KR102401107B1 - Corrosion-inhibiting coating composition - Google Patents

Abstract

It is possible to reduce the rust generation by the salt spray test, and to provide a rust-preventive coating composition having excellent rust-preventive performance.
The rust preventive coating composition of the present invention includes a polyaniline component and a coating film component, and the coating film component is characterized in that it is composed of a phenoxy resin.

Description

Anti-rust paint composition {CORROSION-INHIBITING COATING COMPOSITION}

The present invention relates to a rust preventive coating composition.

Conventionally, an antirust coating composition containing polyaniline and an epoxy resin as a coating film component is known. (For example, refer to Patent Document 1)

Japanese Patent Laid-Open No. 2007-324143

However, the conventional anti-rust coating composition containing polyaniline and an epoxy resin as a coating film component is applied to a copper plate to form a coating film, and then salt spray test is performed according to the method stipulated in Japanese Industrial Standard JIS Z2371. There is a problem in that severe rust occurs.

An object of the present invention is to solve such a problem, it is possible to reduce the occurrence of rust by the salt spray test, and to provide an anti-rust coating composition having excellent anti-rust performance.

MEANS TO SOLVE THE PROBLEM In order to achieve the said objective, this inventor earnestly studied about resin which replaced the said epoxy resin as a coating-film component. As a result, by using a phenoxy resin as a coating-film component, it paid attention to being able to achieve the desired objective, and reached|attained this invention.

Here, the rust-preventive coating composition of the present invention includes a polyaniline component and a coating film component, wherein the coating film component is composed of a phenoxy resin.

When the rust-preventive coating composition of the present invention is applied to an object to be rusted such as a copper plate, the phenoxy resin constituting the coating film component is cured to form a coating film in which the polyaniline component is dispersed. In the antirust coating composition of the present invention, since the polyaniline component is dispersed in the coating film formed by curing the phenoxy resin, it is possible to reduce the occurrence of rust caused by the salt spray test, and excellent antirust performance can be obtained.

In the antirust coating composition of the present invention, as the phenoxy resin, it is possible to appropriately use a polycondensate of bisphenol A and epicrolehydrin or a polycondensate of bisphenol A and hydroxyalkyl ether. In the rust preventive coating composition of the present invention, it is possible to use, for example, 2-hydroxypropyl ether as the hydroxyalkyl ether.

Further, in the rust-preventive coating composition of the present invention, the polyaniline component may be polyaniline particles or may include polyaniline particles, polyvinyl butyral, and an alcohol-based solvent.

Moreover, it is preferable that the rust preventive coating composition of this invention contains the said coating film component in the range of 600-13,000 mass parts with respect to 100 mass parts of polyaniline contained in the said polyaniline component.

When content of the said coating-film component is less than 600 mass parts with respect to 100 mass parts of polyaniline contained in the said polyaniline component, a sufficient coating film may not be formed. Moreover, when content of the said coating-film component exceeds 13,000 mass parts with respect to 100 mass parts of polyaniline contained in the said polyaniline component, sufficient rust prevention performance may not be acquired.

1 is a photograph showing the results of the salt spray test on the coating film formed on the surface of the copper plate by the rust preventive coating composition of Example 1.
2 is a photograph showing the results of the salt spray test on the coating film formed on the surface of the copper plate by the rust preventive coating composition of Example 2.
3 is a photograph showing the results of the salt spray test on the coating film formed on the surface of the copper plate by the rust preventive coating composition of Comparative Example 1.
4 is a photograph showing the results of the salt spray test on the coating film formed on the surface of the copper plate by the rust preventive coating composition of Comparative Example 2.
5 is a photograph showing the results of the salt spray test on the coating film formed on the surface of the copper plate by the rust preventive coating composition of Comparative Example 3.
6 is a photograph showing the results of the salt spray test on the coating film formed on the surface of the copper plate by the rust preventive coating composition of Comparative Example 4.
7 is a photograph showing the results of the salt spray test on the coating film formed on the surface of the copper plate by the rust preventive coating composition of Comparative Example 5;

EMBODIMENT OF THE INVENTION Next, embodiment of this invention is described in more detail, referring an accompanying drawing.

The rust preventive coating composition of this embodiment contains a polyaniline component and a coating-film component, This coating-film component is comprised from a phenoxy resin.

As said phenoxy resin, the polycondensate of bisphenol A and epicrolehydrin, or the polycondensate of bisphenol A and hydroxyalkyl ether is mentioned, for example.

When the phenoxy resin is a polycondensate of bisphenol A and hydroxyalkyl ether, the hydroxyalkyl ether is a compound represented by the following general formula (1).

HO-R-O-R-OH ...(1)

In formula, R is a C1-C5 alkylene group, For example, a methylene group, ethylene group, n-propylene group, i-propylene group, n-butylene group, etc. are mentioned.

In the present embodiment, it is possible to suitably use 2-hydroxypropyl ether represented by the following formula (2) as the hydroxyalkyl ether.

[Tue 1]

As the polycondensate of bisphenol A and epicrolehydrin, for example, jER1255HX30 (trade name) manufactured by Mitsubishi Chemical Corporation can be used. Further, as the polycondensate of bisphenol A and 2-hydroxypropyl ether, for example, Penoto-To YP-5OEK35 (trade name) manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd. can be used.

In addition, as the phenoxy resin, phenoxy resin PKHH (trade name) manufactured by Phenoxy-Associates Co., Ltd., phenoxy resin PKHB (trade name) manufactured by Phenoxy-Associates Co., Ltd., ISOPOXY 506K (trade name) manufactured by Nippon Chemicals Co., Ltd., etc. are used also good

In the rust preventive coating composition of the present embodiment, the polyaniline component may be polyaniline particles themselves, or may be a gel containing polyaniline particles, polyvinyl butyral, and an alcohol solvent.

The polyaniline particles can be obtained as particles having a diameter of about 10 to 50 nm by, for example, precipitating from a reaction solution obtained by oxidative polymerization by adding ammonium persulfate to a mixture of aniline sulfate and sodium dodecyl sulfate.

In addition, the said gel body can be obtained as follows. First, the polyaniline particles obtained by the method as described above are mixed with polyvinyl butyral and an alcohol-based solvent, and then a solid mixture is formed by volatilizing the alcohol-based solvent. In the solid mixture, polyaniline is uniformly dispersed and contained in a matrix of polyvinyl butyral.

Next, the solid mixture is immersed in the alcoholic solvent to swell, and is supplied to a pressure dispersion device together with the alcoholic solvent. The pressure dispersion device supplies the sample together with the solvent to a narrow flow path, and applies a pressure in the range of 5 to 80 Mpa, for example, a pressure in the range of 30 to 50 Mpa to eject the sample from the flow path, thereby uniformly dispersing the sample in the solvent. It is a device that makes As a result, it is possible to obtain a gel body in which the polyaniline particles are uniformly dispersed in the polyvinyl butyral and the alcohol-based solvent.

As the alcohol solvent, a mixed solvent of an alcohol such as isopropanol or methoxypropanol and another organic solvent can be used. As such an alcohol solvent, for example, 10 to 45 parts by mass of isopropanol, 10 to 45 parts by mass of methoxypropanol, 10 to 35 parts by mass of butanol, 5 to 25 parts by mass of xylene, and 5 to 25 parts by mass of ethylbenzene. What is used is mentioned, More specifically, what is comprised by 40 mass parts of isopropanol, 40 mass parts of methoxypropanol, 10 mass parts of butanol, 5 mass parts of xylene, and 5 mass parts of ethylbenzene is mentioned.

And, about the manufacturing method of the said gel upper body, and the physical property, there exists a detailed description in Unexamined-Japanese-Patent No. 2014-37522.

In addition, the rust preventive coating composition of the present embodiment contains the coating film component in the range of 600 to 13,000 parts by mass, preferably in the range of 700 to 11,000 parts by mass, based on 100 parts by mass of the polyaniline contained in the polyaniline component. In the rust preventive coating composition of the present embodiment, by including the coating film component in the above range with respect to 100 parts by mass of polyaniline contained in the polyaniline component, a good coating film can be formed and excellent rust prevention performance can be obtained.

The rust preventive coating composition of this embodiment can be manufactured easily by mixing the said polyaniline component and the said phenoxy resin, and stirring it. For the mixing and stirring, for example, a stirring device such as Despa (trade name) manufactured by Asada Tekko Co., Ltd. and Haifa (trade name) manufactured by Ashizawa Finetech Co., Ltd. can be used.

In addition, the rust-preventive coating composition of the present embodiment can be applied to an object to be rusted such as a copper plate so as to have a thickness of 15 to 60 µm, for example, 30 µm, thereby forming a coating film having excellent anti-rust performance. The application may be performed, for example, by spraying, air spraying, brushing, roller coating, or the like.

In addition, when forming a coating film with the rust preventive coating composition of this embodiment, you may make it provide a top coating layer further on the said coating film. The top coating layer is preferably formed of, for example, a thickness of 15 to 60 µm, for example, 30 µm by using a urethane-based resin.

In addition, the rust-preventive coating composition of this embodiment may further contain another additive in the range which does not exert a bad influence on rust-preventive performance. As said additive, a colored pigment, a plasticizer, a pigment dispersing agent, an emulsifier, a thickener, a scattering inhibitor, etc. are mentioned, for example.

Next, the Example and comparative example of this invention are shown.

Example

[Example 1]

In this example, 3.0 g of polyaniline particles as a polyaniline component and 40 g of a phenoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name: jER1255HX30) composed of a polycondensate of bisphenol A and epicrolehydrin as a coating film component were mixed and stirred to make a coating film A rust preventive coating composition in which polyaniline particles were dispersed in a component (phenoxy resin in this example) was prepared.

Then, on the surface of the SPC copper plate having a length of 150 mm, a width of 75 mm, and a thickness of 1.6 mm, the rust preventive coating composition obtained in this example was applied to a dry thickness of 30 μm, and the coating film component was cured to form a coating film. In addition, a urethane-based resin (manufactured by Suzuka Chemical Co., Ltd., trade name: Eporu) was applied on the coating film to a dry thickness of 30 µm, and cured to form a top coating layer, which was used as a sample.

Next, two lines of 70 mm long and deep scars reaching the surface of the copper plate were formed on the sample to cross each other, and a salt spray device (manufactured by Itabashi Chemical Industry Co., Ltd., trade name: Composite Corrosion Tester BQ-1) was applied. A salt spray test in which 50 g/liter of saline is sprayed on the surface of the copper plate at an amount of 0.0028 liters/minute according to the method prescribed in Japanese Industrial Standards JIS Z 2371 was conducted for 600 hours. The results are shown in FIG. 1 .

[Example 2]

In this example, except that a phenoxy resin (manufactured by Shin-Nitetsu Sumikin Chemical Co., Ltd., trade name: Phenoto-To YP-5OEK35) was used as a coating film component as a component of the coating film, a phenoxy resin consisting of a polycondensate of bisphenol A and 2-hydroxypropyl ether. , A rust-preventive coating composition was prepared in the exact same manner as in Example 1.

Next, a coating film and a top coating layer were formed in the same manner as in Example 1 except that the rust preventive coating composition obtained in this Example was used, and used as a sample.

Next, the salt spray test was performed for 600 hours in the same manner as in Example 1 except that the sample obtained in this Example was used. The results are shown in FIG. 2 .

[Comparative Example 1]

In this comparative example, except that an epoxy resin manufactured by Kansai Paint Co., Ltd. (trade name: ESCO) as a coating film component and ketimine (manufactured by Kansai Paint Co., Ltd., trade name: ESCO curing agent) were used as a curing agent, it was carried out in exactly the same manner as in Example 1 to prevent rust. A coating composition was prepared.

Next, a coating film and a top coating layer were formed in the same manner as in Example 1 except that the rust preventive coating composition obtained in this comparative example was used, and used as a sample.

Then, using the sample, a salt spray test was performed in the same manner as in Example 1, except that the time was set to 576 hours. The results are shown in FIG. 3 .

[Comparative Example 2]

In this comparative example, an anti-rust coating composition was prepared in exactly the same manner as in Example 1, except that an epoxy resin (trade name: Epomarin Primer) manufactured by Kansai Paint Co., Ltd. as a coating film component and polyamideamine were used as a curing agent.

Next, a coating film and a top coating layer were formed in the same manner as in Example 1 except that the rust preventive coating composition obtained in this comparative example was used, and used as a sample.

Then, using the sample, a salt spray test was performed in the same manner as in Example 1, except that the time was set to 576 hours. The results are shown in FIG. 4 .

[Comparative Example 3]

In this comparative example, an antirust coating composition was prepared in the same manner as in Example 1, except that an epoxy resin manufactured by Nippon Paint Co., Ltd. (trade name: Hybon 20-HB) and its dedicated curing agent were used as the coating film component.

Next, a coating film and a top coating layer were formed in the same manner as in Example 1 except that the rust preventive coating composition obtained in this comparative example was used, and used as a sample.

Then, using the sample, a salt spray test was performed in the same manner as in Example 1, except that the time was set to 576 hours. The results are shown in FIG. 5 .

[Comparative Example 4]

In this comparative example, an anti-rust coating composition was prepared in the exact same manner as in Example 1, except that an epoxy resin manufactured by Shindong Paint Co., Ltd. (trade name: Neogose #2300 Primer) and its dedicated curing agent were used as the coating film component.

Next, a coating film and a top coating layer were formed in the same manner as in Example 1 except that the rust preventive coating composition obtained in this comparative example was used, and used as a sample.

Then, using the sample, a salt spray test was performed in the same manner as in Example 1, except that the time was set to 576 hours. The results are shown in FIG. 6 .

[Comparative Example 5]

In this comparative example, an anti-rust coating composition was prepared in the exact same manner as in Example 1, except that an epoxy resin manufactured by China Paint Co., Ltd. (trade name: Ecopin Primer-HB) and its dedicated curing agent were used as the coating film component.

Next, a coating film and a top coating layer were formed in the same manner as in Example 1 except that the rust preventive coating composition obtained in this comparative example was used, and used as a sample.

Then, using the sample, a salt spray test was performed in the same manner as in Example 1, except that the time was set to 576 hours. The result is shown in FIG.

3 to 7, in the case of the rust preventive paint composition (Comparative Examples 1 to 5) using an epoxy resin containing a curing agent as a coating film component, severe rust was confirmed on the copper plate provided with the coating film formed by the rust preventive paint composition. This is clear.

On the other hand, from Figs. 1 and 2, as a coating film component, a rust-preventive coating composition using a phenoxy resin comprising a polycondensate of bisphenol A and epicrolehydrin (Example 1), or bisphenol A and 2-hydroxypropyl ether In the case of the rust preventive coating composition (Example 2) using a phenoxy resin made of a polycondensate of It is clear that it has performance.

Claims (7)

In the rust-preventive coating composition comprising a polyaniline component and a coating film component,
The coating component is a rust preventive coating composition, characterized in that composed of a phenoxy resin. The rust-preventive coating composition according to claim 1, wherein the phenoxy resin is a polycondensate of bisphenol A and epicrolehydrin. The rust-preventive coating composition according to claim 1, wherein the phenoxy resin is a polycondensate of bisphenol A and hydroxyalkyl ether. [Claim 4] The rust-preventive coating composition according to claim 3, wherein the hydroxyalkyl ether is 2-hydroxypropyl ether. [Claim 2] The anti-rust coating composition according to claim 1, wherein the polyaniline component is polyaniline particles. [Claim 2] The anti-rust coating composition according to claim 1, wherein the polyaniline component comprises polyaniline particles, polyvinyl butyral, and an alcohol-based solvent. [Claim 2] The anti-rust coating composition according to claim 1, wherein the coating film component is included in an amount of 600 to 13,000 parts by mass based on 100 parts by mass of polyaniline contained in the polyaniline component.

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