JPH11130465A - Polyvalent metal ion eluting filler and method for producing the same - Google Patents

Abstract

(57) [Problem] To provide a polyvalent metal ion eluting filler which can be used for a dental adhesive or the like and which can achieve both operability and adhesive performance during use. SOLUTION: The initial polyvalent metal ion elution amount obtained by heating a fluoroaluminosilicate glass powder in the absence of an acid or by treating with an organic sulfonic acid is controlled to be as low as 1 to 20 meq / g. And
And the final polyvalent metal ion elution amount is 23 to 50 meq / g.
And polyhydric metal ion eluting filler held high.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention mainly relates to dental adhesives,
The present invention relates to a polyvalent metal ion eluting filler used for dental materials such as glass ionomer cement.

[0002]

2. Description of the Related Art A dental glass ionomer cement is obtained by kneading a fluoroaluminosilicate glass powder as a polyvalent metal ion eluting filler and a polycarboxylic acid in the presence of water and curing the mixture. The properties required for the glass ionomer cement include good adhesiveness to the dentin, high strength of the cured product, low disintegration rate, and good operability. Here, operability refers to ease of use in clinical practice.Specifically, the time from the start of mixing a glass powder and an aqueous solution of a polycarboxylic acid until the viscosity reaches a level that hinders operation. (Operation allowance time). In clinical practice, doctors and dental hygienists work with ample time, so the operating margin is as long as possible,
On the other hand, a cement which hardens rapidly when inserted into the oral cavity is desired.

[0003] The fluoroaluminosilicate glass powder can be applied as a dental adhesive by being combined with an acidic group-containing polymerizable monomer, water and a polymerization initiator. And, in the dental adhesive, similarly to the glass ionomer cement, the operation margin time after mixing the liquid containing the glass powder and the liquid containing the acidic group-containing polymerizable monomer is long, and the tooth It is required to have good adhesiveness to the polymer and excellent physical properties of the cured product.

[0004] The operability and physical properties of the above-mentioned dental glass ionomer cement and dental adhesive are largely dependent on the elution amount and elution rate of polyvalent metal ions from a fluoroaluminosilicate glass powder as a polyvalent metal ion eluting filler. to be influenced. That is, the polyvalent metal ions eluted from the fluoroaluminosilicate glass powder improve the adhesion to the tooth material and the physical properties of the cured body by chelate-crosslinking with a polycarboxylic acid or an acidic group-containing polymerizable monomer or a polymer thereof. On the other hand, if this chelate crosslinking occurs during the operation, the viscosity of the kneaded material increases, and the operation allowance time is shortened.
Therefore, in order to improve the operability, it is considered that the elution rate of the polyvalent metal ion from the polyvalent metal ion-eluting filler should be reduced, and several techniques have been tried so far.

For example, a method has been proposed in which the surface of glass powder is treated with an acid such as hydrochloric acid to remove the calcium on the surface, thereby substantially delaying the curing reaction with the polycarboxylic acid (Japanese Patent Publication No. 59-5536). I have. However, this method removes calcium more than necessary, so that the final amount of ions eluted at the time of curing or after the curing is reduced, so that not only the adhesiveness and various physical properties of the cured body may be reduced, but also the glass The acid or salt thereof remaining in the powder often causes deterioration of physical properties of the cured product. In addition, in order to avoid the latter problem, there is also a problem that when the remaining acid or its salt is to be removed, the water washing process must be repeated using a large amount of water.

As another method, a method of finely pulverizing a glass lump in the presence of a carboxylic acid and subjecting it to a surface treatment (Japanese Patent Application Laid-Open No.
225567), a method of heating glass powder in the presence of carboxylic acid (JP-A-5-97622), and a method of heating glass powder in the presence of carboxylic acid and water (JP-A-5-97622).
97623) has been proposed. However, in any of these methods, since a salt is formed on the glass surface, the occurrence of the above-mentioned problem caused by a decrease in the total amount of polyvalent metal ions finally eluted cannot be avoided.

As described above, the operability can be improved by the above-described methods, but the adhesiveness to the tooth substance and the physical properties of the cured product tend to be low, and it is difficult to achieve both the operability and these physical properties. It was difficult.

[0008]

SUMMARY OF THE INVENTION In the present invention, a polyvalent metal ion-eluting filler which gives a dental ionomer cement or a dental adhesive which is excellent in operability and excellent in adhesiveness to the tooth substance and physical properties of the cured product is provided. The task is to develop it.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to overcome the above technical problems, and as a result, heat-treated fluoroaluminosilicate glass powder in the absence of an acid or treated with an organic sulfonic acid. By doing so, it has been found that the initial polyvalent metal ion elution amount can be reduced while maintaining the final polyvalent metal ion elution amount. Further, when the fluoroaluminosilicate glass powder thus treated is used as a polyvalent metal ion eluting filler for a dental adhesive or the like, the operation allowance time can be extended, and the adhesive property at that time can be increased. It has been found that the cured product has good mechanical properties, and the present invention has been proposed.

That is, the initial polyvalent metal ion elution amount is 1 to 2
0 meq / g, and the final polyvalent metal ion elution amount was 23
It is a polyvalent metal ion-eluting filler characterized by being 〜50 meq / g.

The amount of polyvalent metal ion eluted means that 0.1 g of filler is added at a temperature of 23.degree.
This is the total elution amount of polyvalent metal ions eluted from the filler when immersed in 0 ml, and is a value expressed as an amount per 1 g of the filler (meq / g). Here, the polyvalent metal ion is a metal ion having two or more valences. Representative examples thereof include metal ions such as calcium, strontium, barium, aluminum, zinc, and lanthanoid, and the elution ion thereof. The amount can be measured by ICP emission spectroscopy or atomic absorption spectrometry. The initial polyvalent metal ion elution amount is a polyvalent metal ion elution amount one minute after the filler is immersed under the above conditions, and the final polyvalent metal ion elution amount is 24 hours after the filler immersion. This is the amount of polyvalent metal ion eluted.

Another aspect of the present invention is the above-mentioned method for producing a polyvalent metal ion-eluting filler, wherein a fluoroaluminosilicate glass powder is heat-treated in the absence of an acid.

In this method, since the fluorine on the glass surface is removed by the heat treatment, it is presumed that the elution rate of calcium ions and the like is reduced, and unlike the conventional methods, the total amount of polyvalent metal ions is reduced. The elution rate can be reduced without reducing the amount of elution. Therefore, when the polyvalent metal ion-eluting filler obtained by the method is used for a dental adhesive or the like, the operability can be improved without impairing the adhesiveness or the mechanical properties of the cured product. Also,
Since no acid is required in the above method, there is no concern about the influence of the residual acid or its salt as described above, and no post-treatment such as washing with a large amount of water is required, so that the manufacturing process can be greatly simplified.

Still another aspect of the present invention is a method for producing the polyvalent metal ion-eluting filler, wherein the fluoroaluminosilicate glass powder is treated with an organic sulfonic acid.

When the fluoroaluminosilicate glass powder is treated with an organic sulfonic acid, unlike the case where the fluoroaluminosilicate glass powder is treated with another acid such as hydrochloric acid, the polyvalent metal ion is easily eluted while maintaining the final polyvalent metal ion elution amount. Not only can the amount be controlled, but also the salts generated by the treatment and the residual acid as a treating agent can be easily removed. Becomes possible.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The polyvalent metal ion eluting filler of the present invention is a fluoroaluminosilicate glass filler which elutes polyvalent metal ions such as calcium, strontium, barium and aluminum in the presence of an acidic aqueous solution. The amount of polyvalent metal ion eluted is 1 to 20 meq /
g, and the final polyvalent metal ion elution amount is 23 to 50 me.
q / g.

Here, the initial polyvalent metal ion elution amount means that 0.1 g of the polyvalent metal ion eluting filler is added at a temperature of 23.degree.
When immersed in 10 ml of 0 wt% maleic acid aqueous solution, it is the total amount of polyvalent metal ions per 1 g of filler eluted in 1 minute after immersion, and the final polyvalent metal ion elution amount is 24 hours after immersion of the filler. This is the total amount of polyvalent metal ions per 1 g of the filler eluted in. If the initial polyvalent metal ion elution amount is less than 1 meq / g, the physical properties of the cured product will be reduced. If it exceeds 20 meq / g, the curing time will be too fast, and the operability will be poor. If the final polyvalent metal ion elution amount is less than 23 meq / g, the required elution amount is not reached, and the physical properties of the cured product are reduced. If it exceeds 50 meq / g, most of the filler dissolves, and the strength of the cured product is reduced. The more preferable initial polyvalent metal ion elution amount in the polyvalent metal ion eluting filler of the present invention is 2 to 15 meq / g, and the more preferable final polyvalent metal ion elution amount is 23 to 40 meq / g.

Although the particle size of the polyvalent metal ion-eluting filler of the present invention is not particularly limited, when the polyvalent metal ion-eluting filler of the present invention is used for a dental adhesive, it is dispersed in a monomer or the like. Therefore, the average particle diameter of the filler is preferably 0.01 μm to 2 μm,
05 μm to 1.5 μm is more preferable, and further 0.1 μm
Those having a range of m to 1 μm are most preferred. Particle size is 0.
When it is in the range of from 01 μm to 2 μm, problems such as an increase in viscosity and aggregation of the composition are unlikely to occur, and not only the operability becomes good, but also the physical properties of the cured product are good because the filler does not settle in the monomer. Becomes

In order to reduce the average particle diameter of the polyvalent metal ion-eluting filler of the present invention to within the above range, a wet or dry ball mill, an ultra-visco mill which is a wet and continuous ball mill, and a filler are used. And a nanomizer that crushes the particles by collision.

The method for producing the polyvalent metal ion-eluting filler of the present invention is not particularly limited, but it is preferable to heat the fluoroaluminosilicate glass powder in the absence of an acid or to treat it with an organic sulfonic acid. Can be obtained.

The fluoroaluminosilicate glass used at this time is not particularly limited as long as it is an aluminum and silicon oxyfluoride glass, and those generally used as ion-eluting fillers in dental adhesives and the like can be used without any limitation. it can. For example, the composition is as follows: 10 to 33% by weight of silicon; 4 to 30% by weight of aluminum; 5 to 36% by weight of alkaline earth metal; 0 to 10% by weight of alkali metal; %; Fluorine having a residual oxygen content of 2 to 40% by weight is preferably used. As the alkaline earth metal, calcium, magnesium, strontium, and barium are preferable. Further, as the alkali metal, sodium, lithium,
Potassium is preferred, and sodium is particularly preferred. Further, if necessary, part of the aluminum can be replaced with titanium, yttrium, zirconium, hafnium, tantalum, lanthanum, or the like. Such fluoroaluminosilicate glass is commercially available from Tokuso Ionomer Co., Ltd., manufactured by Tokuyama Corporation, Fujiia Ionomer Type II, manufactured by GC Corporation, and High Bond Glass Ionomer F Co., Ltd., Matsukaze Co., Ltd. And is industrially available.

The shape of the fluoroaluminosilicate glass powder used in the present invention is not particularly limited, and may be pulverized particles obtained by ordinary pulverization or spherical particles produced by a sol-gel method. Although its size is not particularly limited, when it is used for a dental adhesive, it is in the range described above as a suitable particle diameter of the polyvalent metal ion-eluting filler of the present invention before heat treatment or treatment with an organic sulfonic acid. It is preferable to keep it.

When the polyvalent metal ion-eluting filler of the present invention is produced by heat-treating the above-mentioned fluoroaluminosilicate glass powder in the absence of an acid, the method of heat-treating the above-mentioned fluoroaluminosilicate glass powder is not particularly limited. . However, at this time, the heat treatment needs to be performed in the absence of an acid. When the heat treatment is performed in the presence of an acid, a salt is formed with calcium or the like on the glass surface, so that the amount of ions finally eluted decreases, or the acid remains, and the present invention No effect. In particular,
The polyvalent metal ion-eluting filler of the present invention can be suitably obtained by placing a fluoroaluminosilicate glass powder previously ground to a desired particle size in a container such as a crucible and heating in a heater. The heating temperature at this time may be appropriately determined in consideration of the required polyvalent metal ion elution rate and the like, but generally, when the heating temperature is low, the initial polyvalent metal ion elution amount cannot be sufficiently suppressed, Also,
If the heat treatment is performed at an excessively high temperature, the particles need to be sintered and re-crushed.
It is preferred to heat to a temperature range from C to the glass transition point. Further, the heating time in the above-mentioned heat treatment is affected by the treatment amount of the fluoroaluminosilicate glass powder, the shape of the container, and the like, but is preferably 1 hour or more from the viewpoint of the reproducibility of the effects of the present invention.

The heater used in the heat treatment is not particularly limited as long as it can control the temperature, such as an electric furnace or an incubator. However, a heater capable of keeping the temperature in the heater uniform is preferable.

Next, a method for producing the polyvalent metal ion eluting filler of the present invention by treating the fluoroaluminosilicate glass powder with an organic sulfonic acid will be described.

The organic sulfonic acid used in the method is not particularly limited as long as it is an organic compound having a sulfonic acid group, and known compounds can be used without any limitation. Specific examples of the organic sulfonic acid that can be used in the method include methanesulfonic acid, ethanesulfonic acid, 2- (N-morpholino) ethanesulfonic acid, benzenesulfonic acid monohydrate, p-chlorobenzenesulfonic acid, and p-chlorobenzenesulfonic acid. Hydroxybenzene sulfonic acid,
2,5-dimethylbenzenesulfonic acid dihydrate, 4-hydrazinobenzene-1-sulfonic acid, 3-methylaniline-4-sulfonic acid, 3-pyridinesulfonic acid, phenylhydrazine-p-sulfonic acid, p- Toluenesulfonic acid monohydrate, 8-hydroxyquinoline-5-sulfonic acid monohydrate, N-cyclohexyl-2-aminoethanesulfonic acid, N- (2-acetamido) -2-aminoethanesulfonic acid, aniline- o-sulfonic acid, aniline-m
-Sulfonic acid, aniline-p-sulfonic acid, 2-chloro-4-aminotoluene-5-sulfonic acid, m-toluidine-4-sulfonic acid, 1-naphthylamine-6-sulfonic acid, N-2-hydroxylethylpiperazine -N'-
2-ethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and the like can be mentioned. Among these organic sulfonic acids, methanesulfonic acid and benzenesulfonic acid are preferable from the viewpoints of easy removal of residual organic sulfonic acid and salts formed by the treatment, cohesion of the ion-eluting filler after the treatment and easy filtration. It is preferred to use monohydrate, p-toluenesulfonic acid monohydrate.

The method of treatment with the organic sulfonic acid is as follows:
The method is not particularly limited as long as the fluoroaluminosilicate glass powder and the organic sulfonic acid come into contact with each other, but the method is preferably performed by immersing the fluoroaluminosilicate glass powder in an organic sulfonic acid aqueous solution with stirring.

The concentration and amount of the aqueous organic sulfonic acid solution used at this time are not particularly limited, but the concentration of the organic sulfonic acid is generally 1 wt.
%, Preferably in the range of 3 wt% to 10 wt%. The amount of the organic sulfonic acid aqueous solution to be used is 3 times or more the weight of the fluoroaluminosilicate glass powder to be treated from the viewpoint of stirring efficiency and operability.
It is preferable that the weight is 30 times, especially 10 to 20 times the weight.

In the above treatment with an organic sulfonic acid,
Processing temperature, processing time, etc. are not particularly limited,
From the viewpoint of the high effect of the present invention, the processing efficiency, and the like, 25 ° C.
It is preferable to perform the treatment for 1 hour to 5 hours by controlling the temperature within a temperature range of 60 ° C.

After the above treatment, the organic sulfonic acid aqueous solution is removed by filtration or the like, and further washed with water to remove excess organic sulfonic acid or a salt thereof, and then dried with a drier or the like to obtain the polyvalent metal of the present invention. An ion-eluting filler can be obtained.

The polyvalent metal ion-eluting filler of the present invention can be used as a dental adhesive by combining it with an acidic group-containing polymerizable monomer, water, a polymerization initiator and the like. As a preferable composition at this time, 100 parts by weight of a polymerizable monomer containing 5% by weight or more of an acidic group-containing polymerizable monomer and 2-3 parts of the polyvalent metal ion eluting filler of the present invention are used.
0 parts by weight, 3 to 30 parts by weight of water, and 0.1 part by weight of a polymerization initiator.
01 to 10 parts by weight.

The acidic group-containing polymerizable monomer used for the dental adhesive is not particularly limited as long as it has at least one acidic group and at least one polymerizable group in one molecule. Can be used. Specific examples include, for example, polymerizable monomers containing a phosphate group such as 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate; Methacryloyloxy-1,1-undecanedicarboxylic acid,
A polymerizable monomer containing a carboxylic acid group such as 4-methacryloyloxyethyl trimellitate anhydride; and a sulfonic acid group such as 2-acrylamido-2-methylpropanesulfonic acid. Polymerizable monomers.

As the polymerizable monomer used for the dental adhesive, a known compound can be used without any limitation as long as it has at least one polymerizable group in the molecule. Specific examples of compounds that can be preferably used include methyl (meth) acrylate (which means methyl acrylate or methyl methacrylate; the same applies hereinafter), ethyl (meth) acrylate, 2-hydroxyethyl (meth)
Mono (meth) acrylate monomers such as acrylates;
Ethylene glycol di (meth) acrylate, 2,2 '
And polyfunctional (meth) acrylate monomers such as -bis [4- (meth) acryloyloxyethoxyphenyl] propane.

As the polymerization initiator used for the dental adhesive, known ones can be used without any limitation. Such a polymerization initiator is generally roughly classified into a chemical polymerization initiator and a photopolymerization initiator. Examples of the chemical polymerization initiator include a redox type of an organic peroxide such as t-butyl hydroperoxide, cumene hydroperoxide, and benzoyl peroxide, and an amine compound such as N, N-dimethyl-p-toluidine and N-dimethylaniline. A polymerization initiator, a redox-type polymerization initiator composed of a combination of barbituric acid derivatives such as 5-butyl barbituric acid / dilauryl dimethyl ammonium chloride / copper acetylacetone / quaternary ammonium halide / copper compound, and further adhesion For the purpose of improving the strength, sodium benzenesulfinate, which can be decomposed by the acidic compound into the above-described redox-type polymerization initiator to generate a polymerizable radical species, p
Sulfinic acid salts such as sodium toluenesulfinate, monoalkyltriphenylboron, monoalkyltri (p-fluorophenyl) boron, tetraphenylboron, tetrakis (m-methoxyphenyl) boron (the alkyl group is n-butyl, n- A system to which a borate such as a sodium salt, a tetramethylammonium salt, a methylquinolinium salt, or the like of a dodecyl group) is added can also be suitably used. Further, an organic boron compound such as triphenylborane, which initiates polymerization by reacting with oxygen or water, and an organometallic polymerization initiator such as a titanocene derivative may also be used.

As the photopolymerization initiator, camphaquinone, benzyl, 2,4-diethylthioxanthone, 2,4,6-trimethylbenzoyldiphenyl, which itself decomposes upon irradiation with light to form a polymerizable radical species, Phosphine oxide and the like are preferably used, and it is also preferable to add a polymerization accelerator such as N, N-dimethylaniline, p-dimethylaminoacetophenone and ethyl p-dimethylaminobenzoate to this. Further, there are ternary dye / photoacid generator / borates and dye / photoacid generator / sulfinate salts. As the dye used for this, coumarin dyes such as 3-thienoylcoumarin, 3-benzoylcoumarin, 3,3′-carbonylbiscoumarin, and 3,3′-carbonylbis (7-diethylamino) coumarin are preferred. Used. Examples of the photoacid generator include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, and 2- (p-chlorophenyl). Halomethyl-substituted -s-triazine derivatives such as -4,6-bis (trichloromethyl) -s-triazine are preferably used. As the borates and sulfinates, those specifically exemplified in the section of the redox-type polymerization initiator can be similarly used.

Among the above polymerization initiators, the use of a photopolymerization initiator is preferred from the viewpoint of excellent operability. In particular, it is preferable to use a photopolymerization initiator composed of a combination of a dye / photoacid generator / borate or a combination of a dye / photoacid generator / sulfinate.

When the polyvalent metal ion-eluting filler of the present invention is used for a dental adhesive, the acidic group-containing polymerizable monomer, the polymerizable monomer and the catalyst must be used so as not to impair the storage stability. Liquid containing one component (solution A) and liquid containing one component of polyvalent metal ion-eluting filler, polymerizable monomer, water and catalyst (solution B) are separately prepared and mixed immediately before use. Is preferred. At this time, as a method of dispersing the polyvalent metal ion eluting filler in the polymerizable monomer, stirring, ultrasonic waves, a combination of stirring and ultrasonic waves, and the like can be mentioned. Further, there is also a method in which the mixture is applied to the above-mentioned pulverizer together with the polymerizable monomer for a short time. At the time of use, a mixture of the above-mentioned liquid A and liquid B is applied to the cavity of the tooth from which the dental caries has been removed.
Next, when a photopolymerization initiator is used, the adhesive is cured by light irradiation. When a chemical polymerization initiator is used, it is left for several minutes until the adhesive is cured. By filling a restorative material such as a dental composite resin thereon, the tooth and the restorative material can be bonded well.

The polyvalent metal ion-eluting filler of the present invention can be used as a dental glass ionomer cement by mixing it with a polycarboxylic acid in the presence of water. The polycarboxylic acid used at this time is preferably a water-soluble one, and typical examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid, glutaconic acid, fumaric acid, citraconic acid and crotonic acid. And the like and copolymers of these unsaturated carboxylic acids. Although the molecular weight of the polycarboxylic acid is not particularly limited, it is generally 50 in average molecular weight.
Those having a range of 00 to 500,000 are preferred.

When the polyvalent metal ion-eluting filler of the present invention is used as a dental glass ionomer cement, polycarboxylic acid 30 wt% to 70 wt%, water 70 w
A liquid composed of t% to 30% by weight and a powder composed of a polyvalent metal ion-eluting filler are mixed at a ratio of 1 part by weight to 3 parts by weight of powder to 1 part by weight of the liquid immediately before use and kneaded well. Is filled into the cavity of the tooth from which the carious portion has been removed, and a prosthesis such as a metal is mounted thereon, whereby the tooth and the prosthesis can be bonded well.

[0040]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

(1) Abbreviations PM2: bis (2-methacryloyloxyethyl) hydrogen phosphate MAC-10: 11-methacryloyloxy-1,1-
Undecanedicarboxylic acid D26E: 2,2-bis (4- (methacryloxyethoxy) phenyl) propane MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate TCT: 2,4,6-tris (trichloromethyl) -s
-Triazine CDAC: 3,3'-carbonylbis (7-diethylamino) coumarin PBNa: Sodium tetraphenylboron (2) Adhesive composition In Examples and Comparative Examples, the adhesive used in the measurement of the operation allowance time and the adhesive strength was measured. The composition is shown in Table 1. In addition, the polyvalent metal filler produced in the following Examples or Comparative Examples was dispersed and used in the liquid B.

[0042]

[Table 1]

(3) Method of measuring operation allowance For evaluation of the operability, the adhesive was adjusted using the polyvalent metal filler obtained in the examples or comparative examples, and the operation allowance was measured. 0.46 g of the adhesive A solution and 0.67 g of the B solution were placed in a mixing dish, and the time from the start of mixing to the time when stringing was observed was measured, and this was defined as operation allowance time.

(4) Enamel and dentin adhesive strength measuring method Within 24 hours after sacrifice, the bovine anterior teeth were removed, and water was injected.
An enamel or dentin plane was cut out with emery paper so as to be parallel to the lips. Next, after blowing compressed air on these surfaces for about 10 seconds and drying, a double-sided tape having a hole having a diameter of 3 mm is fixed to this surface, and then a paraffin wax having a hole having a thickness of 0.5 mm and a hole having a diameter of 6 mm is removed. A simulated cavity was formed by fixing the same center on the circular hole. The adhesives of Examples and Comparative Examples adjusted immediately before use were applied to the simulated cavity and allowed to stand for 30 seconds. The adhesive was cured by irradiating light with a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation) for 30 seconds. Dental composite resin (Palphic Light Posterior, manufactured by Tokuyama Corporation) was filled thereon, and irradiated with light using a visible light irradiator for 30 seconds to prepare an adhesion test piece.

After the adhesive test piece was immersed in water at 37 ° C. for 24 hours, it was pulled at a crosshead speed of 5 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation) to pull the teeth and the composite resin together. The strength (also simply referred to as “adhesion strength”) was measured.

In each of Examples and Comparative Examples, the tensile adhesive strength was measured for four test pieces prepared under the same conditions, and the average value and the standard deviation (SD) of the tensile adhesive strength at that time were measured. The adhesive strength was determined as follows.

(5) Production of Fluoroaluminosilicate Glass The following two kinds of glasses were used in Examples and Comparative Examples.

F-1: Fluoro-aluminosilicate glass powder (Tokusui ionomer, manufactured by Tokuyama Corporation) is pulverized to an average particle diameter of 0.35 μm using an Ultra Viscomil (New My Mill, manufactured by Mitsui Mining). It was set to 1. As a result of differential thermal analysis, the glass transition point of this glass was 5
80 ° C.

F-2: 60.1 g of silicon dioxide, cryolite 1
17. 0.4 g, aluminum fluoride 10.0 g, aluminum hydroxide 66.5 g, calcium phosphate dihydrate
2 g and 14.5 g of calcium fluoride were uniformly mixed in a mortar and melted at 1400 ° C. for 40 minutes to obtain a transparent glass. The glass was pulverized with an Ultraviscomiler to an average particle size of 0.5 μm to obtain F-2. As a result of differential thermal analysis, the glass transition point of this glass was 630 ° C.

Example 1 10 g of fluoroaluminosilicate glass powder (F-
1) is weighed into an alumina crucible and placed in an electric furnace for 300 minutes.
It heated at 4 degreeC for 4 hours, and obtained the polyvalent metal ion eluting filler (HF-1) of this invention. According to ICP emission spectroscopy, the initial polyvalent metal ion elution amount of this filler was 19.7 me.
q / g (aluminum ion 14.2 meq / g, calcium ion 4.7 meq / g, lanthanum ion 0.8
meq / g) and the final polyvalent metal ion elution amount is 25.0 m.
eq / g (aluminum ion 17.3 meq / g, calcium ion 6.5 meq / g, lanthanum ion 1.
2 meq / g). The average particle diameter of the filler was not changed by the heat treatment.

Examples 2 to 6 In the same manner as in Example 1, heating was performed at the temperature and time shown in Table 2 to obtain HF-2 to H, which are polyvalent metal ion eluting fillers of the present invention.
F-6 was obtained. Table 2 shows the polyvalent metal ion elution amount of each filler. Each filler had an initial polyvalent metal ion elution amount in the range of 1 to 20 meq / g, and a final polyvalent metal ion elution amount in the range of 23 to 50 meq / g. In addition, no change was observed in the average particle diameter of any of the fillers before and after the treatment.

Comparative Example 1 F-1 was used without heat treatment. The initial polyvalent metal ion elution amount of this filler was 22.0 meq / g and the final polyvalent metal ion elution amount was 2
It was 5.1 meq / g.

Comparative Example 2 10 g of F-1 and 0.1 g of maleic acid were weighed into a crucible made of alumina and heated in an electric furnace at 400 ° C. for 4 hours, so that polyvalent metal ion eluting filler (HF-7) was obtained. I got I
According to CP emission spectroscopic analysis, the initial polyvalent metal ion elution amount of this filler was 6.3 meq / g and the final polyvalent metal ion elution amount was 17.2 meq / g. The initial ion elution amount was sufficient, but the final ion The result was that the elution amount was small. It is considered that the final elution amount was reduced because the addition of the acid formed salts with calcium and the like on the glass surface.

[0054]

[Table 2]

Examples 7 to 10 In the same manner as in Example 1 except that F-2 was used instead of F-1 as the fluoroaluminosilicate glass powder, Table 3 was used.
And HF-8 to HF-11, which are high on-eluting fillers of the present invention, were obtained. Table 3 shows the polyvalent metal ion elution amount of each filler. Each filler has an initial polyvalent metal ion elution amount of 1 to 20 me.
q / g, and the final polyvalent metal ion elution amount is 2
It was in the range of 3 to 50 meq / g. In addition, no change was observed in the average particle diameter of any of the fillers before and after the treatment.

Comparative Example 3 F-2 was used without heat treatment. According to ICP emission spectroscopy, the initial ion elution amount of this filler was 26.
At 3 meq / g, the final ion elution amount is 35.9 meq / g.
Met.

Comparative Example 4 HF-12 as a multivalent ion eluting filler was obtained in the same manner as in Comparative Example 2 except that F-2 was used instead of F-1. According to ICP emission spectroscopy, the initial polyvalent metal ion elution amount of this filler was 7.2 meq / g and the final polyvalent metal ion elution amount was 19.1 meq / g, and the acid was added similarly to HF-7. It is considered that the final elution amount was reduced due to the formation of salts with calcium and the like on the glass surface.

[0058]

[Table 3]

Example 11 5 g of methanesulfonic acid and 95 g of water were added to 10 g of F-1 (acid concentration: 5 wt%, aqueous solution: 10 g / g-filler), and the mixture was stirred at a temperature of 50 ° C. for 2 hours. Then, after filtering the filler by centrifugal filtration, the filler was washed with 40 ml of water each time and filtered, and this was repeated four times.
Was neutralized. Thereafter, drying was performed at 130 ° C. for 5 hours to obtain a polyvalent metal ion-eluting filler AF-1. ICP
According to emission spectroscopy, the initial polyvalent metal ion elution amount of this filler was 9.2 meq / g, and the final polyvalent metal ion elution amount was 24.4 meq / g. The average particle diameter of the filler did not change before and after the treatment.

Examples 12 to 19 An acid treatment was carried out with the acid, acid concentration, aqueous solution amount, temperature and time shown in Table 4, and post-treatment was carried out in the same manner as in Example 11, and the polyvalent metal ion eluting filler of the present invention was obtained. AF-2 to AF-
9 was obtained. Table 4 shows the ion elution amount of each filler. Each filler has an initial ion elution amount of 1 to 20.
meq / g, and the final ion elution amount is 23 to
It was in the range of 50 meq / g. In addition, no change was observed in the average particle diameter of any of the fillers before and after the treatment.

Comparative Example 5 4.2 g of concentrated hydrochloric acid and 95.8 g of water were added to 10 g of F-1 (acid concentration: 1.4 wt%, aqueous solution: 10 g / g-filler), and the mixture was stirred at a temperature of 40 ° C. for 3 hours. did. Then, after filtering the filler by centrifugal filtration, the filler was washed with 40 ml of water each time and filtered, and this was repeated eight times.
Was neutralized. Thereafter, drying was performed at 130 ° C. for 5 hours to obtain AF-10 as a polyvalent metal ion eluting filler. IC
According to P emission spectral analysis, the initial polyvalent metal ion elution amount of this filler was 1.5 meq / g, the final polyvalent metal ion elution amount was 15.3 meq / g, and the initial polyvalent metal ion elution amount was 1 to 20 meq / g. g, but the final ion elution amount was small.

The amount of water required for water washing after the acid treatment was twice that of Example 17, although the number of moles of the acid was almost the same.

[0063]

[Table 4]

Example 20 Immediately before use, 0.46 g of the adhesive A solution and 0.67 g of the B solution in which HF-2 as the polyvalent metal ion-eluting filler of the present invention was dispersed were mixed and operated according to the method described above. The margin time and the adhesive strength were measured. Table 5 shows the results. The operation allowance time was 2 minutes and 05 seconds, which was a clinically sufficient time. Furthermore, the adhesive strength was also a high value for both enamel and dentin. Since these fracture surfaces are mainly caused by the interface between the teeth and the adhesive or the cohesive failure of the teeth, it can be said that the strength of the cured adhesive is sufficient.

Examples 21 to 28 In the same manner as in Example 20, the operation allowance time and the adhesive strength were measured using the polyvalent metal ion-eluting filler of the present invention shown in Table 5. Table 5 shows the results. Regardless of the filler used, both the operation allowance time and the adhesive strength were good.

Comparative Examples 6 to 8 In the same manner as in Example 20, the operation allowance time and the adhesive strength were measured using the polyvalent metal ion eluting fillers shown in Table 5. Table 5 shows the results.

Comparative Example 6 is an example in which the initial polyvalent metal ion elution amount was too large because no heat treatment was performed, and the operation time was short and the operability was poor. Also, the adhesive strength was reduced. In Comparative Example 7, the heat treatment was performed in the presence of an acid, and the adhesive strength was lowered because the final polyvalent metal ion elution amount was too small. Comparative Example 8 was treated with hydrochloric acid, and the adhesive strength was lowered because the final polyvalent metal ion elution amount was too small.

[0068]

[Table 5]

[0069]

Since the polyvalent metal ion eluting filler of the present invention has a low initial polyvalent metal ion elution amount of 1 to 20 meq / g, it can be mixed with a polycarboxylic acid or an acidic group-containing polymerizable monomer. No rapid increase in viscosity occurs. Therefore, the operability when used as a dental glass ionomer cement or a dental adhesive is improved. In addition, since the polyvalent metal ion-eluting filler of the present invention has a high final polyvalent metal ion elution amount of 23 to 50 meq / g, when used as a dental glass ionomer cement or a dental adhesive, the cured product strength and tooth The properties after curing, such as the adhesive strength to the quality, are excellent.

Claims (3)

[Claims] 1. The initial polyvalent metal ion elution amount is 1 to 20 m.
eq / g and the final polyvalent metal ion elution amount is 23 to 5
A polyvalent metal ion-eluting filler, which is 0 meq / g. 2. The method for producing a polyvalent metal ion eluting filler according to claim 1, wherein the fluoroaluminosilicate glass powder is heat-treated in the absence of an acid. 3. The method according to claim 1, wherein the fluoroaluminosilicate glass powder is treated with an organic sulfonic acid.
A method for producing the polyvalent metal ion eluting filler according to the above.