JPH04370163A - Coating composition - Google Patents

Abstract

PURPOSE:To provide a coating composition containing a reaction-curable silicone rubber, a specific polysiloxane, a phenol compound, and an organic amine compound, preventing the adhesion of aquatic organisms to structures in water and having an excellent antifouling property for a long period. CONSTITUTION:The objective composition contains (A) a reaction-curable silicone rubber. (B) a polysiloxane having only a silanol group reactive with the component A in the molecule, (C) a compound of the formula (Ph is benzene ring; R is alkyl; n is 0-3; m is an integer of 1-3; R, OH can be bonded to either of the six carbon atoms in the benzene ring, respectively) (e.g. cresol) and (D) an organic amine compound (e.g. aniline).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition that prevents aquatic organisms from adhering to various underwater objects immersed in water.

0002

[Prior Art] The surfaces of underwater objects such as ship bottoms, buoys, fishing nets (aquaculture nets, fixed nets, etc.), underwater pollution prevention membranes, and various intake and drainage pipes for cooling, which are immersed in water, are covered with barnacles,
Various problems occur due to the adhesion of celluloids, mussels, algae, etc. In order to prevent contamination by these organisms,
It is well known that antifouling coatings are applied to the surfaces of objects immersed in water.

[0003]Currently, as an antifouling coating material that utilizes the physical property of silicone rubber such as low surface tension, for example, Japanese Patent Publication No. 53-35974 discloses a coating material using vulcanized silicone rubber as a coating material. JP-A-51-96830 discloses a method using a mixture of an oligomeric silicone rubber having a hydroxyl end group and a silicone oil.

Furthermore, JP-A-53-79980 discloses a mixture of vulcanized silicone rubber and a fluid organic compound containing no metal or silicon. Also,
Japanese Patent Publication No. 60-3433 discloses a mixture of oligomeric cold-setting silicone rubber and liquid paraffin or petrolatum.

[0005]

[Problems to be Solved by the Invention] All of these conventionally known antifouling coatings utilize the low surface tension of the silicone rubber coated surface to prevent aquatic organisms from adhering to the surface. However, the problem with a single silicone rubber film is that the siloxane part, which exhibits low surface tension and is involved in so-called antifouling performance, is fixed at both ends by crosslinking, so there is no flexibility. , the low surface tension during the immersion period cannot be maintained for a long period of time.

[0006] Furthermore, coatings obtained by physically mixing silicone rubber with various fluids such as silicone oil and petrolatum also show that when the coating is immersed in seawater, the silicone - These fluids will be released into the sea from the rubber surface over time. Therefore, in the long run, the above-mentioned drawbacks of the silicone rubber film alone will still be exhibited.

[0007] For these reasons, it has been recognized that all types have drawbacks in their antifouling effects, particularly in their long-term antifouling durability. An object of the present invention is to provide a coating composition that does not have the above-mentioned drawbacks of the prior art and has good antifouling performance.

[0008]

[Means for Solving the Problems] As a result of intensive research on the above points, the present inventors have developed a coating composition that maintains the above-mentioned characteristics of silicone rubber and exhibits a remarkable effect on antifouling durability. The present invention was successfully completed.

That is, the present invention provides A) a reaction-curing silicone rubber; and B) a polysiloxane containing only one silanol group in its molecule that is reactive with the reaction-curing silicone rubber. , C) The following general formula (1); (R)
n -Ph-(OH)m...(1) (wherein Ph is a benzene ring, R is an alkyl group, n is an integer of 0 to 3, m is an integer of 1 to 3, and R and OH group are D) an organic amine compound;
The present invention relates to a coating composition characterized in that it further contains E) a surface lubricant in addition to the four components D to D.

0010

[Structure and operation of the invention] The reaction-curable silicone rubber of component A used in the present invention can be cured by exposure to the atmosphere, by mixing with a catalyst, by heating, or by irradiating with ultraviolet rays. The main component is polyorganosiloxane having siloxane bonds, which hardens through a chemical reaction to give a rubber-like elastic body.

[0011] As an example of a commercially available product of this component A, for example, the product name TSE370RT manufactured by Toshiba Silicone Co., Ltd.
V, YE3085, TSE382RTV, TSE388
W, TSE385RTV, TSE3851, Tosseal 371, Tosseal 381, Tosseal 380, Tosseal 10, Toscoat 10, TSE3033, TSJ3
130, TSJ3150, TSE350RTV, TSE
3562, Tosseal 361, TSE3434RTV,
YE5626, TSE322, TSE325, TSE3
360, TLM1025, TUV6000, TUV60
20, YE5505, etc., and product names KE41, KE42S, KE44, KE45, KE manufactured by Shin-Etsu Chemical Co., Ltd.
45S, KE445, KE347, KE3475, etc., and product names SE5004, SE9175, SE9176, SE91 manufactured by Dow Corning Toray Silicone Co., Ltd.
85, SE9186, SE9188, SE9189, S
Examples include H780, SH781, SE792, SE5070, etc., but are not necessarily limited to these.

The polysiloxane as the component B used in the present invention contains only one silanol group in the molecule that is reactive with the reaction-curing silicone rubber as the component A. When combined with other ingredients, when immersed in water, it combines with the water repellency of silicone rubber to maintain water repellency over a long period of time, and exhibits an excellent antifouling effect. This is because it contains only one silanol group in the molecule, so it bonds at only one point in the silicone rubber, and as a result, the polysiloxane group, which is fixed at one end, can move freely on the coating surface. On the other hand, because one end is fixed, it does not come off as easily as silicone rubber coatings, and its low surface tension is maintained over a long period of time, providing a good coating surface with antifouling performance. be.

In the polysiloxane of component B, the organic group bonded to the silicon atom is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an aryl group such as a phenyl group, or a fluoro-substituted group. Examples include those consisting of an alkyl group and an aryl group. As a commercially available product, for example, the product name FM-091 manufactured by Chitsuso Co., Ltd.
1, FM-0921, FM-0925, etc.
One or more of these may be selected and used, but the invention is not necessarily limited to these.

The amount of the polysiloxane (B component) to be used is appropriately determined by taking into consideration the drying properties, adhesion properties, etc. based on the reaction-curing silicone rubber (A component) and the antifouling performance. Generally, the proportion of component B in the total amount of both components A and B is normally in the range of 0.1 to 90% by weight, preferably 0.5 to 86% by weight.

In the present invention, in addition to the above-mentioned components A and B, a compound represented by the general formula (1) as component C,
By using it in combination with the organic amine compound of component D, even better results can be given to the antifouling performance of the silicone rubber film, and the antifouling property and its durability can be further improved.

Examples of the compound represented by the general formula (1) as component C include methylphenol, ethylphenol, butylphenol, octylphenol, nonylphenol, decylphenol, and dodecylphenol. Examples include alkylphenols at ortho, meta, and para positions having linear or branched alkyl groups. In addition, dialkylphenols consisting of the same alkyl group as above,
Trialkylphenols, monoalkylcatechols, dialkylcatechols, trialkylcatechols, monoalkylresorcinols, dialkylresorcinols, trialkylresorcinols monoalkylhydroquinones, dialkylhydroquinones, trialkylhydroquinones, monoalkylpyrogallols,
Dialkylpyrogallols, trialkylpyrogallols, monoalkylphloroglucinols, dialkylphloroglucinols, trialkylphloroglucinols, monoalkylhydroxyhydroquinones, dialkylhydroxyhydroquinones and trialkylhydroxyhydroquinones, phenol, catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, etc., and one or more of these may be selectively used. However, it is not necessarily limited to these.

The organic amine compound of component D includes methyl group, ethyl group, propyl group, octyl group, nonyl group,
Primary, secondary, or tertiary alkylamines containing one or more types of linear, branched, or cyclic alkyl groups such as dodecyl groups; primary such as ethylenediamine, hexamethylenediamine, and triethylenediamine; , secondary or tertiary alkylene diamines, ortho-, meta-, or para-substituted anilines such as aniline, methylaniline, nitroaniline, chloroaniline, and bromoaniline, and phenylenediamines such as methyl-diaminobenzene and halogeno-diaminobenzene. In addition, aliphatic modified amines and aromatic modified amines that are used as epoxy curing agents can be mentioned, and one or more of these can be selected and used, but it is not necessarily limited to these. Not.

The amounts of the compound represented by the general formula (1) as component C and the organic amine compound as component D are determined based on the performance such as drying properties and adhesion based on the reaction-curing silicone rubber as component A. Furthermore, it is appropriately set in consideration of the antifouling performance and the synergistic effect of the polysiloxane as component B used in combination. Generally, the total proportion of component C and component D in the total amount of four components A to D is usually in the range of 0.1 to 95% by weight, preferably 0.5 to 90% by weight. It's good to have one. Further, within this range, the proportion of component C in the total amount of the four components A to D is usually 0.1 to 90% by weight, preferably 0.5 to 85% by weight, and the proportion of component D is , usually 0.
The content is preferably 1 to 90% by weight, preferably 0.5 to 85% by weight.

[0019] In the present invention, excellent antifouling properties can be exhibited by the combination of the above four components A to D.
In addition to these four components, by further using component E, a surface lubricant, the antifouling property and its durability can be further improved.

As the surface slipping agent of component E, various substances known to impart surface slipping properties to the coating can be used. A typical example is ■JIS-K2
Petroleum wax specified in 235, ■JIS-K223
Liquid paraffin specified in 1, ■ 55 at 25°C
Silicone with a kinematic viscosity of 000 centistokes or less
■Fatty acids with 8 or more carbon atoms and their esters having a melting point of -5℃ or higher, ■6000 at 26℃
Examples include polybutene having a kinematic viscosity of 0 centistokes or less.

[0021] As a specific example of the above (■), JIS-K22
35 120P, 125P, 130P, 135P, 14
Paraffin wax such as 0P, 145P, 150P, 155P, 150M, 160M of JIS-K2235,
Examples include microcrystalline waxes such as 170M, 180M, and 190M, and petrolatum such as JIS-K2235 No. 1, No. 2, No. 3, and No. 4.

[0022] Specific examples of the above (■) include ISOVG10,
ISOVG15, ISOVG32, ISOVG68, I
Examples include products equivalent to SOVG100.

[0023] As a specific example of the above (■), Shin-Etsu Chemical Co., Ltd. (
Co., Ltd. product name KF96L-0.65, KF96L-2
．． 0, KF96-30, KF96-100, KF96H
-50000, KF965, KF50, KF54, KF
69, FL100, etc., manufactured by Toshiba Silicone Co., Ltd. with product names TSF440, TSF410, TSF4440, TS
F431, TSF433, TSF404, TFA420
0, YF3860, YF3818, YF3965, YF
3841, YF3953, TSF451, TSF400
, FQF501, etc., Toray Dow Corning Silico
Product names: SH200, SH510, SH35 manufactured by N Co., Ltd.
31, SH230, FS1265, etc.

The most common silicone oil mentioned above is dimethyl silicone oil, but other silicone oils include methylphenyl silicone oil, polyether silicone oil, cyclic polysiloxane oil, and alkyl-modified silicone oil.
Other materials such as silicone oil, methylchlorinated phenyl silicone oil, higher fatty acid-modified silicone oil, and fluorosilicone oil may also be used.

Specific examples of the above (①) include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid,
Stearic acid, cerotic acid, montanic acid, melisic acid,
Examples include lauroleic acid, oleic acid, vaccenic acid, gadoleic acid, whale oil acid, shark oil acid, and diuniperinic acid. In addition, esters of these carboxylic acids include stearyl stearate, butyl laurate, octyl palmitate, butyl stearate, and isopropyl stearate.
Cetyl palmitate, seryl cerotate, myricyl palmitate, merisyl merisate, spermaceti, beeswax, carnauba wax, montan wax, white wax, tristearin, tripalmitin, triolein, myristodilaurin, caprylolauro Myristicin, stearopalmitolein, monostearin, monopalmitin, distearin, dipalmitin, beef tallow, lard, horse tallow, mutton tallow, cod liver oil, coconut oil, palm oil, wax, kapok oil, cacao oil, cacao Examples include fat, China fat, and Iritupe fat.

[0026] As a specific example of the above (■), Nippon Oil & Fats Co., Ltd.
Product name: Nitsusan Polybutene 0N, 06N, 015N
, 3N, 5N, 10N, 30N, 200N, 0SH, 0
6SH, 015SH, 3SH, 5SH, 10SH, 30
Examples include SH and 200SH.

In the present invention, one or more of the above-mentioned surface lubricants are selected and used, and the amount used is determined by the drying amount based on the reaction-curing silicone rubber of component A. It is appropriately set in consideration of performance such as adhesiveness and adhesion, antifouling performance, and the synergistic effect of components B to D used together. Generally, the proportion of the surface lubricant component E in the total amount of the five components A to E is preferably 80% by weight or less, particularly preferably 70% by weight or less.

The coating composition of the present invention is characterized by containing the above four components A to D or five components A to E as essential components, and the composition containing these components is usually Use by diluting with a solvent.

Examples of organic solvents used for this 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, alcohol solvents such as isopropyl alcohol and butyl alcohol, ether solvents such as dioxane and diethyl ether, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. , methyl cellosolve, ethyl cellosolve, cellosolve acetate, and other cellosolve solvents, and one or more of these may be used.

[0030] The coating composition of the present invention may contain, if necessary,
Various compounding agents such as coloring pigments, extender pigments, anticorrosive pigments, dyes, anti-sagging agents, plasticizers, anti-color separation agents, anti-settling agents, antifoaming agents, and antifouling agents may be added.

[0031]

[Effects of the Invention] As described above, the coating composition of the present invention has
By using the four components A to D or the five components A to E in combination, the conventional silicone rubber alone or silicone rubber can be used in combination.
The antifouling effect is significantly improved compared to when used in combination with oil, petrolatum, etc., and the antifouling property is maintained for a long period of time. Therefore, the coating obtained from the coating composition of the present invention has extremely good antifouling properties in underwater structures such as ship bottoms, fishing nets and various cooling water pipes, and marine pollution prevention films that require prevention of aquatic biological fouling. It is effective and can prevent biofouling of substrates submerged in water over a long period of time.

[0032]

[Examples] Next, Examples and Comparative Examples of the present invention will be described in more detail. Note that all parts in the examples are parts by weight.

Examples 1 to 19 Using the four components A to D or the five components A to E, the compositions shown in Tables 1 to 5 below (the values in the tables are weight %) were prepared.
Mix and disperse with a homomixer at 2000 rpm to obtain 19
A seed coating composition was prepared.

[0034] In addition, among the blended ingredients, used as component A,
KE45S (50% by weight toluene solution), KE42, K
E445 is a trade name manufactured by Shin-Etsu Chemical Co., Ltd.
The SE5004 is manufactured by Toray Dow Corning Silicone (
YE5505 (50% by weight toluene solution) is a product name manufactured by Toshiba Silicone Corporation. FM-0911, FM-0921, F used as component B
M-0925 is a trade name manufactured by Chitsuso Corporation.

[0035] Petrolatum No. 1 used as component E is a JIS-K2235 petroleum wax and ISOV
G10 is JIS-K2231 liquid paraffin, KF
96-100, KF54, and FL100 (all trade names manufactured by Shin-Etsu Chemical Co., Ltd.) are silicone oils, and Nitsusan Polybutene 06N (trade names manufactured by Nippon Oil & Fats Co., Ltd.) is polybutene.

[0036] Also, Disparon 6900-20X [trade name manufactured by Kusumoto Kasei Co., Ltd.] and Aerosil 300 [
[Product name manufactured by Nippon Aerosil Co., Ltd.] are all additives for preventing sagging.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

[Table 5]

Comparative Examples 1 to 4 Four types of coating compositions were prepared in the same manner as Examples 1 to 19 using the formulations shown in Table 6 below.

[0043]

[Table 6]

[0044] Above Examples 1 to 19 and Comparative Examples 1 to 4
The following antifouling performance test was conducted for each coating composition. The results are shown in Table 7 below.

<Antifouling performance test> Each coating composition was applied to both sides of a painted plate (100 mm x 200 mm x 1 mm) prepared by applying a tar-vinyl anti-corrosion paint to a sandblasted steel plate in advance, with a dry film thickness of one side. A test plate was prepared by spray painting twice to a thickness of 120 μm and then air-drying it indoors for 7 days. This test board was immersed in water for 24 months in Yura Bay, Sumoto City, Hyogo Prefecture, and the ratio of the area occupied by attached organisms (adhesion area) on the test board was measured over time.

[0046]

[Table 7]

From the results shown in Table 7 above, in Examples 1 to 19, there was no attachment of living things even after 24 months, and it is clear that the coating composition of the present invention maintains excellent antifouling performance even over a long period of time. It is. On the other hand, in Comparative Example 1, attachment of organisms was already observed after 3 months, and in Comparative Examples 2 to 4,
However, after 6 months, adhesion of living organisms was observed, and the antifouling performance was poor.

Claims (2)

[Claims] [Claim 1] A) reaction-curing silicone rubber, and B
) A polysiloxane containing only one silanol group in the molecule that is reactive with this reaction-curing silicone rubber, and C) the following general formula (1); (R) n -Ph-(OH )m...(1)
(In the formula, Ph is a benzene ring, R is an alkyl group, n is 0-
D) an organic amine compound; A paint composition characterized by containing. 2. The coating composition according to claim 1, further comprising E) a surface lubricant in addition to the four components A to D.