JP5013854B2 - Adhesive between dental alginate impression material and impression metal tray - Google Patents

Description

  The present invention relates to an adhesive suitably used for bonding a metal tray used for taking an impression and an alginate impression material in an impression material used for shaping a tooth or the like.

  In general, an alginate impression material is used to mold a tooth for restoration of a tooth. The alginate impression material utilizes the fact that a gel-like cured product can be obtained by kneading alginate as a base material and calcium sulfate as a curing material with water. To mold a tooth, generally, a tray imitating a dentition is placed with a mixture of a base material and a curing material before curing, and the tray is pressed against the tooth so as to wrap the teeth in the oral cavity. This is done by removing the body from the teeth and removing it from the oral cavity.

  The tray is mainly made of brass, brass plated with nickel or the like, or made of metal such as stainless steel, and has a net shape, a plate shape, or a punch hole. However, when taking an impression using such a metal tray, particularly a plate-like one having a small contact area with the impression material, if the tray and the cured body are removed from the tooth as a unit, the tray and the cured body are taken. As a result, there is a problem in that the cured body is greatly deformed, and as a result, an impression with high accuracy cannot be obtained.

  In order to solve this problem, an adhesive for bonding a metal tray and an impression material cured body containing an alkaline earth metal compound has been proposed (see Patent Documents 1 and 2). there were. Specifically, a brass metal tray that was used for a long period of time had a significant decrease in adhesion. Also, in such a metal tray made of brass, if the surface is plated, the adhesion is relatively good, but even in such a case, the plating gradually increases during repeated use in clinical practice. When peeled off, there was a problem that the adhesiveness of the surface rapidly decreased.

Japanese Patent Laid-Open No. 10-175812 JP 2000-160106 A

  An object of the present invention is to provide an adhesive between a metal tray and an alginate impression material having a stable adhesive force regardless of the difference in the surface state of the metal tray.

  As a result of diligent research to solve such problems, the present inventors applied or sprayed a liquid composition in which trivalent metal ions were dissolved in water or an organic solvent on the surface of the metal tray. It has been found that a stable adhesive force with the impression material can be obtained, and the present invention has been completed.

That is, the present invention comprises a solution containing at least one trivalent metal ion selected from aluminum ions, iron ions, lanthanum ions, and manganese ions at a concentration of 0.05 to 2 mmol / g. An adhesive between a dental alginate impression material and an impression metal tray.

  Further, it has been found that when fine particles are dispersed in the liquid composition, uniformity can be maintained without causing liquid aggregation when applied or sprayed on the surface of the metal tray.

That is, in another invention, an average particle size is further added to a solution containing at least one trivalent metal ion selected from aluminum ions, iron ions, lanthanum ions, and manganese ions at a concentration of 0.05 to 2 mmol / g. An adhesive between a dental alginate impression material and an impression metal tray, comprising fine particles of 1 μm or less.

  By using the adhesive of the present invention, the metal tray and the alginate impression material are firmly bonded. This high adhesive strength is good even when the metal tray is made of brass and has been used for a long time, or when the surface is plated and the plating is partially peeled off. Demonstrated. Further, the adhesive of the present invention is less likely to be non-uniform due to liquid aggregation on the metal surface due to the presence of fine particles, and can reproduce a stable adhesive force. Therefore, in operation, the impression material cured body can take a highly accurate and stable impression without causing partial peeling from the metal tray or deformation associated therewith.

  As the trivalent metal ion used in the present invention, known ones can be applied without limitation. Specifically, group IIIB metal ions such as aluminum and gallium, vanadium, iron, lanthanum, cobalt, And trivalent transition metal ions such as nickel and manganese. Among these, it is preferable to use at least one selected from aluminum ions, iron ions, and lanthanum ions because high adhesive strength can be obtained.

  As a supply source of such trivalent metal ions to the adhesive, a known metal compound that can be dissolved in water or an organic solvent can be used. Examples include metal salts such as chlorides, sulfates and nitrates, and organic compounds such as trisacetylacetonate complex salts and metal alkoxides. For example, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum acetylacetonate, aluminum ethoxy Aluminum isopropoxide, vanadium (III) chloride, vanadium (III) acetylacetonate, ferric chloride, ferric sulfate, ferric nitrate, iron (III) acetylacetonate, lanthanum chloride, lanthanum nitrate, Examples thereof include lanthanum ethoxide.

  Among these, considering the harmfulness to the living body, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum acetylacetonate, aluminum ethoxide, aluminum isopropoxide, ferric chloride, ferric sulfate, ferric nitrate, Iron (III) acetylacetonate is preferred. It is also possible to use a combination of two or more of these compounds.

  The content of these trivalent metal ions needs to be contained in the solution at a concentration of 0.05 to 2 mmol / g. When the amount is less than 0.05 mmol / g, a sufficient adhesion effect cannot be obtained. When the amount is more than 2 mmol / g, the uniformity of the solution is impaired, which is not preferable. In order to better exhibit the adhesive effect, it is particularly preferable that the content of the trivalent metal ion is contained in the solution at a concentration of 0.1 to 1.8 mmol / g.

  The polyvalent metal ion reacts with the carboxyl group of alginic acid, which is the main component of the alginate impression material, and crosslinks. Therefore, the alginate impression material can be adhered to the tray by fixing the polyvalent metal ions on the surface of the metal tray in advance. Since the trivalent metal ion has a higher aggregating ability of alginic acid than the divalent metal ion, the trivalent metal ion is hardly affected by the surface of the metal tray and can stably obtain a high adhesive force.

  In the present invention, water or an organic solvent can be used without any limitation as a solvent for forming a solution. As water, distilled water is usually used. Organic solvents include alcohols such as methanol, ethanol, isopropanol and butanol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as toluene, benzene and xylene, and aliphatic hydrocarbons such as hexane, pentane and butane. Can be given. Of these, low-toxic low-toxic alcohols such as distilled water, ethanol, isopropanol and the like having low toxicity are suitable. Moreover, it is also suitable to use these water and organic solvents in combination.

  As the fine particles used in the present invention, any known fine particles having an average particle diameter of 1 μm or less can be used without any limitation. In addition, as for the shape of the particles, particles having an irregular shape such as spherical particles can be used. Considering the uniform application property of the adhesive and the dispersibility in the adhesive, the average particle diameter of the fine particles is more preferably 0.001 to 0.5 μm. When the average particle diameter exceeds 1 μm, it is difficult to obtain a uniform film when applied to the tray, and it is not preferable because it precipitates and separates in the adhesive.

  Specific examples of the fine particles particularly preferably used include dry fine powder silica, dry fine powder alumina, dry fine powder zirconia, dry fine powder titania, wet amorphous silica, colloidal silica, colloidal alumina, colloidal zirconia, quartz. Inorganic oxides such as fine powders and organic fine powders such as polymethylmethacrylate are used alone or in combination of two or more. In addition, in order to improve the dispersibility in an organic solvent, these fine powders may use a surface treated product in which the particle surface is hydrophobized with methylchlorosilanes or the like.

  The average particle diameter of the fine particles in the present invention is a median diameter measured by a laser diffraction-scattering method.

  The amount of these fine particles is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the solvent. When the amount of the fine particles is less than 0.05 parts by mass, a sufficient effect as a dispersion carrier cannot be obtained, and when the amount is more than 5 parts by mass, the adhesiveness is lowered, which is not preferable.

  The fine particles need to be appropriately dispersed in a solvent in order to exhibit performance as an adhesive. As a method for dispersing the fine particles, a known method can be used without any limitation. Specific examples include ultrasonic dispersion, disperser dispersion, wet ball mill dispersion, and the like.

  The adhesive of the present invention exhibits its effect if each of the above-described components is blended, but other components are blended as necessary within the range that does not impair the effects of the present invention. Also good. Examples of such components include a surfactant for improving the wettability of the adhesive to the metal tray, a thickener for suppressing sedimentation of fine particles, and a trace amount of acid for improving the solubility of the metal compound. Etc.

  The method for using the adhesive of the present invention is not particularly limited. Generally, it is applied to a metal tray with a brush, a spatula, a brush, or sprayed. After application or spraying, it may be left in the air to dry naturally, or it may be dried by applying air.

  Any known alginate impression material to which the adhesive of the present invention is applied can be used without any limitation. Specifically, it is a paste / paste type in which a base paste mainly composed of alginate and a hardener paste mainly composed of calcium sulfate are used, or alginate and calcium sulfate as main components. And the like using a mixture of water and water. More specifically, a base paste having a composition such as potassium alginate, silica powder, potassium hydroxide, polyacrylic acid, water, etc., granular silica, liquid paraffin, zinc oxide, magnesium oxide, trisodium phosphate, fluorinated titanic acid It consists of a hardener paste with a composition of potassium, ultrafine silica, calcium sulfate, etc., and is used by mixing and kneading the base paste and hardener paste, or potassium alginate, silica powder, zinc oxide, magnesium oxide, phosphoric acid There are powders having a composition such as trisodium, potassium fluorinated titanate, calcium sulfate and the like mixed with water and used.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not restrict | limited to these Examples.
(Geling test method)
Solution A was prepared by dissolving 1.5 g of potassium alginate in 98.5 g of distilled water. Also, a solution B was prepared by dissolving a predetermined metal ion in distilled water so that the ion had a predetermined concentration.

  4 g of solution B was weighed into a 10 ml sample bottle, and 0.03 g of solution A was dropped therein to confirm the presence of gelation. Based on the gelation evaluation criteria shown below, the lowest ion concentration that would be “◯” was determined.

Evaluation criteria: ○: The dropped liquid is rounded and gelled into one lump.
Δ: Dropped liquid gels into discrete fibers ×: Does not gel and becomes suspension (adhesion test method)
An appropriate amount of the adhesive of the present invention was applied to a brass plate-like tray with two types of nickel plating described below with a brush, and the solvent was evaporated by air blow and dried. Alginate impression materials were placed on these trays, normal impressions were taken in the oral cavity, and the trays were removed outside the oral cavity after the alginate impression material was cured. The adhesion between the tray at the time of removal and the cured body of the alginate impression material was evaluated according to the evaluation criteria described below.

<Evaluation criteria>
A: Impression material and metal tray are bonded when removed. When both are peeled off by hand, the impression material is totally agglomerated and destroyed.
○: Impression material and metal tray are bonded when removed. Although it is at a level that is not a problem clinically, when both are peeled off by hand, most of them are cohesive failure of the impression material, but some are peeled off from the tray.
(Triangle | delta): The impression material has peeled from the tray in the considerable part at the time of removal.
X: Impression material is completely peeled from the tray when removed.

<Metal tray>
X: New brass plate tray with nickel plating Y: Brass plate tray with nickel plating almost peeled off Reference Example 1
In accordance with the gelation test method described above, liquid B was prepared using lanthanum nitrate so that the trivalent lanthanum ions had the ion concentrations shown in Table 1, and the presence or absence of gelation at each concentration was evaluated. The chemical concentration was determined. The results are shown in Table 1, and the minimum gelation concentration was 1 mmol / L.

Reference Examples 2-10
Table 2 shows the results obtained by conducting the same test as in Reference Example 1 and examining the minimum gelation concentration of various ions. It has been found that trivalent metal ions can gel alginic acid at a lower concentration than monovalent or divalent metal ions.

Example 1
0.5 g of ferric chloride anhydride was dissolved in 9.5 g of distilled water to obtain an adhesive. An adhesion test was performed according to the above test method. As the alginate impression material, a commercially available pasty alginate impression material “Tokuso AP-1” (manufactured by Tokuyama Corporation) was used. The results are shown in Table 3. It was well adhered to both the X and Y trays, and good adhesive force was obtained regardless of the surface state of the tray.

Examples 2-12
In the same manner as in Example 1, an adhesive having the composition shown in Table 3 was prepared and an adhesion test was performed. The results are shown in Table 3, and all showed good adhesive strength.

Comparative Examples 1-6
In the same manner as in Example 1, an adhesive having the composition shown in Table 3 was prepared and an adhesion test was performed. The results are shown in Table 3.

  In Comparative Example 1, trivalent iron ions were used, but since the amount of ions was small, a decrease in adhesive strength was observed in the Y tray where the plating was peeled off. Comparative Examples 2 to 5 were systems to which divalent metal ions were added, but all had good adhesion to a new tray, but the adhesion to Y tray decreased. Comparative Example 6 was a system to which monovalent metal ions were added, but there was no adhesion to any tray.

Example 13
An adhesive was prepared by dissolving 0.1 g of ferric chloride anhydride in 9.9 g of distilled water and further dispersing 0.5 g of fumed silica having an average primary particle system of 15 nm using an ultrasonic disperser. Using this adhesive, an adhesion test was conducted in the same manner as in Example 1. As a result, the evaluation was “◎” for both X and Y trays, and the adhesive strength was good.

Example 14
1 g of aluminum nitrate is dissolved in 9 g of ethanol, and 0.5 g of spherical silica-zirconia filler (γ-methacryloyloxypropyltrimethoxysilane surface-treated product) having an average primary particle size of 0.2 μm is dispersed using a disperser. An adhesive was prepared. Using this adhesive, an adhesion test was conducted in the same manner as in Example 1. As a result, the evaluation was “◎” for both X and Y trays, and the adhesive strength was good.

Comparative Example 7
Dissolve 1 g of aluminum nitrate in 9 g of ethanol, and disperse 0.5 g of amorphous silica-zirconia particles (γ-methacryloyloxypropyltrimethoxysilane surface-treated product) having an average primary particle system of 3.0 μm using a disperser. An adhesive was prepared. Using this adhesive, an adhesion test was conducted in the same manner as in Example 1. As a result, the evaluation for both trays X and Y was “Δ”. The average particle size of the particles contained in this adhesive exceeded 1 μm, and when the adhesive was dried with air on the tray, liquid aggregation occurred unevenly on the tray surface.

Example 15
Using the adhesive of Example 11, an alginate impression material was subjected to an adhesion test using a powder type “Tokuso A-lα” (manufactured by Tokuyama Corporation). As a result, the evaluation was “◎” for both X and Y trays, and the adhesive strength was good.

Claims (2)

A dental alginate impression material comprising a solution containing at least one trivalent metal ion selected from aluminum ion, iron ion, lanthanum ion and manganese ion at a concentration of 0.05 to 2 mmol / g; Adhesive with impression metal tray. Further, the average particle diameter comprising the following fine particles 1 [mu] m, the adhesive of the dental alginate impression material and the impression metal tray of claim 1, wherein.