JP6348106B2 - Dental curable composition - Google Patents

Description

  The present invention relates to a dental curable composition. More specifically, the present invention relates to a dental curable composition that is excellent in sustained release of calcium ions and fluorine ions, which are known as active ingredients for remineralization, and can be suitably used particularly as a dental resin-reinforced glass ionomer cement.

  Amalgam, glass ionomer cement, resin-reinforced glass ionomer cement, composite resin filler, and the like are widely used as materials for filling and repairing the defective part of the tooth affected part. On the other hand, zinc phosphate cement, glass ionomer cement, resin reinforced glass ionomer cement, composite resin cement, etc. are widely used as a material for attaching prosthetics such as crowns, inlays, and bridges to the damaged part of the tooth. It has been. As described above, a wide variety of materials are used in the restoration of the affected part of the tooth.

  Among these, glass ionomer cement and resin reinforced glass ionomer cement (an improved version of glass ionomer cement that incorporates a curing mechanism by polymerization reaction by incorporating a polymerizable monomer and a polymerization initiator into glass ionomer cement) Is a material using a glass ionomer reaction in which a polymer acid mainly composed of an acid such as polyalkenoic acid and a basic fluoroaluminosilicate glass are cured in the presence of water, and has a feature of high biocompatibility.

  In recent years, the so-called remineralization treatment that promotes remineralization by replenishing minerals from the material to the remaining tooth after cutting without carving the part affected by caries as much as possible has attracted attention. Cement and resin-reinforced glass ionomer cements are widely recognized as restorative materials that can be expected to have a remineralization action because they gradually release fluorine ions, which are known as active ingredients for remineralization. However, hydroxyapatite, which is a major component of enamel and dentin teeth, is one of calcium phosphates composed of calcium and phosphorus. Supplying only ions is not sufficiently promoted.

  On the other hand, Patent Document 1 proposes a glass powder for glass ionomer cement containing apatite, and describes that it can be configured as a resin-reinforced glass ionomer cement. According to Patent Document 1, the inclusion of apatite improves the mechanical strength, particularly bending strength, tensile strength, and fracture toughness of the resin-reinforced glass ionomer cement. Moreover, since it contains apatite, it has not only fluorine ions but also sustained release of calcium ions. However, as a result of studies by the present inventors, it has been found that the resin-reinforced glass ionomer cement described in Patent Document 1 has insufficient calcium ion sustained release.

  On the other hand, Patent Document 2 describes a dental cement containing a calcium ion source, a phosphate ion source, a resin monomer component, and a polymerization initiator. Furthermore, it is described that the dental cement includes a source of fluoride ions, and it is described that fluoride-containing glass can be used as the source of fluoride ions. Patent Document 2 uses a calcium phosphate compound such as anhydrous dicalcium phosphate as a source of both calcium ions and phosphate ions, or a calcium ion source such as calcium chloride, and a phosphate ion source. Are separately used. However, Patent Document 2 relates to a resin cement rather than a resin-reinforced glass ionomer cement. Since there is no curing mechanism by a glass ionomer reaction, not only the biocompatibility remains doubtful, but the present inventors have studied. However, it was found that the resin cement described in Patent Document 2 also has a low calcium ion sustained release property.

JP 2001-354509 A Special table 2007-524635 gazette

  The present invention provides a dental curable composition that can be suitably used for a resin-reinforced glass ionomer cement, and is excellent in sustained release of not only fluorine ions but also calcium ions. With the goal.

  As a result of continual research to solve the above-mentioned problems, the inventors of the present invention have developed a glass ionomer reaction with fluoroaluminosilicate glass, polyalkenoic acid and water, acidic calcium phosphate particles and basic calcium phosphate particles, or calcium compound particles not containing phosphorus. A dental curable composition incorporating compounds relating to three types of curing modes, ie, a hydration reaction with a mixture of water and water, and a polymerization reaction with a polymerizable monomer and a polymerization initiator, in a specific ratio, respectively. It has been found that it has properties suitable for reinforced glass ionomer cement and is excellent in the sustained release of calcium ions and fluorine ions, which are known as active ingredients for remineralization, and has led to the completion of the present invention.

  The present invention relates to fluoroaluminosilicate glass particles (A), acidic calcium phosphate particles (B1) and basic calcium phosphate particles (B2) or a mixture of phosphorous-free calcium compound particles (B3) (B), polyalkenoic acid (C) A dental curable composition containing a polymerizable monomer having no acidic group (D), water (E), and a polymerization initiator (F), the fluoroaluminosilicate glass particles (A) and 30 to 99 parts by weight of the fluoroaluminosilicate glass particles (A), 1 to 70 parts by weight of the mixture (B), and 100 to 100 parts by weight of the mixture (B), and the polyalkenoic acid (C) 1 to 60 parts by weight, 5 to 90 parts by weight of the polymerizable monomer (D) having no acidic group, 1 to 40 parts by weight of water (E), and the polymerization initiation (F) is a dental curable composition containing 0.01 to 20 parts by weight.

  In one embodiment of the dental curable composition of the present invention, the acidic group-containing polymerizable monomer (G) is further added to 100 parts by weight of the fluoroaluminosilicate glass particles (A) and the mixture (B). In contrast, 0.1 to 30 parts by weight are contained.

  The present invention is also a dental resin-reinforced glass ionomer cement using a dental curable composition.

  ADVANTAGE OF THE INVENTION According to this invention, the dental curable composition excellent in the sustained release of the calcium ion and fluorine ion known as an active ingredient of remineralization is provided. The dental curable composition of the present invention is useful for filling and repairing a defective part of a tooth affected part, and for joining a defective part of a tooth affected part and a prosthesis, and particularly suitably used as a dental resin-reinforced glass ionomer cement. be able to.

Hereinafter, the present invention will be specifically described. The fluoroaluminosilicate glass particles (A) used in the present invention contain Si ²⁺ , Al ³⁺ , O ²⁻ , F ⁻ as basic ion components constituting the glass, and further contain other metal ions as necessary. Particles made of glass and having a valence of 2 or more that can react with the polyalkenoic acid powder (C) described later, such as ions of strontium, calcium, zinc, aluminum, iron, zirconium, etc. It refers to glass particles having a property of elution. It reacts with the polyalkenoic acid (C) to cure by ionic crosslinking and contributes to the sustained release of fluorine ions. Specific examples thereof include fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. Among these, fluoroaluminosilicate glass and barium fluoroaluminosilicate glass are preferable. The fluoroaluminosilicate glass particles (A) may be used in combination of not only one type but also a plurality of types as appropriate.

  The method for producing the fluoroaluminosilicate glass particles (A) used in the present invention is not particularly limited. In general, the raw materials are weighed at a predetermined weight ratio and thoroughly mixed, and then melted at a high temperature of 1100 ° C. or higher, and the melt that has been melted homogeneously is rapidly cooled to form a glass frit. It can be produced by pulverization using a machine, a jet mill or the like. Alternatively, a commercially available fluoroaluminosilicate glass powder may be used as it is, or a commercially available product may be further pulverized. The average particle size of the fluoroaluminosilicate glass particles (A) is preferably 0.02 to 35 μm. When the average particle diameter of the fluoroaluminosilicate glass particles (A) is less than 0.02 μm, the average particle diameter is too small to be manufactured, and the viscosity of the resulting dental curable composition is increased. There is a risk of passing. The average particle size of the fluoroaluminosilicate glass particles (A) is more preferably 0.5 μm or more, and most preferably 1 μm or more. On the other hand, when the average particle diameter of the fluoroaluminosilicate glass particles (A) exceeds 35 μm, the surface of the resulting dental curable composition may be rough and rough, or the operability may be reduced. The average particle size of the fluoroaluminosilicate glass particles (A) is more preferably 20 μm or less, and most preferably 10 μm or less. Here, the average particle diameter of the fluoroaluminosilicate glass particles (A) used in the present invention is determined as a median diameter (d50) measured using a laser diffraction particle size distribution analyzer.

  The fluoroaluminosilicate glass particles (A) may be used after being surface-treated with a known surface treatment agent such as a silane coupling agent as necessary. Examples of the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. , Γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like.

  The dental curable composition of the present invention contains 30 to 99 parts by weight of fluoroaluminosilicate glass particles (A) with respect to 100 parts by weight of the total of fluoroaluminosilicate glass particles (A) and mixture (B). is necessary. When the content of the fluoroaluminosilicate glass particles (A) is less than 30 parts by weight, sufficient sustained release of fluorine ions cannot be obtained. On the other hand, when the content of the fluoroaluminosilicate glass particles (A) exceeds 99 parts by weight, the hydration reaction by the mixture (B) and water is inhibited, and sufficient release of calcium ions and phosphate ions cannot be obtained. . From the viewpoint of releasing calcium ions and fluorine ions, the content of the fluoroaluminosilicate glass particles (A) is preferably in the range of 50 to 98 parts by weight, and more preferably in the range of 75 to 97 parts by weight. . In particular, in the dental curable composition of the present invention, when the content of the fluoroaluminosilicate glass particles (A) is in the range of 90 to 97 parts by weight, the amount of fluorine ions released is maximized, which is most preferable. .

The acidic calcium phosphate particles (B1) used in the present invention are not particularly limited, and anhydrous calcium monohydrogen phosphate [CaHPO ₄ ] particles, tricalcium phosphate [Ca ₃ (PO ₄ ) ₂ ] particles, anhydrous dihydrogen phosphate Calcium [Ca (H ₂ PO ₄ ) ₂ ] particles, amorphous calcium phosphate [Ca ₃ (PO ₄ ) ₂ .xH ₂ O] particles, acidic calcium pyrophosphate [CaH ₂ P ₂ O ₇ ] particles, calcium monohydrogen phosphate At least one selected from the group consisting of dihydrate [CaHPO ₄ · 2H ₂ O] particles and calcium dihydrogen phosphate monohydrate [Ca (H ₂ PO ₄ ) ₂ · H ₂ O] particles. Preferably there is. Among these, anhydrous calcium monohydrogen phosphate [CaHPO ₄ ] particles, tricalcium phosphate [Ca ₃ (PO ₄ ) ₂ ] particles, anhydrous calcium dihydrogen phosphate [Ca (H ₂ PO ₄ ) ₂ ] particles, and More preferably, at least one selected from the group consisting of calcium monohydrogen phosphate dihydrate [CaHPO ₄ .2H ₂ O] particles is used, and anhydrous calcium monohydrogen phosphate [CaHPO ₄ ] particles and phosphoric acid mono At least one selected from the group consisting of calcium hydride dihydrate [CaHPO ₄ .2H ₂ O] particles is more preferably used. In particular, anhydrous calcium monohydrogen phosphate [CaHPO _4] from the viewpoint of the release of calcium ions. ] Particles are preferably used.

  The average particle diameter of the acidic calcium phosphate particles (B1) used in the present invention is preferably 0.3 to 10 μm. When the average particle size is less than 0.3 μm, the acidic calcium phosphate particles (B1) are excessively dissolved in water (E), so that calcium ions and phosphate ions released from the dental curable composition of the present invention are used. In addition to the loss of balance, the operability of the paste may be reduced. The average particle diameter of the acidic calcium phosphate particles (B1) is more preferably 0.4 μm or more, and most preferably 0.5 μm or more. On the other hand, when the average particle size exceeds 10 μm, the acidic calcium phosphate particles (B1) are hardly dissolved in water (E), and the balance between calcium ions and phosphate ions released from the dental curable composition of the present invention is balanced. There is a risk of collapse. The average particle size of the acidic calcium phosphate particles (B1) is more preferably 5 μm or less, and most preferably 3 μm or less. The average particle diameter of the acidic calcium phosphate particles (B1) is determined in the same manner as the average particle diameter of the fluoroaluminosilicate glass particles (A).

  The production method of the acidic calcium phosphate particles (B1) used in the present invention is not particularly limited. Commercial products may be used as they are, or may be used by appropriately pulverizing and adjusting the particle diameter. In that case, a pulverizing apparatus such as a ball mill, a likai machine, or a jet mill can be used. Moreover, acidic calcium phosphate raw material powder is pulverized with a liquid medium such as alcohol using a lykai machine, a ball mill or the like to prepare a slurry, and the resulting slurry is dried to obtain acidic calcium phosphate particles (B1). it can. A ball mill is preferably used as the pulverizer at this time, and alumina or zirconia is preferably used as the material of the pot and ball.

The basic calcium phosphate particles (B2) used in the present invention are not particularly limited, and tetracalcium phosphate [Ca ₄ (PO ₄ ) ₂ O] particles and octacalcium phosphate pentahydrate [Ca ₈ H ₂ (PO ₄ ) At least one selected from the group consisting of ₆ · 5H ₂ O] particles is preferred. Among these, tetracalcium phosphate [Ca ₄ (PO ₄ ) ₂ O] particles are particularly preferably used from the viewpoint of calcium ion release.

  The average particle size of the basic calcium phosphate particles (B2) used in the present invention is preferably 0.6 to 35 μm. When the average particle size is less than 0.6 μm, the basic calcium phosphate particles (B2) are excessively dissolved in water (E), so that calcium ions and phosphoric acid released from the dental curable composition of the present invention are used. Not only is the ion balance lost, the operability of the paste may be reduced. The average particle diameter of the basic calcium phosphate particles (B2) is more preferably 1 μm or more, and most preferably 3 μm or more. On the other hand, when the average particle size exceeds 35 μm, the operability of the obtained paste may be lowered. Moreover, it becomes difficult to dissolve in water (E), and the balance between calcium ions and phosphate ions released from the dental curable composition of the present invention may be lost. The average particle diameter of the basic calcium phosphate particles (B2) is more preferably 20 μm or less, and most preferably 10 μm or less. The average particle diameter of the basic calcium phosphate particles (B2) is determined in the same manner as the average particle diameter of the fluoroaluminosilicate glass particles (A).

  The production method of the basic calcium phosphate particles (B2) used in the present invention is not particularly limited. Commercially available basic calcium phosphate particles may be used as they are, or may be appropriately pulverized to adjust the particle size. As the pulverization method, a method similar to the pulverization method of the acidic calcium phosphate particles (B1) can be employed.

The phosphorus-free calcium compound (B3) used in the present invention is not particularly limited, and calcium hydroxide [Ca (OH) ₂ ], calcium oxide [CaO], calcium chloride [CaCl ₂ ], calcium nitrate [Ca ( NO ₃ ) ₂ · nH ₂ O], calcium acetate [Ca (CH ₃ CO ₂ ) ₂ · nH ₂ O], calcium lactate [C ₆ H ₁₀ CaO ₆ ], calcium citrate [Ca ₃ (C ₆ H ₅ O) ₇ ) ₂ · nH ₂ O], calcium metasilicate [CaSiO ₃ ], dicalcium silicate (Ca ₂ SiO ₄ ), tricalcium silicate (Ca ₃ SiO ₅ ), calcium carbonate [CaCO ₃ ] and the like. , One or more of these are used. Among these, calcium hydroxide, calcium oxide, calcium metasilicate, dicalcium silicate, and tricalcium silicate are preferable and calcium hydroxide is more preferable from the viewpoint of the precipitation ability of the hydroxyapatite component.

  The average particle size of the phosphorus-free calcium compound (B3) used in the present invention is preferably 0.3 to 12 μm. When the average particle size is less than 0.3 μm, the dissolution in water (E) becomes excessive, so that not only the balance of calcium ions and phosphate ions released from the dental curable composition of the present invention is lost. The operability of the paste may be reduced. The average particle size of the calcium compound (B3) not containing phosphorus is more preferably 0.5 μm or more, and most preferably 1 μm or more. On the other hand, when the average particle diameter of the calcium compound (B3) containing no phosphorus exceeds 12 μm, the calcium compound (B3) containing no phosphorus is difficult to dissolve in water (E), and the dental curable composition of the present invention. There is a risk that the balance between calcium ions and phosphate ions released from the object may be lost. The average particle size of the calcium compound (B3) containing no phosphorus is more preferably 9.0 μm or less, and most preferably 5 μm or less. The average particle diameter of the calcium compound (B3) not containing phosphorus is determined in the same manner as the average particle diameter of the fluoroaluminosilicate glass particles (A).

  The manufacturing method of the calcium compound (B3) which does not contain phosphorus used by this invention is not specifically limited. Commercial products may be used as they are, or may be used by appropriately pulverizing and adjusting the particle diameter. As the pulverization method, a method similar to the pulverization method of the acidic calcium phosphate particles (B1) can be employed.

  In the dental curable composition of the present invention, the acidic calcium phosphate particles (B1), the basic calcium phosphate particles (B2), and the calcium compound (B3) not containing phosphorus are the acidic calcium phosphate particles (B1) and the basic calcium phosphate particles. Used as a mixture (B) with (B2) or calcium compound particles (B3) not containing phosphorus. In each mixture, the blending ratio of the acidic calcium phosphate particles (B1) and the basic calcium phosphate particles (B2) and the blending ratio of the acidic calcium phosphate particles (B1) and the calcium compound not containing phosphorus (B3) are not particularly limited. From the viewpoint of the balance between the amount of calcium ions and the amount of phosphate ions, the total Ca / P ratio of the acidic calcium phosphate particles (B1) and the basic calcium phosphate particles (B2), and the acidic calcium phosphate particles (B1) and phosphorus are included. The total Ca / P ratio of the calcium compound (B3) is preferably 1.10 to 1.95, more preferably 1.30 to 1.80, and most preferably Is used at a blending ratio of 1.50 to 1.70. Further, the blending ratio (B1 / B2) of the acidic calcium phosphate particles (B1) and the basic calcium phosphate particles (B2), and the blending ratio of the acidic calcium phosphate particles (B1) and the calcium compound (B3) not containing phosphorus (B1 / B3). ) Is preferably 40/60 to 60/40 in molar ratio.

  In the dental curable composition of the present invention, it is necessary to contain 1 to 70 parts by weight of the mixture (B) with respect to 100 parts by weight of the total of the fluoroaluminosilicate glass particles (A) and the mixture (B). . When the mixture (B) is less than 1 part by weight, the release amount of calcium ions and phosphate ions becomes insufficient. The content of the mixture (B) is preferably 2 parts by weight or more, and particularly preferably 3 parts by weight or more. On the other hand, when the mixture (B) exceeds 70 parts by weight, the hydration reaction with the mixture (B) and water becomes predominant, and the reaction for producing thermodynamically stable hydroxyapatite proceeds rapidly. The release amount of calcium ions and phosphate ions released from the dental curable composition of the present invention is lowered. Further, since the glass ionomer reaction derived from the fluoroaluminosilicate glass particles (A) is inhibited, sufficient sustained release of fluorine ions cannot be obtained. From the viewpoint of achieving both the release of fluorine ions and calcium ions released from the dental curable composition of the present invention, the content of the mixture (B) is preferably 50 parts by weight or less, and 25 parts by weight or less. More preferably, the amount is 10 parts by weight or less.

  The polyalkenoic acid (C) used in the present invention is a carboxylic group or other group capable of reacting with a cation eluted from the fluoroaluminosilicate glass particles (A) as a constituent of the glass ionomer reaction to form a poly salt. It is an organic polymer having an acidic group, and contributes to the expression of adhesiveness to tooth and dental prosthesis. The polyalkenoic acid (C) is preferably a (co) polymer of an unsaturated carboxylic acid such as an unsaturated monocarboxylic acid or unsaturated dicarboxylic acid. Examples of these (co) polymers include acrylic acid, methacrylic acid, and the like. Homopolymers such as acid, 2-chloroacrylic acid, 2-cyanoacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid; copolymers of these unsaturated carboxylic acids; And copolymers of these unsaturated carboxylic acids and monomers that can be copolymerized, and these can be used alone or in combination of two or more. In the case of a copolymer with a copolymerizable monomer, the proportion of unsaturated carboxylic acid units is preferably 50 mol% or more based on the total structural units. The copolymerizable monomer is preferably an ethylenically unsaturated polymerizable monomer such as styrene, acrylamide, acrylonitrile, methyl methacrylate, acrylates, vinyl chloride, allyl chloride, vinyl acetate, 1,1,6. -A trimethyl hexamethylene dimethacrylate ester etc. can be mentioned. Among these polyalkenoic acids, acrylic acid, maleic acid and itaconic acid homopolymers, acrylic acid and maleic acid copolymers, and acrylic acid and itaconic acid At least one selected from the group consisting of polymers is preferable, and a copolymer of acrylic acid and itaconic acid is particularly preferable. Furthermore, what is a polymer of the weight average molecular weight 5,000-50,000 which does not contain a polymerizable ethylenically unsaturated double bond is preferable. When the weight average molecular weight is less than 5,000, the strength of the cured product tends to be low, and there is a possibility that the adhesive force to the tooth will be lowered, more preferably 10,000 or more, and more than 35,000. Most preferred. Further, when the weight average molecular weight exceeds 50,000, the operability may be lowered, more preferably 45,000 or less, and most preferably 40,000 or less.

  The method for producing the polyalkenoic acid (C) used in the present invention is not particularly limited, and may be used as long as a commercially available product is available. In particular, when blended as a powder, it is often preferable to further grind commercial products. In that case, a pulverizing apparatus such as a ball mill, a likai machine, or a jet mill can be used. Alternatively, the polyalkenoic acid powder (C) can be obtained by pulverizing the polyalkenoic acid powder together with a liquid medium such as alcohol using a lykai machine, a ball mill or the like to prepare a slurry, and drying the obtained slurry. As a drying device at this time, it is preferable to use a spray dryer.

  In the dental curable composition of the present invention, it is necessary to contain 1 to 60 parts by weight of the polyalkenoic acid (C) with respect to 100 parts by weight of the total of the fluoroaluminosilicate glass particles (A) and the mixture (B). is there. When content of polyalkenoic acid (C) is less than 1 weight part, the adhesiveness with respect to a dentine and a dental prosthesis becomes low. The content of polyalkenoic acid (C) is preferably 3 parts by weight or more, and more preferably 5 parts by weight or more. On the other hand, when content of polyalkenoic acid (C) exceeds 60 weight part, operativity falls or mechanical strength falls. The blending amount of the polyalkenoic acid (C) is preferably 40 parts by weight or less, and more preferably 25 parts by weight or less.

  The polymerizable monomer (D) having no acidic group used in the present invention is a polymerizable monomer that undergoes radical polymerization reaction to be polymerized by a polymerization initiator (F) described later, for example, α-cyanoacrylic acid ester, (meth) acrylic acid ester, α-halogenated acrylic acid ester, crotonic acid ester, cinnamic acid ester, sorbic acid ester, maleic acid ester, itaconic acid ester, (meth) acrylamide And derivatives thereof, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives and the like. Among these, (meth) acrylic acid esters, (meth) acrylamide and derivatives thereof are preferably used. In this specification, both methacryl and acryl are comprehensively expressed with (meth) acryl.

  Specific examples of the polymerizable monomer (D) having no acidic group used in the present invention are shown below. A monomer having one olefinic double bond is defined as a monofunctional monomer, and is expressed as a bifunctional monomer, a trifunctional monomer, or the like depending on the number of olefinic double bonds.

  Monofunctional monomers: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (Meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl ( (Meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, N-2-hydroxyethyl (meth) acrylamide, 3-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundeci Trimethoxysilane, (meth) acrylamide.

  Bifunctional monomer: ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (the number of oxyethylene groups is 9 or more Glycerol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, dipentaerythritol di (meth) Acrylate, bisphenol A diglycidyl (meth) acrylate (2,2-bis [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] propane), 2,2-bis [4- (meth) acryloyloxy Ethoxyphenyl Propane, 2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 1,2-bis [3- (meth) acryloyloxy-2-hydroxypropoxy] ethane, pentaerythritol di (meth) acrylate, [2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl)] dimethacrylate, 1,3-di (meth) acrylolyloxy-2-hydroxypropane, and the like.

  Trifunctional or higher monomers: trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, N, N ′-( 2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxymethyl- 4-oxyheptane and the like.

  Any of the above polymerizable monomers (D) having no acidic group may be used alone or in combination of two or more. The compounding quantity of the polymerizable monomer (D) which does not have an acidic group is used in the range of 5-90 weight part with respect to a total of 100 weight part of fluoroaluminosilicate glass particle (A) and a mixture (B). . From the viewpoint of operability and mechanical strength, the range of 20 to 80 parts by weight is preferable, and the range of 40 to 70 parts by weight is more preferable.

  It is preferable that the dental curable composition of the present invention further contains a polymerizable monomer (G) having an acidic group as the polymerizable monomer. The polymerizable monomer (G) having an acidic group contributes to further improvement in adhesion to a tooth and a dental prosthesis. Examples of the polymerizable monomer include at least one acidic group such as a phosphoric acid group, a phosphonic acid group, a pyrophosphoric acid group, a carboxylic acid group, a sulfonic acid group, and thiophosphoric acid, and an acryloyl group, Examples thereof include polymerizable monomers having a polymerizable unsaturated group such as a methacryloyl group, a vinyl group, and a styrene group. Specific examples of the compound include the following.

  Examples of phosphoric acid group-containing polymerizable monomers include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, and 4- (meth) acryloyloxybutyl dihydrophosphate. Genphosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl Dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 11- (meth) acrylate Royloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyl dihydrogen phosphate, 20- (meth) acryloyloxyeicosyl dihydrogen phosphate, Bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- ( (Meth) acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyloxynonyl] hydrogen phosphate, bis [10- (meth) acryloyl Xyldecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl-2-dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2′- Bromoethyl hydrogen phosphate, 2-methacryloyloxyethyl (4-methoxyphenyl) hydrogen phosphate, 2-methacryloyloxypropyl (4-methoxyphenyl) hydrogen phosphate, glycerol phosphate di (meth) acrylate, dipentaerythritol phosphate penta ( Examples thereof include polymerizable monomers such as (meth) acrylate and acid chlorides thereof.

  Examples of the phosphonic acid group-containing polymerizable monomer include 2- (meth) acryloyloxyethyl phenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, and 6- (meth) acryloyloxyhexyl-3. -Phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonoacetate, 10- (meth) acryloyloxydecyl-3- Examples thereof include polymerizable monomers such as phosphonoacetate and acid chlorides thereof.

  Examples of the pyrophosphate group-containing polymerizable monomer include bis [2- (meth) acryloyloxyethyl pyrophosphate], bis [4- (meth) acryloyloxybutyl pyrophosphate], and bis [6- (meta ) Acryloyloxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate, and acid chlorides thereof. It is done.

  Examples of the carboxylic acid group-containing polymerizable monomer include maleic acid, methacrylic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxybutyloxycarbonylphthalic acid, 4- (meth). Acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloyloxydecyloxycarbonylphthalic acid, and acid anhydrides thereof; 5- (meth) acryloylaminopentylcarboxylic acid Acid, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 8- (meth) acryloyloxy-1,1-octanedicarboxylic acid, 10- (meth) acryloyloxy-1,1-decanedicarboxylic acid, 11- (Meth) acryloyl Polymerizable monomers such as carboxymethyl-1,1-undecane dicarboxylic acid, and chlorides, etc. These acids.

  Examples of the sulfonic acid group-containing polymerizable monomer include polymerizable monomers such as 2- (meth) acrylamide-2-methylpropane sulfonic acid, styrene sulfonic acid, 2-sulfoethyl (meth) acrylate, and the like. Examples thereof include acid chlorides.

  Examples of the thiophosphate group-containing polymerizable monomer include polymerizable monomers such as 10- (meth) acryloyloxydecyl dihydrogendithiophosphate, and acid chlorides thereof.

  Among these polymerizable monomers (G) having an acidic group, a polymerizable monomer having a phosphoric acid group or a thiophosphoric acid group is used because of its excellent adhesiveness to a tooth and a dental prosthesis. Is preferred. Among these, a divalent phosphate group-containing polymerizable monomer having an alkyl group or alkylene group having 6 to 20 carbon atoms in the main chain in the molecule is more preferable, such as 10-methacryloyloxydecyl dihydrogen phosphate. Most preferred is a divalent phosphate group-containing polymerizable monomer having an alkylene group having 8 to 12 carbon atoms in the main chain.

  The polymerizable monomer (G) having an acidic group may be used alone or in combination of two or more. The blending amount of the polymerizable monomer having an acidic group is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the total of the fluoroaluminosilicate glass particles (A) and the mixture (B). The range of 1 to 10 parts by weight is more preferable, and the range of 0.1 to 5 parts by weight is most preferable.

  The water (E) used in the present invention is preferably one that does not contain impurities that adversely affect the curing of the composition and the development of adhesive strength with the teeth. Water and ion exchange water are preferred.

  Content of water (E) is 1-40 weight part with respect to a total of 100 weight part of a fluoroaluminosilicate glass particle (A) and a mixture (B) in the dental curable composition of this invention. When the content of water (E) is less than 1 part by weight, glass ionomer reaction with fluoroaluminosilicate glass particles (A) and polyalkenoic acid (C) and water (E), water with mixture (B) and water (E) The sum reaction does not occur sufficiently. The content of water (E) is preferably 2 parts by weight or more. On the other hand, when content of water (E) exceeds 40 weight part, the mechanical strength of hardened | cured material falls. The content of water (E) is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, and most preferably 10 parts by weight or less from the viewpoint of the mechanical strength of the cured product. .

  The polymerization initiator (F) used in the present invention can be selected from known chemical polymerization initiators and / or photopolymerization initiators used in the general industry.

  Regarding the chemical polymerization initiator in the polymerization initiator (F), from the viewpoint of adhesion and storage stability, a peroxide, an aromatic secondary amine and / or an aromatic tertiary amine, and an aromatic sulfinate are used. A ternary chemical polymerization initiator is included as a preferred specific example.

  Examples of the peroxide used for the chemical polymerization initiator include inorganic peroxides such as peroxodisulfate, diacyl peroxides, peroxyesters, peroxycarbonates, dialkyl peroxides, and peroxyketals. And organic peroxides such as ketone peroxides and hydroperoxides. Specific examples of peroxodisulfate include sodium peroxodisulfate, potassium peroxodisulfate, aluminum peroxodisulfate, and ammonium peroxodisulfate. Examples of diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, lauroyl peroxide, and the like. Examples of peroxyesters include t-butyl peroxybenzoate, bis-t-butyl peroxyisophthalate, t-butyl peroxy-2-ethylhexanoate, and the like. Examples of peroxycarbonates include t-butyl peroxyisopropyl carbonate. Examples of dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, and the like. Examples of peroxyketals include 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis ( t-hexylperoxy) cyclohexane and the like. Examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl acetoacetate peroxide. Examples of hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, p-diisopropylbenzene peroxide, and the like.

  Examples of the aromatic sulfinate used for the chemical polymerization initiator include benzenesulfinic acid, p-toluenesulfinic acid, o-trienesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, and 2,4. , 6-trimethylbenzenesulfinic acid, 2,4,6-triisopropylbenzenesulfinic acid, chlorobenzenesulfinic acid, lithium salt such as naphthalenesulfinic acid, sodium salt, potassium salt, rubidium salt, cesium salt, magnesium salt, calcium salt Strontium salt, iron salt, copper salt, zinc salt, ammonium salt, tetramethylammonium salt, tetraethylammonium salt and the like.

  Examples of the aromatic secondary amine and / or aromatic tertiary amine used for the chemical polymerization initiator include N-methylaniline, N-methyl-p-toluidine, N-methyl-m-toluidine, N- Methyl-o-toluidine, N-ethanol-p-toluidine, N-ethanol-m-toluidine, N-ethanol-o-toluidine, ethyl p-methylaminobenzoate, ethyl m-methylaminobenzoate, o-methylamino Ethyl benzoate, p-methylaminoanisole, m-methylaminoanisole, o-methylaminoanisole, 1-methylaminonaphthalene, 2-methylaminonaphthalene, N, N-dimethylaniline, N, N-dimethyl-p-toluidine N, N-dimethyl-m-toluidine, N, N-dimethyl-o-toluidine, N, N-die Nor-p-toluidine, N, N-diethanol-m-toluidine, N, N-diethanol-o-toluidine, ethyl p-dimethylaminobenzoate, ethyl m-dimethylaminobenzoate, ethyl o-dimethylaminobenzoate, Examples thereof include p-dimethylaminoanisole, m-dimethylaminoanisole, o-dimethylaminoanisole, 1-dimethylaminonaphthalene and 2-dimethylaminonaphthalene.

  Examples of the photopolymerization initiator in the polymerization initiator (F) include α-diketones, ketals, thioxanthones, acylphosphine oxides, and α-aminoacetophenones. Specific examples of α-diketones include camphorquinone, benzyl, and 2,3-pentanedione. Specific examples of ketals include benzyl dimethyl ketal and benzyl diethyl ketal. Specific examples of thioxanthones include 2-chlorothioxanthone and 2,4-diethylthioxanthone. Specific examples of acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, dibenzoylphenylphosphine oxide, and bis (2,6-dimethoxy). Benzoyl) phenylphosphine oxide, tris (2,4-dimethylbenzoyl) phosphine oxide, tris (2-methoxybenzoyl) phosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2, 3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyl-bis (2,6-dimethylphenyl) phosphine oxide, 2,4,6- Water-soluble acylphosphine oxide compounds trimethyl benzoyl ethoxyphenyl phosphine oxide and KOKOKU 3-57916 Patent Publication discloses the like. Specific examples of α-aminoacetophenones include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl-2-diethylamino-1- (4-morpholinophenyl). ) -Butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -propanone-1 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -pentanone-1, 2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -pentanone-1.

  One type of polymerization initiator (F) may be used alone, or a plurality of types may be used in combination. The blending amount of the polymerization initiator (F) (the total amount of compounds contained as the polymerization initiator) is 0.01 to 20 with respect to a total of 100 parts by weight of the fluoroaluminosilicate glass particles (A) and the mixture (B). It is the range of a weight part, The range of 0.1-10 weight part is preferable, The range of 0.5-5 weight part is more preferable. In addition, in order to make a kit for producing the dental curable composition of the present invention, it is preferable to appropriately package components used as a polymerization initiator (F) in consideration of storage stability.

  In the dental curable composition of the present invention, in order to increase the polymerization initiating ability of the polymerization initiator (F) (chemical polymerization initiator and / or photopolymerization initiator), aliphatic amines and aromatic amines are further added. Polymerization accelerators such as aldehydes, aldehydes, and thiol compounds may be used in combination.

  The dental curable composition of the present invention may contain an X-ray contrast agent as necessary. This is because monitoring of the filling operation and changes after filling can be tracked. Examples of the X-ray contrast agent include one selected from barium sulfate, bismuth carbonate, bismuth oxide, zirconium oxide, ytterbium fluoride, iodoform, barium apatite, barium titanate, lanthanum glass, barium glass, strontium glass, and the like. Or two or more are mentioned.

The dental curable composition of the present invention may further contain a filler for the purpose of improving fluidity and improving the mechanical strength of the cured product. One type of filler may be blended, or a plurality of types may be blended in combination. As the filler, minerals based on silica such as kaolin, clay, mica, mica; silica based, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , BaO, La ₂ O ₃ , Examples thereof include ceramics and glasses containing SrO, ZnO, CaO, P ₂ O ₅ , Li ₂ O, Na ₂ O and the like. As the glass, soda glass, lithium borosilicate glass, zinc glass, borosilicate glass, and bioglass are preferably used. Crystal quartz, alumina, titanium oxide, yttrium oxide, and aluminum hydroxide are also preferably used.

  The above X-ray contrast agent and filler may be used after surface treatment with a known surface treatment agent such as a silane coupling agent as necessary. Examples of the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. , Γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like.

  When the above-mentioned X-ray contrast agent and / or filler is further blended in the dental curable composition of the present invention, the blending amount is 100 weights in total of the fluoroaluminosilicate glass particles (A) and the mixture (B). It is preferably used in the range of 50 parts by weight or less with respect to parts.

  In the dental curable composition of the present invention, a known water-soluble fluorinated compound can be further blended within a range that does not adversely affect the adhesiveness in order to increase the amount of fluorine ions released. For example, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, beryllium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride, zinc fluoride, aluminum fluoride, Manganese fluoride, copper fluoride, lead fluoride, silver fluoride, antimony fluoride, cobalt fluoride, bismuth fluoride, tin fluoride, silver diammine fluoride, sodium monofluorophosphate, potassium titanium fluoride, fluoride Water-soluble metal fluorides such as stannate and fluorosilicate can be exemplified, and one or more of these can be used. In blending, it is preferable to use, for example, a method of forming metal fluoride into fine particles or a method of coating the metal fluoride with polysiloxane.

  Furthermore, the dental curable composition of this invention may contain a well-known stabilizer, dye, a pigment, etc. as needed.

  The dental curable composition of the present invention can be a kit in which the components of the dental curable composition are packaged as a product form. In order to obtain a kit in a product form, various forms are conceivable, and examples thereof include two-material forms such as powder / liquid, paste / liquid, and paste / paste. In any form, it is difficult to coexist three components of fluoroaluminosilicate glass powder (A), polyalkenoic acid (C) and water (E) in one material from the viewpoint of storage stability. Similarly, it is difficult to allow the mixture (B) and water (E) to coexist in one material from the viewpoint of storage stability. From the viewpoint of storage stability, it is preferable to take a powder / liquid packaging form such as the following (1) to (6).

  Packaging form (1): Fluoroaluminosilicate glass particles (A), mixture (B), powder material containing polyalkenoic acid (C) and polymerization initiator (F), polymerizable monomer having no acidic group ( D) A powder-type dental curable composition kit packaged in a liquid material containing water (E) and a polymerization initiator (F).

  Packaging form (2): powder material containing fluoroaluminosilicate glass particles (A), mixture (B) and polymerization initiator (F), polyalkenoic acid (C), polymerizable monomer having no acidic group ( D) A powder-type dental curable composition kit packaged in a liquid material containing water (E) and a polymerization initiator (F).

  Packaging form (3): powder containing fluoroaluminosilicate glass particles (A), mixture (B), polyalkenoic acid (C) and polymerization initiator (F), polyalkenoic acid (C), no acidic group A powder-type dental curable composition kit packaged in a liquid material containing a polymerizable monomer (D), water (E) and a polymerization initiator (F).

  Packaging form (4): Fluoroaluminosilicate glass particles (A), mixture (B), powder containing polyalkenoic acid (C) and polymerization initiator (F), polymerizable monomer having no acidic group ( D) A powder liquid type dental curable composition kit packaged in a liquid material containing a polymerizable monomer (G) having an acidic group, water (E) and a polymerization initiator (F).

  Packaging form (5): powder material containing fluoroaluminosilicate glass particles (A), mixture (B) and polymerization initiator (F), polyalkenoic acid (C), polymerizable monomer having no acidic group ( D) A powder liquid type dental curable composition kit packaged in a liquid material containing a polymerizable monomer (G) having an acidic group, water (E) and a polymerization initiator (F).

  Packaged form (6): Fluoroaluminosilicate glass particles (A), mixture (B), powder material containing polyalkenoic acid (C) and polymerization initiator (F), polyalkenoic acid (C), no acidic group Powder type dental use packaged in a polymerizable material (D), a polymerizable monomer (G) having an acidic group, water (E) and a liquid material containing a polymerization initiator (F) Curable composition kit.

  Among the above forms, from the viewpoint of storage stability, the powder liquid type dental curable composition kit shown in the packaging forms (1) and (4) in which the polyalkenoic acid (C) is blended only in the powder material The powder liquid type dental curable composition kit shown in the packaging form (4) is more preferable because of its excellent adhesion to the tooth and the dental prosthesis.

  Here, in the kit of the product form of the dental curable composition of the present invention, the weight ratio (X / Y) of the powder material (X) to the liquid material (Y) is 1.0 to 5.0. Preferably, this makes it possible to develop performances such as powder liquid kneadability and mechanical strength sufficient as a dental curable composition. The weight ratio (X / Y) of the powder material (X) to the liquid material (Y) is more preferably 1.2 to 3.6, and most preferably 1.4 to 3.0.

  The dental curable composition of the present invention is excellent in sustained release of calcium ions and fluorine ions, which are known as active ingredients for remineralization. Moreover, the dental curable composition of this invention has the favorable adhesiveness with respect to prosthetics, such as a zirconia, and the favorable adhesiveness with respect to a tooth | gear. And the hardened | cured material of the dental curable composition of this invention has favorable mechanical strength (bending strength etc.). Therefore, the dental curable composition of the present invention can be suitably used as a dental material used for filling and repairing a defective part of a tooth affected part, and for attaching a defective part of a tooth affected part and a prosthesis. It can be suitably used as a resin-reinforced glass ionomer cement.

  Specifically, the dental curable composition of the present invention is used, for example, as follows. That is, in the case of filling restoration, the dental curable composition of the present invention in the form of a single paste is filled into the dental cavity after a conventional dental cavity cleaning. When a prosthesis such as a crown or inlay is used for bonding, the book is made into a single paste after the surface of the tooth cavity or abutment is cleaned and the surface of the prosthesis is cleaned. The dental curable composition of the invention is applied to the tooth cavity and the abutment tooth surface and / or the prosthesis surface. As described above, by using the dental curable composition of the present invention, it is possible to repair a tooth defect portion having a high degree of completion.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all.

  In this example, the average particle size of fluoroaluminosilicate glass particles (A), acidic calcium phosphate particles (B1), basic calcium phosphate particles (B2), calcium compounds not containing phosphorus (B3) and polyalkenoic acid (C) The particle size distribution was measured using a laser diffraction type particle size distribution measuring apparatus (“SALD-2100 type” manufactured by Shimadzu Corporation), and the median diameter calculated from the measurement result was defined as the average particle diameter.

[Preparation of fluoroaluminosilicate glass particles (A)]
<Fluoroaluminosilicate glass particles>
A commercially available fluoroaluminosilicate glass (G018-117, manufactured by SCHOTT, average particle size: 40.0 μm) and 200 g of zirconia balls having a diameter of 20 mm were mixed with 400 ml of an alumina grinding pot (“Type A-3HD Pot Mill” manufactured by Nikkato Co., Ltd.) ) And pulverization for 15 hours at a rotational speed of 150 rpm, to obtain fluoroaluminosilicate glass particles having an average particle diameter of 4 μm.

[Preparation of acidic calcium phosphate particles (B1)]
<Anhydrous calcium monohydrogen phosphate particles>
Commercially available anhydrous calcium monohydrogen phosphate particles (Taihei Chemical Industry Co., Ltd., average particle size 15.0 μm) 50 g, 95% ethanol (Wako Pure Chemical Industries, Ltd. “Ethanol (95)”) 120 g, and a diameter of 10 mm Into a 400 ml alumina grinding pot (“Type A-3 HD pot mill” manufactured by Nikkato Co., Ltd.), wet grinding was performed for 24 hours at a rotational speed of 120 rpm. After the ethanol was distilled off with a rotary evaporator, the resulting slurry was dried at 60 ° C. for 6 hours, and further vacuum dried at 60 ° C. for 24 hours to obtain anhydrous calcium monohydrogen phosphate particles having an average particle diameter of 1.0 μm. Obtained.
<Tricalcium phosphate particles>
Commercially available α-tricalcium phosphate (manufactured by Taihei Chemical Industrial Co., Ltd., average particle size 1 μm) was used as it was.
<Anhydrous calcium dihydrogen phosphate particles>
Commercially available anhydrous calcium dihydrogen phosphate (manufactured by Taihei Chemical Industrial Co., Ltd., average particle size 1 μm) was used as it was.

[Preparation of Basic Calcium Phosphate Particles (B2)]
<Tetracalcium phosphate particles>
Commercially available anhydrous calcium monohydrogen phosphate particles (Product No. 1430, JT Baker Chemical Co., NJ) and calcium carbonate (Product No. 1288, JT Baker Chemical Co., NJ) and equimolar After adding to water and stirring for 1 hour, it was filtered and dried. The obtained cake-like equimolar mixture was heated at 1500 ° C. for 24 hours in an electric furnace (FUS732PB, manufactured by Advantech Toyo Co., Ltd.), and then cooled to room temperature in a desiccator to prepare a tetracalcium phosphate lump. Furthermore, it grind | pulverized roughly in the mortar, and adjusted the particle size in the range of 0.5-3 mm except the fine powder and the tetracalcium phosphate lump by carrying out the afterglow, and obtained crude tetracalcium phosphate. The obtained crude tetracalcium phosphate was crushed with a NanoJet Mizer (NJ-100 type, manufactured by Aisin Nano Technologies Co., Ltd.) with a pulverization pressure condition of raw material supply pressure: 0.7 MPa / crushing pressure: 0.7 MPa, and a treatment amount condition of 8 kg. / Hr was processed once to obtain tetracalcium phosphate particles having an average particle diameter of 5.0 μm.

[Preparation of calcium compound (B3) containing no phosphorus]
<Calcium hydroxide>
50 g of commercially available calcium hydroxide (manufactured by Kawai Lime Industry Co., Ltd., average particle size 14.5 μm), 99.5% ethanol (“Ethanol, Dehydrated (99.5)” manufactured by Wako Pure Chemical Industries, Ltd.) 240 g, and diameter 480 g of 10 mm zirconia balls was added to a 1000 ml alumina grinding pot (“HD-B-104 pot mill” manufactured by Nikkato Co., Ltd.), and wet vibration grinding was performed for 15 hours at a rotational speed of 1500 rpm. After distilling off ethanol with a rotary evaporator, the obtained slurry was dried at 60 ° C. for 6 hours to obtain calcium hydroxide having an average particle diameter of 1.0 μm.
<Calcium metasilicate>
50 g of commercially available calcium metasilicate (manufactured by Wako Pure Chemical Industries), 99.5% ethanol (“Ethanol, Dehydrated (99.5)” manufactured by Wako Pure Chemical Industries, Ltd.) 240 g, and 480 g of zirconia balls having a diameter of 10 mm In addition to a 1000 ml alumina grinding pot (“HD-B-104 pot mill” manufactured by Nikkato Co., Ltd.), wet vibration grinding was performed at a rotational speed of 1500 rpm for 15 hours. After the ethanol was distilled off by a rotary evaporator, the obtained slurry was vacuum-dried at 60 ° C. for 6 hours to obtain calcium silicate having an average particle size of 5.0 μm.

[Preparation of polyalkenoic acid (C)]
<Polyalkenoic acid>
When the polyalkenoic acid was added to the liquid material, a commercially available polyalkenoic acid (manufactured by Nissei Chemical Industry Co., Ltd.) was used as it was. In addition, when adding to the powder material, a commercially available polyalkenoic acid (manufactured by Nissei Chemical Industry Co., Ltd.) is nanojet mizer (NJ-100 type, manufactured by Aisin Nanotechnology Co., Ltd.), and the pulverization pressure condition is the raw material supply pressure: 0.7 MPa / Crushing pressure: 0.7 MPa, the treatment amount condition was 8 kg / hr, and obtained by carrying out one treatment. The average particle size of the obtained polyalkenoic acid powder was 3 μm.

[Polymerizable monomer having no acidic group (D)]
The compounds indicated by the following abbreviations were used.
HEMA: 2-hydroxyethyl methacrylate Bis-GMA: 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane # 801: 1,2-bis (3-methacryloyloxy-2-hydroxy Propyloxy) ethane GDMA: glycerol dimethacrylate

[Water (E)]
Water (E) used commercially available Japanese Pharmacopoeia purified water (manufactured by Takasugi Pharmaceutical Co., Ltd.) as it was.

[Polymerization initiator (F)]
The compounds indicated by the following abbreviations were used.
<Peroxide>
KPS: potassium peroxodisulfate (average particle size: 2.5 μm)
<Aromatic tertiary amine>
DEPT: N, N-bis (2-hydroxyethyl) -p-toluidine <aromatic sulfinate>
TPSS: sodium 2,4,6-triisopropylbenzenesulfinate

[Polymerizable monomer having acidic group (G)]
The compounds indicated by the following abbreviations were used.
MDP: 10-methacrylolyloxydecyl dihydrogen phosphate

[Others]
<Hydroxyapatite>
Commercially available hydroxyapatite (HAP-100, manufactured by Taihei Chemical Industrial Co., Ltd.) was used as it was.
<Polymerization inhibitor>
BHT: 2,6-di-tert-butyl-4-methylphenol

(Preparation of powder material)
Fluoroaluminosilicate glass particles (A) weighed with the compositions shown in Tables 1 to 3; acidic calcium phosphate particles (B1) and basic calcium phosphate particles (B2), or acidic calcium phosphate particles (B1) and phosphorus-free calcium compounds (B3) ), Or hydroxyapatite; polymerization initiator (F); and, if necessary, polyalkenoic acid powder (C) is added to a high-speed rotary mill (“SM-1” manufactured by AS ONE Co., Ltd.) at a rotational speed of 1000 rpm for 3 minutes. The powder material was obtained by mixing.

(Preparation of liquid material)
Polymerizable monomer (D), water (E), polymerization initiator (F) having no acidic group weighed with the composition shown in Tables 1 to 3, and polyalkenoic acid powder (C) and acidic group as required A liquid material was prepared by stirring the polymerizable monomer (G) having a viscosity of 24 hours with a magnetic stirrer.

[Examples 1 to 24]
0.1 g of the powder material having the composition shown in Tables 1 and 2 is precisely weighed, and the liquid material having the composition shown in Tables 1 and 2 is added thereto so that the weight ratio of the powder solution shown in Tables 1 and 2 is reached. A paste was prepared by kneading on (85 × 115 mm) for 30 seconds, and fluorine ion release properties, calcium ion release properties, bending strength, and adhesion to zirconia were evaluated by the test methods described below. The obtained evaluation results are summarized in Tables 1 and 2.

[Comparative Examples 1 to 10]
0.1 g of the powder material having the composition shown in Table 3 was precisely weighed, and the liquid material having the composition shown in Table 3 was added to the powder liquid weight ratio shown in Table 3, and on the kneaded paper (85 × 115 mm). The paste was prepared by kneading for 30 seconds, and the fluorine ion releasing property, calcium ion releasing property, bending strength and adhesiveness to zirconia were evaluated by the measurement methods described below. The evaluation results obtained are summarized in Table 3.

[Measurement method of fluorine ion release properties]
Each dental curable composition of Examples and Comparative Examples (paste obtained by kneading powder material and liquid material) was placed in a mold having a diameter of 15 mm and a thickness of 1 mm, and a 37 ° C. incubator. The cured product was taken out of the mold and immersed in 4 ml of 0.2 M phosphate buffer (pH 7, 37 ° C.) after being allowed to stand inside for 1 hour to cure. After soaking for 28 days, 2 ml of the TISAB solution was added, and the fluoride ions eluted in the phosphate buffer were quantified using a fluoride ion electrode (Thermo SCIENTIFIC).

[Measurement method of calcium ion release]
Each dental curable composition of Examples and Comparative Examples (paste obtained by kneading powder material and liquid material) was placed in a mold having a diameter of 15 mm and a thickness of 1 mm, and a 37 ° C. incubator. The cured product was taken out of the mold and immersed in 5 ml of ion-exchanged water (37 ° C.). After immersion for 28 days, 5 ml of KCl aqueous solution (15 g / l) was added, and calcium ions eluted in ion-exchanged water were quantified using a calcium ion electrode (manufactured by HORIBA).

[Measurement method of bending strength]
Each dental curable composition of Examples and Comparative Examples (paste obtained by kneading powder material and liquid material) was filled in a mold (2 mm × 2 mm × 25 mm), and the upper and lower sides were pressed with a slide glass. Then, it was left to stand in a 37 ° C. incubator for 1 hour to be cured. A test piece obtained by removing the cured product from the mold is immersed in water at 37 ° C. for 24 hours, and then a three-point bending test at a crosshead speed of 1 mm / min using a universal testing machine (manufactured by Shimadzu Corporation). The bending strength was measured by the method. The bending strength is an average value of measured values for five test pieces.

[Measurement method of tensile bond strength to zirconia]
After the surface of a rectangular parallelepiped (1 cm × 1 cm × 5 mm) zirconia sintered body (manufactured by Kuraray Noritake Dental Co., Ltd., trade name “sword”) is polished with # 1000 silicon carbide paper under running water to make a smooth surface, The surface water was blown with air and dried. An adhesive tape having a thickness of about 150 μm having a round hole with a diameter of 5 mm was attached to the smooth surface after drying to regulate the adhesion area. Each dental curable composition of Examples and Comparative Examples (paste obtained by kneading powder material and liquid material) is one end surface of a stainless steel cylindrical rod (diameter 7 mm, length 2.5 cm) ( The end surface on the side where the dental curable composition was built is placed so that the center of the round hole and the center of the stainless steel cylindrical rod substantially coincide with each other. A stainless steel cylindrical rod was pressed and adhered perpendicularly to the smooth surface to prepare a sample for testing. Seven test samples were prepared. After removing the excess dental curable composition that protruded from the periphery of the stainless steel cylindrical rod when pressed, the test sample was allowed to stand at room temperature for 30 minutes and immersed in distilled water. A test sample immersed in distilled water was allowed to stand for 24 hours in a thermostat maintained at 37 ° C., and then the tensile adhesive strength was examined. The tensile bond strength was measured with a universal testing machine (manufactured by Shimadzu Corporation) with the crosshead speed set to 2 mm / min. The tensile bond strength with respect to zirconia is an average value of the measured values of seven test samples.

  As shown in Tables 1 and 2, the dental curable compositions of the present invention produced in Examples 1 to 24 exhibit high fluorine ion release properties and calcium ion release properties, and also have high bending strength, which is higher than that of zirconia. Even high adhesion was exhibited. On the other hand, as shown in Table 3, the dental curable composition not containing the mixture (B) prepared in Comparative Example 1 had extremely low calcium ion release properties. Similarly, the dental curable composition not containing the mixture (B) prepared in Comparative Example 2 and containing hydroxyapatite also had extremely low calcium ion release properties. Moreover, the dental curable composition containing no fluoroaluminosilicate glass particles and polyalkenoic acid produced in Comparative Example 3, and the dental curable composition containing too little of the fluoroaluminosilicate glass particles produced in Comparative Examples 4 and 5 Had low calcium ion release and fluorine ion release. Further, the excessively mixed dental curable composition of polyalkenoic acid prepared in Comparative Example 6 and the excessively water-borne dental curable composition prepared in Comparative Example 7 had low bending strength. The dental curable composition containing no polyalkenoic acid prepared in Comparative Example 8 had a low calcium ion releasing property and did not exhibit adhesion to zirconia. The dental curable composition not containing polyalkenoic acid prepared in Comparative Example 9 but containing the acidic group-containing polymerizable monomer (G) showed adhesion to zirconia, but low calcium ion release properties. The dental curable composition which does not contain polyalkenoic acid prepared in Comparative Example 10 but contains an acidic group-containing polymerizable monomer (G) and contains only the component (B1) of the mixture (B) has a calcium ion releasing property. Was low.

  The dental curable composition of the present invention is useful for filling and repairing a defective part of a tooth affected part, and for joining a defective part of a tooth affected part and a prosthesis, and particularly suitably used as a dental resin-reinforced glass ionomer cement. be able to.

Claims (6)

  Fluoroaluminosilicate glass particles (A), acidic calcium phosphate particles (B1) and basic calcium phosphate particles (B2) or a mixture of phosphorous-free calcium compound particles (B3) (B), polyalkenoic acid (C), acidic groups A dental curable composition containing a polymerizable monomer (D), water (E), and a polymerization initiator (F) not having the fluoroaluminosilicate glass particles (A) and the mixture (B ) Containing 30 to 99 parts by weight of the fluoroaluminosilicate glass particles (A), 1 to 70 parts by weight of the mixture (B), and 1 to 60 parts of the polyalkenoic acid (C). 5 to 90 parts by weight of the polymerizable monomer (D) not containing the acidic group, 1 to 40 parts by weight of the water (E), and the polymerization initiator (F). Dental curable composition comprising .01～20 parts.   The acidic group-containing polymerizable monomer (G) is further contained in an amount of 0.1 to 30 parts by weight with respect to a total of 100 parts by weight of the fluoroaluminosilicate glass particles (A) and the mixture (B). Dental curable composition. The dental curable composition is in a two-material form, and has a powder material containing fluoroaluminosilicate glass particles (A), a mixture (B), a polyalkenoic acid (C) and a polymerization initiator (F), and an acidic group. The dental curable composition according to claim 1 or 2, wherein the dental curable composition is packaged in a liquid material containing a polymerizable monomer (D), water (E) and a polymerization initiator (F). The liquid material contains an acidic group-containing polymerizable monomer (G), and the content of the acidic group-containing polymerizable monomer (G) is such that the fluoroaluminosilicate glass particles (A) and the mixture (B) The dental curable composition according to claim 3, which is 0.1 to 30 parts by weight with respect to 100 parts by weight in total. The dental curable composition according to claim 3 or 4, wherein the liquid material further contains polyalkenoic acid (C). A dental resin-reinforced glass ionomer cement using the dental curable composition according to any one of claims 1 to 5 .