JPH0578617A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating composition, comprising a polysiloxane containing only one silanol group having reactivity with a reaction curing type silicone rubber in the molecule in the silicone rubber, capable of preventing fouling by aquatic organisms and applicable to ship bottom parts, fishing nets, etc. CONSTITUTION:The objective coating composition is obtained by blending (B) a polysiloxane containing only one silanol group having reactivity with (A) a reaction curing type silicone rubber consisting essentially of a polyorganosiloxane, having siloxane bonds and capable of curing by chemical reaction according to exposure to the open air, mixing a catalyst, heating or irradiation with ultraviolet rays and providing a rubber-like elastomer in the molecule and, as necessary, (C) a surface slip agent (e.g. dimethyl silicone oil) in the component (A). The resultant coating composition is capable of preventing underwater structures such as ship bottom parts, fishing nets and various cooling water pipes, underwater submerged substrates such as marine pollution preventive films, etc., from being fouled by attachment of organisms for a long period.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coating composition for preventing the adhesion of aquatic organisms to various underwater objects immersed in water.

[0002]

2. Description of the Related Art Barnacles are attached to the surface of underwater objects such as ship bottoms, buoys, fishnets (aquaculture nets, stationary nets, etc.), water pollution control membranes, and various intake and drainage pipes for cooling that are immersed in water.
Various obstacles are caused by the attachment of cerpra, mussel, algae and the like. To prevent contamination by those organisms,
It is well known that an antifouling coating agent is applied to the surface of an underwater immersion product.

At present, as the antifouling coating agent, those using an antifouling agent such as an organotin copolymer and cuprous oxide are often used. However, due to the problem of environmental pollution, a pollution-free antifouling coating agent has been demanded, and for example, Japanese Patent Publication No. 53-35974 discloses that a vulcanized silicone rubber is used as a coating agent. In Japanese Patent Laid-Open No. 51-96830,
The use of a mixture of oligomeric silicone rubber with hydroxyl end groups and silicone oil is shown. Further, JP-A-53-79980 discloses a mixture of a vulcanized silicone rubber and a fluid organic compound containing no metal or silicon. Furthermore, Japanese Patent Sho 60
No. 3433 discloses a mixture of an oligomeric room temperature curable silicone rubber and liquid paraffin or petrolatum.

[0004]

These conventionally known antifouling coating agents are intended to prevent the adhesion of aquatic organisms to the surface by utilizing the low surface tension of the silicone rubber coated surface. However, the problem is that in a silicone rubber single film, the siloxane part that exerts a low surface tension and is involved in the so-called antifouling property is fixed by cross-linking at both ends, so there is no degree of freedom and low It seems that the surface tension cannot be maintained for a long time. In addition, the coating obtained by physically mixing silicone oil, petrolatum, etc. with silicone rubber also shows that when the coating film is immersed in seawater, these fluids will flow from the silicone rubber surface over time due to the physical mixing. The body will be released into the sea. Therefore, in the long term, the drawbacks of the silicone rubber single film are exhibited. From these facts, in any of the types, it was recognized that the antifouling effect, particularly the long-term antifouling durability, had a problem.

An object of the present invention is to provide a non-toxic coating composition which has the above-mentioned drawbacks of the prior art and which has good antifouling performance while taking advantage of the characteristics of silicone rubber.

[0006]

According to the present invention, a reaction-curable silicone rubber contains a polysiloxane containing only one silanol group reactive in the reaction-curable silicone rubber in its molecule. Characteristic coating composition,
And a coating composition characterized by further containing a surface slip agent in the coating composition.

The reaction-curable silicone rubber used in the present invention (referred to as component (1)) is chemically reacted by exposing it to the atmosphere, mixing a catalyst, heating, or irradiating with ultraviolet rays. It is mainly composed of a polyorganosiloxane having a siloxane bond, which cures to give a rubber-like elastic body. For example, trade name TSE370RTV, YE3085 manufactured by Toshiba Silicone Co., Ltd.
TSE382RTV, TSE388W, TSE385R
TV, TSE3851, Tosseal 371, Tosseal 381, Tosseal 380, Tosseal 10, Toskote 10, TSE3033, TSJ3130, TSJ31
50, TSE350RTV, TSE3562, Tosseal 361, TSE3434RTV, YE5626, TS
E322, TSE325, TSE3360, TLM10
25, TUV6000, TUV6020, YE5505
Etc., product name KE41, KE manufactured by Shin-Etsu Chemical Co., Ltd.
42S, KE44, KE45, KE45S, KE44
5, KE347, KE3475, etc., and product name SE5004, S manufactured by Toray Dow Corning Silicone Co., Ltd.
E9175, SE9176, SE9185, SE918
6, SE9188, SE9189, SH780, SH7
81, SE792, SE5070, etc.,
It is not necessarily limited to these.

By combining the above-mentioned reaction-curable silicone rubber with a polysiloxane containing only one silanol group which reacts with these (referred to as component (2)), it is combined with the water repellency of the silicone rubber during immersion. ,
Further, it is possible to obtain a coating composition that maintains water repellency for a long period of time and, as a result, exhibits excellent antifouling curing. As a polysiloxane containing only one silanol group in the molecule, an organic group bonded to a silicon atom in the polysiloxane may be an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, or a phenyl group. Examples thereof include those having an aryl group, a fluoro-substituted alkyl group and an aryl group. For example, Chisso Corporation
Product names FM-0911, FM-0921, FM-0
925 and the like, and one kind or two or more kinds thereof are selected and used, but not limited thereto.

The polysiloxane used in the present invention, which contains only one silanol group having reactivity with the reaction-curable silicone rubber in the molecule, is bonded to the silicone rubber at only one point in the silicone rubber, and therefore only one end is formed. Since the fixed polysiloxane group can move freely on the surface of the coating film and one end is fixed, it does not separate from the silicone rubber coating film and maintains low surface tension for a long time, resulting in antifouling performance. To give a good coating surface.

In the present invention, as described above, the amount of the polysiloxane containing only one silanol group in the molecule is such that the dryness based on the above reaction-curable silicone rubber,
It is appropriately set in consideration of performance such as adhesion and antifouling performance. In general, the ratio of polysiloxane containing only one silanol group in the molecule to the total amount of reaction-curable silicone rubber and polysiloxane containing only one silanol group in the molecule is 0.1%. As described above, it is preferably 90% by weight or less.

Further, in the present invention, excellent antifouling property can be exhibited only by a combination of the above-mentioned reaction-curable silicone rubber and polysiloxane containing only one silanol group which reacts with them in the molecule. The antifouling property can be improved by further using a surface lubricant (referred to as component (3)) together with these. Further, the surface slip agent has a synergistic effect by being used in a mixed system of the above-mentioned reaction-curable silicone rubber and a polysiloxane containing only one silanol group reactive with the reaction-curable silicone rubber in the molecule. It is important in that it can be demonstrated and the antifouling performance can be further sustained.

Therefore, as such a surface slipping agent that can be used in the present invention, various substances known to impart a surface slipping property to a coating film can be mentioned. Typical examples thereof are petroleum wax specified in JIS-K2235, liquid paraffin specified in JIS-K2231, silicone oil having a kinematic viscosity of 55,000 centistokes or less at 25 ° C, -5 ° C or more. C8 or more fatty acids and their esters having a melting point of, organic amines having an alkyl group or an alkenyl group having 12 to 20 carbon atoms, and polybutene having a kinematic viscosity of 60,000 centistokes or less at 26 ° C.

As a specific example of the above, JIS-K22
35 120P, 125P, 130P, 135P, 14
Paraffin wax such as 0P, 145P, 150P, 155P, JIS-K2235 150M, 160M,
Microcrystalline waxes such as 170M, 180M and 190M, and JIS-K2235 No. 1, 2
No. 3, No. 4, No. 4, etc. are mentioned.

As a concrete example of the above, ISOVG1
0, ISOVG15, ISOVG32, ISOVG6
8, equivalent products of ISOVG100, and the like. As a specific example of the above, trade name K manufactured by Shin-Etsu Chemical Co., Ltd.
F96L-0.65, KF96L-2.0, KF96-
30, KF96-100, KF96H-50000, K
F965, KF50, KF54, KF69, FL10
0, trade name TSF440, T manufactured by Toshiba Silicone Co., Ltd.
SF410, TSF4440, TSF431, TSF4
33, TSF404, TFA4200, YF3860,
YF3818, YF3965, YF3841, YF39
53, TSF451, TSF400, FQF501, trade name SH manufactured by Toray Dow Corning Silicone Co., Ltd.
200, SH510, SH3531, SH230, FS
1265 and the like. Dimethyl silicone oil is most commonly used as the above silicone oil, but other methyl phenyl silicone oil, polyether silicone oil, cyclic polysiloxane oil, alkyl modified silicone oil, methyl chlorinated phenyl silicone oil, higher fatty acid modified silicone. Other materials such as oil and fluorosilicone oil may be used.

Further, specific examples of the above include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, cerotic acid, montanic acid, melissic acid, laureleic acid, oleic acid, vaccenic acid, gadoleic acid. , Whale oil acid, shark oil acid, diuniperic acid and the like. Further, as the esters of these carboxylic acids, stearyl stearate, butyl laurate, octyl palmitate, butyl stearate, isopropyl stearate, cetyl palmitate, ceryl cerotate, myricyl palmitate, melisyl melissate, spermaceti, beeswax,
Carnauba wax, Montan wax, Mushi white wax, Tristearin,
Tripalmitin, triolein, myristodilaurin,
Caprylolauromyristin, stearopalmitoolein, monostearin, monopalmitin, distearin,
Examples thereof include dipalmitin, beef tallow, lard, horse fat, sheep fat, cod liver oil, coconut oil, palm oil, wood wax, kapok oil, cocoa oil, cocoa butter, Chinese fat and illipe fat.

Specific examples of the above include dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, tallow alkylamine, cocoalkylamine, soybean oil alkylamine, didodecylamine, ditallow hydrogenated alkylamine. , Dodecyldimethylamine, cocoalkyldimethylamine, tetradecyldimethylamine, hexamethyldimethylamine,
Octadecyl dimethylamine etc. are mentioned.

Specific examples of the above include Nippon Oil & Fats Co., Ltd.
Product name made by Nissan Polybutene 0N, 06N, 015
N, 3N, 5N, 10N, 30N, 200N, 0SH,
06SH, 015SH, 3SH, 5SH, 10SH, 3
Examples include 0SH and 200SH. In the present invention, one kind or two or more kinds are selected and used from the above-mentioned various surface lubricants, and the amount thereof is such that the dryness and adhesion based on the reaction-curable silicone rubber are It is appropriately set in consideration of the performance and the antifouling performance.
Generally, the ratio of the surface lubricant in the total amount of the reaction-curable silicone rubber and the surface lubricant is 80% by weight or less.

As described above, the coating composition of the present invention comprises the above-mentioned reaction-curable silicone rubber, and a polysiloxane containing only one silanol group reactive with the reaction-curable silicone rubber in the molecule. Or, it is characterized in that they further contain a surface lubricant, and they are usually diluted with an organic solvent before use. The organic solvent used for the above purpose, xylene, aromatic hydrocarbon solvents such as toluene, hexane, aliphatic hydrocarbon solvents such as heptane, ethyl acetate, ester solvents such as butyl acetate, isopropyl alcohol, butyl alcohol Alcohol solvents such as, dioxane, ether solvents such as diethyl ether, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, cellosolve solvents such as cellosolve acetate, and the like alone or a mixed solvent thereof. Can be mentioned.

Further, in the coating composition of the present invention, if necessary, a coloring pigment, an extender pigment, an anticorrosive pigment, a dye, an anti-sagging agent, a plasticizer, an anti-separation agent, an anti-settling agent, an antifoaming agent, an antifouling agent. There is no problem with adding agents.

[0020]

As compared with the conventional silicone rubber alone or in combination with silicone oil or petrolatum, the coating composition of the present invention has a significantly improved antifouling effect, and the antifouling property is maintained for a long period of time. Therefore, the bottom of the ship, the underwater structures such as fishnets and various cooling water pipes, which require the prevention of underwater biological contamination,
Further, in the case of marine pollution prevention film, the film obtained by the present invention shows a very good antifouling effect, and can prevent the biofouling stain of the submerged submerged substrate for a long period of time.

[0021]

EXAMPLES The present invention will be specifically described below with reference to polymer production examples, examples and comparative examples. Parts in the examples represent parts by weight. Examples 1 to 19 Using reaction-curable silicone rubber, the compounding composition shown in the following Tables 1 to 3 (numerical values in the table are% by weight) gives 2,000 rpm.
19 kinds of coating compositions were prepared by mixing and dispersing with a homomixer.

Among the compounding ingredients, YE5505 (50 wt% toluene solution) is KE4 manufactured by Toshiba Silicone Co., Ltd.
5S (50 wt% toluene solution), KE42, KE347
5 and KE445 are SE manufactured by Shin-Etsu Chemical Co., Ltd.
5004 is a trade name of a reaction-curable silicone rubber manufactured by Toray Dow Corning Silicone Co., Ltd. Also FM
-0911, FM-0921 and FM-0925 are
It is a trade name of polysiloxane manufactured by Chisso Corporation and having only one silanol group.

Furthermore, paraffin wax 120P
And Petrolatum No. 1 are JIS-K2235 petroleum waxes, ISOVG10 and ISOVG100.
Is liquid paraffin of JIS-K2231. Further, KF96-100, KF54, FL100 [trade name of Shin-Etsu Chemical Co., Ltd.] is silicone oil,
Nissan Polybutene 06N and 200N (trade name of NOF CORPORATION) are polybutene.

Oil Blue 2N (trade name of Orient Chemical Co., Ltd.) is a dye, Disparon 6900-2.
Both 0X [trade name of Kusumoto Kasei Co., Ltd.] and Aerogel 300 [trade name of Nippon Aerogel Co., Ltd.] are anti-sagging additives. Comparative Examples 1 to 4 In the same manner as in Examples 1 to 19, four types of coating compositions having the composition shown in Table 3 below were prepared.

The following antifouling performance tests were conducted on the coating compositions of Examples 1 to 19 and Comparative Examples 1 to 4 described above. That is, each paint composition is applied to a sandblasted steel plate with a tar vinyl anticorrosive paint applied in advance.
(100 × 200 × 1mm), the dry film thickness is 120μm on each side
Then, the test plate was prepared by spray coating twice so that it would be naturally dried in a room for 7 days.

This test plate was immersed in water for 24 months in Yura Bay, Sumoto City, Hyogo Prefecture, and the ratio of the area occupied by adherent organisms (adhered area) on the film of the test plate was measured over time. The results are shown in Table 4. From the results of Table 4, in each example,
No living organisms attached even after 24 months, or even 1%
It is clear that the coating composition of the present invention retains excellent antifouling performance even over a long period of time.

On the other hand, in Comparative Example 1, the adherence of organisms was already observed after 3 months, and in Comparative Examples 2 to 4 also the adherence of organisms was observed after 6 months, showing poor antifouling performance. there were.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

[0031]

[Table 4]

Claims (2)

[Claims] 1. A coating composition comprising a reaction-curable silicone rubber and a polysiloxane containing only one silanol group reactive with the reaction-curable silicone rubber in the molecule. 2. The reaction-curable silicone rubber contains a polysiloxane containing only one silanol group reactive with the reaction-curable silicone rubber in the molecule, and a surface lubricant. Coating composition.