JP2005170813A - Dental curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chemical polymerization type dental repairing material which has excellent flowability, can easily be spread even over all the corners of deep cavities, gives cured products having excellent mechanical strengths such as compression strength and flexural strength, and has excellent miscibility and kneadability, when used. <P>SOLUTION: This dental curable composition comprising (A) a polymerizable monomer, (B) inorganic fillers comprising 40 to 90 mass % of amorphous inorganic particles having an average particle diameter of 1 to 6μm, 10 to 60 mass % of spherical inorganic particles having an average particle diameter of 0.05 to 1μm, and 0 to 10 mass % of inorganic particles having particle diameters of <0.05μm, and (C) a chemical polymerization initiator comprising a tertiary amine and an organic peroxide, is divided and packaged into two pastes comprising a paste containing the tertiary amine and a paste containing the organic peroxide in a viscosity ratio of 1:3 to 3:1. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable composition suitable as a dental restorative material. More specifically, the present invention relates to a dental curable composition excellent in both fluidity and mechanical strength of a cured product.

  Dental restoration material is a composite material mainly composed of a polymerizable monomer, filler, and polymerization initiator, and can restore the tooth because it can give the same color tone as natural tooth color and is easy to operate. In recent years, it has been widely used as a material for this purpose. The use site is wide, such as the restoration of the entire crown from the shallow cavity and the construction of an abutment that fills the gap of the root after extraction.

  Such dental restorative materials are required to have high mechanical strength that can withstand high occlusal pressure due to mastication and the like, and in order to prevent dropping from the restoration site, etc., the thermal expansion coefficient is as high as possible. Physical and engineering properties are required, such as being close to 0 and polymerization shrinkage during polymerization and curing being as small as possible.

  For the purpose of obtaining such good physical and engineering properties, the dental restorative material is blended with an inorganic filler. Generally, the greater the blending ratio of the inorganic filler, the better the mechanical strength. Thermal expansion coefficient and polymerization shrinkage are also small.

  Furthermore, as a performance required for a dental restorative material, in the case of repairing a shallow cavity and the entire crown near the surface layer of a tooth, an aesthetic property close to that of a natural tooth is required. On the other hand, when repairing deep cavities such as gaps in the root of the tooth after extraction and narrow caries, fluidity that easily spreads to the site is required.

  The part that requires aesthetics is a part that can be visually identified from the outside. Usually, in repairing such a site, a so-called photopolymerization initiator of a type that initiates polymerization by light irradiation has been used as a polymerization initiator. Since a dental restorative material using such a photopolymerization initiator does not start polymerization unless it is irradiated with light, it can be manufactured and stored even in the state of one paste in which all the components are mixed, under light shielding. Is possible.

  On the other hand, when repairing deep cavities, the irradiated light does not reach the site sufficiently, so polymerization using a photopolymerization initiator becomes insufficient, and various physical properties such as mechanical strength May be inferior. Therefore, so-called chemical polymerization initiators are mainly used, in which the polymerization initiator is composed of two components and generates a polymerization initiating species when these components are brought into contact (even at room temperature). Therefore, the dental restorative material used for this purpose is manufactured and stored in a state of being divided into two parts (usually two pastes), and is generally used by mixing and kneading immediately before use. .

  Therefore, a dental restorative material blended with such a chemical polymerization initiator is required to have fluidity that reaches every corner of a deep cavity and to be easily kneaded during use. This is because in the case of a material that is difficult to knead, there is a possibility that mechanical strength is lowered due to mixing of bubbles or insufficient kneading during mixing and kneading.

  However, increasing the blending ratio of the inorganic filler to obtain the good physical and engineering properties as described above will increase the viscosity of the resulting dental restorative material (paste) geometrically, resulting in good fluidity. There is a problem that it becomes difficult to obtain.

  As a chemically-polymerized dental restorative material having excellent physical and mechanical properties such as mechanical strength and excellent fluidity that easily spreads to a deep cavity after extraction, particles 20 to 20 having an average particle diameter of 1 to 100 μm A combination of 95% by mass and 80-5% by mass of spherical particles having an average particle diameter of 0.1-1 μm has been proposed (for example, Patent Document 1). In the technique described in Patent Document 1, the shape of particles having an average particle diameter of 1 to 100 μm is not particularly limited. However, in the example described in Patent Document 1, such particles have an average value. Spherical particles having a particle diameter of 5 μm or 18 μm, or amorphous particles having an average particle diameter of 9 μm are used. These dental restorative materials are excellent in fluidity, and the mechanical strength of the cured body exceeds 300 MPa in compressive strength. However, the bending strength is about 90 to 120 MPa, and it is still There was room for improvement in this regard.

  On the other hand, in dental restoration materials using photopolymerization initiators, various combinations of inorganic fillers to be blended have been studied in order to achieve both good physical properties and operability (for example, And Patent Documents 2 to 4). Such a photopolymerization type dental restoration material has a bending strength of a hardened body exceeding 200 MPa, and is excellent in mechanical strength. However, these photopolymerization-type dental restorative materials are used for sites that can be irradiated with light as described above, and have excellent operability (having an appropriate viscosity), but their fluidity is In order to obtain a dental restorative material that needs to contain a chemical polymerization initiator, there was a great room for improvement. Further, since such a photopolymerization type dental restorative material is provided as one paste, there is no problem of mixing and kneading at the time of use, and therefore provides a solution to that point. Not a thing.

JP-A-6-107516 JP 2000-26226 A JP 2000-53519 A International Publication No. 02/005752 Pamphlet

  Therefore, it has excellent fluidity, easily spreads in every corner even in deep cavities, and its cured body has excellent mechanical strength such as compressive strength and bending strength. Furthermore, it is mixed and kneaded during use. There has been a demand for a chemical polymerization type dental restorative material that is also excellent in properties.

  The present inventors have intensively studied to solve the above problems. Based on the technique disclosed in Japanese Patent Laid-Open No. Hei 6-107516, various types of fillers and other conditions for obtaining a hardened body with higher strength were studied. As a result, as the average particle diameter of 1 μm or more, the average particle diameter is in the range of 1 to 6 μm, and by adopting an irregular shape as the particles, the bending strength is particularly good. I found it. As a result of further studies, the present invention has been completed.

That is, a dental curable composition comprising (A) a polymerizable monomer, (B) an inorganic filler, and (C) a chemical polymerization initiator composed of a tertiary amine and an organic peroxide,
The inorganic filler (B-1) has an average particle size of 40 to 90% by mass with an average particle size of 1 to 6 μm, and (B-2) an average particle size of 0.05 to 1 μm. 10 to 60% by mass of spherical inorganic particles and (B-3) 0 to 10% by mass of inorganic particles having a particle size of less than 0.05 μm,
The dental curable composition is divided into two pastes, a paste (I) containing a tertiary amine and a paste (II) containing an organic peroxide, and the paste (I) And paste (II) is a dental curable composition characterized in that the viscosity ratio is in the range of 1: 3 to 3: 1.

  The dental curable composition obtained by the combination of the fillers according to the present invention has excellent fluidity and physical and engineering properties such as mechanical strength of the cured product, which have been difficult to achieve in the past. .

  The dental curable composition of the present invention comprises (A) a polymerizable monomer, (B) an inorganic filler, and (C) a chemical polymerization initiator composed of a tertiary amine and an organic peroxide as essential components. Include as.

  The (A) polymerizable monomer is not particularly limited, and for example, a known monomer used as a dental restoration material can be used. Examples of the polymerizable monomer that can be suitably used include polymerizable polymerizable monomers having an acryloyl group and / or a methacryloyl group. Specific examples of such a polymerizable monomer include the following [A-1 ]-[A-4] each monomer shown is mentioned.

[A-1] Monofunctional vinyl monomer Methacrylate such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and acrylates corresponding to these methacrylates; or acrylic acid, methacrylic acid, p-methacryloyloxybenzoic acid, N-2-hydroxy-3-methacryloyloxypropyl-N-phenylglycine, 4-methacryloyloxyethyl trimellitic acid and its anhydride, 6-methacryloyloxyhexamethylenemalonic acid, 10-methacryloyl Oxydecamethylenemalonic acid, 2-methacryloyloxyethyl dihydrogen phosphate, 10-methacryloyloxydecame Chilene hydrogen phosphate, 2-hydroxyethyl hydrogen phenyl phosphonate, etc.

[A-2] Bifunctional vinyl monomer [A-2-1] Aromatic compound type 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy)- 2-hydroxypropoxyphenyl] propane, 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxy) Phenyl) propane), 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) ) Propane, 2 (4-methacryloyloxydiethoxy) Nyl) -2 (4-methacryloyloxydiethoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxyditriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2 Corresponding to-(4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane; and these methacrylates Acrylate; methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, or polymers corresponding to these methacrylates Diaducts obtained from addition of a vinyl monomer having an —OH group such as acrylate and a diisocyanate compound having an aromatic group such as diisocyanate methylbenzene or 4,4′-diphenylmethane diisocyanate.

[A-2-2] Aliphatic compound type ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol Dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate; and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl Vinyl monomers having —OH groups such as methacrylates such as methacrylates or acrylates corresponding to these methacrylates And diadducts obtained from the addition of diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate); acrylic anhydride, methacrylic anhydride, 1,2 -Bis (3-methacryloyloxy-2-hydroxypropoxy) ethyl, di (2-methacryloyloxypropyl) phosphate and the like.

[A-3] Trifunctional vinyl monomer Trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, methacrylates such as pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, acrylates corresponding to these methacrylates, and the like.

[A-4] Tetrafunctional vinyl monomer Pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexyl isocyanate), 4 Diadducts obtained from the addition of diisocyanate compounds such as 1,4-diphenylmethane diisocyanate and tolylene-2,4-diisocyanate and glycidol dimethacrylate.

  In addition, it is also possible to suitably employ a precious metal adhesive monomer described in JP-A-10-1409, JP-A-10-1473, JP-A-8-113763, or the like.

  These polymerizable monomers may be used alone, but in order to improve both the operability and the mechanical strength of the cured product, an aliphatic polyfunctional (bifunctional or higher) monomer and It is preferable to use a mixture of aromatic polyfunctional monomers. Usually, aliphatic monomers tend to be pastes with lower viscosity and better operability, while aromatic monomers tend to have better mechanical strength of cured products Is strong. Generally, an aliphatic polyfunctional monomer and an aromatic polyfunctional monomer are mixed so that the viscosity of the polymerizable monomer (mixture thereof) is in the range of 0.1 to 50 poise. Are preferably used. More preferably, it is the range of 1-10 poise.

  In addition, although the reason is unknown, when the dental curable composition of the present invention is used as a restoration material, an adhesive used for bonding with an adherend is a dual cure type (photo-chemical polymerization type). It is more preferable to employ those having an OH group and / or an NH group as the polymerizable monomer in that the adhesiveness when the adhesive is irradiated with light is improved.

  The inorganic filler used in the dental curable composition of the present invention includes (B-1) irregular inorganic particles having an average particle diameter of 1 μm or more and 6 μm or less, and (B-2) an average particle diameter of 0.05 μm. Above, spherical inorganic particles of 1 μm or less, and (B-3) compounded as necessary, the inorganic particles having a particle size of less than 0.05 μm, and when the total of inorganic fillers is 100% by mass, These are each blended in the range of (B-1) 40 to 90% by mass, (B-2) 10 to 60% by mass, and (B-3) 0 to 10% by mass. Here, the average particle diameter is a particle diameter in which particles having a particle diameter of 0.05 μm or more are calculated and the value of the integrated distribution is 50% in the particle diameter-volume integrated distribution.

  The material (component) of these inorganic particles is not particularly limited, and a material similar to a known inorganic filler can be used as a compounding component of the dental curable composition. Specifically, silica glass, borosilicate glass, soda glass, aluminosilicate glass, fluoroaluminosilicate glass, glass containing heavy metals (for example, barium, strontium, zirconium); crystallized glass in which crystals are deposited on these glasses , Glass ceramics such as crystallized glass on which crystals of diopside, leucite, etc. are precipitated; composite inorganic oxides such as silica-zirconia, silica-titania, silica-alumina; or group I metals in these composite oxides An oxide added with an oxide; a metal inorganic oxide such as silica, alumina, titania, zirconia; and the like can be used. A composite oxide containing silica and a group IV metal oxide as main constituents is suitable because the obtained cured product is easily imparted with transparency close to a tooth and less harmful to the living body. . More preferably, the cured product obtained can be imparted with X-ray contrast properties, and further, a cured product with higher wear resistance can be obtained, and the refractive index is comparable to that of the polymerizable monomer. The curable composition can be imparted with high visible light transparency, and this increases the curing depth when performing dual cure (photo-chemical) polymerization as described later, so silica-zirconia is mainly used. A composite oxide as a constituent component is particularly preferably used.

  The (B-1) amorphous inorganic particles in the present invention have an average particle size of 1 μm or more and 6 μm or less, and preferably have an average particle size of 3 μm or more and 5 μm or less. When the shape of the particles is spherical, or when the average particle size is larger than 6 μm, the fluidity is excellent, but the bending strength is inferior. If the average particle size is less than 1 μm, it becomes difficult to achieve both physical properties such as fluidity and mechanical strength of the cured product.

  The above (B-1) amorphous inorganic particles preferably have a maximum particle size of 40 μm or less (not including particles having a particle size of more than 40 μm) because stable mechanical and physical strength can be obtained. Furthermore, in order to achieve a high inorganic filler content, it is more preferable to employ (B-1) an inorganic filler having a variation coefficient of amorphous inorganic particles of 0.70 or more. The variation coefficient is a variation coefficient defined by JIS-Z8101-1 [standard deviation (σ) / average value]. The variation coefficient is an index representing the spread of the particle size distribution, and the larger the value, the wider the particle size distribution.

  Further, (B-1) the irregular shaped inorganic particles are not necessarily manufactured and obtained as single particles as long as the average particle size is in the above range, and the average particle size and the material (component) are different. It may be obtained by mixing two or more inorganic particles.

  The (B-2) spherical inorganic particles in the present invention have an average particle size of 0.05 μm or more and 1 μm or less, preferably an average particle size of 0.1 μm or more and 0.5 μm or less. When the shape of the particles is not spherical, the fluidity is inferior.

  The term “spherical” as used herein means that the particles observed with a scanning electron microscope (hereinafter abbreviated as “SEM”) are rounded, and the average homogeneity obtained by dividing the particle diameter in the direction perpendicular to the maximum diameter by the maximum diameter. Is 0.6 or more.

  In addition, the (B-2) spherical inorganic particles are not necessarily manufactured and obtained as single particles as long as the average particle size is within the above range, and the average particle size and the material (component) are not necessarily obtained. It may be obtained by mixing two or more different inorganic particles.

  The dental curable composition of the present invention contains 40 to 90% by mass of (B-1) amorphous inorganic particles in the total inorganic filler to be blended, and (B-2) spherical inorganic particles. It is necessary to mix | blend in the ratio of 10-60 mass% in the total inorganic filler. By setting it within this range, both excellent fluidity and mechanical properties can be achieved.

  Further, in the dental curable composition of the present invention, in addition to the above-mentioned (B-1) amorphous inorganic particles and (B-2) spherical inorganic particles, (B-3) inorganic particles having a particle diameter of less than 0.05 μm. If the particles are 10% by mass or less in the inorganic filler, they may be present. The particle having such a particle size has almost no influence on the fluidity and particle size, and therefore the particle may be indefinite or spherical.

  Since particles having such a particle size act as a thixotropic adjuster, it is possible to finely adjust fluidity and the like by blending as necessary.

  In the present invention, the (B-1) amorphous inorganic particles, (B-2) spherical inorganic particles, and (B-3) inorganic particles have a hydrophobic surface for the purpose of improving dispersibility in the polymerizable monomer. It is preferable to use one that has been processed. Such a hydrophobizing treatment is not particularly limited, and a known method is employed without limitation.

  Illustrative examples of typical hydrophobizing treatment methods include silane coupling agents such as γ-methacryloyloxyalkyltrimethoxysilane, γ-methyltrimethoxysilane, γ-methacryloyloxyalkylmonomethyldimethoxysilane, hexamethyldithiophene as hydrophobizing agents. Treatment with an organosilicon compound such as silazane, monomethyltrichlorosilane, dimethyldichlorosilane, a titanate coupling agent, an aluminate coupling agent, a method using a zirco-aluminate coupling agent, There is a method of graft polymerization of a monomer. Such a treatment may be performed after mixing (B-1) amorphous inorganic particles, (B-2) spherical inorganic particles, and (B-3) inorganic particles. May be.

  The dental curable composition of the present invention contains (C) a chemical polymerization initiator composed of a tertiary amine and an organic peroxide. It is known that by combining a tertiary amine as a polymerization accelerator with an organic peroxide, (radical) polymerization is initiated at a temperature much lower than the decomposition temperature of the organic peroxide alone. As long as it functions as such a polymerization initiator, any known tertiary amine and organic peroxide may be used in combination.

  Such tertiary amines are generally classified roughly into an aromatic tertiary amine having an aromatic group bonded to a nitrogen atom and an aliphatic tertiary amine having only an aliphatic group bonded thereto. Specific examples of these tertiary amines are as follows.

[C-1] Aromatic tertiary amine N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-dihydroxyethyl-p- Toluidine, toluidine-type aromatic tertiary amines such as N, N-dimethyl-3,5-xylidine; N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, Aniline aromatic tertiary amines such as N, N-dibenzylaniline, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, N, N-dihydroxyethylaniline; p -Dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid Aromatic tertiary amines having a carbonyl group bonded to an aromatic ring such as benzoic acid amyl ester and N, N-dimethylanthranic acid methyl ester; p-dimethylaminophenethyl alcohol, p-dimethylaminostilbene, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-α-naphthylamine and the like.

[C-2] Aliphatic tertiary amines tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N- Examples thereof include dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol and the like.

  The tertiary amine compounds may be used alone or in combination of two or more.

  Among these, it is particularly preferable to use toluidine-based aromatic tertiary amines from the viewpoint of curability (polymerization activity) when combined with an organic peroxide.

  Moreover, as an organic peroxide, if it is a thing which can be used for dentistry, a well-known organic peroxide can be used without a restriction | limiting in particular. Typical organic peroxides include hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide, dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide, acetyl peroxide and lauroyl peroxide. And diacyl peroxides such as benzoyl peroxide. These may be used alone or in admixture of two or more.

  Among these organic peroxides, diacyl peroxides are preferable and benzoyl peroxide is most preferable from the viewpoint of polymerization activity in combination with a tertiary amine, storage stability, and the like.

  In the dental curable composition of the present invention, the blending ratio of the above-mentioned (A) polymerizable monomer, (B) inorganic filler, (C) a chemical polymerization initiator composed of a tertiary amine and an organic peroxide. Is not particularly limited, and may be appropriately determined according to the use, but when used as a dental restoration material for building an abutment, (A) the polymerizable monomer is 100 parts by mass. On the other hand, (B) the inorganic filler is preferably 220 to 900 parts by mass (preferably 300 to 500 parts by mass). At this time, the (C) chemical polymerization initiator is not particularly limited as long as it is an amount effective for the polymerization of the polymerizable monomer used. On the other hand, the tertiary amine is 0.01 to 10 parts by mass (preferably 0.1 to 5 parts by mass), and the organic peroxide is 0.01 to 10 parts by mass (preferably 0.1 to 5 parts by mass). Degree.

  As described above, the chemical polymerization initiator composed of the tertiary amine and the organic peroxide in the present invention starts to polymerize at room temperature when contacted in the polymerizable monomer. Therefore, these tertiary amines and organic peroxides need to be divided into separate packages.

  In the present invention, as the above dividing method, the above-mentioned polymerizable monomer, inorganic filler, and other optional components described later are appropriately divided so that the viscosity ratio is 1 to 3 (lower viscosity paste viscosity). 2) in the range of 1), and a tertiary amine is added to one paste {Paste (I)} and an organic peroxide is added to the other paste {Paste (II)} There is.

  When the viscosity ratio of the two pastes is out of the above range, it becomes difficult to mix and knead the two pastes, and mechanical strength is likely to decrease due to mixing of bubbles and insufficient kneading. In terms of easier mixing and kneading, the viscosity ratio of the paste (I) and the paste (II) is more preferably in the range of 1: 1.5 to 1.5: 1.

  In the present invention, the method for bringing the viscosity ratio between the paste (I) and the paste (II) within the above range is not particularly limited, and any of the polymerizable monomer, inorganic filler and other components to be blended can be selected. In both pastes, the inorganic filler (B-1) contains 40 to 90% by mass of amorphous inorganic particles having an average particle diameter of 1 μm or more and 6 μm or less, (B- 2) Spherical inorganic particles having an average particle size of 0.05 μm or more and 1 μm or less, and 10 to 60% by mass; and (B-3) 0 to 10% by mass of inorganic particles having a particle size of less than 0.05 μm. Is preferred. By using such a paste, mixing and mixing of both pastes becomes easier.

  More preferably, both the paste (I) and the paste (II) have the same type and blending ratio of the polymerizable monomer and the inorganic filler to be blended. Thereby, not only the compositional uniformity in the dental curable composition of the present invention obtained by mixing and kneading is improved, but also the manufacture of each paste is facilitated.

  The dental curable composition of the present invention includes (A) a polymerizable monomer, (B) an inorganic filler, and (C) a chemical polymerization initiator comprising a tertiary amine and an organic peroxide. In addition, you may mix | blend other well-known components as a compounding component of a dental curable composition in the range which does not impair the effect of this invention. Examples of such components include photopolymerization initiators, other chemical polymerization initiators, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, butylhydroxytoluene, and styrene derivatives described in JP-A-9-17621. Polymerization retarders such as UV absorbers, pigments, antibacterial agents, metal salts, organic fillers, organic-inorganic composite fillers, and the like.

  By blending a photopolymerization initiator, the dental curable composition of the present invention can be a so-called dual cure dental curable composition that can be cured by both chemical polymerization and photopolymerization. is there. That is, it is possible to improve the operability by surely polymerizing a portion where light is difficult to reach with a chemical polymerization initiator and quickly curing the vicinity of the surface of the curable composition by light irradiation.

  Specific examples of such photopolymerization initiators include photopolymerization initiators such as α-diketones, acylphosphine oxides, thioxanthones, α-aminoacetophenones, combinations of aryl borates and photoacid generators. Is mentioned.

  Examples of α-diketones include camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, p, p'-dimethoxybenzyl, p, p'-dichlorobenzylacetyl, 1,2-phenanthrenequinone, 1,4-phenanthrene. Examples include quinone, 3,4-phenanthrenequinone, and 9,10-phenanthrenequinone.

  Acylphosphine oxides include benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5 , 6-tetramethylbenzoyldiphenylphosphine oxide and the like.

  Examples of thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone.

  2-Benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl as α-aminoacetophenones -Dimethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-dimethylamino-1- (4- Morpholinophenyl) -pentanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -pentanone-1, and the like.

  Aryl borates include tetraphenyl boron, tetra (p-fluorophenyl) boron, tetra (p-chlorophenyl) boron, trialkyl (p-fluorophenyl) boron, trialkyl (3,5-bistrifluoromethyl) phenyl boron, Dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, dialkyldi (3,5-bistrifluoromethyl) phenylboron, monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, Monoalkyltri (p-fluorophenyl) boron, monoalkyltri (3,5-bistrifluoromethyl) phenylboron (wherein the alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.) Salts, lithium salts, potassium salts, magnesium salts, tetrabutylammonium salts, tetramethylammonium salts and the like.

  Examples of the photoacid generator include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis ( Trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-bromopheny ) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -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- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(O-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2 (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine Halomethyl group-substituted s-triazine derivatives such as diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, bis (m-nitrophenyl) iodonium, p- tert-butylphenylphenyliodonium, methoxyphenylphenyliodonium, chloride such as p-octyloxyphenylphenyliodonium, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, Examples thereof include diphenyliodonium salt compounds such as trifluoromethanesulfonate.

  In addition, when using a photoacid generator, you may add photosensitizers, such as pigment | dyes which can sensitize and decompose this photoacid generator.

  As the photopolymerization initiator used in the present invention, it is particularly preferable to use α-diketones, and it is most preferable to use camphorquinone.

  Further, for these photopolymerization initiators, especially α-diketones, tertiary amines act as polymerization accelerators and can obtain better polymerization activity, and thus are obtained when photopolymerization is performed. The strength of the cured body is further improved. Such a tertiary amine is not particularly limited, and may be a tertiary amine similar to the tertiary amine exemplified as a component of the chemical polymerization initiator in the present invention. Aromatic tertiary amines to which a carbonyl group is bonded are particularly preferred.

  The dental curable composition of the present invention must contain a tertiary amine. Therefore, when a photopolymerization initiator is added to the curable composition of the present invention, the initiation of photopolymerization is inevitably required. The polymerization accelerator of the agent is also blended.

  As described above, the tertiary amine as the polymerization accelerator in the chemical polymerization initiator is preferably a toluidine-based aromatic tertiary amine, while the tertiary amine as the polymerization accelerator of the photopolymerization initiator is Since aromatic tertiary amines in which a carbonyl group is bonded to an aromatic ring are preferable, when the curable dental composition of the present invention is of a dual cure type, as the tertiary amine, toluidine is used. It is more preferable to blend both an aromatic tertiary amine and an aromatic tertiary amine having a carbonyl group bonded to an aromatic ring.

  The blending amount in the case of blending these photopolymerization initiators is not particularly limited, and may be appropriately set within a known range according to the type of the photopolymerization initiator used, for example, blending α-diketones When it does, it is about 0.01-10 mass parts (preferably 0.1-5 mass parts) with respect to 100 mass parts of polymerizable monomers.

  Furthermore, when α-diketones are blended, the polymerization rate when photopolymerization is performed can be improved by further blending the above-mentioned photoacid generator. The amount of the photoacid generator is not particularly limited, but is usually 0.005 to 10 parts by mass (preferably 0.03 to 5 parts by mass) with respect to 100 parts by mass of the polymerizable monomer. )

  In the dental curable composition of the present invention, when the photopolymerization initiator is blended, it may be blended in both paste (I) and paste (II), or may be blended in either one. good. If only paste (II) is blended, curing due to ambient light (indoor light) is difficult to occur. Therefore, until paste (I) and paste (II) are mixed and kneaded, they remain under ambient light for a considerable time. Therefore, operability in a clinical use state can be improved. On the other hand, if it is blended only in the paste (I), the paste (I) can be used as a dental curable composition having photopolymerization alone, and when used in a site where chemical polymerization activity is not required, It can be used alone as a photo-curable material that can be used without being mixed and kneaded with the paste (II). Moreover, if it mix | blends with both paste (I) and paste (II), the uniformity at the time of mixing and kneading | mixing can be made more favorable.

  Further, in the dental curable composition of the present invention, in addition to the chemical polymerization initiator (C) composed of a tertiary amine and an organic peroxide, an accelerator for the chemical polymerization initiator, other A chemical polymerization initiator can also be used in combination.

  Accelerators for chemical polymerization initiators consisting of tertiary amines and organic peroxides include sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate, lithium p-toluenesulfinate, p-toluenesulfine Examples thereof include sulfinates such as potassium acid, sodium m-nitrobenzenesulfinate, and sodium p-fluorobenzenesulfinate.

  Examples of other chemical polymerization initiators include combinations of acidic compounds and aryl borates, combinations of acidic compounds and aryl borates with a metal complex, barbituric acid, and alkylborane.

  The acidic compound may be an inorganic acid or an organic acid, but preferably an organic acid having a polymerizable functional group. Examples of such a compound include (meth) acrylic acid, 2-hydroxyethyl acid phosphate, 4- (meth) acryloxyethyl trimellitic acid or its anhydride, 11- (meth) acryloxyundecyl-1,1- Examples thereof include dicarboxylic acid and 2- (meth) acrylamide-2-methylsulfonic acid.

  Examples of the aryl borates include those exemplified as the components of the photopolymerization initiator.

  Examples of the metal complex include divanadium tetroxide (IV), vanadium oxide acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1,3-butanedionate) vanadium. Examples include vanadium compounds such as (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), and ammonium metavanadate (V).

  Examples of the barbituric acid include 5-butyl barbituric acid and 1-benzyl-5-phenylbarbituric acid.

  As the alkyl borane, tributyl borane, tributyl borane partial oxide, triphenyl borane and the like are preferably used.

  When optional components such as the above sulfinates and other chemical polymerization initiators are blended in the curable composition of the present invention, they may be blended in either paste (I) or paste (II), and storage stability And other physical properties as appropriate.

  The method for producing the dental curable composition of the present invention is not particularly limited, and may be performed according to a known method for producing a dental curable composition. For example, a predetermined amount of an inorganic filler, It can be prepared by mixing a polymerizable monomer, a tertiary amine or an organic peroxide, and the above-described various optional components blended as necessary, and kneading until a uniform paste is obtained. In addition, an inorganic filler and a polymerizable monomer are mixed to prepare a uniform paste, which is then divided into two parts, one containing a tertiary amine and the other containing an organic peroxide. A method of kneading may be used. In this case, the various optional components to be blended may be appropriately selected in consideration of whether they are blended in both pastes or only one of the pastes.

  The use of the dental curable composition of the present invention is not particularly limited as long as it is for dental use. However, the dental curable composition is excellent in fluidity and mechanical strength. It is preferably used as a repair material (composite resin). When used as a dental restoration material, it can be used for restoration of the entire crown from a shallow cavity, especially for the construction of an abutment in place of the removed tooth or pulp in a deep cavity. It is preferred to use.

  The use method in the case of constructing such an abutment is described as follows. The dental curing of the present invention is performed after treating the cavity with a dental direct restoration adhesive to the cavity of the tooth to be repaired in the oral cavity. A method in which a composition is filled and polymerized and cured after forming into a tooth shape (direct method), and a water-soluble or water-insoluble separation material is applied to the cavity of the tooth to be restored, and the present invention is applied thereto. After filling the dental curable composition and taking out the polymerized and cured material, it was further polymerized by chemical polymerization, photopolymerization and thermal polymerization, and then adhered using an adhesive for dental indirect restoration (Direct indirect method), a method of performing tooth restoration by forming into a tooth shape with a cavity model outside the oral cavity, and curing it after polymerization and using an adhesive for indirect dental restoration in the oral cavity (Indirect method). When filling the cavity of a tooth, a syringe type filling device or the like may be used, or in combination with a post for building an abutment such as a fiber post made of an organic-inorganic composite material reinforced with metal or glass fiber. It can also be used. In molding, a mold such as dental strips, core former, or temporary crown may be used.

  When the dental curable composition of the present invention is used for abutment construction as described above, it is usually adhered to a tooth using a dental adhesive. The adhesive may be any known adhesive for teeth, and may be a chemical polymerization type, a photopolymerization type, or a photo-chemical polymerization type. Because it has the advantage of being able to cure quickly by photopolymerization light irradiation and the advantage of reliable bonding even in deep cavities where chemical polymerization light does not reach, photo-chemistry It is preferable to use a polymerization type adhesive (or an adhesive system).

  Such a photo-chemical polymerization type adhesive is usually composed of a polymerizable monomer, a chemical polymerization initiator, and a photopolymerization initiator. As the said polymerizable monomer, the thing similar to the various polymerizable monomers mentioned above as a compounding component of the dental curable composition of this invention is used. In particular, 4-methacryloyloxyethyl trimellitic acid and its anhydride, 6-methacryloyloxyhexamethylenemalonic acid, 10-methacryloyloxydecamethylenemalonic acid, 2- A polymerizable monomer having an acidic group such as methacryloyloxyethyl dihydrogen phosphate, 10-methacryloyloxydecamethylene dihydrogen phosphate, 2-hydroxyethyl hydrogen phenyl phosphonate is a fully polymerizable monomer. It is preferable to use those containing 1 to 50% by mass.

  Moreover, as a photoinitiator, the thing similar to the photoinitiator mentioned above as a compounding component of the dental curable composition of this invention is used, and alpha-diketone is especially preferable. Also in this case, it is preferable to use a tertiary amine in combination as a polymerization accelerator.

  As the chemical polymerization initiator, those similar to the chemical polymerization initiator described above as a compounding component of the dental curable composition of the present invention can be used, but in view of obtaining particularly high adhesive strength, International Publication No. 03 / The chemical polymerization initiator described in No. 027153 is preferable. Specifically, it is a composition in which an acidic compound, an aryl borate compound, an organic peroxide, a + IV and / or + V vanadium compound is blended as a chemical polymerization initiator component. In this case, if a polymerizable monomer having an acidic group as described above is used as the polymerizable monomer, there is no need to separately add an acidic compound. Specific examples of these aryl borate compounds, organic peroxides, + IV and / or + V vanadium compounds are as described above as the components of the dental curable composition of the present invention.

  Specifically, a particularly preferable photo-chemical polymerization type adhesive is described. A radical polymerizable monomer having no acidic group, an aryl borate compound, an organic peroxide, an acidic compound (especially a polymerizable monomer having an acidic group). Body), a + IV and / or + V valent vanadium compound, and a photopolymerization initiator, an aryl borate compound and an organic peroxide, an acidic compound, and a + IV and / or + V valent vanadium compound. Is a type of adhesive that is divided into two parts so that they do not enter the same package, and is mixed and used immediately before use.

  When using a dental adhesive, it is preferable to use a dental pretreatment material in combination. As the pretreatment material, a known pretreatment material may be appropriately selected and used according to the type (composition) of the adhesive to be used. For example, the above-mentioned radical polymerizable monomer having no acidic group, aryl borate compound, organic peroxide, acidic compound (especially polymerizable monomer having acidic group), + IV and / or + V valent vanadium compound And a photo-chemical polymerization type adhesive containing a photopolymerization initiator, a pretreatment material containing a polymerizable monomer having an acidic group, a + IV and / or + V vanadium compound, and water Particularly high adhesive strength can be obtained by using. In this case, the polymerizable monomer having an acidic group, the + IV and / or + V vanadium compound are the same as those described above as the components of the dental curable composition of the present invention.

  EXAMPLES Hereinafter, although the content of this invention is demonstrated in detail by an Example, this invention is not limited to these Examples. In addition, the definitions of various quantities relating to the properties of the materials shown in the text and the examples and the measuring methods thereof are as follows.

(1) Measurement of the particle size of the inorganic filler and the coefficient of variation of the particle size The particle size of the inorganic filler was measured using a laser scattering particle size distribution measuring apparatus (BeCkmAn Coulter, LS230). Here, the average particle diameter is a particle diameter at which the value of the integrated distribution is 50% in the particle diameter-volume integrated distribution. The particle size (99%) is a particle size at which the value of the integrated distribution is 99% in the particle size-volume integrated distribution. Further, the coefficient of variation of the particles was obtained from the number average diameter and the standard deviation. The measurement range of this particle size distribution measuring apparatus is a particle size of 0.05 μm to 2 mm.

(2) Specific surface area Shimadzu Corporation, Flowsorb II 2300 was used. The measurement principle is the BET method.

(3) Preparation Method of Paste (I) and Paste (II) A matrix solution was prepared by adding a predetermined ratio of tertiary amine or organic peroxide and photopolymerization initiator to the polymerizable monomer. Next, the filler and the matrix liquid were put in an agate mortar and sufficiently kneaded to obtain a uniform paste to prepare paste (I) and paste (II).

(4) Three-point bending strength test Paste (I) and paste (II) are kneaded immediately before use, filled in a mold made of polytetrafluoroethylene having 2 × 2 × 25 mm prismatic holes, and the upper part is polypropylene The film was pressed with care so that no air bubbles would enter the film. A test piece was prepared by storing in a temperature-controlled room at 37 ° C. for 1 hour, followed by chemical polymerization. The test piece was mounted on a testing machine (manufactured by Shimadzu Corporation, Autograph AG-1), and the three-point bending fracture strength was measured at a crosshead speed of 1.0 mm / min.

(5) Compressive strength Paste (I) and paste (II) were kneaded immediately before use, and if necessary, chemically polymerized at 37 ° C. for 1 hour in the dark, and then immersed in water at 37 ° C. for 24 hours. A test piece was used. Its size and shape are cylindrical with a diameter of 4 mm and a height of 6 mm. Compressive strength of the test piece was measured with a testing machine (manufactured by Shimadzu Corporation, Autograph AG-1) at a crosshead speed of 10 mm / min.

(6) Thermal expansion coefficient A test piece was produced by irradiating light to each of the three ends of the mold at three ends of the mold with a visible light irradiator (manufactured by Tokuyama Dental Co., Ltd., Tokuso Power Light) for 30 seconds each. The size and shape are the same as those used in the three-point bending strength test. The measurement was determined by a linear expansion coefficient between 0 ° C. and 60 ° C. using a thermal analyzer (TMA120C) manufactured by Seiko Instruments Inc.

(7) Viscosity measurement Viscosity measurement Viscosity measurement device (manufactured by ITS, CS rheometer) 0.1 g of the prepared paste is placed, and the viscosity measurement is started while maintaining at 23 ° C. Was the viscosity of the dental curable composition. The measurement conditions of the viscosity measuring apparatus were a cone diameter of 2 cm, a cone inclination angle of 1 °, and a measurement gap of 100 μm.

(8) Surface treatment method of inorganic particles The inorganic particles were surface treated with γ-methacryloxypropyltrimethoxysilane (manufactured by Nippon Unicar Co., Ltd., trade name “A-174”).

(9) Marginal sealing test method A cave having a diameter of φ4.5 mm and a depth of 4 to 5 mm was formed in the bovine tooth crown, and the surface of the cave was further polished and flattened. The prepared primer was applied and left for 20 seconds. Adhesive packaging 1 and 2 were sampled drop by drop, mixed and applied to the cavity, followed by light irradiation for 10 seconds. Subsequently, a separately prepared curable composition was filled, pressed with a polypropylene film, and cured by chemical polymerization at 37 ° C. for 1 hour. After storing in 37 ° C. water for one day, the portion protruding from the cavity is polished and removed, and a thermal cycle test at 4 ° C. and 60 ° C. is performed 500 times. After immersing in a 0.1% basic fuchsin aqueous solution for 24 hours (37 ° C.), it is polished in half in the longitudinal direction of the teeth, and the penetration of the pigment is observed. The evaluation was performed according to the criteria shown below, with one sample being performed at two locations on the side wall of the crown and the side wall of the cervical region, and eight samples were set as one set, and the average value was obtained.

  No pigment penetration, score 0, score 2 when slightly enameled, score 3 for enamel-dentin interface, score 4 for dentin, score 5 for foveal bottom It was.

The raw materials used in the examples and comparative examples are as follows.
(A) Polymerizable monomer bismethacryloylethoxyphenylpropane (hereinafter abbreviated as D-2.6E)
2,2-bis [4 (2-hydroxy-3-methacryloxypropoxy) phenyl] propane (hereinafter abbreviated as Bis-GMA)
Triethylene glycol dimethacrylate (hereinafter abbreviated as 3G)
1,6-bis (methacrylethyloxycarbonylamino) -2,2-4-trimethylhexane (hereinafter abbreviated as UDMA)
A mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate (hereinafter abbreviated as PM).
11-methacryloyloxy-1,1-undecanedicanbonic acid (hereinafter abbreviated as MAC-10)
2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA)
(B) Amorphous inorganic particles having an average particle size of 1 μm or more and 6 μm or less Amorphous silica-zirconia, γ-methacryloxypropyltrimethoxysilane surface-treated product, average particle size: 4.2 μm (hereinafter abbreviated as b-1) .) Particle size (99%) <30 μm Specific surface area 2.89 m ² / g Coefficient of variation 0.84
Amorphous silica-zirconia, γ-methacryloxypropyltrimethoxysilane surface-treated product, average particle size: 3.0 μm (hereinafter abbreviated as b-2) particle size (99%) <30 μm Specific surface area 4.13 m ² / g coefficient of variation 0.82
Amorphous silica-zirconia, γ-methacryloxypropyltrimethoxysilane surface-treated product, average particle size: 5.0 μm (hereinafter abbreviated as b-3) particle size (99%) <50 μm Specific surface area 1.86 m ² / g coefficient of variation 0.72
Amorphous silica-zirconia, γ-methacryloxypropyltrimethoxysilane surface-treated product, average particle size: 8.0 μm (hereinafter abbreviated as b-4) particle size (99%) <30 μm Specific surface area 1.37 m ² / g coefficient of variation 0.41
Amorphous silica-zirconia, γ-methacryloxypropyltrimethoxysilane surface-treated product, average particle size: 0.8 μm (hereinafter abbreviated as b-5) particle size (99%) <10 μm Specific surface area 9.1 m ² / g coefficient of variation 0.31
(C) Average particle size 0.05 μm or more and 1 μm or less of spherical inorganic particles Spherical silica-zirconia, average particle size: 0.1 μm (hereinafter abbreviated as c-1).
Spherical silica-zirconia, average particle size: 0.6 μm (hereinafter abbreviated as c-2).
(D) Particle size Amorphous inorganic particle fine powder silica of less than 0.05 μm, average particle size: 0.015 μm (hereinafter abbreviated as d-1) particle size 5 to 50 nm
(E) Tertiary amine ethyl 4-dimethylaminobenzoate (hereinafter abbreviated as DMBE)
4-dimethylaminoacetophenone (hereinafter abbreviated as DMA)
N, N-dihydroxyethyl-p-toluidine (hereinafter abbreviated as DEPT)
N, N-dimethylaminoethyl methacrylate (hereinafter abbreviated as DMEM)
(F) Organic peroxide benzoyl peroxide (hereinafter abbreviated as BPO)
1,1,3,3-tetramethylbutyl hydroperoxide (hereinafter abbreviated as perocta H)
(G) Photopolymerization initiator camphorquinone (hereinafter abbreviated as CQ)
(H) Polymerization inhibitor 2,6-di-t-butyl-4-methylphenol (hereinafter abbreviated as BHT)
Hydroquinone monomethyl ether (hereinafter abbreviated as HQME)
(I) Aryl borate compound tetraphenyl boron triethanolamine salt (hereinafter abbreviated as PhBTEOA)
(J) Vanadium compound bis (maltolate) oxovanadium (IV) (hereinafter abbreviated as BMOV)
(K) Other acetone water Example 1
Paste (I): [(b-1) + (c-1)] as an inorganic filler is 400 parts by mass, and when the inorganic filler is 100% by mass, (b-1) is 70% by mass and ( C-1) 30% by mass, Bis-GMA 60 parts by mass as a polymerizable monomer, 40 parts by mass 3G, DEPT 1.3 parts by mass as a tertiary amine, DMBE 1 part by mass, BHT as a polymerization inhibitor It prepared according to the said preparation method using 0.05 mass part. The viscosity of paste (I) was 1160 poise.

  Paste (II): [(b-1) + (c-1)] as an inorganic filler is 400 parts by mass, and when the inorganic filler is 100% by mass, (b-1) is 70% by mass and ( c-1) 30% by mass, Bis-GMA 60 parts by mass as a polymerizable monomer, and 3G 40 parts by mass, BPO 1.3 parts by mass, CQ 1 part by mass, BHT 0.05 parts by mass as a polymerization inhibitor Was prepared according to the above preparation method. The viscosity of paste (II) was 1140 poise.

The physical properties of the paste (I) and paste (II) that were taken in equal amounts and kneaded at room temperature for 30 seconds and cured were as follows. The bending strength was 149 MPa, the compressive strength was 310 MPa, and the thermal expansion coefficient was 21.8 × 10 ⁻⁶ / ° C. The inorganic filling rate here is (mass part of inorganic filler) / [(mass part of inorganic filler) + (mass part of polymerizable monomer)].

Examples 2-7
Paste (I) and paste (II) were prepared in the same manner as in Example 1 with the compositions shown in Table 1. The physical properties of the paste (I) and paste (II) were measured by taking equal amounts of paste (I) and paste (II) for 30 seconds and curing. Table 2 shows the composition of the inorganic filler after mixing the two pastes and the measurement results of the physical properties. The paste (I) and paste (II) were mixed in equal mass. In any composition, paste viscosity, bending strength, compressive strength, and coefficient of thermal expansion are excellent.

Comparative Examples 1-5
Paste (I) and paste (II) were prepared in the same manner as in Example 1 with the compositions shown in Table 3. The physical properties of the paste (I) and paste (II) were measured by taking equal amounts of paste (I) and paste (II) for 30 seconds and curing. Table 4 shows the inorganic filler composition after mixing both pastes and the measurement results of the physical properties.

  Comparative Example 1 is an example in which particles having an average particle size of 8.0 μm are used as the amorphous inorganic particles. In this case, the bending strength was inferior to that of the example.

  Comparative Example 2 is an example where particles having an average particle diameter of 0.8 μm are used as the irregular shaped particles. In this case, the viscosity was high, and bending strength and compressive strength were higher than those of the examples.

  Comparative Example 3 is an example in which a paste is prepared so that the irregular viscosity is 25% by mass and the spherical particle is 75% by mass to have an appropriate viscosity. In this case, bending strength and compressive strength were inferior.

  Comparative Example 4 is an example in which the paste is adjusted with only irregular shaped particles. In this case, the viscosity of the paste was high and the bending strength was inferior to that of the example.

  Comparative Example 5 is an example in which the viscosity of (I) paste and (II) paste is about 1: 6. Also in this case, bending strength was inferior compared with the Example.

Example 8
In a solution consisting of 2.0 g PM, 0.7 g UDMA, 3.0 g water, 4.3 g acetone, 0.02 g vanadium compound (BMOV), 0.03 g polymerization inhibitor (BHT) and 0.2 g of amine compound (DMEM) was dissolved to obtain a uniform solution, which was used as a pretreatment material. The pH of this pretreatment material was about 1.7.

  Separately, in a monomer liquid consisting of 2.0 g of HEMA, 3.0 g of D-2.6E, and 5.0 g of 3G, 0.3 g of PhBTEOA as an aryl borate compound and 0.4 g of an organic peroxide under light shielding Perocta H, 0.03 g of CQ as a photopolymerization initiator, 0.01 g of BHT and 0.005 g of HQME as a polymerization inhibitor were added to obtain a homogeneous solution. To this solution, 0.1 g DMBE was further added and mixed until uniform (adhesive packaging 1).

  A monomer liquid consisting of 1.6 g PM, 0.7 g MAC-10, 3.0 g D-2.6E, 4.7 g 3G, 0.0005 g BMOV, 0.03 g BHT, 0.2 g Was added to make a uniform solution (adhesive packaging 2).

  Using the pretreatment material and adhesive packaging 1 and 2 prepared as an adhesive system, and the composition described in Example 1 as the curable composition, the adhesive performance test was performed according to the edge sealing test method described above.

The result of the edge sealing test was 4.0, and it was confirmed that the adhesive performance was almost equal to that of a general photopolymerization type direct repair adhesive.

Claims (5)

A dental curable composition comprising (A) a polymerizable monomer, (B) an inorganic filler, and (C) a chemical polymerization initiator comprising a tertiary amine and an organic peroxide,
The inorganic filler (B-1) has an average particle size of 40 to 90% by mass with an average particle size of 1 to 6 μm, and (B-2) an average particle size of 0.05 to 1 μm. 10 to 60% by mass of spherical inorganic particles and (B-3) 0 to 10% by mass of inorganic particles having a particle size of less than 0.05 μm,
The dental curable composition is divided into two pastes, a paste (I) containing a tertiary amine and a paste (II) containing an organic peroxide, and the paste (I) And the paste (II) have a viscosity ratio in the range of 1: 3 to 3: 1.   Both paste (I) and paste (II) comprise (A) a polymerizable monomer and (B) an inorganic filler, and the inorganic filler contained in any paste is (B-1 40) to 90% by mass of amorphous inorganic particles having an average particle size of 1 μm to 6 μm, (B-2) 10 to 60% by mass of spherical inorganic particles having an average particle size of 0.05 μm to 1 μm, and ( B-3) The dental curable composition according to claim 1, comprising 0 to 10% by mass of inorganic particles having a particle diameter of less than 0.05 µm.   The dental curable composition according to claim 1 or 2, further comprising (D) a photopolymerization initiator.   The dental curable composition according to claim 1, which is a curable composition for building a dental abutment. (A) a polymerizable monomer having an acidic group, a + IV and / or + V-valent vanadium compound, and a dental pretreatment material containing water, (ii) a polymerizable monomer having no acidic group, aryl A dental adhesive containing a borate compound, an organic peroxide, an acidic compound, a + IV and / or + V valent vanadium compound, and a photopolymerization initiator; An abutment construction kit comprising a composition.