WO2015152129A1 - Curable composition for dental use and method for producing same - Google Patents

Abstract

Provided is a curable composition for dental use, said composition containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or a salt thereof (C), polyalkenoic acid (D), and water (E), and being characterized by including 35-75 parts by weight of fluoroaluminosilicate glass particles (A) in relation to 100 parts by weight of the total quantity of the curable composition for dental use, and including 1-30 parts by weight of calcium phosphate particles (B), 0.1-10 parts by weight of ethylenediaminetetraacetic acid or a salt thereof (C), 10-40 parts by weight of polyalkenoic acid (D), and 13-90 parts by weight of water (E) in relation to 100 parts by weight of the fluoroaluminosilicate glass particles. The present invention thus provides a curable composition for dental use that has a long handling time, has a fast curing time in the oral cavity, and has excellent recalcification ability.

Description

Dental curable composition and method for producing the same

The present invention relates to a dental curable composition that has both an operation time and a curing time as compared with a conventional glass ionomer cement and has an effect of improving the remineralization ability of a tooth.

Glass ionomer cement is used by reacting a polymer acid mainly composed of an acid such as polycarboxylic acid and glass powder for glass ionomer cement in the presence of water and curing. Glass ionomer cement has good affinity for living organisms, has excellent adhesion to dental materials such as enamel and dentin, and teeth made of fluorine contained in glass powder. In the dental field, filling of carious cavity, bonding of crown inlay bridge and orthodontic band, cavity back layer, root canal It is a material widely used for filling sealers, abutment construction and preventive filling.

Glass ionomer cement has excellent characteristics, but when clinical use is considered, ease of use, that is, operability is regarded as important. The operability refers to the characteristics of the kneaded product from the start of kneading of the glass powder, polyalkenoic acid and water to a certain time, and is strongly influenced by the operating time defined by JIS and the curing time. In actual clinical practice, a cement is desired that is as long as possible in order to allow dental hygienists and doctors to perform their work with sufficient margins, while rapidly hardening when placed in the oral cavity.

On the other hand, with the so-called 8020 exercise (improving oral hygiene, preserving the tooth quality (MI)) that tries to keep 20 or more teeth even after the age of 80, the site affected by caries is as much as possible. In recent years, remineralization treatment has been attracting attention, in which the remaining caries-affected site is restored to its original state without being cut. Glass ionomer cement is also widely recognized as a restorative material that may be able to reduce the amount of tooth cutting by gradually releasing fluorine ions known as an active ingredient of remineralization. However, hydroxyapatite, the main component of enamel and dentin teeth, is a compound composed of calcium and phosphorus. Efficient remineralization of caries-affected sites is only possible with fluoride ions in the teeth. Supply is not fully promoted.

Non-Patent Document 1 describes that by adding 15% β-TCP to glass ionomer cement powder, remineralization of enamel is promoted and acid resistance of the remineralization site is improved. Yes. However, when calcium phosphate is added for the purpose of remineralization, the acid resistance of the enamel that has come into contact with the cured product is improved, while the reactivity between calcium phosphate and polyalkenoic acid is high, and the reaction between them begins immediately after kneading. In addition, there is a problem that sufficient operation time cannot be secured. In addition, a combination of calcium phosphate and polyalkenoic acid has a problem in that the curing time in the oral cavity is delayed because sufficient crosslinking reaction does not proceed.

Patent Document 1 describes a glass powder for glass ionomer cement containing apatite. According to this, compared with the case where the glass powder for conventional dental glass ionomer cement is used, the mechanical strength, particularly the three-point bending strength and the tensile strength are improved, which is insufficient in conventional dentistry. It is said that the glass ionomer cement can be applied to filling a cavity where a large load is applied. However, the operation time and setting time when preparing the cement are not necessarily in an appropriate range, and the remineralization ability may be insufficient, and improvement has been desired.

As described in the above-mentioned prior literature, in the conventional technology so far, when calcium phosphate is added to improve the remineralization ability, there is a problem that the operability and the curing time required in the clinic cannot be achieved at the same time. Therefore, improvement of these problems has been desired.

JP 2001-354509 A

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

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

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

Moreover, the said subject is a dental curable composition containing fluoroaluminosilicate glass particle (A), calcium phosphate particle (B), ethylenediaminetetraacetic acid or its salt (C), polyalkenoic acid (D), and water (E). A method comprising the steps of comprising: fluoroaluminosilicate glass particles (A) and calcium phosphate particles (B) as essential components; and at least selected from the group consisting of ethylenediaminetetraacetic acid or a salt thereof (C) and polyalkenoic acid (D) Powder material (X) containing one kind as an optional component, water (E) as an essential component, and at least one selected from the group consisting of ethylenediaminetetraacetic acid or a salt thereof (C) and polyalkenoic acid (D) The weight ratio (X / Y) of the powder material (X) to the liquid material (Y) containing the liquid material (Y) 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 as.

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

Moreover, the said subject is a dental curable composition kit which consists of a powder material (X) and a liquid material (Y), Comprising: A fluoroaluminosilicate glass particle (A) and a calcium phosphate particle (B) are included as an essential component. A powder material (X) containing at least one selected from the group consisting of ethylenediaminetetraacetic acid or a salt thereof (C) and polyalkenoic acid (D) as optional components; water (E) as essential components; A liquid material (Y) containing at least one selected from the group consisting of acetic acid or a salt thereof (C) and polyalkenoic acid (D) as an optional component, and a weight ratio of the powder material (X) and the liquid material (Y) This can be solved by providing a dental curable composition kit characterized by being used by mixing so that (X / Y) is 1.0 to 5.0. Moreover, the said subject is a dental curable composition kit which consists of a powder material (X) and a liquid material (Y), Comprising: A fluoroaluminosilicate glass particle (A), a calcium phosphate particle (B), and ethylenediaminetetraacetic acid or The powder (X) containing the salt (C) as an essential component, the polyalkenoic acid (D) as an optional component, the polyalkenoic acid (D) and the water (E) as essential components, and ethylenediaminetetraacetic acid or a salt thereof The liquid material (Y) containing (C) as an optional component is mixed so that the weight ratio (X / Y) of the powder material (X) and the liquid material (Y) is 1.0 to 5.0. It is also solved by providing a dental curable composition kit characterized in that it is used.

According to the present invention, a dental curable composition having a sufficient operation time, a fast curing time in the oral cavity, and excellent remineralization ability is provided. As a result, the operation time is as long as possible. On the other hand, it is possible to provide a material that hardens rapidly when inserted into the oral cavity. Remineralization treatment can be performed in which the affected area is restored by the material.

The dental curable composition of the present invention is a dental containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or a salt thereof (C), polyalkenoic acid (D) and water (E). A curable composition for use, comprising 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, and 100 parts by weight of fluoroaluminosilicate glass particles (A) 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), 10 to 40 parts by weight of polyalkenoic acid (D), and It contains 13 to 90 parts by weight of water (E). With the dental curable composition of the present invention, the operation time is as long as possible, while it is possible to provide a material that hardens rapidly when inserted into the oral cavity, and the site affected by caries is cut as much as possible. Therefore, remineralization treatment can be performed in which the remaining caries-affected site is returned to the original state by the material. The mechanism of action is not always 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 cement that cures via an acid-base reaction (glass ionomer reaction). Since the reactivity of the polyalkenoic acid (D) to the calcium phosphate particles (B) is higher than the reactivity to the fluoroaluminosilicate glass (A), the operation time is not sufficiently secured, and the presence of excess calcium ions causes negative effects. It is considered that the reaction with polyalkenoic acid (E) having ions (carboxyl group, —COO ⁻ ) is not driven sufficiently. On the other hand, since ethylenediaminetetraacetic acid or a salt thereof (C) is present in the system, ethylenediaminetetraacetic acid or a salt thereof (C) that is more reactive than polyalkenoic acid (D) with respect to calcium phosphate particles (B) is calcium. By chelating the ions, the reaction time of the polyalkenoic acid (D) and the calcium phosphate particles (B) is delayed, so that it seems that sufficient operation time can be secured. In addition, ethylenediaminetetraacetic acid or a salt thereof (C) chelates calcium ions and is thought to contribute to a crosslinking reaction, so that it eventually promotes curing and seems to accelerate the curing time in the oral cavity. . The presence of calcium phosphate particles (B) can effectively release the ions of calcium and phosphorus, which are the main constituent elements of teeth, in addition to the sustained release of fluorine inherent in glass ionomer cement. It is possible to make it.

The dental curable composition of the present invention is a dental containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or a salt thereof (C), polyalkenoic acid (D) and water (E). It is necessary that the fluoroaluminosilicate glass particles (A) are contained in an amount of 35 to 75 parts by weight with respect to 100 parts by weight of the total amount of the dental curable composition. When the content of fluoroaluminosilicate glass particles (A) is less than 35 parts by weight, sufficient machinery is sufficient because sufficient fluoroaluminosilicate glass particles (A) are insufficient to form a three-dimensional network structure by glass ionomer reaction. There is a possibility that the mechanical strength cannot be obtained, and it is preferably 40 parts by weight or more, 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 excessively present and sufficient strength to withstand clinical use cannot be secured. 70 parts by weight or less, and more preferably 65 parts by weight or less.

The average particle size 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 produce, and furthermore, the paste obtained by mixing with the liquid material has a high viscosity. 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 size of the fluoroaluminosilicate glass particles (A) exceeds 35 μm, the paste properties may be unfavorable, for example, the paste obtained by mixing with the liquid material does not exhibit sufficient viscosity. In addition, the feeling of roughness during kneading of the paste may be increased, and the operability may be impaired. Further, when applied to the oral cavity, the patient may be given an impression that the touch is not good. The average particle size 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 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 pulverized. In that case, a pulverizing apparatus such as a ball mill, a likai machine, or a jet mill can be used. Moreover, you may use the well-known fluoroaluminosilicate glass particle conventionally used as a powder component of dental glass ionomer cement. For example, meteorite, alumina, aluminum hydroxide, aluminum oxalate, mullite, calcium oxalate, strontium oxalate, sodium oxalate, aluminum carbonate, calcium carbonate, strontium carbonate, sodium carbonate, sodium fluoride, calcium fluoride, fluoride A glass raw material 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 pulverized to produce a fine powder. . In that case, a pulverizing apparatus such as a ball mill, a likai machine, or a jet mill can be used. In addition, after cooling, the obtained glass body (frit) is pulverized by a pulverizing means such as a ball mill and, if necessary, subjected to classification treatment such as sieving so that glass having a desired average particle size and particle size distribution is obtained. A powder can be obtained. Also, fluoroaluminosilicate glass particles (A) are prepared by pulverizing fluoroaluminosilicate glass raw material powder together with a liquid medium such as alcohol using a lykai machine, ball mill or the like, and drying the obtained slurry. You can also get 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.

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) with respect 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, the release amount of calcium ions and phosphate ions for causing sufficient remineralization may be insufficient. The content of the calcium phosphate particles (B) is preferably 2 parts by weight or more, and particularly preferably 3 parts by weight or more. On the other hand, when the calcium phosphate particles (B) exceed 30 parts by weight, the reaction between the polyalkenoic acid (D) and the calcium phosphate particles (B) is more than the reaction between the polyalkenoic acid (D) and the fluoroaluminosilicate glass particles (A). Since it is fast, there is a possibility that an appropriate operation time cannot 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) include 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. (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 · 5H 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) ₂ ] particles and at least one selected from the group consisting of 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 xH 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, and tricalcium phosphate [Ca ₃ (PO ₄ ) _2. And 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. In particular, tetracalcium phosphate [Ca ₄ (PO ₄ ) ₂ O] particles are more preferably used from the viewpoint of remineralization ability.

The average particle diameter of the calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more used in the present invention is preferably 0.3 to 35 μm. When the average particle diameter is less than 0.3 μm, the viscosity of the paste obtained by mixing with the liquid material becomes high and there is a possibility that the desired paste properties are not 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, the paste properties such that the paste obtained by mixing with the liquid material does not exhibit sufficient viscosity may be unfavorable. Furthermore, the feeling of roughness when kneading the paste is 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 the 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 calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more used in the present invention is not particularly limited. Commercially available calcium phosphate particles having a Ca / P molar ratio of 1.30 or more may be used as they are, or may be used by appropriately pulverizing and adjusting the particle diameter. As a pulverization method, a method similar to the pulverization method of calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30, which will be described later, can be employed.

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 are anhydrous calcium monohydrogen phosphate [CaHPO ₄ ] particles, anhydrous calcium dihydrogen phosphate [Ca (H ₂ PO ₄ ) ₂ ] particles, acidic calcium pyrophosphate [CaH ₂ P ₂ O ₇ ] particles, calcium monohydrogen phosphate dihydrate [CaHPO ₄ · 2H ₂ O] particles, and calcium dihydrogen phosphate monohydrate It is preferably at least one selected from the group consisting of [Ca (H ₂ PO ₄ ) ₂ .H ₂ O] particles. Among these, anhydrous calcium monohydrogen phosphate [CaHPO ₄ ] particles, anhydrous calcium dihydrogen phosphate [Ca (H ₂ PO ₄ ) ₂ ] particles, and calcium monohydrogen phosphate dihydrate [CaHPO ₄ .2H _2]. O] At least one selected from the group consisting of particles is more preferably used, and anhydrous calcium monohydrogen phosphate [CaHPO ₄ ] particles and calcium monohydrogen phosphate dihydrate [CaHPO ₄ .2H ₂ O]. At least one selected from the group consisting of particles is more preferably used, and anhydrous calcium monohydrogen phosphate [CaHPO ₄ ] particles are particularly 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. When 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, 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, the paste properties such that the paste obtained by mixing with the liquid material does not exhibit sufficient viscosity may be unfavorable. Furthermore, the feeling of roughness when kneading the paste is increased, and the operability may be impaired. The average particle diameter of the 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 the 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 such an average particle diameter and having a Ca / P molar ratio of less than 1.30 is not particularly limited, and if a commercially available product is available, it may be used. It is often preferable to further grind the commercial product. In that case, a pulverizing apparatus such as a ball mill, a likai machine, or a jet mill can be used. Further, by preparing a slurry by pulverizing calcium phosphate raw material powder having a Ca / P molar ratio of less than 1.30 together with a liquid medium such as alcohol using a lykai machine, a ball mill or the like, and drying the obtained slurry It is also possible to obtain calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30. 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.

Here, when the calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more and the calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 are used in combination, the Ca / P molar ratio is used. By increasing the average particle size of the calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more as compared with the average particle size of the calcium phosphate particles (B2) having a particle size of less than 1.30, the solubility balance between the two is improved. It becomes appropriate, and it becomes possible to maintain the pH in the composition in the vicinity of neutrality. As a result, the precipitation of hydroxyapatite becomes smooth and the remineralization effect can be improved. Specifically, the average particle diameter of the calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more is at least twice the average particle diameter of the calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30. More preferably, it is more preferably 4 times or more, and particularly preferably 7 times or more. On the other hand, the average particle diameter of the calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more is 35 times or less than the average particle diameter of the calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30. Is more preferably 30 times or less, and particularly preferably 25 times or less. 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 blending ratio is not particularly limited. From the viewpoint of promoting remineralization by precipitation of apatite, the total Ca / P ratio 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, it is preferably 1.50 to 1.70. By this, the dental curable composition of this invention with a high remineralization effect can be obtained.

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 thereof (C) with respect to 100 parts by weight of the fluoroaluminosilicate glass particles (A). When the content of ethylenediaminetetraacetic acid or its salt (C) is less than 0.1 parts by weight, there is a possibility that sufficient operation time cannot be secured. The content of ethylenediaminetetraacetic acid or a salt thereof (C) 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 a salt thereof (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. In addition, such ethylenediaminetetraacetic acid or a salt thereof (C) may be added and blended as a powder, or may be blended by adding as a liquid material. Furthermore, ethylenediaminetetraacetic acid and ethylenediaminetetraacetate may be blended simultaneously.

In the present invention, fluoroaluminosilicate glass particles (A) / ethylenediaminetetraacetic acid or a salt thereof (C) composite is prepared by previously mixing fluoroaluminosilicate glass particles (A) with ethylenediaminetetraacetic acid or a salt thereof (C). The method of obtaining (P) is preferably employed. In that case, it is preferable that the composite (P) is obtained by mechanochemically combining the fluoroaluminosilicate glass particles (A) with ethylenediaminetetraacetic acid or a salt thereof (C). As a mechanochemical compounding method, a method using a dry pulverization apparatus such as a ball mill, a lycaic machine, a jet mill, etc., is preferably employed for fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or a salt thereof (C). Is done.

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

In the present invention, the composite (P) is preferably obtained by heat-treating fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or a salt thereof (C). As described above, the heat treatment is preferably performed by mixing fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or a salt thereof (C) in water and then applying heat at 70 to 150 ° C. for drying. When drying, a dryer is preferably used. When the heat treatment temperature is less than 70 ° C., it is inefficient when drying in large quantities, and the internal moisture may not evaporate sufficiently. The heat treatment temperature is more preferably 75 ° C. or higher, and particularly preferably 80 ° C. or higher. On the other hand, when the heat treatment temperature exceeds 150 ° C., ethylenediaminetetraacetic acid or a salt thereof (C) is 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, and particularly preferably 130 ° C. or less.

In the present invention, a method of obtaining calcium phosphate particles (B) / ethylenediaminetetraacetic acid or a salt thereof (C) complex (Q) by previously mixing calcium phosphate particles (B) with ethylenediaminetetraacetic acid or a salt thereof (C). Is preferably employed. In that case, it is preferable that the composite (Q) is obtained by mechanochemically combining the calcium phosphate particles (B) with ethylenediaminetetraacetic acid or a salt thereof (C). As a method for complexing mechanochemically, a method in which the calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt thereof (C) are used in a dry pulverization apparatus such as a ball mill, a lykai machine, or a jet mill is preferably employed.

In the present invention, calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt thereof (C) are mixed in water and dried to dry the 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 thereof (C). As described above, the heat treatment is preferably performed by mixing calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt thereof (C) in water and then applying heat at 70 to 250 ° C. for drying. When drying, a dryer is preferably used. When the heat treatment temperature is less than 70 ° C., it is inefficient when drying in large quantities, and the internal moisture may not evaporate sufficiently. The heat treatment temperature is more preferably 75 ° C. or higher, and particularly preferably 80 ° C. or higher. 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) is strongly bonded to the 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, and particularly preferably 150 ° C. or less.

In the present invention, calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more and ethylenediaminetetraacetic acid or a salt thereof (C) are mixed in advance, and calcium phosphate particles (B1) / ethylenediaminetetraacetic acid or a salt thereof ( C) A complex (Q) can be obtained. Further, calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 and ethylenediaminetetraacetic acid or a salt thereof (C) are mixed in advance to obtain calcium phosphate particles (B2) / ethylenediaminetetraacetic acid or a salt thereof (C). A complex (Q) can also be obtained. As a method for obtaining the complex (Q), the method described above is preferably employed. Calcium phosphate particles (B1) / ethylenediaminetetraacetic acid or a salt thereof (C) complex (Q) may be used in combination with calcium phosphate particles (B2) / ethylenediaminetetraacetic acid or a salt (C) complex (Q) thereof. . Among them, calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more and ethylenediaminetetraacetic acid or a salt thereof (C) are mixed in advance to obtain calcium phosphate particles (B1) / ethylenediaminetetraacetic acid or a salt thereof (C). Obtaining the complex (Q) is a preferred embodiment of the present invention.

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). When the content of the polyalkenoic acid (D) is less than 10 parts by weight, the three-dimensional network structure formed by the glass ionomer reaction cannot be sufficiently formed, so that sufficient mechanical strength may not be obtained. The amount 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 required to react with fluoroaluminosilicate glass particles (A) to form a glass ionomer to form a three-dimensional network structure. New polyalkenoic acid (D) may cause poor curing. Moreover, the viscosity at the time of kneading may be too high and kneading may be 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, and uraconic acid, or copolymers of two or more of these unsaturated carboxylic acids, and these A copolymer of an unsaturated carboxylic acid and a copolymerizable monomer may be mentioned, and these may be used alone or in combination of two or more. From the viewpoint of improving the adhesive strength and mechanical strength of the tooth, 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. And a copolymer of itaconic acid. Further, a polymer having a weight average molecular weight of 5,000 to 50,000 which does not contain a polymerizable ethylenically unsaturated double bond is preferred. When the weight average molecular weight is less than 5,000, the strength of the cured product is high. It tends to be low, and there is a possibility that the adhesive force to the tooth will be lowered, and it is more preferably 10,000 or more, and particularly preferably 35,000. Further, when the weight average molecular weight exceeds 50,000, the viscosity at the time of kneading may be too high and kneading may be difficult, and it is more preferably 45,000 or less, particularly 40,000 or less. Preferably there is.

The production method of polyalkenoic acid (D) used in the present invention is not particularly limited, and it may be used as long as a commercially available product is available. In particular, when adding to the powder material, it is often preferable to further grind the commercial product. In that case, a pulverizing apparatus such as a ball mill, a likai machine, a jet mill, or a spray dryer can be used. Alternatively, the polyalkenoic acid powder (D) 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 pulverizing apparatus at this time, it is preferable to use a spray dryer.

Furthermore, the polyalkenoic acid (D) used in the present invention may be added and blended in the form of powder, or may be blended in addition to the liquid material. In either case, a curable composition is formed. can do. In the present invention, the polyalkenoic acid (D) added to both the powder material and the liquid material has a sufficient amount for securing the adhesiveness and mechanical strength while maintaining the liquid material at an appropriate viscosity. Since it becomes possible to mix | blend, it is preferable.

Water (E) used in the present invention is an indispensable component in the liquid material for obtaining the dental curable composition of the present invention. That is, the reaction in which the liquid material and the fluoroaluminosilicate glass particles (A), which are the main components of the powder material, are mixed and cured is a neutralization reaction between the fluoroaluminosilicate glass particles (A) and the polyalkenoic acid (D). Because it proceeds in the presence of water. Further, the dental glass ionomer cement has a property of adhering to the tooth surface in the presence of water, and it is necessary that water is 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). When the content of water (E) is less than 13 parts by weight, the three-dimensional network structure formed by the glass ionomer reaction cannot be sufficiently formed, and thus sufficient mechanical strength may not be obtained. There is a possibility that sufficient hydration reaction may not occur with the calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more and the calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30. More preferably, it is more than 15 parts by weight. On the other hand, when the content of water (E) exceeds 90 parts by weight, the fluoroaluminosilicate glass particles (A) in the paste after the powder liquid kneading, the calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more. ) And Ca / P molar ratio of calcium phosphate particles (B2) having a molar ratio of less than 1.30, the cured product may not be obtained. 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.

The dental curable composition of the present invention preferably contains 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 for the purpose of adjusting (retarding) the curing reaction between the powder material and the acid component. Preferable tartaric acid for this purpose includes D-tartaric acid, L-tartaric acid and DL-tartaric acid, and L-tartaric acid is particularly preferred from the viewpoint of the strength and aesthetics of the resulting cured product. When the tartaric acid content is less than 0.3 parts by weight, there is a possibility that sufficient operation time may not be ensured until the powder material and the liquid material are kneaded and adapted to the patient. Particularly preferred is 2 parts by weight or more. 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, and particularly preferably 5 parts by weight or less. It is preferable. Such tartaric acid may be added and blended as a powder, or may be blended as a liquid material. Furthermore, the fluoroaluminosilicate glass particles (A) have a Ca / P molar ratio of 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 may be used as long as a commercially available product is available. In particular, when adding to the powder material, it is often preferable to further grind the commercial product. In that case, a pulverizing apparatus such as a ball mill, a likai machine, a jet mill, or a spray dryer can be used. In addition, tartaric acid powder can be obtained by pulverizing tartaric acid powder together with a liquid medium such as alcohol by using a laika machine, a ball mill or the like to prepare a slurry, and drying the obtained slurry.

The dental curable composition of the present invention may contain an X-ray contrast agent as necessary. This is because it is possible to monitor the filling operation of the composition paste after kneading and follow the changes after filling. 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 X-ray contrast agent can be blended into the powder material, blended into the liquid material, or blended into the composition paste being kneaded.

The dental curable composition of the present invention may further contain a filler that can be expected to improve the fluidity of the powder material and improve 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; based on silica; Al ₂ O ₃ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , BaO, La ₂ O ₃ , Examples 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.

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 pigments to be blended include organic pigments (colored pigments) made of synthetic organic dyes or natural organic dyes, and inorganic pigments obtained from synthetic minerals or natural minerals. Discoloration due to hydrogen sulfide is noticeable when an inorganic pigment is blended, and is hardly recognized when an organic pigment is blended. Accordingly, the pigment is preferably an organic pigment that is not easily affected by hydrogen sulfide, which is considered to cause discoloration in the oral cavity.

Examples of organic pigments include New Coxin, Quinoline Yellow WS (trade name, manufactured by Red Fuji Chemical Industry Co., Ltd.), PV Fast Red BNP, Graphol Yellow 3GP (trade name, manufactured by Clariant Japan Co., Ltd.), Fast Green FCF (trade name, manufactured by Kanto Chemical Co., Ltd.), Blue No. 404 (trade name, manufactured by Daito Kasei Kogyo Co., Ltd.), 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 name, manufactured by Ciba Specialty Chemicals, Inc.).

If the amount does not cause discoloration, an inorganic pigment may be blended together with the organic pigment in order to impart a deep color tone unique to the tooth to the restoration site of the tooth. Inorganic pigments such as petals, zinc white, titanium dioxide, carbon, ultramarine, etc. are preferably non-toxic, and black inorganic pigments (such as iron oxide) are originally used to prevent black changes. May be. Preferable inorganic pigments include KN-320, 100ED, YELLOW-48 (above, trade name, manufactured by Toda Kogyo Co., Ltd.) and the like.

The method for producing the dental curable composition of the present invention is not particularly limited. Fluoroaluminosilicate glass particles (A) and calcium phosphate particles (B) are included as essential components, and at least one selected from the group consisting of ethylenediaminetetraacetic acid or a salt thereof (C) and polyalkenoic acid (D) is included as an optional component Liquid material (X), containing water (E) as essential components, and containing at least one selected from the group consisting of ethylenediaminetetraacetic acid or its salt (C) and polyalkenoic acid (D) as optional components ( Y) is mixed so that the weight ratio (X / Y) of the powder material (X) to the liquid material (Y) is 1.0 to 5.0, whereby a dental curable composition can be obtained. it can. For example, a powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), and ethylenediaminetetraacetic acid or a salt thereof (C), and a liquid material containing polyalkenoic acid (D) and water (E) A dental curable composition is obtained by mixing (Y) so that the weight ratio (X / Y) of the powder material (X) and the liquid material (Y) is 1.0 to 5.0. Can do. Powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or salts thereof (C) and polyalkenoic acid (D), and liquid material (Y) containing water (E) Can also be obtained by mixing the powder material (X) and the liquid material (Y) so that the weight ratio (X / Y) is 1.0 to 5.0. . A powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or a salt thereof (C) and polyalkenoic acid (D), polyalkenoic acid (D) and water (E) The dental curable composition is also prepared by mixing the liquid material (Y) containing the powder material (X) and the liquid material (Y) so that the weight ratio (X / 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 a salt thereof (C) as essential components, and polyalkenoic acid (D) as optional components, and polyalkenes A method for producing a dental curable composition comprising an acid (D) and water (E) as essential components and a liquid material (Y) containing ethylenediaminetetraacetic acid or a salt thereof (C) as optional components is preferred. Adopted. Specifically, a powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or a salt thereof (C) and polyalkenoic acid (D), polyalkenoic acid (D) and A method for producing a dental curable composition in which a liquid material (Y) containing water (E) is mixed, or fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), and ethylenediaminetetraacetic acid or a salt thereof (C ) And a liquid material (Y) containing polyalkenoic acid (D) and water (E) are preferably employed, and a fluoroaluminosilicate glass is suitably employed. Powder (X) containing particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or a salt thereof (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 curable 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. It is preferable that this makes it possible to develop performances such as powder liquid kneading property and mechanical strength sufficient as a glass ionomer cement. The weight ratio (X / Y) of the powder material (X) to the liquid material (Y) is more preferably 1.5 to 4.5, and more preferably 1.8 to 3.8. More preferably, they are mixed.

Here, in the presence of water (E), the fluoroaluminosilicate glass particles (A) react with the polyalkenoic acid (D) to be cured, and the 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, hydroxyapatite is produced, so that the fluoroaluminosilicate glass particles (A) have a Ca / P molar ratio of 1.30. The above calcium phosphate particles (B1), calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30, ethylenediaminetetraacetic acid or a salt thereof (C), polyalkenoic acid (D) and water (E) are mixed in advance. It cannot be stored as a dental curable composition. From such a point of view, at least one selected from the group consisting of ethylenediaminetetraacetic acid or a salt thereof (C) and polyalkenoic acid (D) containing fluoroaluminosilicate glass particles (A) and calcium phosphate particles (B) as essential components. Powder material (X) containing as optional components, water (E) as essential components, and at least one selected from the group consisting of ethylenediaminetetraacetic acid or its salt (C) and polyalkenoic acid (D) as optional components The dental curable composition used by mixing the liquid material (Y) containing the powder material (X) and the liquid material (Y) so that the weight ratio (X / Y) is 1.0 to 5.0. One of the embodiments of the present invention is a product kit. Further, a powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B), ethylenediaminetetraacetic acid or a salt thereof (C) as essential components, and polyalkenoic acid (D) as an optional component, and polyalkene Liquid (Y) containing acid (D) and water (E) as essential components and ethylenediaminetetraacetic acid or a salt thereof (C) as optional components, and weight of powder (X) and liquid (Y) One embodiment of the present invention 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 ( The powder material (X) containing C) and the liquid material (Y) containing polyalkenoic acid (D) and water (E), the weight ratio (X / Y) of the powder material (X) and the liquid material (Y) One of the embodiments of the present invention is a dental curable composition kit used by mixing so as to be 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, ethylenediaminetetraacetic acid or a salt thereof ( C) and powder material (X) containing polyalkenoic acid (D) and liquid material (Y) containing water (E), weight ratio (X / Y) of powder material (X) and liquid material (Y) One of the embodiments of the present invention is a dental curable composition kit used by mixing so as to be 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, 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 the powder material (X) and the liquid material (Y) One embodiment of the present invention is a dental curable composition kit used by mixing so that the ratio (X / Y) is 1.0 to 5.0. Further, 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, polyalkenoic acid (D) Powder material (X) containing ethylenediaminetetraacetic acid or a salt thereof (C), liquid material (Y) containing polyalkenoic acid (D) and water (E), powder material (X) and liquid material (Y) One embodiment of the present invention is a dental curable composition kit that is used by mixing so that the weight ratio (X / Y) is 1.0 to 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 its 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) The dental curable composition kit used by mixing so that the weight ratio (X / Y) is 1.0 to 5.0, or fluoroaluminosilicate glass particles (A), and the Ca / P molar ratio is 1. 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 powder (X) containing ethylenediaminetetraacetic acid or a salt thereof (C), polyalkenoic acid ( ) And the liquid material (Y) containing water (E) are mixed so that the weight ratio (X / Y) of the powder material (X) and the liquid material (Y) is 1.0 to 5.0. The dental curable composition kit to be used is suitably employed, and the fluoroaluminosilicate glass particles (A), calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more, and a Ca / P molar ratio of 1.30. Less than calcium phosphate particles (B2), ethylenediaminetetraacetic acid or a salt thereof (C) and a polyalkenoic acid (D) powder material (X), and a polyalkenoic acid (D) and a liquid material (Y) containing water (E) Is used more suitably for dental curable composition kits that are used by mixing so that the weight ratio (X / Y) of powder material (X) to liquid material (Y) is 1.0 to 5.0 Is done.

Here, in the dental curable composition kit of the present invention, the powder material (X) and the liquid material (Y) are mixed and used so that the weight ratio (X / Y) is 1.0 to 5.0. It is preferable to perform this, and this makes it possible to develop performances such as powder-liquid kneading property and mechanical strength sufficient as a glass ionomer cement. More preferably, the powder material (X) and the liquid material (Y) are mixed and used so that the weight ratio (X / Y) is 1.5 to 4.5, and becomes 1.8 to 3.8. It is more preferable to use them in a mixed manner. Moreover, the dental curable composition of this invention is used suitably as a glass ionomer cement.

Hereinafter, the present invention will be specifically described with reference to examples. In this example, 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, ethylenediamine tetra The average particle size of acetic acid or its salt (C), tartaric acid, and polyalkenoic acid (D) was measured using a laser diffraction particle size distribution analyzer (“SALD-2100 type” manufactured by Shimadzu Corporation), and the measurement results The median diameter calculated from the above was defined as the average particle diameter.

[Preparation of powder and liquid materials for glass ionomer cement]
(1) Preparation of fluoroaluminosilicate glass particle (A) Fluoroaluminosilicate glass particle (A) is a commercially available fluoroaluminosilicate glass (G018-117, manufactured by SCHOTT, average particle diameter: 40.0 μm). Obtained by crushing.

Fluoroaluminosilicate glass particles: The average particle size of 30 μm is obtained by pulverizing 100 g of commercially available fluoroaluminosilicate glass (G018-117, manufactured by SCHOTT, average particle size of 40.0 μm) and 200 g of zirconia balls having a diameter of 20 mm from 400 ml of alumina. In addition to the pot (“Type A-3HD Pot Mill” manufactured by Nikkato Co., Ltd.), it was obtained by grinding for 5 hours at a rotational speed of 150 rpm.

Fluoroaluminosilicate glass particles: The average particle size is 4 μm, and 100 g of 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 are pulverized from 400 ml of alumina. It was obtained by grinding in a pot (“Type A-3HD Pot Mill” manufactured by Nikkato Corporation) for 15 hours at a rotation speed of 150 rpm.

Fluoroaluminosilicate glass particles: The average particle size of 0.5 μm is a commercially available fluoroaluminosilicate glass (G018-117, manufactured by SCHOTT, average particle size of 40.0 μm) made of NanoJet Mizer (NJ-100 type, Aisin Nano Technologies) Manufactured), and the pulverization pressure conditions were as follows: the raw material supply pressure: 0.7 MPa / the pulverization pressure: 0.7 MPa, and the treatment amount condition of 8 kg / hr.

(2) Surface-treated fluoroaluminosilicate glass (A) (composite (P))
The fluoroaluminosilicate glass (A) was treated with ethylenediaminetetraacetic acid or a salt thereof (C) and tartaric acid by the following method.

EDTA 2% mechanochemically treated fluoroaluminosilicate glass particles: 100 g of 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 crushing pot (“Type A-3HD pot mill” manufactured by Nikkato Co., Ltd.) and crushing at a rotational speed of 150 rpm for 5 hours.

EDTA heat-treated fluoroaluminosilicate glass particles: 100 g of fluoroaluminosilicate glass (A) having an average particle size of 0.5 μm, 4 μm, and 30 μm was added to 100 g of distilled water, stirred for 10 minutes, and then commercially available sodium edetate An aqueous solution prepared by dissolving 1.0 g (1% treatment), 2.0 g (2% treatment), and 4.0 g (4% treatment) 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 dried and heat-treated on a stainless steel vat with a dryer at 90 ° C. for 16 hours.

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

(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. It was obtained by grinding crude tetracalcium phosphate. 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, the cake-like equimolar mixture obtained by filtration and drying is heated in an electric furnace (FUS732PB, manufactured by Advantech Toyo Co., Ltd.) at 1500 ° C. for 24 hours. Then, the tetracalcium phosphate block was prepared by cooling to room temperature in a desiccator. Further, the mixture was roughly crushed in a mortar and then sieved to remove fine powder and tetracalcium phosphate lump, and the particle size was adjusted to a range of 0.5 to 3 mm to obtain crude tetracalcium phosphate.

Tetracalcium phosphate particles: An average particle size of 30 μm is obtained by adding 100 g of crude tetracalcium phosphate and 200 g of zirconia balls having a diameter of 20 mm to a 400 ml alumina grinding pot (“Type A-3HD pot mill” manufactured by Nikkato Corporation) It was obtained by grinding for 5 hours at a rotational speed of 150 rpm.

Tetracalcium phosphate particles: An average particle size of 19.0 μm is obtained by adding 100 g of crude tetracalcium phosphate and 200 g of zirconia balls having a diameter of 20 mm in a 400 ml alumina grinding pot (“Type A-3HD 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: The average particle diameter is 5.0 μm. Crude tetracalcium phosphate is crushed with Nanojet Mizer (NJ-100 type, manufactured by Aisin Nano Technologies). The pressure was 0.7 MPa, the treatment amount condition was 8 kg / hr, and the treatment was performed once.

Tricalcium phosphate particles: Commercially available α-tricalcium phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.) was used as it was for an average particle size of 12 μm.

(4) Preparation of calcium phosphate particles (B2) having a Ca / P molar ratio of less than 1.30 Anhydrous calcium monohydrogen phosphate particles (B2) used in this example are commercially available anhydrous calcium monohydrogen phosphate particles (Taipei It was obtained by pulverizing the chemical industry Co., Ltd. product, average particle size 15.0 μm) by the method shown below.

Anhydrous calcium monohydrogen phosphate particles: The average particle size of 5.0 μm is 50 g of commercially available anhydrous calcium hydrogen phosphate particles (produced by Taihei Chemical Industrial Co., Ltd., average particle size of 15.0 μm), 95% ethanol (Wako Pure Chemical Industries, Ltd.) 120 g of “Ethanol (95)” manufactured by Co., Ltd.) and 240 g of zirconia balls having a diameter of 10 mm were added to a 400 ml alumina grinding pot (“Type A-3 HD pot mill” manufactured by Nikkato Co., Ltd.) at a rotational speed of 120 rpm. The slurry obtained by performing the wet pulverization for 24 hours was obtained by evaporating ethanol with a rotary evaporator, drying at 60 ° C. for 6 hours, and further vacuum drying at 60 ° C. for 12 hours.

Anhydrous calcium monohydrogen phosphate particles: The average particle size of 1.0 μm is 50 g of commercially available anhydrous calcium hydrogen phosphate particles (Taihei Chemical Industry Co., Ltd., average particle size of 15.0 μm), 95% ethanol (Wako Pure Chemical Industries, Ltd.) 120 g of “Ethanol (95)” manufactured by Co., Ltd.) and 240 g of zirconia balls having a diameter of 10 mm were added to a 400 ml alumina grinding pot (“Type A-3 HD pot mill” manufactured by Nikkato Co., Ltd.) at a rotational speed of 120 rpm. The slurry obtained by performing wet pulverization for 24 hours was obtained by distilling off ethanol with a rotary evaporator, followed by drying at 60 ° C. for 6 hours and further vacuum drying at 60 ° C. for 24 hours.

Anhydrous calcium monohydrogen phosphate particles: An average particle size of 0.5 μm is obtained by using commercially available anhydrous calcium hydrogen phosphate particles (manufactured by Taihei Chemical Sangyo Co., Ltd., average particle size of 15.0 μm) as a nanojet mizer (NJ-100 type Aisin Nano Technologies Co., Ltd.), and the pulverization pressure conditions were as follows: the raw material supply pressure: 0.7 MPa / the pulverization pressure: 0.7 MPa and the treatment amount condition of 8 kg / hr.

Anhydrous calcium dihydrogen phosphate particles: Commercially available anhydrous calcium dihydrogen phosphate (manufactured by Taihei Chemical Industrial Co., Ltd.) was used as it was for an average particle size of 1 μm.

As ethylenediaminetetraacetic acid or a salt thereof (C), commercially available sodium edetate hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used as it was. However, only when added to the powder material, an average particle size of 15 to 25 μm was obtained by pulverizing for about 1 hour in an agate mortar.

(5) Surface-treated calcium phosphate particles (B) (complex (Q))
The treatment with ethylenediaminetetraacetic acid or its salt (C) on the calcium phosphate particles (B) was carried out by the method shown 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 was obtained by adding 200 g of a ball into a 400 ml alumina grinding pot (“Type A-3HD pot mill” manufactured by Nikkato Co., Ltd.) and grinding at a rotational speed of 150 rpm for 5 hours.

EDTA heat treated calcium phosphate particles: 100 g of tetracalcium phosphate particles having an average particle size of 5.0 μm, 19.0 μm, and 30 μm, and tricalcium phosphate having an average particle size of 1.0 μm were added to 300 g of distilled water, After stirring for 10 minutes, 7.0 g (7% treatment), 12.5 g (12.5% treatment), and 14.0 g (14.0% treatment) of commercially available sodium edetate hydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 0% treatment) was added to each 300 g of distilled water and stirred for 10 minutes. The resulting slurry was dried on a stainless steel vat with a 90 ° C. dryer for 16 hours and heat-treated.

(6) Preparation of tartaric acid Commercially available L-tartaric acid (manufactured by Iwata Chemical Industry Co., Ltd.) was used as it was. However, only when added to the powder material, an average particle size of 15 to 25 μm was obtained by pulverizing for about 1 hour in an agate mortar.

(7) Preparation of polyalkenoic acid (D) When polyalkenoic acid (D) is added to the liquid material, a commercially available polyalkenoic acid (manufactured by Nissei Chemical Industry Co., Ltd.) is used as it is. The pulverized one was used.

Commercially available polyalkenoic acid (manufactured by Nissei Chemical Industry Co., Ltd.) using NanoJet Mizer (NJ-100 type, manufactured by Aisin Nanotechnology Co., Ltd.), and pulverizing pressure conditions: raw material supply pressure: 0.7 MPa / grinding pressure: 0.7 MPa, throughput The condition was 8 kg / hr, and it was obtained by processing once. The average particle size of the obtained polyalkenoic acid powder was 3 μm.

(8) Preparation of water (E) As water (E), commercial 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 compositions shown in Tables 1 to 4, calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more, and Ca / P molar ratio of 1 .. Less than 30 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 ASONE Corporation) In addition, a powder material was obtained by mixing for 3 minutes at a rotational speed of 1000 rpm.

(10) Preparation of liquid material Ethylenediaminetetraacetic acid or a salt thereof (C), L-tartaric acid (manufactured by Iwata Chemical Co., Ltd.), polyalkenoic acid powder (D) (Nissei Chemical Co., Ltd.) weighed in the compositions shown in Tables 1 to 4 A liquid material was prepared by stirring water (E) for 24 hours with a magnetic stirrer.

[Operation time test]
0.15 g of the powder material having the composition shown in Tables 1 to 4 is precisely weighed, and then the liquid material having the composition shown in Tables 1 to 4 is added to the powder liquid weight ratio shown in Tables 1 to 4 and kneaded. A paste was prepared. The stopwatch was started, the powder was divided into two equal parts using the attached kneading stick, the liquid was added to the first section and mixed, and the rest was added, and kneaded uniformly within a total of 30 seconds. About 40 mg of a small amount of paste was placed on a glass plate by 40 seconds after the start of kneading, and another glass was pressed. Every 90 seconds from 90 seconds after the start of kneading, the uppermost glass was moved about 2 mm, and a shearing force was applied. Whether or not the material was physically uniform was visually judged, and the time during which a uniform thin layer was formed twice in succession was defined as the operation time.

[Curing time test]
The curing time test method conformed to ISO9917-1. 1.0 g of the powder material having the composition shown in Tables 1 to 4 is precisely weighed, and then the liquid material having the composition shown in Tables 1 to 4 is added and kneaded so as to have the powder-liquid weight ratio shown in Tables 1 to 4. A paste was prepared. Stop the watch, start the glass plate and mold on the aluminum foil with the kneaded cement, and then cover it with aluminum foil, and keep the temperature and humidity (37 ° C, humidity 95%) by 1 minute. It was thrown into. After 2 minutes, the aluminum foil was removed. After 2 minutes and 30 seconds, a Vicat needle (400 g, with 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 an interval of 30 seconds, and the time until no indentation could be confirmed was calculated as the curing time.

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

(2) Evaluation criteria A for operability: Familiarity immediately after the start of kneading of the powder material and the liquid material is good, and a paste can be obtained by kneading for 20 seconds with a dental kneading rod. The resulting paste has good elongation and is not rough.
B: Although the familiarity immediately after the start of the kneading of the powder material and the liquid material is slightly worse, the paste can be obtained by kneading for 20 seconds with a dental kneading rod. The paste stretches well, but it may feel rough during some mixing.
C: Familiarity immediately after the start of kneading of the powder material and the liquid material is poor, and kneading with a dental kneading rod is required for 30 seconds to obtain a paste. The paste stretches well, but it may feel rough during some mixing.
D: Familiarity immediately after the start of kneading of the powder material and the liquid material is poor, and kneading with a dental kneading rod is required for 30 seconds or more to obtain a paste, or kneading cannot be performed. When kneaded, the elongation of the paste is poor, and it hardens on the kneaded paper within 2 minutes, and the operation time cannot be secured. Also, there may be a feeling of roughness during kneading.
A to C are actual usage levels.

[Preparation of bovine teeth for remineralization]
The center of the buccal side of the healthy bovine incisor was polished with a rotary polishing machine using # 80 and # 1000 polishing paper to expose the dentin. The polished surface of the bovine teeth was further polished using a lapping film (# 1200, # 3000, # 8000, manufactured by Sumitomo 3M Co., Ltd.) to make it smooth. This dentin part was left with a window of a 7 mm test part in each of the vertical axis direction and the horizontal axis direction with respect to the teeth (hereinafter referred to as “dentin window”), and the surroundings were masked with nail polish and air-dried for 1 hour. This bovine tooth is immersed in 150 ml of 50 mM demineralization solution diluted with acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) for 1 week, decalcified, and then washed with water for 30 minutes or more to remineralize the bovine teeth. The bovine tooth used for was 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) were weighed into weighing pans, 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, a 10% aqueous sodium hydroxide solution was added dropwise to measure pH 7.0 while measuring the acidity of this solution with a pH meter (F55, Horiba, Ltd.). Next, this solution was added to a 1000 ml volumetric flask and the volume was increased to obtain 1000 ml of simulated saliva.

[Remineralization test]
The remineralized bovine teeth prepared above are immersed in distilled water and allowed to stand for 30 minutes, and then the powder material and the liquid material for the half of the dentin window are shown in Tables 1 to 4 on the kneaded paper. About 0.1 g of paste obtained by mixing for 30 seconds at a powder / liquid ratio was applied, and cured by incubating at 37 ° C. and 100% RH for 60 minutes. Then, it preserve | saved at 37 degreeC in simulated saliva for 2 weeks, keeping the state which the hardened | cured material adhered to the bovine tooth for a remineralization test. The simulated saliva was changed every day (n = 5).

[Evaluation of remineralization ability]
(1) Preparation of Epoxy Resin Epoxy resin was prepared according to the Luft method, and an epoxy resin and a curing agent were uniformly mixed and then an accelerator was added. Disposyringe with 100 ml disposable cup, 41 ml of Rubeak 812 (epoxy resin, manufactured by Nacalai Tesque), 31 ml of Rubeac MNA (curing agent, manufactured by Nacalai Tesque), and 10 ml of Rubeak DDSA (curing agent, manufactured by Nacalai Tesque) Was added to a disposable cup and stirred for 10 minutes. To this, 1.2 ml of Rubeak DMP-30 (accelerator, manufactured by Nacalai Tesque Co., Ltd.) weighed with a disposable syringe was gradually dropped while stirring, and the mixture was stirred for 10 minutes after the addition.

(2) Preparation of hardness measurement sample Calcified bovine teeth were taken out from the simulated saliva, washed with water, and then immersed in a 70% aqueous ethanol solution in a vial. Immediately after immersion, the vial was transferred into a desiccator and placed under reduced pressure for 10 minutes. Thereafter, the vial was taken out 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 was immersed in the second 100% ethanol as it was overnight. On the next day, a 1: 1 mixed solvent of propylene oxide and ethanol and 100% propylene oxide (twice) were sequentially subjected to the same operation and immersed in the second propylene oxide as it was overnight. Furthermore, the same operation was performed for epoxy resin: propylene oxide = 1: 1 mixed solution, epoxy resin: propylene oxide = 4: 1 mixed solution, and epoxy resin 100% (twice). For these, the immersion time was 2 hours. Finally, a bovine tooth sample was put in a plastic container containing an epoxy resin, and a curing reaction was performed at 45 ° C. for 1 day and at 60 ° C. for 2 days. After the curing, the polyethylene container and the precision low speed cutter (BUEHLER, ISOMET1000) were cut in a direction perpendicular to the demineralized surface to obtain a section having a thickness of about 1 mm including the cross section of the test portion. This section was polished using a wrapping film (# 1200, # 3000, # 8000, manufactured by Sumitomo 3M Limited) to obtain a sample for hardness measurement (n = 5).

(3) Hardness measurement Using a nanoindenter (ENT-1100a, manufactured by Elionix Co., Ltd.), the cross section of the demineralized part and the remineralized part was measured with a load of 2 mN. In addition, measurement performed operation which performed 10 points | pieces by a 40 micrometer space | interval from the surface layer about 3 rows about each of a demineralization part and a remineralization part, and computed the average of the hardness in each depth. Further, as a control, three-point hardness was also measured for a healthy dentin having a depth of 600 μm which was not decalcified, and an average value was calculated. The remineralization ability was quantified by the following formula as a hardness recovery rate.

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

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

Comparative Examples 1-11
A composition was prepared with the composition shown in Table 4 by the procedure shown above, and operability, operation time, curing time, and remineralization ability were evaluated. The evaluation results obtained are summarized in Table 4. As the hydroxyapatite particles (5 μm) used in Comparative Example 8, commercially available hydroxyapatite (HAP-100, manufactured by Taihei Chemical Industrial Co., Ltd.) was used as it was.

Claims (14)

1. 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),
   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,
   1 to 30 parts by weight of calcium phosphate particles (B) and 0.1 to 10 parts by weight of ethylenediaminetetraacetic acid or a salt thereof (C) per 100 parts by weight of fluoroaluminosilicate glass particles (A), and polyalkenoic acid (D ) And 10 to 40 parts by weight of water (E), and 13 to 90 parts by weight of water (E).
2. The dental curable composition according to claim 1, wherein the calcium phosphate particles (B) include calcium phosphate particles (B1) having a Ca / P molar ratio of 1.30 or more.
3. 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.
4. The dental curable composition according to any one of claims 1 to 3, which is a glass ionomer cement.
5. A method for producing 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). ,
   Fluoroaluminosilicate glass particles (A) and calcium phosphate particles (B) are included as essential components, and at least one selected from the group consisting of ethylenediaminetetraacetic acid or a salt thereof (C) and polyalkenoic acid (D) is included as an optional component Powder material (X),
   A liquid material (Y) containing water (E) as an essential component, and containing at least one selected from the group consisting of ethylenediaminetetraacetic acid or a salt thereof (C) and polyalkenoic acid (D) as an optional component,
   The dental material according to any one of claims 1 to 3, wherein the powder material (X) and the liquid material (Y) are mixed so that the weight ratio (X / Y) is 1.0 to 5.0. A method for producing a curable composition.
6. Powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt thereof (C) as essential components, and polyalkenoic acid (D) as an optional component, and polyalkenoic acid ( The method for producing a dental curable composition according to claim 5, wherein D and the liquid (Y) containing water (E) as essential components and ethylenediaminetetraacetic acid or a salt thereof (C) as optional components are mixed. .
7. Fluoroaluminosilicate glass particles (A) / ethylenediaminetetraacetic acid or a salt thereof (C) complex (P) is prepared by previously mixing fluoroaluminosilicate glass particles (A) with ethylenediaminetetraacetic acid or a salt thereof (C). The manufacturing method of the dental curable composition of Claim 5 or 6 which has a process to obtain.
8. 8. The dental curable composition according to claim 7, wherein the composite (P) is obtained by heat-treating fluoroaluminosilicate glass particles (A) and ethylenediaminetetraacetic acid or a salt thereof (C). Method.
9. The dental hardening according to claim 7, wherein the composite (P) is obtained by mechanochemically combining the fluoroaluminosilicate glass particles (A) with ethylenediaminetetraacetic acid or a salt thereof (C). Method for producing a composition.
10. A step of obtaining calcium phosphate particles (B) / ethylenediaminetetraacetic acid or a salt thereof (C) complex (Q) by previously mixing calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt thereof (C). 10. A method for producing a dental curable composition according to any one of 5 to 9.
11. 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).
12. The dental curable composition according to claim 10, wherein the composite (Q) is obtained by mechanochemically combining calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt thereof (C). Manufacturing method.
13. A dental curable composition kit comprising a powder material (X) and a liquid material (Y),
    Fluoroaluminosilicate glass particles (A) and calcium phosphate particles (B) are included as essential components, and at least one selected from the group consisting of ethylenediaminetetraacetic acid or a salt thereof (C) and polyalkenoic acid (D) is included as an optional component Powder material (X),
    A liquid material (Y) containing water (E) as an essential component, and containing at least one selected from the group consisting of ethylenediaminetetraacetic acid or a salt thereof (C) and polyalkenoic acid (D) as an optional component,
    A dental curable composition kit, which is used by mixing so that the weight ratio (X / Y) of the powder material (X) and the liquid material (Y) is 1.0 to 5.0.
14. A dental curable composition kit comprising a powder material (X) and a liquid material (Y),
    Powder material (X) containing fluoroaluminosilicate glass particles (A), calcium phosphate particles (B) and ethylenediaminetetraacetic acid or a salt thereof (C) as essential components, and polyalkenoic acid (D) as an optional component;
    A liquid material (Y) containing polyalkenoic acid (D) and water (E) as essential components, and containing ethylenediaminetetraacetic acid or a salt thereof (C) as optional components,
    A dental curable composition kit, which is used by mixing so that the weight ratio (X / Y) of the powder material (X) and the liquid material (Y) is 1.0 to 5.0.