JP4787479B2 - Antifouling paint, antifouling sheet and method for producing the same - Google Patents

Description

  The present invention relates to an antifouling paint, an antifouling sheet and a method for producing the same.

  In recent years, various functional materials have been developed and applied to a wide range of fields. Conventionally, as a pollution prevention treatment method, a method of forming a pollution prevention coating film on the surface of an article such as a building, a building material material, a vehicle, or civil engineering using a pollution prevention coating has been carried out. In particular, fluorine resins, silicone resins, acrylic resins, urethane resins, copolymers thereof, and the like are used as coating film forming components of antifouling paints because of their excellent durability. However, antifouling coatings formed from these paints, when exposed to the outdoors for a long time, deteriorated due to ultraviolet rays in the natural environment, resulting in a decrease in gloss, occurrence of cracks in the coating, and water resistance deterioration due to rain ( There is a problem that the surface of the coating film changes, such as hydrolysis degradation), adhesion of oil components and the like, and contamination by rainwater. In the antifouling treatment method for solving these problems, in “Super water / oil repellent surface by fractal structure” of Non-Patent Document 1, wetting factor is formed by forming a fine uneven structure on the coating film surface. It has been introduced that it imparts water and oil repellency to the coating. However, it is very difficult to apply the coating material to the article to develop the above-described functions with the current coating technique.

  In addition, paints containing fluororesins that are soluble in organic solvents and contain reactive groups are used as antifouling paints for many buildings, building materials, vehicles, and machines (Patent Documents 1 and 2). However, as described above, the coating film made of these anti-contamination paints has the problem of durability due to ultraviolet rays and the problem that oil component adhesion and streak-like contamination due to rainwater occur. Further, in Non-Patent Document 2, it is considered that the fluororesin generates highly toxic carbonyl fluoride, perfluoroisobutylene, hydrogen fluoride, and the like due to the generation of polymer fume heat and thermal decomposition, and is highly toxic to the human body. Similarly, telomers that are fluorine compounds are the same, and in addition, safety to the human body has not been confirmed.

JP-A-61-57609 Japanese Patent Laid-Open No. 63-183212 Magazine "Surface" vol. 35 No. 12 (1997) 9-19 Fluoropolymer Product Handling Manual, May 2000, pages 15, 16 (Japan Fluoropolymer Industry Association)

  Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art and provide a pollution prevention paint, a pollution prevention sheet, and a method for producing the same, which exhibit long-term pollution prevention performance.

The above object is achieved by the present invention described below. That is, the present invention provides a colloidal silica sol, which is formed by using a basic catalyst (A) and the hydrophilic polymer (B) contains as an essential component, the colloidal silica sol (A) is a methylation or ethyl silicate oligomer The composition formula of the raw material is SiO _n (OH) _m (OR) _o (n = 1.5 to 1.95, m = 0.1 to 1.0, o = 0 to 0.5, n + 0.5 m + 0 .5o = 2.0 and a ratio, wherein R is Turkey Roidarushirika which have a large number of silanol groups (-Si-OH) on the front surface of Ru indicated by CH ₃ or C ₂ H ₅₎ To provide anti-pollution paint.

In pollution paints of the present invention, the silica of the colloidal silica sol (A) is a silica content of 6%, it is ultra fine particles of average particle size 1 nm to 1 nm; colloidal silica sol (A) silica in The use ratio (mass ratio) of the hydrophilic polymer (B) is preferably silica: hydrophilic polymer = 5: 95 to 99: 1.

  In the antifouling paint of the present invention, the hydrophilic polymer (B) is polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, modified polyvinyl pyrrolidone, hydrophilic acrylic polymer, hydrophilic urethane polymer, cellulose compound, water-soluble compound. At least one selected from reactive nylon, polyvinyl formal, polyvinyl acetal and polyvinyl benzal; and further comprising at least one selected from the group consisting of alumina sol, surfactant, ultraviolet absorber and cross-linking agent; The agent is preferably at least one selected from the group consisting of carbodiimide compounds, organometallic complex compounds, polyisocyanate compounds, oxazoline compounds and epoxy compounds.

Further, the present invention provides a pollution control sheet comprising a base sheet and a pollution control layer provided on one surface of the base sheet, wherein the pollution control layer is formed from the pollution control paint of the present invention. A pollution control sheet is provided. In the pollution prevention sheet of the present invention, the contact angle of the pollution prevention layer with respect to water is preferably 20 degrees or less; and the thickness of the pollution prevention layer is preferably 0.01 μm to 10 μm.
In addition, the present invention provides a method for producing a pollution control sheet, characterized in that the pollution control paint of the present invention is applied to one surface of a base sheet, and a pollution prevention layer is formed at a temperature of room temperature to 120 ° C. provide.

The coating film made of the antifouling paint of the present invention has a mechanism in which the outermost surface becomes hydrophilic by silanol-OH groups, a water film is formed by water vapor such as rain, and the contaminants flow down. As a technique introduced in the magazine (Environmental purification catalyst by photocatalyst, 36, 524 to 530 (1994)), the inventors further developed a phenomenon in which a photocatalytic effect and a pollution prevention effect can be obtained by making the surface hydrophilic. The present invention has been reached through development.
In the present invention, the term “sheet” is used to include both “sheet” and “film”.

  ADVANTAGE OF THE INVENTION According to this invention, the antifouling paint which shows antifouling performance for a long term, a fouling prevention sheet, and its manufacturing method can be provided.

Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention.
The antifouling paint of the present invention is characterized in that it contains an inorganic-organic composite comprising two components of a colloidal silica sol (A) and a hydrophilic polymer (B) formed using a basic catalyst. The colloidal silica sol used in the present invention is an aqueous dispersion of colloidal silica formed using a basic catalyst, and the colloidal silica is a compound represented by the formula SiO _n (OH) _m (OR) _o . And it has many silanol groups on the particle | grain surface. Due to the presence of the silanol group, the sol is excellent in stability, and the anti-contamination layer containing the colloidal silica is hydrophilic, has excellent adhesion to the base material, and is crosslinked with an appropriate crosslinking agent (self-crosslinking, organic By the inorganic crosslinking, it is possible to increase the hardness of the contamination prevention layer. On the other hand, colloidal silica sol formed using an acidic catalyst is inferior in stability and is not suitable for the purpose of the present invention.

As shown in FIG. 1, a general silica sol formed using a basic catalyst has silanol groups on the outside of the particle, but the composition formula is SiO _n (OH) _m (OR) _o ( n = 1.95-2.0, m = 0-0.1, o = 0-0.5, ratio of n + 0.5m = 2.0, R is CH ₃ or C ₂ H ₅ ) Represented. As the colloidal silica sol used in the present invention, the long-chain colloidal silica sol shown in FIG. 2 synthesized from a polyalkoxysiloxane derivative can also be used. This silica sol has a composition formula of SiO _n (OH) _m (OR) _o (n = 1.5 to 1.95, m = 0.1 to 1.0, o = 0 to 0.5, n + 0.5 m + 0. 5 o = 2.0 ratio, R is CH ₃ or C ₂ H ₅ ), and the number of silanol groups (—Si—OH) is large.

  Various colloidal silica sols as described above are commercially available. Colloidal silica sols are ultrafine particles having an average particle diameter of 1 nm to 200 nm having silanol groups (—Si—OH) on the surface and / or silanols on the surface. A sol made of long-chain silica having a group (—Si—OH) is preferable. In addition, colloidal silica sol is formed using methyl silicate monomer, ethyl silicate monomer, methyl silicate oligomer or ethyl silicate oligomer as raw materials, silica sol formed using basic catalyst, sodium silicate as raw material, and using basic catalyst It is preferable to be a silica sol. Examples of the colloidal silica sol as described above include, as trade names, Snowtex (manufactured by Nissan Chemical Co., Ltd.), Cataloid S (manufactured by Catalytic Chemical Industry Co., Ltd.), Ludox (manufactured by Grace Co., Ltd.), silica doll (Nippon Chemical Industry Co., Ltd.). Quartron (manufactured by Fuso Chemical Co., Ltd.), Adelite (manufactured by Asahi Denka Kogyo Co., Ltd.), MKC silicate MSH (manufactured by Mitsubishi Chemical Co., Ltd.) and the like can be obtained from the market and used in the present invention. .

  The hydrophilic polymer used in the present invention is polyvinyl alcohol, modified polyvinyl alcohol (a copolymer of acrylamide, unsaturated carboxylic acid, sulfonic acid monomer, cationic monomer, unsaturated silane monomer, unsaturated ethylene oxide monomer, etc.) , Polyvinyl pyrrolidone, modified polyvinyl pyrrolidone (copolymerized with vinyl acetate, unsaturated imidazole, vinyl caprolactone, etc.), polyacrylic acid, polyacrylates, polyacrylamide, polyisopropylacrylamide, polyformamide, polyethylene glycol, starch, modified Starch, gelatin, casein, algin, cellulose compounds (carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, etc.), water-soluble nylon Polyvinyl formal, polyvinyl acetal, polyvinyl benzal, polyurethanes, chitins, and chitosans and the like. The hydrophilic polymers listed above are preferred compounds used in the present invention, and the present invention is not limited to these exemplified compounds. Accordingly, not only the above-exemplified compounds but also any other compounds that are currently commercially available and can be easily obtained from the market can be used in the present invention.

  The antifouling paint of the present invention requires that the aqueous colloidal silica sol and the hydrophilic polymer are contained in an aqueous medium, and the use ratio of silica and the hydrophilic polymer (B) in the colloidal silica sol (A). (Mass ratio) is preferably in the range of silica: hydrophilic polymer = 5: 95 to 99: 1, and more preferably in the range of silica: hydrophilic polymer = 20: 80 to 95: 5. In the above, if the amount of the hydrophilic polymer used is too large, there is a problem in that the contact angle with respect to the water of the contamination prevention layer to be formed is increased and the time until the contamination prevention property is exerted becomes longer. When the amount of the hydrophilic polymer used is too small, when the antifouling paint is applied to the substrate and dried, the antifouling layer is uneven due to cracks, which causes problems such as poor appearance and transparency. In addition, the solid content concentration of the antifouling paint of the present invention is preferably in the range of about 5 to 15% by mass, and if the solid content concentration is too low, coating unevenness and drying time are required when forming the antifouling layer. On the other hand, if the solid content concentration is too high, the liquid stability of the antifouling paint is lowered.

  The liquid medium of the antifouling paint of the present invention is mainly water, and it is preferable to use ion exchange water as the water. A mixture of water and an organic solvent can also be used as a liquid medium. Preferred organic solvents include, for example, ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), alcohol solvents (methanol, ethanol, isopropanol, etc.), ether solvents (dioxane, tetrahydrofuran, etc.), ester solvents (acetic acid, etc.) Ethyl, butyl acetate, isobutyl acetate, etc.), glycol ether ester solvents (ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, etc.), amides And solvent based solvents (such as dimethylformamide and dimethylacetamide) and lactam solvents (such as n-methyl-2-pyrrolidone). Of these, alcohols such as methanol, ethanol and isopropanol are preferably used.

  The antifouling paint of the present invention can further contain a crosslinking agent. The crosslinking agent may be added to the antifouling paint from the beginning, or may be added to the antifouling paint when the antifouling paint is applied. As the cross-linking agent, a cross-linking agent utilizing a hydrophilic group possessed by the hydrophilic polymer, for example, a carboxyl group or a hydroxyl group can be used. As the crosslinking agent, for example, conventionally known ones such as epoxy crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents, water-dispersed isocyanates or metal complex crosslinking agents can be used, and particularly limited. Not. For example, as an epoxy-based crosslinking agent, conventionally known commercially available epoxy resins such as “Epicoat” (manufactured by Yuka Shell Epoxy Co., Ltd.) can be added and used. As the carbodiimide-based crosslinking agent, a commercially available product having a trade name of “Carbodilite” (manufactured by Nisshinbo Co., Ltd.) can be obtained and used. As the oxazoline-based cross-linking agent, a commercial product of “Epocross” trade name (manufactured by Nippon Shokubai Co., Ltd.) can be obtained and used.

  As the water-dispersed isocyanate-based crosslinking agent, a commercial product of “Duranate” (trade name, manufactured by Asahi Kasei Chemicals) can be obtained and used. Alternatively, as the metal complex-based crosslinking agent, titanium organic compound-based, zirconium organic compound-based commercially available under the trade name “Orgatics” (manufactured by Matsumoto Pharmaceutical Co., Ltd.) are available, and aluminum, chromium, cobalt, Copper, iron, nickel, vanadium, zinc, indium, calcium, magnesium, manganese, yttrium, cerium, strontium, palladium, barium, molybdenium, lanthanum, marketed under the trade name “Narsem” (manufactured by Nippon Kagaku Sangyo Co., Ltd.) Tin acetylacetone complexes are available and can be used. These crosslinking agents are particularly effective for improving the water resistance of the antifouling layer to be formed in an appropriate amount. However, if the amount of use is excessive, the antifouling property of the antifouling layer is lowered. The solid content is 10 parts by mass or less, preferably 0.01 to 1.0 part by mass based on 100 parts by mass of the solid content.

  Moreover, you may add a small amount of conventionally well-known surfactant to the pollution control paint of this invention as needed. Examples of these surfactants include glycerin monooleate, glycerin laurate, glycerin caprate, diglycerin oleate, diglycerin laurate, and triglycerin oleate, and polyoxyethylene alkyl ethers and other polyoxyethylene alkyl ethers. Examples include ethylene fatty alcohol ethers, polyethylene glycol fatty acid esters such as polyethylene glycol oleate and polyethylene glycol laurate, and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan trioleate. Although the usage-amount of these surfactant is not specifically limited, When using, 0.01-5 mass parts normally with respect to 100 mass parts of solid content of a pollution control coating material, Preferably it is 0.1-1. It is the range of mass parts.

  In addition to the hydrophilic polymer, other resin binders may be added to the antifouling paint of the present invention. These resin binders are not particularly limited. For example, conventionally known silicone resins, polyester resins, polyamide resins, polyimide resins, polystyrene resins, polyurethane resins, polycarbonate resins, norbornene resins, and cellulose resins. Examples thereof include a resin, a polyvinyl butyral resin, and a polyvinyl acetate resin. Although the usage-amount of these resin is not specifically limited, When using, it is usually 800 mass parts or less with respect to 100 mass parts of solid content of a pollution control coating material, Preferably it is the range of 5-500 mass parts.

  If necessary, an additive may be added to the antifouling coating material of the present invention. For example, antioxidants (hindered phenols, phosphites, thioethers, etc.), light stabilizers (hindered amines, etc.), UV absorbers (benzophenones, benzotriazoles, etc.), gas discoloration stabilizers (hydrazines, etc.) ), A metal deactivator, or a combination of two or more of these.

  Furthermore, inorganic fine particles and organic fine particles other than colloidal silica can be appropriately used in the antifouling paint of the present invention as required. As the inorganic fine particles, for example, alumina sol can be used. Examples of the alumina sol as described above include alumina sol-100, alumina sol-200, alumina sol-520 (manufactured by Nissan Chemical Industries, Ltd.), cataloid AS (manufactured by Catalytic Chemical Industries, Ltd.), and alumina clear sol (manufactured by Kawaken Fine Chemicals). Etc.) can be obtained from the market and used in the present invention. Examples of the organic fine particles include silicone resin fine particles, fluororesin fine particles, acrylic resin fine particles, urethane resin fine particles, polyethylene resin fine particles, and reactive siloxane.

  Examples of the object to be subjected to antifouling treatment by the antifouling paint of the present invention include inorganic glass, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyolefin resins such as polyethylene and polypropylene, polycarbonate resins, polymethyl methacrylate resins, and polyvinyl chloride resins. , Cellulose ester resins, polyimide resins, polyamide resins, transparent resin films such as polysulfone, injection molded products, cast molded products, and the like. The present invention relates to a resin mainly composed of an α-polyolefin copolymer from ethylene used in an agricultural film, particularly a single-layer to multi-layer polyolefin resin film or polyethylene terephthalate formed from linear low density polyethylene (LLDPE). It is useful for imparting antifouling properties to polyester films such as.

  In addition, when a contamination prevention layer is provided on these plastic films, the corona discharge treatment and plasma treatment are applied to the plastic films prior to the application of the pollution prevention paint in order to impart adhesion strength and durability of the coating film to the plastic film. It is preferable to perform surface treatment such as undercoating treatment, heat treatment, dust removal treatment or alkali treatment. For these surface treatments for plastic films, the present invention can be carried out using surface treatment techniques well known in the industrial field. In order to form a pollution prevention layer of the pollution prevention paint on the molded article, any coating method is adopted. For example, any method such as spray method, dipping method, flow coating method, roll coating method, bar coating method, curtain flow method, spin coating method, screen printing method, and brush coating may be used.

The antifouling paint according to the present invention is applied to the surface of an article, forcedly dried or naturally dried, and a liquid dispersion medium is volatilized to form a coating film. As a forced drying method, a hot air drying method or an infrared radiation method can be employed. The heating temperature for forced drying is 50 ° C. to 100 ° C., and the thickness of the contamination prevention layer is preferably in the range of 0.01 to 10 μm, particularly 0.05 to 2.0 μm. In the case of using a crosslinking agent, sufficient performance is exhibited by aging at room temperature to 120 ° C. for several minutes to several days, more preferably 50 ° C. to 80 ° C. for 1 day to 3 days after drying.
Moreover, it is preferable that the contact angle with respect to the water of a pollution prevention layer is 20 degrees or less.

  According to the present invention, contamination resistance, hydrophilicity, anti-condensation, antistatic properties, adhesion, high hardness, mechanical strength, scratch resistance, abrasion resistance, light resistance, heat resistance, solvent resistance, solvent resistance Provided is a paint that provides a coating film excellent in chemical resistance and stain resistance. The paint is useful as a paint for plastics, a paint for glass, a paint for building materials, a paint for vehicles, a paint for electronic devices, etc. for the purpose of preventing contamination.

  EXAMPLES Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In the following examples, “parts” and “%” are based on mass unless otherwise specified.

Example 1
In 100 parts of colloidal silica sol (trade name: MKC silicate MSH6, manufactured by Mitsubishi Chemical Corporation, silica content: 6.0%, average particle diameter of colloidal silica of 1 to 100 nm), it is dissolved in advance while stirring with a high-speed disper. 10.6 parts of 10% aqueous solution of polyvinyl alcohol (trade name PVA-217, manufactured by Kuraray Co., Ltd., saponification degree 88%, average polymerization degree 1,700) was slowly added over 15 minutes, and further stirred for 30 minutes. Thus, the antifouling paint of the present invention was obtained. The antifouling paint is applied on a polyethylene terephthalate (hereinafter referred to as “PET”) film so that the dry antifouling layer has a thickness of 1.0 μm, and dried in an oven at 120 ° C. for 2 minutes to obtain the contamination of the present invention. A protective film was obtained.

Example 2
It replaces with the polyvinyl alcohol of Example 1, and uses polyvinyl alcohol (Brand name PVA-117, the Kuraray Co., Ltd. make, saponification degree 98.5%, average degree of polymerization 1,700), and is the same as Example 1. Thus, the antifouling paint of the present invention and the antifouling film having a film thickness of 1.0 μm were obtained.

Example 3
The present invention was carried out in the same manner as in Example 1 except that polyvinyl alcohol (trade name PVA-205, manufactured by Kuraray Co., Ltd., saponification degree 88%, average polymerization degree 500) was used in place of the polyvinyl alcohol of Example 1. The antifouling paint and the antifouling film having a film thickness of 1.0 μm were obtained.

Example 4
It replaced with the polyvinyl alcohol of Example 1, and carried out similarly to Example 1 except having used 3.6 parts of acrylic polymer aqueous solution (Brand name John Krill 501 and Johnson polymer Co., Ltd. product, solid content 29.5%). The antifouling paint of the present invention and the antifouling film having a film thickness of 1.0 μm were obtained.

Example 5
Except that the amount of the polyvinyl alcohol aqueous solution used in Example 1 was 40.0 parts, the antifouling paint of the present invention and the antifouling film having a film thickness of 1.0 μm were obtained in the same manner as Example 1.

Example 6
Example 1 except that 0.05 parts of water-dispersed isocyanate (trade name Duranate WB40-100, manufactured by Asahi Kasei Chemicals) as a crosslinking agent was added to the antifouling paint of Example 5 and cured at 50 ° C. for 3 days. Similarly, the antifouling paint of the present invention and the antifouling film having a film thickness of 1.0 μm were obtained.

Comparative Example 1
A comparative example was prepared in the same manner as in Example 1 except that 2.2 parts of an acrylic emulsion (trade name John Krill 741, manufactured by Johnson Polymer Co., Ltd., solid content 49%) was used instead of the polyvinyl alcohol of Example 1. An antifouling paint and an antifouling film having a thickness of 1.0 μm were obtained.

Comparative Example 2
Ethyl silicate (trade name ethyl silicate 40, manufactured by Colcoat Co.) 0.3 part and silane coupling agent (trade name SH 6040, manufactured by Toray Dow Corning Co., Ltd.) 0.46 part, 2N hydrochloric acid 0.01 part, aluminum isopropoxide 0 .05 parts, 0.04 part of 35% hydrochloric acid, 0.09 part of water, 0.40 part of ethanol, 0.01 part of N, N-dimethylbenzylamine and a solution obtained by stirring at 25 ° C. for 10 minutes Add a solution obtained by mixing 20.40 parts of 25% polyacrylic acid aqueous solution (number average molecular weight 130,000) and 78.60 parts of methanol, and stir at 25 ° C. for 2 minutes to form a transparent antifouling paint Got. The antifouling paint was applied on a PET film so that the dry antifouling layer had a thickness of 4.0 μm and dried in an oven at 150 ° C. for 10 minutes to obtain a comparative antifouling film.

Test Example The performance of the antifouling paints and antifouling films of Examples and Comparative Examples obtained above was tested on the following items, and the results shown in Table 1 were obtained.
<Film-forming properties>
After the antifouling paint was applied to the film and dried, the resulting antifouling layer was visually observed for cracks.
No cracks: ○
There is a crack: ×

<Transparency>
Using a direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd., the haze value of the antifouling film was measured.
Haze value = Measured value−Haze value of substrate Haze value is less than 1.0: ○
A haze value of 1.0 to less than 5.0: Δ
Haze value is 5.0 or more: ×

<Pollution prevention>
The appearance of the test piece and the initial test piece after outdoor exposure for one year in the Tokyo area was visually observed.
No change in appearance compared to initial test piece: ○
Some dirt was found on the coating film:
Significant contamination of the coating film: ×

<Light resistance>
After the sunshine weatherometer test (temperature: 83 ° C., no water, 200 hours), the change in appearance was visually observed.
No change in appearance compared to initial test piece: ○
The gloss of the coating film was slightly lowered:
The coating film showed a decrease in gloss and cracks: ×

<Contact angle>
Using a contact angle meter CA-A type manufactured by Kyowa Interface Science Co., Ltd., water droplets were made 0.01 ml and contacted with the antifouling layer surface of the antifouling film, and measurement was performed at 20 ° C. after 1 minute.

<Water resistance>
40 degreeC warm water was dripped at the pollution prevention layer surface of the pollution prevention film, the load 100g was applied, the rubbing test was done, and it evaluated by the frequency | count that the pollution prevention layer peeled.
Less than 10 rubbing times: ×
Number of rubbing times 10 to less than 19: △
More than 19 rubbing times: ○

<Hot water resistance>
After immersing the antifouling film in warm water at 80 ° C. for 2 minutes, the moisture on the surface was wiped off and the change of the antifouling layer was observed.
No change at all: ◎
Almost no change: ○
Slight change: △
There is considerable change: ×

<Adhesion>
The adhesion between the antifouling layer of the antifouling film and the substrate PET film was determined by a cross cut test (cellophane tape peeling cross-cut method).
95% or more of non-peeled cells: ◎
Less than 95% to 70% of non-peeled cells: ○
Less than 70% to 40% of non-peeled cells:
Less than 40% of non-peeled cells: ×

<Scratch resistance>
The antifouling film surface of the antifouling film was rubbed with Scotch Bright (manufactured by Sumitomo 3M Co., Ltd.) with a load of about 10 g / cm ² to visually check the surface for scratches.
0 to 5 scratches that can be confirmed: ○
6-10 scratches that can be confirmed: △
11 or more scratches that can be confirmed: ×

  As described above, the antifouling paint of the present invention exhibits a high level of antifouling performance, and exhibits superior durability compared to conventional antifouling paints. Further, the antifouling paint of the present invention can be produced by a simple method and is very useful industrially.

The figure explaining colloidal silica typically. The figure explaining colloidal silica typically.

Claims (10)

Colloidal silica sol which is formed by using a basic catalyst (A) and a hydrophilic polymer and (B) contains as an essential component, the colloidal silica sol (A) is a methylation or ethyl silicate oligomer as a raw material, its composition The formula is SiO _n (OH) _m (OR) _o (n = 1.5 to 1.95, m = 0.1 to 1.0, o = 0 to 0.5, n + 0.5 m + 0.5 o = 2.0 and a ratio, R represents represented by CH ₃ or C ₂ H _5), pollution paints, characterized in that the benzalkonium Roidarushirika which have a large number of silanol groups (-Si-OH) on the front surface.   The antifouling paint according to claim 1, wherein the silica of the colloidal silica sol (A) is an ultrafine particle having an average particle diameter of 1 nm to 100 nm and having a silica content of 6%.   The antifouling paint according to claim 1, wherein a use ratio (mass ratio) of silica and the hydrophilic polymer (B) in the colloidal silica sol (A) is silica: hydrophilic polymer = 5: 95 to 99: 1.   The hydrophilic polymer (B) is polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, modified polyvinyl pyrrolidone, hydrophilic acrylic polymer, hydrophilic urethane polymer, cellulose compound, water-soluble nylon, polyvinyl formal, polyvinyl acetal and polyvinyl benzal. The antifouling paint according to claim 1, which is at least one selected from the group consisting of:   The antifouling paint according to claim 1, further comprising at least one selected from the group consisting of an alumina sol, a surfactant, an ultraviolet absorber and a crosslinking agent.   The pollution control paint according to claim 5, wherein the crosslinking agent is at least one selected from the group consisting of a carbodiimide compound, an organometallic complex compound, a polyisocyanate compound, an oxazoline compound, and an epoxy compound.   In the pollution control sheet which consists of a base material sheet and the pollution control layer provided in one side of this base material sheet, this pollution control layer is from the pollution control paint according to any one of claims 1 to 6. A contamination prevention sheet characterized by being formed.   The pollution prevention sheet according to claim 7 whose contact angle to water of a pollution prevention layer is 20 degrees or less.   The pollution prevention sheet according to claim 7 whose film thickness of a pollution prevention layer is 0.01 micrometer-10 micrometers.   An antifouling sheet characterized in that the antifouling paint according to any one of claims 1 to 6 is applied to one surface of a base material sheet, and an antifouling layer is formed at a temperature of room temperature to 120 ° C. Production method.

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