JPH02674A - Underwater antifouling coating - Google Patents

Abstract

PURPOSE:To obtain the subject agent prevented from being denatured during its production, freed of limitation on a pot life and improved in wet-on-wet coatability, storage stability, etc., by mixing a specified (co)polymer with an antifouling agent. CONSTITUTION:A monomer (a) of formula I [wherein X1-2 are each H or CH3 and may be in the cis or trans form; either of Y1-2 is formula II, and the other is H, an alkyl, a (substituted) phenyl or formula II; n is 2-5; m >= 0; R1-3 are each an alkyl, an alkoxyl, a (substituted) phenyl or a (substituted) phenoxy; R4-5 are each R1 or an organosiloxane of formula III; and R1-3 are each R1] is reacted with, optionally, at most 95wt.% vinyl polymerizable monomer (b) copolymerizable with component (a) in the presence of a vinyl polymerization initiator to obtain a (co)polymer (A), of a weightaverage MW of 1000-1500000. A mixture of component A with 0.1-65wt.% antifouling agent (E) is optionally mixed with 1-70 wt. %, based on the total of components A and C, surface lubricant (C).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an underwater antifouling coating containing a polymer having an organosilyl group or an organosiloxane group in its side chain.

[Conventional technology]

The surfaces of underwater objects immersed in seawater, such as ship bottoms, buoys, fishing nets (aquaculture nets for yellowtail and scallops, fixed salmon nets, etc.), underwater pollution prevention sheets, and various intake and drainage pipes for cooling, contain Fujibo, Various problems occur due to the attachment of celluloids, mussels, algae, etc. It is well known that an underwater antifouling coating agent is applied to the surface of objects immersed in seawater in order to prevent staining by these organisms. This coating material can be roughly divided into the following 41 types:

b) Products that use antifouling agents such as organic tin copolymers and cuprous oxide that have an anti-adhesion effect on living things and are slightly soluble in seawater.

For example, regarding coating materials using organic tin compounds as antifouling agents, Japanese Patent Publication No. 40-21426,
No. 4-9579, Japanese Patent Publication No. 4613392, Japanese Patent Publication No. 49-20491, Japanese Patent Publication No. 11647-1987
This method is disclosed in Japanese Patent Publication No. 52-48170, etc.

(1) An antifouling coating agent that does not use an antifouling agent and does not dissolve in seawater, and is vulcanized and three-dimensionally crosslinked by the action of catalyst 5 moisture.
Uses silicone rubber that forms a film.

For example, Japanese Patent Publication No. 53-35974 discloses a coating using vulcanized silicone rubber, and Japanese Patent Publication No. 51-96830 discloses an oligomeric silicone rubber having a hydroxyl terminal group. A mixture of rubber and silicone oil is shown.

Further, JP-A-53-79980 discloses a mixture of vulcanized silicone rubber and a fluid organic compound that does not contain metal or silicone. Furthermore, Japanese Patent Publication No. 60-3433 discloses a marine biofouling prevention product containing a mixture of oligomeric room-temperature curing silicone rubber (for example, Shin-Etsu Chemical Co., Ltd.'s product names KE45TS, KE44 RTV, etc.) and liquid paraffin or petrolatum. Paints for use are shown.

[Problem to be solved by the invention]

These conventionally known underwater antifouling coatings are used depending on the purpose because they can exhibit performance depending on their type, but they all have drawbacks as described below, and it is difficult to improve them. It was strongly desired.

First, there are two types of coating materials mentioned above.

One is that the resin that forms the coating film does not dissolve in seawater.
Antifouling agents are the only type of coating that prevents the attachment of marine organisms by dissolving into seawater. This type of antifouling coating has a good initial antifouling effect. However, after the antifouling agent on the surface of the paint film is eluted and lost, the antifouling agent in the deeper part of the paint film gradually elutes. Because it is slow, it has the disadvantage that the antifouling effect becomes insufficient in the long term.

The other type of coating material is one in which both the resin and the antifouling agent that form the coating are dissolved in seawater. The antifouling effect of this coating may be due to the antifouling agent alone or to both the antifouling agent and the resin component (organic tin copolymer, etc.), but in either case, the coating surface is eluted, so it is always active. Since the antifouling coating surface is maintained, the antifouling effect can be maintained for a longer period of time than the former. However, even in the latter case, there is a limit to wear of the coating film, and the current situation is that satisfactory effects are not obtained.

In addition, all of the mouth coatings utilize the slipperiness of the silicone rubber coated surface to prevent aquatic organisms from adhering to the surface, and like the coating in A. Although it has the advantage of having no eluted components that may cause water pollution, the silicone rubber used to form the film has the following problems in that it undergoes three-dimensional crosslinking to form a film during use. .

First, there is the problem of curing properties after painting. For example, as disclosed in Japanese Patent Publication No. 60-3433, an underwater antifouling coating agent using an oligomeric cold-curing silicone rubber that hardens under the action of moisture in the air to form a film is applied to the surface to be coated. When applied, the crosslinking agent that controls the curing and condensation reaction of silicone rubber is activated by atmospheric moisture and temperature.
For this reason, 1) the surface of the coating film hardens quickly, which on the contrary impedes the curing of the deep part of the coating film, resulting in insufficient curing, and as a result, there is a great risk that the coating film will peel off from the surface to be coated and cause blistering. Furthermore, since moisture penetrates into the interior slowly, the time required for curing becomes longer. In addition, ii) When such an underwater antifouling coating is used in a high temperature and high humidity location, only the hydrolysis of the crosslinking agent takes priority, and the crosslinking density does not increase, resulting in a decrease in the physical properties of the coating film. become. iii) Furthermore, in dry areas, since there is little moisture in the atmosphere, hydrolysis of the crosslinking agent is difficult to occur and the curing of the film is extremely slow. In order to prevent this, catalysts such as tin compounds and platinum are sometimes used as curing accelerators, but their catalytic effects tend to be insufficient at low temperatures.

Second, there is the problem of overcoatability. Normally, the solvent of the topcoat coating material slightly invades the surface of the undercoat and mixes at the interface, improving interlayer adhesion. However, since the base silicone rubber is three-dimensionally crosslinked and cured, does not attack the silicone rubber surface, resulting in poor adhesion.

Thirdly, there is the issue of pot life. Actual painting work can take longer than planned due to the size and complexity of the object to be painted, and sometimes it rains after painting has begun and the surface to be painted gets wet, or the atmosphere becomes too humid and the painting process is delayed. A situation may arise where an interruption occurs and the coating, which has already been opened and stirred, has to sit for a longer time than planned. In such cases, coating materials with a pot life are extremely inconvenient in painting operations.

Fourth, there is the issue of storage stability. Underwater antifouling coatings may be stored for a long period of time from the time they are manufactured until they are used, but those that harden due to moisture have short storage stability unless dry nitrogen gas is sealed during manufacture. Also, -
There was a problem in that when the variable magnification cover was opened, moisture from the atmosphere entered, causing the surface of the coating to harden and thicken, making it difficult to reuse.

[Means to solve the problem]

As a result of intensive research into the above-mentioned points, the present inventors have found that they do not have the various problems of the previously known underwater antifouling coatings, which are made using silicone rubber alone or in combination with silicone oil, paraffin, etc. Furthermore, the sliding angle of the film surface is smaller than these, and good antifouling properties can be expected, especially compared to the above-mentioned underwater antifouling coating agent using a conventionally known organic tin copolymer containing an antifouling agent. In addition to using a specific solvent-volatile polymer that is expected to have even better antifouling properties, we have succeeded in obtaining an underwater antifouling coating that combines this with an antifouling agent and a surface lubricant.

That is, the present invention provides the following general formula (1);
In the formula, X, X2 is a hydrogen atom or a methyl group,
The side groups may be in either cis or trans form. Y, Y2 is one of the two (a); R4R [wherein, n is an integer of 2 to 5, and m is a real number of 0 or more. Each of R1-R1 is a group selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxydyl group, or a substituted phenoxydyl group,
They may be the same group or different groups. R
4, R2 is the same group as R1-R3 above or the following formula (b); -0-3i -R7,...(b) R'3 (However, in the formula, R', ~R' 3 is a group selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxydyl group, a substituted phenoxydyl group, or an organosiloxane group represented by the formula (bl), and is the same group as each other. A group selected from the organosiloxane groups represented by ] is an organic group represented by the formula, and the other is a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group, or a monomer A represented by the above formula (an organic group represented by al). A copolymer consisting of one or more polymers and/or one or more of the above monomers and one or more vinyl polymerizable monomers B that can be copolymerized with these. , a first invention relating to an underwater antifouling coating agent containing an antifouling agent as an essential component; and a second invention relating to an underwater antifouling coating agent containing as follows.

[Structure of the invention]

In the underwater antifouling coating of the present invention, as one of its essential components, one or more types of polymers, ie, fil homopolymer or copolymer, are added to the monomer represented by the above general formula (1). (hereinafter referred to as polymer A), or a combination of one or more of the above monomers A and one or more of the vinyl polymerizable monomers B that can be copolymerized with these monomers. polymer (hereinafter referred to as copolymer AB)
). Moreover, the above-mentioned polymer A and copolymer AB may be used in combination as necessary.

Both polymer A and copolymer AB have an organosilyl group or an organosiloxane group derived from monomer A in their side chains, so they can be combined with an antifouling agent or with a surface lubricant. The film formed from the coating material contains good slipperiness, and this film, and the antifouling agent contained in the film, effectively prevents aquatic organisms from adhering to the surface of underwater objects. . The present inventors have found that such adhesion prevention effect is more pronounced than that of the conventional underwater antifouling coating agent, as shown in the examples described below.

In addition, since the above-mentioned polymer A and copolymer AB are easily soluble in organic solvents, a solvent solution of a coating material containing this and an antifouling agent or a surface lubricating agent may be immersed in seawater. It can be easily formed into a uniform film by applying it to the surface of the object and drying it. Moreover, unlike the conventional reaction curing type, the above-mentioned polymer A and copolymer AB are essentially non-reactive, so that the formation of the above-mentioned film is difficult due to atmospheric humidity or temperature. It has excellent pot life and storage stability as a solution. Furthermore, when a similar or other coating is overcoated on this coating, the coating is attacked by the solvent of the topcoat, resulting in excellent interlayer adhesion with the topcoat.

That is, all of the drawbacks of the conventional underwater antifouling coatings are eliminated by using the polymer A and/or copolymer AB.

Polymer A and copolymer AB exhibiting such effects
Monomer A for obtaining is one having an organosilyl group or an organosiloxane group in the molecule represented by the above general formula (1), and in this formula (1), X + ,
Xz is a hydrogen atom or a methyl group, and the side group can be either cis or trans as geometric isomer. In addition, in formula (1), Y+ and Yz are one of the other formulas (a); Ra R+ CIIH2nbe5i-0←-S iRz...(a
lRs is an organic group represented by R3, and the other is a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group, or an organic group represented by the above formula (a). The number of carbon atoms in the above alkyl group is usually up to about 5, and the substituents for the substituted phenyl group include halogen, alkyl groups with up to about 5 carbon atoms, alkoxyl groups, acyl groups, etc. be.

In the above formula (a), m is the number of organosiloxane groups, which can be a real number of 0 or more, but is usually up to about io or ooo.

In addition, since the organosiloxane group is introduced by dehydration condensation or addition reaction, the monomer A is usually a mixture of different repeating numbers of organosiloxane groups. Therefore, the above m value should be expressed as their average value (seedlings), and it is for this reason that it is expressed as the above real number. From this point of view, in the examples described later, the above-mentioned seedlings are used. n is an integer from 2 to 5, that is, 2°3.4 or 5;

In addition, in the formula (al, R, -R, are both alkyl groups,
It is a group selected from an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxydyl group, or a substituted phenoxydyl group, and the number of carbon atoms in the above alkyl group and alkoxyl group is usually up to about 5, and the above Examples of the substituent of the substituted phenyl group and the substituted phenoxyl group include halogen, an alkyl group having up to about 5 carbon atoms, an alkoxyl group, and an acyl group. These R1 to R3 may be the same group or different groups.

Furthermore, in the formula (al, R4 and R5 are the same groups as R1-R3 above or the following formula (b); m R4 and R5 may be the same group or different groups. Note that R4 and R6 are the groups selected from the above R4 and R5.
1-R4, these groups and RI''
' Of course, the group R3 may be the same group or a different group.

In the above formula fbl, R'1 to R'3 are all an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxydyl group, a substituted phenoxydyl group, or a formula (bl
A group selected from organosiloxane groups represented by Examples of the group include halogen, an alkyl group having up to about 5 carbon atoms, an alkoxyl group, and an acyl group. These R'8 to R'3 may be the same group or different groups.

Monomer A like this is easily available as a commercial product. Examples of synthesis include maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester [all unsaturated acids in which X+ and Xi in the above general formula (1) are both hydrogen atoms], or these α -Methyl substituted product [unsaturated acid in which one of X in the general formula (11) is a hydrogen atom and the other is a methyl group], α・α dimethyl substituted product of these [X in the general formula (1)]
+, X2 are both methyl groups], an organosilyl compound having the above R1 to R3 in the molecule or an organosiloxane compound having the above R4 to R5 in the molecule is dehydrated and condensed with various unsaturated acids such as Alternatively, an ester of an unsaturated acid similar to the above and an unsaturated alcohol of the above formula (according to the number of n in al) such as vinyl alcohol or allyl alcohol is obtained, and an organosilyl compound or an organosiloxane compound similar to the above is obtained. There is a method of conducting an addition reaction.

In addition, examples of the vinyl polymerizable monomer B used together with the above monomers to obtain the copolymer AB include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic acid. Ethyl methacrylates such as 2-hydroxyethyl, ethyl acrylate, butyl acrylate, acrylic acid 2
- Acrylic esters such as ethylhexyl and 2-hydroxyethyl acrylate, maleic esters such as dimethyl maleate and diethyl maleate, amaric esters such as dimethyl fumarate and diethyl fumarate, styrene, vinyltoluene, α -Methylstyrene, vinyl chloride, vinyl acetate, butadiene, acrylamide, acrylonitrile, methacrylic acid, acrylic acid,
Examples include maleic acid, fumaric acid, crotonic acid, crotonic esters, itaconic acid, itaconic esters, and the like.

Such vinyl polymerizable monomer B acts as a modifying component to impart various performances to the antifouling film depending on the purpose of use, and also has a higher molecular weight than monomer A alone. It is also a convenient component for obtaining coalescence. The amount of monomer B to be used is set within an appropriate range, taking into consideration the above-mentioned performance and the antifouling effect based on monomer A. - For boat fishing, the proportion of monomer B in the total amount of monomer A is 95% by weight or less,
Particularly preferably, it is 90% by weight or less.

That is, if the proportion of monomer A constituting copolymer AB is at least 5% by weight, particularly preferably at least 10% by weight, based on this monomer A (because the antifouling effect can be sufficiently exhibited), , the amount of monomer B used may be appropriately set within the above range.

Polymer A and copolymer AB are produced by combining monomer A as described above or monomer B together with monomer A in the presence of a vinyl polymerization initiator.
It can be obtained by polymerization using various conventional methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization. Examples of the vinyl polymerization initiator include ab compounds such as abbisisobutyronitrile and triphenylmethylazobenzene, benzoyl peroxide, diter
Examples include peroxides such as t-butyl peroxide.

The weight average molecular weight of Polymer A and Copolymer AB obtained by the above method is generally 1.000 to 1° soo, o.
It is desirable that it be in the range of oo. If the molecular weight is too low,
It is difficult to form a film that can withstand use, and if the temperature is too high, the viscosity is high when used as a coating material, and the resin solid content is low, so only a thin film can be obtained with one application.
A problem arises in that several coats of paint are required to obtain a dry film thickness greater than 30 cm.

The antifouling agent used as one of the essential components in the present invention includes a wide range of conventionally known antifouling agents. Broadly speaking, there are organic compounds containing metals, organic compounds not containing metals, and inorganic compounds.

Examples of metal-containing organic compounds include organotin compounds, organocopper compounds, organonickel compounds, and organozinc compounds, and also include maneb, manseb, propineb, and the like. In addition, metal-free organic compounds include N-triheromethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted aminot 3
-Chiplysine-2,4-dione, dithiocyano compounds, etc. Further, examples of inorganic compounds include copper compounds such as cuprous oxide, copper powder, copper thiocyanate, copper carbonate, copper chloride, and copper sulfate, zinc sulfate, zinc oxide, and nickel sulfate.

Among the organic compounds containing the above metals, organotin compounds include triphenyltin halides such as triphenyltin chloride and triphenyltin fluoride, and tricyclohexyltin halides such as tricyclohexyltin chloride and tricyclohexyltin fluoride. , tributyltin halides such as tributyltin chloride, tributyltin fluoride, triphenyltin hydroxide, tricyclohexyltin hydroxide, bis(triphenyltin) α
・α′-dibromosuccinate, bis(tricyclohexyltin)-α・α′-dibromosuccinate, bis(tributyltin)-α・α′-dibromosuccinate, bis-
(triphenyltin) oxide, bis-(tricyclohexyltin) oxide, bis(tributyltin) oxide, triphenyltin acetate, tricyclohexyltin acetate, tributyltin acetate, triphenyltin monochloroacetate, triphenyltin versatate, Examples include triphenyltin dimethyldithiocarbameth and triphenyltin nicotinic acid ester.

Examples of organic copper compounds include copper oxine, copper nonylphenol sulfonate, copper bis(ethylenediamine)-bis(U decylbenzenesulfonate), copper acetate, copper naphthenate, copper bis(pentachlorophenolic acid), and the like. Furthermore, as organic nickel compounds,
Examples of organic zinc compounds include nickel acetate and nickel dimethyldithiocarbamate, and examples of organic zinc compounds include zinc acetate, zinc carbazate, and zinc dimethyldithiocarbamate.

Furthermore, among the above metal-free organic compounds, N
-1-lihalomethylthiophthalimide, N-1
-lichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide, etc., and dithiocarbamic acids include bis(dimethylthiocarbamoyl) disulfide, ammonium N-methyldithiocarbamate,
Examples of N-arylmaleimide include ammonium ethylenebis(dithiocarbamate), milneb, etc.
2,4,6-Dolichlorophenyl)maleimide, N-4
-1-lylmaleimide, N-3-chlorophenylmaleimide, N-(4-n-butylphenyl)maleimide, N
-(anilinophenyl)maleimide, N-(2,3-xylyl)maleimide, and the like.

In addition, 3-substituted amino 3-thiazolidine = 2.4-
Examples of the dione include 3-benzylideneamino-1,3-thiazolidine-2,4-dione, 3-(4-methylbenzylideneamino)-1,3thiazolidine-2,4-dione, and 3-(2-hydroxybenzylideneamino)-1,3-thiazolidine-2,4-dione. )-1・3
-thiazolidine-2,4-dione, 3-(4-dimethylaminobenzylideneamino)-1,3-thiazoline 2.
4-dione, 3-(2,4-dichlorohenzylideneamino)-1,3-thiazolidine-2,4-dione, etc.
Examples of dithiocyano compounds include dithiocyanomethane,
Examples include dithiocyanoethane and 2,5-dithiocyanothiophene.

In the present invention, one or more antifouling agents are selected from among the various antifouling agents mentioned above, and the amount used depends on the surface slipperiness of the coating of polymer A and/or copolymer AB. It is set within an appropriate range, taking into consideration the synergistic effect between the antifouling effect expected from the antifouling agent and the chemical antifouling effect of the antifouling agent. - in the shell polymer A and/or copolymer AB
It is desirable that the proportion of the antifouling agent in the total amount of the antifouling agent is 0.1 to 65% by weight. If the antifouling agent is too small, the synergistic effect described above cannot be expected, and if the antifouling agent is too large, film defects such as cracks and peeling tend to occur in the formed underwater antifouling film, making it difficult to obtain effective antifouling properties.

In the present invention, in addition to the above-mentioned polymer A and/or copolymer AB and antifouling agent, a surface lubricant can be used. As surface lubricating agents that can be used in the present invention, there are various substances known to impart slipperiness to the coating surface. Representative examples include ■J [5K
Petroleum wax specified in 2235, ■JISK223
Liquid paraffin specified in 1, 55 at 025°C
Silicone oil having a kinematic viscosity of 0.000 centistokes or less; ■ Fatty acid having 8 or more carbon atoms and its ester having a melting point of −5° C. or higher; ■ Organic amine having an alkyl group or alkenyl group having 12 to 20 carbon atoms; 02
Examples include polybutenes having a kinematic viscosity of 60,000 centistokes or less at 5°C.

Specific examples of the above ■ include paraffin wax, microcrystalline wax, petrolatum, etc.
As a specific example, I 5OVGI 01lsOVG1
5, [5OVG32, l5OVG68, fsOVGlo
Specific examples of the products corresponding to o above (■) include product names KF96L-0,65 and KF96L- manufactured by Shin-Etsu Chemical Co., Ltd.
2,0, KF96-30, KF96H-50,0
00, KF965, KF50, KF54, KF69, Toshiba Silicone product name TSF440, TSF410
, TSF4440, TSF431. TSF433,TS
F404, TFA4200, YF3860, YF381
8, YF3841 YF3953, TSF45I, East silicone product name 5H200, 5H510, S
Examples include H3531, SH230, and FS1265.

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, alkyl-modified silicone oil, methylchlorinated phenyl silicone oil, and higher fatty acid-modified silicone oil. Other materials such as oil, fluorosilicone oil, etc. may also be used.

Specific examples of the above (■) include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, cerotic acid, montanic acid, melisic acid, lauroleic acid, oleic acid, vaccenic acid, gadoleic acid, and whale oil. Examples include whale oil acid, juniberic acid, and the like. In addition, examples of esters of these carboxylic acids include stearyl stearatoptyl laurate, octyl palmitate,
Butyl stearate, isopropyl stearate, cetyl palmitate, seryl cerotate, myricyl palmitate, merisylmerisate, spermaceti, beeswax, carnauba wax, montan wax, mushi wax, tristearin, tolpalmitin, triolein, myrist Dilaurin, caprylolauromyristin, stearopalmitolein, monostearin, monopalmitin, distearin, civalmitin, beef tallow, lard, horse tallow, mutton tallow, cod liver oil, coconut oil, palm oil, wood wax, kapok oil, Examples include cacao butter, China butter, and irritsube butter.

Further, specific examples of the above (■) include dodecylamine, tetradodecylamine, hexadecylamine, octadecylamine, oleylamine, beef tallow alkylamine, cocoalkylamine, soybean oil alkylamine, didodecylamine, di-tallow hydrogenated alkylamine, Specific examples of the above (■) include dodecyldimethylamine, cocoalkyldimethylamine, tetradecyldimethylamine, hexamethyldimethylamine, and octadecyldimethylamine.
Product name Nirasan Polybutene ON, manufactured by NOF N, 06
N,,015N,3N,5N,ION.

3ON, 20ON, O5H, 06SH1015SH, 3
SH, 5SH, 10S)! , 30SH, 2003H, etc.

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 amount of the above-mentioned polymer A and/or copolymer AB and the antifouling agent. It is set within an appropriate range, taking into consideration the drying properties, adhesion properties, and antifouling performance. - For boat fishing, the proportion of the surface lubricant in the total amount of the polymer A and/or copolymer AB and the surface lubricant is 1 to 70% by weight, especially 5 to 50% by weight. is preferred.

As mentioned above, the underwater antifouling coating of the present invention contains the above-mentioned polymer A and/or copolymer AB and an antifouling agent as essential components, or further contains the above-mentioned surface lubricant. They are included as essential components, and both coating materials are usually used after being diluted with an organic solvent. For this reason,
As the polymerization method for obtaining the polymer A and/or the copolymer AB, it is particularly desirable to employ a solution polymerization method or a bulk polymerization method. In the solution polymerization method, the reaction solution after polymerization can be used as it is or after being diluted with a solvent, and in the bulk polymerization method, the reaction product after polymerization can be used after adding a solvent.

Organic solvents 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. Examples include alcohol solvents such as, ether solvents such as dioxane and diethyl ether, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, alone or in combination.

The amount of organic solvent used is such that the concentration of polymer A and/or copolymer AB in the solution is usually 5 to 80% by weight, particularly preferably 30 to 70% by weight! It is preferable to set it within a range of i%. The viscosity of the solution at this time is generally preferably 150 voids or less/25° C. so that it can be easily formed into a film.

The underwater antifouling coating of the present invention thus constructed may contain a coloring agent such as a pigment such as Bengara, titanium dioxide, or a dye, if necessary. Further, ordinary anti-sagging agents, anti-color separation agents, anti-settling agents, anti-foaming agents, etc. may be added.

In order to form an antifouling film on the surface of an object to be immersed in seawater using the underwater antifouling coating agent of the present invention, for example, after applying the coating agent as a solution to the surface of the object by an appropriate means, It is sufficient to simply remove the solvent by drying at room temperature or under heat. As a result, an antifouling film with good surface slipperiness and a synergistic effect with the antifouling agent is uniformly formed.

[For production]

The above-mentioned polymer A and/or copolymer AB used in the present invention both have an organosilyl group or an organosiloxane group derived from monomer A, so that the formed film has strong surface slipping properties. It is something that is given. Therefore, this coating itself has the function of physically preventing the adhesion of marine organisms. In addition, vinyl polymerizable monomer B is used to impart appropriate surface slipperiness to the coating of copolymer AB, and to obtain a polymer with a higher molecular weight than monomer A alone. It acts as a convenient regulatory component.

The antifouling agent used in the present invention chemically prevents the adhesion of marine organisms, and has a synergistic effect with the strong surface slipperiness of the film obtained from Polymer A and/or Copolymer AB. Improves and sustains stain resistance. However, the combined use of an antifouling agent does not necessarily improve the surface slipperiness of the coating.

As mentioned above, in the combination of polymer A and/or copolymer AB with an antifouling agent in the first invention, polymer A
It is considered that the antifouling performance of the coating is maintained stably over a long period of time because the copolymer AB and/or the copolymer AB have a function of appropriately controlling excessive elution and insufficient elution of the antifouling agent.

Furthermore, by using the surface lubricant used in the second invention in combination with the above-mentioned polymer A and/or copolymer AB and an antifouling agent, the antifouling agent can achieve antifouling performance even in sea areas where marine organisms are actively breeding. This is important in achieving further long-term sustainability. The inventors' speculation regarding the above facts is that the surface smoothing effect based on the use of a surface lubricant, the polymer A and/or
Alternatively, this may be due to the fact that the surface slipperiness of the coating is reinforced and maintained over a long period of time due to the deterioration prevention effect of the coating composed of the copolymer AB and the antifouling agent.

〔Effect of the invention〕

The above-mentioned specific polymer used in the underwater antifouling coating of the present invention has no reactivity itself, has solvent-volatile drying properties, and forms a thermoplastic coating that is insoluble in seawater. Therefore, the underwater antifouling coating of the present invention has the following advantages compared to conventional antifouling coatings.

First, during production of the coating material, there is no risk of deterioration due to antifouling agents, and the coating material is stable. There is no need to fill in inert gas when canning, and there is no limit on pot life. It dries quickly and is not affected by poor curing in the deep parts of the film or by humidity or temperature during drying, so blistering and peeling are less likely to occur. Excellent interlayer adhesion when the same type of coating or other coatings are overlaid on top of the coating.

Since the coating does not wear out even when it comes into contact with seawater, it can maintain its antifouling performance over a long period of time. This value is clearly lower than the surface slipperiness of conventional crosslinked silicone antifouling coatings, confirming the poor antifouling effect.

Therefore, the present invention can be applied to ship bottoms, undersea structures such as fishing nets and cooling water pipes, where it is necessary to prevent damage to marine organisms, and marine pollution prevention membranes used to prevent teta sludge in marine civil engineering works. The resulting coating exhibits a remarkable antifouling effect and can prevent biofouling and loss of submerged substrates.

〔Example〕

The present invention will be specifically explained below with reference to polymer production examples, examples, and comparative examples. In the examples, parts represent parts by weight, viscosity represents a foam viscosity measurement value at 25°C, and molecular weight represents a weight average molecular weight determined by CPC.

Production Examples 1 to 7 In a flask equipped with a stirrer, add solvent a according to the formulation shown in Table 2.
The mixture of monomer A, monomer B and polymerization catalyst a was added dropwise into the flask over 6 hours while stirring, and after the dropwise addition was completed, the mixture was kept at the same temperature for 30 minutes. held. Then, the mixture of solvent and polymerization catalyst was added to 20
The mixture was added dropwise over a period of minutes, and stirring was continued for 5 hours at the same temperature to complete the polymerization reaction. Finally, add diluent to dilute,
Each polymer solution ① to ② was obtained.

Production Example 8 In a heat-resistant and pressure-resistant container, monomer A,
Monomer B and polymerization catalyst a were charged, the container was completely sealed, and the temperature was raised to a predetermined reaction temperature while shaking, and further shaking was continued at the same temperature for 8 hours to complete the reaction. Next, a diluting solvent was added and dissolved by shaking for 3 hours to obtain a polymer solution (2).

Production Example 9.10 In a flask equipped with a stirrer, add solvent a according to the formulation in Table 2.
, monomer A and polymerization catalyst a were charged, the temperature was raised to a predetermined reaction temperature while stirring, and stirring was continued at the same temperature for 6 hours to obtain polymer solutions IX and X.

In addition, monomer A (A I
"' A I.) is the general 2 (X+ in 11,
Xz.

These cis-trans geometric isomerisms, Yl, Yz (n, m (seedling), R1 to Rs when one or both of these are m groups represented by formula (a)) are shown in Table 1 below. It has the structure shown in .

Examples 1 to 20 Using polymer solutions ① to An underwater antifouling coating was prepared.

In addition, among the ingredients, petrolatum No. 1 is JISK223
5 petroleum wax, l5OVCIO is JIS
K2231 liquid paraffin.

Further, the silicone oil with the trade name TSF433 is manufactured by Toshiba Silicone ■. In addition, nirasan polybutene 0
6N is polybutene manufactured by NOF ■.

In addition, Oil Blue 2N (trade name manufactured by Orient Chemical) is a dye, Dice Baron 6900-20× [Tanemoto Kasei@
[trade name] manufactured by Nippon Aeroseal@) and Aeroseal 300 [trade name manufactured by Nippon Aeroseal@] are both anti-sag additives.

Comparative Example 1 Same as Examples 1 to 20, except that KE45TS C (product name, manufactured by Shin-Etsu Chemical Co., Ltd.; oligomeric room-temperature curing silicone rubber 50% by weight toluene solution) was used instead of the polymer solutions ■ to X. Then, an underwater antifouling coating having the formulation shown in Table 3 below was prepared.

Comparative Example 2 An underwater antifouling coating having the composition shown in Table 3 was prepared in the same manner as in Examples 1 to 20, except that an organic tin copolymer solution was used instead of the polymer solution 1-X. was prepared.

The above-mentioned organotin copolymer solution is a copolymer solution polymerized using 40 parts of methyl methacrylate, 20 parts of octyl acrylate, and 40 parts of tributyltin methacrylate.
The copolymer has a weight average molecular weight of 90.000 and is a transparent 50% by weight solution in xylene.

Each of the coating materials of Examples 1 to 20 and Comparative Examples 1 and 2 below was subjected to the following physical performance test, measurement of the surface sliding angle of the coating, and antifouling performance test to evaluate the performance. The results were as shown in Table 4 below.

<Physical Performance Test> The storage stability, drying properties, and adhesion of each coating material were measured by the following methods.

8) Storage stability: Pour each coating into a 1250 cc mayonnaise bottle 2QQ.
I put it in a cc container and sealed it with a lid. Is this temperature 70°C+?
The storage stability was determined by the degree of viscosity increase of each sample after 2 weeks of storage in a thermostatic chamber at 75% m degree. When the increase rate was less than 10% from the initial viscosity, it was evaluated as ○, when it was 10% or more and less than 100%, and when it was 100% or more, it was evaluated as ×.

B) Drying property It was carried out according to the method of JIS K5400.5.8.

That is, the measurement was performed on a glass plate coated with each coating agent to a wet film thickness of 100 μm using a film applicator. ○ if the semi-curing drying time is less than 1 hour;
1 hour or more and less than 3 hours was evaluated as △, and 3 hours or more was evaluated as ×. Note that each test plate was dried in a thermostatic chamber at a temperature of 20° C. and a humidity of 75%.

C) Adhesion The test was carried out according to the method of the substrate eye test of JTS K5400.6.15. That is, each coating agent was applied to a steel plate (
150 x 70 x 1 mm) and kept at 20°C for one week.
The coating was dried in a thermostatic chamber with a humidity of 75%, and a cut was made in a cross pattern reaching the base layer with a length of 20 mm using a cutter knife.

10 with an Erichsen tester from the back of the test plate at the center.
An extrusion of mm was performed. At that time, adhesion was determined by the length of peeling from the center of the cross-cut uneven portion of the coating surface. The evaluation was ○ when the peeling was O, △ when the peeling was less than 5 cods, and × when the peeling was 5 dragons or more.

Measurement of surface sliding angle of coating> Figure 1 (A) for each test plate used in the drying test.
, using the slip angle measuring machine shown in (B),
The surface slip angle of 1 was measured. The above-mentioned measuring device consists of a transparent glass plate 1, on which one end A side is fixed by a fixing jig 2, and the other end B side is supported by a column 3, and is moved upward along this column 3. It is composed of a movable plate 4 provided so as to be movable.

First, as shown in FIG. 1(A), a test plate 5 is placed on a transparent glass plate I with the coating side facing upward.
Place it horizontally with the movable plate 4 interposed therebetween, and on this test plate 5, the distance γ from one end A of the movable plate 4, that is, from the fixing jig 2, is 18511.
0゜2 m with a syringe at the position! ! droplets of sterile filtered warm water are added to form water droplets 6. Then, as shown in FIG. 1(B), move the other end B side of the movable plate 4 along the column 3 by 1 mm.
/second to tilt the test plate 5.

The inclination angle α at which the water droplets on the test plate 5 begin to slide was measured, and this was taken as the surface slip angle of the coating.

The above measurements were performed in a constant temperature room with a temperature of 25'C and a humidity of 75%, and each test plate was measured three times.
It was expressed as the average value.

<Antifouling performance test> Each coating was applied to a coated plate (100x200x1
A test plate was prepared by spray painting on both sides of the sample (mm) twice so that the dry film thickness was 120 μm on one side.

This test board was immersed in seawater for 24 months in Aioi Bay, Aioi City, Hyogo Prefecture, which is a sea area with heavy biofouling, and the ratio of the area occupied by the biofouling organisms (adhesion area) on the test coating was measured over time. did.

As is clear from the results in Table 4 above, Examples 1 to 20
All of the storage stability, drying properties, and adhesion were good. In addition, the surface slip angle is 8
．． The range is 0 to 9.9 degrees.

In addition, even in Examples 1 to IO in which no surface lubricant was used, the temperature was within the range of 9.9 degrees, which means that the coating itself of the specific polymer of the present invention has strong surface slip properties. It shows that it has. In the antifouling performance test, no biological adhesion was observed until at least 24 months had passed.

On the other hand, Comparative Example 1 is a silicone rubber-based coating and has shortcomings in storage stability, drying properties, and adhesion. The antifouling property was also unsatisfactory, as evidenced by the high value of the surface sliding angle. Comparative Example 2 is an anti-lη coating based on a tin copolymer, but it is slightly inferior in storage stability and antifouling properties, and the coating surface is more hydrophilic, so it exhibits a high surface slip angle. There is.

[Brief explanation of the drawing]

FIGS. 1A and 1B are side views showing a method for measuring the surface slip angle of an antifouling coating formed from an underwater antifouling coating.

Claims (2)

[Claims] (1) The following general formula (1); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) {However, in the formula, X_1 and X_2 are hydrogen atoms or methyl groups, and both groups are cis It may be in either form or trans form. One of Y_1 and Y_2 is the following formula (a); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(a) [However, in the formula, n is an integer of 2 to 5, and m is a real number of 0 or more. It is. Each of R_1 to R_3 is a group selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group, or a substituted phenoxyl group, and even if they are the same group, they may be different groups. You can. R_4 and R_5 are the same groups as R_1 to R_3 above or the following formula (b); ▲ There are numerical formulas, chemical formulas, tables, etc. ▼... (b) (However, in the formula, R'_1 to R'_3 are all groups selected from alkyl groups, alkoxyl groups, phenyl groups, substituted phenyl groups, phenoxyl groups, substituted phenoxyl groups, or organosiloxane groups represented by formula (b), and are the same as each other. A group selected from the organosiloxane groups represented by You can. ] It is an organic group represented by these, and the other is a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group, or an organic group represented by the above formula (a). }, and/or one or more of the above monomers A and one or more of the vinyl polymerizable monomers B that can be copolymerized with these. An underwater antifouling coating agent containing a copolymer consisting of at least one species and an antifouling agent as essential components. (2) The following general formula (1); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) {However, in the formula, X_1 and X_2 are hydrogen atoms or methyl groups, and both groups are cis It may be in either form or trans form. One of Y_1 and Y_2 is the following formula (a); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(a) [However, in the formula, n is an integer of 2 to 5, and m is a real number of 0 or more. It is. Each of R_1 to R_3 is a group selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group, or a substituted phenoxyl group, and even if they are the same group, they may be different groups. You can. R_4 and R_5 are the same groups as R_1 to R_3 above or the following formula (b); ▲ There are numerical formulas, chemical formulas, tables, etc. ▼... (b) (However, in the formula, R'_1 to R'_3 are all alkyl groups, alkoxyl groups, phenyl groups, substituted phenyl groups,
A group selected from a phenoxyl group, a substituted phenoxyl group, or an organosiloxane group represented by formula (b), which may be the same group or different groups) m R_4 and R_5 may be the same group or different groups. ] It is an organic group represented by these, and the other is a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group, or an organic group represented by the above formula (a). }, and/or one or more of the above monomers A and one or more of the vinyl polymerizable monomers B that can be copolymerized with these. An underwater antifouling coating containing as essential components a copolymer consisting of at least one species, an antifouling agent, and a surface lubricant.