JPH10114616A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition containing a composite filler exhibiting a constant yellow color degree, giving a cured product having a nearly colorless and transparent color tone without deteriorating operability an mechanical strength, and capable of repairing teeth. SOLUTION: This curable composition comprises (a) a polymerizable monomer, (b) an inorganic filler having an average particle diameter of 0.01-1μm, (c) a composite filler having a yellow color degree of <=20 and comprising a polymer containing an inorganic filler having an average particle diameter of 0.01-1μm, and (d) a polymerization initiator in a (a)/[(b)+(c)]/(d) weight ratio of 100/(100-1000)/(0.1-5) and in a (b)/(c) weight ratio of 1/(0.2-3). The colored composite filler obtained by mixing the component (a) with the component (b), polymerization-curing the mixture and subsequently grinding the product is decolored with a peroxide into a yellow color degree of <=20. Thereby, teeth can be repaired with the nearly colorless and transparent repairing composition having an enamel color in the use of a dental composite repairing material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition, and more particularly to a curable composition which gives a cured product suitable as a dental composite restoration material. More specifically, an object of the present invention is to provide a curable composition that provides a cured product that can reproduce an enamel color or the like that is nearly colorless and has high transparency without sacrificing operability and strength.

[0002]

2. Description of the Related Art As a composite restoration material, a curable composition comprising a polymerizable monomer and an inorganic filler is used, but in order to improve the surface lubricity of the cured product, a finer inorganic material is used. A filler is used. However, a curable composition using a filler consisting of a fine inorganic filler alone has poor operability when filling the cavity of a tooth, and thus a fine inorganic filler and a polymerizable monomer are mixed and polymerized. After curing, a composite filler produced by pulverizing to several tens of μm using a pulverizer or the like was used in combination.

[0003]

However, when the inorganic filler and the polymerizable monomer are mixed, polymerized and cured, and then pulverized, the obtained composite filler is colored. It was difficult to produce a colorless and transparent color at the tip. Therefore, the present invention provides high mechanical properties and high lubricity of a polished surface of a hardened material and a suitable consistency and a colorless and transparent color, which could not be achieved by a dental composite restoration material manufactured by a conventional technique. An object of the present invention is to provide a curable composition which gives a cured product having a different color tone.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to overcome the above-mentioned problems, and found that a composite obtained by mixing an inorganic filler and a polymerizable monomer, polymerizing and curing, and then pulverizing the mixture. The present inventors have found that the filler is decolorizable, and that the use of this decolorized composite filler can improve the transparency of the cured product without impairing other physical properties, and have completed the present invention. .

That is, the present invention relates to a polymerizable monomer (a), an inorganic filler (b) having an average particle size in the range of 0.01 to 1 μm, and an inorganic filler (b) having an average particle size in the range of 0.01 to 1 μm. A composite filler comprising a filler-containing polymer and having a yellowness of 20 or less
(c) and a polymerization initiator (d), a polymerizable monomer
(a) For 100 parts by weight, the inorganic filler (b) and the composite filler (c) are 100 to 1000 parts by weight in total, and the weight ratio of the inorganic filler and the composite filler ((b) / (c)) is 0.2-
3 is a curable composition containing the polymerization initiator (d) in a proportion of 0.1 to 5 parts by weight.

One component of the curable composition of the present invention is a polymerizable monomer (a). The polymerizable monomer is not particularly limited, and a known monomer generally used as a dental monomer can be used. A typical example that is generally preferably used is a polymerizable monomer having an acryloyl group and / or a methacryloyl group. A specific example is as follows.

A) Monofunctional vinyl monomers Methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, and glycidyl methacrylate; and acrylates corresponding to these methacrylates. I) Aromatic compounds 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy)
-2-hydroxypropoxyphenyl] propane (hereinafter abbreviated as bis-GMA), 2,2-bis (4-
(Methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl)
Propane (hereinafter abbreviated as D-2.6E), 2,2-
Bis (4-methacryloyloxydiethoxyphenyl)
Propane), 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4
-Methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxydiethoxyphenyl) propane, 2 ( 4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxyditriethoxyphenyl) propane,
(4-methacryloyloxydipropoxyphenyl)-
2 (4-methacryloyloxytriethoxyphenyl)
Methacrylates such as propane, 2-2bis (4-methacryloyloxypropoxyphenyl) propane, 2-2bis (4-methacryloyloxyisopropoxyphenyl) propane, and acrylate (II) aliphatic compound-based compounds corresponding to these methacrylates Things Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate (hereinafter abbreviated as 3G), butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol dimethacrylate,
Methacrylates such as 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and acrylates corresponding to these methacrylates c) Trifunctional vinyl monomer trimethylolpropane trimethacrylate Methacrylates such as trimethylol ethane trimethacrylate, pentaerythritol trimethacrylate, and trimethylol methane trimethacrylate; and acrylates corresponding to these methacrylates. D) tetrafunctional vinyl monomers pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate A vinyl monomer having the same is also preferably used. These polymerizable monomers can be used alone, or two or more polymerizable monomers can be used in combination. Inorganic filler (b) used in the present invention
Is an inorganic filler having an average particle diameter in the range of 0.01 to 1 μm. Any known inorganic filler having an average particle diameter in the above range can be used without particular limitation.
Further, as long as the average particle diameter is within the above range, the inorganic filler does not necessarily have to be a single group, and may be mixed particles of two or more different groups. In this case, the average volume particle diameter of a mixture of a plurality of groups is used as the average particle diameter. Regarding the shape of the particles, irregularly shaped particles including spherical particles can be used.

Specific examples of inorganic fillers that are generally preferably used include, for example, dry ultrafine powder silica, dry ultrafine powder alumina, dry ultrafine powder zirconia, dry ultrafine powder titania, amorphous silica, and silica. Zirconia, silica-titania, silica-titania-barium oxide, quartz,
It is an inorganic oxide such as alumina. Further, a small amount of a metal oxide of Group I of the periodic table was present in the inorganic oxide for the purpose of easily obtaining a dense inorganic oxide when the inorganic oxide was fired at a high temperature. A composite oxide can also be used.

The inorganic filler is preferably subjected to a surface treatment prior to mixing with the polymerizable monomer component. As the surface treatment method, treatment with a generally used silane coupling agent, for example, an organosilicon compound such as γ-methacryloyloxyalkyltrimethoxysilane, hexamethyldisilazane or the like is preferable.

As the composite filler (c) used in the present invention, known composite fillers having an average particle diameter of 0.01 to 1 μm and comprising a polymer containing an inorganic filler having a yellowness of 20 or less are known. Can be used without particular limitation. As the inorganic filler contained in the composite filler, the above-mentioned inorganic filler can be used without any particular limitation. Further, as the polymerizable monomer serving as a raw material of the polymer, the above-described polymerizable monomer can be suitably used. Usually, the amount of the inorganic filler in the composite filler is preferably in the range of 50 to 90% by weight in order to obtain high mechanical properties.

The most important requirement in the present invention is that the composite filler has a yellowness of 20 or less. In general, a composite restoration material for dental use adjusts the color tone of natural teeth by adding a pigment.However, when the composite filler has a yellowness of 20 or more, it is almost colorless and has high transparency such as enamel color. In adjusting the incisal color, the target yellow density may be exceeded before the pigment is added, which causes a problem that color matching becomes difficult.

The present inventors have pursued the cause of the coloring of the composite filler, and as a result, it has been found that the pulverization during the production process of the composite filler has the cause of the coloring. At the same time, the method of decolorizing the composite filler colored by pulverization was examined. As a result, it was found that the decolorization could be easily performed by peroxide and the yellowness could be reduced to 20 or less, more preferably 15 or less.

The composite filler used in the present invention comprises:
It can be manufactured by the following method. The inorganic filler having an average particle diameter of 0.01 to 1 μm, a polymerizable monomer, and a predetermined amount of a polymerization initiator are blended and heated depending on the type of the polymerization initiator, or This is a method of irradiating light, polymerizing, and then pulverizing. As a pulverizing method, a ball mill, a vibrating ball mill, a jet mill, or the like can be used. The degree of pulverization is generally an average particle diameter of 1 to 50 μm
Is preferably within the range. The composite filler thus obtained usually has a yellowness of 30 or more.

Decolorization is performed to reduce the yellowness of the composite filler to 20 or less. A peroxide can be suitably used for decolorization. Known peroxides can be used as the peroxide. Specifically, hydrogen peroxide, sodium peroxide, ash powder, sodium hypochlorite, sodium chlorite, sulfur dioxide, sodium hydrogen sulfite, and hydrosulfide can be suitably used. The peroxide adhering to the composite filler, if mixed with a polymerizable monomer in a later step, may promote polymerization and reduce the storage stability of the curable composition. It is preferable to deactivate the remaining peroxide. In particular, hydrogen peroxide has the advantage that it does not leave an alkali component after use and is easily deactivated.

For decolorization, a solvent is used for dispersing the composite filler and dissolving the peroxide.
Known solvents can be used without any particular limitation as long as the solvent dissolves the peroxide. Decoloring is performed by dispersing the composite filler in the solvent, dissolving the peroxide and stirring. At this time, by heating to an appropriate temperature, the bleaching time can be shortened. Thereafter, by filtering and drying, a decolorized composite filler can be obtained.

Prior to mixing with the polymerizable monomer component, the composite filler is usually used after surface treatment.
As the surface treatment method, a surface treating agent for surface treating the above-mentioned inorganic filler can be suitably used.

Next, as the polymerization initiator (d) used in the present invention, either a thermal polymerization initiator or a photopolymerization initiator can be used. As the thermal polymerization initiator, general peroxides or azo compounds can be used. Specifically, dicumyl peroxide, benzoyl peroxide, azobisisobutyronitrile and the like are suitable.

As the photopolymerization initiator, known initiator systems such as α-diketone-reducing agent, ketal-reducing agent and thioxanthone-reducing agent are preferably used. Examples of the α-diketone include camphorquinone, benzyl, 2,3-pentadione, and 3,4-heptadione. Benzyl dimethyl ketal as ketal,
Benzyl diethyl ketal, benzyl (2-methoxyethyl ketal) and the like can be mentioned. Examples of thioxanthone include thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2-chlorothioxanthone. Reducing agents as one component of the photopolymerization initiator include tertiary amines such as 2- (dimethylamino) ethyl methacrylate, ethyl 4-dimethylaminobenzoate, N-methyldiethanolamine, lauryl aldehyde, dimethylamino benzaldehyde, and terephthalic acid. Aldehydes such as aldehyde, 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid, thiobenzoic acid and the like can be mentioned.

In the curable composition of the present invention, the inorganic filler (b) and the composite filler (c) are each composed of 100 polymerizable monomers (a).
A total amount of 100 to 1000 parts by weight, preferably 200 to 900 parts by weight, is added to the weight of the inorganic filler (b) and the composite filler (c) ((b) / ( c)) is a ratio of 0.2 to 3, preferably 0.3 to 2.

When the total amount of the inorganic filler (b) and the composite filler (c) is not within the above range with respect to the polymerizable monomer, the effect of the present invention is hardly exhibited. That is, inorganic filler
When the total amount of (b) and the composite filler (c) is less than 100 parts by weight, the mechanical strength of the curable composition after polymerization and curing decreases. Conversely, if it is more than 1000 parts by weight, the mixed particles cannot be uniformly dispersed in the polymerizable monomer, resulting in low mechanical strength. Further, when the above ratio ((b) / (c)) is smaller than 0.2, the dispersibility of the filler in the polymerizable monomer becomes poor even if the total amount satisfies the above range. However, it is difficult to obtain a cured product having high mechanical strength, and when the above ratio is more than 3, the consistency is increased and the operability is deteriorated.

The polymerization initiator (d) is a polymerizable monomer (a) 10
It is blended at a ratio of 0.1 to 5 parts by weight with respect to 0 parts by weight. If the amount of the polymerization initiator (d) is less than 0.1 part by weight, polymerization of the curable composition becomes insufficient, and conversely,
If the amount is more than 5 parts by weight, the mechanical strength of the cured product decreases.

The curable composition of the present invention may contain known additives as long as the effect is not significantly impaired. Examples of such additives include a polymerization inhibitor, a pigment, and an ultraviolet absorber.

The method for curing the curable composition of the present invention may be selected in accordance with the type of the polymerization initiator. For example,
When a polymerization initiator for photopolymerization is used, it is generally preferable to irradiate light for 10 seconds or more, preferably for 30 seconds to 1 hour. When a polymerization initiator for thermal polymerization is used, a method of heating at a temperature of 60 to 200 ° C, particularly 80 to 120 ° C, for 10 minutes to 20 hours, particularly 20 minutes to 1 hour is preferable. In this case, the polymerization is preferably performed under an atmosphere of an inert gas such as nitrogen or helium, or steam.

The physical properties of the curable composition produced in the above steps are as follows: the viscosity of the curable composition is 300 g or less, the bending strength of the cured product of the curable composition is 60 MPa or more, Is 40% or more, L * is 50 or more, a * is 5 or less, b * is 15 or less, and transparency is 0.5 or more.

In the present invention, the average particle diameter is particularly preferably from 0.01 to 1
Inorganic filler (b) containing at least one kind of spherical inorganic oxide fine particles selected from the group consisting of silica, alumina, silica zirconia, and silica titania having a mean particle size of 0 μm and From a polymer containing an inorganic filler containing at least one type of spherical inorganic oxide fine particles selected from the group consisting of silica, alumina, silica zirconia, and silica titania in the range of 0.01 to 1 μm. A composite filler having a yellowness of 20 or less (c)
Has a weight ratio ((b) / (c)) of 0.4 to 2 and a total amount of 70 to 85% by weight, and the polymerizable monomer containing a photopolymerization initiator is 15 to 30% by weight. %. Such a curable composition has good operability, and the cured product has a good color tone, and is particularly excellent in lubricity and bending strength.

[0026]

As will be understood from the above description, the curable composition of the present invention can provide a cured product having a nearly colorless and transparent color tone without lowering operability and mechanical strength. . Therefore, in the use of a dental composite restoration material, it is possible to restore a tooth with an enamel color or the like which is nearly colorless and has high transparency. Further, the curable composition of the present invention can be used without particular limitation in applications other than the above-mentioned dental composite restoration material.

[0027]

The present invention will be described more specifically with reference to the following Examples and Comparative Examples, but the present invention is not limited to these Examples. The physical properties of the curable compositions shown in the following Examples and Comparative Examples were measured according to the following methods.

(1) Average Particle Size A scanning or transmission electron micrograph of the powder is taken, and the number of particles observed per unit field of view of the photograph (n);
And the particle size (diameter Xi) were determined and calculated by the following equation.

[0029]

(Equation 1)

(2) Yellowness of composite filler Polymerizable monomer (D-2.6E / 3G (weight ratio) = 70 /
30) 40 parts by weight and 60 parts by weight of the composite filler are kneaded,
Pasted. The paste was placed in a mold having a hole of 7 mmφ × 3 mm, and both sides were pressed with a polypropylene film. Using a spectrophotometer (SQ-300H) manufactured by Nippon Denshoku, measurement was performed with a white background to determine the yellowness (YI).

Yellowness (YI) = 100 (1.28X−
1.06Z) / Y (X, Y, Z: tristimulus values) (3) Preparation and curing method of paste of curable composition First, surface of composite filler and inorganic filler with γ-methacryloyloxypropyltrimethoxysilane Processing was performed. On the other hand, a predetermined ratio of a photopolymerization initiator to the polymerizable monomer was added to prepare a matrix monomer. The above-mentioned composite filler, inorganic filler and matrix monomer were placed in an agate mortar and kneaded sufficiently in a dark place to obtain a uniform curable composition paste. After filling the above curable composition paste into a mold corresponding to each measurement shown below and curing it by sufficiently irradiating light, it is taken out from the mold and immersed in 37 ° C. water for 24 hours to obtain a sample piece. used.

(4) A prism-shaped sample piece having a bending strength of 2 × 2 × 25 mm was mounted on a tester (Autograph 5000D, manufactured by Shimadzu Corporation), and the distance between fulcrums was 20 mm and the crosshead speed was 0.5 mm / min. The point bending fracture strength was measured.

(5) Lubricity A 10 mmφ × 2 mm disk was buffed and used as a sample of the curable composition. Using a variable angle gloss meter manufactured by Tokyo Denshoku Co., Ltd., a test piece having an area defined by a black plate having a hole of 6 mmφ was irradiated with light at an angle of 45 °, and the light source was irradiated with 9% of light.
The reflectance of light at the light receiving portion at 0 degrees was measured, and the value was regarded as lubricity.

(6) Consistency The consistency of the curable composition was measured using a sun rheometer. A load detecting unit was inserted into the curable composition at a speed of 240 mm / min, and when a load of 1.5 kg was detected, 1 was detected.
Hold the detector for seconds. Thereafter, when the detecting portion was raised at a speed of 240 mm / min, the stress generated by sticking of the curable composition was defined as the consistency.

(7) Color tone of curable composition The paste was placed in a mold having a hole of 7 mmφ × 3 mm, and both sides were pressed with a polypropylene film. After irradiating with a visible light irradiator (power light) manufactured by Tokuyama Co., Ltd. for 30 seconds and curing, remove it from the mold and use a Nippon Denshoku spectrophotometer (SQ-300H) to give a white background. The color tone (L * a * b *) was measured.

(8) Transparency of the curable composition The paste was placed in a mold having a hole of 7 mmφ × 3 mm, and both sides were pressed with a polypropylene film. After irradiating with a visible light irradiator (trade name: Power Light) manufactured by Tokuyama for 30 seconds, curing, and then removing from the mold, the Y value of tristimulus value was measured using a Nippon Denshoku spectrophotometer (SQ-300H). The measurements were made with black and white background colors.

Opacity = Y value when the background color is black / Y value when the background color is white Transparency = 1-opacity Production Example 1 80 g of tetraethyl silicate (product name: ethyl silicate 28, manufactured by Nippon Colcoat Chemical Co., Ltd.) Mix with 400 g of isobutyl alcohol (manufactured by Tozen Petrochemical Co.)
5 g of a 5% sulfuric acid aqueous solution was added, and the mixture was hydrolyzed while stirring at 40 ° C. for about 1 hour. Thereafter, a solution of 35 g of tetrabutyl zirconate (manufactured by Nippon Soda Co., Ltd.) and a methanol solution of sodium methylate (concentration: 28% by weight) in 200 g of isobutyl alcohol was mixed with stirring, and tetraethyl silicate and tetrabutyl zirconate were mixed. A mixed solution of nate was prepared. Next, 3 l of internal volume with a stirrer
4 g of tetraethyl silicate was added to a glass container while stirring in an ammoniacal alcohol solution in which 1000 g of methanol and 250 g of 25% aqueous ammonia were introduced.
After stirring for 0 minutes, the above mixed solution of tetraethyl silicate and tetrabutyl zirconate was added dropwise over about 6 hours. During the reaction, the temperature of the reaction tank was kept at 40 ° C. After the completion of the reaction, the solvent was distilled off from the turbid reaction solution and dried to obtain 9
The mixture was calcined at 50 ° C. for 1 hour to obtain silica-zirconia particles.
The average particle size of the silica-zirconia particles is 0.18 μm.
m, the shape was spherical. The obtained inorganic filler was further surface-treated with γ-methacryloyloxypropylmethoxysilane.

The obtained inorganic filler (A-1) is a matrix monomer bis-solvent in which 0.5% by weight of a polymerization initiator benzoyl peroxide is previously dissolved in a mortar.
GMA / 3G (weight ratio 60/40) was added to the inorganic filler (A-
1) 100 parts by weight were added to 300 parts by weight and mixed to form a paste. This was polymerized at 95 ° C. in an N 2 atmosphere for 1 hour. The polymer was pulverized with a roll crusher and further pulverized with a vibration ball mill for 30 minutes to obtain a composite filler. The obtained composite filler was further surface-treated with γ-methacryloyloxypropylmethoxysilane. This composite filler (B
-1) The average particle size was 18 μm and the yellowness was 30.

50 g of this composite filler was added to 75 m of ethanol.
1, 30% hydrogen peroxide solution in a mixture of 6.6 ml,
The mixture was refluxed at 0 ° C., and then filtered, washed and dried to obtain a decolorized composite filler. Three types of composite fillers having different reflux times during production were produced. The obtained three types of composite fillers were further surface-treated with γ-methacryloyloxypropylmethoxysilane. Each filler (C-1, C-2,
Table 1 summarizes the reflux time and yellowness of C-3).

[0040]

[Table 1]

Production Example 2 80 g of tetraethylsilicate (manufactured by Nippon Colcoat Chemical Co., Ltd., product name: ethylsilicate 28) was added to methanol 20
Then, the mixture was mixed with 0 g, and 2.5 g of a 0.04% hydrochloric acid aqueous solution was added, followed by hydrolysis at 30 ° C. with stirring for about 1 hour. afterwards,
To this solution, add tetrabutyl titanate (Nippon Soda Co., Ltd.) 1
A solution of 0 g and 5 g of a potassium methylate methanol solution (concentration: 30% by weight) dissolved in 100 g of isopropyl alcohol was mixed with stirring to prepare a mixed solution (A) of tetraethylsilicate and tetrabutyl titanate. Next, 5.0 g of barium bisisopentoxide and 80 g of tetraethyl silicate were dissolved in 700 g of methanol, and the solution was refluxed at 90 ° C. under a nitrogen atmosphere for 30 minutes. Thereafter, the temperature was returned to room temperature, and this was used as a mixed solution (B). Further, the mixed solution (A) and the mixed solution (B) were mixed to obtain a mixed solution (C). Next, 3,000 g of methanol and 25 g of methanol were placed in a 10-liter glass container with a stirrer.
The above mixed solution (C) was stirred for about 5 minutes into an ammoniacal alcohol solution into which 750 g of aqueous ammonia was introduced.
It was dropped over time. During the reaction, the temperature of the reaction vessel was set at 40
C. After the completion of the reaction, the solvent was distilled off from the turbid reaction vessel liquid, dried and calcined at 950 ° C. for 1 hour to obtain silica-titania-barium oxide particles. The average particle diameter of the silica-titania-barium oxide particles was 0.25 μm, and the shape was spherical. The obtained inorganic filler was further surface-treated with γ-methacryloyloxypropylmethoxysilane.

A matrix monomer D-2 in which 0.5% by weight of a polymerization initiator azobisisobutyronitrile was previously dissolved in the obtained inorganic filler (A-2) in a mortar.
6E / 3G (weight ratio 70/30) was replaced with an inorganic filler (A-
2) 100 parts by weight were added and mixed with 250 parts by weight to form a paste. This was polymerized at 95 ° C. in an N 2 atmosphere for 1 hour. The polymer was pulverized with a roll crusher and further pulverized with a vibration ball mill for 30 minutes to obtain a composite filler. The obtained composite filler was further surface-treated with γ-methacryloyloxypropylmethoxysilane. This composite filler (B
-2) The average particle size was 20 μm and the yellowness was 31.

50 g of the composite filler was added to 75 m of ethanol.
1, 30% hydrogen peroxide solution in a mixture of 6.6 ml,
The mixture was refluxed at 0 ° C. for 5 hours, and then filtered, washed and dried to obtain a decolorized composite filler. The obtained composite filler is further γ
-Surface treatment with methacryloyloxypropylmethoxysilane. The yellowness of the composite filler (C-4) is 12.
It was 0.

Production Example 3 A composite filler (C-5) was obtained in the same manner as in Production Example 1, except that a 30% aqueous sodium hypochlorite solution was used instead of the hydrogen peroxide solution. The reflux was performed for 5 hours. The yellowness of this composite filler was 14.5.

Example 1 The composite filler (C-1) obtained in Production Example 1 and the inorganic filler (A-1) obtained in Production Example 1 were mixed at a weight ratio of 1: 1. Camphorquinone, N, N-
Dimethyl-P-toluidine and malic acid were added in 0.5 parts each.
Part by weight dissolved matrix monomer bis-GMA /
100 parts by weight of 3G (weight ratio 60/40) were mixed in a mortar with 400 parts by weight of the total amount of the composite filler (C-1) and the inorganic filler (A-1) to obtain a curable composition. . Furthermore, after irradiating the curable composition with light to polymerize and cure, various properties were evaluated. The results are shown in Table 2.

[0046]

[Table 2]

Example 2 A curable composition was obtained in the same manner as in Example 1 except that the composite filler was changed to (C-2). Was evaluated. Table 2 summarizes each physical property.

Example 3 A curable composition was obtained in the same manner as in Example 1 except that the composite filler was changed to (C-3). Was evaluated. Table 2 summarizes each physical property.

Example 4 A curable composition was obtained in the same manner as in Example 1 except that the inorganic filler was changed to (A-2). Was evaluated. Table 2 summarizes each physical property.

Example 5 In Example 1, the matrix monomer was changed to D-2.6E
/ 3G (weight ratio 70/30) except that the weight ratio was changed. Furthermore, after irradiating with light and polymerizing and curing in the same manner as in Example 1, various characteristics were evaluated. Table 2 summarizes each physical property.

Example 6 A curable composition was obtained in the same manner as in Example 1 except that the composite filler to be blended was changed to (C-4). Furthermore, after irradiating with light and polymerizing and curing in the same manner as in Example 1, various characteristics were evaluated. Table 2 summarizes each physical property.

Example 7 A curable composition was obtained in the same manner as in Example 1 except that the composite filler to be blended was changed to (C-5). Furthermore, after irradiating with light and polymerizing and curing in the same manner as in Example 1, various characteristics were evaluated. Table 2 summarizes each physical property.

Comparative Example 1 The procedure was performed except that the composite filler (B-1) obtained in Production Example 1 and the inorganic filler (A-1) obtained in Production Example 1 were mixed at a weight ratio of 1: 1. A curable composition was obtained in the same manner as in Example 1. Furthermore, after irradiating the curable composition with light to polymerize and cure, various properties were evaluated. The results are shown in Table 2.

Comparative Example 2 In Example 1, only the inorganic filler (A-1) was added without adding the composite filler. That is, a matrix monomer bis-GMA / 3G in which 0.5 parts by weight of camphorquinone, N, N-dimethyl-P-toluidine and malic acid were previously dissolved as a polymerization initiator (weight ratio: 60/4).
0) 250 parts by weight of the inorganic filler (A-1) was added to 100 parts by weight and mixed in a mortar to obtain a curable composition. Further, after irradiating with light and polymerizing and curing as in Example 1, various properties were evaluated. The results are shown in Table 2.

Claims (1)

[Claims] A polymerizable monomer (a) having an average particle size of 0.01
Inorganic filler (b) in the range of ~ 1 μm, average particle size of 0.0
A composite filler (c) having a yellowness of 20 or less, which is composed of a polymer containing an inorganic filler in the range of 1 to 1 μm, and a polymerization initiator (d), and 100 weight parts of a polymerizable monomer (a) Parts, the total amount of the inorganic filler (b) and the composite filler (c) is 10
0 to 1000 parts by weight, the weight ratio of the inorganic filler and the composite filler ((b) / (c)) is 0.2 to 3, and the polymerization initiator (d) is 0.1 to 5 A curable composition formulated in parts by weight.