JPS6021663B2 - Coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coating composition, and more particularly, to a coating composition comprising:
A novel coating composition comprising a mixture containing a fluoroolefin/cyclohexyl vinyl ether copolymer and an epoxy resin.

The present applicant discovered that a new fluorine-containing copolymer with high rigidity and soluble in solvents could be obtained by polymerizing fluoroolefin and cyclohexyl vinyl ether (hereinafter abbreviated as CHVE), and 52-92
59 (Japanese Patent Publication No. 55-44083). The fluoroolefin/CHVE copolymer has a high rigidity and is soluble in solvents such as mineral spirits and ethyl acetate, and when applied as a coating material, it is easy to apply, transparent and hard. It has the advantage that a coating film can be easily obtained, and it is also used as a material for various moldings. Furthermore, the fluoroolefin/
CHVE-based copolymers can be easily crosslinked in the presence of oxygen by heat treatment at 170 qo or more or by the action of Korean radiation containing ultraviolet rays with a wavelength of 2800△ or less, improving mechanical strength at high temperatures and improving resistance. Solvent property is imparted (Tokukano Sho 52-92215
(Japanese Patent Laid-Open No. 54-46286), etc.). According to the research of the present inventor, the above-mentioned fluoroolefin/CHVE copolymer is added to and mixed with epoxy resin, which is known as an anticorrosion coating material, and the mixture is used to form coating films on various surfaces. , the following advantages can be obtained. That is, the weather resistance of the coating film is improved and the adhesion to the substrate is also good. Then, the crosslinking reaction of the fluoroolefin/CHVE copolymer can proceed smoothly and advantageously under normal curing conditions for epoxy resins. As a result, it has become an extremely excellent anti-corrosion coating material with excellent adhesion and resistance, and is not only capable of forming a smooth coating film with good gloss, but also has excellent compatibility with various pigments and colorants. It is also useful as a colored protective layer over a wide range of areas. Thus, the present invention has been completed based on the above findings, and the molar ratio of fluoroolefin/cyclohexyl vinyl ether is 30/70 to 30/70.
A coating composition comprising a mixture containing a fluoroolefin/cyclohexyl vinyl ether copolymer and an epoxy resin having a fluoroolefin/cyclohexyl vinyl ether copolymer having an intrinsic viscosity of 70/30 and an intrinsic viscosity of 0.1 to 2 m/d as measured at 30/d in tetrahydrofuran. It provides something new.

According to the composition of the present invention, it is possible to form an excellent anticorrosion coating film on the surface of various substrates. In particular, it is possible to form a coating film with significantly improved tarp resistance, and when used in combination with an epoxy resin, it is possible to form a coating film that firmly adheres to various surfaces. Furthermore, it is possible to form a glossy and smooth coating film, and it can be colored with a pigment over a wide range, which is advantageous for forming a beautiful protective coating film. As described below, the coating film made from the composition of the present invention is easily crosslinked or cured, and has better adhesion and other physical properties. 3 In the present invention, as the fluoroolefin/CHVE copolymer, one in which the fluoroolefin is preferably a perhaloolefin, particularly preferably tetrafluoroethylene or chlorotrifluoroethylene, is used, and the mole of fluoroolefin CfWE is Ratio is 30/70 to 70/3
0 and an intrinsic viscosity of 0.1 to 2 m/d m as measured at 30°C in tetrahydrofuran is preferably employed. It is also possible to employ 4 units containing units based on other comonomers along with fluoroolefin and CHVE units. Examples of comonomers include olefins such as ethylene, propylene, and isobutylene, vinyl halides such as vinyl chloride and vinylidene chloride, unsaturated carboxylic acid esters such as methyl methacrylate, vinyl acetate, n-
Examples include vinyl carboxylates such as pinyl butyrate, alkyl vinyl ethers such as ethyl pinyl ether and n-butyl vinyl ether, and fluorovinyl ether. Particularly suitable are alkyl vinyl ethers in which the alkyl group has 1 to 8 carbon atoms. The content of the comonomer can be appropriately selected depending on the type or purpose, but it is usually 40 mol% or less, particularly about 5 to 35 mol%. zo In the composition of the present invention, the mixing ratio of the fluoroolefin/CHVE copolymer and the epoxy resin is not particularly limited. Can be varied over a wide range. Usually, 5 to 10 parts by weight, preferably about 10 to 8 parts by weight of the fluoroolefin/CHVE copolymer are used per 10 parts by weight of the epoxy resin. As the epoxy resin, conventionally known or well-known ones are arbitrarily adopted,
Usually, materials useful as anti-corrosion coating materials are selected.
c) Epoxy resins are made of epoxy compounds such as epichlorohydrin and glycerol dichlorohydrin, alcohols such as pentaerythritol, polyhydric alcohols such as glycol and glycerin, and bisphenol A.
It can be produced by condensation with polyhydric organic compounds such as dihydric phenols and trihydric phenols. Usually, an epoxy resin obtained by condensation of bisphenol A and epichlorohydrin is used. Other epoxy resins include
There are epoxidized novolak resins such as diglycidyl ether of bisphenol A, epoxy cresol novolaks and epoxyphenol novolaks. Further examples include alicyclic epoxy resins, silicone-modified epoxy resins, and esterified epoxy resins. As a commercially available epoxy paint that is easily available, Eponix No. manufactured by Dainippon Toyo Co., Ltd. 110, M. 3100 or Epomarine paint manufactured by Kansai Paint. Epoxy resins contain curing agents and/or accelerators to enable curing.

Examples of accelerators include tertiary amines such as penzyldimethylamine, Lewis bases such as imidazole, and Lewis bases of boron trifluoride complex and monoethylamine. Examples include primary or secondary amines such as tetramine, polyamides, polyesters, carboxylic acids, anhydrides such as maleic anhydride, phenolic compounds, and alcohols. The composition of the present invention may take various forms.

That is, it may be in a liquid or powder form that has been conventionally employed in coating forming compositions. Depending on the form
Various types of epoxy resins that are commercially available as liquids or solids may be employed. Generally, a solution form of an organic solvent is preferable because it can form a good coating film on the surface of the base material, and a solid epoxy resin such as methyl ethyl ketone,
It is preferable to employ the solution as a solution in a ketone solvent such as methyl isoptyl ketone or a cyclic ether solvent such as tetrahydrofuran. Of course, it may be in the form of an aqueous emulsion or a powder coating. The fluoroolefin/CHVE copolymer may also be used in the form of a powder, an organic solution, an aqueous emulsion, etc., depending on the form. The composition of the present invention may contain suitable pigments, stabilizers, lubricants, fillers, and other appropriate additives as long as they do not impair the properties of the coating layer formed from the specific mixture.

With such additives, it is possible to improve color tone, thermal stability, abrasion resistance, non-stick properties, surface hardness, etc.
In particular, the fact that the composition can be freely colored by adding pigments is suitable for use as a protective layer for interior and exterior building materials, etc., taking advantage of the glossy beauty of the anticorrosion coating film formed by the composition of the present invention. There are no particular limitations on the method of forming a coating layer on the surface of various substrates using the composition of the present invention, such as applying a solution or powder of a specific mixture, or spraying, heating, and removing a solvent or dispersed soot. Examples include methods such as volatilization or fusion of powder, but from the viewpoint of smoothness of the formed coating film, a method of applying a solution and drying is preferably employed.

In the present invention, the coating film is crosslinked and cured. Crosslinking of fluoroolefin/Cm'E copolymers is described, for example, in Tokusho Sho 52-92215 specification and Japanese Patent Application Sho 52
170 to 35,000, preferably 190 to 35,000 in the presence of oxygen, as described in Japanese Patent No.
Heat at a temperature of about 300°C for 1 to 200 degrees, preferably for about 5 to 12 minutes, or use a light source that generates short wavelength ultraviolet rays such as a carbon arc lamp, hydrogen discharge tube, or low-pressure mercury lamp. , wavelength 28 in the presence of oxygen
It can be easily progressed by applying a forehead ray containing ultraviolet rays of 00△ or less. Particularly when heating is used, the epoxy resin can also be cured. Of course, the curing of the eboxy resin may be performed by other means. The composition of the present invention can be used, for example, in steel, aluminum, iron,
It can be widely used as a material for forming protective coatings on metal surfaces such as brass, wood products, and colored coatings on glass plates and wood products.

Specifically, Epoxy resin is used for corrosion protection, for example, it is extremely useful for long-term protective coating of tanks, pumps, pipes, etc. related to factory equipment, or maintenance-free anti-corrosive coating of bridges, outdoor structures, etc. . Next, examples of the present invention will be explained in more detail.
It goes without saying that the present invention is not limited to the above description.

In addition, the performance test method of the coating film made from the composition of the present invention will be described below. 1 Adhesion Durability 1-1 Goban Boiling Test Draw 11 vertical and horizontal lines on the test piece at 1-skin intervals to create ION hard goblets.

After boiling this in boiling water for 2 hours and removing the water,
A cellophane adhesive tape was pasted on top of this, and the tape was pulled straight upward at once, and its adhesion was evaluated based on the number of stitches remaining/100. For example, 100/10
0 indicates that no peeling was observed and good adhesion was observed. (According to the method according to JIS-K5400) 1
12. On the drawing Eriksen test specimen, the helix light 1 side, 1 rotation phase gap 2
．． 20 spirals on the 5th side were drawn at a constant speed of 1 rotation per second using a drawing tester, and then pushed out using an Eriksen tester so that the test piece had a height of 5 ribs with the drawn portion outside.
The degree of peeling of the coating film was visually determined.

2.Weather Resistance Using a Sunshine Weatherometer device manufactured by Suga Test Instruments Co., Ltd., after a certain period of irradiation test, the 60 degree surface gloss specified in JIS-K5400 was measured, and the gloss retention rate was calculated based on the pre-test gloss. was calculated.

This gloss retention rate and appearance observation were used as evaluation criteria.
3 Surface glossiness Measured using the 60 degree surface gloss measurement method specified in JIS-K5400.

Example 1 Eponix #110 manufactured by Dainippon Toyo Co., Ltd. was diluted with a special thinner to obtain chlorotrifluoroethylene with a molar ratio of chlorotrifluoroethylene and CHVE of 50/50 and an intrinsic viscosity of 0.6. /CHVE binary copolymer A or chlorotrifluoroethylene/CHVE/ethyl having a molar ratio of chlorotrifluoroethylene, CHVE, and ethyl vinyl ether of 50/15/35 and an intrinsic viscosity of 0.61. Vinyl ether terpolymer B and titanium dioxide were added in the following proportions, and the mixture was fed in a ball mill for 2 hours.

The obtained coating composition was applied to a base-treated lead steel plate using a film applicator, and baked for 210 qo x 20 minutes.

A glossy white coated zinc steel sheet with a film thickness of 25 r was prepared.
Table 1 shows the results of the physical property test of the coating film. As can be seen from Table 1, this coating film has excellent adhesion durability and weather resistance is greatly improved compared to the comparative example. Example 2 As a fluoroolefin/CHVE-based copolymer, chlorotrifluoroethylene has a molar ratio of chlorotrifluoroethylene, CHVE, and glycidyl vinyl ether of 50/48-2 and an intrinsic viscosity of 0.58. /CH
A white coated zinc steel sheet was prepared using the VE/glycidyl vinyl ether tricopolymer in the same manner as in Example 1, except that it was cured by co-crosslinking with Eponix #110 used in Example 1.

This coating showed excellent adhesion durability and weather resistance. The test results are shown in Table 1 below. Table 1 Comparative Example In Example 1, chlorotrifluoroethylene/CH
When we measured the physical properties of the coating film obtained using a coating composition that did not contain the VE copolymer, similar results were obtained for adhesion durability, but regarding weather resistance, the gloss retention rate was lower after 20 feeding hours. was less than 50%.

Claims (1)

[Claims] 1. The molar ratio of fluoroolefin/cyclohexyl vinyl ether is 30/70 to 70/30, and the intrinsic viscosity measured at 30°C in tetrahydrofuran is 0.1.
A coating composition comprising a mixture containing a fluoroolefin/cyclohexyl vinyl ether copolymer and an epoxy resin at a concentration of ~2 g/dl. 2. The composition according to claim 1, wherein the fluoroolefin is tetrafluoroethylene. 3. The composition according to claim 1, wherein the fluoroolefin is chlorotrifluoroethylene. 4 The molar ratio of fluoroolefin/cyclohexyl vinyl ether is 30/70 to 70/30, and the third component is 5 to 40 mol% of alkyl vinyl ether whose alkyl group has 1 to 8 carbon atoms based on the total monomers. Contains
Claim 1, 2, or 3 uses a fluoroolefin/cyclohexyl vinyl ether copolymer having an intrinsic viscosity of 0.1 to 2 g/dl as measured in tetrahydrofuran at 30°C. Composition of. 5. The composition according to claim 1, wherein the content of the fluoroolefin/cyclohexyl vinyl ether copolymer is 5 to 100 parts by weight per 100 parts by weight of the epoxy resin.