JP2012111785A - Antifouling coating composition and antifouling coating fluid containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling coating composition which is reduced in environmental burden, has excellent antifouling property and mechanical strength, and can form an antifouling coating film while capable of retaining excellent durability underwater.SOLUTION: The antifouling coating composition is characterized by containing (A) 1-20 wt.% of solid oil and (B) 80-99 wt.% of a polyol resin.

Description

  The present invention relates to an antifouling paint composition and an antifouling paint liquid containing the same. More specifically, an antifouling paint composition capable of producing an antifouling coating film for water-resistant organisms that achieves both high antifouling performance and a low environmental load, and an antifouling paint in which the composition is dispersed in a solvent. It is about liquid.

  There is a problem that aquatic organisms such as seaweeds, shellfish and microorganisms adhere to the surface of underwater structures, water pipes, fishing nets, and ship bottoms that are used in water for a long period of time. In particular, when such aquatic organisms breed in a ship, the resistance of the bottom surface of the ship increases, causing a decrease in the fuel use efficiency of the ship. In addition, removing such aquatic organisms from the bottom of the ship requires a great deal of labor, which increases the maintenance cost of the ship. In addition, aquatic organisms adhere to fish nets such as aquaculture nets and stationary nets, and breeding may cause problems such as acid deficiency of fish caught due to clogging of the nets. When aquatic organisms adhere to the water supply and drainage pipes and propagate, there is a problem that cooling water supply and drainage circulation is hindered and cooling efficiency is lowered.

  As a method for suppressing such damage, the use of an antifouling paint that prevents the above-mentioned adhesion and propagation of aquatic organisms has been performed. Conventionally, an antifouling paint containing an antifouling agent containing an organic compound such as organic tin has been used as such an antifouling paint, particularly an antifouling paint for ships (for example, Patent Document 1). Such antifouling paints not only exhibit antifouling effects by releasing organic compounds that are toxic to aquatic organisms, but also the paint itself gradually dissolves in water, so the bottom surface of the ship can always be kept clean. it can. However, since such toxic organic compounds have an adverse effect on the human body and biological systems, antifouling paints for ships with particularly low environmental loads have been studied in recent years.

  As an antifouling paint such as a marine antifouling paint having a small environmental load, a silyl ester antifouling paint composition (for example, Patent Document 2) has been proposed. An antifouling coating composition (for example, Patent Document 3) containing a conventionally used vehicle such as copper oxide in a copolymer of an unsaturated monomer such as methacrylate has been proposed.

Japanese Patent Application Laid-Open No. 60-94471 JP-A-4-264170 Japanese Patent Laid-Open No. 2008-1896

However, the silyl ester antifouling paint composition disclosed in Patent Document 2 is inferior in antifouling performance as compared with an antifouling paint containing organic tin as an antifouling agent, and the stability of the coating film is insufficient. Therefore, the coating film tends to become brittle, and cracks and peeling may occur.
Further, the vehicle such as the copper compound antifouling agent contained in the antifouling paint disclosed in Patent Document 3 is less toxic than the conventional organic tin as described above, but it is a large amount in a large tanker or the like. When used, the adverse effects on the biological system cannot be avoided.

As described above, there is actually no antifouling coating film formed from the conventional antifouling paints that satisfies both the antifouling performance and the low environmental load.
Under such circumstances, the object of the present invention is to form an antifouling coating film that has a low environmental load, is excellent in antifouling properties and mechanical strength, and has excellent durability even in water. It is to provide an antifouling coating composition.

The present inventors consider that it is more effective to solve the above problems to suppress the adhesion of aquatic organisms to the coating film than to suppress the propagation of aquatic organisms with an antifouling agent. A study was conducted focusing on the surface adhesion suppression.
Originally, solid fats and oils have a low affinity with water, so they have the effect of suppressing the adhesion of aquatic organisms, but they are used as antifouling coatings for water because they lack durability and hardness in water. Not.
On the other hand, although a specific polyol resin can form a coating film excellent in durability and mechanical strength, it has hydrophilic properties, and therefore, aquatic organisms are easily attached thereto, and the antifouling property in water is insufficient.
Moreover, since solid fats and oils are hydrophobic and polyol resin is hydrophilic, it was made very difficult to mix both uniformly.
However, as a result of repeated diligent research by the present inventors, the compatibility between the solid fat and the polyol resin is not high, and both are easy to separate, but the mixing ratio of both is within a suitable fixed range, and the uniform composition A coating composition can be obtained, and a coating film comprising the coating composition can suitably suppress the adhesion of aquatic organisms and can obtain the property of being able to maintain excellent durability in water for a long period of time. The headline and the present invention were completed.

That is, the present invention relates to the following inventions.
<1> An antifouling coating composition containing (A) solid oil and fat: 1 to 20% by weight and (B) polyol resin: 80 to 99% by weight.
<2> (A) The antifouling coating composition according to <1>, wherein the solid fat is paraffin wax.
<3> (B) The antifouling coating composition according to <1>, wherein the polyol resin is an acrylic polyol resin.
<4> The antifouling coating composition according to <3>, wherein the acrylic polyol resin is a silicon-modified acrylic polyol resin.
<5> The antifouling coating composition according to <1>, further comprising (C) natural resin: 1 to 5 parts by weight with respect to 100 parts by weight of the total of (A) solid oil and fat and (B) polyol resin.
<6> (C) The antifouling coating composition according to <5>, wherein the natural resin is rosin.
<7> An antifouling coating liquid obtained by dispersing the antifouling coating composition according to any one of <1> to <6> in a solvent.
<8> The antifouling coating liquid according to <7>, wherein the ratio of the antifouling coating composition to the solvent is 55 to 70/30 to 45 (weight ratio).
<9> The antifouling coating liquid according to <7>, wherein the solvent comprises a hydrocarbon solvent and an ester solvent.
<10> The antifouling coating liquid according to <9>, wherein the hydrocarbon solvent is an aliphatic or aromatic solvent having 6 to 8 carbon atoms.
<11> The antifouling coating liquid according to <10>, wherein the hydrocarbon solvent is a solvent containing hexane as a main component.
<12> The antifouling coating liquid according to <9>, wherein the ester solvent is butyl acetate.
<13> A marine antifouling coating film comprising the antifouling coating composition according to any one of <1> to <6>.
<14> A nuclear power transmission water pipe comprising the antifouling coating composition according to any one of <1> to <6>. <15> The antifouling according to any one of <1> to <6>. A dirty paint film for marine structures, comprising a dirty paint composition.
<16> An aquaculture net comprising the antifouling coating composition according to any one of <1> to <6>.

  The antifouling paint composition of the present invention has a low environmental impact, is excellent in antifouling properties and mechanical strength, and can form a sustainable antifouling coating film with excellent durability even in water. it can.

It is a photograph of the sample board | substrate 3 (there is no antifouling coating film) of a seawater exposure test (after one year). It is a partially expanded photograph of FIG.

  Hereinafter, the present invention will be described in detail.

The present invention relates to an antifouling coating composition containing (A) solid oil and fat: 1 to 20% by weight and (B) polyol resin: 80 to 99% by weight (hereinafter simply referred to as “the coating composition of the present invention”). In some cases).
The antifouling paint composition of the present invention is characterized by containing (A) a solid fat having an action of suppressing adhesion of aquatic organisms and (B) a polyol resin having an action of improving the durability of the coating film. In particular, by including both of them in a specific composition, it is possible to suitably suppress the adhesion of aquatic organisms and to obtain the property that excellent durability can be maintained in water for a long period of time.
Moreover, although mentioned later in detail, when specific natural resin is further added to this composition, adhesiveness with a base material will improve, and it will become possible to suppress especially peeling of a coating film.
Hereinafter, the components of the coating composition of the present invention will be described in detail.

[(A) Solid fat / oil]
Solid fats and oils (hereinafter referred to as component (A)) used in the present invention are solid or semi-solid fats and oils (waxes) that are solid or semi-solid at room temperature. Petroleum waxes such as so-called paraffin wax and micro wax, natural waxes, Any of synthetic waxes may be used, but paraffin wax is preferred in that a suitable effect for preventing adhesion of the underwater composition can be obtained and it can be easily obtained.
Paraffin wax is a solid or semi-solid oil (wax) that is solid or semi-solid at room temperature, which is mainly composed of straight-chain paraffinic hydrocarbons having about 18 to 30 carbon atoms. Generally, it is separated and refined from petroleum distillation oil. Manufactured.
Paraffin wax is usually distinguished by its melting point. According to JIS K 2235, there are 8 types of paraffin wax from 120 paraffin (melting point: 48.9 ° C to 51.7 ° C) to 155 paraffin (melting point: 68.3 ° C to 71.0 ° C). Is stipulated. These tend to have lower flexibility as the melting point is higher, and those having an appropriate melting point are used depending on the application. For example, 135 paraffin is suitable for ship bottom paints that do not melt at room temperature and have adequate flexibility, and 155 paraffin is suitable for applications that have a relatively high temperature environment such as a drainage conduit for power plants. used. Examples of commercially available products include “PARAFFINWAX-135” and “PARAFFINWAX-155” manufactured by Nippon Seiwa Co., Ltd., as suitable examples.

[(B) Polyol resin]
The polyol resin (hereinafter referred to as component (B)) used in the present invention is a resin generally used as a main component of a polyurethane resin, and is a polyether polyol resin, a polyester polyol resin, an acrylic polyol resin, an epoxy. A polyol resin etc. are mentioned. Among these, acrylic polyol resins, for example, acrylic polyol resins having 2 to 3 functional groups can be preferably used. Furthermore, a silicon-modified acrylic polyol resin obtained by modifying an acrylic polyol resin with silicon is preferably used.

As the silicon-modified acrylic polyol resin suitably used in the present invention,
(I) a polycondensation product obtained by dealcoholizing an alkoxysilyl group-containing organopolysiloxane and a hydroxyl group-containing acrylic resin,
(II) a copolymer of a polysiloxane macromonomer having an organopolysiloxane chain and a polymerizable unsaturated group and another polymerizable unsaturated monomer,
And so on.

The silicon-modified acrylic polyol preferably has a hydroxyl value in the range of 20 to 100 mgKOH / g and a number average molecular weight in the range of 10,000 to 50,000.
As a silicon-modified acrylic polyol, a commercially available product can be cited as a suitable example, Kessio (main agent) (manufactured by Kawakami Paint Co., Ltd.).

The polyol resin imparts flexibility, mechanical strength and durability to the coating film made of the present coating composition, but the following method is used to adjust the flexibility (hardness) of the coating film. Can be added as needed.
(1) An isocyanate component that reacts with the polyol resin to form a urethane bond is added.
By this method, the hardness of the coating film can be increased.
(2) A plasticizer is added.
By this method, the hardness of the coating film can be lowered.

  The isocyanate component (1) serves as a curing agent for the (B) polyol resin. For example, aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexane diisocyanate; hydrogenated xylylene diisocyanate, 4,4′- And cycloaliphatic diisocyanates such as methylene bis (cyclohexyl isocyanate); aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate. These can be used alone or in combination of two or more.

  The addition amount of the isocyanate component is appropriately selected depending on the type and amount of the (B) polyol resin contained in the coating composition of the present invention and the target hardness of the antifouling coating film. B) It is about 1-30 weight part with respect to 100 weight part of polyol resin.

  The plasticizer is not particularly limited as long as it is compatible with the coating composition of the present invention, and examples thereof include silicone elastomers, DOA (dioctyl adipate), DOP (dioctyl phthalate) and the like. The addition amount of the plasticizer is usually 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the (B) polyol resin.

  The composition ratio of (A) solid oil and fat to (B) polyol resin in the antifouling coating composition in the present invention is (A) solid oil and fat: 1 to 20% by weight and (B) polyol resin: 80 to 99% by weight. %, Preferably (A) solid fat / oil: 1 to 10% by weight and (B) polyol resin: 90 to 99% by weight. If the solid fat is less than 1% by weight, the adhesion control of aquatic organisms will be insufficient. On the other hand, if the solid fat exceeds 20% by weight, they cannot be separated and mixed uniformly.

Furthermore, (C) natural resin (hereinafter referred to as component (C)) can be added to the coating composition of the present invention in order to enhance the adhesion to the base substrate.
The component (C) has a function as a binder for the paint, and has an effect to improve the adhesion to the substrate. In particular, by adding the component (C), it is possible to enhance the adhesion when the coating composition of the present invention is directly formed on a substrate made of metal such as aluminum or stainless steel.

As component (C), specifically, coumarone / indene resin, terpene resin, terpene / phenol resin, aromatic hydrocarbon-modified terpene resin, terpene hydrogenated resin, terpene / phenolic hydrogenated system Examples thereof include resins, rosin resins, hydrogenated rosin ester resins, rosin-modified phenol resins, and alkylphenol resins.
Among these, rosin-based resin, hydrogenated rosin ester-based resin, rosin containing rosin as a constituent component at least because it has good compatibility with other components and can have appropriate hardness after the coating film is cured. Modified phenolic resins are preferably used.

  The solvent for dissolving the component (C) is not particularly limited as long as it can dissolve the component (C). For example, butyl acetate can be mentioned as a suitable example.

  As content of solid fats and oils (component (A)), polyol resin (component (B)), and natural resin (component (C)) used for the antifouling paint composition of the present invention, component (A) and component When the total amount of (B) is 100 parts by weight, the content of component (C) is 1 to 5 parts by weight (preferably 2 to 4 parts by weight).

  The antifouling paint composition of the present invention can be synthesized by stirring in a solvent or in the absence of a solvent, but is usually dispersed in a solvent and used in a marine antifouling paint liquid (hereinafter referred to as “antifouling”). , And sometimes simply referred to as “paint liquid”).

The solvent may be any solvent that can disperse the antifouling coating composition of the present invention. Specifically, carboxylic acids such as acetic acid, propionic acid, and butyric acid;
Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-ethylhexanol, cyclohexanol, 1-hexanol, 2-hexanol, 1-octanol, 2-octanol, 3-octanol Ethers such as diglyme, diphenyl ether, dibenzyl ether, diallyl ether, tetrahydrofuran (THF), dioxane;
Amides such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide;
Ketones such as cyclohexanone; aromatic hydrocarbons such as toluene, xylene, dodecylbenzene;
Aliphatic hydrocarbons such as pentane, hexane, heptane, and octane;
Esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, amyl acetate, ethyl formate, butyl propionate, methoxypropyl acetate, γ-butyrolactone, di (n-octyl) phthalate;
Examples include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. The above can be mixed and used.
Among these, from the viewpoint of improving the stability of the antifouling coating composition of the present invention and making the coating workability and the coating film drying property suitable, it is desirable to include aliphatic hydrocarbons and esters. Hexane is preferred as the aliphatic hydrocarbon, and butyl acetate is preferred as the ester.

  The antifouling coating composition of the present invention can be produced by a known method. The order of blending the components during production is arbitrary.

In the present invention, in addition to the components (A), (B) and (C), other conventionally known additional components may be added as necessary.
Examples thereof include compatibilizers for components (A), (B) and (C), antifouling agents having killing power to aquatic organisms, pigments, wetting agents, reaction accelerators, precipitation inhibitors and the like.
These contents are not particularly limited as long as the object of the present invention is not impaired, but is usually 30 parts by weight or less, preferably 10 parts by weight or less, and particularly preferably 3 parts by weight or less. is there. When the content is larger than 30 parts by weight, the antifouling performance of the coating film is remarkably lowered, and the coating film tends to crack or peel off.

  As a compatibilizing agent for the components (A), (B) and (C), it is preferable to add a surfactant such as soap. The soap as the surfactant contains one or more fatty acids selected from linear saturated fatty acids or linear unsaturated fatty acids and salts thereof, and examples of the linear saturated fatty acids include lauric acid, myristic acid, palmitic acid , Stearic acid, arachidic acid, behenic acid and the like. Examples of linear unsaturated fatty acids include zomarinic acid, oleic acid, elaidic acid, gadoleic acid, erucic acid, linoleic acid, linolenic acid, ricinoleic acid and the like. Moreover, 1 or more types chosen from said linear saturated fatty acid or linear unsaturated fatty acid can also be added directly as a compatibilizing agent.

  In addition, as the antifouling agent having killing power to aquatic organisms, known ones can be used, but these enhance the antifouling performance of the coating film, but if adding too much, the environmental load increases. Therefore, it is desirable to avoid using as much as possible.

  Examples of pigments include extender pigments, rust preventive pigments, and colored pigments. Specifically, talc, clay, calcium carbonate, barium sulfate, zirconium oxide, zinc white, bengara, carbon black, silica powder, and cyanine coloration. Examples thereof include pigments, chromium oxide, aluminum molybdate, zinc molybdate, calcium molybdate, aluminum phosphate, and barium metaborate, which are used as one or a mixture of two or more according to the purpose.

The base substrate to which the coating liquid of the present invention is applied is not particularly limited, and any material such as a metal, a resin, and an inorganic material may be used.
In particular, as a base material used as a ship bottom, for example, a zinc phosphate-treated dull steel plate and a galvanized steel plate can be mentioned. In addition, you may form the coating film which consists of a well-known undercoat for the objective of a rust prevention etc. on a metallic base substrate.

  The application method of the antifouling coating liquid of the present invention to the base substrate is not particularly limited, and can be performed by a conventionally known application method. For example, a spray coating method, a roll coating method, a brush coating method, a bar coater coating method, or the like can be appropriately employed.

  The drying time of the coating film after the antifouling coating liquid of the present invention is applied to the base substrate varies depending on the composition and the coating amount in the antifouling coating liquid, but is at least 20 minutes to 60 minutes after application. It is possible. By setting the drying time to 20 minutes or longer, the fluidity of the coating film can be maintained for a sufficient time, and a flat and uniform continuous film can be formed without special leveling treatment. By setting the drying time to 60 minutes or less, problems such as dripping can be prevented.

  The curing time of the coating film varies depending on the composition and the coating amount in the antifouling coating liquid, but is usually cured in about one day at room temperature.

The film thickness of the antifouling coating film of the present invention is not particularly limited as long as the effect of the present invention can be obtained, and is usually about 1 to 200 μm, preferably from the viewpoint of forming a smooth coating film. The thickness is about 10 to 100 μm.
The antifouling coating film of the present invention has a hardness of about 1B, depending on the composition of the antifouling coating composition, the drying time, and the like. Therefore, it is hard to be damaged even in water, and the coating film is difficult to peel off.

The coating film of the present invention can be easily peeled off using a conventionally known release agent.
Therefore, the construction fails for any reason, and when the coating film is cracked or clouded or after use, the coating film can be peeled off and re-executed.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “parts” and “%” are based on weight.

The materials used in the examples are as follows.

Component (A): Solid fat (paraffin)
“PARAFFINWAX-135” manufactured by Nippon Seiwa Co., Ltd.
Component (B): Polyol resin
"Keshiso (main agent)" manufactured by Kawakami Paint Co., Ltd.
(Solid content 62%, butyl acetate 34%, additive 4%)
Ingredient (C): Natural resin
Harima Chemicals Co., Ltd. “Rosin”
Ingredient (D): Fatty acid / fatty acid salt mixture
Rocket Soap Co., Ltd. “Sun Rocket”
Solvent (a): Hydrocarbon solvent
“Normal hexane” manufactured by Nippon Petrochemical Co., Ltd.
(Normal hexane 60%, methylpentane 8%, methylcyclopentane 30%, other hydrocarbons 2%)
Solvent (b): Ester solvent
Butyl acetate

As a method for measuring the characteristics described in the following examples and comparative examples, the measurement was performed under the following conditions.
<Adhesion between coating film and substrate>
Based on JIS K5600-5-6 (1991), the adhesive force of each antifouling coating film was measured.

<Removability of coating surface>
It measured based on JISZ0237 (2000).

<Weather resistance>
It measured based on JISK5600-7-7 (1991).

<Seawater resistance test> (Neutral resistance salt spray)
It measured based on JISZ2371 (acceleration test: 1000h).

"Example 1"
(1) Preparation of coating liquid 1 500 g of the component (A) was put in a mixing container containing 20 L of the solvent (a), and mixed well at room temperature to obtain a mixed solution. The mixture was then filtered and the filtrate was collected.
A coating liquid 1 was obtained by adding 300 g of the component (B) and 30 g of the solvent (b) to 100 g of the filtrate and mixing the mixture at room temperature until uniform.

(2) Production of sample substrate 1 A 50 × 120 × 1.2 mm steel plate is brush-coated with a rust-preventing base coating (manufactured by Daishin Paint Co., Ltd., Epon mild) and dried at room temperature for about one day. A base coating was formed.
The sample substrate 1 was obtained by applying the coating liquid 1 by brush coating so that the dry film thickness was 20 to 30 μm on the steel sheet on which the base coating film was formed and drying it at room temperature for 1 day.
Table 1 shows the results of evaluating the adhesion between the coating film and the substrate, the peelability of the coating film surface, and the weather resistance of the sample substrate 1.

"Example 2"
(1) Preparation of coating liquid 2 In a mixing container containing 20 L of the solvent (a), 500 g of the component (A) and 60 g of the component (D) are placed and mixed well at room temperature to obtain a mixed solution. It was. The mixture was then filtered and the filtrate was collected.
A coating liquid 2 was obtained by adding 300 g of the component (B) and 30 g of the solvent (b) to 100 g of the filtrate and mixing the mixture at room temperature until uniform.

(2) Preparation of sample substrate 2 The coating liquid 2 is applied to the steel sheet on which the same undercoat film as in Example 1 is formed by brush coating so that the dry film thickness is 20 to 30 μm. A sample substrate 2 was obtained by drying at room temperature.
Table 1 also shows the results of evaluating the adhesion between the coating film and the substrate, the peelability of the coating film surface, and the weather resistance of the sample substrate 2.

"Example 3"
(1) Preparation of coating liquid 3 In a mixing container containing 20 L of the solvent (a), 500 g of the above component (A) and 60 g of the component (D) are put and mixed well at room temperature to obtain a mixed solution. It was. The mixture was then filtered and the filtrate was collected.
To 100 g of this filtrate, 300 g of component (B) and 10 g of component (C) dissolved in 30 g of solvent (b) were added and mixed until uniform at room temperature to obtain paint liquid 3.

(2) Preparation of sample substrate 3 The coating liquid 3 is applied to the steel sheet on which the same undercoat film as in Example 1 is formed by brush coating so that the dry film thickness is 20 to 30 μm. A sample substrate 3 was obtained by drying at room temperature.
Table 1 also shows the results of evaluating the adhesion between the coating film and the base material, the peelability of the coating film surface, and the weather resistance with respect to the sample substrate 3. In addition, as a result of the seawater resistance test (neutral salt sprayability), almost no rust was observed on the paint surface.

“Comparative Example 1”
(1) Preparation of coating liquid 4 500 g of the component (A) was put in a mixing container containing 20 L of the solvent (a), and mixed well at room temperature to obtain a mixed solution. The mixture was then filtered and the filtrate was collected.
30 g of the solvent (b) was added to 100 g of the filtrate, and mixed at room temperature until uniform, thereby obtaining a coating liquid 4.

(2) Production of Sample Substrate 4 The coating liquid 4 is applied to the steel sheet on which the same undercoat film as in Example 1 is formed by brush coating so that the dry film thickness is 20 to 30 μm. The sample substrate 4 was obtained by drying at room temperature.
Table 1 shows the results of evaluating the adhesion between the coating film and the substrate, the peelability of the coating film surface, and the weather resistance of the sample substrate 4.

"Comparative Example 2"
(1) Preparation of coating liquid 5 In a mixing container containing 20 L of the solvent (a), 500 g of the component (A) and 60 g of the component (D) are placed and mixed well at room temperature to obtain a mixed solution. It was. The mixture was then filtered and the filtrate was collected.
30 g of the solvent (b) was added to 100 g of the filtrate, and mixed at room temperature until uniform, thereby obtaining a coating liquid 5.

(2) Preparation of sample substrate 5 The coating liquid 5 is applied to the steel sheet on which the same undercoat film as in Example 1 is formed by brush coating so that the dry film thickness is 20 to 30 μm. A sample substrate 5 was obtained by drying at room temperature.
Table 1 also shows the results of evaluating the adhesion between the coating film and the base material, the peelability of the coating film surface, and the weather resistance with respect to the sample substrate 5.

<Seawater exposure test>
The sample substrate 3 was used to conduct a seawater exposure test, and the antifouling property of the antifouling coating composition was evaluated.
Ten sample substrates 3 are immersed in seawater for 12 hours / day using the fullness of tides, otherwise the seawater is exposed under conditions of atmospheric exposure, and the state of biological attachment during one year is visually observed. did. FIG. 1 shows a photograph of the sample substrate 3 (partially without antifouling coating film) in the seawater exposure test (after one year). FIG. 2 shows a partially enlarged photograph of FIG.

  As a result, in the portion where the antifouling coating film was formed, the adhesion of aquatic organisms to the coating film surface could not be confirmed at any point in the year of exposure to seawater. On the other hand, adhesion of aquatic organisms such as barnacles was confirmed from about one month of exposure to seawater in the part where the antifouling coating film was not formed (the part without the base coating film, only the base coating film). Further, rust was generated in the portion without the base coating film.

Example 4
(1) Preparation of coating liquid 2 The coating liquid 2 was obtained in the same procedure as in Example 2 above.

(2) Preparation of sample substrate 6 Sample substrate 6 was prepared in the same manner as in Example 2 except that a 50 × 120 × 2 mm aluminum substrate (without base coating) was used instead of the steel plate (with base coating) in Example 2. 6 was obtained.
Table 2 shows the results of evaluating the adhesion between the coating film and the substrate, the peelability of the coating film surface, and the weather resistance with respect to the sample substrate 6.

"Example 5"
(1) Preparation of coating liquid 3 The coating liquid 3 was obtained in the same procedure as in Example 3 above.

(2) Preparation of sample substrate 7 Sample substrate 7 was prepared in the same manner as in Example 3 except that a 50 × 120 × 2 mm aluminum substrate (without base coating) was used instead of the steel plate (with base coating) in Example 3. 7 was obtained.
Table 2 shows the results of evaluating the adhesion between the coating film and the substrate, the peelability of the coating film surface, and the weather resistance of the sample substrate 7.

“Comparative Example 3”
(1) Preparation of coating liquid 5 The coating liquid 5 was obtained in the same procedure as the comparative example 2.

(2) Preparation of sample substrate 8 A sample substrate was prepared in the same manner as in Comparative Example 2 except that a 50 × 120 × 2 mm aluminum substrate (without base coating) was used instead of the steel plate (with base coating) in Comparative Example 2. 8 was obtained.
Table 2 also shows the results of evaluating the adhesion between the coating film and the substrate, the peelability of the coating film surface, and the weather resistance of the sample substrate 8.

"Example 6"
The mixing ratio of the component (A) and the component (B) was changed to evaluate the mixing property of the solution and the properties of the formed coating film.
When the total of the component (A) and the component (B) is 100% by weight of the solid fat in the component (A) and the solid component in the component (B), the amount of the solid fat in the component (A) is It added to the solvent which mixed solvent (a): solvent (b) = 1: 1, and was mixed so that it might become 0.5, 1, 5, 10, 15, 20, 30 (weight%). As a result, the solution could be evenly mixed until the solid fat content was 20% by weight, but both components were separated when the amount exceeded 20% by weight.
Moreover, although the amount of the solid fat of component (A) was 0.5 to 20% by weight, a coating film having a uniform thickness could be formed. The peelability was insufficient. Moreover, the coating film had sufficient hardness up to 10% by weight of the solid fat, but when it exceeded 10% by weight, the coating film was softened.

  The antifouling coating film comprising the antifouling coating composition of the present invention has high adhesion to the substrate and peelability of the coating film surface, and can suppress the adhesion and propagation of aquatic organisms over a long period of time. It is extremely promising.

Claims (16)

  An antifouling paint composition comprising (A) solid fat and oil: 1 to 20% by weight and (B) polyol resin: 80 to 99% by weight.   The antifouling coating composition according to claim 1, wherein (A) the solid fat is paraffin wax.   (B) The antifouling coating composition according to claim 1, wherein the polyol resin is an acrylic polyol resin.   The antifouling coating composition according to claim 3, wherein the acrylic polyol resin is a silicon-modified acrylic polyol resin.   The antifouling coating composition according to claim 1, further comprising (C) a natural resin: 1 to 5 parts by weight with respect to a total of 100 parts by weight of (A) the solid fat and the (B) polyol resin.   (C) The antifouling paint composition according to claim 5, wherein the natural resin is rosin.   An antifouling paint liquid obtained by dispersing the antifouling paint composition according to any one of claims 1 to 6 in a solvent.   The antifouling paint liquid according to claim 7, wherein the ratio of the antifouling paint composition to the solvent is 55 to 70/30 to 45 (weight ratio).   The antifouling paint liquid according to claim 7, wherein the solvent comprises a hydrocarbon solvent and an ester solvent.   The antifouling paint liquid according to claim 9, wherein the hydrocarbon solvent is an aliphatic or aromatic solvent having 6 to 8 carbon atoms.   The antifouling paint liquid according to claim 10, wherein the hydrocarbon solvent is a solvent containing hexane as a main component.   The antifouling coating liquid according to claim 9, wherein the ester solvent is butyl acetate.   A marine antifouling coating film comprising the antifouling coating composition according to any one of claims 1 to 6.   A nuclear power transmission conduit comprising the antifouling coating composition according to any one of claims 1 to 6.   An antifouling paint film for marine structures comprising the antifouling paint composition according to any one of claims 1 to 6.   An aquaculture net comprising the antifouling paint composition according to any one of claims 1 to 6.