JP2539145B2 - Dental composite resin - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dental composite material, and more particularly to a dental composite resin having high mechanical strength, excellent abrasion resistance and aesthetics, and a low coefficient of thermal expansion.

[0002]

2. Description of the Related Art Currently, a composite resin in which a polymerizable monomer is mixed with an inorganic filler is used for repairing a tooth defect. As the inorganic filler, crushed quartz having a particle size of several tens of μm and microfiller having a particle size of 10 to 40 nm are used. However, when a crushed quartz product is used, mechanical strength and surface hardness can be obtained, but aesthetic properties such as surface lubricity and abrasion resistance are inferior. In addition, although the one using the microfiller is excellent in aesthetics, it is inferior in mechanical strength and is inferior in operability. Further, it has been proposed to use amorphous silica produced by hydrolysis of silicate ester and having a particle size of 0.1 μm to 1.0 μm and a standard deviation of the particle size distribution of 1.30 or less (Japanese Patent Publication No. 1-57082) has excellent aesthetics, but has insufficient mechanical strength such as bending strength, and the narrow particle distribution results in a low compounding amount and high thermal expansion coefficient as in the case of ultrafine silica. .

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a dental composite resin which solves the above-mentioned problems and which is excellent in aesthetics, has high mechanical strength and has a low coefficient of thermal expansion. .

[0004]

[Means for Solving the Problems] As a result of intensive studies on the dental composite resin excellent in both aesthetic properties and mechanical strength, the present inventors have found that the polymerizable monomer and the vaporized
Metal Conversion (Vaporized Met)
al Combustion method ( Japanese Patent Publication No. 1-5520 )
See V.1 below. M. C. The composite resin for dentistry that is made by combining the synthetic quartz true spherical filler synthesized by the above method) has excellent surface lubricity, abrasion resistance, and mechanical properties such as bending strength. I found it.

Here, the dental composite resin includes not only a cavity repair material but also a crown material, an artificial tooth and the like. The dental composite resin currently used is a curable paste-like composition containing a polymerizable monomer and an inorganic filler for the purpose of improving mechanical strength and lowering the thermal expansion coefficient. To be done.

The polymerizable monomer used in the present invention includes bisphenol A-glucidyl methacrylate adduct (Bis-GMA), 2,2-bis (4- (methacryloxyethoxy) phenyl) propane, 2,2. -Bis (4
-(Methacryloxydiethoxy) phenyl) propane,
Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, urethane dimethacrylate (UDMA) and the like are used.

The synthetic quartz true spherical filler used in the present invention is the same as the V. M. C. Was synthesized by the method
is there. V. M. C. What is the method?
Ignite, continuously form self-combustion flame, at high temperature of several thousand degrees
Silicon dioxide particles are synthesized by a gas phase reaction.
V. M. C. Synthetic silica spherical filler obtained by the method
Is a true sphere with ultrafine particles, reduced impurities and high purity
It has features such as. In addition, the particle size distribution is narrow,
Any average particle size can be obtained within 5μ, and the coefficient of thermal expansion is small
It has excellent thermal properties and electrical properties. like this
Synthetic quartz true spherical fillers are available from Admatex, Tatsumori, etc.
Available as "Admafine SO" from
It With a method other than this, for example, a filler produced by hydrolysis of a silicate ester has low mechanical strength such as bending strength, and thus the object of the present invention is not achieved. The particle size of the filler to be used is preferably 2 μm or less, and if the particle size is larger than this, lubricity at the time of polishing the surface is deteriorated. Further, by using a filler having a wide distribution such that the CV value of the particle size is 40% or more, the filling rate of the filler can be increased as compared with the case of using a filler having a narrow distribution. The particle size of the filler can be measured by a commonly used method, for example, a transmission type or scanning type electron microscope is preferably used. The average particle diameter and the CV value are calculated by the formulas described later by measuring the diameter of the filler existing per unit area of the micrograph. It is preferred to make diameter measurements on 200 or more particles to reduce error. If the shape of the filler is not spherical, abrasion resistance, lubricity, etc. cannot be satisfied. The shape of the filler can be confirmed from the above-mentioned micrograph.

A polymerization initiator is used in the dental composite resin of the present invention, and known ones generally used for dentistry can be used (for example, benzoyl peroxide and tertiary amine, camphor). Quinones and tertiary amines). Further, other additives can be added if necessary. These additives include radical polymerization inhibitors, coloring pigments, ultraviolet absorbers and the like.

[0009]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

-Measurement of average particle diameter and CV value of the filler A transmission electron microscope photograph of the filler is taken, and the particle diameter (diameter Li) of the filler and the number (n) of the filler in the unit field of view of the photograph are obtained to obtain the following formula I, Average particle size and CV depending on II and III
The value was calculated.

[0011]

[Equation 1]

[0012]

[Equation 2]

[0013]

(Equation 3)

Method of making composite resin paste
And curing method A filler which was surface-treated with γ-methacryloxypropyltrimethoxysilane was mixed with a polymerizable monomer in which camphorquinone and N, N-dimethylaminoethylmethacrylate were dissolved by 1% by weight to form a paste. . This paste was put in a mold and sandwiched on both sides with glass plates to cure by irradiating each side for 2 minutes with a commercially available dental visible light irradiator, and then stored in 37 ° C. water for 24 hours.

Measurement of bending strength A sample was prepared with a mold of 2 × 2 × 25 mm, and Autograph AGS-100 (manufactured by Shimadzu Corporation) was used as a measuring device.
A three-point bending test was performed at a fulcrum distance of 20 mm and a crosshead speed of 0.75 mm / min.

-Measurement of compressive strength A sample was prepared with a mold having a diameter of 4 mm and a thickness of 5 mm, and the sample was measured at a crosshead speed of 2 mm / min using a universal testing machine (Strograph T: manufactured by Toyo Seiki Co., Ltd.).

Measurement of coefficient of thermal expansion A sample was prepared with a mold having a diameter of 5 mm and a height of 20 mm. Using a thermal analyzer (TMA-10: manufactured by SEIKO Denshi Sangyo), once heat from room temperature to 131 ° C at a temperature rising rate of 2 ° C / min, and once again under the same conditions, the coefficient of thermal expansion from room temperature to 80 ° C I asked.

Toothbrush abrasion test A sample was prepared with a mold having a diameter of 10 mm and a thickness of 10 mm, and the toothbrush abrasion ratio was obtained from the abrasion volume after the toothbrush was abraded under a load of 100 g for 10000 m.

(Example 1) Admafine SO-C2 (manufactured by Tatsumori Co., Ltd.) was used as a filler. The average particle size of this filler was 0.5 μm, and the CV value was 43%. Urethane dimethacrylate (UDMA) as the polymerizable monomer,
A mixture (UDMA: 3G = 7: 3) of triethylene glycol dimethacrylate (3G) (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used, and 83 wt% of a filler was blended and mixed and kneaded to prepare a paste. The operability of the paste was good. Table 1 below shows the results of the bending strength, compression strength, thermal expansion coefficient, and toothbrush wear test after curing. When the cured product was polished using Soflex (manufactured by 3M Co.), the surface smoothness was good.

Example 2 Example 1 was repeated except that Admafine SO-32H (manufactured by Tatsumori Co., Ltd.) having an average particle size of 1.5 μm and a CV value of 45% was used as a filler, and the compounding amount was 82% by weight.
I went the same way. The evaluation results are shown in Table 1 below.

(Example 3) 2,2-as the polymerizable monomer
A mixture of bis (4- (methacryloxyethoxyethoxy) phenyl) propane (D4E), trimethylolpropane trimethacrylate (TMPT) and 3G (D4E:
The same procedure as in Example 1 was performed except that 3G: TMPT) = (7: 2: 1) was used. The results are shown in Table 1 below.

(Comparative Example 1) Methanol 0.6 in a beaker
l, 50 g of ethyl silicate dissolved in 120 ml of methanol was added dropwise to 30 ml of aqueous ammonia (ammonia concentration 25%) while stirring at a liquid temperature of 20 ° C. over 30 minutes. After completion of the reaction, the solvent was removed by an evaporator, the residue was dried and calcined at 1000 ° C. for 1 hour. The silica particles had an average particle size of 0.52 μm and a CV value of 5%. A paste was prepared, cured and evaluated in the same manner as in Example 1 except that the silica particles were used. In this case, the blending amount was 75% or less in the range in which the viscosity of the paste could be manipulated. The results are also shown in Table 1 below.

(Comparative Example 2) As a filler, Hipresica (manufactured by Ube Nitto Kasei Co., Ltd.) synthesized by a hydrolysis method of silicon alkoxide was used. The filler used had an average particle size of 0.5 μm and a CV value of 8%. A paste was prepared, cured and evaluated in the same manner as in Example 2 except that this filler was used, and the blending amount within the operable range was 75% or less. The results are also shown in Table 1 below.

[0024]

[Table 1]

[0025]

INDUSTRIAL APPLICABILITY As described in detail above, according to the present invention, it is excellent in mechanical strength such as bending strength and compressive strength, has a low coefficient of thermal expansion, and is excellent in abrasion resistance. We can provide composite resin.

Claims (1)

(57) [Claims] 1. A polymerizable monomer in an amount of 10 to 40 parts by weight and a vaporized metal conversion (Vaporized Metal Comb).
synthetic spherical sphere filler 90 synthesized by the ustion method
A dental composite resin characterized by comprising -60 parts by weight.