JP2001200240A - Antifoulant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a antifoulant composition which gives a high antifoulancy on a surface of an outer wall of an outdoor building, an automobile body, other items or the like with an easy and simple method. SOLUTION: The antifoulant composition contains (A) a silica sol whose colloid particle has a shape of chain. The chain shaped colloid particle has an average length of about 40-200 nm. The antifoulant composition may contain a copolymer (B) of a hydrophobic vinyl monomer and an aliphatic unsaturated carboxylic acid salt. The copolymer (B) contains a copolymer of at least one hydrophobic vinyl monomer selected from the group consisting of a styrene monomer, an olefin monomer and a vinyl ether monomer and at least one aliphatic unsaturated carboxylic acid salt selected from the group consisting of a salt of maleic acid or a half ester of it and (meth)acrylic acid salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling agent composition, and more particularly, to imparting antifouling properties to the surface of outdoor buildings, automobile bodies, mechanical equipment, various articles, etc., or their coating films. The present invention relates to an antifouling agent composition and a wet tissue-type antifouling cleaner containing the antifouling agent composition.

[0002]

2. Description of the Related Art Dust floating in the air and dust accumulated on the roof of an outdoor building are carried or washed away by rain, and the outer wall of the outdoor building, the body of an automobile, the surface of a mechanical device, or the like. Flow down. As a result, contaminants adhere to the outer walls and other surfaces along the path of rainwater, and when the surface dries,
Dirt such as stripes appears there.

[0003] Japanese Patent No. 2756474 discloses that a photocatalytic film containing a photocatalytic semiconductor material such as titanium oxide and silica is formed on the surface of a base material, and the film is made hydrophilic by photoexcitation of the photocatalytic semiconductor material. There is disclosed a technique for expressing the material and thereby preventing contamination of the base material. However, this method requires special undercoating or special techniques such as high-temperature baking, so that not only is the operation and operation complicated, but the surface does not become hydrophilic unless exposed to light, and the desired There is a disadvantage that the effect is not exhibited.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an antifouling agent composition capable of imparting a high antifouling property to the outer wall of an outdoor building, the body of an automobile, or the surface of various articles by a simple method. Is to provide. Another object of the present invention is to provide an antifouling agent composition having high wettability to water and capable of easily washing off contaminants attached to the surface of a building or the like with water. Still another object of the present invention is to provide
An object of the present invention is to provide an antifouling composition having excellent gloss and weather resistance. Another object of the present invention is to provide a wet tissue-type anti-fog cleaner capable of forming an anti-fog coating having high anti-fouling properties on an object to be applied uniformly by a simple operation without unevenness.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result of using the silica sol having a specific shape of colloidal particles, it was found that the coating film on the outer wall of a building or the body of an automobile was used. It has been found that dirt can be prevented from adhering to the surface and the like, and even if dirt adheres, it can be easily removed with water, and the present invention has been completed.

That is, the present invention provides an antifouling agent composition characterized in that the colloidal particles contain a chain-like silica sol (A). The average length of the chain colloidal particles is about 40 to 200 nm. This antifouling agent composition may further include a copolymer (B) of a hydrophobic vinyl monomer and an aliphatic unsaturated carboxylate. The antifouling agent composition containing such a copolymer (B) has remarkably high antifouling performance and excellent gloss and weather resistance. The copolymer (B) includes at least one hydrophobic vinyl monomer selected from a styrene monomer, an olefin monomer and a vinyl ether monomer, and maleic acid or a half ester thereof. And a copolymer with at least one kind of aliphatic unsaturated carboxylate selected from salts and (meth) acrylates. The amount of the copolymer (B) is about 20 to 1000 parts by weight based on 100 parts by weight of the nonvolatile matter of the silica sol (A). The copolymer (B)
Is particularly excellent in terms of antifouling properties, gloss, weather resistance and the like.

[0007] The antifouling agent composition is further selected from a nonionic surfactant (C), an anionic surfactant (D), a water-absorbing polymer material (E), and a spherical silica sol (F). It may contain at least one type of component.
According to the antifouling agent containing such a component, the above-mentioned various properties can be further improved. Preferred nonionic surfactants (C) include at least one nonionic surfactant having an HLB in the range of 4.0 to 16.0 and at least one nonionic surfactant selected from polyoxyethylene polyoxypropylene block copolymers. An ionic surfactant is included. The present invention
Further, there is provided a wet tissue type antifouling cleaner in which a nonwoven fabric is impregnated with the above antifouling agent composition.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The features of the antifouling composition of the present invention are as follows.
The point is that the colloidal particles contain a chain-like silica sol (A) as an essential component instead of a spherical shape. In such an antifouling agent containing a silica sol (A) in which the colloid particles have a chain shape, compared with the case of using a normal silica sol in which the colloid particles are spherical, the adhesion to the object and the abrasion resistance are improved. It is excellent in water resistance, and the formed film has very high hydrophilicity, so that it is possible to prevent contaminants such as dust from adhering to the surface, and even if contaminants adhere to the surface, it is easily washed away with water. be able to.

The average length of the chain colloidal particles may be within a range that does not impair the dispersibility and the like.
nm, preferably about 40 to 200 nm. Further, the thickness of the chain colloidal particles is, for example, 5 to 20 n.
m.

The dispersion medium constituting the silica sol is not particularly limited as long as it is a solvent capable of dispersing silica in a colloidal form. For example, water; methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol,
Examples thereof include alcohols such as ethylene glycol; hydrocarbons such as toluene and xylene; and mixed solvents thereof. Water or an aqueous solvent containing water is preferable from the viewpoint of safety and the like.

[0011] Silica sol (A) having colloidal particles in the form of a chain is commercially available. For example, trade names "Snowtex-UP" and "Snowtex-OUP" (both of which are listed below)
Nissan Chemical Industries, Ltd.) can be used. The content of silica in the silica sol is usually about 1 to 40% by weight, preferably about 10 to 30% by weight.

The content of the silica sol (A) in the antifouling agent composition can be appropriately selected according to the purpose of use, the method of use, the place of use, and the like. Is usually about 0.001 to 20% by weight, preferably about 0.005 to 10% by weight.

In a preferred embodiment of the present invention, a copolymer of the silica sol (A) in which the colloid particles have a chain shape, a hydrophobic vinyl monomer (b1) and an aliphatic unsaturated carboxylate (b2) is used. (B) is used in combination. When these components are combined, the antifouling property and weather resistance are further improved, and the surface gloss of the coating is significantly improved.

The copolymer (B) of the hydrophobic vinyl monomer (b1) and the aliphatic unsaturated carboxylate (b2) is the same as the hydrophobic vinyl monomer (b1) and the aliphatic unsaturated carboxylate (b2). It does not mean only a polymer obtained by polymerizing a saturated carboxylate (b2), but also a structural unit corresponding to a hydrophobic vinyl monomer (b1) and an aliphatic unsaturated carboxylic acid as a structural unit of the polymer. It means a copolymer having a structural unit corresponding to the salt (b2).

The hydrophobic vinyl monomer (b1) constituting the copolymer (B) is not particularly limited as long as it is a hydrophobic polymerizable vinyl compound.
For example, styrene monomers such as styrene, α-methylstyrene, and vinyl toluene; olefin monomers such as ethylene, propylene, isobutylene, and 1-pentene;
And vinyl ether monomers such as vinyl methyl ether. The hydrophobic vinyl monomers (b1) can be used alone or in combination of two or more.

The aliphatic unsaturated carboxylate (b)
2) As aliphatic unsaturated dicarboxylic acids such as maleic acid, itaconic acid and citraconic acid or half esters thereof (for example, alkyl esters such as methyl ester, ethyl ester, isopropyl ester and butyl ester; cycloalkyl such as cyclohexyl ester) Alkyl esters; aryl esters such as phenyl esters; aralkyl esters such as benzyl esters); salts of aliphatic unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid.

Examples of the salt include ammonium salts; salts with amines such as methylamine, ethylamine, diethylamine, triethylamine, morpholine, pyrrolidine, piperidine, ethanolamine, diethanolamine and triethanolamine; and alkali metals such as lithium, sodium and potassium. And salts of alkaline earth metals such as magnesium and barium. Among these salts, ammonium salts and salts with amines are preferred.

The aliphatic unsaturated carboxylate (b2) can be used alone or in combination of two or more. Preferred aliphatic unsaturated carboxylate salts include salts of maleic acid or its half esters, salts of (meth) acrylic acid, and the like.
The copolymer (B) contains the hydrophobic vinyl monomer (b
1) It may contain a small amount of a structural unit corresponding to a monomer other than the aliphatic unsaturated carboxylate (b2).

As specific examples of the copolymer (B), for example,
Copolymer of styrene-based monomer such as styrene-maleate copolymer, styrene-maleic acid half-ester salt copolymer and aliphatic unsaturated dicarboxylic acid or half-ester salt thereof; ethylene- (meth) Copolymers of olefin monomers such as acrylate copolymers and salts of aliphatic unsaturated monocarboxylic acids; isobutylene-maleate copolymers, isobutylene-maleic acid half-ester salt copolymers and the like Copolymers of olefin monomers and aliphatic unsaturated dicarboxylic acids or salts of half esters thereof; vinyl ethers such as vinyl methyl ether-maleate copolymer and vinyl methyl ether-maleic acid half ester salt copolymer Copolymers of a system monomer and a salt of an aliphatic unsaturated dicarboxylic acid or a half ester thereof are exemplified.

The composition ratio of the hydrophobic vinyl monomer (b1) and the aliphatic unsaturated carboxylate (b2) in the copolymer (B) varies depending on the combination of the monomers. ) / Latter (b2) (molar ratio) = 5 / 95-95 /
5, preferably about 30/70 to 90/10, and more preferably about 60/40 to 85/15. The weight average molecular weight of the copolymer (B) is generally from 1000 to 100.
000, preferably about 1,000 to 10,000.
The carboxyl group in the copolymer (B) may be completely neutralized or partially neutralized.

The copolymer (B) can be produced by a conventional or known method. For example, the copolymer (B) comprises (i) an aliphatic unsaturated carboxylic acid (aliphatic unsaturated carboxylic acid) corresponding to the hydrophobic vinyl monomer (b1) and the aliphatic unsaturated carboxylic acid salt (b2). Dicarboxylic acid, aliphatic monocarboxylic acid, etc.) and then neutralizing the carboxyl group by adding a base such as ammonia, amine, alkali metal hydroxide, alkaline earth metal hydroxide, (Ii) the hydrophobic vinyl monomer (b1) and an aliphatic unsaturated carboxylic acid anhydride (such as an aliphatic unsaturated dicarboxylic acid anhydride) corresponding to the aliphatic unsaturated carboxylic acid salt (b2) After copolymerization, the acid anhydride group is converted to 2 by hydrolysis or alcoholysis.
A method of converting one carboxyl group or one carboxyl group and one ester group and then adding the base to neutralize the carboxyl group (if the hydrolysis is performed with a base, it is not necessary to add a base) Etc.

The amount of the copolymer (B) used varies depending on the type of the polymer, but it is 0 to 1000 parts by weight, preferably 20 to 1000 parts by weight, based on 100 parts by weight of the nonvolatile matter of the silica sol (A). More preferably, 50 to 50
It is about 0 parts by weight. When the amount of the copolymer (B) is 100
If the amount exceeds 0 parts by weight, the transparency and water resistance of the coating tend to decrease.

The antifouling composition of the present invention is further selected from a nonionic surfactant (C), an anionic surfactant (D), a water-absorbing polymer material (E) and a spherical silica sol (F). At least one of the components described above.

The nonionic surfactant (C) includes, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether (preferably polyoxyethylene C _8-18 alkyl ether); polyoxyethylene oleyl ether and the like. Polyoxyethylene alkenyl ethers; polyoxyethylene alkylaryl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether and polyoxyethylene dodecyl phenyl ether (preferably polyoxyethylene C _8-12 alkyl phenyl ether) Polyoxyethylene lanolin alcohol ether; polyoxyethylene sorbitan monolaurate;
Polyoxyethylene sorbitan fatty acid esters (preferably polyoxyethylene sorbitan mono C _10-20 fatty acid esters) such as polyoxyethylene sorbitan monopalmitate and polyoxyethylene sorbitan monooleate; polyoxyethylene oleate, polyoxyethylene stearate , Polyoxyethylene fatty acid esters such as polyoxyethylene distearate (preferably polyoxyethylene _C12-18 fatty acid esters); polyoxyethylene hydrogenated castor oil; polyoxyethylene polyoxypropylene block copolymer; glycerin monostearate Glycerin fatty acid esters; sorbitan fatty acid esters such as sorbitan monostearate; sucrose fatty acid esters such as sucrose stearic acid ester; Fatty acid alkanolamides, such as acid diethanolamide; and cellulose ethers and the like.

Among these nonionic surfactants,
Polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene alkyl ether, sorbitan monolaurate and the like are preferred. These are commercially available, for example, trade names "Epan U-103" (Daiichi Kogyo Seiyaku Co., Ltd.), trade names "Neugen ET-97" (Daiichi Kogyo Seiyaku Co., Ltd.), trade names " REODOL SP-L1
0 "(manufactured by Kao Corporation) and the like. The nonionic surfactant (C) can be used alone or in combination of two or more.

The HLB of the nonionic surfactant (C) is as follows:
For example, 4.0-16.0, preferably 6.0-13.
0, and more preferably about 7.0 to 9.5. When the HLB of the nonionic surfactant is less than 4.0, the solubility in silica sol using water as a dispersion medium is reduced, and the nonionic surfactant is easily separated into an oil. If the HLB exceeds 16.0, the effect of addition becomes small.

The preferred nonionic surfactant (C), even if the HLB is unknown, includes a polyoxyethylene polyoxypropylene block copolymer. In this polyoxyethylene polyoxypropylene block copolymer, the balance between hydrophilicity and hydrophobicity is adjusted by changing the content of polyoxyethylene (hydrophilic part) and polyoxypropylene (hydrophobic part). The polyoxyethylene polyoxypropylene block copolymer has a polyoxyethylene content of 10 to 80.
It is preferably about mol%, more preferably 20 to 50 mol%. The polyoxyethylene content is 10 mol%
If it is less than 10, the solubility in water becomes poor.
If it exceeds mol%, the water solubility becomes too high and water resistance tends to be poor.

When the nonionic surfactant (C) is added to the antifouling agent composition, coatability, water retention, water resistance, and durability of the antifouling performance are further improved. The amount of the nonionic surfactant (C) to be used is generally 0 to 50 in terms of the active ingredient, based on 100 parts by weight of the nonvolatile matter of the silica sol (A).
0 (for example, about 5 to 500 parts by weight), preferably 30 to
It is about 300 parts by weight. If the amount of the nonionic surfactant (C) exceeds 500 parts by weight, the transparency, scratch resistance and water resistance of the coating tend to decrease.

Examples of the anionic surfactant (D) include aliphatic monocarboxylates such as sodium laurate, N-acyloyl glutamates such as sodium lauryloylglutamate, and alkylbenzenesulfonic acids such as sodium dodecylbenzenesulfonate. Salt, naphthalene sulfonate-formaldehyde condensate, dialkyl sulfosuccinate such as sodium di (2-ethylhexyl) sulfosuccinate, alkyl sulfate such as sodium dodecyl sulfate, alkyl polyoxyethylene sulfate such as dodecyl polyoxyethylene sulfate And alkyl phosphates such as sodium monolauryl phosphate. The anionic surfactant (D) can be used alone or in combination of two or more.

When the anionic surfactant (D) is added to the antifouling composition, the dispersibility and coating properties of the nonionic surfactant (C) are improved. The amount of the anionic surfactant (D) to be used is usually 0 to 100 parts by weight of the nonvolatile matter of the silica sol (A) in terms of the active ingredient.
The amount is 200 parts by weight (for example, about 5 to 200 parts by weight), preferably about 10 to 100 parts by weight. When the amount of the anionic surfactant (D) exceeds 200 parts by weight, the transparency, scratch resistance and water resistance of the coating are liable to decrease.

Examples of the water-absorbing polymer material (E) include polyoxyalkylene (for example, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, polytetramethylene glycol, etc.),
Poly N-vinylacetamide, polyacrylate, starch-acrylic acid graft copolymer, vinyl alcohol-maleic acid copolymer, saponified vinyl acetate-acrylic ester copolymer, isobutylene-maleic acid copolymer, poly Examples include saponified acrylonitrile, starch-acrylonitrile graft copolymer, carboxymethylcellulose, and derivatives thereof. The water-absorbing polymer materials (E) can be used alone or in combination of two or more.

When the water-absorbing polymer material (E) is added to the antifouling agent composition, coatability, antifouling property, water retention, water resistance and the like are improved. The amount of the water-absorbing polymer material (E) to be used is generally 0 to 500 parts by weight (for example, about 0.5 to 500 parts by weight), preferably 100 parts by weight of the nonvolatile matter of the chain silica sol (A). Is about 5 to 200 parts by weight.

In the silica sol (F) having a spherical colloidal particle shape, the average particle size of the colloidal particle is, for example, 4 from the viewpoint of the stability of the antifouling agent composition and the transparency of the coating film.
About 100 nm, preferably about 4 to 20 nm. Spherical silica sol (F) is commercially available, for example, trade names “Snowtex 20”, “Snowtex XS”, “Snowtex AK”, “Snowtex C” (all manufactured by Nissan Chemical Industries, Ltd.) Etc. can be used.

When the spherical silica sol (F) is added to the antifouling agent composition, scratch resistance and the like are improved. The amount of the spherical silica sol (F) to be used is usually 0 to 100 parts by weight of the nonvolatile content of the chain silica sol (A).
It is about 50 parts by weight (for example, about 0.5 to 50 parts by weight), preferably about 1 to 30 parts by weight.

The antifogging agent composition of the present invention may contain, in addition to the components described above, if necessary, a range within which the effects of the present invention are not impaired.
Other components, for example, cationic surfactants, amphoteric surfactants, pH adjusters, inorganic substances other than silica, organic electrolytes, dispersants, antioxidants, ultraviolet absorbers, weathering agents, preservatives, defoamers Agent and a resin other than the component (E).

In the antifouling composition of the present invention, the colloidal particles are added to a chain-like silica sol (A), and if necessary, the above (B) to (B).
It can be prepared by adding and mixing the component (F) and other components, and a solvent (for example, the solvent exemplified above) for adjusting the concentration to a desired concentration.

The object to which the antifouling agent composition of the present invention is applied is not particularly limited as long as pollutants such as dust and refuse easily adhere thereto.
Examples include outdoor buildings, building outer walls, automobile bodies, mechanical equipment, and various articles. The material of these objects to be applied is, for example, plastic, ceramic, glass, metal or the like, and the surface may be coated with a coating film such as a paint.

According to the present invention, after applying the antifouling agent composition to the object without requiring a complicated operation such as baking,
The hydrophilic antifouling coating can be formed by a simple method of drying. As a method of applying the antifouling agent composition, a conventional coating method, for example, a roll coating method,
Dip coating, brush coating, spray coating, bar coating, knife coating, and the like can be used. Further, it can be applied to an object to be applied with a nonwoven fabric impregnated with an antifouling composition.

The wet tissue type antifouling cleaner of the present invention is obtained by impregnating a nonwoven fabric with the antifouling agent composition of the present invention. The non-woven fabric is not particularly limited as long as it is a sheet-like material obtained by arranging fibers in a web shape, a mat shape, or the like, and bonding the fibers with each other by an adhesive or a fusion force of the fibers themselves. It may be obtained by any method such as the method. The fibers constituting the nonwoven fabric include acrylic fibers such as polyacrylonitrile fibers, polyester fibers such as polyalkylene glycol terephthalate fibers, polyamide fibers, polyurethane fibers, polyurea fibers, polyolefin fibers, polyolefin fibers, and polystyrene fibers. Synthetic fiber such as vinyl chloride fiber, polyvinylidene chloride fiber, polyfluoroethylene fiber, polyvinyl alcohol fiber, polyvinylidene cyanide fiber; regenerated fiber such as rayon; semi-synthetic fiber such as acetate human silk; cotton, etc. Natural fibers. These fibers can be used alone or in combination of two or more.

Among the above fibers, synthetic fibers are preferable.
In terms of fiber strength, flexibility, thermal properties, water absorption, etc.,
A nonwoven fabric composed of at least one fiber selected from acrylic fibers and polyester fibers is more preferable. In particular, a nonwoven fabric made of an acrylic fiber and a polyester fiber, for example, a nonwoven fabric obtained by mixing an acrylic fiber and a polyester fiber, a nonwoven fabric having a multilayer structure of an acrylic fiber layer and a polyester fiber layer, and the like are preferable. In the nonwoven fabric composed of the acrylic fiber and the polyester fiber, the ratio of both fibers is not particularly limited, but generally, acrylic fiber / polyester fiber (weight ratio) = about 1/99 to 99/1, preferably 30 / 7
About 0 to 99/1, more preferably 60/40 to 95
About / 5.

The length and thickness of the fibers constituting the nonwoven fabric can be appropriately selected within a range that does not impair the applicability, etc. In general, the length of the fibers is about 1 to 50 mm, and the thickness of the fibers is It is about 10 to 100 μm. The nonwoven fabric may have a single-layer structure or a multilayer structure. The basis weight (weight per unit area) of the nonwoven fabric can be appropriately selected within a range that does not impair coatability and the like, and varies depending on the type of fiber and the like.
It is about 60 g / m ² , preferably about 20 to 40 g / m ² .

In the antifouling cleaner, the impregnating amount of the antifouling agent composition may be within a range that does not impair the applicability and the like, but is generally about 3 to 30 g per 1 m ^{2 of} nonwoven fabric.
Preferably, it is about 6 to 20 g. The antifouling cleaner can be manufactured by impregnating a nonwoven fabric of an appropriate size with an antifouling agent composition by a conventional method. The production efficiency can be significantly improved by performing the operation of impregnating the nonwoven fabric in the storage container of the antifouling cleaner.

The antifouling cleaner is put into a distribution process in a form sealed in a storage container (storage bag, storage case, storage can, etc.) in order to avoid drying. In this case, the antifouling cleaner is usually stored in a unit of about 1 to 20 sheets in a folded state or a nori-wound state in consideration of storability, ease of removal, ease of use, and the like. Is stored inside.

The storage container is, for example, polyethylene,
It can be formed of a single or composite material of a plastic film such as polypropylene, polyester, polyamide, polyvinyl chloride, polyvinylidene chloride, cellophane, or a composite material of these with a metal foil such as an aluminum foil, or a metal plate.

As a preferable container for storing the wet tissue type antifouling cleaner, a storage bag made of an airtight sheet substrate (for example, a composite sheet of a plastic film and an aluminum foil) can be mentioned. As a storage bag,
Envelope shape formed by center seal and both ends seal,
Although a pillow-shaped thing is mentioned, what provided the opening-and-closing lid which can be opened and closed repeatedly is preferable.

In a more preferred embodiment of the storage bag, a detachable cut portion for forming an outlet for a wet tissue type antifouling cleaner is provided on one surface of the bag body made of an airtight sheet substrate. An opening / closing lid made of an airtight film is provided to cover the cut portion, and a pressure-sensitive adhesive layer is formed over substantially the entire surface of the opening / closing lid on the bag body side, and the opening / closing lid is formed by the pressure-sensitive adhesive layer. Affixed to the bag body. The cut portion may be formed so as to be partially separable, or may be formed so as to be entirely separable. Further, one end of the opening / closing lid can be fixed to the storage bag by, for example, heat sealing, an adhesive or the like. In such a storage bag, by pulling up the lid while peeling it off from the bag body, a part of the bag body is cut off at the cut portion and pulled up while being adhered to the adhesive layer of the lid. An outlet for the cleaner is formed. Then, the wet tissue-type antifouling cleaner in the bag can be picked up by hand from the outlet and taken out for use, and the opening / closing lid is returned to its original position and adhered to the periphery of the outlet, thereby re-attaching. The inside of the bag can be sealed. According to such a storage bag, since it can be repeatedly opened and closed, only a desired number of sheets can be used when desired, and there is an advantage that sealing properties are excellent.

According to the above-mentioned wet tissue type antifouling cleaner, a hydrophilic antifouling coating can be uniformly and uniformly dispersed by a simple method of quickly wiping it by hand and drying it without complicated work such as baking. Can be formed.

Drying after application of the antifouling composition can be carried out by any of natural drying and forced drying. The application amount of the antifouling agent composition is, for example, 0.00
About 1 to ² g / m ² , preferably 0.005 to 1 g / m ²
It is about.

The antifouling film thus formed has high hydrophilicity and high wettability with water, so that dust containing a large amount of lipophilic components is not easily adhered to the film, and even if it adheres, it is easily washed with water. Can be washed away. Further, it has excellent water resistance and durability, and does not easily peel off even when exposed to running water or rubbed with a finger. Further, in particular, the antifouling agent composition containing the copolymer (B) has excellent gloss on the surface of the coating, high weather resistance, and maintains wettability with water and gloss even when exposed to the outdoors for a long time. Also, damage to the antifouling coating is extremely small.

[0050]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Silica sol having colloidal particles in a chain shape [Snowtex-UP, manufactured by Nissan Chemical Industries, Ltd., silica content 2
0% by weight], 1.5 parts by weight, nonionic surfactant [Epan U-103, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] 0.3 parts by weight (active ingredient: 0.3 parts by weight), anionic interface Activator [Ravanol SF-7K, manufactured by Matsumoto Yushi Co., Ltd.] 0.1 part by weight (active ingredient: 0.04 part by weight), poly N-vinylacetamide aqueous solution (nonvolatile content 10% by weight) [GE-19
1L, manufactured by Showa Denko KK] and 53.1 parts by weight of water to prepare an antifouling composition.

Example 2 2.0 parts by weight of a silica sol having colloidal particles in a chain shape (Snowtex-OUP, manufactured by Nissan Chemical Industries, Ltd., silica content: 15% by weight), a nonionic surfactant [ Epan U-103, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] 0.4 parts by weight (active ingredient: 0.4 parts by weight), anionic surfactant [Ravanol SF-7K, manufactured by Matsumoto Yushi Co., Ltd.] 1 part by weight (active ingredient: 0.04 part by weight), an aqueous solution of poly N-vinylacetamide (nonvolatile content: 10% by weight) [GE-19
1 L, manufactured by Showa Denko KK] 1.5 parts by weight, styrene-maleic acid half ester copolymer resin [SMA1735
2, manufactured by Elf Atochem Japan Ltd.], 2.5 parts by weight of an aqueous solution of an ammonium salt (resin content 20% by weight, completely neutralized with ammonia) and 93.5 parts by weight of water to mix An agent composition was prepared.

Evaluation Test The following evaluation tests were performed on each of the antifouling agent compositions obtained in the above Examples. (Glossiness) A nonwoven fabric made of 90% acrylic fiber / 10% polyester fiber with a basis weight of 30 g / m ² [trade name “Charelia (Part No. C1)
030) ", the Asahi Kasei Co., Ltd.], 1m ² per 11g
It was applied to the painted surface of a coated steel plate which had been impregnated and subjected to acrylic coating (for automobile body) of white, black and blue metallic colors, and was naturally dried at room temperature until the surface was dried to form an antifouling film. The surface gloss of the coating after drying was visually observed, and the gloss was evaluated according to the following criteria. ：: There is no coating unevenness and glossiness of the coating. Δ: There is no coating unevenness but coating is poor. ×: There is coating unevenness and coating is poor.

(Wetness to Water) The antifouling agent composition was applied to the painted surface of a coated steel plate having been subjected to acrylic coating (for an automobile body) in the same manner as in the case of the gloss evaluation.
Until the surface dried, it was air-dried at room temperature to form an antifouling coating. The coated steel sheet thus prepared was temporarily
The contact state of the antifouling agent-coated surface with water when immersed in water at ℃ and pulled up was observed, and the water wettability was evaluated based on the following criteria. ：: A thin water film is formed on the surface, and the state is maintained until drying starts. Δ: A water film is formed on the surface, but gradually flows down. ×: A water film is not formed and repels water.

(Weather resistance) The antifouling agent composition is applied to the painted surface of a coated steel plate having been subjected to acrylic coating (for an automobile body) in the same manner as in the case of the gloss evaluation, and the surface is dried. After drying naturally at room temperature, an antifouling film was formed.
The coated steel sheet thus prepared was exposed outdoors for 5 months, the state of the surface coating was observed, and the weather resistance was evaluated according to the following criteria. ：: There is no decrease in wettability to water and no damage to the film, and the gloss is maintained. は: There is no decrease in wettability to water, but the film is partially damaged. ×: The wettability to water disappears. Or the coating is missing

(Anti-fouling property) The anti-fouling agent composition is applied to the painted surface of a coated steel sheet which has been subjected to an acrylic coating (for an automobile body) in the same manner as in the case of the gloss evaluation, and the surface is dried. Until then, air-drying was performed at room temperature to form an antifouling film.
The coated steel sheet prepared as described above was exposed outdoors for 5 months, and the stained state of the surface was compared with that of an untreated product, and the antifouling property was evaluated according to the following criteria. ：: The amount of stain adhered is clearly smaller than that of the untreated product. ：: The amount of adhered stain is slightly smaller than that of the untreated product. X: There is no difference in the amount of stain attached compared to the untreated product. Table 1 shows the evaluation results.

[0057]

[Table 1]

[0058]

According to the antifouling agent composition of the present invention, an antifouling coating can be easily formed on the outer wall of an outdoor building or the surface of a car body without the need for special techniques. High antifouling property can be provided. Even if contaminants adhere to the surface of the antifouling coating, it can be easily washed away with water. In particular, the antifouling composition containing the silica sol (A) having a specific shape and the specific copolymer (B) has excellent gloss on the surface of the coating film and has high antifouling performance and gloss even when exposed to the outdoors for a long time. Characteristics can be maintained.

Claims (8)

[Claims] 1. An antifouling composition comprising a colloidal particle containing a chain-like silica sol (A). 2. The chain colloidal particles having an average length of 40 to 2
The antifouling agent composition according to claim 1, which has a thickness of 00 nm. 3. The antifouling composition according to claim 1, further comprising a copolymer (B) of a hydrophobic vinyl monomer and an aliphatic unsaturated carboxylate. 4. The copolymer (B) is a styrene monomer,
At least one hydrophobic vinyl monomer selected from an olefin-based monomer and a vinyl ether-based monomer, and at least one selected from a salt of maleic acid or a half ester thereof and a (meth) acrylate salt; The antifouling composition according to claim 3, which is a copolymer with an aliphatic unsaturated carboxylate. 5. The antifouling composition according to claim 3, wherein the copolymer (B) is contained in an amount of 20 to 1,000 parts by weight based on 100 parts by weight of the nonvolatile matter of the silica sol (A). 6. A nonionic surfactant (C),
The protection according to any one of claims 1 to 5, comprising at least one component selected from an anionic surfactant (D), a water-absorbing polymer material (E), and a spherical silica sol (F). Soil composition. 7. The non-ionic surfactant (C) is HLB
Is the at least one nonionic surfactant selected from the group consisting of a nonionic surfactant in the range of 4.0 to 16.0 and a polyoxyethylene polyoxypropylene block copolymer. Composition. 8. A wet tissue type antifouling cleaner comprising a nonwoven fabric impregnated with the antifouling agent composition according to any one of claims 1 to 7.