JP3248191B2 - Paint composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art The surface of an underwater object such as a ship bottom, a buoy, a fish net (aquaculture net or a stationary net), an underwater pollution prevention film, and various suction / drainage pipes for cooling is buried in a barnacle,
Various obstacles occur due to adhesion of serpula, mussels, algae and the like. To prevent pollution by those organisms,
It is well known that an antifouling coating is applied to the surface of a submerged object.

At present, many antifouling coating agents using antifouling agents such as organotin copolymers and cuprous oxide are used. However, due to the problem of environmental pollution, a pollution-free antifouling coating agent has been demanded. For example, Japanese Patent Publication No. 53-35974 discloses a coating agent using a vulcanized silicone rubber as a coating agent. In JP-A-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, Tokiko Sho 60
Japanese Patent No. -3433 discloses a mixture of an oligomeric cold-setting silicone rubber and liquid paraffin or petrolatum.

[0004]

These conventional antifouling coating agents are intended to prevent the adhesion of living organisms to the surface by utilizing the low surface tension of the surface coated with silicone rubber. However, as a problem, the silicone rubber alone film exhibits a low surface tension, and the siloxane portion involved in the so-called antifouling performance is fixed at both ends by cross-linking. It seems that the surface tension cannot be maintained for a long time. Also, a coating obtained by physically mixing silicone oil, petrolatum, etc. with silicone rubber, due to the physical mixing, when the coating is immersed in seawater, these fluids flow from the silicone rubber surface over time. The body will be released into the sea. Therefore, in the long term, it shows the disadvantages of the silicone rubber single film. From these facts, it was found that each type had a problem in the antifouling effect, particularly the long-term antifouling durability.

[0005] An object of the present invention is to provide a non-toxic coating composition which does not have the above-mentioned drawbacks of the prior art and has good antifouling performance while utilizing the features of silicone rubber.

[0006] The present invention relates to a method for preparing a reaction-curable silicone rubber as a reactive group for the reaction-curable silicone rubber.
One only look including a silanol group in the molecule, the silanol groups
An underwater antifouling coating composition characterized by containing a polysiloxane containing no silanol group other than the above, and an underwater antifouling coating composition further comprising a specific surface lubricant in the underwater antifouling coating composition. It is an antifouling paint composition.

[0007] The reaction-curable silicone rubber (referred to as component (1)) used in the present invention is subjected to a chemical reaction by exposing it to the atmosphere, mixing a catalyst, heating, or irradiating ultraviolet rays. It is mainly composed of a polyorganosiloxane having a siloxane bond, which cures to give a rubber-like elastic body. In the present invention, generally a condensation type
One-part RTV rubber (room temperature cured silicone rubber)
Of those, further limited to those not based on dehydrocondensation reaction
I do. For example, TSE3 (trade name, manufactured by Toshiba Silicone Co., Ltd.)
70RTV, YE3085, TSE382RTV, TS
E388W, TSE385RTV, TSE3851, Toss seal 371, Toss seal 381, Toss seal 38
0, Toss seal 10, Toss coat 10, TSE303
3, TSJ3130, TSJ3150, TSE350R
TV, TSE3562, Tosseal 361, TSE34
34RTV, YE5626, TSE322, TSE32
5, TSE3360, TLM1025, TUV600
0, TUV6020, YE5505, etc., and product names KE41, KE42S, KE44 manufactured by Shin-Etsu Chemical Co., Ltd.
KE45, KE45S, KE445, KE347, KE
3475, etc., and trade names SE5004, SE9175, SE9 manufactured by Dow Corning Toray Silicone Co., Ltd.
176, SE 9185, SE 9186, SE 9188,
SE9189, SH780, SH781, SE792,
SE5070 and the like, but are not necessarily limited thereto.

By combining the above-mentioned reaction-curable silicone rubber with a polysiloxane containing only one silanol group in the molecule (referred to as component (2)), the silicone rubber is combined with the water repellency of the silicone rubber during immersion. ,
Furthermore, a coating composition that maintains water repellency for a long period of time and, as a result, exhibits excellent antifouling curing can be obtained. As a polysiloxane containing only one of these silanol groups 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 include an aryl group, a fluoro-substituted alkyl group and an aryl group. For example, Chisso Corporation
Trade names FM-0911, FM-0921, FM-0
925 and the like, and one or more of them can be selectively used, but the present invention is not necessarily limited thereto.

The polysiloxane having only one silanol group reactive with the reaction-curable silicone rubber in the molecule used in the present invention is bonded to the silicone rubber at only one point in the silicone rubber. The fixed polysiloxane group can move freely on the coating surface and one end is fixed, so it does not separate from the silicone rubber coating 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 determined based on the dryness based on the reaction-curable silicone rubber,
It is appropriately set in consideration of performance such as adhesion and antifouling performance. Generally, the ratio of the polysiloxane containing only one silanol group in the molecule to the total amount of the reaction-curable silicone rubber and the polysiloxane containing only one silanol group in the molecule is 0.1%. As described above, the content is preferably 90% by weight or less.

In the present invention, excellent antifouling properties can be exhibited only by a combination of the above reaction-curable silicone rubber and a polysiloxane containing only one silanol group which reacts with the above-mentioned silicone rubber. By using a surface lubricating agent (referred to as component (3)) together with these, the antifouling property can be improved. In addition, the surface lubricating agent has a synergistic effect when used in combination with the above-mentioned reaction-curable silicone rubber and a polysiloxane containing only one silanol group having a reactivity with the above-mentioned silicone rubber in the molecule. It is important in that it is exhibited and the antifouling performance is further maintained.

Thus, examples of such a surface lubricating agent that can be used in the present invention include various substances known to impart surface lubricating properties to a coating film. As typical examples, 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 higher A fatty acid having 8 or more carbon atoms and its ester, an organic amine having an alkyl group or an alkenyl group having 12 to 20 carbon atoms, and a polybutene having a kinematic viscosity of 60,000 centistokes or less at 26 ° C.

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

As a specific example of the above, ISOVG1
0, ISOVG15, ISOVG32, ISOVG6
8, each equivalent of ISOVG100, and the like. As a specific example of the above, a product 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 made 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 Dow Corning Toray Silicone Co., Ltd.
200, SH510, SH3531, SH230, FS
1265 and the like. The above silicone oil is most commonly dimethyl silicone oil, but other methylphenyl 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, melicic acid, lauroleic acid, oleic acid, vaccenic acid, and gadolinic acid. , Whale oil, shark oil, diuniperic acid, and the like. Further, as esters of these carboxylic acids, stearyl stearate, butyl laurate, octyl palmitate, butyl stearate, isopropyl stearate, cetyl palmitate, seryl cellulose, myristyl palmitate, merisil melisate, spermaceti, beeswax,
Carnauba wax, montan wax, insect white wax, tristearin,
Tripalmitin, triolein, myristodilaurin,
Caprylo lauromyristin, stearopalmito olein, monostearin, monopalmitin, distearin,
Examples include dipalmitin, beef tallow, lard, horse tallow, sheep tallow, cod liver oil, coconut oil, palm oil, wood wax, kapok oil, cocoa oil, cocoa butter, china fat, and illipe fat.

Specific examples of the above include dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, tallowalkylamine, cocoalkylamine, soybean oilalkylamine, didodecylamine, ditallow hydrogenated alkylamine. , Dodecyldimethylamine, cocoalkyldimethylamine, tetradecyldimethylamine, hexamethyldimethylamine,
Octadecyldimethylamine and the like.

As a specific example of the above, Nippon Oil & Fats Co., Ltd.
Nissan Polybutene 0N, 06N, 015
N, 3N, 5N, 10N, 30N, 200N, 0SH,
06SH, 015SH, 3SH, 5SH, 10SH, 3
0SH, 200SH and the like. In the present invention, one kind or two or more kinds are selected and used from the various surface lubricants as described above, and the amount used is such as drying property based on the reaction-curable silicone rubber, adhesion and the like. It is appropriately set in consideration of the performance and the antifouling performance.
Generally, the ratio of the surface lubricant to 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. Alternatively, these are further characterized by further containing a surface lubricant, and are usually used after being diluted with an organic solvent. 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, isopropyl alcohol, and butyl alcohol. Alcohol solvents such as dioxane, diethyl ether, etc .; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; cellosolve solvents such as methyl cellosolve, ethyl cellosolve, cellosolve acetate; No.

The coating composition of the present invention may further contain a coloring pigment, an extender pigment, an anticorrosive pigment, a dye, an anti-sagging agent, a plasticizer, an anti-segregation agent, an anti-settling agent, an antifoaming agent, It is safe to add 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 remarkably improved antifouling effect, and the antifouling property is maintained for a long period of time. For this reason, underwater structures such as ship bottoms, fish nets and various cooling water pipes that require prevention of underwater biofouling,
Further, in a marine pollution prevention film or the like, the film obtained by the present invention exhibits an extremely good antifouling effect, and can prevent biological adhesion fouling of a submerged substrate in water for a long time.

[0021]

EXAMPLES The present invention will be specifically described below with reference to production examples, examples and comparative examples of polymers. Parts in the examples represent parts by weight. Examples 1 to 19 Using a reaction-curable silicone rubber, the composition shown in the following Tables 1 to 3 (the numerical values in the table are% by weight) was 2,000 rpm.
Were mixed and dispersed by a homomixer of No. 1 to prepare 19 kinds of coating compositions.

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

Furthermore, paraffin wax 120P
And Petrolatum 1 are petroleum waxes of JIS-K2235, and are ISOVG10 and ISOVG100.
Is liquid paraffin according to JIS-K2231. Further, KF96-100, KF54 and FL100 (trade names manufactured by Shin-Etsu Chemical Co., Ltd.) are silicone oils,
Nissan polybutene 06N and 200N (trade names manufactured by NOF Corporation) are polybutenes.

Oil Blue 2N (trade name of Orient Chemical Co., Ltd.) is a dye, Dispalon 6900-2.
OX (trade name, manufactured by Kusumoto Kasei Co., Ltd.) and AERILIL 300 (trade name, manufactured by Nippon Aerosil Co., Ltd.) are both 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 Table 3 below were prepared.

The coating compositions of Examples 1 to 19 and Comparative Examples 1 to 4 were subjected to the following antifouling performance test. That is, a coating plate obtained by applying a tar vinyl-based rust-preventive coating to a sandblasted steel plate in advance with each coating composition.
(100 × 200 × 1mm) 120μm on both sides
After spray coating twice so as to obtain, the sample was naturally dried in a room for 7 days to prepare a test plate.

The test plate was immersed in water for 24 months in Yura Bay, Sumoto City, Hyogo Prefecture, and the ratio of the occupied area (adhered area) of the attached organisms on the test plate coating was measured over time. Table 4 shows the results. From the results in Table 4, in each example,
1 month after 24 months, no or no organisms
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, organisms were found to adhere after three months, and in Comparative Examples 2 to 4, organisms were found to adhere after six months, indicating poor antifouling performance. there were.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

[0031]

[Table 4]

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 183/04-183/16 C09D 5/14

Claims (2)

(57) [Claims] 1. A condensation type one-component RTV silicone rubber,
As a reactive group for the RTV silicone rubber, only seeing containing one silanol group in the molecule, other than the silanol group
An underwater antifouling coating composition comprising a polysiloxane containing no silanol group . 2. A condensation type one-component RTV silicone rubber,
As a reactive group for the RTV silicone rubber, only seeing containing one silanol group in the molecule, other than the silanol group
From silanol group-free polysiloxanes, and petroleum waxes, liquid paraffin, silicone oils, fatty acids having 8 or more carbon atoms and esters thereof, organic amines having 12 to 20 alkyl or alkenyl groups, and polybutene. An underwater antifouling paint composition comprising at least one surface lubricant selected.