JPH0768545B2 - Detergent composition and cleaning method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a cleaning composition and a cleaning method, and more particularly to a cleaning method capable of efficiently and completely removing contamination such as inside fine cracks and narrow corners. The present invention relates to an agent composition and a cleaning method.

(Prior Art and Its Problems) Conventionally, it has been common to mainly use a surfactant as a method for cleaning an article soiled with oil, dust, dirt, paint, ink, etc. There is a problem that it is very difficult to remove contaminants such as fine cracks existing on the surface of an article and corners of a complicated shape.

Therefore, an object of the present invention is to provide a technique for effectively and completely removing dirt that is difficult to remove.

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

That is, the present invention is a cleaning composition comprising a water-swellable polymer and a film-forming resin dissolved or dispersed in a liquid medium, and a cleaning method using the composition.

(Function) When a coating composition is formed on the surface of a contaminated article to be cleaned by using a detergent composition containing a water-swellable polymer and a film-forming resin in a liquid medium, the coating will form fine particles of the article. Spreads in cracks and every corner. After that, preferably when water is applied to the above film, the film swells with water and can be easily peeled off, and it can be easily peeled off while adhering contaminants to the surface, so that it is extremely easy to contaminate inside fine cracks and corners. Can be removed.

In particular, the specific block polymer-type or graft polymer-type water-swellable polymer preferably used in the present invention has both a lipophilic segment and a hydrophilic segment, and therefore both oily and hydrophilic stains are present. It can be effectively removed.

(Preferred Embodiment) The water-swellable polymer used in the present invention is a polymer that absorbs water and expands when contacted with water, but does not dissolve in water, and its swelling degree is generally 2 To about 1,000 times, with 5 to 500 sites being preferred. 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, partially crosslinked sodium poly (meth) acrylate, alkali neutralized product of crosslinked isobutylene-maleic anhydride copolymer, sodium salt of crosslinked carboxymethyl cellulose, crosslinked polyethylene oxide, polyoxyethylene chain-containing polyurethane, etc. Therefore, 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, thioglycolic acid, maleic 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 high water solubility, and if it is too large, the water swellability will be insufficient, so the preferred average molecular weight range is 1,000 to 20,000, preferably 1,500 to 15,0
The range is 00. 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. These block copolymers or graft copolymers have an affinity for lipophilic substances (contamination) in their lipophilic segments and also have an affinity for hydrophilic substances (contamination) due to their hydrophilic segments, so that they can be used for various types of contamination. It is possible.

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. 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. The above-mentioned polymer may be neutralized at the time of synthesis as described above, or may be made to exhibit a high degree of swelling by neutralization after coating or washing.

The water-swellable polymer used in the present invention preferably has an average particle size of 100 μm or less, but those giving more preferable results are those having an average particle size of 20 μm or less. If the particle size is too large, cleaning of fine cracks and corners becomes insufficient.

The film-forming resin used in the present invention may be any conventionally known film-forming resin, but particularly preferably a hydrophobic elastic material, for example, natural rubber, polyisoprene,
Butyl rubber, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, polychlorobrene, ethylene-propylene copolymer, acrylic rubber, ethylene-vinyl acetate copolymer, polyvinyl butyral resin,
Any known material having rubber elasticity, such as a silicone resin or a urethane polymer, may be used.

The detergent composition of the present invention is prepared by dissolving or dispersing the water-swellable polymer and the film-forming resin 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 acetoate, dimethylformamide, dimethyl sulfoxide, pentane, hexane, cyclohexane, heptane, octane, mineral spirits, petroleum ether, gasoline, benzene, toluene, xylene, chloroform. , Organic solvents such as carbon tetrachloride, perchlorethylene and trichlorethylene.

The detergent composition of the present invention is obtained by dispersing or dissolving the water-swellable polymer and the film-forming resin in the organic solvent, and the concentration of the obtained liquid composition is about solid. The preferred range is 5 to 50% by weight, and the water-swellable polymer and the film-forming resin are water-swellable polymer.
The film-forming resin is used in an amount of 2 to 200 parts by weight, preferably 5 to 100 parts by weight, per 0 parts by weight. When 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 releasability becomes insufficient, which is not preferable.

The detergent composition of the present invention contains the above-mentioned three components as essential components, but it is possible to further use an anionic, cationic, nonionic or other surfactant in order to further improve the cleaning ability. By further adding a small amount of dye / pigment, the peeled state can be easily confirmed with the naked eye after peeling the coating film. Further, if necessary, a small amount of a water-soluble resin, an antistatic agent, a fragrance, an ultraviolet absorber, unless the object of the present invention is hindered.
Additives such as stabilizers, foaming agents, various alkaline agents and acid agents can be added.

The cleaning composition of the present invention as described above is obtained by the dipping method,
The surface of the article to be cleaned 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, a dipping method or a spray method is preferable.

After coating, the organic solvent is evaporated by natural drying or heat drying to form a film. Then, when peeling it off, it may be peeled as it is, but preferably by immersing in water or spraying water to attach water, the coating film expands rapidly and peels easily, In addition to being naturally separated, it can be easily and uniformly separated by hand. At this time, as described above, it is possible to neutralize during washing so as to have a high swelling property. In particular, since the water-swellable polymer in the composition of the present invention does not dissolve in water and has almost no components that dissolve in the wash water, the advantage that the post-treatment of the used water is simply filtration is required. is there.

By peeling the coating film as described above, all the contaminants attached to the surface of the article to be cleaned are removed together with the coating film, and an excellent cleaning effect is exhibited. In particular, contamination in fine cracks and complicated corners, which are difficult to clean by the usual method, can be removed very easily.

Articles to which the cleaning composition and cleaning method of the present invention can be applied,
For example, glass, plastic, iron, steel, stainless steel, aluminum, concrete, tiles,
It is not particularly limited to ceramics and the like, and the shape thereof may be any of spherical, plate-like, rod-like moldings, etc., and is particularly effective for cleaning articles having irregularities or complicated shapes.

(Effects) According to the present invention as described above, a film is formed on the surface of a contaminated article to be cleaned by using a detergent composition containing a water-swellable polymer and a film-forming resin in a liquid medium. The coating then extends into the microscopic cracks of the article and into all corners. After that, preferably, when water is applied to the film, the film swells with water and can be easily peeled off, and since the contaminants can be easily peeled off while adsorbed on the surface, it is extremely easy to contaminate inside fine cracks or corners. Can be removed.

In particular, the specific block polymer-type or graft polymer-type water-swellable polymer preferably used in the present invention has both a lipophilic segment and a hydrophilic segment, so that both oily and hydrophilic contaminations are effective. Can be removed.

Further, in the method of the present invention, only water is used for cleaning,
Furthermore, almost no component is dissolved in the water used, and therefore the post-treatment of the water used is extremely simple and does not pollute the surroundings.

(Example) Next, an Example is given and this invention is demonstrated concretely. In the text, parts and% are based on weight unless otherwise specified.

Example 1 (Polystyrene)-(polybutadiene)-(polystyrene) block copolymer (polystyrene content 30%)
Of water-swellable polymer obtained by adding thioglycolic acid to unsaturated double bond of and neutralizing with caustic soda
The present invention is prepared by mixing 85 parts of 20% cyclohexane / toluene / dioxane dispersion (50 times) (average particle size 0.1 μm) and 20% xylene solution of butyl 268 (isoprene-isobutylene rubber, manufactured by Nippon Synthetic Rubber Co., Ltd.). The cleaning composition of was obtained.

A polyamide-nitrified cotton type resin and phthalocyanine blue were placed in a ball mill and dispersed to form an ink. After the ink was taken out, the ball (30 to 40 mm in diameter) was rotated together with the above cleaning composition in a ball mill container for about 1 hour, and then put into a 50th Saran net to separate the ball.
The excess solvent adhering to the ball is naturally air dried, and after drying it is immersed in water to swell the coating on the ball surface, remove the swelling with running water, and dry it. Had been removed.

On the other hand, the balls washed with only the solvent (toluene-methyl ethyl ketone-isopropyl alcohol) by the same method had a blue color remaining in the fine streaks on the surface, and a pale blue color remained as a whole, and the cleaning was incomplete.

Example 2 80 parts of a water-swellable polymer obtained by graft-polymerizing 20 parts of a polymerizable polystyrene having a terminal methacroyl group (molecular weight of about 6,000) with sodium acrylate was mixed with a mixed solvent system of cyclohexane-kerosene-methanol. Finely dispersed to a particle size of 0.5 to 1.0 μm (water swelling degree about 60 times, solid content 25%) 70.6
Parts and 29.4 parts of 15% acrylic rubber solution (Teisan rubber # 5001, manufactured by Teikoku Kagaku) were mixed to obtain a cleaning composition of the present invention.

When the above cleaning composition was applied to the blade of a ventilation fan (made by Polypro) that was soiled with oil and treated in the same manner as in Example 1, the ventilation fan was completely cleaned and became clean.

Example 3 8 parts of a polymerizable polystyrene having a terminal metacloyl group (molecular weight of about 10,000), 12 parts of a polymerizable polybutyl acrylate having a terminal metacloyl group (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% Asablene T-431 solution
57 parts, 5 parts of process oil, 250 parts of kerosene and a small amount of perfume were mixed to obtain a cleaning composition of the present invention.

After the above-mentioned cleaning composition of the present invention was applied by spraying and air-dried to a window glass soiled with dirt, dust, etc., the surface was swollen by spraying water on the surface, and the film was peeled off from the glass in a dusty state. Contamination such as was taken into the peeled film and the glass was thoroughly washed.

Example 4 A detergent was prepared in the same manner as in Example 2 except that the water-swellable polymer in Example 2 was replaced with partially crosslinked sodium polyacrylate, and the detergent was applied to an oil-stained Polypropylene ventilation fan and air-dried. Let After swelling the formed film with water, the film was removed with running water. As a result, the oil stains on the ventilation fan were almost clean.

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Claims (6)

[Claims] 1. A detergent composition comprising a water-swellable polymer and a film-forming resin dissolved and / or dispersed in a liquid medium. 2. The film-forming resin is an elastic resin.
The cleaning composition according to. 3. The detergent composition according to claim 1, wherein the water-swellable polymer has an ionic hydrophilic group, and the ionic group is free or salt-forming. 4. The detergent composition according to claim 1, wherein the water-swellable polymer is a block or graft copolymer of a hydrophobic segment and a hydrophilic segment. 5. A cleaning composition formed by dissolving and / or dispersing a water-swellable polymer and a film-forming resin in a liquid medium is applied to the surface of an object to be cleaned and dried, and then the formed film is formed. A cleaning method characterized by peeling. 6. The cleaning method according to claim 5, wherein the coating film is swollen with water at the time of peeling.