JP2016193875A - Manufacturing method for highly dispersable particulate inorganic filler and dental curable composition comprising particulate inorganic filler - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the following problem: inorganic fillers are generally added to composite resins for increase in the mechanical strength and in the operability thereof; specifically, inorganic fillers with a median diameter of less than 0.5 μm are added for increased operability, and inorganic filler with a median diameter in a range from 0.5 μm to 100 μm are added for increased mechanical strength which is brought by further increase in the filling rate; with respect to the increase in the filling rate, inorganic fillers are surface-treated by a silane coupling agent to improve wettability, which results in the increase in the filling rate, further leading to increase in the elasticity modulus of the hardening body to thereby increase the mechanical strength; however, the conventional silane coupling treatment is limited in the increase in the wettability, so that sufficient filling rate cannot be achieved, and thus the mechanical strength cannot be increased sufficiently.SOLUTION: A particulate inorganic filler is manufactured by a method comprising the steps of: (1) surface-treating inorganic particulates with a silane coupling agent; and (2) suspending the inorganic particulates treated by the silane coupling agent in a water-containing organic solvent and adding an electrolyte to the suspended inorganic particulates. It is found that the thus manufactured particulate inorganic filler is highly dispersable in a dental curable composition composed of a radical polymerizable monomer, and that the particulate inorganic filler can be filled in the dental curable composition at a higher filling rate.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a method for producing a highly dispersible fine particle inorganic filler and a dental curable composition containing the fine particle inorganic filler.

In the dental field, a curable composition called a composite resin is used daily in clinical practice to repair a tooth defect. This is a dental material that forms a radical polymerized cured body by applying external energy such as light irradiation after filling the uncured paste before radical polymerization into the defect site such as teeth, and repairs the defect such as teeth. is there.

Generally, (meth) acrylic acid derivative monomers such as methyl methacrylate, triethylene glycol dimethacrylate, and urethane dimethacrylate are used for this composite resin. These radically polymerizable monomers such as (meth) acrylic acid derivative monomers are cured by forming a network polymer by breaking the carbon-carbon double bond into a single bond. Further, not only radically polymerizable monomers but also so-called fillers such as inorganic fillers are added to the composite resin for the purpose of improving mechanical strength and operability. Among these inorganic fillers, fine particle inorganic fillers with a median diameter of less than 0.5 μm are mainly used for viscosity adjustment, wear resistance, polishing glossiness and mechanical strength improvement for improving the operability of the composite resin. It has been added. In addition, an inorganic filler having a median diameter in the range of 0.5 μm to 100 μm is added to improve the mechanical strength by further increasing the filling rate. Moreover, these inorganic fillers are surface-treated with a silane coupling agent having a radical polymerizable group, so that the filling rate is increased by improving the wettability. This increase in the filling rate of the inorganic filler greatly contributes to the improvement of the mechanical strength. That is, as the filling rate increases, the elastic modulus of the cured body increases and the mechanical strength improves. For this purpose, γ-methacryloxypropyltrimethoxysilane has been widely used as a silane coupling agent in the dental field.

However, surface treatment of an inorganic filler with γ-methacryloxypropyltrimethoxysilane has a limitation in improving wettability between radical polymerizable monomers due to the short carbon chain. As a result, a sufficient increase in filling rate could not be achieved, and the mechanical strength was not sufficiently improved. Therefore, for the purpose of improving the filling rate, a method using a silane coupling agent having a long alkylene chain, a method using a radically polymerizable monomer with high hydrophobicity (Patent Documents 1, 2, and 3), a polymerizable group A method using a large number of silane coupling agents (Patent Document 4) has been proposed.

However, when the method described in Patent Document 1 is applied to a dental restorative material, there is room for improvement in mechanical strength, and there is a limit to the radical polymerizable monomer that can be used. Similarly, when the methods described in Patent Documents 2 to 3 are applied to a dental restoration material, there is a limit in increasing the filling rate of the fine inorganic filler having a median diameter of less than 0.5 μm, resulting in mechanical There was room for improvement in strength. Moreover, when the method of patent document 4 was applied to the dental material, the water resistance was low and the durability of the material was insufficient. As described above, the compatibility between the durability and mechanical strength of the material depending on the silane coupling agent in the prior art is insufficient, and there is room for further improvement. Furthermore, the synthesis of the silane coupling agent described in Patent Documents 1 to 3 requires the use of an expensive platinum complex for hydrosilylation, which increases the cost of the product and raises the price of the final product. That is, in the prior arts of Patent Documents 1 to 4, there is a limit to increasing the filling rate of the fine inorganic filler having a median diameter of less than 0.5 μm.

JP-A-2-134307 Japanese Patent Laid-Open No. 2-200689 JP-A-3-70778 JP 2010-229054

An inorganic filler is added to the dental composite resin for the purpose of improving mechanical strength and operability. This inorganic filler is surface-treated with a silane coupling agent having a radical polymerizable group, and the filling rate is increased by improving the wettability. Conventionally, in the dental field, γ-methacryloxypropyltrimethoxysilane has been widely used as a silane coupling agent. However, surface treatment of an inorganic filler with γ-methacryloxypropyltrimethoxysilane has a limitation in improving wettability between radical polymerizable monomers due to the short carbon chain. Therefore, for the purpose of further improving the wettability, a method using a silane coupling agent having a long alkylene chain, a method using a radically polymerizable monomer having a high hydrophobicity, and a silane coupling agent having many polymerizable groups. A method to do so has been proposed. However, any method has a limit in increasing the filling rate of the inorganic filler, and as a result, there is room for improvement in mechanical strength.

As a result of intensive studies by the inventors, (1) a step of surface-treating inorganic fine particles with a silane coupling agent, and (2) an electrolyte added by suspending inorganic fine particles treated with a silane coupling agent in a water-containing organic solvent High-dispersibility in dental curable compositions is possible by making the fine particle inorganic filler produced by the method characterized by comprising The present invention has been completed.

(1) From the step of subjecting the inorganic fine particles to a surface treatment with a silane coupling agent and (2) the step of suspending the inorganic fine particles treated with the silane coupling agent in a water-containing organic solvent and adding an electrolyte. The fine particle inorganic filler produced by the production method can be highly dispersed in the dental curable composition, and as a result, the fine particle inorganic filler can be highly filled in the dental curable composition. It was. Conventionally, when a filler having a small median diameter is blended in a dental curable composition, the blending amount of the filler cannot be increased due to a rapid thickening behavior. However, in the present invention, even when a fine particle inorganic filler produced using inorganic fine particles having a median diameter of less than 0.5 μm is blended in a dental curable composition, it does not show a sharp thickening behavior. High filling can be achieved and high fluidity can be maintained.

The production method of the present invention is for producing a finely divided inorganic filler that can be highly dispersed in a dental curable composition, (1) a step of subjecting inorganic fine particles to a surface treatment with a silane coupling agent, and (2) It comprises a step of suspending inorganic fine particles treated with a silane coupling agent in a water-containing organic solvent and adding an electrolyte for treatment.

In the production method of the present invention, the inorganic fine particles to be surface-treated with the silane coupling agent are not particularly limited, and any inorganic fine particles can be used. Specifically, silicon dioxide, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, aluminosilicate glass , Barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, and the like. In particular, fluoroaluminosilicate barium glass, fluoroaluminosilicate strontium glass, fluoroaluminosilicate glass, and the like used for dental glass ionomer cement, resin-reinforced glass ionomer cement, resin cement, and the like can be suitably used. The fluoroaluminosilicate glass referred to here has silicon oxide and aluminum oxide as a basic skeleton and contains an alkali metal for introducing non-crosslinkable oxygen. Furthermore, there is no problem even if an alkaline earth metal containing strontium as a modifying / coordinating ion, fluorine, or a lanthanoid series element incorporated in the skeleton in order to impart radiopacity. These can be used alone or in admixture of two or more. Among these, it is preferable to use silicon oxide such as silicon dioxide, aluminum oxide such as dialuminum trioxide, and zirconium oxide such as zirconium dioxide. Further, the shape of the inorganic fine particles is not particularly limited, and may be spherical or indefinite.

Further, the median diameter of the inorganic fine particles is not particularly limited, but in order to more efficiently express the high dispersibility in the dental curable composition of the fine particle inorganic filler produced by the production method of the present invention, the median diameter is preferably set to 0.1. A median diameter of less than 5 μm is preferred, more preferably in the range of 10 nm to 0.5 μm.

Ａは、Ｈ_２Ｃ＝ＣＨ‐，Ｈ_２Ｃ＝Ｃ（ＣＨ_３）‐，Ｈ_２Ｃ＝ＣＨ‐Ｃ_６Ｈ_４‐基を表し（Ｃ_６Ｈ_４はフェニレン基を示す）、Ｂは、‐Ｃ（Ｏ）‐Ｏ‐，‐Ｃ（Ｏ）‐Ｓ‐，‐Ｃ（Ｏ）‐ＮＨ‐，‐ＮＨ‐Ｃ（Ｏ）‐ＮＨ‐，‐ＮＨ‐Ｃ（Ｏ）‐Ｓ‐，‐ＮＨ‐Ｃ（Ｏ）‐Ｏ‐基を表し、Ｚは、Ｃ_１〜Ｃ_３０の直鎖または分岐鎖のアルキレン基を表し、Ｙは、‐ＮＨ‐，‐Ｓ‐，‐ＮＨ‐Ｃ（Ｏ）‐Ｓ‐，‐ＮＨ‐Ｃ（Ｏ）‐ＮＨ‐，‐Ｃ（Ｏ）‐Ｓ‐，‐Ｃ（Ｏ）‐Ｏ‐，‐ＣＨ（ＯＨ）‐ＣＨ_２‐Ｓ‐，‐ＣＨ（ＯＨ）‐ＣＨ_２‐Ｏ‐，‐ＮＨ‐Ｃ（Ｏ）‐Ｏ‐基を表し、Ｒ^２は、Ｃ_１〜Ｃ_３０の直鎖または分岐鎖のアルキレン基で、‐Ｓ‐，‐ＮＨ‐，‐ＮＲ^４‐（Ｒ^４はアルキレン基を示す），‐ＣＨ_２‐Ｃ_６Ｈ_４‐（Ｃ_６Ｈ_４はフェニレン基を示す），‐Ｃ（Ｏ）‐Ｏ‐，‐Ｏ‐基を含み得、Ｒ^３はＣ_１〜Ｃ_６の直鎖または分岐鎖のアルキル基を表し、Ｒ^１はＣ_１〜Ｃ_１６の直鎖または分岐鎖のアルキル基、フェニル基またはハロゲン原子を表しｎが０のときには少なくとも１以上のハロゲン原子がＳｉに結合する。なお、ａは１〜６，ｎは０〜３である。以下に代表的な化合物の化学構造を具体的に一部記載する。

The silane coupling agent that can be used in the treatment step with the silane coupling agent that is the production method of the present invention is not particularly limited as long as it has a radical polymerizable group in the molecule. Specifically, any silane coupling represented by the following chemical structure can be used.

A represents H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ — group (C ₆ H ₄ represents a phenylene group), B represents -C (O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH-, -NH-C (O) -S-,- Represents an NH—C (O) —O— group, Z represents a C _{1 to} C ₃₀ linear or branched alkylene group, and Y represents —NH—, —S—, —NH—C (O ) -S-, -NH-C (O) -NH-, -C (O) -S-, -C (O) -O-, -CH (OH) -CH ₂ -S-, -CH (OH ) —CH ₂ —O—, —NH—C (O) —O—, wherein R ² is a C _{1 to} C ₃₀ linear or branched alkylene group, —S—, —NH—, -NR ⁴ - ^{(R 4} represents an alkylene group), - _CH 2 -C _{6 4} - _(C 6 _{H 4} represents a phenylene group), - C (O) -O -, - comprise an O- group, ^{R 3} represents a linear or branched alkyl group of _C 1 -C ₆ , R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group, a phenyl group or a halogen atom, and when n is 0, at least one halogen atom is bonded to Si. In addition, a is 1-6 and n is 0-3. Hereinafter, specific chemical structures of typical compounds are partially described.

Ａは、Ｈ_２Ｃ＝ＣＨ‐，Ｈ_２Ｃ＝Ｃ（ＣＨ_３）‐，Ｈ_２Ｃ＝ＣＨ‐Ｃ_６Ｈ_４‐基を表し（Ｃ_６Ｈ_４はフェニレン基を示す）、Ｂは、‐Ｃ（Ｏ）‐Ｏ‐，‐Ｃ（Ｏ）‐Ｓ‐，‐Ｃ（Ｏ）‐ＮＨ‐，‐ＮＨ‐Ｃ（Ｏ）‐ＮＨ‐，‐ＮＨ‐Ｃ（Ｏ）‐Ｓ‐，‐ＮＨ‐Ｃ（Ｏ）‐Ｏ‐基を表し、Ｚは、Ｃ_１〜Ｃ_６０の直鎖または分岐鎖のアルキレン基で、‐ＣＨ（ＯＨ）‐ＣＨ_２‐Ｓ‐，‐ＣＨ（ＯＨ）‐ＣＨ_２‐Ｏ‐基を含み得、Ｄは、Ｃ_２〜Ｃ_６０の２価から４価の直鎖または分岐鎖のアルキレン基を表し、‐Ｃ（Ｏ）‐Ｏ‐，‐Ｃ（Ｏ）‐Ｓ‐，‐Ｃ（Ｏ）‐ＮＨ‐，‐ＮＨ‐Ｃ（Ｏ）‐ＮＨ‐，‐Ｓ‐，‐ＮＨ‐Ｃ（Ｏ）‐Ｓ‐，‐ＮＨ‐Ｃ（Ｏ）‐Ｏ‐を含み得、および／または３価のトリアジン分子骨格または２価のバルビツール酸分子骨格を有し、Ｅは、‐ＮＨ‐，‐ＮＲ^４‐（Ｒ^４はアルキレン基を示す），‐Ｏ‐，‐Ｓ‐，‐ＮＨ‐Ｃ（Ｏ）‐Ｓ‐，‐ＮＨ‐Ｃ（Ｏ）‐ＮＨ‐，‐Ｃ（Ｏ）‐Ｓ‐，‐ＮＨ‐Ｃ（Ｏ）‐Ｏ‐，‐Ｃ（Ｏ）‐Ｏ‐基を表し、Ｒ^２は、Ｃ_１〜Ｃ_６０の直鎖または分岐鎖のアルキレン基で、‐Ｓ‐，‐ＮＨ‐，‐ＣＨ_２‐Ｃ_６Ｈ_４‐（Ｃ_６Ｈ_４はフェニレン基を示す），‐Ｃ（Ｏ）‐Ｏ‐，‐Ｏ‐基を含み得、Ｒ^１はＣ_１〜Ｃ_１６の直鎖または分岐鎖のアルキル基、フェニル基またはハロゲン原子を表しｎが０のときには少なくとも１以上のハロゲン原子がＳｉに結合し、Ｒ^３はＣ_１〜Ｃ_６の直鎖または分岐鎖のアルキル基を表す。なお、ｑとｒの和はＤの価数に等しく、ｒは１以上の正の整数であり、ｎは０〜３、ａは１〜６である。以下に代表的な化合物の化学構造を具体的に一部記載する。

A represents H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ — group (C ₆ H ₄ represents a phenylene group), B represents -C (O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH-, -NH-C (O) -S-,- NH—C (O) —O— group, wherein Z is a C _{1 to} C ₆₀ linear or branched alkylene group, —CH (OH) —CH ₂ —S—, —CH (OH) — CH ₂ —O— group may be included, and D represents a C _{2 to} C ₆₀ divalent to tetravalent linear or branched alkylene group, —C (O) —O—, —C (O) -S-, -C (O) -NH-, -NH-C (O) -NH-, -S-, -NH-C (O) -S-, -NH-C (O) -O- And / or a trivalent triazine molecular skeleton or a divalent buffer. It has a rubituric acid molecular skeleton, and E represents —NH—, —NR ⁴ — (R ⁴ represents an alkylene group), —O—, —S—, —NH—C (O) —S—, —NH -C (O) -NH-, -C (O) -S-, -NH-C (O) -O-, -C (O) -O- group, R ² represents C ₁ -C ₆₀ A straight-chain or branched-chain alkylene group represented by —S—, —NH—, —CH ₂ —C ₆ H ₄ — (C ₆ H ₄ represents a phenylene group), —C (O) —O—, — R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group, a phenyl group or a halogen atom, and when n is 0, at least one or more halogen atoms are bonded to Si, ³ represents a linear or branched alkyl group of _C 1 -C _6. The sum of q and r is equal to the valence of D, r is a positive integer of 1 or more, n is 0 to 3, and a is 1 to 6. Hereinafter, specific chemical structures of typical compounds are partially described.

Ａは、Ｈ_２Ｃ＝ＣＨ‐，Ｈ_２Ｃ＝Ｃ（ＣＨ_３）‐，Ｈ_２Ｃ＝ＣＨ‐Ｃ_６Ｈ_４‐基を表し（Ｃ_６Ｈ_４はフェニレン基を示す）、Ｂは、‐Ｃ（Ｏ）‐Ｏ‐，‐Ｃ（Ｏ）‐Ｓ‐，‐Ｃ（Ｏ）‐ＮＨ‐，‐ＮＨ‐Ｃ（Ｏ）‐ＮＨ‐，‐ＮＨ‐Ｃ（Ｏ）‐Ｓ‐，‐ＮＨ‐Ｃ（Ｏ）‐Ｏ‐基を表し、Ｚは、Ｃ_１〜Ｃ_６０の直鎖または分岐鎖のアルキレン基を表し、Ｒ^２はＣ_１〜Ｃ_６の直鎖または分岐鎖のアルキル基を表し、Ｒ^１はＣ_１〜Ｃ_１６の直鎖または分岐鎖のアルキル基、フェニル基またはハロゲン原子を表しｎが０のときには少なくとも１以上のハロゲン原子がＳｉに結合する。なお、ａは１〜６，ｎは０〜３である。以下に代表的な化合物の化学構造を具体的に一部記載する。

A represents H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ — group (C ₆ H ₄ represents a phenylene group), B represents -C (O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH-, -NH-C (O) -S-,- It represents NH-C (O) -O- _group, Z is a straight-chain or branched alkylene group of _C 1 ~C _60, ^{R 2} is straight or branched alkyl group of _C 1 -C ₆ R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group, a phenyl group or a halogen atom, and when n is 0, at least one or more halogen atoms are bonded to Si. In addition, a is 1-6 and n is 0-3. Hereinafter, specific chemical structures of typical compounds are partially described.

Ａは、Ｈ_２Ｃ＝ＣＨ‐，Ｈ_２Ｃ＝Ｃ（ＣＨ_３）‐，Ｈ_２Ｃ＝ＣＨ‐Ｃ_６Ｈ_４‐基を表し（Ｃ_６Ｈ_４はフェニレン基を示す）、Ｒ^２はＣ_１〜Ｃ_６の直鎖または分岐鎖のアルキル基を表し、Ｒ^１はＣ_１〜Ｃ_１６の直鎖または分岐鎖のアルキル基、フェニル基またはハロゲン原子を表しｎが０のときには少なくとも１以上のハロゲン原子がＳｉに結合する。なお、ｎは０〜３である。などである。以下に代表的な化合物の化学構造を具体的に一部記載する。

これらは、単独で又は２種以上を混合して用いることができる。また、シランカップリング剤の処理濃度、乾式及び／又は湿式等の処理方法、さらに真空、凍結、大気等の熱処理方法などのいずれにおいても特に制限はなく、使用する設備等においても特に制限はない。異なるメジアン径である二種類以上の無機微粒子を同時にシランカップリング剤により表面処理して次工程の処理に用いることもできる。またそれらを別々に処理し後に、それらを混合して次工程の処理に用いることもできる。

A represents H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ — group (C ₆ H ₄ represents a phenylene group), and R ² represents C _{1 to} C _{6 represents} a linear or branched alkyl group, R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group, a phenyl group, or a halogen atom, and when n is 0, at least 1 or more Are bonded to Si. In addition, n is 0-3. Etc. Hereinafter, specific chemical structures of typical compounds are partially described.

These can be used alone or in admixture of two or more. In addition, there are no particular restrictions on the treatment concentration of the silane coupling agent, treatment methods such as dry and / or wet, and heat treatment methods such as vacuum, freezing, and air, and there is no particular restriction on the equipment used. . Two or more types of inorganic fine particles having different median diameters can be simultaneously surface-treated with a silane coupling agent and used for the next step. Moreover, after processing them separately, they can also be mixed and used for the next process.

In the production method of the present invention, inorganic fine particles subjected to silane coupling treatment are dispersed in a water-containing organic solvent to prepare a suspension system, and the organic solvent used at that time is used without any limitation as long as it is compatible with water. be able to. Specific examples include acetone, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, tetrahydrofuran, 1,4-dioxane and the like. Moreover, these can be used individually or in mixture of 2 or more types. Here, there is no limitation on the water content contained in the water-containing organic solvent. Moreover, the mixing ratio of the inorganic fine particles subjected to the silane coupling treatment and the water-containing organic solvent is not particularly limited. In the production method of the present invention, the electrolyte added to the suspension system for treatment is not particularly limited as long as it is slightly soluble in water. Salts of inorganic acids and / or (and / or) organic acids are not particularly limited. Any salt can be used without any problem. Moreover, any of a normal salt, an acidic salt, a basic salt may be sufficient, and a mixture thereof may be sufficient. Preferred are alkali metal salts, alkaline earth metal salts, and transition metal salts, and more preferred are alkali metal salts and alkaline earth metal salts. Specific examples of inorganic acid salts include hydrochlorides such as lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, beryllium chloride, magnesium chloride, calcium chloride, strontium chloride, and barium chloride. Lithium sulfate, lithium hydrogen sulfate, sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, rubidium sulfate, rubidium hydrogen sulfate, cesium sulfate, cesium hydrogen sulfate, beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, etc. Such as sulfate. Nitrates such as lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate, cesium nitrate, beryllium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate; Lithium phosphate, dilithium hydrogen phosphate, lithium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, rubidium phosphate, dirubidium hydrogen phosphate, dihydrogen phosphate Phosphate salts such as rubidium, cesium phosphate, dicesium hydrogen phosphate, cesium dihydrogen phosphate, beryllium phosphate, magnesium phosphate, calcium phosphate, strontium phosphate, and barium phosphate. Lanthanoid series salts. Specific examples of salts of organic acids include carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, and barium carbonate. Examples thereof include acetates such as lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, beryllium acetate, magnesium acetate, calcium acetate, strontium acetate, and barium acetate. These can be used alone or in admixture of two or more. Further, there are no particular restrictions on the treatment concentration of the electrolyte, the treatment method such as dry and / or wet, and the heat treatment method such as vacuum, freezing, and air, and there is no particular restriction on the equipment used.

The fine particle inorganic filler obtained by the production method of the present invention is highly dispersed by being highly dispersed in a dental curable composition containing a radical polymerizable monomer, a polymerization initiator and / or a polymerization accelerator. It becomes possible to do. The blending amount of the fine particle inorganic filler in the dental curable composition is not particularly limited, but is preferably in the range of 0.5 to 95% by weight, more preferably in the range of 5 to 90% by weight. When it is 0.5 wt% or less, the mechanical (physical) strength of the paste cured product is low, which is not preferable. On the other hand, if it is 95% by weight or more, the viscosity of the prepared paste is too high. In addition, when inorganic fine particles produced by the production method of the present invention using inorganic fine particles having a median diameter of less than 0.5 μm are blended in a dental curable composition, the tendency to thicken is suppressed, so that high filling is achieved. Is possible. Furthermore, in addition to the fine particle inorganic filler produced by the production method of the present invention using inorganic fine particles having a median diameter of less than 0.5 μm, the fine particles produced by the production method of the present invention using inorganic fine particles having a median diameter of more than 0.5 μm When an inorganic filler is used in combination with a dental curable composition, a higher filling becomes possible. The ratio of the highly dispersible fine particle inorganic filler of the present invention and the inorganic filler having a median diameter of more than 0.5 μm in the dental curable composition is not particularly limited, but preferably 0.5 to 95 weight. %. Further, the ratio of the highly dispersible fine particle inorganic filler of the present invention and the inorganic filler having a median diameter exceeding 0.5 μm in the dental curable composition is not particularly limited.

As the radically polymerizable monomer used in the dental curable composition of the present invention, those used in the dental field can be used without any limitation. Specifically, for example, 7,7,9-trimethyl-4,13-dioxo-3 synthesized by urethane reaction of 2,2,4-trimethylhexamethylene diisocyanate and 2-hydroxyethyl methacrylate (HEMA). , 14-dioxa-5,12-diazahexadecane-1,16-diyl dimethacrylate (UDMA), HEMA and HEA and 2,4-toluylene diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate or hexamethylene diisocyanate By radically polymerizable monomers synthesized by urethane reaction with benzene, and reaction of aliphatic and / or aromatic diisocyanates with glycerol (meth) acrylate and 3-methacrylol-2-hydroxypropyl ester Urethane diacrylates and to be, 1,3-bis (2-isocyanate, 2-propyl) urethane reaction products of a compound having a benzene and hydroxy group. More specifically, 2,7,7,9,15-pentamethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyl diacrylate, 2,7, 7,9,15-pentamethyl-4,13-18-trioxo-3,14,17-trioxa-5,12-diazaicos-19-enyl methacrylate, 2,8,10,10,15-pentamethyl-4,13 , 18-Trioxo-3,14,17-trioxa-5,12-diazaikos-19-enyl methacrylate, 2,7,7,9,15-pentamethyl-4,13-dioxo-3,14-dioxa-5 12-diazahexadecane-1,16-diylbis (2-methylacrylate), 2,2 '-(cyclohexane-1,2-diylbis (methylene)) bis ( Zandiyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) diacrylate, 2-((2-(((1- (acryloyloxy) propan-2-yloxy) carbonylamino) methyl) cyclohexyl ) Methylcarbamoyloxy) propyl methacrylate, 2,2 '-(cyclohexane-1,2-diylbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) bis (2-methyl acrylate), 2,2 ′-(bicyclo [4.1.0] heptane-3,4-diylbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2 , 1-Diyl) diacrylate, 2-((4-(((1- (acryloyloxy) propane 2-yloxy) carbonylamino) methyl) bicyclo [4.1.0] heptan-3-yl) methylcarbamoyloxy) propyl methacrylate, 2,2 ′-(bicyclo [4.1.0] heptane-3,4 -Diylbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) bis (2-methylacrylate), 7,7,9-trimethyl-4,13-dioxo -3,14-dioxa-5,12-diazahexadecane-1,16-diyl diacrylate, 7,7,9-trimethyl-4,13,18-trioxo-3,14,17-trioxa-5,12 -Diazaicos-19-enyl methacrylate, 8,10,10-trimethyl-4,13,18-trioxo-3,14,17-trioxa -5,12-diazaikos-19-enyl methacrylate, 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diylbis (2-methyl acrylate) ), 4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyl diacrylate, 4,13,18-trioxo-3,14,17-trioxa-5,12- Diazaicos-19-enyl methacrylate, 4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diylbis (2-methyl acrylate), 2- (1- (2-((2 -(Acryloyloxy) ethoxy) carbonylamino) -4,4-dimethylcyclohexyl) ethylcarbamoyloxy) ethyl methacrylate 2- (1- (2-((2- (acryloyloxy) ethoxy) carbonylamino) ethyl) -5,5-dimethylcyclohexylcarbamoyloxy) ethyl methacrylate, 2- (2-(((1- (methacrylic Leuoxy) propan-2-yloxy) carbonylamino) methyl) -2,5,5-trimethylcyclohexylcarbamoyloxy) propane-1,3-diylbis (2-methylacrylate), 2- (2-(((1 -(Methacryloyloxy) propane-2-yloxy) carbonylamino) methyl) -2,5,5-trimethylcyclohexylcarbamoyloxy) propane-1,3-diyl diacrylate, 2- (2-(((1- (Acryloyloxy) propan-2-yloxy) carbonylamino) methyl) -2,5,5-to Methylcyclohexylcarbamoyloxy) propane-1,3-diylbis (2-methylacrylate), 3- (15- (2- (acryloyloxy) ethyl) -3,12,19-trioxo-2,13,18-trioxa- 4,11-diazahenicos-20-enyl) pentane-1,5-diyl diacrylate, 3- (15- (2- (acryloyloxy) ethyl) -3,12,19-trioxo-2,13,18-trioxa- 4,11-diazahenicos-20-enyl) pentane-1,5-diylbis (2-methyl acrylate), 2,2 '-(cyclhexane-1,2-diylbis (methylene)) bis (azanediyl) bis (oxomethylene) ) Bis (oxy) bis (ethane-2,1-diyl) diacrylate, 2-((2-(((2- (A Acryloyloxy) ethoxy) carbonylamino) methyl) cyclohexyl) methylcarbamoyloxy) ethyl methacrylate, 2,2 ′-(cyclhexane-1,2-diylbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) Bis (ethane-2,1-diyl) bis (2-methyl acrylate), 2,15-bis (cyclohexyloxymethyl) -4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1 , 16-diyldiacrylate, 2,15-bis (cyclohexyloxymethyl) -4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diylbis (2-methylacrylate), 2,15-bis (cyclohexyloxymethyl) -4,13,18- Rioxo-3,14,17-trioxa-5,12-diazaicos-19-enyl methacrylate, 1,18-bis (cyclohexyloxy) -5,14-dioxo-4,15-dioxa-6,13-diazaoctadecane -2,17-diyl diacrylate, 1- (cyclohexyloxy) -17- (cyclohexyloxymethyl) -5,14,19-trioxo-4,15,18-trioxa-6,13-diazahenicos-20-ene- 2-yl methacrylate, 1,18-bis (cyclohexyloxy) -5,14-dioxo-4,15-dioxa-6,13-diazaoctadecane-2,17-diylbis (2-methyl acrylate), 7,7 , 9-Trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexade -1,16-diylbis (2-methyl acrylate), 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyl diacrylate, 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) bis (2-methacrylate), 2,2' -(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) diacrylate, 2- (3-(((2- (acryloyloxy) ) Ethoxy) carbonylamino) methyl) benzylcarbamoyloxy) ethyl methacrylate, 2,2 '-(1,3-phenylenebis (methylene)) bis (Methylazanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) bis (2-methacrylate), 2,2 '-(1,3-phenylenebis (methylene)) bis (methyl Azandiyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) diacrylate, 2-((3-((((2- (acryloyloxy) ethoxy) carbonyl) (methyl) amino) methyl ) Benzyl) (methyl) carbamoyloxy) ethyl methacrylate, 2,2 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) Bis (2-methyl acrylate), 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis ( Xoxomethylene) bis (oxy) bis (propane-2,1-diyl) diacrylate, 2- (3-(((2- (acryloyloxy) ethoxy) carbonylamino) methyl) benzylcarbamoyloxy) propyl methacrylate, 2- ( 3-((((1- (acryloyloxy) propan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) ethyl methacrylate, 4,4 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bis Oxomethylene) bis (oxy) bis (4,1-phenylene) bis (2-methyl acrylate), 4,4 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bisoxomethylene) bis (oxy ) Bis (4,1-phenylene) diacrylate, 4- (3-(((4 (Acryloxy) phenoxy) carbonylamino) methyl) benzylcarbamoyloxy) phenyl methacrylate, 4,4 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (butane) -4,1-diyl) bis (2-methylacrylate), 4,4 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (butane-4) 1-diyl) diacrylate, 4- (3-(((4- (acryloyloxy) butoxy) carbonylamino) methyl) benzylcarbamoyloxy) butyl methacrylate, 2,2 ′-(1,3-phenylenebis (methylene) ) Bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3-phenoxy) Cypropane-2,1-diyl) bis (2-methylacrylate), 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3-phenoxy Propane-2,1-diyl) diacrylate, 2- (3-(((1- (acryloyloxy) -3-phenoxypropan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) -3-phenoxypropyl methacrylate 2-2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (phenylamino) propane-2,1-diyl) bis (2- Methyl acrylate), 2-2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (o Somethylene) bis (oxy) bis (3- (phenylamino) propane-2,1-diyl) diacrylate, 2- (3-(((1- (acryloyloxy) -3- (phenylamino) propan-2-yloxy ) Carbonylamino) methyl) benzylcarbamoyloxy) -3- (phenylamino) propyl methacrylate, 2,2 '-(1,3phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (Phenylthio) propane-2,1-diyl) bis (2-methyl acrylate), 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) Bis (3- (phenylthio) propane-2,1-diyl) diacrylate, 2- (3-(((1- ( Acryloxy) -3- (phenylthio) propan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) -3- (phenylthio) propyl methacrylate, 2,2 '-(1,3-phenylenebis (methylene)) bis (Azandiyl) bis (oxomethylene) bis (oxy) bis (3- (benzyloxy) propane-2,1-diyl) bis (2-methylacrylate), 2,2 '-(1,3-phenylenebis (methylene) )) Bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (benzyloxy) propane-2,1-diyl) diacrylate, 2- (3-(((1- (acryloyloxy) -3- (Benzyloxy) propan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy)- 3- (benzyloxy) propyl methacrylate, 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (methacryloyloxy) propane- 2,1-diyl) dibenzoate, 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (acryloyloxy) propane-2,1 -Diyl) dibenzoate, 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (2-phenylacetoxy) propane-2,1 -Diyl) bis (2-methyl acrylate), 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) Bis (oxomethylene) bis (oxy) bis (3- (2-phenylacetoxy) propane-2,1-diyl) diacrylate, 2- (3-(((1- (acryloyloxy) -3- (2-phenyl) Acetoxy) propan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) -3- (2-phenylacetoxy) propyl methacrylate 2,2 '-(2,2'-(1,3-phenylene) bis (propane) -2.2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) bis (2-methacrylate), 2,2 '-(2,2'-( 1,3-phenylene) bis (propane-2.2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1 Diyl) diacrylate, 2- (2- (3- (2-((2- (acryloyloxy) ethoxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) ethyl methacrylate, 2, 2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (methylazanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1- Diyl) bis (2-methacrylate), 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (methylazanediyl) bis (oxomethylene) bis (Oxy) bis (ethane-2,1-diyl) diacrylate, 2-((2- (3- (2-(((2- (acryloyloxy) ethoxy) carbonyl) (methyl) a Mino) propan-2-yl) phenyl) propan-2-yl) (methyl) carbamoyloxy) ethyl methacrylate, 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2,2) -Diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) bis (2-methyl acrylate), 2,2 '-(2,2'-(1,3 -Phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) diacrylate, 2- (2- (3- (2 -((2- (acryloyloxy) ethoxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) propyl methacrylate, 2- (2- ( -(2-((1- (acryloyloxy) propan-2-yloxy) carbonylamino) propan-2-ylcarbamoyloxy) ethyl methacrylate, 4,4 '-(2,2'-(1,3-phenylene) bis (Propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (4,1-phenylene) bis (2-methyl acrylate), 4,4 '-(2,2'- (1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (4,1-phenylene) diacrylate, 4- (2- (3- (2-((4- (acryloyloxy) phenoxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) phenylmeta Relate, 4,4 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (butane-4) 1-diyl) bis (2-methacrylate), 4,4 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (Oxy) bis (butane-4,1-diyl) diacrylate, 4- (2- (3- (2-((4-acryloyloxy) butoxy) carbonylamino) propan-2-yl) phenyl) propane-2- Ylcarbamoyloxy) butyl methacrylate, 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) Bis (oxy) bis (3-phenoxypropane-2,1-diyl) bis (2-methacrylate), 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2,2- Diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3-phenoxypropane-2,1-diyl) diacrylate, 2- (2- (3- (2-((1- (acryloyloxy)) -3-Phenoxypropan-2-yloxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) -3-phenoxypropyl methacrylate, 2,2 '-(2,2'-(1, 3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (phenylamino) pro -2,1-diyl) bis (2-methacrylate), 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis ( Oxomethylene) bis (oxy) bis (3- (phenylamino) propane-2,1-diyl) diacrylate, 2- (2- (3- (2-((1- (acryloyloxy) -3- (phenylamino) ) Propan-2-yloxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) -3- (phenylamino) propyl methacrylate, 2,2 '-(2,2'-(1 , 3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (phenylthio) propane-2,1-di ) Bis (2-methyl acrylate), 2,2 ′-(2,2 ′-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis ( Oxy) bis (3- (phenylthio) propane-2,1-diyl) diacrylate, 2- (2- (3- (2-((1- (acryloyloxy) -3- (phenylthio) propan-2-yloxy) Carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) -3- (phenylthio) propyl methacrylate, 2-2 '-(2,2'-(1,3-phenylene) bis (propane) -2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (3-benzyloxy) propane-2,1-diyl) bis (2-methylacrylate) 2-2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl) bis (azanediyl) bis (oxomethylene) bis (3- (benzyloxy) propane-2,1 -Diyl) diacrylate, 2- (2- (3- (2-((1- (acryloyloxy) -3- (benzyloxy) propan-2-yloxy) carbonylamino) propan-2-yl) phenyl) propane- 2-ylcarbamoyloxy) -3- (benzyloxy) propyl methacrylate, 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) Bis (oxomethylene) bis (oxy) bis (3- (methacryloyloxy) propane-2,1-diyl) dibenzoate, 2,2 '-(2,2'-(1,3-pheny ) Bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (acryloyloxy) propane-2,1-diyl) dibenzoate, 2,2 ′-( 2,2 '-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (2-phenylacetoxy) propane-2 1-diyl) bis (2-methacrylate), 2,2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (Oxy) bis (3- (2-phenylacetoxy) propane-2,1-diyl) diacrylate, 2- (2- (3- (2-((1- (acryloyloxy) -3- (2- Eniruasetokishi) propan-2-yloxy) carbonyl amino) propan-2-yl) phenyl) propan-2 dolphins Le Bamo acetoxyphenyl) -3- (such as 2-phenyl-acetoxy) propyl methacrylate.

As the polymerization initiator used in the dental curable composition of the present invention, a polymerization initiator used in the industry can be selected and used, and among them, a polymerization initiator used for dental use is preferably used. . Hereinafter, specifically, among the polymerization initiators contained in the dental curable composition of the present invention, as the photopolymerization initiator, (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or thioxanthones Quaternary ammonium salts, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, α-aminoketone compounds, and the like. Further, the proportion thereof is preferably 0.5% by weight to 5% by weight with respect to the radical polymerizable monomer. If the concentration is lower than 0.5% by weight, the amount of unpolymerized radically polymerizable monomer increases, so that the mechanical strength decreases. Further, when the concentration is higher than 5% by weight, the degree of polymerization is lowered and the mechanical strength is lowered.

Specific examples of (bis) acylphosphine oxides used as photopolymerization initiators include, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6- Dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- ( 2,6-dimethylphenyl) phosphonate and the like. Examples of the bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, and the like (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide.

Specific examples of thioxanthones or quaternary ammonium salts of thioxanthones used as photoinitiators include, for example, thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3- (9-oxy -9H-thioxanthen-4-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (1-methyl-9-oxy-9H-thioxanthen-4-yloxy) -N , N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy- 3- (3,4-Dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N Trimethyl-1-propanaminium chloride, 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, 2-hydroxy -3- (1,3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride and the like.

Specific examples of the α-diketone used as the photopolymerization initiator include, for example, diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4, 4'-oxybenzyl, acenaphthenequinone, etc. are mentioned.

Specific examples of the coumarin compound used as the photopolymerization initiator include 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin, 3- Benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3- (p- Nitrobenzoyl) coumarin, 3- (p-nitrobenzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3 ′ -Carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3 Benzoylbenzo [f] coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo [f] coumarin, 7-Methoxy-3- (p-nitrobenzoyl) coumarin, 3- (p-nitrobenzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoyl-6-nitrocoumarin-3-benzoyl-7-diethylaminocoumarin , 7-dimethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-diethylamino) coumarin, 7-methoxy-3- ( 4-methoxybenzoyl) coumarin, 3- ( -Nitrobenzoyl) benzo [f] coumarin, 3- (4-ethoxycinnamoyl) -7-methoxycoumarin, 3- (4-dimethylaminocinnamoyl) coumarin, 3- (4-diphenylaminocinnamoyl) coumarin, 3 -[(3-Dimethylbenzothiazol-2-ylidene) acetyl] coumarin, 3-[(1-methylnaphtho [1,2-d] thiazol-2-ylidene) acetyl] coumarin, 3,3′-carbonylbis (6 -Methoxycoumarin), 3,3'-carbonylbis (7-acetoxycoumarin), 3,3'-carbonylbis (7-dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin 3- (2-Benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2-benzimidazoloyl)- 7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dioctylamino) coumarin, 3-acetyl-7- (dimethylamino) coumarin, 3,3'-carbonylbis (7-dibutylaminocoumarin) ), 3,3′-carbonyl-7-diethylaminocoumarin-7′-bis (butoxyethyl) aminocoumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2 , 3,6,7-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one, 10- (2-benzothiazoyl ) -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one Such compounds.

Among the coumarin compounds, 3,3′-carbonylbis (7-diethylaminocoumarin) and 3,3′-carbonylbis (7-dibutylaminocoumarin) are particularly preferable.

Specific examples of anthraquinones used as photopolymerization initiators include, for example, anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethyl. Anthraquinone, 1-hydroxyanthraquinone and the like can be mentioned.

Specific examples of benzoin alkyl ethers used as photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Specific examples of α-aminoketones used as photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

Among photopolymerization initiators, it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides and salts thereof, α-diketones, and coumarin compounds. As a result, a composition having excellent photocurability in the visible and near-ultraviolet regions and having sufficient photocurability can be obtained using any light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp.

Of the polymerization initiators contained in the dental curable composition of the present invention, an organic peroxide is preferably used as the chemical polymerization initiator. The organic peroxide used for said chemical polymerization initiator is not specifically limited, A well-known thing can be used. Typical organic peroxides include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, peroxydicarbonate, and the like.

Specific examples of the ketone peroxide used as the chemical polymerization initiator include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methyl cyclohexanone peroxide, and cyclohexanone peroxide.

Specific examples of hydroperoxides used as chemical polymerization initiators include, for example, 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydro Examples thereof include peroxide and 1,1,3,3-tetramethylbutyl hydroperoxide.

Specific examples of the diacyl peroxide used as the chemical polymerization initiator include, for example, acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2 , 4-dichlorobenzoyl peroxide, lauroyl peroxide, and the like.

Specific examples of dialkyl peroxides used as chemical polymerization initiators include, for example, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di- (T-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne .

Specific examples of peroxyketals used as chemical polymerization initiators include, for example, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butyl). Peroxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane and 4,4-bis (t-butylperoxy) valeric acid-n -Butyl ester and the like.

Specific examples of peroxyesters used as chemical polymerization initiators include, for example, α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2 , 4-Trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate , Di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-tilperoxyacetate, t-butylperoxybenzoate and t-butylperoxymale Rick acid etc. are mentioned.

Specific examples of peroxydicarbonates used as chemical polymerization initiators include, for example, di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-tert-butylcyclohexyl) peroxide. Examples thereof include oxydicarbonate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate.

Among organic peroxides, diacyl peroxide is preferably used from the overall balance of safety, storage stability and radical generating ability, and benzoyl peroxide is particularly preferably used.

Specific examples of the polymerization accelerator used in the dental curable composition of the present invention include, for example, amines, sulfinic acid and salts thereof, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, Examples include vanadium compounds, halogen compounds, aldehydes, and thiol compounds.

Amines used as polymerization accelerators are classified into aliphatic amines and aromatic amines. Specific examples of aliphatic amines include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary fats such as diisopropylamine, dibutylamine and N-methyldiethanolamine. N-methylethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, tri Ethanolamine monomethacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine, etc. Such as tertiary aliphatic amines. Among these, tertiary aliphatic amines are preferable from the viewpoint of curability and storage stability of the composition, and among these, N-methyldiethanolamine and triethanolamine are more preferably used.

Specific examples of aromatic amines include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, N, N -Bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-tert-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl) ) -3,5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-to Idin, N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethyl Aminobenzoic acid methyl ester, N, N-dimethylaminobenzoic acid-n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid-2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone Examples include butyl 4-dimethylaminobenzoate and the like. Among these, N, N-di (2-hydroxyethyl) -p-toluidine, 4-N, N-dimethylaminobenzoic acid ethyl ester, N, N-, from the viewpoint of imparting excellent curability to the composition. Examples thereof include dimethylaminobenzoic acid-n-butoxyethyl ester and 4-N, N-dimethylaminobenzophenone.

Specific examples of sulfinic acid and salts thereof used as polymerization accelerators include, for example, p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, p-toluene. Calcium sulfinate, benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfinate 2,4,6-trimethylbenzenesulfinate potassium, 2,4,6-trimethylbenzenesulfinate lithium, 2,4,6-trimethylbenzenesulfinate calcium, 2,4,6-triethyl Benzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate Calcium, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfin Lithium oxalate, calcium 2,4,6-triisopropylbenzenesulfinate, etc., especially sodium benzenesulfinate, sodium p-toluenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate Masui.

Specific examples of the borate compound used as a polymerization accelerator include a borate compound having one aryl group in one molecule. For example, trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p -Fluorophenyl) boron, trialkyl (3,5-bistrifluoromethyl) phenylboron, trialkyl [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl ) Phenyl] boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl (p- Butyloxyphenyl) boron, trialkyl (m-butyloxyphenyl) boron , Trialkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (wherein the alkyl group is at least one selected from the group consisting of n-butyl, n-octyl, n-dodecyl, etc.) Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethyl A quinolinium salt, a butyl quinolinium salt, etc. are mentioned.

Further, specific examples of the borate compound having two aryl groups in one molecule include, for example, dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, dialkyldi (3,5 -Bistrifluoromethyl) phenyl boron, dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron , Dialkyldi (m-nitrophenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi ( p-octyloxyph Nyl) boron and dialkyldi (m-octyloxyphenyl) boron (wherein the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group and n-dodecyl group), lithium salt Salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt and butylquinolinium Examples include salt.

Furthermore, specific examples of the borate compound having three aryl groups in one molecule include, for example, monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron. , Monoalkyltri (3,5-bistrifluoromethyl) phenyl boron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] Boron, monoalkyltri (p-nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p-butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri ( p-Butyloxyphenyl) boron, monoalkyltri (m-butyloxypheny) ) Boron, monoalkyltri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (wherein the alkyl group is selected from n-butyl group, n-octyl group, n-dodecyl group, etc.) Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethyl A quinolinium salt, a butyl quinolinium salt, etc. are mentioned.

Furthermore, specific examples of borate compounds having four aryl groups in one molecule include, for example, tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5- Bistrifluoromethyl) phenyl boron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron , Tetrakis (m-nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis ( p-octyloxyphenyl) boron, tetrakis m-octyloxyphenyl) boron, (p-fluorophenyl) triphenylboron, (3,5-bistrifluoromethyl) phenyltriphenylboron, (p-nitrophenyl) triphenylboron, (m-butyloxyphenyl) tri Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutyl of phenylboron, (p-butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron and (p-octyloxyphenyl) triphenylboron Examples include ammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, and butylquinolinium salt.

Among these aryl borate compounds, it is more preferable to use a borate compound having 3 or 4 aryl groups in one molecule from the viewpoint of storage stability. These aryl borate compounds may be used alone or in combination of two or more.

Specific examples of the babituric acid derivative used as a polymerization accelerator include, for example, barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5 -Butyl barbituric acid, 5-ethyl barbituric acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid 1,3-dimethyl-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, , 3-Dimethyl-5-cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1- Chlohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methyl Barbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, and These salts (especially alkali metals or alkaline earth metals are preferred) Gerare, the salts of these barbituric acids include sodium 5-butyl barbituric acid, etc. 1,3,5-trimethyl barbituric acid sodium and 1-cyclohexyl-5-ethyl barbituric sodium tool acid.

Specific examples of particularly suitable barbituric acid derivatives include, for example, 5-butyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5 -Phenyl barbituric acid and sodium salts of these barbituric acids.

Specific examples of the triazine compound used as a polymerization accelerator include, for example, 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trick (Romethyl) -s-triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s- Triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -Styryl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (O-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-butoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-trimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-biphenylyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- [2- {N, N-bis (2-hydroxyethyl) amino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- {N-hydroxyethyl-N-ethylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-methylamino} ethoxy ] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, and the like.

Among the triazine compounds exemplified above, 2,4,6-tris (trichloromethyl) -s-triazine is particularly preferable in terms of polymerization activity, and 2-phenyl-4 in terms of storage stability. , 6-Bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (4-biphenylyl) -4,6-bis ( Trichloromethyl) -s-triazine. You may use the said triazine compound 1 type or in mixture of 2 or more types.

Specific examples of the copper compound used as the polymerization accelerator include acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like.

Specific examples of tin compounds used as polymerization accelerators include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. Can be mentioned. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

The vanadium compound used as a polymerization accelerator is preferably an IV and / or V vanadium compound. Specific examples of IV and / or V valent vanadium compounds include, for example, divanadium tetroxide (IV), vanadium acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), Oxobis (1-phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammon metavanadate (V), etc. Is mentioned.

Specific examples of halogen compounds used as polymerization accelerators include, for example, dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide. Etc.

Specific examples of aldehydes used as polymerization accelerators include terephthalaldehyde and benzaldehyde derivatives. Examples of the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like. Among these, pn-octyloxybenzaldehyde is preferably used from the viewpoint of curability.

Specific examples of the thiol compound used as the polymerization accelerator include 3-mercaptopyrrolopyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

The preparation method and physical properties of the dental curable composition according to the present invention will be described in detail, but the present invention is not limited to these descriptions. Abbreviations used in the examples are shown below.

<Inorganic fine particles with a median diameter of less than 0.5 μm>
OX-50: fine particle silica (manufactured by Nippon Aerosil Co., Ltd.) median diameter 40 nm
<Inorganic fine particles with a median diameter exceeding 0.5 μm>
Fuselex-X: fused silica (manufactured by Tatsumori) median diameter 3 μm
<Silane coupling agent>
KBM-503: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone)
8-MOTMSi: 8-methacryloyloxyoctyltrimethoxysilane <radical polymerizable monomer>
UDMA: Di (methacryloxyethyl) trimethyl hexamethylene diurethane 2G: Diethylene glycol dimethacrylate

Examples 1-6
According to the formulation described in Table 1, the dental curable composition of the present invention was prepared. That is, OX-50, KBM-503, and dehydrated ethanol were weighed into a 500 mL beaker and sufficiently stirred with a magnetic stirrer, and then a 150 W-28 KHz ultrasonic wave was irradiated for 10 minutes to obtain a uniform suspension. This suspension was transferred to a 500 mL separable four-necked flask equipped with a stirrer, a Dimroth condenser and a thermometer, and an aqueous phosphoric acid solution was added while stirring. Thereafter, the mixture was refluxed for 5 hours in a boiling water bath. After completion of the reflux, the temperature was returned to room temperature, transferred to a 500 mL plastic container (made of polypropylene), and an electrolyte (crystals on a sieve having a mesh size of 250 μm) and distilled water were added. Thereafter, the mixture was shaken with a MIX ROTOR VMR-5R manufactured by ASONE for 12 hours at a rotation speed of 30 rpm. After 12 hours, the electrolyte was removed with a filter cloth having a mesh size of 50 μm. Next, the monomer liquid was added to the fine particle inorganic filler ethanol suspension of the present invention present in the filtrate under light shielding, and after sufficient stirring, ethanol and water were distilled off with an evaporator. Thereafter, ethanol and water were completely removed under a condition of 1000 rpm-5 KPa-15 min with a Planetary Vacuum mixer ARV-310 manufactured by Thinky, and the dental curable composition of the present invention was obtained. A cured product was prepared from the dental curable composition thus obtained according to ISO 4049, and bending strength was determined using an Instron universal testing machine (Instron 5567, manufactured by Instron). In addition, photopolymerization was performed by irradiating with light for 30 seconds in Matsupuri Griplight II. Moreover, the dynamic viscoelasticity of the prepared dental curable composition was measured using RHEOPLUS Physica MCR-301 (Anton paar rheometer), measurement conditions: measurement jig: PP20 [d = 1 mm], swing angle gamma: 5% , Frequency f = 0.1. . . It calculated | required at 100 Hz and the measurement temperature of 25 degreeC.
Examples 7-18
According to the formulation described in Table 2 and Table 3, the dental curable composition of the present invention was prepared and evaluated in the same procedure as in Examples 1-6. As described in the table, the silane coupling surface treatment was also performed in the presence of inorganic fine particles Fuselex-X having a median particle size of 0.5 μm.
Comparative Example Before carrying out the comparative example, a silane coupling agent having a longer alkylene chain than KBM-503 was synthesized with reference to the example of JP-A-2-200689.
Synthesis of 8-methacryloyloxyoctyltrimethoxysilane (8-MOTMSi) 30 g of 7 -octenyl methacrylate and hydroquinone in a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser 0.1 g of monomethyl ether and 0.4 mL of a 1 wt% tetrahydrofuran solution of chloroplatinic acid hexahydrate were added and heated to 40 ° C. To this, 25 g of trichlorosilane was slowly added dropwise with stirring in a nitrogen atmosphere. The dropping speed was adjusted so that the temperature of the reaction mixture did not exceed 45 ° C. After completion of the dropwise addition, the mixture was heated to 60 ° C., and the reaction was continued for 6 hours for aging. As a result, 8-methacryloyloxyoctyltrichlorosilane was synthesized. Next, 100 mL of methanol and 30 g of triethylamine were placed in a four-necked flask (1 L volume) equipped with a stirring blade, a thermometer, a dropping funnel and a condenser, and cooled to 0 ° C. To this mixture, 8-methacryloyloxyoctyltrichlorosilane synthesized earlier was slowly dropped from a dropping funnel. After completion of dropping, the mixture was further stirred at room temperature for 12 hours. The solvent of this reaction mixture was distilled off under reduced pressure, a large amount of diethyl ether was added to the residue, the insoluble material was filtered off, and then the ether was distilled off under reduced pressure to obtain 40 g of crude 8-methacryloyloxyoctyltrimethoxysilane. This crude product was separated and purified by column chromatography. In addition, 95 vol% benzene and 5 vol% acetonitrile were used as developing solvents. WAKOGEL-LP60 was used for the silica gel. The yield was about 50%. As a result of analyzing the purified product by gas chromatograph mass spectrometry (GCMS-QP2010 Plus Shimadzu), the purity was 95%. Further, as a result of FT-IR analysis (FT / IR-6300 made by JASCO), disappearance of silane absorption at 2190 cm ⁻¹ was confirmed.
Comparative Examples 1-2
A dental curable composition was prepared according to the formulation described in Table 4. That is, weigh OX-50, KBM-503 or synthesized 8-MOTMSi as a silane coupling agent, and dehydrated ethanol in a 500 mL beaker and thoroughly stir with a magnetic stirrer, then irradiate with 150 W-28 KHz for 10 minutes. And a uniform suspension was obtained. This suspension was transferred to a 500 mL separable four-necked flask equipped with a stirrer, a Dimroth condenser and a thermometer, and an aqueous phosphoric acid solution was added while stirring. Thereafter, the mixture was refluxed for 5 hours in a boiling water bath. After completion of the reflux, the mixture was returned to room temperature, transferred to a 500 mL plastic container (made of polypropylene), and shaken with a MIXROTORVMR-5R manufactured by ASONE for 12 hours at a rotation speed of 30 rpm. After 12 hours, the mixture was filtered with a filter cloth having an opening of 50 μm. Next, the monomer solution was added to the ethanol suspension of the silane coupling surface-treated OX-50, which was the filtrate, under a light-shielding condition, and after sufficient stirring, ethanol and water were distilled off with an evaporator. Thereafter, ethanol and water were completely removed under a condition of 1000 rpm-5 KPa-15 min using a Planetary Vacuum mixer ARV-310 manufactured by Thinky Co. to obtain a dental curable composition. A cured product was prepared from the dental curable composition thus obtained according to ISO 4049, and bending strength was determined using an Instron universal testing machine (Instron 5567, manufactured by Instron). In addition, photopolymerization was performed by irradiating with light for 30 seconds in Matsupuri Griplight II. Moreover, the dynamic viscoelasticity of the prepared dental curable composition was measured using RHEOPLUS Physica MCR-301 (Anton paar rheometer), measurement conditions: measurement jig: PP20 [d = 1 mm], swing angle gamma: 5% , Frequency f = 0.1. . . It calculated | required at 100 Hz and the measurement temperature of 25 degreeC.
Comparative Examples 3-6
According to the formulation described in Table 5, a dental curable composition was prepared and evaluated in the same procedure as in Comparative Examples 1 and 2. As described in the table, the silane coupling surface treatment was also performed in the presence of inorganic fine particles Fuselex-X having a median particle size of 0.5 μm.

Evaluation Test Results Table 6 shows the bending test results. In addition, FIGS. 1-1 to 1-3 show the results of complex viscosity measurement. As can be seen from Table 6, the dental curable composition containing the fine particle inorganic filler produced by the production method of the present invention [Examples 1 to 6 (OX-50 filling rate 40 wt%), Examples 7 to 12 ( OX-50 filling rate 23.1 wt%, Fuselex-X filling rate 61.7 wt%) and Examples 13 to 18 (OX-50 filling rate 24.5 wt%, Fuselex-X filling rate 65.5 wt%)] Compared to the dental curable compositions of Comparative Example 2 and Comparative Example 5 using the technology, high bending strength was exhibited. In Comparative Examples 1, 3, 4, and 6, even the paste could not be prepared. This is presumably because the dispersibility of the filler in the monomer liquid is poor. In addition, as can be seen from FIG. 1-1, the dental curable compositions of Examples 1 to 6 were significantly reduced in complex viscosity as compared with the dental curable composition of Comparative Example 2. In the dental curable composition of Comparative Example 2, although the paste was prepared, it was already in an excessively filled state and exhibited a complex viscosity that was difficult to use clinically. This is because the balance between the amount of the monomer liquid and the total surface area of the filler is broken, and it is considered that the brittleness of the cured body is increased and weak bending strength is exhibited. Further, the dental curable compositions of Examples 13 to 18 were maintained in good operability (appropriate complex viscosity) while maintaining the bending strength of Examples 7 to 12 (filling rate of inorganic filler 85 wt%). A strength increase of 13% was achieved compared to the curable composition. In Comparative Examples 4 and 6, even paste preparation was impossible. As can be seen from FIG. 1-3, the dental curable compositions of Examples 13 to 18 exhibited a complex viscosity that was clinically sufficiently usable even though the filling rate of the inorganic filler was 90 wt%. . That is, by using the technique of the present invention, it is possible to achieve both a high filling rate and strength while maintaining a clinically usable complex viscosity that could not be achieved by the conventional technique.

Industrial applicability

The present invention makes it possible to highly fill a dental curable composition with a fine particle inorganic filler having a median diameter of less than 0.5 μm without depending on the molecular structure of a silane coupling agent and a radical polymerizable monomer. Is. By using the technique of the present invention, it is possible to provide a dental curable composition that provides high mechanical strength without using a novel silane coupling agent, radical polymerizable monomer, or the like. In addition, it has become possible to develop a dental curable composition having a high content of fine particle inorganic filler and excellent fluidity. Therefore, it can be said that the industrial applicability of the present invention is great.

Claims (7)

(1) A fine particle inorganic filler comprising a step of surface-treating inorganic fine particles with a silane coupling agent, and (2) a step of adding an electrolyte to the suspension system containing the inorganic fine particles obtained by (1) and treating the suspension. Manufacturing method. 2. The method for producing a fine inorganic filler according to claim 1, wherein the electrolyte is a salt of an inorganic acid or a salt of an organic acid. The method for producing a fine particle inorganic filler according to claim 1, wherein the solvent used in the suspension system is a hydrous organic solvent. The method for producing a fine particle inorganic filler according to claim 1, wherein the inorganic fine particles are any one of silicon oxide, aluminum oxide, and zirconium oxide. A dental curable composition comprising a fine particle inorganic filler, a radical polymerizable monomer, a polymerization initiator and / or a polymerization accelerator obtained by the production method according to claim 1. The dental curable composition according to claim 5, comprising a fine particle inorganic filler obtained by the production method according to any one of claims 1 to 4 using the inorganic fine particles having a median particle size of less than 0.5 µm. . 5. The fine particle inorganic filler obtained by the production method according to claim 1, wherein the inorganic fine particle having a median particle diameter of less than 0.5 μm and the inorganic fine particle having a median particle diameter of more than 0.5 μm are used simultaneously or separately. The dental curable composition according to claim 5.