JPH0578618A - 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 and alkylphenols, etc., in the silicone rubber, capable of preventing fouling by aquatic organisms and usable for 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 (C) a compound expressed by the formula (Ph is benzene ring; R is alkyl; (n) is an integer of 0-3; (m) is an integer of 1-3) 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 The surface of underwater objects such as ship bottoms, buoys, fishing nets (aquaculture nets, stationary nets, etc.), underwater pollution prevention membranes, various intake and drainage pipes for cooling, which are immersed in water, have barnacles,
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 an antifouling coating agent utilizing the physical property of silicone rubber, which has a small surface tension,
For example, Japanese Examined Patent Publication (Kokoku) No. 53-35974 discloses a vulcanized silicone rubber used as a coating agent, and Japanese Laid-Open Patent Publication (Kokai) No. 51-96830 discloses an oligomeric silicone rubber having a hydroxyl end group. And a mixture of silicone oil with silicone oil is shown. Furthermore, JP-A-53-799
Japanese Patent Publication No. 80 discloses a mixture of vulcanized silicone rubber and a fluid organic compound containing no metal or silicon. Furthermore, Japanese Patent Publication No. 60-3433 discloses a mixture of an oligomeric room temperature curable silicone rubber and liquid paraffin or petrolatum.

[0004]

These conventionally known antifouling coating agents utilize the low surface tension of the silicone rubber coated surface to prevent the adhesion of aquatic organisms to the 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 so-called antifouling properties is fixed by crosslinking at both ends, so there is no degree of freedom and the low level during dipping. It is considered 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 will be 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 coating composition having good antifouling performance without the above-mentioned drawbacks of the prior art.

[0005]

Means for Solving the Problems As a result of intensive studies on the above points, the present inventors have found a coating composition which maintains the characteristics of the silicone rubber and has a remarkable effect on antifouling durability. The present invention was completed successfully. That is, the present invention provides a polysiloxane containing only one silanol group having reactivity with a reaction-curable silicone rubber in the molecule, and a general formula (a): (R). _n --Ph- (OH) _m (wherein Ph represents a benzene ring, R represents an alkyl group, n represents an integer of 0 to 3, and m represents an integer of _{1 to} 3. In addition, R and The OH group may be bonded to any of the six carbon atoms forming a benzene ring.), And a coating composition comprising:
The coating composition further comprises a surface lubricant.

The reaction-curable silicone rubber (referred to as component (1)) used in the present invention 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 that cures to give a rubber-like elastic body. For example, trade names TSE370RTV and 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 reaction-curable silicone rubber with polysiloxane containing only one silanol group which reacts with them (referred to as component (2)), it is combined with the water repellency of the silicone rubber during immersion. ,
Furthermore, it is possible to obtain a coating composition that maintains water repellency for a long period of time and, as a result, exhibits an excellent antifouling effect. 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 reactive with the reaction-curable silicone rubber in the molecule, is bonded to the silicone rubber at only one point in the silicone rubber. 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 drying property based on the reaction-curable silicone rubber is
It is appropriately set in consideration of performance such as adhesion and antifouling performance. Generally, the proportion of polysiloxane containing only one silanol group in the molecule is 0.1% by weight in the total amount of reaction-curable silicone rubber and polysiloxane containing only one silanol group in the molecule. As described above, it is preferably 90% by weight or less.

The general formula (a): (R), which is used in combination with the above reaction-curable silicone rubber and a polysiloxane containing only one silanol group which reacts with these (referred to as component (2)). _n --Ph- (OH) _m (wherein Ph represents a benzene ring, R represents an alkyl group, n represents an integer of 0 to 3, and m represents an integer of _{1 to} 3. In addition, R and The OH group can bind to any of the six carbon atoms forming the benzene ring.) (Referred to as component (3)) exhibits a better synergistic effect on the antifouling effect of the silicone rubber coating. To do. Examples thereof include ortho-, meta-, and para-position alkylphenols having a linear or branched alkyl group such as methylphenol, ethylphenol, butylphenol, octylphenol, nonylphenol, decylphenol, and dodecylphenol. Furthermore, dialkylphenols, trialkylphenols, monoalkylcatechols, dialkylcatechols, trialkylcatechols, monoalkylresorcinols, dialkylresorcinols, trialkylresorcinols, monoalkylhydroquinones consisting of the above alkyl groups. , Dialkylhydroquinones, trialkylhydroquinones,
Monoalkyl pyrogallols, dialkyl pyrogallols, trialkyl pyrogallols, monoalkyl phloroglucinols, dialkyl phloroglucinols, trialkyl phloroglucinols, monoalkyl hydroxyhydroquinones, dialkyl hydroxyhydroquinones, trialkyl hydroxyhydroquinones , Phenol, catechol, resorcinol, hydroquinone,
Pyrogallol, phloroglucinol, hydroxyhydroquinone and the like can be mentioned, and one kind or two or more kinds thereof are selectively used, but not limited thereto.

In the present invention, as described above, the amount of the component (3) represented by the general formula (a) is set such that the reaction-curable silicone rubber has properties such as drying property and adhesiveness and further protection. It is appropriately set in consideration of the stain performance.
Generally, reaction-curable silicone rubber and component (2)
The proportion of the component (3) in the total amount of the component and the component (3) is preferably 0.1% by weight or more and 90% by weight or less.

Further, in the present invention, excellent antifouling property can be exhibited only by the combination of the above reaction-curable silicone rubber with the component (2) and the component (3). Antifouling property can also be improved by using an agent (referred to as component (4)). Further, the surface slip agent is composed of the above-mentioned reaction-curable silicone rubber, and polysiloxane (component (2)) and component (3) containing only one silanol group reactive with it. When used in combination with a mixed system, a synergistic effect is exhibited, and it is important in that the antifouling performance is further prolonged.

Therefore, as such a surface slipping agent which can be used in the present invention, various substances known to impart 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, 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, ISOVG10,
ISOVG15, ISOVG32, ISOVG68, I
Each equivalent of SOVG100 etc. are mentioned. As a specific example of the above, the product name KF96 manufactured by Shin-Etsu Chemical Co., Ltd.
L-0.65, KF96L-2.0, KF96-30,
KF96-100, KF96H-50000, KF96
5, KF50, KF54, KF69, FL100, trade name TSF440, TSF41 manufactured by Toshiba Silicone Co., Ltd.
0, TSF4440, TSF431, TSF433, T
SF404, TFA4200, YF3860, YF38
18, YF3965, YF3841, YF3953, T
SF451, TSF400, FQF501, trade name SH200 manufactured by Toray Dow Corning Silicone Co., Ltd.,
SH510, SH3531, SH230, FS1265
Etc. 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.

As specific examples of the above, 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, Examples thereof include whale oil acid, shark oil acid, and juniperic acid. Further, as the ester 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, white wax. , Tristearin, tripalmitin, triolein, myristodilaurin, caprylolauromyristin, stearopalmitoolein, monostearin, monopalmitin, distearin, dipalmitin, beef tallow, lard, horse fat, sheep fat, cod liver oil ,
Examples thereof include coconut oil, palm oil, wood wax, kapok oil, cocoa oil, cocoa butter, Chinese fat, and illipe fat.

Further, specific examples of the above include Nissan Polybutene 0N, 06N, 0 manufactured by Nippon Oil & Fats Co., Ltd.
15N, 3N, 5N, 10N, 30N, 200N, 0S
H, 06SH, 015SH, 3SH, 5SH, 10S
H, 30SH, 200SH and the like. 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.
It is preferably below 60% by weight.

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. And component (3), or a component which further contains a surface lubricant, and is usually diluted with an organic solvent before use.

Examples of the organic solvent used for the above purpose include aromatic hydrocarbon solvents such as xylene and toluene, aliphatic hydrocarbon solvents such as hexane and heptane, ester solvents such as ethyl acetate and butyl acetate, and isopropyl alcohol. , Alcoholic solvents such as butyl alcohol,
Ether solvents such as dioxane and diethyl ether,
Examples thereof include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and cellosolve solvents such as methyl cellosolve, ethyl cellosolve and cellosolve acetate, which may be used alone or as a mixed solvent thereof.

Further, in the coating composition of the present invention, a coloring pigment, an extender pigment, an anticorrosive pigment, a dye, an anti-sagging agent, a plasticizer, an anti-color separation agent, an anti-settling agent, an antifoaming agent, an anti-foaming agent and It does not matter if you add dirt.

[0021]

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 fishing nets and various underwater structures such as various cooling water pipes, which need to prevent underwater biological pollution,
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 time.

[0022]

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.

KE45S (50% by weight)
Toluene solution), KE42, and KE445 are trade names of reaction-curable silicone rubbers manufactured by Shin-Etsu Chemical Co., Ltd., and SE5004 manufactured by Toray Dow Corning Silicone Co., Ltd. In addition, FM-0911 and FM-0921
And FM-0925 are trade names of silicone rubber having only one silanol group, manufactured by Chisso Corporation.

Furthermore, paraffin wax 120P
Petrolatum No. 1 is a petroleum wax of JIS-K2235, and ISOVG10 is a liquid paraffin of JIS-K2231. Furthermore, KF96-100, K
F54, 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, Disparlon 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 kinds of coating compositions having the composition shown in the following Table 3 were prepared. Examples 1 to 1 above
Each of the coating compositions of 19 and Comparative Examples 1 to 4 was subjected to the following antifouling performance test. That is, each coating composition,
7 days after spray-coating twice on both sides of a coated board (100 × 200 × 1mm) prepared by applying tar vinyl-based anticorrosive paint to a sandblasted steel sheet in advance so that the dry film thickness is 120 μm on each side, A test plate was prepared by naturally drying in a room.

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,
It is clear that even after 24 months, there is no attachment of organisms, and the coating composition of the present invention retains excellent antifouling performance for 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 the adherence of organisms was observed after 6 months, showing poor antifouling performance. there were.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

Claims (2)

[Claims] 1. A polysiloxane containing only one silanol group reactive in a reaction-curable silicone rubber in the molecule, and a general formula (a): (R) _n −. Ph- (OH) _m (wherein Ph represents a benzene ring, R represents an alkyl group, n represents an integer of 0 to 3, and m represents an integer of 1 to 3. In addition, R and OH are A coating composition comprising a compound represented by the formula (1) which can bind to any of the six carbon atoms forming a benzene ring. 2. A polysiloxane containing only one silanol group having reactivity with a reaction-curable silicone rubber in the molecule, and a general formula (a): (R) _n −. Ph- (OH) _m (wherein Ph represents a benzene ring, R represents an alkyl group, n represents an integer of 0 to 3, and m represents an integer of 1 to 3. In addition, R and OH are A coating composition comprising a compound represented by the formula (1) which can bind to any of the six carbon atoms forming a benzene ring and a surface lubricant.