16 hours and then heated at 90°C for 3 hours to obtain inorganic microparticles (BF-1-2) with a surface treatment layer. The average particle size of the resulting inorganic microparticles (BF-1-2) was 0.2 μm.

[0164] [Manufacturing Example 3] - Manufacturing of inorganic fine particles (BF-1-3) 100 parts by weight of commercially available barium glass (GM27884 NanoFine180, manufactured by Schott, average particle size 0.2 μm, refractive index: 1.53), 11 parts by weight of 8-methacryloyloxyoctyltrimethoxysilane, and 170 parts by weight of toluene were placed in a three-neck flask and stirred at room temperature for 2 hours. After the toluene was distilled off under reduced pressure, the mixture was vacuum dried at 40°C for 16 hours and then heated at 90°C for 3 hours to obtain inorganic microparticles (BF-1-3) with a surface treatment layer. The average particle size of the resulting inorganic microparticles (BF-1-3) was 0.2 μm.

[0165] [Manufacturing Example 4] - Manufacturing of inorganic fine particles (BF-1-4) 100 parts by weight of commercially available barium glass (GM27884 NanoFine180, manufactured by Schott, average particle size 0.2 μm, refractive index: 1.53), 11 parts by weight of 11-methacryloyloxyundecyltrimethoxysilane, and 170 parts by weight of toluene were placed in a three-neck flask and stirred at room temperature for 2 hours. After the toluene was distilled off under reduced pressure, the mixture was vacuum dried at 40°C for 16 hours and then heated at 90°C for 3 hours to obtain inorganic microparticles (BF-1-4) with a surface treatment layer. The average particle size of the resulting inorganic microparticles (BF-1-4) was 0.2 μm.

[0166] [Manufacturing Example 5] Manufacturing of inorganic fine particles (BF-1-5) A commercially available surface-treated silica-coated ytterbium fluoride (SG-YBF100WSCMP10, primary particle average particle size: 110 nm, refractive index: 1.54, manufactured by Sukgyung AT) was used as is.

[0167] [Manufacturing Example 6] Manufacturing of other inorganic agglomerated particles (BF-2e-1) The water in a commercially available silica-ytterbium oxide aqueous dispersion (SG-YBSO30SW, manufactured by Sukgyung AT, average primary particle size: 30 nm) was removed using an evaporator, and the resulting solid component was ground for 180 minutes in a planetary ball mill (Fritsch, Germany, "Classic Line P-6", zirconia balls). The resulting powder was calcined for 1 hour in an electric furnace set at 800°C and then further ground for 180 minutes in the planetary ball mill. The resulting powder was surface-treated with 10 parts by mass of 3-methacryloyloxypropyltrimethoxysilane per 100 parts by mass to obtain other inorganic agglomerated particles (BF-2e-1). The resulting inorganic agglomerated particles (BF-2e-1) had an average particle size of 5.7 μm, a refractive index of 1.53, and a specific surface area of ​​95.8 m. 2 / g.

[0168] [Manufacturing Example 7] ·Production of light-diffusing inorganic agglomerated particles (BF-2d-1) 100 parts by mass of agglomerated silica "Silica Microbead P-500 (average primary particle size: 12 nm, average aggregate particle size: 2 μm)" (manufactured by JGC Catalysts and Chemicals Co., Ltd.), 20 parts by mass of 3-methacryloxypropyltrimethoxysilane, and 170 parts by mass of toluene were placed in a three-neck flask and stirred for 2 hours at room temperature. After the toluene was distilled off under reduced pressure, the mixture was vacuum dried at 40°C for 16 hours and then heated at 90°C for 3 hours to obtain silane-treated light-diffusing inorganic agglomerated particles (BF-2d-1). The silane-treated light-diffusing inorganic agglomerated particles (BF-2d-1) had an average particle size of 1.6 μm, a refractive index of 1.44, and a specific surface area of ​​99 m. 2 / g, and the pore volume was 0.19 mL / g.

[0169] [Manufacturing Example 8] - Manufacturing of light-diffusing organic-inorganic composite filler (BC-d-1) 70 parts by weight of Bis-GMA, 30 parts by weight of 3G, and 0.5 parts by weight of benzoyl peroxide were mixed and uniformly dissolved to obtain a polymerizable monomer-containing composition. Meanwhile, colloidal silica powder with an average particle size of 0.04 μm (Aerosil® OX50, manufactured by Nippon Aerosil Co., Ltd.) was surface-treated with γ-methacryloxypropyltrimethoxysilane by standard methods. 100 parts by weight of the surface-treated colloidal silica and 100 parts by weight of the polymerizable monomer were kneaded to obtain a paste-like composition. The composition was heated under reduced pressure at 130°C for 3 hours to polymerize, and the resulting cured product was further pulverized in a ball mill to obtain a surface-untreated organic-inorganic composite filler. 100 parts by weight of the surface-untreated organic-inorganic composite filler was further surface-treated with 1 part by weight of γ-methacryloxypropyltrimethoxysilane to obtain a light-diffusing organic-inorganic composite filler (BC-d-1). The light-diffusing organic-inorganic composite filler (BC-d-1) had an average particle size of 11 μm and a refractive index of 1.50.

[0170] [Manufacturing Example 9] ·Manufacture of light-diffusing organic-inorganic composite filler (BC-d-2) 70 parts by weight of UDMA, 30 parts by weight of DD, and 0.5 parts by weight of benzoyl peroxide were mixed and uniformly dissolved to obtain a polymerizable monomer-containing composition. Meanwhile, colloidal silica powder with an average particle size of 0.04 μm (Aerosil® OX50, manufactured by Nippon Aerosil Co., Ltd.) was surface-treated with γ-methacryloxypropyltrimethoxysilane using a standard method. 100 parts by weight of the surface-treated colloidal silica and 100 parts by weight of the polymerizable monomer were kneaded to obtain a paste-like composition. The composition was heated under reduced pressure at 130°C for 3 hours to polymerize, and the resulting cured product was further pulverized in a ball mill to obtain a surface-untreated organic-inorganic composite filler. 100 parts by weight of the surface-untreated organic-inorganic composite filler was further surface-treated with 1 part by weight of γ-methacryloxypropyltrimethoxysilane to obtain a light-diffusing organic-inorganic composite filler (BC-d-2). The light-diffusing organic-inorganic composite filler (BC-d-2) had an average particle size of 15 μm and a refractive index of 1.49.

[0171] [Manufacturing Example 10] · Manufacturing of organic-inorganic composite filler (BC-e-1) 100 parts by weight of the inorganic filler (BF-1-2) prepared above was added to 100 parts by weight of a polymerizable monomer mixture (1:1 mass ratio) of Bis-GMA and 3G, in which 1% by weight of azobisisobutyronitrile (AIBN) had been dissolved as a polymerization initiator. The mixture was mixed to form a paste. This was then heated and polymerized at 100°C under reduced pressure for 5 hours. The resulting polymerized and cured material was ground using a vibrating ball mill to an average particle size of approximately 5 μm. 100 g of the resulting powder was surface-treated by refluxing at 90°C for 5 hours in 200 mL of an ethanol solution containing 2% by weight of γ-methacryloyloxypropyltrimethoxysilane to obtain organic-inorganic composite filler (BC-e-1). The resulting organic-inorganic composite filler (BC-e-1) had an average particle size of 5.2 μm and a refractive index of 1.54.

[0172] [Manufacturing Example 11] Manufacturing of other inorganic particles (BF-3-1) 100 parts by weight of commercially available barium glass (8235 UF1.5, manufactured by Schott, average particle size 1.5 μm, refractive index: 1.55), 2 parts by weight of 3-methacryloyloxypropyltrimethoxysilane, and 170 parts by weight of toluene were placed in a three-neck flask and stirred at room temperature for 2 hours. After the toluene was distilled off under reduced pressure, the mixture was vacuum dried at 40°C for 16 hours and then heated at 90°C for 3 hours to obtain inorganic particles (BF-3-1) with a surface treatment layer. The average particle size of the obtained inorganic particles (BF-3-1) was 1.5 μm.

[0173] (Polymerization initiator (C)) CQ: Camphorquinone TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

[0174] (Colorant (D)) D-1: Titanium oxide D-2: Iron Black D-3: Yellow iron oxide D-4: Bengala

[0175] (Polymerization accelerator (E)) PDE: ethyl 4-(N,N-dimethylamino)benzoate

[0176] (Additive (F)) TIN: "Tinuvin 326" (manufactured by BASF Japan Ltd.) (ultraviolet absorber) BHT: 3,5-di-t-butyl-4-hydroxytoluene (polymerization inhibitor)

[0177] [Examples 1 to 10 and Comparative Examples 1 to 5] (Dental Composite Resins) Dental curable compositions were prepared by mixing and kneading the materials and proportions listed in Table 1 at room temperature (23°C) in a dark place, homogenizing the mixture, and vacuum degassing. These dental curable compositions were subjected to the tests described above. The results are shown in Table 2.

[0178] [Table 1]

[0179] [Table 2]

[0180] As shown in Table 2, the dental hardenable composition of the present invention exhibits good color matching with a wide range of natural teeth colors for the cavity floor of a Class I cavity, even with a single dental hardenable composition. Among the dental hardenable compositions of the present invention, Example 1 and others exhibit high color matching with Class IV cavities due to their light diffusibility, and also exhibit good smoothness durability due to the inclusion of a specific filler (B). Comparative Examples 1 to 5 exhibit poor color matching because the spectral reflectance ratios are not within the preferred range. [Industrial Applicability]

[0181] The dental curable composition of the present invention exhibits good color matching with a wide range of natural tooth colors with only one type of composition, has good smoothness durability, and is suitable for use as a dental composite resin, etc.

Claims

1. A dental curable composition comprising a polymerizable monomer (A), a filler (B), a polymerization initiator (C), and a colorant (D), The ratio R of the spectral reflectance at wavelengths of 650 nm, 700 nm, and 750 nm to the spectral reflectance at a wavelength of 600 nm when a 1.0 mm thick cured product of the dental curable composition is measured against a white background using a spectrocolorimeter. 650 / 600 , R 700 / 600 , and R 750 / 600 are all within the range of 97% to 103%.

2. 2. The dental curable composition according to claim 1, wherein a contrast ratio defined by the following formula (1) in a cured product having a thickness of 1.0 mm is 0.35 to 0.65: Contrast ratio = Y b / Y w (1) (where Y b represents the Y value of the XYZ color system measured on a black background, and Y w represents the Y value of the XYZ color system measured against a white background.)

3. 3. The dental curable composition according to claim 1, wherein a cured product having a thickness of 0.25 mm has a light diffusivity LD defined by the following formula (2) of 0.0001 to 0.99: LD=(I 5 / cos5°) / I 0 (2) (where I represents the luminous intensity of light transmitted through the cured product, and I 0 , and I 5 represent the luminous intensity of transmitted light in directions tilted at 0 degrees and 5 degrees relative to the direction perpendicular to the sample plate (the direction of incident light).

4. 4. The dental curable composition according to claim 1, wherein a chromaticity index a* / w of a 1.0 mm-thick cured product is −3.0 to 2.0 in the L*a*b* color system when measured with a standard white plate placed behind the cured product.

5. 5. The dental curable composition according to claim 1, wherein the filler (B) comprises inorganic fine particles (BF-1) having an average particle size of 0.05 to 1 μm.

6. 6. The dental curable composition according to claim 1, wherein the filler (B) contains inorganic agglomerated particles (BF-2) formed by agglomeration of inorganic primary particles (x), and the inorganic primary particles (x) have an average particle size of 0.001 to 1 μm.

7. 7. The dental curable composition according to claim 6, wherein the inorganic agglomerated particles (BF-2) contain light-diffusing inorganic agglomerated particles (BF-2d), and the refractive index of the light-diffusing inorganic agglomerated particles (BF-2d) satisfies the following formula (3): 0.03 <nP-nF BF-2d | <1.0 (3) (where nP is the refractive index of the polymer obtained by polymerizing the polymerizable monomer (A), nF BF-2d represents the refractive index of the light-diffusing inorganic agglomerated particles (BF-2d).

8. 8. The dental curable composition according to claim 1, wherein the filler (B) comprises an organic-inorganic composite filler (BC) containing inorganic primary particles (x), and the inorganic primary particles (x) have an average particle size of 0.001 to 1 μm.

9. 9. The dental curable composition according to claim 8, wherein the organic-inorganic composite filler (BC) comprises a light-diffusing organic-inorganic composite filler (BC-d), and the refractive index of the light-diffusing organic-inorganic composite filler (BC-d) satisfies the following formula (7): 0.03 <nP-nF BC-d | <1.0 (7) (where nP is the refractive index of the polymer obtained by polymerizing the polymerizable monomer (A), nF BC-d represents the refractive index of the light-diffusing organic-inorganic composite filler (BC-d).

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