JP2023176641A - Dental curable composition - Google Patents

Abstract

To provide a dental curable composition applicable to natural teeth in a variety of tones only with a single-colored filling and restorative material, in the restoration of various parts of teeth such as cavities and incisal angles.SOLUTION: Provided is a dental curable composition comprising: (A) an amorphous composite metal oxide filler containing SiO2, ZrO2 and Al2O3; (B) a spherical SiO2 filler with an average particle diameter of 50 nm or less; (C) a (meth)acrylate polymerizable monomer; and (D) a coloring material, a blending ratio (mass ratio) of the SiO2 filler (B) and the composite metal oxide filler (A) being 1: 0.8 to 1: 8, the transmittance (Tt) of a cured body with a thickness of 1 mm after polymerization and curing of the curable composition being 52 or more and 66 or less, the turbidity (haze value) being 85 or more and 98 or less, and in a L*a*b* color system, the L* value being 70 or more and 77 or less, a* value being -0.5 or more and 1.5 or less, and b* value being 11 or more and 19 or less.SELECTED DRAWING: None

Description

The present invention relates to dental curable compositions.

Conventionally, curable compositions used to repair teeth damaged due to caries, fracture, etc., have been known to use structural colors that are developed due to light interference, diffraction, refraction, scattering, etc. of spherical fillers. (For example, Patent Document 1 and Patent Document 2).
Patent Document 1 describes a curable composition containing a polymerizable monomer component (A), a spherical filler (B) having an average particle diameter within the range of 230 nm to 1000 nm, and a polymerization initiator (C), In the state where a cured product with a thickness of 1 mm was formed, the brightness (V) of the Munsell display system measurement value of colored light under a black background, measured using a color difference meter, was less than 5, and the chroma (C ) is 0.05 or more, and the brightness (V) as measured by the Munsell display system under a white background is 6 or more, and the chroma (C) is less than 2. things are listed.

Patent Document 2 describes that the polymerizable monomer component (A) has an average primary particle diameter in the range of 100 nm or more and 1000 nm or less, and in the number-based particle size distribution, 90% or more of the total number of particles is of the average primary particle diameter. an inorganic spherical filler (B) existing in the range of 5% before and after, an amorphous inorganic filler (C) with an average particle diameter in the range of 100 nm to 1000 nm, and a polymerization initiator (D), The refractive index at 25°C of the inorganic spherical filler (B): n _FB is larger than the refractive index at 25°C of the polymer obtained by polymerizing the polymerizable monomer component (A): n _p Characteristic dental curable compositions are described.

Since the curable compositions described in Patent Documents 1 and 2 utilize light colored by structural colors, they do not use coloring substances such as pigments, and can harmonize with the shaded tone of natural teeth. It is possible to carry out repairs that maintain harmony with the environment over a long period of time. Furthermore, since the curable composition described in Patent Document 2 has moderate opacity, it can be used to improve the incisal angle in anterior tooth defects, particularly in class III cavities that do not contain deep dentine (interproximal cavities of anterior teeth). In the restoration of class IV cavities (proximal cavities of anterior teeth that include the incisal angle), high color compatibility can be achieved without using a composite resin (CR) for the base. .

However, the curable compositions described in Patent Document 1 and Patent Document 2 need to exhibit structural color, and the particle size, refractive index, and shape of the spherical and amorphous inorganic fillers, as well as their blending ratio, are limited. Therefore, the degree of freedom in composition design was low and composition design was difficult. For this reason, without using technology to express structural color, by color design using coloring materials such as pigments, only a single color filling and restorative material can harmonize with the tone of natural teeth, which have shades of light and shade, and can be used as a base material. There is a need for a technique that blends with natural teeth in the restoration of class III or class IV cavities without the use of CR.

International Publication No. 2017/069274 Japanese Patent Application Publication No. 2020-011917

The present invention provides a dental curable composition that can be matched with natural teeth of various tones using only a single-colored filling and restorative material in the restoration of various parts of teeth such as cavities and incisal angles. The purpose is to

As a result of intensive research to solve the above-mentioned problems, the present inventors discovered that the dental curable composition shown below can achieve the above-mentioned objects, and completed the present invention.

That is, the present invention is as follows.
Item 1.
(A) an amorphous composite metal oxide filler containing SiO ₂ , ZrO ₂ and Al ₂ O ₃ ;
(B) spherical SiO ₂ filler with an average particle diameter of 50 nm or less,
A dental curable composition containing (C) a (meth)acrylate polymerizable monomer and (D) a coloring material,
The blending ratio (mass ratio) of the (B) SiO ₂ filler and the (A) composite metal oxide filler is 1:0.8 to 1:8,
The transmittance (Tt) of a cured product having a thickness of 1 mm after polymerization and curing of the curable composition is 52 or more and 66 or less,
Turbidity (haze value) is 85 or more and 98 or less,
The L ^* value (lightness) in the L ^* a ^* b ^* color system is 70 or more and 77 or less,
a ^* value (chromaticity) is -0.5 or more and 1.5 or less, and
A dental curable composition having a b ^* value (chromaticity) of 11 or more and 19 or less.
Item 2.
Item 2. The dental curable composition according to item 1, wherein the colorant (D) contains at least one selected from the group consisting of a red pigment, a yellow pigment, a black pigment, and a white pigment.
Item 3.
The coloring material (D) includes a red pigment, a yellow pigment, a black pigment, and a white pigment,
Their content is
(A) an amorphous composite metal oxide filler containing SiO ₂ , ZrO ₂ and Al ₂ O ₃ ;
For a total of 100 parts by mass of the (B) spherical SiO ₂ filler with an average particle diameter of 50 nm or less and the (C) (meth)acrylate polymerizable monomer,
0.0003 to 0.0009 parts by mass of red pigment,
0.0004 to 0.0011 parts by mass of yellow pigment,
Item 3. The dental curable composition according to Item 1 or 2, wherein the black pigment is 0.0003 to 0.003 parts by mass, and the white pigment is 0.05 to 0.18 parts by mass.
Item 4.
Item 4. The dental curable composition according to any one of Items 1 to 3, wherein a cured product having a thickness of 1 mm after polymerization and curing of the dental curable composition has an opal value of 10 or more and 23 or less.
Item 5.
A tooth color standard pellet with a diameter of 15 mm and a thickness of 1 mm corresponding to shades A1 to A4 of the shade guide used as a tooth color standard;
The color tone of the cured product when the cured product having a diameter of 15 mm and a thickness of 1 mm after polymerization and curing of the dental curable composition is stacked on the tooth color reference pellet,
Item 5. The dental curable composition according to any one of Items 1 to 4, which has a color difference (ΔE) of 10.5 or less.
Item 6.
The ratio of the Y value ₍ Y B ) on a black background to the Y value (Y _W ) on a white background of a cured product having a thickness of 1 mm after polymerization and curing of the dental curable composition (Y _B /Y _W : Item 6. The dental curable composition according to any one of items 1 to 5, wherein the dental curable composition has a contrast ratio of 0.43 or more and 0.58 or less.
Section 7.
The dental curable composition is formed into a disk shape with a diameter of 12 mm and a thickness of 1 mm, and a cut is made to divide the dental curable composition in half with a 1 mm thick metal plate,
Any one of Items 1 to 6, wherein when left standing at 37°C, the divided dental curable composition deforms and the time until the divided dental curable compositions come into contact with each other is 300 seconds or more. The dental curable composition according to item 1.
Section 8.
Items 1 to 7, wherein the dental curable composition has an elongation rate (consistency) of 160% or more when 0.65 g of the dental curable composition is molded into a spherical shape and a 3.25 kg weight is placed on top and left to stand for 60 seconds. The dental curable composition according to any one of the items.
Item 9.
Item 9. The dental curable composition according to any one of Items 1 to 8, which is a paste.
Item 10.
The composite metal oxide filler (A) is a filler that is secondary particles with an average particle size of 2 to 8 μm, which are obtained by partially bonding primary particles with an average particle size of 0.1 to 0.9 μm by sintering. , the dental curable composition according to any one of Items 1 to 9.
Item 11.
A cured product obtained by polymerizing and curing the dental curable composition according to any one of Items 1 to 10.
Item 12.
A dental material obtained by polymerizing and curing the dental curable composition according to any one of Items 1 to 10.

According to the present invention, there is provided a dental hardenable composition that can be matched with natural teeth of various tones using only a single-colored filling and restorative material in the restoration of various parts of teeth such as cavities and incisal angles. can be provided. Further, the dental curable composition of the present invention has excellent shape retention of the tooth crown shape, so it has high operability and can easily form the crown shape of a missing front tooth, a molar tooth, etc.

FIG. 1 is a schematic diagram illustrating a method for evaluating color tone compatibility. FIG. 2 is a schematic diagram illustrating sensory evaluation of color tone compatibility. FIG. 3 is a schematic diagram illustrating a method for evaluating shielding performance (contrast ratio). FIG. 4 is a schematic diagram illustrating sensory evaluation of shielding properties. FIG. 5 is a schematic diagram illustrating a method for evaluating shape retention. FIG. 6 is a schematic diagram illustrating a consistency evaluation method.

The present invention will be explained in detail below.

1. Dental curable composition The dental curable composition of the present invention comprises (A) an amorphous composite metal oxide filler containing SiO ₂ , ZrO ₂ and Al ₂ O ₃ , (B) an average particle size of 50 nm or less. contains a spherical SiO ₂ filler, (C) a (meth)acrylate polymerizable monomer, and (D) a coloring material,
The blending ratio (mass ratio) of the (B) SiO ₂ filler and the (A) composite metal oxide filler is 1:0.8 to 1:8,
The transmittance (Tt) after polymerization and curing of the curable composition is 52 or more and 66 or less,
Turbidity (haze value) is 85 or more and 98 or less,
The L ^* value in the L ^* a ^* b ^* color system is 70 or more and 77 or less, the a ^* value is -0.5 or more and 1.5 or less, and the b ^* value is 11 or more and 19 or less.
As a result, the dental curable composition of the present invention can be matched with natural teeth of various tones using only a single color filling and restorative material in the restoration of various parts of teeth such as cavities and incisal angles. I can do it.

The dental curable composition of the present invention can also be referred to as a dental filling material, a dental filling and restoration material, a dental composite resin, and the like. Moreover, the material can also be referred to as the agent.

Each component added to the dental curable composition of the present invention will be explained below.

(A) Amorphous composite metal oxide filler containing SiO ₂ , ZrO ₂ and Al ₂ O ₃ The dental curable composition of the present invention contains (A) SiO ₂ , ZrO ₂ and Al ₂ O ₃ It contains an amorphous composite metal oxide filler (hereinafter sometimes referred to as "component A" or "composite metal oxide filler") as an essential component.

The composite metal oxide filler is preferably a filler that is secondary particles with an average particle size of 2 to 8 μm, which are obtained by partially bonding primary particles with an average particle size of 0.1 to 0.9 μm by sintering. .
Note that the term "amorphous" means that the shape of the primary particle observed with a SEM (Scanning Electron Microscope) has a large number of irregular corners and faces. Moreover, the amorphous composite metal oxide filler means a filler made of particles obtained by crushing or grinding.

The content of the composite metal oxide filler in the dental curable composition is usually 10 to 80% by mass, preferably 20 to 75% by mass, and more preferably 25 to 70% by mass.
Only one kind of the composite metal oxide filler can be used, or two or more kinds of different composite metal oxide fillers can be mixed.

The composite metal oxide filler, that is, the agglomerated secondary particles to which the sintered primary particles are bonded, are particles made of porous SiO ₂ -Al ₂ O ₃ -ZrO ₂ amorphous material prepared by a sol-gel method. It is produced through the steps of pulverizing into the above particle size to obtain gel particles, aggregating the gel particles, and firing the agglomerates.
By the firing, the primary particles are sufficiently sintered, but secondary particles with weak bonds between the sintered primary particles are formed, and the composite metal oxide filler used in the present invention is produced from these secondary particles.
The dental curable composition of the present invention has a large bending property by containing a filler (secondary particles, average particle size = 2 to 8 μm) to which primary particles with an average particle size of about 0.1 to 0.9 μm are bonded. Gives strength. The surface of the filler (secondary particles) has irregularities, and when the polymerizable monomer enters into these irregularities and hardens, a fitting effect (also called an anchor effect) occurs, increasing mechanical strength. considered to be a thing.

The filler used in the present invention is made of SiO ₂ -Al ₂ O ₃ -ZrO ₂ based gel fine particles (primary particles after sintering), which are dried and then fired at a high temperature, so the surface of the primary particles is sufficiently sintered. are doing. Therefore, its specific surface area is small, and a dental curable composition using this filler has a low water absorption rate and is excellent in durability under humid conditions such as in the oral cavity.

Manufacturing method of composite metal oxide filler The composite metal oxide filler used in the present invention is prepared by coprecipitating and drying a mixture of an alkoxysilane, a hydrolyzable zirconium compound, and a hydrolyzable aluminum compound by a sol-gel method. A process of forming a gel body (A1 process), a process of pulverizing the gel body to form fine particles (primary particles) (A2 process), and a process of forming secondary particles by firing the primary particles (A3 process) ) and, if necessary, a step of surface treatment with a silane coupling material (step A4).

Specifically, in the A1 step, an alkoxysilane, a hydrolyzable aluminum compound, and a hydrolyzable zirconium compound are uniformly mixed in a solvent, and SiO ₂ is 50 to 95% by mass (preferably 60 to 85% by mass). ), ZrO ₂ 0.1 to 30% by mass (preferably 10 to 20% by mass) and Al ₂ O ₃ 0.1 to 30% by mass (preferably 0.3 to 10% by mass) were prepared. , an alkaline solution is mixed to simultaneously hydrolyze each component to precipitate gel particles of the reaction product.

Among the compositions of the composite metal oxide filler in the present invention, the refractive index (nD) of SiO ₂ is 1.46, ZrO ₂ is 2.2, Al ₂ O ₃ is 1.76, and the content of each component is Accordingly, the refractive index (nD) of the composite metal oxide filler changes approximately according to the additive law. Further, in order to impart X-ray contrast properties to the dental material, ZrO ₂ component can be included.
Note that it is also possible to introduce three components such as TiO ₂ , CeO ₂ , and Y ₂ O that increase the refractive index ( _nD ) of the composite metal oxide filler, but the amount must be 3% by mass or less based on the total weight of the final filler. It is desirable to keep it to a small amount.

Here, the alkoxysilane is not particularly limited, and includes, for example, the general formula: Si(OR) ₄ (R is an alkyl group, preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, tert-butyl group, etc.); partially hydrolyzed oligomers of tetraalkoxysilane, and the like. Among these, as the alkoxysilane, ethoxysilane, methoxysilane, and methylsilicate oligomer (SiO ₂ content = 52 wt%, (CH ₃ O) ₁₀ Si ₄ = approximately tetramer, MS51 manufactured by Mitsubishi Chemical Corporation) are preferable. Methyl silicate oligomers are more preferred because they are inexpensive and easy to handle.

Hydrolyzable aluminum compounds are not particularly limited, and include, for example, Al nitrate (Al(NO ₃ ) ₃ ), Al acetate (Al(OAc) ₃ ), Al acetylacetonate salt, etc., which are inexpensive and easily decomposed by heat. aluminum salts; trialkoxyaluminum compounds represented by Al(OR) ₃ (R represents an alkyl group, preferably an n-propyl group, isopropyl group, n-butyl group, tert-butyl group, etc.); . The aluminum salt can usually be used as an aqueous solution.

The hydrolyzable zirconium compound has the general formula: Zr(OR') ₄ (R' is an alkyl group, preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group). etc.); ZrO(NO ₃ ) _{2.nH 2} O; ZrOCl _{2.nH 2} O, and the like. Among these, ZrO(NO ₃ ) ₂ ·nH ₂ O, ZrOCl ₂ ·nH ₂ O and ZrO(NO ₃ ) ₂ ·nH ₂ O are preferred. n represents an integer from 1 to 10.

As a specific method for producing a composite metal oxide filler, aluminum nitrate (Al(NO ₃ ) _{3.9H 2} O) is dissolved in water or alcohol, and a zirconium compound (for example, ZrO(NO ₃ ) ₂ ) is added to this solution. aqueous solution) and mix thoroughly. An alkoxysilane, such as methyl silicate oligomer, is added to the mixed solution to form a uniform and transparent raw material mixed solution. The inorganic oxide content in the obtained raw material mixed solution is in the range of about 1 to 35% by mass, preferably in the range of about 3 to 10% by mass. This is because if the content of a solvent such as water or alcohol is high, drying takes time and becomes uneconomical, and if the solvent is low, the subsequent neutralization stirring operation becomes difficult.

The raw material mixed solution (sol) prepared as described above can be gelled by hydrolysis and coprecipitation reaction by adding an alkaline solution.
The alkaline solution is not particularly limited, and for example, aqueous ammonia is preferable because it dissolves the raw material mixture solution, dissolves in water at any ratio, and does not remain in the filler after drying and heat treatment. The amount of ammonia water needs to exhibit basicity when mixed with the raw material mixture solution, and one guideline is generally an amount that brings the pH to about 7 to 9, preferably about pH 8. For example, about 2 times dilution of commercially available ammonia water (content: 35 wt%) can be used.

The method of mixing the raw material mixture solution and the alkaline solution is not particularly limited, and for example, to prevent component imbalance in the coprecipitate caused by different hydrolysis conditions with alkali in each raw material component. , it is desirable to add them all at once. There are no particular limitations on the stirring speed, reaction temperature, or time; for the purpose of homogeneous reaction, vigorous stirring is performed for rapid neutralization, and by obtaining an aggregate of coprecipitated fine particles (jelly-like gel), the unbalanced components can be reduced. It can be prevented.
The sol-gel body obtained by the above operation is subjected to evaporation removal of the solvent, excess ammonia, water, etc., and drying using a conventional evaporator or dryer. The drying temperature is not particularly limited, and is, for example, in the range of 40 to 150°C, preferably 70 to 120°C.

Next, the dried gel body is washed with water to remove by-products such as ammonium nitrate. For example, after sufficiently drying the gel body using a blower dryer, etc., ethanol is added to the dried product, and wet pulverization is performed using a planetary mill, bead mill, etc. into gel particles with an average particle size of 0.1 to 0.9 μm. Then, ethanol is removed by evaporation and dried to obtain gel fine particle powder. This fine particle powder is made into particles having an average particle diameter of 3 to 20 μm using an air flow mill such as a jet mill, and then fired in an electric furnace.

In the firing of the particles, sintering of the primary particles and formation of secondary particles (average particle diameter of 3 to 10 μm) in which the primary particles are bonded are important. The optimum heat treatment conditions (temperature, time, etc.) are appropriately selected depending on the content of the _three components SiO ₂ , ZrO ₂ and Al ₂ O.
For example, it is preferable that the temperature increase rate is about 20° C. per minute at the fastest, and usually about 3 to 10° C. per minute. The firing temperature is about 800 to 1200°C, preferably about 1000 to 1190°C, more preferably 1050 to 1150°C.

The secondary particles produced by the above method are adjusted to have an appropriate particle size distribution by methods such as crushing and blending. The inorganic filler as a secondary particle is an amorphous particle (particle size = 1 to 50 μm) in which sintered primary particles with an average particle size of about 0.1 to 0.9 μm are bonded to each other by neck formation, and they have sharp edges. It has a broad particle size distribution, uneven particle size, and an uneven surface. The secondary particles after firing can be pulverized using a pneumatic pulverizer as needed to adjust the average particle size to 2 to 8 μm.

The average particle size and particle size distribution in the present invention are measured using, for example, a laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, SALD-2200). The average particle size means the volume average particle size because the particle size distribution determined by laser diffraction/scattering method is measured on a volume basis.
The particle size of the gel fine particles (primary particles) and particles (secondary particles) before firing is determined by using distilled water as a solvent, setting the refractive index to 1.45 ± 0.10, and introducing the powder into a particle size distribution measuring device. Measurements were taken after 5 minutes of ultrasonic dispersion. Further, the particle size of the particles (secondary particles) after firing was measured under the condition that the refractive index was 1.50±0.10.

(B) Spherical SiO ₂ filler with an average particle size of 50 nm or less The dental curable composition of the present invention contains a spherical SiO ₂ filler with an average particle size of 50 nm or less (hereinafter referred to as “component B” or “ultrafine SiO 2 filler”). ₂ filler). Note that the spherical shape includes not only a true spherical shape but also a substantially spherical shape. The ultrafine SiO ₂ filler is not particularly limited as long as it is a known SiO ₂ filler whose primary particles have an average particle diameter of 50 nm or less, and examples thereof include colloidal silica, fumed silica, and the like. The average particle diameter of the ultrafine SiO ₂ filler may be 50 nm or less, preferably in the range of 10 to 50 nm.
Only one type of the ultrafine SiO ₂ filler can be used, or two or more different types of ultrafine SiO ₂ filler can be mixed.

The content of the ultrafine SiO ₂ filler contained in the dental curable composition is usually 5 to 45% by mass, preferably 7 to 30% by mass, and more preferably 9 to 20% by mass.
The blending ratio (mass ratio) of the (B) ultrafine particle SiO ₂ filler and the (A) composite metal oxide filler is 1:0.8 to 1:8, and 1:0.9 to 1: 8 is preferred, and 1:1 to 1:7 is more preferred.

The ultrafine particle SiO ₂ filler of component B is a SiO ₂ filler that does not contain ZrO ₂ and Al ₂ O ₃ . On the other hand, component A is a composite metal oxide filler containing SiO ₂ , ZrO ₂ and Al ₂ O ₃ and always contains SiO ₂ , ZrO ₂ and Al ₂ O ₃ . Therefore, the A component and the B component can be clearly distinguished. Furthermore, the A component and the B component are not colorants and can be clearly distinguished from the D component.

(C) (meth)acrylate polymerizable monomer The dental curable composition of the present invention contains a (meth)acrylate polymerizable monomer (hereinafter referred to as "component C", "polymerizable monomer", or "monomer"). ) may need to be added. Note that (meth)acrylate means acrylate or methacrylate.

The polymerizable monomer is not particularly limited and can be used as long as it is a (meth)acrylate polymerizable monomer (monomer) that can be used for dental purposes. For example, (meth)acrylic ester (for example, in the case of an alkyl ester, the alkyl group has 1 to 12 carbon atoms; in the case of an ester containing an aromatic group, the carbon number is 6 to 12. Monofunctional (meth)acrylates such as those containing substituents such as chains (including the number of carbon atoms); polyalkylene glycol di(meth)acrylates (alkylene group has 2 to 20 carbon atoms), ethylene glycol oligo Merged (meth)acrylate (dimer to decamer), di(meth)acrylate containing bisphenol A, urethane (meth)acrylate which is a reaction product of 2 moles of (meth)acrylate having a hydroxyl group and 1 mole of diisocyanate, etc. di(meth)acrylates; tri(meth)acrylates such as trimethylolpropane tri(meth)acrylate; and polyfunctional (meth)acrylates such as tetra(meth)acrylates such as pentaerythritol tetra(meth)acrylate. . Specifically, monomers disclosed in JP-A-50-042696 or JP-A-56-152408 are suitable.

Examples of the monofunctional (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. ) acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate , glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, allyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, methoxypolyethylene glycol ( meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, glycerol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, phenyl( meth)acrylate, pentaerythritol mono(meth)acrylate, dipentaerythritol mono(meth)acrylate, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, caprolactone-modified dipentaerythritol (meth)acrylate, caprolactone-modified 2-hydroxyethyl (meth)acrylate Examples include acrylate.

Examples of the polyfunctional (meth)acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate. meth)acrylate, 1,3-butylene glycol di(meth)acrylate 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate ) acrylate, glycerol di(meth)acrylate, bisphenol A di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, ethylene oxide modified bisphenol A glycidyl di(meth)acrylate, 2,2-bis(4-methacryloxy) propoxyphenyl)propane, 7,7,9-trimethyl-4,13-dioxa-3,14-dioxo-5,12-diazahexadecane-1,16-diol di(meth)acrylate, neopentyl glycol hydroxypivalic acid ester di (meth)acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol ester di(meth)acrylate, trimethylolethane di(meth)acrylate, trimethylolpropane di(meth)acrylate, urethane di(meth)acrylate (1,6-bis( (meth)acryloyloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane), reaction product of 3-chloro-2-hydroxypropyl(meth)acrylate and methylcyclohexane diisocyanate, 2-hydroxypropyl( Reaction products of meth)acrylate and methylcyclohexane diisocyanate, reaction products of 2-hydroxypropyl(meth)acrylate and methylenebis(4-cyclohexylisocyanate), reaction products of 2-hydroxypropyl(meth)acrylate and trimethylhexamethylene diisocyanate. Reaction products, 2-hydroxyethyl (di(meth)acrylates such as reaction products of methacrylate and isophorone diisocyanate, reaction products of 3-chloro-2-hydroxypropyl (meth)acrylate and isophorone diisocyanate; trimethylol Tri(meth)acrylates such as methane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate; penta Examples include tetra(meth)acrylates such as erythritol tetra(meth)acrylate and dipentaerythritol tetra(meth)acrylate.

The (meth)acrylate polymerizable monomer is preferably a polyfunctional (meth)acrylate, such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate (DEGDMA), triethylene glycol dimethacrylate (TEGDMA), or trimethylolpropane di(meth). Acrylates, urethane dimethacrylate (UDMA) and bisphenol A glycidyl dimethacrylate (Bis-GMA) are more preferred, with DEGDMA, TEGDMA, UDMA and Bis-GMA being particularly preferred.

These (meth)acrylate-based polymerizable monomers can be used alone, but it is preferable to use a mixture of two or more types of polymerizable monomers. It is more preferable to use di(meth)acrylates, and it is particularly preferable to use a mixture of two or more di(meth)acrylates in order to adjust the viscosity.

The content of the polymerizable monomer contained in the dental curable composition is usually 10 to 35% by mass, preferably 15 to 30% by mass, and more preferably 20 to 25% by mass.

In addition to the above-mentioned (meth)acrylate-based polymerizable monomer, the dental curable composition of the present invention contains the above-mentioned (meth)acrylate-based monomer for ease of polymerization, adjustment of viscosity, or adjustment of other physical properties. It is also possible to mix and polymerize other polymerizable monomers than the polymerizable monomer.

(D) Coloring material The dental curable composition of the present invention needs to contain a coloring material (hereinafter also referred to as "component D"). As the colorant (coloring agent), known pigments used in general dental treatment can be used without particular limitation. The coloring material may be either an inorganic pigment or an organic pigment. Examples of the inorganic pigments include iron oxide color pigments, aluminum oxide color pigments, titanium oxide color pigments, zirconium oxide pigments, and the like. Examples of organic pigments include isoindolinone and pigment red.

The coloring material (D) preferably includes at least one selected from the group consisting of a red pigment, a yellow pigment, a black pigment, and a white pigment, and includes a red pigment, a yellow pigment, a black pigment, and a white pigment. is more preferable.
Specific examples of the red pigment include ferric oxide (iron (III) oxide), pigment red, and the like.
Specific examples of the yellow pigment include isoindolinone, nickel titanium yellow, and chromium oxide.
Specific examples of the black pigment include triiron tetroxide (triiron tetroxide), amorphous carbon (carbon black), and the like.
Specific examples of the white pigment include zirconium oxide, titanium white (titanium dioxide), zinc oxide, and the like. Note that the white pigment is sometimes referred to as an emulsifying agent.

When the coloring material includes a red pigment, a yellow pigment, a black pigment, and a white pigment, the content of the D component is such that the red pigment is 0.00 parts by mass with respect to a total of 100 parts by mass of the A component, B component, and C component. 0003 to 0.0009 parts by mass, yellow pigment 0.0004 to 0.0011 parts by mass, black pigment 0.0003 to 0.003 parts by mass, and white pigment 0.05 to 0.18 parts by mass. Preferably, the red pigment is 0.0004 to 0.0008 parts by mass, the yellow pigment is 0.0005 to 0.001 part by mass, the black pigment is 0.0004 to 0.002 part by mass, and the white pigment is 0.07 to 0.07 parts by mass. More preferably, it is 0.15 parts by mass. In addition, the blending ratio of red pigment, yellow pigment, black pigment, and white pigment is 0.3 to 1 mass % of red pigment and 0.2 to 1.6 mass % of yellow pigment to 100 mass % of white pigment. %, the black pigment is preferably 0.3 to 4% by mass, the red pigment is 0.5 to 0.8% by mass, the yellow pigment is 0.4 to 1.1% by mass, and the black pigment is 0.4 to 3% by mass. % is more preferable.

(E) Optional components The dental curable composition of the present invention may further contain optional components other than the above-mentioned components, if necessary. Optional components can be blended within a range that does not impair the effects of the dental curable composition of the present invention. Examples of optional components include known additives such as polymerization initiators, polymerization accelerators, fluorescent materials, polymerization inhibitors, antioxidants, antibacterial agents, X-ray contrast materials, stabilizers, ultraviolet absorbers, and discoloration inhibitors. can be mentioned. These can be used alone or in an appropriate combination of two or more.

When blending optional components, it is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, based on 100% by mass of the dental curable composition. It can be added at a ratio of

The dental curable composition has excellent shape retention. Specifically, the dental curable composition was formed into a disk shape with a diameter of 12 mm and a thickness of 1 mm, a cut was made to divide it into halves with a metal plate of 1 mm thickness, and when it was left to stand at 37 ° C., it was divided. The time it takes for the dental curable composition to deform and come into contact is preferably 300 seconds or more, more preferably 360 seconds or more, and even more preferably 420 seconds or more.

The dental curable composition has excellent consistency (elongation rate). Specifically, when 0.65 g of the dental curable composition is molded into a spherical shape, a 3.25 kg weight is gently placed on top, and the elongation rate (consistency) is 160% or more when left to stand for 60 seconds. It is preferably 180% or more, more preferably 200% or more. The spherical shape includes not only a true sphere but also a substantially spherical shape.

2. Manufacturing method of dental curable composition The dental curable composition of the present invention comprises (A) an amorphous composite metal oxide filler containing SiO ₂ , ZrO ₂ and Al ₂ O ₃ , (B) average particles. It can be manufactured by blending the SiO ₂ filler with a diameter of 50 nm or less, (C) (meth)acrylate polymerizable monomer, and (D) coloring material in the above-mentioned specific proportions.

The mixing ratio (mixing ratio) of each component in the above dental curable composition can be adjusted as appropriate depending on the viscosity and intended use. For example, the total amount of the (A) composite metal oxide filler and the (B) SiO ₂ filler is preferably 300 to 650 parts by mass relative to 100 parts by mass of the (meth)acrylate polymerizable monomer (C). is 350 to 600 parts by mass, more preferably 400 to 550 parts by mass, and (D) a coloring agent, and if necessary, a polymerization initiator, a polymerization accelerator, a colored pigment, an emulsifier, an opalization material, Additives such as a fluorescent material, a polymerization inhibitor, an antioxidant, an antibacterial agent, an X-ray contrast material, a stabilizer, an ultraviolet absorber, and an anti-discoloration agent can be appropriately blended. In addition, when the dental curable composition contains a polymerization initiator, it must be handled with care, and must be stored in a sealed container in a dark place and at a low temperature.

The method for producing the dental curable composition includes the steps of taking a predetermined amount of each of the above-mentioned components into a container, sufficiently kneading and dispersing them, and then obtaining a paste, and kneading the paste under reduced pressure or vacuum treatment. It is preferable to include a step of stirring. By using such a method, a clay-like or paste-like dental curable composition that is uniform and free of air bubbles can be obtained.
A cured product of the dental curable composition can be obtained by polymerizing the dental curable composition according to a known polymerization (light and heating) method.

3. Method for Curing Dental Curable Composition The dental curable composition of the present invention can be polymerized and cured by irradiation with light. The method of polymerizing and curing by light irradiation varies depending on the type of photopolymerization initiator, and ultraviolet wavelengths can also be used, but polymerization and curing are usually performed by irradiating light with visible light wavelengths that are harmless to the human body. The wavelength of the light is, for example, preferably in the range of 250 to 700 nm, more preferably 300 to 500 nm, even more preferably 350 to 490 nm.

The light source in the above wavelength range is not particularly limited, and for example, light such as an LED lamp, a halogen lamp, a xenon lamp, a metal halide lamp, a laser, a fluorescent lamp, and sunlight can be used.

The irradiation time of the light may vary depending on the thickness, transparency, color tone, and amount of irradiation light of the dental prosthesis etc. obtained from the dental curable composition, but may be determined appropriately according to the desired polymerization time. . Light irradiation is preferably performed for about 5 seconds to 3 minutes, more preferably 10 seconds to 120 seconds, and even more preferably 20 seconds to 60 seconds.

The dental curable composition includes not only the state before curing but also the cured product (cured product or cured film) obtained by irradiating the dental curable composition with light. Since it is currently impossible or impractically difficult to completely specify the structure of this cured product, the cured product is described using product-by-process claims.

The transmittance (Tt) of a cured body having a thickness of 1 ± 0.05 mm after polymerizing and curing the dental curable composition is 52 or more and 66 or less, preferably 53 or more and 62 or less, and 53 or more and 60 or less. is more preferable.

The turbidity (haze value) of a cured product having a thickness of 1 ± 0.05 mm after polymerizing and curing the dental curable composition is 85 or more and 98 or less, preferably 88 or more and 98 or less, and 92 or more and 98 or less. The following are more preferable.

The L ^* value in the L ^* a ^* b ^* color system of the cured product having a thickness of 1±0.05 mm after polymerizing and curing the dental curable composition is 70 or more and 77 or less, and 71 or more and 76 The following is preferable, more preferably 72 or more and 75 or less, the a ^* value is -0.5 or more and 1.5 or less, preferably -0.2 or more and 1.2 or less, and more preferably 0.1 or more and 0.9 or less. Preferably, the b ^* value is 11 or more and 19 or less, preferably 13 or more and 18 or less, and more preferably 14 or more and 18 or less.
Also, from the a ^* value and b ^* value, the following formula A: C ^* = {(a ^* ) ² + (b ^* ) ² } ^1/2
Accordingly, the C ^* value representing saturation can be calculated. The C ^* value of a cured product having a thickness of 1 ± 0.05 mm after polymerizing and curing the dental curable composition is 11 or more and 20 or less, preferably 13 or more and 19 or less, and more preferably 14 or more and 18 or less. . In addition, in general, the chromaticity of the material used as a dental crown has a b ^* value larger than an a ^* value, and a C ^* value is often approximated to a b ^* value.

The transmittance, turbidity ^{, L* value, a* value, and b* value in} the L ^* a ^* b ^* color system of the cured product after polymerizing and curing the dental curable composition are the above numerical values. By satisfying the range, it becomes possible to use one type of dental curable composition (single composition) to make the color tone of the repaired portion blend in with the color tone of the natural tooth.

The opaliness of the dental curable composition is determined by the L ^* a ^* b* ^{a* value} in the color system of a cured product having a thickness of 1±0.05 mm after polymerizing and curing the dental curable composition. From the and b ^* values, it can be calculated as an opal value using the following equation 1.
Formula 1: (Opal value) = {(a _w ^* - a ^* _B ) ² + (b _W ^* - b ^* _B ) ² } ^1/2
In formula 1,
a _w ^* : a ^* value of the cured product of the dental curable composition on a white background a _B ^* : a ^* value of the cured product of the dental curable composition on a black background b _w ^* : dental cure on a white background b ^* value of the cured product of the dental curable composition b _B ^* : b ^* value of the cured product of the dental curable composition on a black background

Note that opaliness means having an opal effect, and the opal effect means the same unique visible light scattering effect as opal. More specifically, there are particles in the substance that have a size similar to the wavelength of light, and these particles scatter the short wavelength region of visible light, causing the light transmitted through the substance to take on a yellowish tinge, causing scattering. It means that the light has a bluish tinge.
Regarding the opal value of natural teeth, it is known that when the thickness of the natural tooth is 0.7 to 1.3 mm, the opal value is about 10 to 23. From this, the opal value of the cured product having a thickness of 1±0.05 mm after polymerizing and curing the dental curable composition is preferably 10 or more and 23 or less, more preferably 11 or more and 20 or less. , more preferably 12 or more and 19 or less.
Therefore, by setting the opal value of the cured product of the dental curable composition after polymerization and curing to 10 or more and 23 or less, it is possible to obtain a color tone close to that of natural teeth.

The cured product obtained by polymerization and curing of the dental curable composition of the present invention has excellent color tone compatibility. The color tone compatibility is evaluated by the color difference (ΔE) between the color tone of the cured product of the dental curable composition of the present invention layered on the tooth color reference pellet and the color tone of the tooth color reference pellet.
Here, a shade guide "VITA (registered trademark) PAN classic" by VITA is often used as a tooth color standard (teeth color sample). The shade guide is divided into A type, B type, C type, and D type, each having a different color tone. Since most Japanese people fall into type A, tooth color reference pellets corresponding to the shade of type A were used to evaluate tone compatibility.
Specifically, the diameter of the color tone corresponding to the A type shade of the shade guide used as a tooth color reference (for example, the color tone corresponding to A1, A2, A3, A3.5, and A4 shades, etc.) is 15 ± 0.5 mm. , L ₂ ^* , a ₂ ^* , and b ₂ ^* are measured using a spectrophotometer using tooth color reference pellets with a thickness of 1±0.05 mm. Further, after polymerizing and curing the dental curable composition, a cured product (evaluation pellet) with a diameter of 15 ± 0.5 mm and a thickness of 1 ± 0.05 mm was stacked on the tooth color reference pellet, and the state was For the evaluation pellet, L ₁ ^* , a ₁ ^* , and b ₁ ^* were measured using a spectrophotometer, and the color tone of the evaluation pellet stacked on the tooth color standard pellet and the tooth color standard were calculated using the following formula 2. Calculate the color difference (ΔE) from the pellet color tone. Note that Δ is read as delta and means "difference."

Formula 2: ΔE={(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2
ΔL ^* = L ₁ ^* - L ₂ ^*
Δa ^* = a ₁ ^* - a ₂ ^*
Δb ^* = b ₁ ^* - b ₂ ^*
here,
L ₁ ^* : Brightness of the evaluation pellet stacked on the tooth color reference pellet a ₁ ^* , b ₁ ^* : Chromaticity of the evaluation pellet stacked on the tooth color reference pellet L ₂ ^* : Lightness of the tooth color reference pellet Lightness a ₂ ^* , b ₂ ^* : chromaticity of tooth color reference pellet

The color difference (ΔE) between the color tone of the evaluation pellet stacked on the tooth color reference pellet and the color tone of the tooth color reference pellet is preferably 10.5 or less, more preferably 10.3 or less. , more preferably 10.1 or less.

Generally, the color difference (ΔE) that is recognized as the same color is said to be 3.2 or less, which is within the range of class A tolerance (1.6 to 3.2). When ΔE is 10.5, it is within the range of Class C tolerance (6.5 to 13.0), and this is a color difference corresponding to the next color (1 step) on the Munsell color chart.
Clinically, a portion of a tooth crown is filled with a dental curable composition and visually checked to see if the color matches. However, when filling only a portion with a dental curable composition during color measurement, the color difference before and after filling becomes small, so there is a measurement error during color measurement, and color tone compatibility due to slight composition differences is evaluated. difficult to do.
Therefore, in the evaluation of color tone compatibility, in order to increase the color difference obtained by colorimetry, we purposely layered the evaluation pellet so as to cover the entire top surface of the tooth color standard pellet and measured the color, and compared it with the clinical usage method. Evaluation was made under harsh conditions.
For example, if the color difference when filling 25% of the colorimetric range is ΔE = 1, then the color difference when filling 50% of the colorimetric range is ΔE = 2. The color difference tends to change depending on the filling ratio.
From the above, the conditions for evaluating color tone compatibility are severe, and the obtained color difference value is not a value that indicates color tone compatibility in clinical practice. This is merely a condition for relative evaluation in evaluating color tone compatibility. Taking these things into consideration, in the evaluation of color tone compatibility, the color difference was set at 10.5 or less, rather than 3.2 or less.
In the evaluation of color tone compatibility, if the color difference is 10.5 or less, when the filling range is about 25%, the color difference will be 3.2 or less, which is less than the A class tolerance, and the color tone of the filled area will be different from that of the surrounding area. It can be blended well with the teeth.
That is, if the ΔE is 10.5 or less, the color tone compatibility is high, and it is considered that sufficient color tone compatibility can be obtained using the dental curable composition.

The dental curable composition of the present invention has appropriate shielding properties. The shielding property of the dental curable composition of the present invention is determined by measuring the color difference in an XYZ display system using a spectrophotometer on a cured product having a thickness of 1 ± 0.05 mm after polymerizing and curing the dental curable composition. The contrast ratio determined as the ratio (Y _B /Y _W ) of the Y value (Y _B ) on the black background to the Y value (Y _W ) on the white background obtained when performing this was used as an index.
In addition, basic research has shown that if the contrast ratio is 0.42 or less, if the underlying color of the filling area is discolored, it may not be possible to sufficiently mask that color. On the other hand, it is known that when the contrast ratio is 0.59 or more, the transparency of the filled area becomes insufficient and it becomes difficult to reproduce the texture of the tooth. In other words, it is preferable to set the contrast ratio, which affects the shielding performance and transparency, to a value that is neither high nor low.
Therefore, the contrast ratio is preferably 0.43 or more and 0.58 or less, more preferably 0.45 or more and 0.55 or less.

It can be said that the closer the contrast ratio is to 0, the lower the shielding ability (higher transparency), and the closer it is to 1, the higher the shielding ability (lower transparency). Therefore, if the contrast ratio of the cured product of the dental curable composition is 0.43 or more and 0.58 or less, and the repaired area has appropriate shielding properties, it is possible to harmonize with the surrounding teeth without causing discomfort. becomes.

4. Applications The dental curable composition of the present invention can be suitably used as a dental filling and restorative material, but is not limited thereto, and can also be suitably used for other applications. Other uses include, for example, dental cement and restorative materials for building abutments.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the technical scope of the present invention is not limited to these examples.

The raw materials used in Examples and Comparative Examples are shown below.

[(A) Amorphous composite metal oxide filler containing SiO ₂ , ZrO ₂ and Al ₂ O ₃ ]
As component A, the one produced according to Production Example 1 below was used.
Manufacturing example 1
10 parts by mass of aluminum nitrate (Al(NO ₃ ) _{3.9H 2} O, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and AP-1 (denatured ethanol, manufactured by Nippon Alcohol Sales Co., Ltd., 87% ethanol, 13% isopropyl alcohol) 15 parts by mass were mixed and dissolved. Next, 118 parts by mass of Zircosol ZN (zirconium nitrate aqueous solution, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., ZrO ₂ content = 25 wt%) was added to the obtained solution, and further MS51 (methyl silicate oligomer, manufactured by Mitsubishi Chemical Corporation) was added. 280 parts by mass of SiO ₂ content = 52 wt%) and 430 parts by mass of distilled water were added. Thereafter, the resulting mixture was mixed with a stirrer for 60 minutes to prepare a transparent and uniform raw material mixture. Next, when 127 parts by mass of a 2-fold diluted ammonia aqueous solution (for example, manufactured by Nacalai Tesque Co., Ltd., NH ₃ = 28%) is added to the previously prepared raw material mixture while stirring, it becomes a coprecipitated gel and becomes a jelly. It became a situation. This gelled product was taken out and dried at 100° C. to remove excess ammonia, water and solvent to obtain a dry gel. The dried gel was washed with water and filtered to remove the ammonium nitrate produced as a by-product, and then dried again. Note that if a large amount of ammonium nitrate remains, gas will be generated during firing and there is a risk of explosion, so it is necessary to wash thoroughly with water.

100 parts by mass of this dry gel was dispersed in 250 parts by mass of AP-1, and a bead mill (MULUTI-LABO, manufactured by Shinmaru Enterplases Co., Ltd.) filled with a specified amount of zirconia balls having a diameter of 0.65 mm was used to disperse 100 parts by mass of this dry gel into 250 parts by mass of AP-1. It was ground for a while to make a slurry. When the particle size and particle size distribution of this slurry were measured, the average particle size was 0.6 μm, and the particle size was not pulverized to less than 0.2 μm.
The slurry was collected and dried to remove the solvent. The particles at this stage correspond to the primary particles of the finished filler. Next, this pulverized dry gel was processed with a jet mill (manufactured by Hosokawa Micron Co., Ltd., 100AFG/50ATP) to obtain an average particle size of gel powder of about 20 μm. This flocculated gel was placed in an alumina dish, heated to 1100°C (270°C per hour) in an electric furnace, held at the same temperature for 3.5 hours, and then taken out of the furnace and left to cool. A powder was obtained.

This fired gel was pulverized using the jet mill described above to obtain an amorphous composite metal oxide filler containing SiO ₂ , ZrO ₂ and Al ₂ O ₃ . The average particle diameter of the composite metal oxide filler is 5.5 μm (10% D: 0.4 μm, 50% D: 10.1 μm, 90% D: 26.9 μm), and is in the range of about 0.5 to about 50 μm. It was recognized that the polydisperse system was widely distributed.
100 parts by mass of this composite metal oxide filler was suspended in 200 parts by mass of alcohol solvent (AP-1), and 9 parts by mass of γ-MPTS (TSL-8370, manufactured by Momentive Performance Materials Japan) was added. Ultrasonic dispersion was performed for 1 hour. Thereafter, the solvent was removed using an evaporator, and then dried at 80°C for 2 hours under reduced pressure, and then at 110°C for 1 hour under reduced pressure to obtain a composite metal oxide filler surface-treated with a silane coupling agent. Ta.

[(B) Spherical SiO ₂ filler with an average particle diameter of 50 nm or less]
SiO ₂ filler with an average particle diameter of 50 nm (Admanano (registered trademark) YA050C, manufactured by Admatex Co., Ltd.)
_SiO2 filler with an average particle size of 15 nm (MEK-ST, manufactured by Nissan Chemical Co., Ltd.)

[(C) (meth)acrylate polymerizable monomer]
UDMA: 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate (NF-501 urethane dimethacrylate, manufactured by Mitsubishi Chemical Corporation)
TEGDMA: Triethylene glycol dimethacrylate (NK Ester 3G, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Bis-GMA: Bisphenol A glycidyl di(meth)acrylate (D-GMAP, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[(D) Coloring material]
Ferric oxide: red pigment (manufactured by Dainichiseika Kagyo Co., Ltd.)
Isoindolinone: Yellow pigment (manufactured by Dainichiseika Kagyo Co., Ltd.)
Triiron tetroxide: black pigment (manufactured by Dainichiseika Kagyo Co., Ltd.)
Zirconium oxide: white pigment (SPZ zirconium oxide, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.)

[(E) Optional component]
Photoinitiator
CQ: Camphorquinone (Camphorquinone, manufactured by Tokyo Chemical Industry Co., Ltd.)
Polymerization accelerator
DMABE: Ethyl p-dimethylaminobenzoate (Ethyl p-dimethylaminobenzoate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

(Example 1)
A polymerizable monomer mixture (M1) is obtained by mixing 85 parts by mass of UDMA, 10 parts by mass of TEGDMA, 5 parts by mass of Bis-GMA, 0.3 parts by mass of CQ, and 0.6 parts by mass of DMABE. was prepared. To 22.0 parts by mass of the obtained polymerizable monomer mixture (M1), 39.0 parts by mass of component A obtained in Production Example 1 and 39.0 parts of SiO ₂ filler with an average particle diameter of 50 nm as component B were added. Part by mass was added. To 100 parts by mass of the obtained mixture, 0.00075 parts by mass of ferric oxide (red), 0.0006 parts by mass of isoindolinone (yellow), and 0 parts of triiron tetroxide (black) were added as colorants. 0.002 parts by mass and 0.1 parts by mass of zirconium oxide (white) were added, and the mixture was mixed and defoamed under light shielding to obtain a dental curable composition.

(Examples 2-3 and 6-12)
Each dental curable composition was produced in the same manner as in Example 1, except for using the blending ratios shown in Tables 1 to 4 below.

(Example 4)
A polymerizable monomer mixture (M2) is obtained by mixing 45 parts by mass of UDMA, 10 parts by mass of TEGDMA, 45 parts by mass of Bis-GMA, 0.3 parts by mass of CQ, and 0.6 parts by mass of DMABE. was prepared. To 23.5 parts by mass of the obtained polymerizable monomer mixture (M2), 65.6 parts by mass of component A obtained in Production Example 1, and 10.9 parts of SiO ₂ filler with an average particle diameter of 50 nm as component B. Part by mass was added. To 100 parts by mass of the obtained mixture, 0.00075 parts by mass of ferric oxide (red), 0.0006 parts by mass of isoindolinone (yellow), and 0 parts of triiron tetroxide (black) were added as colorants. 0.002 parts by mass and 0.1 parts by mass of zirconium oxide (white) were added, and the mixture was mixed and defoamed under light shielding to obtain a dental curable composition.

(Example 5)
A polymerizable monomer mixture (M1) is obtained by mixing 85 parts by mass of UDMA, 10 parts by mass of TEGDMA, 5 parts by mass of Bis-GMA, 0.3 parts by mass of CQ, and 0.6 parts by mass of DMABE. was prepared. To 30.0 parts by mass of the obtained polymerizable monomer mixture (M1), 60.0 parts by mass of component A obtained in Production Example 1, and 10.0 parts of SiO ₂ filler with an average particle diameter of 15 nm as component B. Part by mass was added. To 100 parts by mass of the obtained mixture, 0.00075 parts by mass of ferric oxide (red), 0.0006 parts by mass of isoindolinone (yellow), and 0 parts of triiron tetroxide (black) were added as colorants. 0.002 parts by mass and 0.1 parts by mass of zirconium oxide (white) were added, and the mixture was mixed and defoamed under light shielding to obtain a dental curable composition.

(Comparative Examples 1 to 10)
Comparative compositions were produced in the same manner as in Example 1 except for using the blending ratios shown in Tables 1 to 4 below.

(Reference examples 1 to 3)
Commercially available dental filling and restorative materials that are monochromatic and harmonize with multiple shades of color were used as Reference Examples 1 to 3.

Evaluation of cured products of dental curable compositions The cured products obtained by polymerizing and curing the dental curable compositions of Examples 1 to 12 and Comparative Examples 1 to 10 were evaluated for transmittance, turbidity, color tone, and opal. The properties, color tone compatibility, and hiding properties were measured or evaluated by the following methods. Furthermore, for the dental filling and restorative materials of Reference Examples 1 to 3, the color compatibility and concealment properties of the cured products were measured by the following method.

[Transmittance and turbidity]
The dental curable compositions of Examples 1 to 12 and Comparative Examples 1 to 10 were filled into molds (inner diameter 15 mm, thickness 1 mm), and a photopolymerizer (LED CURE Master, Denken High Dental Co., Ltd.) was placed on both sides of the molds. A cured product (test piece) with a diameter of 15±0.5 mm and a thickness of 1±0.05 mm was prepared by irradiating the polymer with light having a wavelength of 460 nm (manufactured by Akihabara Co., Ltd.) for 15 seconds to polymerize and cure the product. The transmittance and turbidity of this test piece were measured using a turbidimeter (NDH4000, manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Tables 1 to 4.

If the pass standard transmittance was 52 to 66%, it was judged as a pass (〇), and if it was less than 52% or more than 66%, it was judged as a fail (×).
If the turbidity was 85 to 98, it was judged as a pass (〇), and if it was less than 85 or over 98, it was judged as a fail (x).

[Color tone]
Regarding the color tone of the cured products with a thickness of 1 ± 0.05 mm after polymerization and curing of the dental curable compositions of Examples 1 to 12 and Comparative Examples 1 to 10, the same disc-shaped as in the measurement of transmittance and turbidity was examined. The L ^* value, a ^* value, and b ^* value of the test piece according to the L ^* a ^* b ^* color system were measured using a spectrophotometer (CM3610A, manufactured by Konica Minolta, Inc.). The color measurement conditions were: light source: D65 light source, viewing angle: 2° (degrees). Colorimetry was performed for white and black as background colors, and the average value thereof was calculated. The results are shown in Tables 1 to 4.

If the acceptance standard lightness (L ^* ) was 70 to 77, it was judged as a pass (〇), and if it was less than 70 or more than 77, it was judged as a fail (x).
If the chromaticity (a ^* ) was -0.5 to 1.5, it was judged as a pass (〇), and if it was less than -0.5 or more than 1.5, it was judged as a fail (x).
If the chromaticity (b ^* ) was 11 to 19, it was judged as a pass (〇), and if it was less than 11 or more than 19, it was judged as a fail (x).

[Opal nature]
Regarding the opalescence of the cured products after polymerization and curing of the dental curable compositions of Examples 1 to 12 and Comparative Examples 1 to 10, the same disc-like thickness as in the measurement of transmittance and turbidity was 1 ± 0.05 mm. The index (opal value) indicating the opal nature of the test piece was measured using a spectrophotometer (CM3610A, manufactured by Konica Minolta, Inc.). The color measurement conditions were: light source: D65 light source, viewing angle: 2° (degrees), background color: white and black. The results are shown in Tables 1 to 4.

If the pass standard opal value was 10 or more and 23 or less, it was judged as a pass (〇), and if it was less than 10 or more than 23, it was judged as a fail (×).

[Color compatibility]
FIG. 1 shows a schematic diagram illustrating a method for evaluating color tone compatibility. Hereinafter, a method for evaluating color tone compatibility will be explained with reference to FIG.
Tooth color standard pellets with a diameter of 15 ± 0.5 mm and a thickness of 1 ± 0.05 mm, which have color tones corresponding to A1, A3, and A4 shades of VITA's shade guide "VITA (registered trademark) PAN classic" used as a tooth color standard. (Produced using TMR-Z Fill 10. Universal, manufactured by YAMAKIN Co., Ltd.) The color tone was measured in the same manner as the color tone measurement described above. Next, the dental curable compositions of Examples 1 to 12, Comparative Examples 1 to 10, and Reference Examples 1 to 3 were polymerized and cured to a diameter of 15 ± 0.5 mm and a thickness of 1 ± 0.05 mm. Three pellets for each evaluation were prepared. An evaluation pellet was placed on top of each tooth color reference pellet, and in this state, the color tone of the evaluation pellet was measured in the same manner as in the measurement of the color tone. Note that glycerin was applied between the pellets to prevent air spaces from forming. The color difference (ΔE) between the tooth color reference pellet and the evaluation pellet is calculated by formula 1: ΔE = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2
ΔL ^* = L ₁ ^* - L ₂ ^*
Δa ^* = a ₁ ^* - a ₂ ^*
Δb ^* = b ₁ ^* - b ₂ ^*
(L ₁ ^* : Brightness of the evaluation pellet stacked on the tooth color reference pellet a ₁ ^* , b ₁ ^* : Chromaticity of the evaluation pellet stacked on the tooth color reference pellet L ₂ ^* : Tooth color reference pellet brightness a ₂ ^* , b ₂ ^* : chromaticity of tooth color reference pellet)
I asked for it from The results are shown in Tables 1 to 5. In the table, for example, "vs. A1" indicates that the pellet placed below the evaluation pellet is a tooth color reference pellet having a color tone corresponding to the A1 shade.

If the acceptance criterion ΔE was 10.5 or less, it was marked as a pass (○), and if it exceeded 10.5, it was marked as a fail (×).

FIG. 2 shows a schematic diagram illustrating the sensory evaluation of color tone compatibility. Hereinafter, a sensory evaluation method for color tone compatibility will be explained with reference to FIG.
A class I cavity was formed in an artificial tooth (molar tooth) having a color tone corresponding to the A1, A3, and A4 shades of VITA's shade guide "VITA (registered trademark) PAN classic" used as a tooth color standard. The dental curable compositions of Example 2, Example 11, Example 12, Comparative Example 9, and Comparative Example 10 were filled into the cavities of the artificial teeth and photopolymerized. Each artificial tooth was observed under daylight white fluorescent light by three people with normal color vision, and scored using the following evaluation criteria.
5 points: The color tone of the artificial tooth and the color tone of the filling area are completely blended, and the boundary cannot be distinguished at all. 4 points: The color tone of the artificial tooth and the color tone of the filling area are blended, and the boundary cannot be distinguished. 3 points: 2 points: The color tone of the artificial tooth and the color tone of the filling area are almost blended, and the boundary is barely distinguishable; 1 point: The color tone of the artificial tooth and the color tone of the filling area are not blended, and the boundary is partially distinguishable; 1 point: The color tone of the artificial tooth and the color tone of the filling area do not match at all, and the boundaries are easily distinguishable.

Passing Criteria Calculate the average score of three people for each of the three artificial teeth, and if the average score for all three is 3 points or more, it is considered a pass (〇), and if the average score for even one is less than 3 points If so, it was marked as a failure (x).
The A-type shade guides are numbered according to the brightness of the color (the smaller the number, the brighter), and are arranged in the order of A1, A2, A3, A3.5, and A4. Therefore, if the evaluation results for A1 and A3 are pass, it can be assumed that the evaluation result for A2 is pass, and if the evaluation results for A3 and A4 are pass, it can be estimated that the evaluation result for A3.5 is pass.
In addition, Example 11 is an example in which the amount of addition of component D (coloring material) is the largest among Examples 1 to 12, and Example 12 is an example in which the amount of addition of component D (coloring material) is the largest among Examples 1 to 12. Since this is an example in which the amount is the smallest, if the results of the sensory evaluation of color tone compatibility in Examples 11 and 12 are passed, the results of the sensory evaluation of color tone compatibility in Examples 1 to 10 are also passed. It can be estimated that

[Shielding property]
FIG. 3 shows a schematic diagram illustrating a method for evaluating shielding performance (contrast ratio). Hereinafter, a method for evaluating shielding performance (contrast ratio) will be explained with reference to FIG.
The evaluation pellets of Examples 1 to 12, Comparative Examples 1 to 10, and Reference Examples 1 to 3 prepared in the evaluation of color tone compatibility were placed on a white board and a black board, and the respective color tones were The measurement was performed in the same manner as the color tone measurement, and the ratio of the Y value (Y _B ) on the black background to the Y value (Y _W ) on the white background was determined (Y _B /Y _W : contrast ratio). The results are shown in Tables 1 to 5.

If the acceptance criterion Y _B /Y _W was within the range of 0.43 to 0.58, it was marked as a pass (〇), and if it was less than 0.43 or more than 0.58, it was marked as a fail (x).

FIG. 4 shows a schematic diagram illustrating the sensory evaluation of shielding properties. Hereinafter, a method for sensory evaluation of shielding properties will be described with reference to FIG.
In addition, the sensory evaluation of the shielding property was evaluated based on the sense of transparency. If the shielding property is low, that is, if the transparency is too high, the background of the filled area will be visible. On the other hand, if the shielding property is high, that is, if the transparency is too low, the background of the filled area cannot be seen at all. In either case, it is undesirable because it gives a sense of discomfort when compared with the surrounding teeth of the filling site.
A class IV cavity was formed in an artificial tooth (incisor) having a color tone corresponding to A2 of VITA's shade guide "VITA (registered trademark) PAN classic" used as a tooth color standard. The dental curable compositions of Example 2, Example 11, Example 12, Comparative Example 9, and Comparative Example 10 were filled (built up) into the cavities of the artificial teeth and photopolymerized. Each artificial tooth was placed on a black background and observed under daylight white fluorescent light by three people with normal color vision, and scored using the following evaluation criteria.
4 points: The transparency of the artificial tooth and the transparency of the filling area are very close, and the boundary cannot be distinguished at all. 3 points: The transparency of the artificial tooth and the transparency of the filling area are very close, and the boundary cannot be distinguished at all. 2 points: : The transparency of the artificial tooth and the filling area are different, and the border can be partially distinguished. One point: The transparency of the artificial tooth and the filling part are very different, and the border can be easily distinguished.

Passing Criteria If the average score of the three participants was 3 points or more, it was considered a pass (〇), and if it was less than 3 points, it was judged a fail (×).
In addition, Example 11 has the lowest transmittance and highest turbidity among Examples 1 to 12, and Example 12 has the highest transmittance among Examples 1 to 12, and Since this is an example with the lowest turbidity, if the results of the sensory evaluation of shielding properties in Examples 11 and 12 are passed, the results of the sensory evaluation of shielding properties in Examples 1 to 10 are also passed. It can be estimated that

Evaluation of dental curable compositions Shape retention and consistency of the dental curable compositions of Examples 1 to 5 and 11 to 12 and Comparative Examples 1 to 2 and 9 to 10 were measured by the following methods. Or evaluated.

[Shape retention]
FIG. 5 shows a schematic diagram illustrating a method for evaluating shape retention. Hereinafter, a method for evaluating shape retention will be described with reference to FIG. 5.
The dental curable compositions of Examples 1 to 5 and 11 to 12 and Comparative Examples 1 to 2 and 9 to 10 were left to stand for 60 minutes in a thermostat set at 37°C, and then flattened. It was filled into a mold (inner diameter 12 mm, thickness 1 mm) on a stand (black), and formed into a disk shape, which was used as an evaluation sample. Three samples were prepared for each evaluation. The evaluation sample was cut vertically from above so as to be divided into halves with a metal plate (thickness: 1 mm), and then placed in the chamber of the thermostat. After 180 seconds, 240 seconds, and 300 seconds have passed since the evaluation sample was divided, visually check whether the divided evaluation sample is deformed and stuck together (the evaluation sample covers the black base and cannot be seen). It was confirmed and evaluated as follows. The results are shown in Tables 1 to 4.
1 point: less than 180 seconds 2 points: less than 240 seconds 3 points: less than 300 seconds 4 points: 300 seconds or more

Acceptance Criteria The average score of the three sheets was taken as the score of the evaluation sample, and if the average score was 4 points, it was determined to be passed (〇), and if the average score was less than 4 points, it was determined to be failed (×).

[Consistency]
FIG. 6 shows a schematic diagram illustrating the consistency evaluation method. The consistency evaluation method will be described below with reference to FIG.
0.65 g of the dental curable compositions of Examples 1 to 5 and 11 to 12 and Comparative Examples 1 to 2 and 9 to 10 were weighed out using an electronic balance and formed into a spherical shape to provide evaluation samples. Place the evaluation sample on the polyester film, place another polyester film on the evaluation sample, place it on the center of the bottom of the device equipped with a guide so that force is applied vertically, and place a 3.25 kg weight on top of the guide. It was placed gently along the line and compressed for 60 seconds. After removing the weight, the diameter of the evaluation sample was measured at 45 degree intervals (4 locations), the elongation rate determined from the following formula was taken as the consistency value, and the average value was taken as the consistency of the evaluation sample. Note that, since the diameter of the sample before compression is approximately 8 mm, the elongation rate was determined for all samples by assuming that the diameter of the sample before compression was 8 mm (fixed value). The measurements were performed in an environment of 25°C.
L _X = (L ₁ - L ₀ )/L ₀ ×100
L _X : Elongation rate [%] = Consistency [%]
L ₀ : Sample diameter before compression [mm]
L ₁ : Sample diameter after compression [mm]
Note that shape retention and consistency vary depending on the composition ratio of component A, component B, component C, and component D, but the content of component D in the dental curable composition is different from other components. Since the amount is extremely small, it is expected that it will have almost no effect on shape retention and consistency. Therefore, Examples 6 to 10 and Comparative Examples 3 to 8, which differ from Example 2 in only the D component, are considered to exhibit the same shape retention and consistency as Example 2.

Pass criteria If the elongation rate was 160% or more, it was marked as pass (○), and if it was less than 160%, it was marked as fail (x).

As an overall judgment, if all items passed, it was marked as "〇", and if even one item failed, it was marked as "x".
These results are shown in Tables 1-5.

<Results>
From the test results in Tables 1 to 4, the dental curable compositions of Examples 1 to 12 passed all evaluation items and also passed the overall evaluation.
In the curable composition of Comparative Example 1, the blending ratio of component B and component A was 1:10, and the ratio of component A was too high, so the consistency (elongation rate) was rejected.
The curable composition of Comparative Example 2 had a blending ratio of component B and component A of 1:0.75, which was too low, and therefore failed in shape retention.
The curable compositions of Comparative Examples 3 to 6 failed in color tone compatibility because the chromaticity (a ^* and/or b ^* ) of the cured products was outside the numerical range.
The curable compositions of Comparative Examples 7 and 8 failed in color tone compatibility because the lightness (L ^* ) and/or chromaticity (a ^* ) of the cured products were out of the numerical range.
In the curable composition of Comparative Example 9, the transmittance of the cured product was lower than 52, so the color tone compatibility and shielding properties were rejected.
The curable composition of Comparative Example 10 failed in color tone compatibility and shielding properties because the transmittance, turbidity, and lightness (L ^* ) of the cured product were outside the predetermined numerical ranges.
From Table 5, the composite resins of Reference Examples 1 and 2 both have color compatibility of the cured product with A4 shade outside the predetermined numerical range, and compared to the dental curable composition of the present invention, the color compatibility The performance and shielding properties were rejected.
Reference Example 3 passed the test for color tone compatibility, but failed for the shielding property.

Claims (12)

(A) an amorphous composite metal oxide filler containing SiO ₂ , ZrO ₂ and Al ₂ O ₃ ;
(B) spherical SiO ₂ filler with an average particle diameter of 50 nm or less,
A dental curable composition containing (C) a (meth)acrylate polymerizable monomer and (D) a coloring material,
The blending ratio (mass ratio) of the (B) SiO ₂ filler and the (A) composite metal oxide filler is 1:0.8 to 1:8,
The transmittance (Tt) of a cured product having a thickness of 1 mm after polymerization and curing of the curable composition is 52 or more and 66 or less,
Turbidity (haze value) is 85 or more and 98 or less,
The L ^* value (lightness) in the L ^* a ^* b ^* color system is 70 or more and 77 or less,
a ^* value (chromaticity) is -0.5 or more and 1.5 or less, and
A dental curable composition having a b ^* value (chromaticity) of 11 or more and 19 or less. The dental curable composition according to claim 1, wherein the colorant (D) contains at least one selected from the group consisting of a red pigment, a yellow pigment, a black pigment, and a white pigment. The coloring material (D) includes a red pigment, a yellow pigment, a black pigment, and a white pigment,
Their content is
(A) an amorphous composite metal oxide filler containing SiO ₂ , ZrO ₂ and Al ₂ O ₃ ;
For a total of 100 parts by mass of the (B) spherical SiO ₂ filler with an average particle diameter of 50 nm or less and the (C) (meth)acrylate polymerizable monomer,
0.0003 to 0.0009 parts by mass of red pigment,
0.0004 to 0.0011 parts by mass of yellow pigment,
The dental curable composition according to claim 1, wherein the black pigment is 0.0003 to 0.003 parts by mass, and the white pigment is 0.05 to 0.18 parts by mass. The dental curable composition according to claim 1, wherein a cured product having a thickness of 1 mm after polymerization and curing of the dental curable composition has an opal value of 10 or more and 23 or less. A tooth color standard pellet with a diameter of 15 mm and a thickness of 1 mm corresponding to shades A1 to A4 of the shade guide used as a tooth color standard;
The color tone of the cured product when the cured product having a diameter of 15 mm and a thickness of 1 mm after polymerization and curing of the dental curable composition is stacked on the tooth color reference pellet,
The dental curable composition according to claim 1, having a color difference (ΔE) of 10.5 or less. The ratio of the Y value ₍ Y B ) on a black background to the Y value (Y _W ) on a white background of a cured product having a thickness of 1 mm after polymerization and curing of the dental curable composition (Y _B /Y _W : The dental curable composition according to claim 1, wherein the dental curable composition has a contrast ratio of 0.43 or more and 0.58 or less. The dental curable composition is formed into a disk shape with a diameter of 12 mm and a thickness of 1 mm, and a cut is made to divide the dental curable composition in half with a 1 mm thick metal plate,
The dental treatment according to claim 1, wherein the divided dental curable composition is deformed when left standing at 37°C, and the time required for the divided dental curable compositions to come into contact with each other is 300 seconds or more. curable composition for use. According to claim 1, the elongation rate (consistency) when 0.65 g of the dental curable composition is molded into a spherical shape and a 3.25 kg weight is placed on top and left to stand still for 60 seconds is 160% or more. dental curable composition. The dental curable composition according to claim 1, which is a paste. The composite metal oxide filler (A) is a filler that is secondary particles with an average particle size of 2 to 8 μm, which are obtained by partially bonding primary particles with an average particle size of 0.1 to 0.9 μm by sintering. , the dental curable composition according to claim 1. A cured product obtained by polymerizing and curing the dental curable composition according to claim 1. A dental material obtained by polymerizing and curing the dental curable composition according to claim 1.