JP6501189B2 - Dental curable composition and method for producing the same - Google Patents

Description

  The present invention relates to a dental hardenable composition which has both the operation time and the hardening time as well as the effect of improving the remineralizing ability to dentin as compared with the conventional glass ionomer cement.

  Glass ionomer cement is used by reacting a polymer acid containing an acid such as polycarboxylic acid as a main component with a glass powder for a glass ionomer cement in the presence of water and curing. Glass ionomer cements have good affinity to the living body, have excellent adhesion to teeth such as enamel and dentin, and furthermore, teeth due to fluorine contained in glass powder. In the dental field, it has characteristics such as quality remineralization and anti-cariogenic activity, so in the dental field, filling of cavity, insertion of crown-inlay-bridge and orthodontic band, lining of cavity, root canal It is a material widely used for sealers for filling, construction of abutments and preventive filling.

  Glass ionomer cements have excellent features, but ease of use, i.e. operability, is important when considering their clinical use. The processability refers to the characteristics of the glass powder, polyalkenoic acid and water from the start of kneading until a certain time, and is strongly affected by the operation time and curing time defined by JIS and the like. In actual practice, it is desirable for cement hygienists and doctors to operate as long as possible and to have a working time as long as possible, while a cement that hardens rapidly when inserted into the oral cavity.

  On the other hand, with the so-called 8020 exercise (improvement of oral hygiene and preservation of dental substance (MI: Minimal Intervention)), which tries to keep at least 20 teeth at 80 years of age, it is possible to minimize the area affected by caries. In recent years, remineralization treatments that bring back the damaged part of the caries affected by material without scraping have been spotlighted in recent years. Glass ionomer cement is also widely recognized as a restorative material that can release fluoride ion, which is known as an active ingredient of remineralization, and reduce the cutting amount of dentin. However, hydroxyapatite, which is the main component of enamel and dentin tooth material, is a compound consisting of calcium and phosphorus, and efficient remineralization of the caries affected area requires only fluoride ion to the tooth material. Supply is not enough to promote.

  Non-Patent Document 1 describes that incorporation of 15% β-TCP into a glass ionomer cement powder promotes remineralization of enamel and improves the acid resistance of the remineralization site. There is. However, when calcium phosphate is added for the purpose of remineralization, the acid resistance of the enamel in contact with the cured product is improved, while the reactivity between calcium phosphate and polyalkenoic acid is high, and the reaction with each other starts immediately after kneading. However, there was a problem that sufficient operation time was not secured. In addition, since a sufficient crosslinking reaction does not proceed with the combination of calcium phosphate and polyalkenoic acid, there is also a problem that the curing time in the oral cavity is delayed.

  Patent Document 1 describes a glass powder for glass ionomer cement containing apatite. According to this, the mechanical strength, particularly the three-point bending strength and the tensile strength are improved as compared with the case where the conventional glass powder for dental glass ionomer cement is used, and it is insufficient in the conventional dentistry. It is said that glass ionomer cement can be applied to the filling of a cavity or the like which has been considered to be heavily loaded. However, the operation time and the hardening time at the time of preparing cement may not necessarily be in the appropriate range, and remineralization ability may be insufficient in some cases, and improvement has been desired.

  As described in the above-mentioned prior documents, in the prior art, when calcium phosphate is added to improve the remineralizing ability, there is a problem that the operability required in the clinic and the curing time can not be compatible. Yes, there is a need to improve these problems.

JP 2001-354509 A

Hong, Y. W. et al, The effect of nano-sized β-tricalcium phosphate on remineralization in glass ion donor dental cement, Key Engineering Materials, 2008, 361-363 (pt. 2, Bioceramics), pp. 861-864

  The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a dental curable composition having a long operation time, a fast curing time in the oral cavity, and excellent remineralizing ability. It is.

  The subject is a dental curable composition comprising fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or a salt thereof (C), polyalkenoic acid (D) and water (E). Calcium phosphate particles (containing 35 to 75 parts by weight of fluoroaluminosilicate glass particles (A) with respect to 100 parts by weight of the total dental curable composition) and 100 parts by weight of fluoroaluminosilicate glass particles (A) 1 to 30 parts by weight of B), 0.1 to 10 parts by weight of ethylenediaminetetraacetic acid or a salt thereof (C), 10 to 40 parts by weight of polyalkenoic acid (D), and 13 to 10 of water (E) The problem is solved by providing a dental hardenable composition characterized in that it comprises 90 parts by weight.

  At this time, the calcium phosphate particles (B) preferably contain at least a calcium phosphate particle (B1) having a molar ratio of Ca / P of 1.30 or more, and the molar ratio of Ca / P of the calcium phosphate particles (B) is 0.8. It is preferable that it is -2.2. In addition, it is preferable that it is a glass ionomer cement.

  Moreover, the said subject also contains a dental curable composition containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or a salt thereof (C), polyalkenoic acid (D) and water (E). A method of producing a fluoroaluminosilicate glass particle (A) and a calcium phosphate particle (B) as essential components, and at least one selected from the group consisting of ethylenediaminetetraacetic acid or a salt thereof (C) and a polyalkenoic acid (D) At least one selected from the group consisting of a powder material (X) containing one kind as an optional component, water (E) as an essential component, ethylenediaminetetraacetic acid or a salt thereof (C) and a polyalkenoic acid (D) The weight ratio (X / Y) of the powder material (X) to the liquid material (Y) of the liquid material (Y) containing as an optional component is 1.0 to 5.0 It is solved by providing a method for producing a dental curable composition to be mixed urchin.

  At this time, powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B) and ethylenediaminetetraacetic acid or its salt (C) as essential components, and polyalkenoic acid (D) as optional components, It is preferable to mix with a liquid material (Y) containing polyalkenoic acid (D) and water (E) as essential components and containing ethylenediaminetetraacetic acid or its salt (C) as an optional component. By previously mixing fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or a salt (C) thereof, fluoroaluminosilicate glass particles (A) / ethylenediaminetetraacetic acid or a salt (C) complex (P) can be obtained. It is preferred to have the process of obtaining. It is preferable that the complex (P) is obtained by heat-treating the fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or its salt (C), and the complex (P) is It is preferable that the fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or a salt thereof (C) be obtained by mechanochemically complexing. Having a step of obtaining calcium phosphate particles (B) / ethylenediaminetetraacetic acid or a salt (C) complex (Q) by previously mixing calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt (C) thereof It is suitable. It is preferable that complex (Q) is obtained by heat-treating calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt (C) thereof, and complex (Q) is calcium phosphate particles ( It is preferable that it is obtained by mechanochemically complexing B) and ethylenediaminetetraacetic acid or a salt thereof (C).

Also, the object is achieved by a dental curable composition kit consisting a powder material (X) liquid material and (Y), fluoroaluminosilicate glass particles (A), the calcium phosphate particles (B) and ethylenediaminetetraacetic acid Or a powder (X) containing the salt (C) as an essential component and optionally containing a polyalkenoic acid (D), and containing polyalkenoic acid (D) and water (E) as essential components, ethylenediaminetetraacetic acid or its salt liquid material containing salt (C) as an optional component and (Y), the weight ratio of the powder material (X) and the liquid material (Y) (X / Y) is Ri Do and 1.0 to 5.0, dental The composition contains 35 to 75 parts by weight of fluoroaluminosilicate glass particles (A) per 100 parts by weight of the total curable composition, and calcium phosphate particles (B) is 1 per 100 parts by weight of fluoroaluminosilicate glass particles (A). 30 parts by weight, 0.1 to 10 parts by weight of ethylenediaminetetraacetic acid or a salt thereof (C), 10 to 40 parts by weight of polyalkenoic acid (D), and 13 to 90 parts by weight of water (E) The problem is also solved by providing a dental curable composition kit characterized in that the powder material (X) and the liquid material (Y) are mixed and used.

  According to the present invention, there is provided a dental curable composition having a sufficient operation time, a quick curing time in the oral cavity, and excellent remineralization ability. As a result, the operation time is as long as possible, while it becomes possible to provide a material that hardens rapidly when it is inserted into the oral cavity, and it does not scrape the site affected by the caries as much as possible. It is possible to remineralize the diseased site with materials.

  The dental curable composition of the present invention comprises a fluoroaluminosilicate glass particle (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or a salt thereof (C), a polyalkenoic acid (D) and water (E). Curable composition, which comprises 35 to 75 parts by weight of fluoroaluminosilicate glass particles (A) to 100 parts by weight of the total dental curable composition, and 100 parts by weight of fluoroaluminosilicate glass particles (A) And 1 to 30 parts by weight of calcium phosphate particles (B), 0.1 to 10 parts by weight of ethylenediaminetetraacetic acid or a salt thereof (C), and 10 to 40 parts by weight of polyalkenoic acid (D), and It is characterized by including 13 to 90 parts by weight of water (E). The dental hardenable composition of the present invention makes it possible to provide a material which is as long as possible in operation time but which hardens rapidly when it is placed in the oral cavity, and at the same time it is possible to abrade the site affected by caries as much as possible. In addition, remineralization treatment that restores the remaining caries affected area by the material becomes possible. The mechanism of action is not necessarily clear, but the following mechanism is presumed.

When calcium phosphate particles (B) are present in fluoroaluminosilicate glass particles (A), polyalkenoic acid (D) and water (E) which are starting materials for glass ionomer cements that cure via acid-base reaction (glass ionomer reaction) Since the reactivity of polyalkenoic acid (D) to calcium phosphate particles (B) is higher than that to fluoroaluminosilicate glass (A), the operation time is not sufficiently secured, and the presence of excess calcium ions causes negative ions (carboxyl group, -COO ^-) reaction with polyalkene acid (E) with is considered not forced sufficiently. On the other hand, ethylenediaminetetraacetic acid or its salt (C), which is more reactive than polyalkenoic acid (D) to calcium phosphate particles (B) due to the presence of ethylenediaminetetraacetic acid or its salt (C) in this system, is calcium. By chelating the ions, the reaction time between the polyalkenoate (D) and the calcium phosphate particles (B) is delayed, so it seems that a sufficient operation time can be secured. Further, ethylenediaminetetraacetic acid or a salt thereof (C) is believed to chelate calcium ions and also to contribute to the crosslinking reaction, so it will ultimately accelerate curing and appears to accelerate the curing time in the oral cavity . Since the presence of calcium phosphate particles (B) can impart the release of ions of calcium and phosphorus, which are the main constituent elements of tooth substance, in addition to the sustained release of fluorine originally possessed by glass ionomer cement, effective recalcification of tooth substance Is also possible.

  The dental curable composition of the present invention comprises a fluoroaluminosilicate glass particle (A), a calcium phosphate particle (B), ethylenediaminetetraacetic acid or a salt thereof (C), a polyalkenoic acid (D) and water (E). It is a curable composition for use, and it is necessary to contain 35 to 75 parts by weight of fluoroaluminosilicate glass particles (A) with respect to 100 parts by weight of the total amount of the dental curable composition. When the content of the fluoroaluminosilicate glass particles (A) is less than 35 parts by weight, sufficient mechanical properties of the fluoroaluminosilicate glass particles (A) for forming a three-dimensional network structure by the glass ionomer reaction are insufficient. There is a possibility that the target strength may not be obtained, and it is preferably 40 parts by weight or more, and more preferably 45 parts by weight or more. On the other hand, when the content of the fluoroaluminosilicate glass particles (A) exceeds 75 parts by weight, the unreacted fluoroaluminosilicate glass particles (A) are present in excess, and sufficient strength for clinical use can not be secured sufficiently. And 70 parts by weight or less, and more preferably 65 parts by weight or less.

  The average particle diameter of the fluoroaluminosilicate glass particles (A) used in the present invention is preferably 0.3 to 35 μm. When the average particle size of the fluoroaluminosilicate glass particles (A) is less than 0.3 μm, the average particle size is too small to manufacture, and furthermore, the viscosity of the paste obtained by mixing with the liquid material is high There is a risk of becoming too much. The average particle size of the fluoroaluminosilicate glass particles (A) is more preferably 0.5 μm or more, and particularly preferably 1 μm or more. On the other hand, when the average particle diameter of the fluoroaluminosilicate glass particles (A) exceeds 35 μm, there is a possibility that the paste property is not preferable, for example, the paste obtained by mixing with the liquid material does not show sufficient viscosity. In addition, there is a possibility that the feeling of roughness during paste mixing may be increased and the operability may be impaired, and furthermore, when applied in the oral cavity, the patient may be given an impression of poor touch. The average particle diameter of the fluoroaluminosilicate glass particles (A) is more preferably 30 μm or less, and particularly preferably 10 μm or less. Here, the average particle diameter of the fluoroaluminosilicate glass particles (A) used in the present invention is measured and calculated using a laser diffraction type particle size distribution measuring device.

  The method for producing the fluoroaluminosilicate glass particles (A) used in the present invention is not particularly limited. A commercially available fluoroaluminosilicate glass powder may be used as it is, or a commercially available product may be further ground. In that case, pulverizing devices such as a ball mill, a lice mill, and a jet mill can be used. Also, known fluoroaluminosilicate glass particles conventionally used as a powder component of dental glass ionomer cement may be used. For example, fluorite, alumina, aluminum hydroxide, aluminum borate, mullite, calcium borate, strontium borate, sodium borate, aluminum carbonate, calcium carbonate, calcium carbonate, strontium carbonate, sodium carbonate, sodium fluoride, calcium fluoride, fluoride Glass raw materials selected from aluminum, strontium fluoride, aluminum phosphate, calcium phosphate, strontium phosphate, sodium phosphate etc. can be weighed, melted at a high temperature of 1000 ° C. or higher, cooled and then crushed to prepare fine powder . In that case, pulverizing devices such as a ball mill, a lice mill, and a jet mill can be used. Further, after cooling, the obtained glass body (frit) is pulverized by a pulverizing means such as a ball mill and optionally subjected to classification treatment such as sieving to obtain a glass having a desired average particle diameter and particle size distribution. Powder can be obtained. In addition, a fluoroaluminosilicate glass raw material powder is pulverized with a liquid medium such as alcohol using a liquifier, a ball mill or the like to prepare a slurry, and the obtained slurry is dried to obtain fluoroaluminosilicate glass particles (A). You can also get At this time, it is preferable to use a ball mill as a grinding apparatus, and alumina and zirconia are preferably adopted as the material of the pot and ball.

  In the dental curable composition of the present invention, it is necessary to contain 1 to 30 parts by weight of calcium phosphate particles (B) to 100 parts by weight of fluoroaluminosilicate glass particles (A). When the amount of calcium phosphate particles (B) is less than 1 part by weight, there is a possibility that the amount of released calcium ion or phosphate ion for expressing sufficient remineralization may not be sufficient. The content of the calcium phosphate particles (B) is preferably 2 parts by weight or more, and more preferably 3 parts by weight or more. On the other hand, when calcium phosphate particles (B) exceed 30 parts by weight, the reaction of polyalkenoate (D) with calcium phosphate particles (B) is more than the reaction of polyalkenoate (D) with fluoroaluminosilicate glass particles (A) Since it is early, there is a possibility that appropriate operation time can not be secured. The content of the calcium phosphate particles (B) is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less.

  In the dental curable composition of the present invention, the calcium phosphate particles (B) are calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more and / or calcium phosphate particles having a Ca / P molar ratio of less than 1.30. It consists of (B2).

The calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more used in the present invention are not particularly limited, and octacalcium phosphate pentahydrate [Ca ₈ H ₂ (PO ₄ ) ₆ · 5 H ₂ O Particles, tricalcium phosphate [Ca ₃ (PO ₄ ) ₂ ] particles, amorphous calcium phosphate [Ca ₃ (PO ₄ ) ₂ · xH ₂ O] particles, hydroxyapatite [Ca ₁₀ (PO ₄ ) ₆ (OH) particles] It is preferable that it is at least one selected from the group consisting of ₂ ] particles and tetracalcium phosphate [Ca ₄ (PO ₄ ) ₂ O] particles. Among these, tricalcium phosphate [Ca ₃ (PO ₄ ) ₂ ] particles, amorphous calcium phosphate [Ca ₃ (PO ₄ ) ₂ · x H ₂ O] particles, hydroxyapatite [Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ) particles, and at least one selected from the group consisting of tetracalcium phosphate [Ca ₄ (PO ₄ ) ₂ O] particles is more preferably used, tricalcium phosphate [Ca ₃ (PO ₄ ) ₂ At least one selected from the group consisting of particles, hydroxyapatite [Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ] particles, and tetracalcium phosphate [Ca ₄ (PO ₄ ) ₂ O] particles, more preferably In particular, tetracalcium phosphate [Ca ₄ (PO ₄ ) ₂ O] particles are more preferably used from the viewpoint of remineralization ability.

  It is preferable that the average particle diameter of the calcium phosphate particle (B1) whose Ca / P molar ratio used by this invention is 1.30 or more is 0.3-35 micrometers. If the average particle size is less than 0.3 μm, the viscosity of the paste obtained by mixing with the liquid material may be high, and the desired paste properties may not be exhibited. The average particle diameter of the calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more is more preferably 0.4 μm or more, and particularly preferably 0.5 μm or more. On the other hand, when the average particle size exceeds 35 μm, paste properties such as a paste obtained by mixing with a liquid material may not exhibit sufficient viscosity may be undesirable. Furthermore, the graininess at the time of paste mixing may be increased, and the operability may be impaired. The average particle diameter of the calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more is more preferably 30 μm or less, and particularly preferably 25 μm or less. Here, the average particle diameter of calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more used in the present invention is calculated in the same manner as the average particle diameter of the fluoroaluminosilicate glass particles (A). .

  The method for producing the calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more used in the present invention is not particularly limited. A calcium phosphate particle having a commercially available Ca / P molar ratio of 1.30 or more may be used as it is, or may be appropriately pulverized to adjust the particle size for use. As a grinding method, a method similar to the grinding method of calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 described later can be adopted.

The calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 used in the present invention are not particularly limited, but anhydrous calcium monohydrogenphosphate [CaHPO ₄ ] particles, anhydrous calcium dihydrogenphosphate [Ca (H) ₂ PO ₄ ) ₂ ] particles, calcium acid pyrophosphate [CaH ₂ P ₂ O ₇ ] particles, calcium monohydrogen phosphate dihydrate [CaHPO ₄ · 2 H ₂ O] particles, and calcium dihydrogen phosphate monohydrate It is preferable that it is at least one selected from the group consisting of [Ca (H ₂ PO ₄ ) ₂ .H ₂ O] particles. Among these, anhydrous calcium monohydrogenphosphate [CaHPO ₄ ] particles, anhydrous calcium dihydrogenphosphate [Ca (H ₂ PO ₄ ) ₂ ] particles, and calcium monohydrogenphosphate dihydrate [CaHPO ₄ · 2H ₂ O] At least one selected from the group consisting of particles is more preferably used, anhydrous calcium monohydrogenphosphate [CaHPO ₄ ] particles, and calcium monohydrogenphosphate dihydrate [CaHPO ₄ · 2H ₂ O] At least one selected from the group consisting of particles is more preferably used, and in particular, anhydrous calcium monohydrogenphosphate [CaHPO ₄ ] particles are preferably used from the viewpoint of remineralization ability.

  The average particle diameter of the calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 used in the present invention is preferably 0.3 to 35 μm. If the average particle size is less than 0.3 μm, the viscosity of the paste obtained by mixing with the liquid material may be too high, and is preferably 0.4 μm or more, and particularly preferably 0.5 μm or more. On the other hand, when the average particle size exceeds 35 μm, paste properties such as a paste obtained by mixing with a liquid material may not exhibit sufficient viscosity may be undesirable. Furthermore, the graininess at the time of paste mixing may be increased, and the operability may be impaired. The average particle diameter of calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 is more preferably 30 μm or less, and particularly preferably 25 μm or less. The average particle diameter of calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 is calculated in the same manner as the average particle diameter of the fluoroaluminosilicate glass particles (A).

  The method for producing calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 having such an average particle diameter is not particularly limited, and a commercially available product may be used if it can be obtained. It is often desirable to further grind commercial products. In that case, pulverizing devices such as a ball mill, a lice mill, and a jet mill can be used. In addition, a calcium phosphate raw material powder having a Ca / P molar ratio of less than 1.30 is pulverized with a liquid medium such as alcohol using a liquifier, a ball mill or the like to prepare a slurry, and the obtained slurry is dried. Calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 can also be obtained. At this time, it is preferable to use a ball mill as a grinding apparatus, and alumina and zirconia are preferably adopted as the material of the pot and ball.

  Here, when using the calcium phosphate particle (B1) whose Ca / P molar ratio is 1.30 or more and the calcium phosphate particle (B2) whose Ca / P molar ratio is less than 1.30 in combination, the Ca / P molar ratio By increasing the average particle size of calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more compared to the average particle size of calcium phosphate particles (B2) having a ratio of less than 1.30, the balance of solubility of both is improved. As appropriate, the pH in the composition can be maintained near neutral. As a result, the precipitation of hydroxyapatite becomes smooth, and the remineralization effect can be improved. Specifically, the average particle diameter of calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more to twice or more the average particle diameter of calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 Is more preferably 4 times or more, and particularly preferably 7 times or more. On the other hand, the average particle diameter of calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more should be 35 times or less of the average particle diameter of calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30. Is more preferably, 30 times or less is more preferable, and 25 times or less is particularly preferable. When calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more and calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 are used in combination, the compounding ratio is not particularly limited. From the viewpoint of promoting remineralization by apatite precipitation, the Ca / P ratio of the total of calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more and calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30. Is preferably used at a blending ratio of 0.8 to 2.2, more preferably 1.10 to 1.95, still more preferably 1.30 to 1.80, In particular, 1.50 to 1.70 is preferable. This makes it possible to obtain the dental curable composition of the present invention having a high remineralization effect.

  In the dental curable composition of the present invention, it is necessary to contain 0.1 to 10 parts by weight of ethylenediaminetetraacetic acid or a salt (C) thereof with respect to 100 parts by weight of the fluoroaluminosilicate glass particles (A). If the content of ethylenediaminetetraacetic acid or its salt (C) is less than 0.1 parts by weight, there is a risk that a sufficient operation time can not be secured. The content of ethylenediaminetetraacetic acid or a salt (C) thereof is preferably 0.2 parts by weight or more, and particularly preferably 0.3 parts by weight or more. On the other hand, when the content of ethylenediaminetetraacetic acid or its salt (C) exceeds 10 parts by weight, the curing time in the oral cavity may be delayed. The content of ethylenediaminetetraacetic acid or a salt thereof (C) is preferably 5 parts by weight or less, and more preferably 3.5 parts by weight or less. The ethylenediaminetetraacetic acid or its salt (C) may be added as it is in the form of powder and may be added or may be added as a liquid material. Furthermore, ethylenediaminetetraacetic acid and ethylenediaminetetraacetic acid salt may be simultaneously blended.

  In the present invention, the fluoroaluminosilicate glass particles (A) / ethylenediaminetetraacetic acid or a salt (C) complex is prepared by previously mixing the fluoroaluminosilicate glass particles (A) with ethylenediaminetetraacetic acid or a salt thereof (C). The method of obtaining (P) is suitably employed. In that case, it is preferable that a composite (P) is obtained by mechanochemically complexing fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or a salt (C) thereof. As a method of mechanochemically complexing, a method using a dry pulverizing apparatus such as a ball mill, lycaing machine, jet mill, etc. of fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or its salt (C) is suitably employed. Be done.

  In the present invention, the fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or a salt thereof (C) are mixed in water and dried to thereby form the fluoroaluminosilicate glass particles (A) / ethylenediaminetetraacetic acid or a salt thereof (C ) Complex (P) can also be obtained.

  In the present invention, the composite (P) is preferably obtained by heat-treating the fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or a salt thereof (C). As heat processing, after mixing fluoroaluminosilicate glass particle (A) and ethylenediamine tetraacetic acid or its salt (C) in water as mentioned above, it is preferable to apply the heat of 70-150 ° C, and to dry. When drying, a drier is preferably used. When the heat treatment temperature is less than 70 ° C., it is inefficient when drying in a large amount, and there is a risk that the internal water may not evaporate sufficiently. As for the heat processing temperature, 75 degreeC or more is more preferable, and especially 80 degreeC or more is preferable. On the other hand, when the heat treatment temperature exceeds 150 ° C., ethylenediaminetetraacetic acid or a salt thereof (C) may be strongly bonded to the fluoroaluminosilicate glass particles (A), and the curing time of the resulting dental curable composition may be delayed. There is. The heat treatment temperature is more preferably 140 ° C. or less, particularly preferably 130 ° C. or less.

  In the present invention, a method of obtaining calcium phosphate particles (B) / ethylenediaminetetraacetic acid or a salt (C) complex (Q) by preliminarily mixing calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt thereof (C) Is preferably employed. In that case, the complex (Q) is preferably obtained by mechanochemically complexing calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt (C) thereof. As a method of complexing mechanochemically, a method using a dry pulverizing apparatus such as a ball mill, a lice mill, a jet mill or the like is suitably adopted as calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt thereof (C).

  In the present invention, calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt thereof (C) are mixed in water and dried to obtain calcium phosphate particles (B) / ethylenediaminetetraacetic acid or a salt thereof (C) complex (Q) You can also get

  In the present invention, the complex (Q) is preferably obtained by heat-treating calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt (C) thereof. As heat processing, after mixing calcium phosphate particle (B) and ethylenediamine tetraacetic acid or its salt (C) in water as mentioned above, it is preferable to apply the heat of 70-250 ° C, and to dry. When drying, a drier is preferably used. When the heat treatment temperature is less than 70 ° C., it is inefficient when drying in a large amount, and there is a risk that the internal water may not evaporate sufficiently. As for the heat processing temperature, 75 degreeC or more is more preferable, and especially 80 degreeC or more is preferable. On the other hand, when the heat treatment temperature exceeds 250 ° C., ethylenediaminetetraacetic acid or its salt (C) itself may be decomposed, or ethylenediaminetetraacetic acid or its salt (C) may be strongly bonded to calcium phosphate particles (B). The curing time of the dental curable composition may be delayed. The heat treatment temperature is more preferably 200 ° C. or less, particularly preferably 150 ° C. or less.

  In the present invention, calcium phosphate particles (B1) / ethylenediaminetetraacetic acid or a salt thereof (a calcium phosphate particle (B1)) / ethylenediaminetetraacetic acid or a salt thereof C) Complex (Q) can be obtained. Further, calcium phosphate particles (B2) / ethylenediaminetetraacetic acid or a salt thereof (C) are prepared by previously mixing calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 and ethylenediaminetetraacetic acid or a salt thereof (C). Complex (Q) can also be obtained. As a method of obtaining the complex (Q), the method described above is suitably adopted. The calcium phosphate particles (B1) / ethylenediaminetetraacetic acid or salt thereof (C) complex (Q) may be used in combination with the calcium phosphate particles (B2) / ethylenediaminetetraacetic acid or salt thereof (C) complex (Q) . Among them, calcium phosphate particles (B1) / ethylenediaminetetraacetic acid or a salt thereof (C) by preliminarily mixing calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more and ethylenediaminetetraacetic acid or a salt thereof (C). It is a preferred embodiment of the present invention to obtain complex (Q).

  In the dental curable composition of the present invention, it is necessary to contain 10 to 40 parts by weight of polyalkenoic acid (D) with respect to 100 parts by weight of fluoroaluminosilicate glass particles (A). If the content of the polyalkenoic acid (D) is less than 10 parts by weight, sufficient three-dimensional network structure formed by the glass ionomer reaction can not be formed sufficiently, and sufficient mechanical strength may not be obtained. The content is more preferably 13 parts by weight or more, and particularly preferably 18 parts by weight or more. On the other hand, when the content of polyalkenoic acid (D) exceeds 40 parts by weight, it exceeds the amount necessary to form a three-dimensional network structure by the glass ionomer reaction with the fluoroaluminosilicate glass particles (A), resulting in an excess not contributing to curing. Polyalkenoic acid (D) may cause curing failure. Further, the viscosity at the time of mixing may be too high to make the mixing difficult. The blending amount of the polyalkenoic acid (D) is more preferably 30 parts by weight or less, and particularly preferably 27 parts by weight or less.

  The polyalkenoic acid (D) used in the present invention is not particularly limited, and is a polymer of unsaturated monocarboxylic acid or unsaturated dicarboxylic acid, which is acrylic acid, methacrylic acid, 2-chloroacrylic acid, 2-cyanoacrylic acid Homopolymers such as acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, utraconic acid, or copolymers of two or more of these unsaturated carboxylic acids, and these Copolymers of unsaturated carboxylic acid and copolymerizable monomers can be mentioned, and these can be used alone or in combination of two or more. From the viewpoint of improving the dental bond strength and mechanical strength, at least one selected from the group consisting of a copolymer of acrylic acid and maleic acid and a copolymer of acrylic acid and itaconic acid is more preferable, particularly acrylic acid. And copolymers of itaconic acid. Furthermore, a polymer having a weight average molecular weight of 5,000 to 50,000 which does not contain a polymerizable ethylenic unsaturated double bond is preferable, and when the weight average molecular weight is less than 5,000, the strength of the cured product is It tends to be low, and the adhesion to the dentin may also decrease, and it is more preferably 10,000 or more, particularly preferably 35,000. When the weight average molecular weight exceeds 50,000, the viscosity at the time of mixing may be too high to make the mixing difficult, and it is more preferably 45,000 or less, particularly preferably 40,000 or less. Is preferred.

  The method for producing the polyalkenoic acid (D) used in the present invention is not particularly limited, and any commercially available product may be used. In particular, it is often preferable to further grind commercial products for addition to powder materials. In that case, a grinding apparatus such as a ball mill, a lice mill, a jet mill, a spray dryer or the like can be used. In addition, a polyalkenoic acid (D) can also be obtained by grinding a polyalkenoic acid powder together with a liquid medium such as alcohol using a liquifier, a ball mill or the like to prepare a slurry, and drying the obtained slurry. As a pulverizer at this time, it is preferable to use a spray drier.

  Furthermore, the polyalkenoic acid (D) used in the present invention may be added as it is in the form of powder or may be added to a liquid material to form a curable composition in any case. can do. In the present invention, when polyalkenoic acid (D) is added to both the powder material and the liquid material, an amount sufficient for securing the dentin adhesiveness and mechanical strength while maintaining the liquid material at an appropriate viscosity is used. It is preferable because it can be blended.

  Water (E) used in the present invention is an essential component in the liquid material for obtaining the dental curable composition of the present invention. That is, the reaction for mixing and curing the liquid material and the fluoroaluminosilicate glass particles (A) which is the main component of the powder material is a neutralization reaction between the fluoroaluminosilicate glass particles (A) and the polyalkenoic acid (D) Because it proceeds in the presence of water. In addition, the dental glass ionomer cement has the property of adhering to the surface of the tooth in the presence of water, and it is necessary for the water to be present in the dental glass ionomer cement liquid according to the present invention.

  In the dental curable composition of the present invention, it is necessary to contain 13 to 90 parts by weight of water (E) with respect to 100 parts by weight of the fluoroaluminosilicate glass particles (A). If the content of water (E) is less than 13 parts by weight, sufficient three-dimensional network structure formed by the glass ionomer reaction can not be formed sufficiently, and sufficient mechanical strength may not be obtained, and There is a possibility that sufficient hydration reaction can not occur with calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more and calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30. More preferably, it is at least 15 parts by weight. On the other hand, when the content of water (E) exceeds 90 parts by weight, fluoroaluminosilicate glass particles (A) in the paste after powder liquid milling, calcium phosphate particles having a Ca / P molar ratio of 1.30 or more (B1 And the Ca / P molar ratio is less than 1.30, the content of calcium phosphate particles (B2) may be reduced, and a cured product may not be obtained. In addition, even when a cured product is formed, the strength of the cured product itself may be reduced. The content of water (E) is more preferably 40 parts by weight or less, and particularly preferably 30 parts by weight or less.

  In the dental curable composition of the present invention, it is preferable to contain 0.3 to 10 parts by weight of tartaric acid with respect to 100 parts by weight of the fluoroaluminosilicate glass particles (A). In the present invention, a predetermined amount of tartaric acid can be added in order to adjust (delay) the curing reaction between the powder material and the acid component. As tartaric acid preferable for this purpose, D-tartaric acid, L-tartaric acid and DL-tartaric acid may be mentioned, but L-tartaric acid is particularly preferable in view of strength of the obtained cured product, improvement of aesthetics and the like. When the content of tartaric acid is less than 0.3 parts by weight, the powder material and the liquid material may be kneaded, and a sufficient operation time until adaptation to the patient may not be secured, and it is more than 1 part by weight In particular, 2 parts by weight or more is preferable. On the other hand, when the content of tartaric acid exceeds 10 parts by weight, the curing time is delayed and may not be cured in a clinically appropriate time, more preferably 7 parts by weight or less, particularly 5 parts by weight or less Is preferred. The tartaric acid may be added as it is in the form of powder and may be added as a liquid material and may be further added. Further, the fluoroaluminosilicate glass particles (A) and the Ca / P molar ratio are 1.30 or more. The calcium phosphate particles (B1) and the calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 can be blended by surface treatment.

  The method for producing tartaric acid used in the present invention is not particularly limited, and a commercially available product may be used if it is available. In particular, it is often preferable to further grind commercial products for addition to powder materials. In that case, a grinding apparatus such as a ball mill, a lice mill, a jet mill, a spray dryer or the like can be used. In addition, tartaric acid can also be obtained by grinding a tartaric acid powder with a liquid medium such as alcohol using a liquifier, a ball mill or the like to prepare a slurry, and drying the obtained slurry.

  The dental curable composition of the present invention may optionally contain an X-ray contrast agent. This is because it is possible to monitor the filling operation of the composition paste after powder liquid grinding and track changes after filling. As an X-ray contrast agent, for example, one selected from barium sulfate, bismuth subcarbonate, 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 X-ray contrast agent can be blended in a powder material, blended in a liquid material, or blended in a composition paste during kneading.

The dental curable composition of the present invention may further contain a filler which can be expected to improve the flowability of the powder material and the mechanical strength of the cured product. The filler may be blended singly or in combination of two or more. The filler is a mineral based on silica such as kaolin, clay, mica, mica etc .; based on silica, Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , BaO, La ₂ O ₃ , Ceramics and glasses containing SrO, ZnO, CaO, P ₂ O ₅ , Li ₂ O, Na ₂ O and the like are exemplified. As the glasses, 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 suitably used.

  A pigment may be blended for the purpose of imparting a predetermined color tone to the dental curable composition of the present invention and improving its aesthetics. The pigment to be blended includes an organic pigment (coloring pigment) consisting of a synthetic organic pigment or a natural organic pigment, and an inorganic pigment obtained from a synthetic mineral or a natural mineral. Discoloration due to hydrogen sulfide is remarkably observed when an inorganic pigment is blended, and hardly observed when an organic pigment is blended. Therefore, as the pigment, an organic pigment which is less susceptible to the action of hydrogen sulfide which is considered to be a cause of discoloration in the oral cavity is preferable.

  As organic pigments, Neucoxin, quinoline yellow WS (above, made by Red Fuji Chemical Industry Co., Ltd., trade name), PV Fast Red BNP, Graphtol Yellow 3 GP (above, Clariant Japan Co., Ltd., trade name), fast Green FCF (Kanto Chemical Co., Ltd., trade name) Blue No. 404 (Daito Kasei Kogyo Co., Ltd., trade name) Yellow 8 GNP, Yellow 3 GNP, Yellow GRP, Yellow 3 RLP, Red 2020, Red 2030, Red BRN, Red Examples include BRNP and Red BN (trade names, manufactured by Ciba Specialty Chemicals, Inc.).

  An inorganic pigment may be blended together with the organic pigment in order to impart a deep color tone unique to the dentin to the restoration site of the tooth, as long as the color does not cause discoloration. As the inorganic pigment, for example, non-toxic pigments such as red iron oxide, zinc oxide, titanium dioxide, carbon, ultramarine (ultramarine) and the like are preferable, and in order to prevent black change, an originally black inorganic pigment (iron oxide etc.) is used May be As a preferable inorganic pigment, KN-320, 100ED, YELLOW-48 (above, the Toda Kogyo Co., Ltd. make, brand name), etc. are mentioned.

  The method for producing the dental curable composition of the present invention is not particularly limited. It contains fluoroaluminosilicate glass particles (A) and calcium phosphate particles (B) as essential components, and optionally contains at least one selected from the group consisting of ethylenediaminetetraacetic acid or its salt (C) and polyalkenoic acid (D) A liquid material containing powder material (X) and water (E) as essential components, and optionally containing at least one selected from the group consisting of ethylenediaminetetraacetic acid or a salt thereof (C) and polyalkenoic acid (D) It is possible to obtain a dental curable composition by mixing Y) such that the weight ratio (X / Y) of the powder material (X) to the liquid material (Y) is 1.0 to 5.0. it can. For example, a powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), and ethylenediaminetetraacetic acid or its salt (C), and a liquid material containing polyalkenoic acid (D) and water (E) To obtain a dental curable composition by mixing (Y) with a powder material (X) and a liquid material (Y) so that the weight ratio (X / Y) is 1.0 to 5.0. Can. Fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or salt thereof (C) and powder material (X) containing polyalkenoic acid (D) and liquid material (Y) containing water (E) The dental curable composition can also be obtained by mixing and mixing the powder material (X) and the liquid material (Y) so that the weight ratio (X / Y) is 1.0 to 5.0. . Powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or its salt (C) and polyalkenoate (D), polyalkenoate (D) and water (E) The dental curable composition is also obtained by mixing the liquid material (Y) containing it so that the weight ratio (X / Y) of the powder material (X) to the liquid material (Y) is 1.0 to 5.0. You can get things.

  Among them, powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B) and ethylenediaminetetraacetic acid or its salt (C) as essential components, and polyalkenoic acid (D) as optional components, and polyalkene A method for producing a dental curable composition, which comprises mixing with a liquid material (Y) containing an acid (D) and water (E) as essential components and ethylenediaminetetraacetic acid or a salt thereof (C) as an optional component Will be adopted. Specifically, powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or its salt (C) and polyalkenoic acid (D), polyalkenoic acid (D) and A method for producing a dental hardenable composition which is mixed with a liquid material (Y) containing water (E), or fluoroaluminosilicate glass particles (A), calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt thereof (C) A method for producing a dental hardenable composition in which powder material (X) containing X) is mixed with liquid material (Y) containing polyalkenoic acid (D) and water (E) is suitably employed, and fluoroaluminosilicate glass Powder material (X) containing particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or its salt (C) and polyalkenoic acid (D), and polyalkene (D) and the manufacturing method of the liquid material (Y) and dental curable composition to mix containing water (E) is employed more preferably.

  Here, in the method for producing a dental hardenable composition of the present invention, the powder material (X) and the liquid material (Y) are mixed so that the weight ratio (X / Y) is 1.0 to 5.0. This is preferable, and thereby, it is possible to develop performances such as powder liquid removability and mechanical strength sufficient as a glass ionomer cement. It is more preferable to mix so that the weight ratio (X / Y) of powder material (X) and liquid material (Y) may be 1.5-4.5, and it may be 1.8-3.8. It is further preferred to mix.

  Here, in the presence of water (E), the fluoroaluminosilicate glass particles (A) and the polyalkenoic acid (D) react and harden, and calcium phosphate particles having a Ca / P molar ratio of 1.30 or more (B1) Hydroxyapatite glass particles (A), Ca / P molar ratio is 1.30, since hydroxyapatite is formed by hydration reaction of calcium phosphate particles (B2) having a molar ratio of Ca / P of less than 1.30. By previously mixing the above calcium phosphate particles (B1), calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30, ethylenediaminetetraacetic acid or its salt (C), polyalkenoic acid (D) and water (E) It can not be stored as a dental hardenable composition. From this point of view, at least one selected from the group consisting of ethylenediaminetetraacetic acid or its salt (C) and polyalkenoic acid (D) containing fluoroaluminosilicate glass particles (A) and calcium phosphate particles (B) as essential components Powder material (X) containing as an optional component, water (E) as an essential component, at least one selected from the group consisting of ethylenediaminetetraacetic acid or its salt (C) and polyalkenoic acid (D) as an optional component A dental hardenable composition which is used by mixing the liquid material (Y) containing it so that the weight ratio (X / Y) of the powder material (X) to the liquid material (Y) is 1.0 to 5.0. It is one of the embodiments of the present invention that it is a product kit. In addition, powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B) and ethylenediaminetetraacetic acid or its salt (C) as essential components, and polyalkenoic acid (D) as optional components, and polyalkene A liquid material (Y) containing an acid (D) and water (E) as essential components and ethylenediaminetetraacetic acid or a salt thereof (C) as an optional component, the weight of the powder material (X) and the liquid material (Y) It is also one of the embodiments of the present invention that it is a dental curable composition kit used by mixing so that the ratio (X / Y) is 1.0 to 5.0.

  Fluoroaluminosilicate glass particles (A), calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more, calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30, and ethylenediaminetetraacetic acid or a salt thereof ( Powder material (X) containing C), liquid material (Y) containing polyalkenoic acid (D) and water (E), weight ratio (X / Y) of powder material (X) to liquid material (Y) It is one of the embodiment of this invention that it is a dental curable composition kit which is mixed and used so that it may be 1.0-5.0. Fluoroaluminosilicate glass particles (A), calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more, calcium phosphate particles having a Ca / P molar ratio of less than 1.30 (B2), ethylenediaminetetraacetic acid or a salt thereof ( C) A powder material (X) containing polyalkenoic acid (D) and a liquid material (Y) containing water (E), the weight ratio (X / Y) of the powder material (X) to the liquid material (Y) It is one of the embodiment of this invention that it is a dental curable composition kit which is mixed and used so that it may be 1.0-5.0. Fluoroaluminosilicate glass particles (A), calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more, calcium phosphate particles having a Ca / P molar ratio of less than 1.30 (B2), ethylenediaminetetraacetic acid or a salt thereof ( C) The powder material (X) containing polyalkenoic acid (D) and the liquid material (Y) containing polyalkenoic acid (D) and water (E), the weight of powder material (X) and liquid material (Y) It is one of the embodiments of the present invention that it is a dental curable composition kit used by mixing so that the ratio (X / Y) is 1.0 to 5.0. In addition, fluoroaluminosilicate glass particles (A), calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more, calcium phosphate particles having a Ca / P molar ratio of less than 1.30 (B2), polyalkenoic acid (D) A powder (X) containing the powder, a liquid material (Y) containing ethylenediaminetetraacetic acid or a salt thereof (C), a polyalkenoic acid (D) and water (E), the powder (X) and the liquid material (Y) It is one of the embodiment of this invention that it is a dental curable composition kit which is mixed and used so that a weight ratio (X / Y) of 1.0 may become 1.0-5.0.

  Among them, fluoroaluminosilicate glass particles (A), calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more, calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30, ethylenediaminetetraacetic acid or the like Powder material (X) containing salt (C) and polyalkenoic acid (D), liquid material (Y) containing polyalkenoic acid (D) and water (E), powder material (X) and liquid material (Y) Dental curable composition kit used by mixing such that the weight ratio of (X / Y) is 1.0 to 5.0, or fluoroaluminosilicate glass particles (A), Ca / P molar ratio is 1. Powder material (X) containing calcium phosphate particles (B1) of 1.30 or more, calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30, and ethylenediaminetetraacetic acid or its salt (C), and polyalkenoic acid (D) And a liquid material (Y) containing water and water (E) in such a way that the weight ratio (X / Y) of the powder material (X) to the liquid material (Y) is 1.0 to 5.0 Dental curable composition kit is suitably employed, wherein the fluoroaluminosilicate glass particles (A), calcium phosphate particles having a Ca / P molar ratio of 1.30 or more (B1), and a Ca / P molar ratio of less than 1.30 Powder material (X) containing calcium phosphate particles (B2), ethylenediaminetetraacetic acid or salt (C) thereof and polyalkenoic acid (D), and liquid material (Y) containing polyalkenoic acid (D) and water (E) , A dental curable composition kit is more preferably adopted which is used by mixing so that the weight ratio (X / Y) of powder material (X) to liquid material (Y) is 1.0 to 5.0. Ru.

  Here, in the dental curable composition kit of the present invention, the powder material (X) and the liquid material (Y) are mixed and used such that the weight ratio (X / Y) is 1.0 to 5.0. It is preferable to do so, and thereby, it is possible to develop performances such as powder liquid dispersibility and mechanical strength which are sufficient as a glass ionomer cement. It is more preferable to mix and use powder material (X) and liquid material (Y) so that a weight ratio (X / Y) may be 1.5-4.5, and it will be 1.8-3.8. It is further preferred to use them as mixed. Further, the dental curable composition of the present invention is suitably used as a glass ionomer cement.

  Hereinafter, the present invention will be specifically described using examples. In this example, fluoroaluminosilicate glass particles (A), calcium phosphate particles (B1) with a Ca / P molar ratio of 1.30 or more, calcium phosphate particles with a Ca / P molar ratio of less than 1.30 (B2), ethylenediamine The average particle diameter of acetic acid or its salt (C), tartaric acid, and polyalkenoic acid (D) was measured using a laser diffraction type particle size distribution measuring apparatus ("SALD-2100" manufactured by Shimadzu Corporation), and the measurement results The median diameter calculated from the above was taken as the average particle diameter.

[Preparation of powder material and liquid material for glass ionomer cement]
(1) Preparation of Fluoroaluminosilicate Glass Particles (A) The fluoroaluminosilicate glass particles (A) were obtained by the following method, which is a commercially available fluoroaluminosilicate glass (G018-117, manufactured by SCHOTT, average particle diameter: 40.0 μm) Obtained by crushing.

  Fluoroaluminosilicate glass particles: 100 g of commercially available fluoroaluminosilicate glass (G018-117, manufactured by SCHOTT, average particle size 40.0 μm) with an average particle diameter of 30 μm, and alumina with 200 g of zirconia balls with a diameter of 20 mm are crushed with 400 ml of alumina It obtained by adding in a pot ("Type A 3 HD pot mill" made by Nikkato Co., Ltd.) and grinding for 5 hours at a rotational speed of 150 rpm.

  Fluoroaluminosilicate glass particles: 100 g of commercially available fluoroaluminosilicate glass (G018-117, manufactured by SCHOTT, average particle size 40.0 μm) with an average particle diameter of 4 μm, and alumina with 200 g of zirconia balls having a diameter of 20 mm are crushed with 400 ml of alumina It obtained by adding in a pot ("Type A 3 HD pot mill" made by Nikkato Co., Ltd.) and pulverizing at a rotational speed of 150 rpm for 15 hours.

  Fluoroaluminosilicate glass particles: an average particle diameter of 0.5 μm is a commercially available fluoroaluminosilicate glass (G018-117, manufactured by SCHOTT, an average particle diameter of 40.0 μm) as a nanojet miser (NJ-100, Aisin Nanotechnologies Corporation) Product), and the grinding pressure condition was as follows: raw material supply pressure: 0.7 MPa / milling pressure: 0.7 MPa, the processing amount condition was 8 kg / hr, and the treatment was performed once.

(2) Surface-treated fluoroaluminosilicate glass (A) (composite (P))
The treatment of fluoroaluminosilicate glass (A) with ethylenediaminetetraacetic acid or its salt (C) and tartaric acid was carried out according to the method shown below.

  EDTA 2% mechanochemically treated fluoroaluminosilicate glass particles: 100 g of the fluoroaluminosilicate glass (A) having an average particle diameter of 4 μm, 2.0 g of commercially available sodium edetate hydrate (manufactured by Wako Pure Chemical Industries, Ltd.), and a diameter of It was obtained by adding 200 g of 20 mm zirconia balls into a 400 ml alumina grinding pot (“Type A-3 HD pot mill” manufactured by Nikkato Co., Ltd.) and grinding for 5 hours at a rotation speed of 150 rpm.

  EDTA heat-treated fluoroaluminosilicate glass particles: 100 g of each fluoroaluminosilicate glass (A) having an average particle diameter of 0.5 μm, 4 μm, and 30 μm is charged into 100 g of distilled water, and after stirring for 10 minutes, commercially available sodium edetate An aqueous solution of 1.0 g (1% treated), 2.0 g (2% treated), and 4.0 g (4% treated) of hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) in 40 g of distilled water In addition, after stirring for 10 minutes, the obtained slurry was obtained by drying and heat-treating in a dryer at 90 ° C. for 16 hours on a stainless steel vat.

  Thermal treatment of tartaric acid fluoroaluminosilicate glass particles: 100 g of the fluoroaluminosilicate glass (A) having an average particle diameter of 4 μm is added to 100 g of distilled water and stirred for 10 minutes, and then commercially available L-tartaric acid (manufactured by Shibata Chemical Industry Co., Ltd.) ) After adding an aqueous solution of 1.0 g (treated with 1%) in 40 g of distilled water and stirring for 10 minutes, the obtained slurry is dried on a stainless steel vat in a dryer at 90 ° C. for 16 hours, It obtained by heat-processing at 200 degreeC.

(3) Preparation of calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more The calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more used in this example were prepared as follows: Obtained by grinding crude tetracalcium phosphate. Equimolar amounts of commercially available anhydrous calcium monohydrogenphosphate particles (Product No. 1430, JT Baker Chemical Co., NJ) and calcium carbonate (Product No. 1288, JT Baker Chemical Co., NJ) The mixture is stirred in water for 1 hour, and the cake-like equimolar mixture obtained by filtration and drying is heated at 1500 ° C. for 24 hours in an electric furnace (FUS732PB, Advantec Toyo Co., Ltd.) A tetracalcium phosphate mass was then prepared by cooling to room temperature in a desiccator. Furthermore, the mixture was roughly crushed in a mortar and then sieved to remove fine powder and tetracalcium phosphate lumps, and the particle size was adjusted in the range of 0.5 to 3 mm to obtain crude tetracalcium phosphate.

  Tetracalcium phosphate particles: Add 100 g of crude tetracalcium phosphate and 200 g of zirconia balls with a diameter of 20 mm into a 400 ml alumina grinding pot ("Type A-3 HD pot mill" manufactured by Nikkato Co., Ltd.) It was obtained by grinding for 5 hours at a rotational speed of 150 rpm.

  Tetracalcium phosphate particles: In an average particle diameter of 19.0 μm, 100 g of crude tetracalcium phosphate and 200 g of zirconia balls having a diameter of 20 mm are put into a 400 ml alumina grinding pot (“Type A-3 HD pot mill” manufactured by Nikkato Corporation) In addition, it was obtained by grinding for 15 hours at a rotational speed of 150 rpm.

  Tetracalcium phosphate particles: With an average particle size of 5.0 μm, crude tetracalcium phosphate is treated with Nanojet Miser (NJ-100, manufactured by Aisin Nano Technologies, Ltd.) under the crushing pressure conditions of the raw material supply pressure: 0.7 MPa / crushing The pressure was 0.7 MPa, and the throughput condition was 8 kg / hr, and it was obtained by treating once.

  Tricalcium phosphate particles: For the average particle diameter of 12 μm, commercially available α-tricalcium phosphate (made by Taihei Kagaku Sangyo Co., Ltd.) was used as it is.

(4) Preparation of calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 The anhydrous calcium monohydrogenphosphate particles (B2) used in this example are commercially available anhydrous calcium monohydrogenphosphate particles Chemical Industry Co., Ltd. (average particle diameter: 15.0 μm) was obtained by grinding according to the following method.

  Anhydrous calcium monohydrogenphosphate particles: The average particle size of 5.0 μm is 50 g of commercially available anhydrous calcium monohydrogenphosphate particles (made by Taiping Kagaku Sangyo Co., Ltd., average particle size 15.0 μm), 95% ethanol (Wako Pure Chemical Industries, Ltd.) Add 120g of "Ethanol (95)" made by Co., Ltd. and 240g of zirconia balls with a diameter of 10mm into a 400ml alumina grinding pot ("Type A-3 HD pot mill" made by Nikkato Co., Ltd.) at a rotation speed of 120rpm The slurry obtained by wet pulverizing for 24 hours was distilled of ethanol by a rotary evaporator, dried at 60 ° C. for 6 hours, and further dried at 60 ° C. for 12 hours under vacuum.

  Anhydrous calcium monohydrogenphosphate particles: The average particle size of 1.0 μm is 50 g of commercially available anhydrous calcium monohydrogenphosphate particles (made by Taiping Kagaku Sangyo Co., Ltd., average particle size 15.0 μm), 95% ethanol (Wako Pure Chemical Industries, Ltd.) Add 120g of "Ethanol (95)" made by Co., Ltd. and 240g of zirconia balls with a diameter of 10mm into a 400ml alumina grinding pot ("Type A-3 HD pot mill" made by Nikkato Co., Ltd.) at a rotation speed of 120rpm The slurry obtained by wet grinding for 24 hours was distilled of ethanol by a rotary evaporator, dried at 60 ° C. for 6 hours, and further dried at 60 ° C. for 24 hours under vacuum.

  Anhydrous calcium monohydrogenphosphate particles: The average particle size of 0.5 μm can be obtained by using commercially available anhydrous calcium monohydrogenphosphate particles (made by Taihei Kagaku Sangyo Co., Ltd., average particle size 15.0 μm) with a nanojet miser (NJ-100 type, Grinding pressure conditions were made into raw material supply pressure: 0.7MPa / grind pressure: 0.7MPa, and processing amount conditions were 8 kg / hr, and it obtained by processing it once by Aisin Nano Technologies company make.

  Anhydrous calcium dihydrogenphosphate particles: For the average particle diameter of 1 μm, commercially available anhydrous calcium dihydrogenphosphate (made by Taihei Kagaku Sangyo Co., Ltd.) was used as it was.

  The ethylenediamine tetraacetic acid or its salt (C) used the commercially available sodium edetate hydrate (made by Wako Pure Chemical Industries, Ltd.) as it was. However, only in the case of adding to the powder material, one having an average particle diameter of 15 to 25 μm was used for grinding for about 1 hour in an agate mortar.

(5) Surface-treated calcium phosphate particles (B) (complex (Q))
The treatment of calcium phosphate particles (B) with ethylenediaminetetraacetic acid or its salt (C) was carried out according to the method described below.

  EDTA 12.5% mechanochemically treated calcium phosphate particles: 100 g of tetracalcium phosphate particles having an average particle diameter of 19 μm, 2.0 g of commercially available sodium edetate hydrate (manufactured by Wako Pure Chemical Industries, Ltd.), and zirconia having a diameter of 20 mm It obtained by adding 200 g of balls in a 400-ml alumina grinding pot ("Type A-3 HD pot mill" manufactured by Nikkato Co., Ltd.) and grinding for 5 hours at a rotational speed of 150 rpm.

  EDTA heat-treated calcium phosphate particles: 100 g of tetracalcium phosphate particles having an average particle diameter of 5.0 μm, 19.0 μm, and 30 μm, and tricalcium phosphate having an average particle diameter of 1.0 μm are respectively added to 300 g of distilled water After stirring for 10 minutes, 7.0 g (7% treatment) of commercially available sodium edetate hydrate (manufactured by Wako Pure Chemical Industries, Ltd.), 12.5 g (12.5% treatment), and 14.0 g (14. An aqueous solution dissolved in 300 g of distilled water (0% treatment) was added, and after stirring for 10 minutes, the obtained slurry was dried and heat-treated in a dryer at 90 ° C. for 16 hours on a stainless steel vat.

(6) Preparation of tartaric acid As tartaric acid, commercially available L-tartaric acid (manufactured by Shibata Chemical Industry Co., Ltd.) was used as it was. However, only in the case of adding to the powder material, one having an average particle diameter of 15 to 25 μm was used for grinding for about 1 hour in an agate mortar.

(7) Preparation of polyalkenoic acid (D) When polyalkenoic acid (D) is added to a liquid material, a commercially available polyalkenoic acid (manufactured by Nichisei Seika Kogyo Co., Ltd.) is used as it is. The crushed one was used.

  Commercially available polyalkenoic acid (manufactured by Nippon Seikagaku Kogyo Co., Ltd.) was milled using Nanojet Miser (NJ-100, manufactured by Aisin Nano Technologies Inc.) under the grinding pressure conditions of the raw material supply pressure: 0.7 MPa / grind pressure: 0.7 MPa, throughput The conditions were 8 kg / hr and were obtained by treating once. The average particle diameter of the obtained polyalkenoic acid powder was 3 μm.

(8) Preparation of water (E) As water (E), commercially available Japanese Pharmacopoeia purified water (manufactured by Takasugi Pharmaceutical Co., Ltd.) was used as it was.

(9) Preparation of powder material Fluoroaluminosilicate glass particles (A) weighed with the composition shown in Tables 1 to 4, calcium phosphate particles having a Ca / P molar ratio of 1.30 or more (B1), a Ca / P molar ratio of 1 .30 or less of calcium phosphate particles (B2) and, if necessary, ethylenediaminetetraacetic acid or a salt thereof (C), tartaric acid and polyalkenoic acid powder (D) in a high-speed rotary mill ("SM-1" manufactured by As One Corporation) In addition, powder materials were obtained by mixing for 3 minutes at a rotational speed of 1000 rpm.

(10) Preparation of liquid material Ethylenediaminetetraacetic acid or its salt (C), L-tartaric acid (manufactured by Shibata Chemical Industry Co., Ltd.) and polyalkenoic acid powder (D) (Daiichi Biochemical Co., Ltd.) weighed according to the compositions shown in Tables 1 to 4 The liquid material was prepared by stirring the product (made by company) and water (E) with a magnetic stirrer for 24 hours.

[Operation time test]
Weigh accurately 0.15 g of the powder material having the composition shown in Tables 1 to 4 and add the liquid material having the composition shown in Table 1 to 4 on this to make the powder liquid weight ratio shown in Tables 1 to 4 and knead The paste was prepared. The stopwatch was started, and the powder was divided into two equal parts using the attached drawing rod, the first division was mixed with the solution, the rest was added, and the mixture was uniformly kneaded within a total of 30 seconds. About 20 mg of a small amount of paste was placed on a glass plate by 40 seconds after the start of mixing, and then another glass was pressed. The top glass was moved about 2 mm and applied a shear force every 15 to 15 seconds after the start of mixing. It was visually judged whether the material was physically uniform, and the time for producing two consecutive and uniform thin layers was taken as the operation time.

[Curing time test]
The test method of curing time conformed to ISO9917-1. Accurately weigh 1.0 g of the powder material having the composition shown in Tables 1 to 4, and add the liquid material having the composition shown in Table 1 to 4 on this to make the powder liquid weight ratio shown in Tables 1 to 4 and knead The paste was prepared. Start the stop watch, fill the mold on the glass plate and aluminum foil with the kneaded cement and then cover the aluminum foil, and keep the temperature and humidity controller (37 ° C, humidity 95%) by 1 minute Put in the After 2 minutes, the aluminum foil was removed. After 2 minutes and 30 seconds, a Vicat needle (400 g, having a flat end with a diameter of 1 mm) was dropped vertically onto the cement surface every 30 seconds, and maintained for 5 seconds. The above operation was repeated at intervals of 30 seconds, and the time until the impression could not be confirmed was calculated as the curing time.

[Operation]
(1) Operability 0.1 g of powder material having the composition shown in Tables 1 to 4 is precisely weighed, and a liquid material having the composition shown in Tables 1 to 4 is shown on Table 1 to 4 for powder liquid weight ratio. The paste was prepared by kneading for 30 seconds on a wasted paper (85 × 115 mm) to be added. The operability of the paste was evaluated according to the following evaluation criteria.

(2) Evaluation criteria for operability A: The familiarity immediately after the start of mixing of the powder material and the liquid material is good, and a paste can be obtained by mixing for 20 seconds with a dental mixing rod. The resulting paste has a good elongation and no roughness.
B: The familiarity immediately after the start of mixing of the powder material and the liquid material is a little bad, but it is possible to obtain a paste by mixing for 20 seconds with a dental mixing rod. Although the growth of the paste is good, it may feel rough during some mixing.
C: The familiarity immediately after the start of mixing of powder material and liquid material is not good, and it takes 30 seconds of mixing with a dental mixing rod to obtain a paste. Although the growth of the paste is good, it may feel rough during some mixing.
D: The familiarity immediately after the start of the mixing of the powder material and the liquid material is poor, and it can not take 30 seconds or more of mixing with a dental mixing rod to obtain a paste, or it can not be mixed. If it can be kneaded, the elongation of the paste is also bad, and it hardens on the kneading paper within 2 minutes and the operation time can not be secured. In addition, you may feel rough during the training.
A to C are actual use levels.

[Preparation of bovine teeth for remineralization]
The buccal center of the healthy incisor teeth was polished using a # 80, # 1000 abrasive paper with a rotary polishing machine to expose dentin. The bovine tooth-polished surface was further polished using a wrapping film (# 1200, # 3000, # 8000, manufactured by Sumitomo 3M) to make it smooth. In this dentin part, windows of 7 mm test parts were left in the longitudinal and transverse directions with respect to the teeth (hereinafter referred to as "dentin windows"), the surroundings were masked with nail polish and air-dried for 1 hour. This bovine tooth is immersed in 150 ml of 50 mM decalcifying solution diluted with acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) for one week to carry out decalcification, and then it is washed with water for 30 minutes or more, thereby remineralizing test Were prepared.

[Preparation of simulated saliva]
Sodium chloride (8.77 g, 150 mmol), potassium dihydrogen phosphate (122 mg, 0.9 mmol), calcium chloride (166 mg, 1.5 mmol), Hepes (4.77 g, 20 mmol) are weighed into weighing dishes, respectively, The mixture was sequentially added to a 2000 ml beaker containing 800 ml of distilled water with stirring. After confirming that the solute was completely dissolved, while measuring the acidity of this solution with a pH meter (F55, HORIBA, Ltd.), a 10% aqueous sodium hydroxide solution was dropped to adjust to pH 7.0. Next, this solution was added to a 1000 ml volumetric flask and made up to obtain 1000 ml of simulated saliva.

[Remineralization test]
The remineralizing bovine tooth prepared above is immersed in distilled water and allowed to stand for 30 minutes, and then the powder material and the liquid material are shown in Tables 1 to 4 on a Japanese paper for half of the dentine window. About 0.1 g of the paste obtained by mixing for 30 seconds at a powder liquid ratio was applied, and incubated at 37 ° C., 100% RH for 60 minutes for curing. Thereafter, the cured product was stored at 37 ° C. for 2 weeks in simulated saliva while keeping the cured product adhered to the remineralization test bovine tooth. Also, simulated saliva was changed daily (n = 5).

[Remineralization ability evaluation]
(1) Preparation of epoxy resin Preparation of the epoxy resin was performed according to the Luft method, and after mixing an epoxy resin and a hardening agent uniformly, the method of adding an accelerator was used. In a 100 ml disposable cup, 41 ml of Rubeak 812 (epoxy resin, made by Nacalai Tesque, Inc.), 31 ml of Rubeak MNA (hardening agent, made by Nacalai Tesque, Inc.), and 10 ml of Rubeak DDSA (hardening agent, made by Nacalai Tesque, Inc.) respectively The mixture was weighed into a disposable cup and stirred for 10 minutes. To this, 1.2 ml of Rubeak DMP-30 (accelerator, manufactured by Nacalai Tesque, Inc.) weighed with a disposable syringe was gradually added dropwise while stirring, and the mixture was further stirred for 10 minutes after the addition.

(2) Preparation of sample for hardness measurement The calcified bovine tooth was taken out from the simulated saliva, washed with water, and immersed in a 70% aqueous ethanol solution in a vial. Immediately after immersion, the vial was transferred into a desiccator and placed under vacuum for 10 minutes. After this, the vial was removed from the desiccator, attached to a low speed stirrer (TR-118, manufactured by AS-ONE), and stirred at a rotational speed of about 4 rpm for 1 hour. The same operation was performed using an 80% aqueous ethanol solution, a 90% aqueous ethanol solution, a 99% aqueous ethanol solution, and 100% ethanol (twice), and the second 100% ethanol was immersed as it was overnight. The next day, the same operation was sequentially performed on a 1: 1 mixed solvent of propylene oxide and ethanol, and 100% (twice) of propylene oxide, and the resultant was immersed in the second propylene oxide as it was overnight. Further, the same operation was performed on an epoxy resin: propylene oxide = 1: 1 mixed solution, an epoxy resin: propylene oxide = 4: 1 mixed solution, and an epoxy resin 100% (twice). The immersion time was 2 hours for these. Finally, a bovine tooth sample was placed in a plastic container containing an epoxy resin, and curing reaction was performed at 45 ° C. for 1 day and at 60 ° C. for 2 days. After completion of curing, it was cut in the direction perpendicular to the decalcified surface by a precision low speed cutter (BUEHLER, ISOMETl 000) together with a polyethylene container to obtain a section of about 1 mm in thickness including the cross section of the test portion. This section was polished using a wrapping film (# 1200, # 3000, # 8000, manufactured by Sumitomo 3M Co., Ltd.) to prepare a sample for hardness measurement (n = 5).

(3) Hardness measurement It measured by 2 mN load about the section of a decalcification part and a remineralization part using a nano indenter (ENT-1100a, product made by Elionix Co., Ltd.). In addition, the measurement performed the operation which performs ten points by 40 micrometers space | interval from a surface layer to a depth direction about three rows about each of a decalcification part and a remineralization part, and computed the average of the hardness in each depth. Furthermore, as a control, the three-point hardness was also measured for a non-decalcified normal dentin having a depth of 600 μm, and the average value was calculated. The remineralization ability was quantified by the following equation as a hardness recovery rate.

Hardness recovery rate (%) = [(average hardness of remineralized part at depth of 360 μm)-(average hardness of demineralized part at depth of 360 μm)] / (of hardness of healthy dentin) Average value) × 100

Examples 1-36
The dental curable composition was prepared with the composition shown in Tables 1 to 4 according to the above-described procedure, and the operability, the operation time, the hardening time and the remineralizing ability were evaluated. The obtained evaluation results are summarized in Tables 1 to 4. As hydroxyapatite particles (5 μm) used in Example 35, commercially available hydroxyapatite (HAP-100, manufactured by Taihei Kagaku Sangyo Co., Ltd.) was used as it was.

Comparative Examples 1 to 11
The composition was prepared with the composition shown in Table 4 according to the above-mentioned procedure, and the operability, the operation time, the curing time and the remineralization ability were evaluated. The obtained evaluation results are summarized in Table 4. In addition, the hydroxyapatite particle (5 micrometers) used for the comparative example 8 used the commercially available hydroxyapatite (HAP-100, Taihei Kagaku Sangyo Co., Ltd. make) as it was.

Claims (13)

A dental curable composition comprising fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or a salt thereof (C), polyalkenoic acid (D) and water (E),
35 to 75 parts by weight of fluoroaluminosilicate glass particles (A) with respect to a total amount of 100 parts by weight of the dental curable composition,
A polyalkenoic acid (D) contains 1 to 30 parts by weight of calcium phosphate particles (B) and 100 to 10 parts by weight of ethylenediaminetetraacetic acid or a salt (C) thereof with respect to 100 parts by weight of fluoroaluminosilicate glass particles (A) A dental hardenable composition comprising 10 to 40 parts by weight of water and 13 to 90 parts by weight of water (E).   The dental curable composition according to claim 1, wherein the calcium phosphate particles (B) contain calcium phosphate particles (B1) having a Ca / P molar ratio of at least 1.30.   The dental curable composition according to claim 1, wherein the Ca / P molar ratio of the calcium phosphate particles (B) is 0.8 to 2.2.   The dental curable composition according to any one of claims 1 to 3, which is a glass ionomer cement. A method for producing a dental curable composition comprising fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or a salt thereof (C), polyalkenoic acid (D) and water (E). ,
It contains fluoroaluminosilicate glass particles (A) and calcium phosphate particles (B) as essential components, and optionally contains at least one selected from the group consisting of ethylenediaminetetraacetic acid or its salt (C) and polyalkenoic acid (D) Powder material (X),
A liquid material (Y) containing water (E) as an essential component and optionally containing at least one selected from the group consisting of ethylenediaminetetraacetic acid or a salt thereof (C) and polyalkenoic acid (D),
The dental use according to any one of claims 1 to 3, characterized in that the powder material (X) and the liquid material (Y) are mixed so that the weight ratio (X / Y) is 1.0 to 5.0. Method of producing a curable composition.   Powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B) and ethylenediaminetetraacetic acid or its salt (C) as essential components and optionally containing polyalkenoic acid (D), and polyalkenoic acid The method for producing a dental curable composition according to claim 5, wherein D) and water (E) are contained as an essential component, and a liquid material (Y) containing ethylenediaminetetraacetic acid or its salt (C) as an optional component is mixed. .   By previously mixing fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or a salt (C) thereof, fluoroaluminosilicate glass particles (A) / ethylenediaminetetraacetic acid or a salt (C) complex (P) can be obtained. The manufacturing method of the dental hardenable composition of Claim 5 or 6 which has a process to obtain.   The production of a dental curable composition according to claim 7, wherein the composite (P) is obtained by heat-treating the fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or its salt (C). Method.   The dental curing according to claim 7, wherein the composite (P) is obtained by mechanochemically complexing fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or a salt thereof (C). Of producing a sex composition.   A process comprising obtaining calcium phosphate particles (B) / ethylenediaminetetraacetic acid or a salt (C) complex (Q) by previously mixing calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt (C) thereof. The manufacturing method of the dental curable composition in any one of 5-9.   The method for producing a dental curable composition according to claim 10, wherein the complex (Q) is obtained by heat-treating calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt thereof (C).   The dental curable composition according to claim 10, wherein the complex (Q) is obtained by mechanochemically complexing calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt thereof (C). Manufacturing method. A dental curable composition kit comprising powder material (X) and liquid material (Y), comprising
Powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B) and ethylenediaminetetraacetic acid or its salt (C) as essential components, and optionally containing polyalkenoic acid (D),
A liquid material (Y) containing polyalkenoic acid (D) and water (E) as essential components and ethylenediaminetetraacetic acid or a salt thereof (C) as an optional component,
Powder material (X) and the weight ratio of the liquid material (Y) (X / Y) is Ri Do and 1.0 to 5.0,
The calcium phosphate particles (B) are contained in an amount of 35 to 75 parts by weight of the fluoroaluminosilicate glass particles (A) per 100 parts by weight of the dental hardenable composition, and 100 parts by weight of the fluoroaluminosilicate glass particles (A). 1 to 30 parts by weight, 0.1 to 10 parts by weight of ethylenediaminetetraacetic acid or a salt thereof (C), 10 to 40 parts by weight of polyalkenoic acid (D), and 13 to 90 parts by weight of water (E) A dental curable composition kit characterized in that the powder material (X) and the liquid material (Y) are mixed and used so as to contain.