JPH0676563B2 - Antifouling composition and method for preventing pollution - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an antifouling agent composition and a method for preventing contamination, and more specifically, it is effective for preventing contamination of various articles and easily peels off a protective film during use. The present invention relates to an antifouling agent composition that can be removed and a method for preventing pollution.

(Prior art and its problems) Conventionally, as a method for temporarily preventing contamination of articles that are easily contaminated with oil, dust, dust, paint, ink, etc., a protective coating is applied to the surface of these articles to form a film. Or, a method of peeling off a plastic film before use is used.

However, in the above method, if the article to be protected has a low surface strength, or if it is made of the same material as the protective coating, it is difficult to peel off the coating, and a part of the coating remains,
There is a problem that the surface of the article is damaged during peeling.

Therefore, an object of the present invention is to provide an antifouling composition and a method for preventing contamination, which are useful for protecting all articles and which are extremely easy to peel off the coating film.

(Means for Solving Problems) The above object is achieved by the present invention described below.

That is, the present invention dissolves a water-swellable polymer and a film-forming polymer selected from a block or graft copolymer having a hydrophobic segment and a hydrophilic segment and a crosslinked hydrophilic polymer in a liquid medium. And / or an antifouling agent composition characterized by being dispersed and a method for preventing contamination using the composition.

(Function) After forming a film on the surface of an article to be protected which is to be prevented from being contaminated by using an antifouling composition containing a water-swellable polymer and a film-forming polymer in a liquid medium, the film is formed. When water is applied to the coating at the time of peeling, the coating swells with water and can be easily peeled off, and can be easily peeled off without damaging the surface of the article to be protected.

In particular, the specific block polymer-type or graft polymer-type water-swellable polymer used in the present invention has both a lipophilic segment and a hydrophilic segment, so that it is suitable for both lipophilic and hydrophilic articles. Does not adhere firmly,
Since they can be easily peeled off, they can be applied together.

(Preferred Embodiment) The water-swellable polymer used in the present invention is a polymer which absorbs water and expands when it comes into contact with water, but does not dissolve in water. It is about 2 to 1,000 times, and preferably about 5 to 500 times. Specifically, for example, starch-sodium polyacrylate graft product, sodium salt of saponified starch-polyacrylonitrile graft product, cellulose-
Sodium polyacrylate graft product, vinyl alcohol-sodium (meth) acrylate- (meth) acrylic acid copolymer, polyoxyethylene chain-containing polyurethane, crosslinked hydrophilic polymer, for example, partially crosslinked poly (meth)
Examples thereof include sodium acrylate, alkali-neutralized products of crosslinked isobutylene-maleic anhydride copolymer, sodium salt of crosslinked carboxymethyl cellulose, crosslinked polyethylene oxide and the like, and any conventionally known one can be used.

In the present invention, particularly preferred water-swellable polymer is a polymer or copolymer (hydrophilic segment) having a hydrophilic group and a hydrophobic polymer chain or copolymer chain (hydrophobic segment) bonded in the form of a block copolymer or a graft copolymer. As described in Examples below, for example, thioglycolic acid, oleic anhydride, acrylic acid or methacrylic acid is added to the double bond of the block copolymer of (polystyrene)-(polybutadiene)-(polystyrene). It is a product obtained by addition or addition polymerization of an acid or the like, or a product obtained by neutralizing these with an alkali.

Further, as particularly preferable graft-type water-swellable polymer, for example, a copolymer of a hydrophobic polymer having an αβ-ethylenically unsaturated group at a terminal and a hydrophilic monomer which gives a hydrophilic polymer. It is a thing. Examples of the hydrophobic polymer having unsaturation at this end include α, β ethylene such as (meth) acryloyl at the end of a homopolymer chain or copolymer chain of styrene, (meth) acrylic acid ester, acrylonitrile, etc. It has a system unsaturated group.

If the molecular weight of the hydrophobic polymer having an unsaturated group is too low, the water-swellable polymer will have a high water solubility, and if it is too large, the water swellability will be insufficient, so that the preferred average molecular weight range is 1,000. To 20,000, preferably 1,500 to 15,000
Is the range.

Most preferred among such block copolymers or graft copolymers are those in which the hydrophilic group of the hydrophilic polymer segment is a carboxylic acid or sulfonic acid or an alkali metal salt thereof.

The above-mentioned water-swellable polymer used in the present invention is preferably fine particles, and these fine particles are prepared by synthesizing the above-mentioned polymer in an organic solvent. Synthesized as having an ionic group such as an acid group or an amino group, a quaternary ammonium group, a pyridinium group, etc., and the state thereof is changed by a base such as an alkali metal or an amine or an acid such as an inorganic acid or a water-soluble organic acid. It is easily obtained by neutralizing with. Further, even if a salt is already formed with a base or an acid, it can be produced in the same manner by making it a free state in an organic solvent and then neutralizing it with a base or an acid. Neutralization of the above polymer may be carried out at the time of synthesis as described above. Alternatively, for example, a high degree of swelling can be exhibited by neutralizing after coating or peeling of the film. That is, the water-swellable polymer may be used in a state where the carboxyl group and the sulfonic acid group are free. In this case, it is preferable to use alkaline water when peeling the coating film as described later.

The film-forming polymer used in the present invention may be any conventionally known film-forming resin such as polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, polyvinyl chloride, etc., but particularly preferred is hydrophobic elasticity. Material, for example, natural rubber, polyisoprene, butyl rubber, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer,
Any known material having rubber elasticity such as polychloroprene, ethylene-propylene polymer, acrylic rubber, ethylene-vinyl acetate copolymer, polybutynyl butyral resin, silicone resin, and urethane polymer can be used.

The antifouling composition of the present invention is prepared by dissolving or dispersing the water-swellable polymer and the film-forming polymer in an organic solvent. Examples of the organic solvent used at this time include methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate, acetone, cyclohexanone, tetrahydrofuran. , Dioxane, methanol, ethanol, isopropyl alcohol, butanol, methyl cellosolve, cellosolve acetate, dimethylformamide, dimethyl sulfoxide, pentane, hexane, cyclohexane,
Organic solvents such as heptane, octane, mineral spirits, petroleum ether, gasoline, benzene, toluene, xylene, chloroform, carbon tetrachloride, perchlorethylene, trichloroethylene and the like can be mentioned. The antifouling composition of the present invention is obtained by dispersing or dissolving the water-swellable polymer and the film-forming polymer in the organic solvent, and the concentration of the obtained liquid composition is solid. About 5 to 50
% Is the preferred range, and the water-swellable polymer and the film-forming polymer are 2 to 200 parts by weight, preferably 5 to 100 parts by weight of the film-forming polymer per 100 parts by weight of the water-swellable polymer.
It is used in the proportion of parts by weight. If the amount of the film-forming resin used is too small, the film-forming property is insufficient. On the other hand, if the amount is too large, the viscosity becomes high and the coatability becomes insufficient, which is not preferable.

The antifouling agent composition of the present invention contains the above-mentioned three components as essential components, and further includes anionic, cationic, nonionic surfactants, colorants, antistatic agents, perfumes, ultraviolet absorbers, stabilizers. Additives such as a foaming agent, various alkaline agents and acid agents can be added.

The antifouling agent composition of the present invention as described above comprises a dipping method,
The surface of the article to be protected is coated by a usual coating method such as spraying, brush coating, or roll coating. Particularly in the case of an article having a complicated surface shape, the dipping method or the spray method is preferable.

After coating, the organic solvent is evaporated by natural drying or heat drying to form a film. Then, when the coated article is used, it may be used as it is, but when it is necessary to peel it, it may be peeled as it is, preferably immersed in water or sprayed with water. When water is applied to the coating film, the coating film expands rapidly to facilitate peeling, and the coating film naturally separates and can be peeled easily and uniformly by hand. At this time, as described above, it is possible to neutralize at the time of peeling to prevent the coating film from getting wet.

Articles to which the antifouling agent composition and the method for preventing pollution of the present invention can be applied are not particularly limited, for example, glass, plastics, iron materials, steel materials, stainless steel, aluminum materials, concrete, tiles, ceramics, and the shape thereof. It may be a spherical, plate-shaped, or rod-shaped molded product, and is particularly effective for protecting articles having irregularities or complicated shapes and preventing contamination.

(Effect) According to the present invention as described above, an antifouling agent composition containing the water-swellable polymer and the film-forming polymer in a liquid medium is used to protect a protected article from contamination. After forming a film on the surface, if water is applied to the film at the time of peeling the film, the film swells with water and can be easily peeled off, and can be easily peeled off without damaging the surface of the article to be protected.

In particular, the specific block polymer-type or graft polymer-type water-swellable polymer which is preferably used in the present invention has both a lipophilic segment and a hydrophilic segment, so that it is both a lipophilic article and a hydrophilic article. Since it can be easily peeled off without being firmly adhered, it can be applied together.

(Example) Next, the present invention will be specifically described with reference to examples. In the text, parts and% are based on weight unless otherwise specified.

Example 1 8 parts of a polymerizable polystyrene having a terminal metacloyl group (a molecular weight of about 10,000), 12 parts of a polymerizable polybutyl acrylate having a terminal metacloyl group (a molecular weight of about 7,000) and 80 parts of sodium acrylate were copolymerized. A product obtained by finely dispersing the obtained water-swellable polymer in a mixed solvent system of cyclohexane-toluene-methanol to 1 to 5 μm (degree of water swelling is about
100 times, solid content 30%) 38 parts, 20% Asaprene T-431 solution
57 parts, 5 parts of process oil, 250 parts of kerosene and a small amount of perfume were mixed to obtain an antifouling composition of the present invention.

After coating the antifouling agent composition on the blade of a ventilation fan (made of polypropylene) and drying it, after actually using it for 1 month, it was wetted with water to swell the film and peeled it off. A surface that was easily peeled off and completely free of contamination appeared.

Example 2 Dispersion of carboxylic acid-free water-swellable polymer which is the same polymer as used in Example 1 (solid content 30%) 72.8 parts, 20%
27.2 parts of a chloroprene toluene solution and 100 parts of methyl ethyl ketone were mixed to obtain an antifouling composition of the present invention.

The composition was applied by spraying on the surface of an aluminum mold and dried to form a film. After leaving it for 1 month in that state, it was immersed in a 10% aqueous solution of sodium acetate for about 1 hour and washed with water. The coating swelled and was easily peeled off, and a surface not contaminated at all appeared. Example 3 Cross-linked sodium polyacrylate 5 parts of powder (150 mesh pass, 300 times water swelling) 20% polyvinyl acetate toluene solution 9
5 parts were mixed to obtain an antifouling composition of the present invention.

Using the above composition in the same manner as in Example 1,
Similar to Example 1, an excellent antifouling effect was obtained.

Claims (4)

[Claims] 1. A water-swellable polymer selected from a block or graft copolymer having a hydrophobic segment and a hydrophilic segment and a cross-linked hydrophilic polymer, and a film-forming polymer in a solvent and a solvent. Or an antifouling agent composition characterized by being dispersed. 2. The antifouling composition according to claim 1, wherein the water-swellable polymer has an ionic hydrophilic group, and the ionic group is free or salt-forming. 3. A water-swellable polymer selected from a block or graft copolymer having a hydrophobic segment and a hydrophilic segment and a crosslinked hydrophilic polymer, and a film-forming polymer are dissolved in a liquid medium and Alternatively, a method for preventing pollution, which comprises applying the antifouling composition that is dispersed to the surface of an object to be protected, drying the film, and then peeling off the coating film formed during use. 4. The method for preventing contamination according to claim 3, wherein the coating film is swollen or neutralized at the time of peeling.