JPH0331373A - Coating composition for preventing deposition of organism - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a (co)polymer having organosilyl group or organosiloxane group on the side chain, an antifouling agent and a surface-smoothing agent and exhibiting excellent long-term antifouling effect. CONSTITUTION:The objective composition contains (A) a (co)polymer of a monomer (mixture) expressed by formula I {X1 and X2 are H or CH3; one of Y1 and Y2 is organic group of formula II [n is 0 or 1; m is >=0; R1 to R3 are alkyl, alkoxy, (substituted) phenyl or (substituted) phenoxy; R4 and R5 are R1 to R3 or organosiloxane of formula III (R6 to R8 are alkyl, phenyl, etc.)] and the other is H, alkyl, (substituted) phenyl or organic group of formula II} and/or (B) a copolymer of the monomer (mixture) of the component A and a monomer copolymerizable therewith, (C) an antifouling agent and (C) a surface-smoothing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a biofouling prevention coating composition 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.), sea pollution prevention sheets, and various intake and drainage pipes for cooling, are covered with Fujibbo, Various problems occur due to the attachment of celluloids, mussels, algae, etc. It is well known that a biofouling prevention paint is applied to the surface of objects immersed in water in order to prevent contamination by these organisms. This type of paint can be roughly divided into two types: 49 types as shown below.

b) Organotin copolymer that has an anti-adhesion effect on living things;
Products using antifouling agents such as cuprous oxide.

For example, regarding biofouling prevention paints using organotin compounds as antifouling agents, Japanese Patent Publications No. 40-21426, Japanese Patent Publication No. 9579-1979, and Japanese Patent Publication No. 46-1339
Publication No. 2, Special Publication No. 49-20491, Special Publication No. 51
This method is disclosed in Japanese Patent Publication No. 11647, Japanese Patent Publication No. 52-48170, etc.

(1) A biofouling prevention paint that does not use antifouling agents and does not dissolve in water, and uses silicone rubber that is vulcanized and three-dimensionally crosslinked to form a film by the action of catalysts, moisture, etc.

For example, Japanese Patent Publication No. 53-35974 discloses the use of vulcanized silicone rubber as the resin component of a paint for preventing biofouling, and Japanese Patent Publication No. 51-9683 discloses
No. 0 discloses the use of a mixture of oligomeric silicone rubber having hydroxyl end groups and silicone oil. 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 biofouling prevention paint that is a mixture of oligomeric room-temperature curing silicone rubber (for example, Shin-Etsu Chemical's product names KE45TS, KE44RTV, etc.) and liquid paraffin or petrolatum. has been done.

[Problem to be solved by the invention]

These conventionally known biofouling prevention paints are used depending on their type, but they all have the following drawbacks, and improvements in these have been strongly desired.

First, there are two types of anti-biofouling paint mentioned in (a) above. One is a type of biofouling prevention paint that prevents aquatic organisms from adhering to the paint by dissolving only the antifouling agent into the water, while the resin that forms the coating does not dissolve in the water. This type of antifouling coating has a good initial antifouling effect, but after the antifouling agent on the surface of the coating is eluted and lost, the antifouling agent deep inside the coating gradually dissolves. However, the elution rate of the antifouling agent slows down as it gets deeper into the coating film, which has the disadvantage that the antifouling effect becomes insufficient over the long term.

The other type is a biofouling prevention paint in which both the resin that forms the coating film and the antifouling agent are dissolved in water. The antifouling effect of this paint may be due only to the antifouling agent or to both the antifouling agent and a resin component (organic tin copolymer, etc.), but in either case, the paint surface is eluted, so
An active antifouling coating surface is always maintained, and the antifouling effect is more durable than the former. however,
Even in this case, the current situation is that there is a limit to the amount of wear of the coating film, or on the contrary, it wears out too much, so that a fully satisfactory effect cannot be obtained.

In addition, all of the above-mentioned mouth biofouling prevention paints utilize the slipperiness of the silicone rubber coating surface to prevent aquatic organisms from adhering to the surface. Although it has the advantage of not having eluted components that may cause water pollution like preventive paints,
The silicone rubber for forming the coating 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 shown in Japanese Patent Publication No. 60-3433, a biofouling prevention paint using an oligomeric cold-curing silicone rubber that hardens under the action of moisture in the air to form a coating film is applied to the surface to be coated. When this occurs, 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 blistering will occur. Furthermore, since moisture penetrates into the interior slowly, the time required for curing becomes longer. Also, ■High temperature.

When such a biofouling prevention paint is used in a high humidity location, only hydrolysis of the crosslinking agent takes priority, and the crosslinking density does not increase, resulting in a decrease in physical properties. ■Furthermore, in dry areas, there is little moisture in the atmosphere, making it difficult for the crosslinking agent to hydrolyze, making the curing of the film extremely slow. In order to prevent this, catalysts such as tin compounds and platinum are sometimes used as curing accelerators, but their catalytic action tends to be insufficient at low temperatures.

Second, there is the problem of overcoatability. Normally, the solvent of the topcoat paint slightly invades the undercoat surface and mixes at the interface, which improves interlayer adhesion. However, overcoatability to silicone rubber is affected by the fact that the base silicone rubber is three-dimensionally crosslinked and cured. The reapplied top coat 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. This may lead to a situation where the paint, which has already been opened and stirred, has to sit for a longer time than planned. In such cases, paints with a pot life are extremely inconvenient in painting operations.

Fourth, there is the issue of storage stability. Anti-biofouling paints can be stored for long periods of time from the time they are manufactured until they are used, but those that harden due to moisture will have short storage stability unless dry nitrogen gas is sealed during manufacture. Also,
- There was a problem in that when the lid of the variable magnification lens was opened, moisture from the atmosphere entered, causing the paint surface to harden and thicken, making it difficult to reuse.

[Means to solve the problem]

As a result of intensive research into the above points, the present inventors found that the present inventors do not have the various problems of the conventionally known biofouling prevention paints that use silicone rubber alone or a combination of silicone rubber and silicone oil, paraffin, etc. Moreover, it is a solvent-volatile type that can be expected to have good antifouling properties, especially when compared to the biofouling prevention paint using an organic tin copolymer containing a conventionally known antifouling agent mentioned above. We succeeded in obtaining a new type of anti-biofouling coating composition using a specific polymer in combination with an antifouling agent and a surface lubricant.

That is, the present invention provides the following general formula (I);
In the formula, X+ and Xz are hydrogen atoms or methyl groups,
Both groups may be either cis or trans. Y,,Y2 is one of the following 2(a); The groups are selected from alkoxyl groups, phenyl groups, substituted phenyl groups, phenoxydyl groups, and substituted phenoxydyl groups, and may be the same or different groups. R,,R, are the same groups as R2-R3 above or the following formula (b); -1-o-5i-R? ...) Rs (In the formula, R4-R3 are all 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 (b). A group selected from the organosiloxane groups represented by may be the same group or different groups] and the other is a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group, or a group represented by the above formula (a). It is an organic group. ) and/or one or more vinyl polymerizable monomers B that can be copolymerized with one or more monomers A A copolymer consisting of more than one species;
The present invention relates to a biofouling prevention coating composition characterized by containing an antifouling agent and a surface lubricant as essential components.

By the way, prior to completion of the present invention, the present applicant has developed a polymer or copolymer using a monomer having a structure having an organosilyl group or an organosiloxane group represented by the above general formula (1). An underwater antifouling coating agent made of the above ingredients and an antifouling agent added thereto has already been proposed in Japanese Patent Application No. 160383/1983.

This underwater antifouling coating agent has a self-polishing property in which the coating film formed from the above polymer or copolymer gradually hydrolyzes from the surface in water. In other words, the resin gradually hydrolyzes from the surface layer of the coating film. By adopting a mechanism in which the antifouling agent dispersed in the resin dissolves into the water at the same time, it exhibits an extremely excellent antifouling effect.

In research following this prior invention, the present inventors
When a surface lubricant is further used in combination with a component consisting of these polymers or copolymers and an antifouling agent, the hydrolysis of the resin coating is appropriately suppressed, and the dissolution of the coating film and antifouling agent is improved. The present inventors have discovered that the surface lubricant itself has an antifouling effect, and that the surface lubricating agent itself has an antifouling effect.This has led to the completion of the present invention.

[Structure of the invention]

In the biofouling prevention coating composition of the present invention, monomer A represented by the above general formula (R) is used as one of the essential components.
or a homopolymer or copolymer (hereinafter referred to as polymer A) of one or more of the above monomers A, or copolymerizable with one or more of the above monomers A. A copolymer with one or more vinyl polymerizable monomers B (hereinafter referred to as copolymer AB) is used. 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 used in coatings containing antifouling agents and surface lubricants. The organosilyl group and organosiloxane group are hydrolyzed as appropriate, and the remaining resin is dissolved, and at the same time, the antifouling agent and surface lubricant are gradually released into the water, which effectively prevents biofouling on the surface of underwater objects. The present inventors have found that such adhesion prevention effect is more pronounced than that of the conventional biofouling prevention paint, as shown in the examples described below. Ta.

In addition, since the above-mentioned polymer A and copolymer AB are easily soluble in organic solvents, a solvent solution of a biofouling prevention coating composition containing them and an antifouling agent and a surface slip agent is immersed in water. By applying it to the surface of the object and letting it dry,
Can be easily and uniformly coated. 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 coating film is difficult due to moisture in the atmosphere. It is not affected by water or temperature, and has excellent pot life and storage stability as a solution. Furthermore, when this coating film is overcoated with the same type or another coating film, the above coating film is attacked by the solvent of the topcoat agent, resulting in excellent interlayer adhesion with the topcoat film. In other words, all the drawbacks of the conventional anti-biofouling paints are eliminated by using the polymer A and/or copolymer AB.

Polymer A and copolymer AB exhibiting such effects
The monomer A for obtaining the monomer A has an organosilyl group or an organosiloxane group in the molecule as shown in the above general formula (1), and in this formula (1),
, , X are hydrogen atoms or methyl groups, and both groups can have either cis or trans form as geometric isomerism. In addition, in formula (1), one of Y and Y2 is an organic group represented by the formula (a): Rs Rs , and the other is a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group, or the above formula (This is an organic group represented by al. The number of carbon atoms in the above alkyl group is usually up to about 5, and the substituents for the above substituted phenyl group include halogen and carbon atoms up to about 5. Examples include alkyl groups, alkoxyl groups, and acyl groups.

In the above formula ta>, n is O or an integer of 1, m is the repeating number of organosiloxane groups, and 0
Although it can take any real number above, it is usually up to about 10°000. 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 the average value (to) of these values, and it is for this reason that it is expressed as the above real number. Also, from this point of view, the examples described later are represented by the above-mentioned seedlings.

In addition, R6-R3 in 2(al) are all 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. The number of carbon atoms in the above alkyl group and alkoxyl group is usually up to about 30, preferably up to about 18. Further, examples of the substituents of the above-mentioned substituted phenyl group and substituted phenoxyl group include halogen, an alkyl group having up to about 5 carbon atoms, an alkoxyl group, and an acyl group. These R1-R1 may be the same group or different groups.

Furthermore, in the formula (al, R,, Rs is R1 to R0 above)
or the following formula (b): 6 OSi R? ... (a group selected from organosiloxane groups represented by bl8), in which m R4 and R5 may be the same group or different groups. , when Rs is a group similar to the above R5-R1, these groups and R
It goes without saying that 5 and R8 may be the same group or different groups.

In the above formula (bl), Rt and ``' Ra are each 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). The number of carbon atoms in the above alkyl group and alkoxyl group is usually up to about 5.
Examples of the substituents for the above-mentioned substituted phenyl group and substituted phenoxyl group include halogen, an alkyl group having up to about 5 carbon atoms, an alkoxyl group, and an acyl group. These R4 to R may be the same group or different groups.

Such monomer A can be easily obtained manually as a commercial product. Examples of synthesis include maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester [all unsaturated acids in which XI and X2 in the above general formula (1) are both hydrogen atoms], or these α-methyl substituted product [an unsaturated acid in which one of XI and 1)
In various unsaturated acids such as
A method of dehydrating and condensing an organosiloxane compound having R3, a method of obtaining an ester of an unsaturated acid similar to the above and organosilyl methyl alcohol or an organosiloxane methyl alcohol, or a method of combining the above unsaturated acid with a corresponding chlorosilane. There is a method of carrying out a dehydrochlorination reaction in the presence of a base (eg, triethylamine, imidazole, etc.).

Examples of vinyl polymerizable monomer B used together with monomer A to obtain copolymer AB include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic acid. Methacrylic esters such as 2-hydroxyethyl, ethyl acrylate, butyl acrylate, acrylic #
Acrylic esters such as 2-ethylhexyl and 2-hydroxyethyl acrylate; maleic esters such as dimethyl maleate and diethyl maleate; fulleric esters such as dimethyl fumarate and diethyl fumarate; styrene; vinyl toluene; Examples include α-methylstyrene, vinyl chloride, vinyl acetate, butadiene, acrylamide, acrylonitrile, methacrylic acid, acrylic acid, maleic acid, fumaric acid, crotonic acid, crotonic ester, itaconic acid, itaconic ester, and the like.

Such vinyl polymerizable monomer B acts as a modifying component to impart various performances to the antifouling coating 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 polymers. 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,
Preferably, the weight is 90 weight or less. That is,
The proportion of monomer A constituting copolymer AB is at least 5
If the amount is 10% by weight, preferably at least 10% by weight, the antifouling effect based on this monomer A 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 methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization according to conventional methods. The above vinyl polymerization initiators include azo compounds such as azobisisobutyronitrile, triphenylmethylazobenzene, benzoyl peroxide, di-tsr
Examples include peroxides such as t-butyl peroxide.

The weight average molecular weight of the polymer A and copolymer AB obtained by the above method is generally 1,000 to 1.

If the molecular weight is too low, it will be difficult to form a paint film that can withstand use, and if it is too high, the viscosity of the paint will be high and the resin solid content will be low. A problem arises in that only a thin coating can be obtained with one coating, and several coatings are required to obtain a certain dry coating thickness.

The antifouling agent used as one of the other essential components in the present invention includes a wide range of conventionally known antifouling agents including metal-containing organic compounds, metal-free organic compounds, and inorganic compounds.

Examples of metal-containing organic compounds include organotin-based compounds, copper-based compounds, organo-nickel-based compounds, and organozinc-based compounds, as well as maneb, manseb, propineb, and the like. In addition, metal-free organic compounds include N-trihalomethylthiophthalimide, dithiocarbamic acid, N-arylmaleimide, 3-substituted amino 3-thiazolidine-2,4-dione, dithiocyano compounds, and triazine compounds. Furthermore, examples of inorganic compounds include copper compounds such as cuprous oxide, copper powder, copper thiocyanate, carbonated steel, steel 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 dimethyldithiocarbamate and triphenyltin nicotinic acid ester.

Examples of organic copper compounds include copper oxine, copper nonylphenol sulfonate, copper bis(ethylenediamine)-bis(dodecylbenzenesulfonate), 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
- Trihalomethylthiophthalimide includes N-trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide, etc., and dithiocarbamic acid includes bis(dimethylthiocarbamoyl) disulfide, ammonium N-methyldithiocarbamate, ethylenebis(dithiocarbamate) ammonium, Milneb etc. are N-(2
・4,6-Trichlorophenyl)maleimide, N-4-
1-lylmaleimide, N-3-chlorophenylmaleimide, N-(4-n-7'tylphenyl)maleimide,
N-(anilinophenyl)maleimide, N-(2,3-
(xylyl)maleimide, etc.

Also, 3-substituted amino 3-thiazolidine-2,4-
Examples of the dione include 3-benzylideneamino 3-thiazolidine-2,4-dione, 3-(4-methylbenzylideneamino)-1,3thiazolidine-2,4-dione,
3-(2-hydroxybenzylideneamino)-1.3-
Thiazolidine-2,4-dione, 3-(4-dimethylaminobenzylideneamino)-1,3-thiazoline=2.
4-dione, 3-1(2,4-dichlorobenzylideneamino)-1,3-thiazolidine-2,4-dione, etc., and dithiocyano compounds include dithiocyanomethane, dithiocyanoethane, 2,5-dithio Examples of triazine compounds include cyanothiophene and 2'-methylthio-4-t-butylamino-6-cycloprobylamino-S triazine.

Other metal-free organic compounds include 2-amino-3-chloro-1,4-naphthoquinone, 2,3-cycloroto-4-naphthoquinone, and 5-IO-dihydro-5.
Examples include lO-dioxanaphtho[2,3-b)-1,4-dithiin-2,3-dicarbonitrile.

In the present invention, one or more antifouling agents are selected from among the various antifouling agents mentioned above, and the amount used is determined by the amount of hydrolysis that the coating film of polymer A and/or copolymer AB has. It is set within an appropriate range, taking into consideration the synergistic effect between the antifouling effect due to the nature and the chemical antifouling effect of the antifouling agent. - For boat fishing, it is desirable that the proportion of the antifouling agent in the total amount of polymer A and/or copolymer AB is 0.1 to 80% by weight. No synergistic effect can be expected, and excessive amounts may cause cracks in the underwater antifouling film formed.
Coating film defects such as peeling are likely to occur, making it difficult to obtain effective antifouling properties.

The surface lubricant used as another essential component in the present invention includes a wide variety of substances known to impart slipperiness to the surface of a coating film. Typical examples include: ■Petroleum wax specified in JISK2235, ■Liquid paraffin specified in JISK2231, 0
Silicone oil having a kinematic viscosity of 55,000 centistokes or less at 25°C; ■ Fatty acids having 8 or more carbon atoms and their esters having a melting point of -5°C or higher; ■ Having an alkyl or alkenyl group having 12 to 20 carbon atoms. Examples include organic amines, polybutenes having a kinematic viscosity of 60°,000 centistokes or less at 025°C.

Specific examples of the above (■) include paraffin wax, microcrystalline wax, petrolatum, etc.
A specific example is I5OVCIO.

l5OVG15, I5OVG32, l5OVG68,
I 5OVCI OO equivalent products, as a specific example of the above
5, KF96L-2,0, KF96-30, KF96H
-50,000S KF965, KF50, KF54,
KF69, product name TSF440 manufactured by Toshiba Silicone ■,
TSF410, TSF4440, TSF431, TSF
433, TSF404, TFA4200, YF3860
, YF3818, YF3841, YF3953, TSF
451, product name 5H200, 5H made by Toshi Silicone ■
510, SH3531, 5H230, 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, 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, balmitic 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, juniperic acid, etc. In addition, esters of these carboxylic acids include stearyl stearate, butyl laurate, octyl palmitate, butyl stearate, isopropyl stearate, cetyl palmitate, ceryl cerotate, myricyl palmitate, melysylmerisate, roasted wax, Wax, carnauba wax, montan wax, mushi wax, tristearin, tolpalmitin, triolein, myristodilaurin, caprylolauromyristin, stearopalmitolein,
Monostearin, monopalmitin, distearin, civalmitin, beef tallow, pork fat, horse tallow, mutton tallow, cod liver oil, coconut oil,
Examples include palm oil, wood wax, kapok oil, cacao butter, Chinese butter, and illipe 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.
Nippon Oil & Fats special product name Nissan Bolibutene 0NS06N
, 015N, 3N, 5N, 1ON.

3ON, 20ON, 03H106SH1015SH, 3
Examples include SH, 5SH, 103H, 30SH, 200SH, and the like.

In the present invention, one or more surface lubricants are selected from among the various surface lubricants described above, and the amount used is as follows:
It is set within an appropriate range, taking into consideration the drying properties, adhesion, and other properties based on B and the antifouling agent, as well as the antifouling performance. −
For boat fishing, the proportion of the surface lubricant in the total amount of polymer A and/or copolymer AB and surface lubricant is 0.1.
~70-% by weight, preferably 0.5-50% by weight.

As mentioned above, the biofouling prevention coating composition of the present invention contains the above-mentioned polymer A and/or copolymer AB, an antifouling agent, and the above-mentioned surface lubricant as essential components. It is usually used after being diluted with an organic solvent.

For this reason, it is particularly desirable to adopt a solution polymerization method or a bulk polymerization method as a polymerization method to obtain polymer A and/or copolymer AB. In the case of bulk polymerization, a solvent can be added to the reactant after polymerization before use.

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 preferably such that the concentration of polymer A and/or copolymer AB in the solution is usually in the range of 5 to 90% by weight, preferably 15 to 85% by weight. The viscosity of the solution at this time is generally 15, which makes it easy to form a coating.
It is preferable that the temperature is 0 void or less/25°C.

The bioadhesion-preventing coating composition of the present invention having the above structure may contain pigments such as titanium dioxide and titanium dioxide, and coloring agents such as dyes, if necessary.

In addition, regular anti-sagging agents, anti-color separation agents, anti-settling agents,
Antifoaming agents and the like may also be added.

Furthermore, since the polymer A and/or copolymer AB used in the present invention are hydrolyzed in the presence of water, when forming a paint, so-called water is used to capture water contained in antifouling agents and pigments. It is desirable to add a binder into the system. Examples of such water binders include trialkyl orthoformates such as trimethyl orthoformate, triethyl orthoformate, tributyl orthoformate, trialkyl orthoacetates such as trimethyl orthoacetate, triethyl orthoacetate, tributyl orthoacetate; trimethyl oxalate,
Trialkyl ortho-oxalates such as triethyl ortho-oxalate and tributyl ortho-oxalate, tetramethyl silicate, tetraethyl silicate, tetrabutyl silicate,
Tetra(2-methoxyethyl)silicate, Tetra(2-methoxyethyl)silicate,
- tetra(substituted) alkyl silicates such as -chloroethyl) silicate, tetra(substituted) aryl silicates such as tetraphenyl silicate and tetrabenzyl silicate, and the above-mentioned tetra(substituted) alkyl silicates and tetra(substituted) aryl silicates. Condensate (
Examples include hydrolyzable ester compounds such as dimer, trimer, tetramer, hexamer, etc., and compounds having isocyanate groups such as phenyl isocyanate, benzenesulfonyl isocyanate, and nate.

In order to form an antifouling coating film on the surface of an object to be immersed in water using the biofouling prevention coating composition of the present invention, for example, the composition as a solution is applied to the surface of the object by an appropriate means. After that, it is sufficient to simply dry it at room temperature or under heat to volatilize and remove the solvent.

[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, and therefore impart hydrolyzability to the formed coating film. It is something to do. In addition, vinyl polymerizable monomer B is used to impart appropriate hydrolyzability to the coating film of copolymer AB, and monomer Ajt
It acts as an advantageous regulating component to obtain higher molecular weight polymers compared to L.

The antifouling agent used in the present invention chemically prevents the adhesion of aquatic organisms, and at the same time the coating film obtained from polymer A and/or copolymer AB is appropriately hydrolyzed and dissolved. The antifouling agent and surface lubricant are also gradually eluted into the water, making it possible to maintain the antifouling effect for a long time. Furthermore, the surface lubricant used in the present invention has a function of adjusting hydrolysis of the coating film and a physical antifouling function, and plays a major role in improving the antifouling property.

As described above, according to the combination system of polymer A and/or copolymer AB, antifouling agent, and surface lubricant in the present invention,
It is considered that the polymer A and/or the copolymer AB have a function of appropriately controlling excessive elution and insufficient elution of the antifouling agent, and the antifouling performance of the coating film is maintained stably over a long period of time.

〔Effect of the invention〕

The above-mentioned specific polymer used in the present invention is not of the type that cures by reaction itself (but has solvent-volatile drying properties to form a thermoplastic coating film, so the polymer used in the present invention The anti-biofouling paint composition has the following advantages compared to conventional anti-biofouling paints.

First, when producing a biofouling prevention paint, there is no need to fill in an inert gas when canned, which is stable and free of the risk of deterioration due to antifouling agents, and there is no limit on pot life. It is quick drying and
It is less susceptible to blistering and peeling because it is not affected by poor curing in the deep parts of the paint film or by humidity or temperature during drying. Excellent adhesion between the eyebrows when the same type of coating or another coating is applied over the coating. Even when the paint film is in contact with water, there is no excessive wear and tear on the paint film, so the antifouling performance can be maintained over a long period of time.

For this reason, it is necessary to prevent aquatic biological fouling in ship bottoms, underwater structures such as fishing nets and cooling water pipes, and even marine pollution prevention membranes used to prevent sludge diffusion in marine civil engineering works.
The coating film obtained by the present invention exhibits a remarkable antifouling effect,
Biofouling and fouling of submerged substrates can be prevented.

〔Example〕

Next, the present invention will be specifically explained using polymer production examples, working examples, and comparative examples. In the examples, parts are parts by weight, viscosity is the foam viscosity measurement value at 25°C, and molecular weight is the weight average molecular weight by GPC. represent.

Production Examples 1 to 7 A flask equipped with a stirrer was charged with solvent a according to the formulation in Table 2 (1 and 2), and the temperature was raised to a predetermined reaction temperature, and while stirring, monomer A1 was added. A mixed solution of B and polymerization catalyst a was dropped into the flask over 6 hours, and after the dropwise addition was completed, the mixture was maintained at the same temperature for 30 minutes.

Then, a mixture of a solvent and a polymerization catalyst was added dropwise over 20 minutes, and stirring was continued for 5 hours at the same temperature to complete the polymerization reaction. Finally, a diluting solvent was added to dilute the solution to obtain each polymer solution I to ■.

Production Example 8.9 In a heat-resistant and pressure-resistant container, monomer A, monomer B, and polymerization catalyst a were charged according to the formulations in Table 2 (1 and 2), and the container was completely sealed and shaken. The temperature was raised to a predetermined reaction temperature, and 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 polymer solutions VW and IK.

Production Example 10 A flask equipped with a stirrer was charged with solvent a, monomer A, and polymerization catalyst a according to the formulations in Table 2 (1 and 2), and the temperature was raised to a predetermined reaction temperature while stirring. Stirring was continued at this temperature for 6 hours to obtain polymer solution X.

In addition, monomer A (A, ~
A. ) is Xl in the general formula (1).

X2+ These cis-trans geometric isomers, Y.

'i'z (when one or both of these is an organic group represented by the formula (al), n, m (animal), R1-R5) has a structure as shown in Table 1 below It is.

Examples 1 to 56 Using polymer solutions ① to
The mixture was mixed and dispersed using a homomixer (M) to prepare 56 kinds of anti-biofouling coating compositions.

Among the ingredients, paraffin wax 120P and petrolatum No. 1 are petroleum waxes according to JIS K2235, and I5OVC-10 is liquid paraffin according to JIS K2231. In addition, the silicone oil with the product name KF-69 is manufactured by Shin-Etsu Chemical Co., Ltd., and the product name is T.
The silicone oil for SF433 is manufactured by Toshiba Silicone ■. Furthermore, Nirasan Polybutene 06N is Nippon Oil & Fats ■
Made of polybutene. All of these were used as a type of surface lubricant.

Additionally, Oil Blue 2N (trade name manufactured by Orient Chemical ■) is a dye, and Disparon 6900-20X (trade name manufactured by Hashimoto Kasei ■) and Aeroseal 300 (trade name manufactured by Nippon Aeroseal ■) are both anti-sagging agents. It is an additive for

Comparative Examples 1 to 4 Examples 1 to 56 except that KE45TS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.; 50% by weight toluene solution of oligomeric room-temperature curing silicone rubber) was used instead of the polymer solutions ■ to X. In the same manner as above, four types of biofouling prevention coating compositions having the formulations shown in Table 6 below were prepared.

Comparative Examples 5 to 9 Five types of compounds having the composition shown in Table 6 below were prepared in the same manner as Examples 1 to 56, except that an organic tin copolymer solution was used instead of the polymer solution Natsu-X. A biofouling prevention coating composition 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.

The following tests were conducted on each of the biofouling prevention coating compositions of Examples 1 to 56 and Comparative Examples 1 to 9. Result is,
The results were as shown in Tables 7 and 8 below.

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

A) Storage stability 200 cc of each anti-biofouling coating composition was placed in a 250 cc mayonnaise bottle, and the bottle was sealed with a lid.

This was stored in a thermostatic chamber at a temperature of 70° C. and a humidity of 75%, and the storage stability was determined based on the degree of viscosity increase of each sample after 2 weeks. Increase rate is 10% from initial viscosity (KU: approx. 70)
○ when it is less than 10%, △ when it is 10% or more and less than 100%.
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 biofouling prevention coating composition to a wet film thickness of 100 μm using a film applicator. When the semi-hardening drying time was less than 1 hour, it was evaluated as 011 hours or more and less than 3 hours as Δ, and when it was 3 hours or more, it 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 Apply each biofouling prevention coating composition to a polished steel plate (150X) with a wet film thickness of 100 μm using a film applicator.
70 x 1 fl) and kept for one week at a temperature of 20°C and a humidity of 7.
A 20 m long X-shaped cut reaching the base layer was made with a cutter knife on the paint film that had been dried in a 5% constant temperature room. The center was extruded with a weight of 10 g++ from the back side of the test plate using an Erichsen tester. At that time, x on the coating surface
Adhesion was determined by the length of peeling from the center of the uneven cut portion. ○ when there is no peeling, △ when less than 5 cranes
When it was 5n or more, it was evaluated as ×.

<Antifouling performance test> Each biofouling prevention paint composition was applied to both sides of a painted board (100x2QOxl Tsuru) made by applying a tarvinyl anti-TI1 paint to a sandblasted steel plate in advance so that the dry film thickness was 120 μm on one side. A test plate was prepared by spray painting the sample twice and drying it in a thermostatic chamber at 20° C. and 75% relative humidity for one week.

For this preliminary test, we conducted 24-month immersion in seawater in Aioi Bay, Aioi City, Hyogo Prefecture, which is a sea area with heavy biofouling, and measured the ratio of the occupied area (adhered area) of attached organisms on the test coating over time. did.

As is clear from the results in Table 7.8 above, Example 1
The bioadhesion-preventing paint compositions of the present invention No. 56 had good storage stability, drying properties, and adhesion, and no bioadhesion was observed in the antifouling performance test until 24 months had passed.

On the other hand, Comparative Examples 1 to 4 were silicone rubber-based biological adhesion prevention coating compositions, but they had shortcomings in storage stability, drying properties, and adhesion, and were also unsatisfactory in antifouling properties. Also,
Comparative Examples 5 to 9 were organic tin copolymer-based biofouling prevention coating compositions, but were somewhat inferior in storage stability and antifouling properties.

Claims (1)

[Claims] 1) The following general formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (However, in the formula, X_1 and X_2 are hydrogen atoms or methyl groups. , both groups may be either cis or trans type.One of Y_1 and Y_2 has the following formula (a); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(a) [However, In the formula, n is an integer of 0 or 1, m is a real number of 0 or more, and R_1 to R_3 are all selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group, or a substituted phenoxyl group. The selected groups may be the same group or different groups. R_4 and R_5 are the same groups as R_1 to R_3 above or the following formula (b); ▲ Numerical formula, chemical formula, There are tables, etc.▼...(b) (However, in the formula, R_6 to R_8 are all alkyl groups, alkoxyl groups, phenyl groups, substituted phenyl groups, phenoxyl groups, substituted phenoxyl groups, or formula (b) A group selected from among the organosiloxane groups represented by the following formulas, which may be the same or different groups: , m R_4, R_5 may be the same group or different groups], and the other is a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group, or the above-mentioned An organic group represented by formula (a).) A polymer of one or more monomers A represented by the formula (a), and/or a copolymer with one or more of the above monomers A. A copolymer consisting of one or more vinyl polymerizable monomers B,
A biofouling prevention coating composition containing an antifouling agent and a surface lubricant as essential components.