JPH0335991B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is applicable to substrates contaminated with water or aqueous substances (hereinafter referred to as water-based substances) and/or oil or oil-based substances (hereinafter referred to as oil-based substances), such as plastics, glass, ceramics, etc. The present invention provides a method for directly coating a polyester resin with an unsaturated vinyl ester resin and/or an unsaturated polyester resin.

Immediately after processing, the substrate is contaminated with water-based substances and/or oil-based substances, and if this can be painted as is without cleaning, it would be very desirable from a labor-saving perspective, and would solve a major technical problem. 1
It is one.

Conventionally, vinyl chloride resin sol has been used for painting oil surfaces, and epoxy resin has been used for painting wet surfaces. In the case of vinyl chloride resin, the sol absorbs the oil present on the surface of the base material, and in the case of epoxy resin, the resin reacts and absorbs the moisture present on the surface of the base material. It is thought that because these resins can sufficiently adhere to the substrate, uniform coating of the substrate soiled with these resins is possible, and therefore sufficient adhesion is achieved.

However, in the case of unsaturated polyester resin and/or unsaturated vinyl ester resin, the vinyl chloride resin sol does not have the effect of absorbing oil and moisture like epoxy resin, so it is difficult to coat oily or wet surfaces. The surface of the base material must be sandblasted, solvent cleaned, detergent cleaned, etc.
It was necessary to perform coating after processing by drying or the like. Furthermore, if the surface of the substrate is contaminated with both hydrogen substances and oil-based substances, many steps are required to clean it, and there has been a demand for the development of a simpler coating method. .

The present inventors have discovered that when coating the surface of a base material contaminated with water-based substances and/or oil-based substances with an unsaturated vinyl ester resin and/or unsaturated polyester resin containing a vinyl monomer, Use a mixed resin liquid containing 0.1 to 20% by weight of (meth)acrylic acid ester of an alcohol having a fluorinated alkyl group and/or alkylene group based on the vinyl monomer originally contained in the resin. It has been found that by using this method, it is possible to uniformly coat the surface of a substrate contaminated with water-based substances and/or oil-based substances, and to obtain a good coated product.

(Meta) with added fluorinated alkyl and/or alkylene groups in this case
Although the effects of acrylic acid ester on the substrate are not clear, the strong water- and oil-repellent properties of this monomer or the polymer produced by polymerization of this monomer prevent water-based substances and oil-based substances at the interface of the substrate. is expelled from the interface and the resin adheres to the interface of the base material, so it is thought that uniform coating is achieved, and this seems to be due to a different mechanism of action than in the case of the vinyl chloride resin or epoxy resin described above.

In order to coat the surface of a base material using the above-mentioned mixed resin liquid, which is a feature of the present invention, the mixed resin liquid can be coated without cleaning the base material surface contaminated with water-based substances and/or oil-based substances. is coated and cured by a conventional method, either by leaving it as it is at room temperature or at an elevated temperature, or by irradiating it with active energy rays such as ultraviolet rays, X-rays, and gamma rays. At this time, if necessary, the contaminated base material surface may be wiped with a cloth or the like and then coated with the mixed resin liquid.

According to the method of the present invention, coating with excellent adhesion can be achieved by applying the mixed resin liquid described above to a substrate soiled with water-based substances and/or oil-based substances.

The unsaturated polyester resin containing a vinyl monomer used in the present invention includes unsaturated polybasic acids such as maleic acid, fumaric acid, maleic anhydride, or their anhydrides, phthalic anhydride, isophthalic acid, adipic acid, etc. An unsaturated polyester obtained by dehydration condensation of a saturated polybasic acid or its anhydride with a polyhydric alcohol such as propylene glycol, ethylene glycol, or glycerin is dissolved in a vinyl monomer. Further, the unsaturated vinyl ester resin containing a vinyl monomer used in the present invention is obtained by reacting a bifunctional or more functional epoxy compound, such as bisphenol A diglycidyl ether, novolac epoxy, etc., with acrylic acid or methacrylic acid. It is a mixture of epoxy (meth)acrylate and vinyl monomer.

The acrylic ester or methacrylic ester of an alcohol having a fluorinated alkyl group and/or alkylene group used in the present invention is one in which some or all of the hydrogens of the alkyl group or alkylene group are replaced with fluorine. is an acrylic ester or methacrylic ester of an alcohol, and the total number of carbon atoms in an alkyl group, an alkylene group, or both of these groups in one molecule is 1 to 30, and is a compound as exemplified below. : (However, m=0-18, n=0-18, R=H or
_CH3CO , X=H or _CH3 , ^R1 =H or _CH3
( _CH2 )n).

Examples of vinyl monomers blended with the above unsaturated polyesters and unsaturated vinyl esters are as follows: styrene, methyl methacrylate, ethyl methacrylate, methyl acrylate, 2-ethylhexyl acrylate, ethylene glycol diacrylate,
Polyethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolpropane diacrylate,
Trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythrit triacrylate, pentaerythrittetraacrylate, pentaerythritute trimethacrylate, pentaerythritutetramethacrylate, etc.

As mentioned above, the unsaturated polyester resin containing a vinyl monomer and the unsaturated vinyl ester resin used in the present invention contain a vinyl monomer such as styrene, but the content is usually less than the total resin amount. It is 10-60% by weight. A feature of the present invention is that a (meth)acrylic acid ester of an alcohol having a fluorinated alkyl group and/or alkylene group is used in an amount of 0.1 to 20% by weight based on the weight of the vinyl monomer. be.

The amount of added fluorinated alkyl group and/or (meth)acrylic ester of alcohol having an alkyl group is determined by the weight of the vinyl monomer in the unsaturated polyester resin containing the vinyl monomer and/or the unsaturated vinyl ester resin. If it is less than 0.1% by weight, coating the surface of the substrate contaminated with water-based substances and/or oil-based substances, which is a feature of the present invention, cannot be uniformly performed.
Further, when the amount added exceeds 20% by weight, adhesion to the surface of the substrate becomes insufficient.

Substrates coated by the method of the present invention include metal products or metal plated surfaces such as iron, aluminum, copper, zinc, tin, and chromium, plastic products such as polymethyl methacrylate, polycarbonate, and polyester, soda glass, and lead glass. and ceramic products such as sintered alumina and sintered silicon carbide, and can be coated to improve coloring, abrasion resistance, corrosion resistance, weather resistance, etc. Coating with the mixed resin liquid can be performed by a conventionally known method.

Curing of the unsaturated polyester resin and/or unsaturated vinyl ester resin containing a vinyl monomer according to the present invention can be carried out by a conventionally known method.

That is, after adding an organic peroxide such as benzoyl peroxide, methyl ethyl ketone peroxide, or kyumene hydroperoxide to a mixed resin liquid and coating the surface of the base material,
It can be cured by heating, or it can be cured at room temperature by using the organic peroxide in combination with cobalt naphthenate, dimethylaniline, or the like. Also, benzoin, benzyl, benzophenone, 2-hydroxy-3-
A photosensitizer such as benzoylpropane, benzoin methyl ether, etc. may be added to a mixed resin liquid and the mixture may be coated on the surface of the substrate and then cured by ultraviolet rays. Furthermore, X-ray and gamma ray curing can also be used. When curing with X-rays or gamma rays, it is not necessary to add a radical initiator. Curing conditions can be carried out exactly the same as for conventional unsaturated polyester resins and/or unsaturated vinyl ester resins without the addition of (meth)acrylic esters of alcohols having fluorinated alkyl groups and/or alkylene groups. can.

A coloring agent, a filler, a leveling agent, a thixotropic agent, an antifoaming agent, etc. can be added to the mixed resin liquid. In particular, the use of a hydraulic filler such as cement in combination is extremely effective as it significantly improves the adhesiveness of wet surfaces.

The present invention will be explained below with reference to Examples.

Example 1 1 mol of maleic anhydride, 1 mol of phthalic anhydride,
2.1 mol of propylene glycol was mixed and heated at 205°C for 8 hours, and the resulting water was separated to produce an unsaturated polyester with an acid value of 30. After cooling 70 kg of this unsaturated polyester to 130℃, styrene 29
Kg, CF ₃ −(CF ₂ ) ₆ −CH ₂ −CH ₂ −O−CO−CH=
It was mixed with a solution consisting of 1 kg of CH ₂ (fluorinated alkyl acrylate), 0.02 kg of hydroquinone and 0.1 kg of paraffin, and cooled to room temperature. To the thus obtained unsaturated polyester resin, 1% by weight of a 50% solution of methyl ethyl ketone peroxide in dimethyl phthalate and 0.5% of cobalt naphthenate (6% Co) were added.
% by weight was added. This mixed resin liquid was coated at a rate of 300 g/m ² on the surface of a zinc steel plate contaminated with oil and water, and after being left at 40°C for 3 hours to completely harden, the surface was polished to give it a glossy finish. I put it out. This coating film is uniform and its adhesion is determined by the goblin test.
It was 100/100, and no peeling was observed. On the other hand, in the above method, when the same product was coated using a mixed resin solution that omitted the fluorinated alkyl acrylate, the coating film was uneven, the goblin test was 0/100, and the coating film was completely coated. Peeled off.

Example 2 Bisphenol A, 1 mole of diglycidyl ether, and 2 moles of acrylic acid were reacted in the presence of a styrene monomer while blowing air to obtain a 60% styrene solution of epoxy acrylate. 10kg of unsaturated vinyl ester resin thus obtained
For, (Fluorinated alkyl acrylate) 0.2 kg was added and mixed uniformly. 0.3% by weight of 2-hydroxy-3-benzoylpropane was added and dissolved as a photosensitizer to this mixed resin solution. The surface of a polycarbonate plate contaminated with cutting oil and water was coated with the resin liquid at a rate of 200 g/m ² , and cured by irradiating it with ultraviolet rays for 10 seconds from a distance of 10 cm using a 2 KW high-pressure mercury lamp. The polycarbonate board is uniformly coated with unsaturated vinyl ester resin,
Adhesion was 100/100 in the cross-cut test, and no peeling of the coating was observed. On the other hand, in the above method, if the same product is coated using a resin liquid without the addition of fluorinated alkyl acrylate, the coating will be uneven, the cross-cut test will be 0/100, and the entire coating will be completely coated. Peeled off.

Example 3 One mole of bisphenol A glycidyl ether having a molecular weight of about 1000 and two moles of methacrylic acid were reacted in the presence of a styrene monomer while blowing air to obtain a 70% styrene solution of epoxy methacrylate.

For 10 kg of unsaturated vinyl ester resin obtained, 0.08 g (fluorinated alkyl methacrylate) and 0.5 kg of polyvinyl methyl ether were added and mixed uniformly. To this resin liquid, add 2% by weight of silicon oxide fine powder as a thixotropic agent, 2% by weight of titanium white as a coloring agent, 3% by weight of glass powder as a filler, and 0.5% by weight of cobalt naphthenate as a hardening accelerator, and mix it with a homomixer. A viscous resin liquid was obtained by stirring. Add 1% by weight of a 50% dimethyl phthalate solution of methyl ethyl ketone peroxide to 100 parts by weight of this resin liquid.
was added. This liquid resin was screen printed onto a glass bottle contaminated with both machine oil and water, and cured by heating at 50°C for 30 minutes. The printed surface of the glass was coated uniformly, and the adhesion was 100/100 in the goblin adhesion test, and no peeling of the coating was observed. On the other hand, in the above method, when a glass bottle contaminated with both machine oil and water was coated using a resin solution omitting the fluorinated alkyl methacrylate, the coating on the coated glass surface was uneven. , and the cross-cut test was 0/100, meaning that the entire coating film was peeled off.

Example 4 The unsaturated polyester obtained in Example 1 and the unsaturated vinyl ester resin obtained in Example 3 were mixed at a weight ratio of 1:1, and the amount of styrene was adjusted to give a resin liquid of 100 weight. The styrene content in the part was 40% by weight. to this (fluorinated alkyl acrylate) was mixed, and 1% by weight of 50% dimethyl phthalate paste of benzoyl peroxide and 0.5% by weight of cobalt naphthenate were added to obtain a uniform resin solution. This resin liquid was coated at a rate of 200 g/m ² on the surface of a sintered aluminum oxide plate contaminated with machine oil and water, and cured by heating at 40°C for 1 hour and then at 50°C for 30 minutes. . This coating film was uniform, the adhesion was 100/100 in the cross-cut test, and no peeling of the coating film was observed.

On the other hand, in the above method, when the same product is coated with a resin liquid manufactured by the same recipe and method except that the fluorinated alkyl acrylate is omitted, the coating film is uneven and has a rough pattern. The test was 0/100 and the coating was completely peeled off.

Example 5 Unsaturated polyester resin obtained in Example 1 (70 kg of unsaturated polyester, 29 kg of styrene, CF ₃
−(CF ₂ ) ₆ −CH ₂ −CH ₂ −O−CO−CH=CH ₂ 1
Kg Hydroquinone 0.02Kg and Paraffin 0.1
After mixing and kneading 30 parts by weight of white Portland cement with 100 parts by weight (consisting of Kg), 1.5 parts by weight of a 50% dimethyl phthalate solution of methyl ethyl ketone peroxide, 1 part by weight of cobalt naphthenate (cobalt content 6%), and dimethyl Aniline 0.2
A resin liquid was obtained by adding parts by weight. This resin liquid was used to paint a steel plate submerged in oily water. In other words, in water with oil floating on the surface,
A 15 cm x 10 cm polished steel plate submerged in a 30 cm depth was pulled up, and the above unsaturated polyester resin liquid was applied to the surface to a thickness of 1 mm and left at 40° C. for 3 hours to completely cure. This coating was uniform. Further, the adhesion was 100/100 in the cross-cut test, and no peeling was observed. On the other hand, when the same product was coated using a mixed resin solution in which the fluorinated alkyl acrylate was omitted in the above method, the coating film was uneven, the cross-cut test was 0/100, and the coating film was completely peeled off. .

Claims (1)

[Scope of Claims] 1. In a method of coating the surface of a substrate soiled with a water-based substance and/or oil-based substance with an unsaturated vinyl ester resin and/or unsaturated polyester resin containing a vinyl monomer, The coating described above is characterized in that coating is performed using a mixed resin liquid containing a (meth)acrylic acid ester of an alcohol having a fluorinated alkyl group and/or an alkylene group in an amount of 0.1 to 20% by weight based on the monomer. Method. 2. The coating method according to claim 1, wherein a hydraulic filler is further added to the mixed resin liquid. 3. The coating method according to claim 2, wherein the hydraulic filler is cement.