KR20170118588A - Corrosion-inhibiting coating composition - Google Patents

Abstract

Provided is a rust-preventive coating composition capable of reducing generation of rust due to salt spray test and having excellent rust-inhibiting properties.
The anti-corrosive coating composition of the present invention comprises a polyaniline component and a coating film component, wherein the coating film component is composed of a phenoxy resin.

Description

{CORROSION-INHIBITING COATING COMPOSITION}

The present invention relates to a rust preventive coating composition.

Conventionally, a rust preventive coating composition containing polyaniline and an epoxy resin as a coating film component is known. (See, for example, Patent Document 1)

Japanese Patent Application Laid-Open No. 2007-324143

However, when the conventional anticorrosive coating composition containing polyaniline and epoxy resin as a coating film component is applied to a copper plate to form a coating film and then subjected to a salt spray test according to the method specified in Japanese Industrial Standard JIS Z2371, There is a problem that rust is generated severely.

It is an object of the present invention to provide a rust-preventive coating composition which can solve such a problem and reduce the generation of rust by the salt spray test and which has excellent rust-inhibitive performance.

In order to achieve the above object, the inventors of the present invention have extensively studied a resin replacing the epoxy resin as a coating film component. As a result, the present inventors have reached the present invention by noting that a desired purpose can be achieved by using a phenoxy resin as a coating film component.

Herein, the anticorrosive coating composition of the present invention is characterized in that in the anticorrosive paint composition comprising a polyaniline component and a coating film component, the coating film component is composed of a phenoxy resin.

When the anticorrosive paint composition of the present invention is applied to an antirust agent such as a copper plate, the phenoxy resin constituting the above-mentioned paint film component is cured to form a coating film in which the polyaniline component is dispersed. Since the polyaniline component is dispersed in the coating film formed by curing the phenoxy resin, the anticorrosive paint composition of the present invention can reduce the generation of rust by the salt spray test and obtain excellent rust inhibitive performance.

In the anticorrosive coating composition of the present invention, it is possible to suitably use, as the phenoxy resin, a polycondensation product of bisphenol A and epichlorohydrin or a polycondensation product of bisphenol A and a hydroxyalkyl ether. In the anti-corrosive coating composition of the present invention, for example, 2-hydroxypropyl ether can be used as the hydroxyalkyl ether.

Further, in the anti-corrosive coating composition of the present invention, the polyaniline component may be polyaniline particles, polyaniline particles, polyvinylbutyral and alcohol-based solvents.

In addition, the anti-corrosive coating composition of the present invention preferably contains the coating film component in a range of 600 to 13,000 parts by mass based on 100 parts by mass of the polyaniline contained in the polyaniline component.

When the content of the coating film component is less than 600 parts by mass based on 100 parts by mass of the polyaniline contained in the polyaniline component, a sufficient coating film may not be formed. When the content of the coating film component exceeds 13,000 parts by mass based on 100 parts by mass of polyaniline contained in the polyaniline component, sufficient rust inhibitive performance may not be obtained.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a photograph showing a result of a salt spray test on a coating film formed on the surface of a copper plate by the rust-preventive coating composition of Example 1. FIG.
2 is a photograph showing a result of a salt spray test on a coating film formed on the surface of a copper plate by the rust-preventive coating composition of Example 2. Fig.
3 is a photograph showing a result of a salt spray test on a coating film formed on the surface of a copper plate by the rust-preventive coating composition of Comparative Example 1. Fig.
4 is a photograph showing the results of a salt spray test on a coating film formed on the surface of a copper plate by the rust-preventive coating composition of Comparative Example 2. Fig.
5 is a photograph showing the result of a salt spray test on a coating film formed on the surface of a copper plate by the rust-preventive coating composition of Comparative Example 3. Fig.
6 is a photograph showing a result of a salt spray test on a coating film formed on the surface of a copper plate by the rust-preventive coating composition of Comparative Example 4. Fig.
7 is a photograph showing the results of a salt spray test on a coating film formed on the surface of a copper plate by the rust-preventive coating composition of Comparative Example 5. Fig.

Next, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The anti-corrosive coating composition of the present embodiment comprises a polyaniline component and a coating film component, and the coating film component is composed of a phenoxy resin.

Examples of the phenoxy resin include a polycondensation product of bisphenol A and epichlorohydrin, or a polycondensation product of bisphenol A and a hydroxyalkyl ether.

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

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

In the formula, R is an alkylene group having 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, an n-propylene group, an i-propylene group and an n-butylene group.

In the present embodiment, as the hydroxyalkyl ether, 2-hydroxypropyl ether represented by the following formula (2) can be appropriately used.

However,

As the polycondensation product of bisphenol A and epichlorohydrin, for example, jER1255HX30 (trade name) manufactured by Mitsubishi Chemical Corporation may be used. As the polycondensation product of bisphenol A and 2-hydroxypropyl ether, for example, Penetoto-YP-5OEK35 (trade name) manufactured by Shin-Nitetsu Sumitomo Chemical Co., Ltd. may be used.

As the phenoxy resin, phenoxy resin PKHH (trade name) manufactured by Phenoxy-Associates, phenoxy resin PKHB (trade name) manufactured by Phenoxy-Associates, and ISOPOXY 506K (trade name) manufactured by Nisshoku Schenectady Chemical Co., It is also good.

In the anticorrosive coating composition of the present embodiment, the polyaniline component may be the polyaniline particle itself, or may be a gelatinous body including polyaniline particles, polyvinyl butyral, and an alcohol-based solvent.

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

Further, the above gel body can be obtained as follows. First, the polyaniline particles obtained as described above are mixed with a polyvinyl butyral and an alcohol-based solvent, and then the alcohol-based solvent is volatilized to form a solid mixture. The solid mixture contains polyaniline uniformly dispersed in a matrix of polyvinyl butyral.

Subsequently, the solid mixture is dipped (immersed) in the alcohol-based solvent to be swollen and supplied to the pressure-dispersion device together with the alcohol-based solvent. The pressurizing and dispersing device is a device in which a sample is supplied to a narrow channel along with a solvent and is ejected from the channel by applying a pressure in the range of 5 to 80 MPa, for example, 30 to 50 MPa, . As a result, it is possible to obtain a gel body in which polyaniline particles are uniformly dispersed in the polyvinyl butyral and the alcohol-based solvent.

As the alcohol-based solvent, a mixed solvent of an alcohol such as isopropanol, methoxypropanol and other organic solvent can be used. Examples of the alcohol-based solvent include 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 More specifically, 40 parts by mass of isopropanol, 40 parts by mass of methoxypropanol, 10 parts by mass of butanol, 5 parts by mass of xylene and 5 parts by mass of ethylbenzene can be cited.

The method and the physical properties of the gel body are described in detail in JP-A-2014-37522.

The anticorrosive coating composition of the present embodiment contains the above coating film component in a range of 600 to 13,000 parts by mass, preferably 700 to 11,000 parts by mass, based on 100 parts by mass of polyaniline contained in the polyaniline component. The rust-preventive coating composition of the present embodiment can form a good coating film and can obtain excellent rust-inhibitive performance by containing the above-mentioned coating film component in the above-described range with respect to 100 parts by mass of polyaniline contained in the polyaniline component.

The anti-corrosive coating composition of the present embodiment can be easily produced by mixing the polyaniline component with the phenoxy resin and stirring the mixture. For the mixing and stirring, for example, a stirrer such as Desera (trade name) manufactured by Asada Tetsuko Co., Ltd. and Haifa (trade name) manufactured by Ashizawa Fine Tech Co., Ltd. can be used.

The anticorrosive paint composition of the present embodiment can be applied to the anticorrosive material such as a copper plate so as to have a thickness of 15 to 60 占 퐉, for example, 30 占 퐉 to form a coating film having excellent antirust performance. The application may be performed by, for example, spraying, air spraying, brushing, roller coating, or the like.

When the coating film is formed by the anti-corrosive coating composition of the present embodiment, a top coating layer may be further provided on the coating film. The top coat layer is preferably formed by a urethane-based resin to have a thickness of 15 to 60 탆, for example, 30 탆.

The rust-preventive coating composition of the present embodiment may further contain other additives insofar as it does not adversely affect the rust-preventive performance. Examples of the additives include coloring pigments, plasticizers, pigment dispersants, emulsifiers, thickeners, and anti-scattering agents.

Next, examples and comparative examples of the present 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 (trade name: jER1255HX30, manufactured by Mitsubishi Chemical Corporation), which is a polycondensation product of bisphenol A and epichlorohydrin as a coating film component, are mixed and stirred, A rust preventive coating composition in which polyaniline particles were dispersed in a component (phenoxy resin in this example) was prepared.

Then, the anticorrosive coating composition obtained in this Example was coated on the surface of an SPC copper plate having a length of 150 mm, a width of 75 mm and a thickness of 1.6 mm so as to have a dry thickness of 30 占 퐉, and the coating film component was cured to form a coating film. Further, a urethane resin (product of SUSUKAFU INC., Trade name: Epolux) was applied on the coating film so that the thickness of the film became 30 탆 in a dry state and cured to form a top coating layer.

Then, the sample was formed so as to have a length of 70 mm so as to intersect with two lines of depth reaching the surface of the copper plate, and a salt spraying apparatus (Itabashi Chemical Co., Ltd., trade name: complex corrosion tester BQ-1) A saline spray test was conducted for 600 hours in which saline solution having a concentration of 50 g / liter was sprayed onto the surface of the copper plate at an amount of 0.0028 liters / minute, in accordance with the method specified in Japanese Industrial Standard JIS Z 2371. The results are shown in Fig.

[Example 2]

In this embodiment, except that a phenoxy resin (trade name: PENOTTO-YP-5OEK35, made by Shin-Nittsu Sumikin Chemical Co., Ltd.) comprising a polycondensation product of bisphenol A and 2-hydroxypropyl ether was used as a coating film component , A rust-preventive coating composition was prepared in exactly the same manner as in Example 1.

Then, a coating film and a top coating layer were formed in exactly 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 carried out 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.

[Comparative Example 1]

In this comparative example, except that epoxy resin (trade name: esco) manufactured by Kansai Paint Co., Ltd. and ketimine (trade name: esco curing agent, manufactured by Kansai Paint Co., Ltd.) To prepare a coating composition.

Then, a coating film and a top coat layer were formed in exactly the same manner as in Example 1, except that the rust-preventive coating composition obtained in this Comparative Example was used.

Next, a salt water spray test was carried out in the same manner as in Example 1 except that the sample was used and the time was changed to 576 hours. The results are shown in Fig.

[Comparative Example 2]

In this Comparative Example, a rust-preventive coating composition was prepared in exactly the same manner as in Example 1, except that epoxy resin (trade name: epomalin primer) manufactured by Kansai Paint Co., Ltd. and polyamideamine were used as a curing agent.

Then, a coating film and a top coat layer were formed in exactly the same manner as in Example 1, except that the rust-preventive coating composition obtained in this Comparative Example was used.

Next, a salt water spray test was carried out in the same manner as in Example 1 except that the sample was used and the time was changed to 576 hours. The results are shown in Fig.

[Comparative Example 3]

In this comparative example, a rust-preventive coating composition was prepared in exactly the same manner as in Example 1, except that epoxy resin (trade name: Hi-Bone 20-HB) manufactured by Nippon Paint Co., Ltd. was used as a coating film component and its exclusive hardener.

Then, a coating film and a top coat layer were formed in exactly the same manner as in Example 1, except that the rust-preventive coating composition obtained in this Comparative Example was used.

Next, a salt water spray test was carried out in the same manner as in Example 1 except that the sample was used and the time was changed to 576 hours. The results are shown in Fig.

[Comparative Example 4]

In this Comparative Example, a rust-preventive coating composition was prepared in exactly the same manner as in Example 1, except that epoxy resin (trade name: Neogose # 2300 primer) manufactured by Shindo Coatings Co., Ltd. and a special curing agent were used as a coating film component.

Then, a coating film and a top coat layer were formed in exactly the same manner as in Example 1, except that the rust-preventive coating composition obtained in this Comparative Example was used.

Next, a salt water spray test was carried out in the same manner as in Example 1 except that the sample was used and the time was changed to 576 hours. The results are shown in Fig.

[Comparative Example 5]

In this comparative example, a rust-preventive coating composition was prepared in exactly the same manner as in Example 1, except that epoxy resin (trade name: EcoPin Primer-HB) manufactured by China Coatings Co., Ltd. was used as a coating film component and its exclusive hardener.

Then, a coating film and a top coat layer were formed in exactly the same manner as in Example 1, except that the rust-preventive coating composition obtained in this Comparative Example was used.

Next, a salt water spray test was carried out in the same manner as in Example 1 except that the sample was used and the time was changed to 576 hours. The results are shown in Fig.

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

On the other hand, from FIGS. 1 and 2, it is understood that a rust-preventive coating composition (Example 1) using a phenoxy resin comprising a polycondensation product of bisphenol A and epichlorohydrin as a coating film component, or bisphenol A and 2-hydroxypropyl ether (Example 2) using a phenoxy resin composed of a polycondensation product of a polycondensate of the present invention, the copper plate provided with the coating film formed by the anticorrosive coating composition is merely such that the generation of a very small amount of rust is confirmed, It is clear that it has performance.

Claims (7)

A rust-preventive coating composition comprising a polyaniline component and a coating film component,
Wherein the coating film component is composed of a phenoxy resin. The anticorrosive coating composition according to claim 1, wherein the phenoxy resin is a polycondensate of bisphenol A and epichlorohydrin. The anti-corrosive coating composition according to claim 1, wherein the phenoxy resin is a polycondensation product of bisphenol A and hydroxyalkyl ether. The anticorrosive coating composition according to claim 3, wherein the hydroxyalkyl ether is 2-hydroxypropyl ether. The anti-corrosive coating composition according to claim 1, wherein the polyaniline component is a polyaniline particle. The anti-corrosive coating composition according to claim 1, wherein the polyaniline component comprises polyaniline particles, polyvinyl butyral, and an alcohol-based solvent. The anti-corrosive coating composition according to claim 1, wherein the coating film component is contained in an amount of 600 to 13,000 parts by mass based on 100 parts by mass of the polyaniline contained in the polyaniline component.

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