KR102066050B1 - Etching agent composition for ceramic and method for treating surface of ceramic using the same - Google Patents

Abstract

The present invention relates to a ceramic surface etchant composition and a method for treating a ceramic surface using the same, wherein the etchant composition does not generate hydrofluoric acid fumes and generates less hydrofluoric acid vapor and thus has excellent workability. The surface treatment method can uniformly etch the ceramic surface for a short time without ultrasonic treatment at room temperature.

Description

Ceramic surface etchant composition and surface treatment method of ceramic using the same {ETCHING AGENT COMPOSITION FOR CERAMIC AND METHOD FOR TREATING SURFACE OF CERAMIC USING THE SAME}

The present invention relates to a ceramic surface etchant composition and a method for treating a ceramic surface using the same, wherein the etchant composition does not generate hydrofluoric acid fumes and generates less hydrofluoric acid vapor and thus has excellent workability. The surface treatment method can uniformly etch the ceramic surface for a short time without ultrasonic treatment at room temperature.

3Y-TZP (3 mol% Yittirium-Tetragonal Zirconia Polycrystal), which has excellent durability and strength, was used as a dental restoration, resulting in aesthetic limitations due to the turbid surface color of zirconia. In order to overcome this limitation, the prosthesis coated with resin or ceramic is attached to the surface of the zirconia. At this time, it was known that the adhesive resin or ceramic peeled off or the zirconia bonded to the prosthesis was separated and dropped to about 30% of the number of procedures. Therefore, there is a need to increase the adhesive strength between zirconia and resin or ceramics for stable fabrication and use of dental restorations. It is also known that the bonding between zirconia and resin or ceramic depends largely on mechanical and physical bonding forces. Therefore, a surface etchant including an acid solvent such as hydrofluoric acid may be used as an effective way to increase the bond strength by increasing the contact surface between zirconia and resin or ceramic by increasing the fine surface roughness of zirconia.

For example, Korean Patent No. 10-1763573 discloses a surface etchant composition of dental zirconia ceramics comprising hydrofluoric acid, sulfuric acid, a catalyst and methyl alcohol. The etchant composition is prepared by mixing hydrofluoric acid, a catalyst and methyl alcohol to prepare a primary mixture, and adding sulfuric acid to the primary mixture to prepare an etchant composition, sealing it in a container, and then heating it to 60 to 80 ° C. It is manufactured through the manufacturing process. In addition, there may be a problem that hydrogen peroxide used as a catalyst decomposes into water and oxygen over time.

Korea Patent Registration No. 10-1763573 Korea Patent Registration No. 10-1539229 Korea Patent Registration No. 10-1544357

In the conventional etchant composition, as the amount of hydrofluoric acid is improved, the ceramic is better etched, but there is a problem in that a lot of hydrofluoric acid fumes and vapors are generated to threaten the health of manufacturers and users. For this reason, the registered patent had to use a catalyst to lower the content of hydrofluoric acid, increase the temperature during etching, and perform ultrasonic treatment.

Accordingly, an object of the present invention is to specifically include an evaporation inhibitor having a lower density than the mixed acid solution to lower the volatility of the hydrofluoric acid, so that no fluorine fume is generated during etching and less hydrofluoric acid vapor is generated, and the etching is performed even at room temperature. It is possible to provide an etchant composition having excellent etching efficiency in a short time without ultrasonication. It is also an object of the present invention to provide an etchant composition prepared in a relatively simple process.

Ceramic surface etchant composition according to the invention comprises hydrofluoric acid, sulfuric acid, evaporation inhibitor and purified water,

The evaporation inhibitor has a density at 0.5 ° C. of 0.5 to 0.8 g / ml.

In addition, the surface treatment method of the ceramic according to the present invention

(1) preparing an etchant composition comprising hydrofluoric acid, sulfuric acid, an evaporation inhibitor and purified water;

(2) surface treating the ceramic with the etchant composition; And

(3) washing the surface treated ceramics,

The evaporation inhibitor has a density at 0.5 ° C. of 0.5 to 0.8 g / ml.

The ceramic surface etchant composition of the present invention lowers the volatility of the hydrofluoric acid so that no hydrofluoric acid fumes are generated during etching, and less hydrofluoric acid vapor is generated, and the ceramic can be etched in a short time without ultrasonic treatment at room temperature. Moreover, the ceramic surface etchant composition of this invention can be manufactured by a comparatively simple process, and it is excellent in productivity. The ceramic surface etchant showed equal or improved etching performance in terms of etching time and efficiency compared to the etchant reported in the prior art document.

1 is a SEM photograph of a zirconia sample before surface treatment.
FIG. 2 is a SEM photograph of a zirconia sample surface treated for 15 minutes using the etchant composition of Preparation Example 1. FIG.
3 is a SEM photograph of a zirconia sample surface-treated for 3 minutes using the etchant composition of Preparation Example 1. FIG.
FIG. 4 is a SEM photograph of a zirconia sample treated for 15 minutes in an ultrasonic cleaner at 60 ° C. after surface treatment for 15 minutes using the etchant composition of Preparation Example 1.
5 is a SEM photograph of zirconia surface-treated at room temperature using the etchant composition of Comparative Example 2.
6 is a SEM photograph of zirconia surface-treated at 70 ° C. using the etchant composition of Comparative Example 2. FIG.
7 is a schematic diagram of hydrofluoric acid vapor cut effect measurement experiment.

The present invention includes hydrofluoric acid, sulfuric acid, evaporation inhibitor and purified water,

The evaporation inhibitor provides a ceramic surface etchant composition having a density at 25 ° C. of 0.5 to 0.8 g / ml.

The etchant composition may include an evaporation inhibitor to improve the workability of the etchant composition by reducing the generation of hydrofluoric acid vapor during etching.

In particular, the evaporation inhibitor has a low density of 0.5 to 0.8 g / ml, or 0.6 to 0.8 g / ml at 25 ° C. and is present on the surface of the mixed acid solution without mixing with the mixed acid solution consisting of hydrofluoric acid, sulfuric acid and purified water. It can effectively block the volatilization of foshan.

The evaporation inhibitor may be one or more selected from the group consisting of cyclo alkanes, alkyl ethers and alkanes.

The cyclo alkanes may be cycloalkanes having 6 to 9 carbon atoms. Specifically, the cyclo alkanes may be cyclohexane or cycloheptane.

In particular, the boiling point of cyclohexane is about 80.7 ° C., which lowers the risk of operation due to lower volatility at room temperature than other immiscible solvents. Solvents with high boiling point are difficult to remove after etching, but cyclohexane is easily removed in a short time (about 5 to 10 minutes) by using a hair dryer or an oven (above 81 ℃) in the air after etching with boiling point of about 80.7 ℃ can do. In addition, cyclohexane has an advantage of low wettability with respect to ZrO _x and does not remain on the surface of the zirconia after etching.

The alkyl ether may be an alkyl ether having 2 to 10 carbon atoms, or 4 to 8 carbon atoms. Specifically, the alkyl ether may be at least one selected from the group consisting of diethyl ether, dipropyl ether, methylpropyl ether, and ethylpropyl ether.

The alkanes may be alkanes having 5 to 10 carbon atoms or 5 to 8 carbon atoms. Examples of the alkanes include heptane, hexane, octane and the like.

The etchant composition can prevent generation of smoke or odor of the mixed acid solution by diluting hydrofluoric acid and sulfuric acid including purified water.

The etchant composition may include hydrofluoric acid, sulfuric acid, evaporation inhibitor and purified water in a volume ratio of 10 to 30: 5 to 20: 20 to 50: 25 to 45. Specifically, the etchant composition may include hydrofluoric acid, sulfuric acid, evaporation inhibitor and purified water in a volume ratio of 10 to 25: 10 to 20: 25 to 45: 25 to 40. More specifically, the etchant composition may include hydrofluoric acid, sulfuric acid, evaporation inhibitor and purified water in a volume ratio of 15 to 20: 10 to 15: 30 to 42: 30 to 40.

The etchant composition may comprise 30 to 65% by volume of hydrofluoric acid and sulfuric acid based on the total volume of the composition. Specifically, the etchant composition may include 30 to 60% by volume, 35 to 60% by volume, or 40 to 60% by volume of hydrofluoric acid and sulfuric acid based on the total volume of the composition. If the hydrofluoric acid and sulfuric acid is included in less than 30% by volume, the ceramic surface is not sufficiently etched, if the hydrofluoric acid and sulfuric acid is contained in excess of 60% by volume, the ceramic is excessively etched to cause a problem that the strength of the ceramic surface is lowered Can be.

More specifically, the etchant composition may comprise 10 to 25 volume percent, or 13 to 20 volume percent hydrofluoric acid, and 10 to 30 volume percent, or 10 to 15 volume percent sulfuric acid, based on the total volume of the composition. .

In addition, the etchant composition may include 5 to 45% by volume, 10 to 45% by volume, or 10 to 40% by volume based on the total volume of the composition. When the evaporation inhibitor is included in the above content range, it is possible to effectively block the generation of steam of hydrofluoric acid. In this case, since the thickness of the evaporation inhibitor layer may be formed even in the same volume of the mixed acid solution according to the bottom area of the container containing the mixed acid solution, the content of the evaporation inhibitor may cover the surface of the mixed acid solution with a thickness of about 5 to 10 mm. Amount is preferred.

The etchant composition may be made of hydrofluoric acid, sulfuric acid, evaporation inhibitor and purified water.

The ceramic that can be etched with the etchant composition may be one or more selected from the group consisting of zirconia, porcelain and lithium disilicate. Specifically, the ceramic may be zirconia or porcelain.

The pH of the purified water measured after leaving the etchant composition and purified water in a closed space for 0.01 to 3 hours may be 7.0 to 8.0. Specifically, the pH of the purified water measured after leaving the etchant composition and purified water in a closed space for 2 to 3 hours may be 7.0 to 7.6, or 7.4 to 7.6. As described above, the pH of the purified water measured after standing is a physical property capable of confirming the degree of generation of hydrofluoric acid vapor during etching, and when the pH of the purified water is within the above range, the volatility of hydrofluoric acid generated from the etchant composition is low, resulting in workability and stability. This may mean that it is excellent.

Surface treatment method of ceramic

Surface treatment method of the ceramic according to the present invention

(1) preparing an etchant composition comprising hydrofluoric acid, sulfuric acid, an evaporation inhibitor and purified water;

(2) surface treating the ceramic with the etchant composition; And

(3) washing the surface treated ceramics,

The evaporation inhibitor has a density at 0.5 ° C. of 0.5 to 0.8 g / ml.

Step (1)

In this step, an etchant composition including hydrofluoric acid, sulfuric acid, an evaporation inhibitor, and purified water is prepared.

Specifically, this step comprises the steps of (i) preparing a mixed acid solution comprising hydrofluoric acid, sulfuric acid and purified water; And (ii) mixing the mixed acid solution and the evaporation inhibitor.

The etchant composition may include hydrofluoric acid, sulfuric acid, evaporation inhibitor and purified water in a volume ratio of 10 to 30: 5 to 20: 20 to 50: 25 to 45. Specifically, the etchant composition may include hydrofluoric acid, sulfuric acid, evaporation inhibitor and purified water in a volume ratio of 10 to 25: 10 to 20: 25 to 45: 25 to 40. More specifically, the etchant composition may include hydrofluoric acid, sulfuric acid, evaporation inhibitor and purified water in a volume ratio of 13 to 20:10 to 15:30 to 42:30 to 40.

Step 2

In this step, the ceramic is surface treated with the etchant composition.

The surface treatment may be performed at 10 to 40 ℃, or 10 to 30 minutes at room temperature. Specifically, the surface treatment may be performed at 15 to 25 ℃ for 10 to 15 minutes.

The surface treatment may be performed by impregnating the ceramic into the etchant composition or by applying the etchant composition to a surface of the ceramic.

Step 3

In this step, the surface-treated ceramic is washed with water.

The surface-treated ceramics are preferably washed with water because mixed acid solution may remain on the surface. For example, the washing may be by immersing the surface-treated ceramic in water, or may wash the surface-treated ceramic with running water. Thereafter, the cyclohexane is evaporated in air for 5 to 10 minutes using a hair dryer or an oven (at least 81 ° C).

The above content is described in more detail by the following examples. However, the following examples are only for illustrating the present invention, and the scope of the examples is not limited thereto.

[ Example ]

Production Example  One. Etchant  Preparation of the composition

A mixed acid solution was prepared by mixing 50% by volume of hydrofluoric acid aqueous solution, 95% by volume of sulfuric acid and purified water at a volume ratio of 18: 7: 9. Thereafter, the mixed acid solution and cyclohexane (evaporation inhibitor) were mixed at a volume ratio of 9: 4 to prepare an etchant composition.

Production Example  2.

An etchant composition was prepared in the same manner as in Preparation Example 1, except that the mixed acid solution and cyclohexane were mixed at a volume ratio of 9: 2.

Production Example  3.

An etchant composition was prepared in the same manner as in Preparation Example 1, except that the mixed acid solution and cyclohexane were mixed at a volume ratio of 9: 3.

Production Example  4.

An etchant composition was prepared in the same manner as in Preparation Example 1, except that the mixed acid solution and cyclohexane were mixed at a volume ratio of 9: 6.

Example  1. Surface treatment

The zirconia sample (manufacturer: Hydential Korea, product name: zirconium block) was added to the etchant composition of Preparation Example 1 at room temperature for 1 minute, 3 minutes 10 minutes, and 15 minutes to perform a surface treatment. The zirconia sample was then washed with purified water and cyclohexane was evaporated with a heat gun for 10 minutes to obtain a surface treated zirconia.

Zirconia surface-treated for 1 and 3 minutes did not have sufficient reaction time and the surface was not sufficiently etched. On the other hand, zirconia surface-treated for 10 or 15 minutes was confirmed that the surface is sufficiently etched.

In addition, the zirconia sample and the surface treated zirconia for 3 or 15 minutes before the surface treatment, SEM image was taken with a scanning electron microscope (FE-SEM, manufacturer: ZEISS, product name: Sigma500) to determine the degree of etching, and as a result Are shown in FIGS. Specifically, FIG. 1 is a SEM photograph of a zirconia sample before surface treatment, FIG. 2 is a SEM photograph of a zirconia sample surface treated for 15 minutes using the etchant composition of Preparation Example 1, and FIG. 3 is an etching of Preparation Example 1 SEM pictures of zirconia samples surface-treated for 3 minutes using the composition.

As shown in FIGS. 1 to 3, the zirconia surface-treated for 3 minutes did not have sufficient etching time, and thus the surface was not sufficiently etched, and the zirconia surface-treated for 15 minutes was sufficiently etched.

In particular, as shown in FIG. 2, the zirconia surface treated for 15 minutes was not only sufficiently free of impurities on the surface, but also had a small grain size of the crystal structure, an increase in the space between the particles, and increased grain roughness. The structure appeared.

Example  2.

A surface treatment of zirconia was performed in the same manner as in Example 1, except that the etchant composition of Preparation Example 2 was used and the surface treatment was performed for 15 minutes.

Visual inspection of the surface treated zirconia for 15 minutes showed that the surface was sufficiently etched.

Example  3.

The surface treatment of zirconia was carried out in the same manner as in Example 1, except that the etchant composition of Preparation Example 3 was used and the surface treatment was performed for 15 minutes.

Visual inspection of the surface treated zirconia for 15 minutes showed that the surface was sufficiently etched.

Example  4.

Using the etchant composition of Preparation Example 4, the surface treatment of zirconia was carried out in the same manner as in Example 1 except that the surface treatment for 15 minutes.

Visual inspection of the surface treated zirconia for 15 minutes showed that the surface was sufficiently etched.

Example  5.

The surface treatment of zirconia was performed in the same manner as in Example 1, except that the etchant composition of Preparation Example 1 was treated for 15 minutes and then treated in an ultrasonic cleaner at 60 ° C. for 15 minutes.

In order to determine the etching degree of the surface-treated zirconia, SEM photographs were taken with a scanning electron microscope (FE-SEM, manufacturer: ZEISS, product name: Sigma500), and the results are shown in FIG. 4.

As shown in FIG. 4, the zirconia treated for 15 minutes in an ultrasonic cleaner at 60 ° C. was very sufficiently etched on the surface.

Comparative example  One.

An etchant composition was prepared in the same manner as in Example 1, except that cyclohexane was not mixed.

Comparative example  2.

An etchant composition was prepared by mixing 8 ml of hydrofluoric acid, 5.3 ml of sulfuric acid, 15 ml of purified water, and about 0.7 ml of hydrogen peroxide.

A zirconia sample (manufacturer: Hydential Korea, product name: zirconium block) was added to the etchant composition at room temperature or 70 ° C. for 15 minutes to perform surface treatment. Since the zirconia samples were washed with purified water, SEM pictures were taken to determine the degree of etching of the surface-treated zirconia, and the results are shown in FIGS. 5 and 6. Specifically, FIG. 5 is an SEM photograph of zirconia surface-treated at room temperature, and FIG. 6 is an SEM photograph of zirconia surface-treated at 70 ° C.

The etchant composition at 70 ° C. was prepared by preheating the etchant composition to 70 ° C. using a hot plate (manufacturer: Corning, product name: PC-420D).

As shown in FIGS. 5 and 6, zirconia surface-treated with the etchant composition at room temperature did not sufficiently etch the surface. In addition, zirconia surface-treated with a solution preheated to 70 ° C. was more etched in surface compared to zirconia surface-treated with an etchant composition at room temperature.

As shown in FIG. 6B, impurities on the zirconia surface were not sufficiently removed as compared with zirconia surface-treated with the etchant composition of Example 1. FIG.

Test Example  1. Determine whether the hydrofluoric acid is reduced

13 ml of the etchant composition of Preparation Example 1, 15 ml of the etchant composition of Preparation Example 4, or 9 ml of the etchant composition of Comparative Example 1 were left together with 6 ml of purified water for 3 hours at room temperature for 3 hours. The pH was measured by a pH meter (manufacturer: Thermo Scientific, product name: EUtech ™, pH700) (see FIG. 7), and the results are shown in Table 1 below.

Further, 9 ml of the etchant composition of Comparative Example 2 with 6 ml of purified water was left at room temperature or 70 ° C. for 3 hours, respectively, and then the pH of the purified water was measured by a pH meter (manufacturer: Thermo Scientific, product name: EUtech ™, pH700).

Neglect time Comparative Example 1 Preparation Example 1 Preparation Example 4 Comparative Example 2 Room temperature 70 ℃ (Volume ratio of mixed acid solution: cyclohexane) 9: 0 9: 4 9: 6 - - 0 7.4 7.5 7.6 7.5 7.6 30 minutes 7.1 7.5 7.5 7.5 6.3 1 hours 6.9 7.5 7.5 7.4 4.5 1 hour 30 minutes 6.4 7.6 7.6 7.0 3.5 2 hours 6.3 7.6 7.6 6.9 3.2 2 hours 30 minutes 5.0 7.5 7.6 6.5 3.0 3 hours 3.8 7.5 7.6 6.2 2.9

As shown in Table 1, the etchant composition of Preparation Examples 1 and 4 there was little change in the pH of the purified water left together, it was confirmed that the generation of hydrofluoric acid significantly reduced. This is believed to be the result of cyclohexane effectively reducing the generation of hydrofluoric acid vapor.

In addition, in Comparative Example 2, the pH of purified water left together at room temperature decreased from 7.5 to 6.2 after 3 hours. The pH of purified water left with the etchant composition of Comparative Example 2 preheated to 70 ° C. dropped from 7.6 to 2.9. This is a result of generating more hydrofluoric acid vapor than the etchant compositions of Preparation Examples 1 and 4.

Test Example  2. Measurement of Hydrofluoric Acid Vapor Reduction Effect According to Evaporation Inhibitor Content

After 13 ml of the etchant composition of Preparation Example 1 or 11 ml of the etchant composition of Preparation Example 2 were left in a closed space with 6 ml of purified water for 24 hours, the pH of the purified water was measured by a pH meter (manufacturer: Thermo Scientific, : EUtech ™, pH700) (see FIG. 7).

As a result, the pH of the purified water left for 24 hours with the etchant composition of Preparation Example 1 was found to have a pH of 6.4, and the pH of the purified water left for 24 hours with the etchant composition of Preparation Example 2 showed a pH of 2.2. For this reason, when the content of the evaporation inhibitor is small, it was difficult to effectively coat the surface of the mixed acid solution, it is difficult to effectively block the generation of hydrofluoric acid vapor.

Claims (10)

Hydrofluoric acid, sulfuric acid, evaporation inhibitors and purified water,
The evaporation inhibitor is at least one selected from the group consisting of cyclo alkanes, alkyl ethers and alkanes,
Wherein the evaporation inhibitor has a density at 0.5 ° C. of 0.5 to 0.8 g / ml.
The method of claim 1,
The etchant composition comprises a hydrofluoric acid, sulfuric acid, evaporation inhibitor and purified water in a volume ratio of 10 to 30: 5 to 20: 20 to 50: 25 to 45, ceramic surface etchant composition.
The method of claim 2,
The etchant composition comprises a hydrofluoric acid, sulfuric acid, evaporation inhibitor and purified water in a volume ratio of 15 to 20: 10 to 15: 30 to 42: 30 to 40, ceramic surface etchant composition.
delete The method of claim 1,
Ceramic cycloetcher composition, wherein the cycloalkane is a cycloalkane of 6 to 9 carbon atoms.
The method of claim 1,
The ceramic surface etchant composition, wherein the ceramic is at least one selected from the group consisting of zirconia, porcelain and lithium disilicate.
The method of claim 1,
The pH of the purified water measured after leaving the etchant composition and purified water in a closed space for 0.01 to 3 hours, the ceramic surface etchant composition.
(1) preparing an etchant composition comprising hydrofluoric acid, sulfuric acid, an evaporation inhibitor and purified water;
(2) surface treating the ceramic with the etchant composition; And
(3) washing the surface treated ceramics,
The evaporation inhibitor is at least one selected from the group consisting of cyclo alkanes, alkyl ethers and alkanes,
The evaporation inhibitor is a surface treatment method of a ceramic, the density of 0.5 to 0.8 g / ㎖ at 25 ℃.
The method of claim 8,
The step (2) is carried out for 10 to 30 minutes at 10 to 40 ℃, the surface treatment method of a ceramic.
The method of claim 8,
The etching agent composition comprises a hydrofluoric acid, sulfuric acid, evaporation inhibitor and purified water in a volume ratio of 10 to 30: 5 to 20: 20 to 50: 25 to 45, ceramic surface treatment method.

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