KR101915892B1 - Method for coating a parylene film on the metal surface - Google Patents

Abstract

The present invention relates to a method for coating a parylene film on a metal surface. More specifically, the present invention relates to a coating method, further including a preprocessing process for increasing adhesion between medical metal and parylene so as to prevent delamination of the parylene film. Accordingly, a biomaterial excellent in chemical resistance, abrasion resistance, corrosion resistance, heat resistance, and water resistance can be obtained through a surface processing method.

Description

METHOD FOR COATING A PARYLENE FILM ON THE METAL SURFACE BACKGROUND OF THE INVENTION [0001]

The present invention relates to a method of coating a paraline thin film on a metal surface, and more particularly, to a method of coating a paraline thin film on a metal surface by a pretreatment process for improving adhesion between a medical metal and a paralin, Coating method.

Recent developments in medical and biotechnology have led to the development of biomaterials for the replacement of hard tissues, such as bones or teeth, which are damaged by an accident or disease. Biomaterials refers to artificial, natural, or composite materials, excluding pharmaceuticals, that restore the function of a damaged tissue or organ by totally or partially replacing damaged tissue or organ in the body. As such biomaterial, metallic materials such as iron, gold, silver, and platinum can be used, and recently, stainless steel is mainly used.

Since biomaterials are used in direct contact with human tissues for a long period of time, they must have biochemical stability and biocompatibility, which are biochemically resistant to corrosion in the human body and do not cause any abnormalities or side effects. However, when the metal materials are directly contacted with the human body, they may cause a biological reaction and a bacterial infection and may cause an inflammatory reaction.

Recently, techniques for coating biomolecules with biostability and biocompatibility on the surface of biomaterials have been developed. As shown in Korean Patent Laid-Open Nos. 10-2012-0088243 and 10-2009-0015009, , Parylene having excellent heat resistance, corrosion resistance, and chemical resistance has been attracting attention. However, paralin has poor adhesion to metallic materials, and in this case, the paralin-coated thin film easily peels off from the metal.

Accordingly, the present inventors have developed a method for stably coating a paraline thin film by increasing the adhesion between the paraline thin film and the metal used as a biomaterial.

Korean Patent Laid-Open Publication No. 10-2012-0088243 (filed on Aug. 08, 2012), a PDMS-based flexible electrode using a perylene coating layer and a manufacturing method thereof, applicant: Gwangju Institute of Science and Technology, Korean Patent Laid-Open No. 10-2009-0015009 (Name of the invention: Method for manufacturing a wire for orthodontic treatment, Applicant: Kim, In-Jae, Published by: February 11, 2009)

It is an object of the present invention to provide a coating method capable of enhancing adhesion between a medical metal surface and a paraline thin film to prevent peeling of the paraline thin film.

It is another object of the present invention to provide a medical metal having biostability and biocompatibility through the coating method.

In order to accomplish the above object, the present invention provides a method for manufacturing a semiconductor device, comprising: a first step of washing a metal with ethanol to remove foreign substances on a metal surface, drying the metal, and adding silane to the solvent, A second step of immersing the metal in the mixed solution prepared in the first step and drying the metal; A third step of washing the unreacted material remaining in the metal dried in step 2 with a solvent and drying the unreacted material; And a fourth step of coating the paraline thin film on the metal that has been dried in the third step.

In the first step, the silane is preferably an alkyltrialkoxysilane. The alkyltrialkoxysilane may be at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, Propyltrimethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, , γ-glycidoxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, dimethyldimethoxysilane, and methylphenyldimethoxysilane. It may be more than one kind.

In the first step, the concentration of silane in the mixed solution is preferably 0.1 to 20% by volume.

The immersion time in the second step is preferably 10 to 60 minutes.

In the fourth step, the paraline thin film may be coated by chemical vapor deposition (CVD), and the composition pressure during the paraline thin film deposition is preferably 5 to 20 mTorr.

Hereinafter, the present invention will be described in detail.

The present invention relates to a coating method for stably coating a paraline thin film by enhancing the adhesion between a paraline thin film and a metal surface by performing a pretreatment process for a medical metal surface. The method preferably comprises: a first step of washing the metal with ethanol to remove foreign substances on the metal surface, followed by drying, and adding silane to the solvent to prepare a mixed solution; A second step of immersing the metal in the mixed solution prepared in the first step and drying the metal; A third step of washing the unreacted material remaining in the metal dried in step 2 with a solvent and drying the unreacted material; And a fourth step of coating the paraline thin film on the metal that has been dried in the third step.

In this case, in the first step, the metal may be one selected from the group consisting of iron, gold, silver, platinum, and stainless steel, although it is not particularly limited as long as it can be used as a biomaterial.

Wherein the ones that can be used as a solvent in step 1 and step 3 is not particularly limited, and is preferably a C ₁ ~ C ₄ alcohol or an aqueous solution thereof, wherein the C ₁ ~ C ₄ alcohols such as methanol, ethanol, Propanol, isopropanol, butanol, and isobutanol.

In the first step, the silane is preferably an alkyltrialkoxysilane. The alkyltrialkoxysilane is a derivative having one carbon-silicon bond and three oxygen-silicon bonds. The alkyltrialkoxysilane can be used as the alkyltrialkoxysilane, but is not limited to, for example, methyltrimethoxysilane, methyltriethoxysilane, Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane, Silane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Acryloyloxypropyltrimethoxysilane,? -Methacryloxypropyltri Methoxysilane, dimethyl dimethoxysilane, and methylphenyl dimethoxysilane.

In the first step, the concentration of silane in the mixed solution is preferably 0.1 to 20% by volume. When the concentration of the silane is less than 0.1 vol%, the surface treatment of the metal does not sufficiently take place, and when the paraline thin film is coated on the metal surface, the paraline thin film may peel off. If the concentration exceeds 20 vol% The paraline thin film may be aggregated.

Further, in the surface treatment method for improving the adhesion of the paraline thin film, not only the concentration of the mixed solution but also the process control of mixing the silane is more important. The silane is added to the solvent to improve the adhesive strength, and the mixture solution is stirred for 10 to 60 seconds and then rested for 2 hours or more to prepare a mixed solution. If the agitation time is too short or too long, and if the dwell time is too short, there is a problem that the adhesion of the paraline thin film can not be improved.

The immersion time in the second step is preferably 10 to 60 minutes. If the immersion time is less than 10 minutes, the surface treatment of the metal is not sufficiently performed, and when the paraline thin film is coated on the metal surface, peeling of the paraline thin film may occur. If it exceeds 60 minutes, The reaction may cause a phenomenon that the paraline thin film is aggregated on the metal surface, which is not preferable.

In the fourth step, the paraline thin film may be coated by chemical vapor deposition (CVD), and the composition pressure during the paraline thin film deposition is preferably 5 to 20 mTorr.

The coating of the paraline thin film by the coating method of the paraffin thin film of the present invention is not limited to the coating of the medical metal but may be applied to various fields requiring surface protection such as electronic and electric parts such as aerospace and semiconductor And can be applied by application.

The method of coating the paraline thin film on the medical metal surface provided in the present invention can maximize the adhesion between the metal and the paralin without affecting the water resistance and fire resistance of the paralin polymer.

Also, by improving the adhesive strength, it is possible to prevent the peeling of the paraline thin film coated on the surface of the medical metal, thereby prolonging the life of the biomaterial, and obtaining a biomaterial excellent in chemical resistance, abrasion resistance, corrosion resistance, heat resistance and water resistance.

FIG. 1 is an atomic force microscope (AFM) image showing a state where a paraline thin film is deposited on the surface of a medical metal according to an embodiment of the present invention.
FIG. 2A is a photograph showing the results of the cross-cut test of Example 1. FIG.
2B is a photograph showing the result of the cross-cut test of Comparative Example 1. Fig.
FIG. 3A is a scanning electron microscope (SEM) photograph showing a boundary surface after a tape is attached to and detached from a surface of a metal on which a paraline thin film is deposited according to Example 1. FIG.
FIG. 3B is a scanning electron microscope (SEM) image showing a boundary surface appearance after a tape is adhered to a surface of a metal deposited with a paraline thin film according to Comparative Example 1. FIG.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.

Examples 1 and 2 and Comparative Examples 1 to 6. Deposition of Paralin Thin Films on Metal Surfaces:

Example 1

Methacryloxypropyltrimethoxysilane (MAPS) was mixed with isopropanol and distilled water at a volume ratio of 1: 1 to prepare a solvent, and γ-methacryloxypropyltrimethoxysilane was diluted to 0.5% by volume. The mixture was stirred for 30 seconds and then kept at rest for 2 hours or longer to prepare a mixed solution. Thereafter, the stainless steel substrate washed with ethanol was completely immersed in the mixed solution for 20 minutes, removed, and dried in the air for 20 minutes. The dried stainless steel substrate was then washed with isopropanol and then dried with nitrogen to complete the surface treatment. Then, paralin was deposited to a thickness of about 5 탆 on a stainless steel substrate having been subjected to surface treatment using a parylene deposition system (PDS-2060PC, SCS, USA). At this time, the composition pressure was 10 mTorr and the deposition rate was 1.5 탆 / hr.

Example 2

Paralin was deposited on the metal in the same manner as in Example 1 except that the concentration of? -Methacryloxypropyltrimethoxysilane in the mixed solution was 5% by volume.

Comparative Example 1

Paralin was deposited on a stainless steel substrate not subjected to the surface treatment in the same manner as in Example 1 above.

Comparative Examples 2 to 6

Paralin was deposited on the metal in the same manner as in Example 1, and the preparation conditions of the mixed solution were as shown in Table 1 below.

Condition Silane concentration (vol%) Stirring time
(second) downtime
(minute) Immersion time
(minute) Example 1 0.5 30 240 20 Example 2 5 30 240 20 Comparative Example 1 - - - - Comparative Example 2 30 30 240 20 Comparative Example 3 0.5 30 240 5 Comparative Example 4 0.5 30 240 120 Comparative Example 5 0.5 5 240 20 Comparative Example 6 0.5 30 60 20

< Test Example  1. Confirm adhesion>

A parasitic stainless steel substrate was grinded vertically on the parylene-coated stainless steel substrate through the above Examples 1 and 2 and Comparative Examples 1 to 6, and then the brush was rubbed about 5 times in a diagonal direction, and a cross-cut The results are shown in Table 2 below.

exam Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Adhesion ○ ○ × ○ × ○ △ △ Aggregation - - - Occur - Occur - -

Adhesion evaluation criteria;

○: No falling of thin film

?: Partial occurrence of thin film falling

X: Thin film almost fell off

Referring to the above Table 2, it was confirmed that the paralin films were almost free from damage in comparison with Comparative Examples 1, 3, 5 and 6 in Examples 1 and 2, and thus the adhesion of the paralin films was excellent And it was found. In the case of Comparative Examples 2 and 4, adhesion was increased as the concentration of? -Methacryloxypropyltrimethoxysilane was increased or the immersion time of the metal was increased, but the phenomenon of aggregation of the paraline thin film occurred I could. Thus, it was confirmed that the concentration and immersion time for maximizing the adhesion without clustering of the paraline thin film on the metal surface were limited.

Claims (6)

In order to remove impurities on the metal surface, the metal is washed with ethanol and dried. The alkyltrialkoxysilane is added to the solvent so as to have a concentration of 0.1 to 20% by volume. The mixture is stirred for 10 to 60 seconds, A first step of manufacturing; A second step of immersing the mixed solution prepared in the first step for 10 to 60 minutes and then drying the metal; A third step of washing the unreacted material remaining in the metal dried in step 2 with a solvent and drying the unreacted material; And a fourth step of coating the paraline thin film on the metal that has been dried in the third step. The method of coating a paraline thin film on a medical metal surface,
The alkyltrialkoxysilane may be selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, gamma -glycidoxypropyltrimethoxysilane, gamma -acryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Wherein the metallic thin film is coated with a paralin thin film on the surface of a medical metal, characterized in that the metallic thin film is at least one selected from the group consisting of monopropyl trimethoxysilane,? -Methacryloxypropyltrimethoxysilane, dimethyl dimethoxysilane and methylphenyl dimethoxysilane How to. delete delete delete delete The method according to claim 1,
Wherein the compositional pressure is 5 to 20 mTorr in the step of depositing the paraline thin film in the fourth step.

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