JPH01121372A - Aquatic antifouling coating agent - Google Patents

Abstract

PURPOSE:To obtain the title coating agent having excellent adhesivity, curability, etc., and effective in preventing the adhesion of aquatic life when applied to a marine construction, by using a copolymer containing an organosilyl group or organosiloxane group on the side chain as an essential component. CONSTITUTION:The objective coating agent contains, as an essential component, a copolymer of (i) a monomer of formula I {X1 and X2 are H or CH3; one of Y1 and Y2 is organic group of formula II [n is 0-5; m is >=0; R1-R3 are alkyl, phenyl, etc.; R4 and R5 are R1-R3 or organosiloxane group of formula III (R1'-R3' are alkyl, phenyl, etc.)], H, alkyl, phenyl, etc.} and/or (ii) a polymerizable vinyl monomer copolymerizable with the component (i).

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.

Many underwater antifouling coatings use antifouling agents such as organic tin copolymers and cuprous oxide, which have an antifouling effect on living things and are slightly soluble in seawater. There is. However, in these cases, harmful substances may be eluted into the seawater, contributing to seawater contamination, and the effects on fish and shellfish may not be ignored.

Therefore, there has been a demand for an underwater antifouling coating that does not use such an antifouling agent and does not dissolve in seawater. Such non-toxic underwater antifouling coatings use silicone rubber that is vulcanized by the action of a catalyst or moisture, or vulcanized by the action of both a catalyst and moisture to three-dimensionally crosslink and form a film. Things can be given.

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 method for preventing marine biofouling, which is a mixture of oligomeric room-temperature curing silicone rubber (for example, Shin-Etsu Chemical Co., Ltd.'s product names KE45TS, KE44RTV, etc.) and liquid paraffin or petrolatum. Paint is shown.

[Problem that the invention seeks to solve]

All of these conventionally known underwater antifouling coatings utilize the slipperiness of the silicone rubber coated surface to prevent aquatic organisms from adhering to the surface. Silicone rubber has the following problem in that it undergoes three-dimensional crosslinking to form a film during use.

The first is curing properties after painting. In other words, curing of silicone rubber occurs through hydrolysis of the crosslinking agent due to atmospheric moisture, or through a condensation reaction initiated by the action of a temperature-sensitive catalyst on the crosslinking agent, so the curing rate varies depending on atmospheric humidity and temperature. In addition, differences in curing strength occur, making it difficult to obtain uniformity of the film. For example, as shown 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 this happens, hardening occurs from the surface of the coating that is in contact with the humid atmosphere and progresses to the inside of the coating, so by hardening the surface first, subsequent moisture permeation is suppressed, resulting in a lack of moisture inside. It is thought that it becomes difficult to obtain uniformity of the film as a result of hardening in deep portions becoming less likely to occur or crosslinking density becoming lower. This results in poor adhesion of the film as a whole, such as peeling off from the object to be coated and blistering. Furthermore, since moisture penetrates into the interior slowly, the time required for curing becomes longer.

For example, when such underwater antifouling coatings are used in high-temperature locations, curing is fast, but only the 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, 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. Therefore, a problem arises in that painted objects cannot be moved in a short period of time. Catalysts such as tin compounds and platinum are sometimes used as curing accelerators to prevent this, but in low-lying wetlands, their catalytic activity decreases, making it difficult for the condensation reaction caused by the crosslinking agent to occur, resulting in extremely slow curing of the film. .

Second, there is the problem of overcoatability. Normally, the solvent of the overcoat coating material slightly invades the undercoat surface and mixes at the interface, which improves the adhesion between the eyebrows, but the overcoatability to silicone rubber is due to the fact that the base silicone rubber undergoes three-dimensional crosslinking and hardening. 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, 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. Another problem was that when the lid of the magnification variable lens was opened, moisture from the atmosphere entered, hardening and thickening the surface of the coating material, making it difficult to reuse it.

[Means for solving problems]

As a result of intensive research into the above-mentioned points, the present inventors have found that the above-mentioned conventional underwater antifouling coatings, which use silicone rubber alone or in combination with silicone oil, paraffin, etc., do not have the various problems. Furthermore, we succeeded in obtaining an underwater antifouling coating using a solvent-volatile polymer that has a smaller slip angle on the membrane surface than these and is expected to have good antifouling properties.

That is, the present invention provides the following general formula (l);
In the formula, XI and xi are hydrogen atoms or methyl groups, both groups may be in the cis or trans form, Y, Yl is one of the formulas (a); [However, the formula In the formula, n is an integer of θ to 5, and m is a real number of 0 or more. Rl''' Rx 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, and even if they are the same groups, they may be different groups. * R41R% is the same group as R1-R3 above or the following formula (b); ', ~R'' 3 are all groups 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 formula (b); , which may be the same or different groups), in which m R4, R% are the same groups, may also be 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 two or more of the above monomers A and one or two of the vinyl polymerizable monomers B that can be copolymerized with these. The first invention relates to an underwater antifouling coating agent containing as an essential component a copolymer consisting of at least one of the above-mentioned polymers and/or copolymers; The second invention relates to an underwater antifouling coating material containing as an essential component one or more surface lubricants that can be substantially maintained.

[Structure of the invention]

In the underwater antifouling coating of the present invention, as an essential component, one or more polymers of monomer A represented by the above general formula (1), that is, a homopolymer or a copolymer (hereinafter referred to as , these are referred to as polymer A), or a copolymer ( Hereinafter, these will be referred to as copolymers AB). Moreover, the above-mentioned polymer A and copolymer AB may be used in combination as necessary.

Such polymer A and copolymer AB both have organosilyl groups or organosiloxane groups derived from monomer A in their side chains, so they impart good slipperiness to the coating formed therefrom. This coating 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 uniform coating can be easily formed by applying a solution of these solvents to the surface of an object to be immersed in seawater and drying it. can be converted into 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 glabellar 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
The 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),
z is a hydrogen atom or a methyl group, and both groups can have either cis or trans form as geometric isomers. Further, in formula (1), one of Yr and Yt is an organic group represented by the following formula (a); and the other is a hydrogen atom, an alkyl group, a phenyl group, a substituted phenyl group, or the above formula (a). It is an organic group represented by 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 (al), m is the repeating number of the organosiloxane group, and can be a real number of 0 or more, but 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 this is also the reason why 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 0 to 5, that is, 0°1, 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 Rr-Rs may be the same group or different groups.

Furthermore, in the formula (al, Ra and Rs are the above RI'''R3
or a group selected from organosiloxane groups represented by the following formula (b); Ra and Rs may be the same group or different groups. Note that R4 and R3 are
, -R,, these groups and R8-
Of course, the group R5 may be the same group or a different group.

In the above formula (b), R'1 to R''3 are all an alkyl group, an alkoxyl group, a phenyl group, a tm phenyl group, a phenoxydyl group, a substituted phenoxydyl group, or the formula (b)
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'1 to R' may be the same group or different groups.

Such monomer A is easily available as a commercial product. Synthesis examples include, for example, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester [all unsaturated acids in which X in the general formula (1) above are both hydrogen atoms], or α-methyl substituted product of [the above general formula (unsaturated acid in which one of Xl and Xt in 11 is a hydrogen atom and the other is a methyl group), α・α′-dimethyl substituted product of these [the above general formula (1)] An organosilyl compound having the above-mentioned R3 to R3 in the molecule or an organosiloxane having the above-mentioned R, -R in the molecule, etc. A method of dehydrating and condensing a compound, or obtaining an ester of an unsaturated acid similar to the above and an unsaturated alcohol such as vinyl alcohol or allyl alcohol according to the number of n in the formula (a), and adding an organosilyl similar to the above. There is a method in which a compound or an organosiloxane compound is subjected to an addition reaction.

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, acrylic esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate, maleic esters such as dimethyl maleate, diethyl maleate, etc. kind, dimethyl fumarate, fumano? Fumaric acid esters such as diethyl acid, styrene, vinyltoluene, α-methylstyrene, hinyl chloride, vinyl acetate, butadiene, acrylamide, acrylonitrile, methacrylic acid, acrylic acid, maleic acid, fumaric acid, crotonic acid, crotonic acid esters , itaconic acid, itaconic acid esters, etc.

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 deuterons or less;
In particular, it is preferably 90% by weight or less. That is, the proportion of monomer A constituting copolymer AB is at least 5% by weight.
If the amount is particularly preferably at least 10% by weight, the amount of monomer B used may be appropriately set within the above range, based on this monomer A (because the antifouling effect can be sufficiently exhibited).

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. Examples of the vinyl polymerization initiator include azo compounds such as azobisisobutyronitrile 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 1.000 to 1.500.0 for -a.
It is desirable that it be in the range of 00. 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 will be high when used as a coating material, and the resin solid content will be low, so only a thin film can be obtained with one coating, and the dry film thickness will be too low for a given yield. The problem is that it takes several coats of paint to get the desired effect.

In the present invention, the above-mentioned polymer A and/or copolymer AB can be used alone to exhibit excellent antifouling properties, but together with this polymer A and/or copolymer AB, these By using as one of the essential components a surface lubricant that can substantially maintain the low surface tension of the film formed from the above, the antifouling properties can be further improved.

Note that the above-mentioned "substantially" means that even if a certain degree of increase in surface tension is observed due to the use of a surface lubricant, the surface tension after the increase does not cause a decrease in antifouling properties, and the above-mentioned duration of the present invention is maintained. This means that the above-mentioned increase to some extent is acceptable as long as the sex-enhancing effect can still be maintained. For example, if the sliding angle of the coating surface measured by the method described below shows a small increase of 1 degree or less, it can be sufficiently used as the surface lubricant of the present invention.

On the other hand, the above-mentioned maintenance does not mean intentionally eliminating cases where the surface tension of the coating is further reduced by the use of a surface lubricant. Even in such a case, the surface tension after addition remains low, and the above-mentioned sustainability improvement effect of the present invention can still be expected. After all, in the surface lubricant of the present invention, "capable of substantially maintaining a low surface tension" means that the surface lubricant of the present invention has a surface lubricant that significantly increases the surface tension of the coating and causes a decrease in antifouling properties. Therefore, other surface lubricants can be widely used as the surface lubricant of the present invention.

As such surface lubricating agents that can be used in the present invention, there are various substances known to impart slipperiness to the coating surface, and representative examples thereof include ■JISK22
Petroleum wax specified in 35, Liquid paraffin specified in JISK2231, 55.0 at 025°C
Silicone oil having a kinematic viscosity of 0.00 centistokes or less; ■ Fatty acids having 8 or more carbon atoms and their esters having a melting point of -5°C or higher; ■ Organic amines having alkyl or alkenyl groups having 12 to 20 carbon atoms; 0.25°C
Examples include polybutene having a kinematic viscosity of 60,000 centistokes or less.

Specific examples of the above (■) include paraffin wax, microcrystalline wax, petrolatum, etc.
As a specific example, l5OVCIO1ISOVG15,
I5OVC32, l5OVG68, l5OVG100
Specific examples of products corresponding to the above (■) include product names KF96L-0,65, KF96L-2, and KF96L-0,65, manufactured by Shin-Etsu Chemical ■.
0, KF96-30, KF96H-50,000, KF
965, KF50, KF54, KF69, Toshiba Silicone brand name TSF440, TSF410. TSF4
440, TSF431, TSF433, TSF404,
TFA4200, YF3860, YF3818, YF3
841. YF3953, TSF451, Toshi Silicone product name 5H200, 5H510, 5H3531,
Examples include 5H230 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, esters of these carboxylic acids include stearyl stearate, butyl laurate, octyl palmitate, butyl stearate, isopropyl stearate, cetyl palmitate, seryl cerotate, myricyl palmitate, melysylmerisate, spermaceti, spermaceti Wax, carnauba wax, montan wax, mushi wax, tristearin, tolpalmitin, triolein, myristodilaurin, caprylolauromyristin, stearopalmitolein,
Monostearin, monovalmitin, distearin, civalmitin, beef tallow, pork intestine, horse tallow, mutton tallow, cod liver oil, coconut oil,
Examples include palm oil, 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, Dodecyldimethylamine, cocoalkyldimethylamine, tetradecyldimethylamine, hexamethyldimethylamine, octadecyldimethylamine, etc. Examples of the above (■) include Nissan Bolibutene ON, 06 manufactured by NOF■.
N, 015N, 3N, 5N, 1 ON.

3ON, 20ON, 03H106SH, 015SH, 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 determined based on the drying properties based on the polymer A and/or copolymer AB. , is set within an appropriate range, taking into consideration performance such as adhesion and 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 1 to 70%.
Preferably it is 50% by weight.

As mentioned above, the underwater antifouling coating of the present invention contains the above-mentioned polymer A and/or copolymer AB as an essential component, or further contains the above-mentioned surface lubricant as an essential component. Both coating materials are usually used after being diluted with an organic solvent. Therefore, 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 preferably such that the concentration of polymer A and/or copolymer AB in the solution is usually in the range of 5 to 80% by weight, particularly preferably 30 to 70% by weight. 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 having such a structure 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, thereby uniformly forming an antifouling film with low surface tension and good slipperiness.

[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, the film obtained by the first invention itself has the function of physically and effectively preventing the adhesion of marine organisms. In addition, vinyl polymerizable monomer B
acts as a convenient regulating component to impart appropriate surface slipperiness to the coating of copolymer AB, if necessary, and to obtain a polymer having a higher molecular weight than monomer A alone. be.

Furthermore, by using the surface lubricant used in the second invention in combination with the above-mentioned polymer A and/or copolymer AB, the antifouling performance can be maintained for a long time even in sea areas where marine life is actively breeding. This is important for achieving sustainability. The present inventors' preliminary measurements regarding the above facts indicate that the surface of the coating is improved due to the surface smoothing effect based on the use of a surface lubricant, the deterioration prevention effect of the coating made of polymer A and/or copolymer AB, etc. This is thought to be due to the fact that the slipperiness is reinforced and maintained over a long period of time.

〔Effect of the invention〕

The above-described 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 film that is insoluble in seawater.
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, supporting its excellent antifouling effect.

Therefore, it is necessary to prevent the fouling of marine organisms in the bottom of ships, underwater structures such as fishing nets and cooling water pipes, and even in marine pollution prevention membranes used to prevent the spread of sludge during marine civil engineering works.
The film obtained by the present invention exhibits a remarkable antifouling effect,
Biofouling of submerged substrates can be prevented.

〔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 GPC.

Production Examples 1 to 15 In a flask equipped with a stirrer, add solvent a according to the formulation in Table 3.
was charged, the temperature was raised to a predetermined reaction temperature, and a mixed solution of monomer A (Al to Al5), monomer B, and polymerization catalyst a was dropped into the flask over 6 hours while stirring, and the dropwise addition was completed. Afterwards, it was kept at the same temperature for 30 minutes. Next, a mixture of solvent and polymerization catalyst was added dropwise over 20 minutes, and the mixture was further heated at the same temperature for 5 minutes.
Stirring was continued for hours to complete the polymerization reaction. Finally, a diluting solvent was added for dilution to obtain each polymer solution 1-XV.

Production Examples 16-18 In a heat-resistant and pressure-resistant container, monomer A was added according to the formulation in Table 3.
(A + h ” A Ia ), monomer B and polymerization catalyst a are charged, the mixture is completely sealed and the temperature is raised to a predetermined reaction temperature while shaking, and further shaking is 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 XVI to X■.

Production Example 19.20 In a flask equipped with a stirrer, add solvent a according to the formulation in Table 3.
, monomer A (A11.Ago), 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 x■, xx.

In addition, monomer A (A r
~A za) is X,,X, in the general formula (1).

These cis-trans geometric isomers, Yt, Yt (
The formula (n, m (seedling), R1 to Rs when one or both of these is an organic group represented by al) is the following 1.
It has the structure shown in Table 2.

Examples 1 to 40 Using polymer solution r-xx, 2.000 r
Forty types of underwater antifouling coatings were prepared by mixing and dispersing using a PM homomixer.

Among the ingredients, paraffin wax 120P and petrolatum No. 1 are JIS K2235' petroleum waxes, and 15OVCIO is JIS K2231 liquid paraffin. Also, the product name is KF-69, KF-
The silicone oil No. 96-30 is manufactured by Shin-Etsu Chemical Co., Ltd., and the silicone oil with the trade name TSF433 is manufactured by Toshiba Silicone ■. Furthermore, Nirasan Polybutene 06N and ION are polybutenes manufactured by NOF ■.

In addition, Oil Blue 2N (trade name manufactured by Orient Kagaku ■) is a dye, and Disparon 6900-20X [trade name manufactured by Hashimoto Kasei Toki] and Aeroseal 300 (trade name manufactured by Nippon Aeroseal ■) are both additives for preventing sagging. It is a drug.

Comparative Examples 1 to 4 Instead of the polymer solutions ■ to XX, KE45TS [trade name manufactured by Shin-Etsu Chemical ■; oligomeric room temperature curing silicone rubber 50! % toluene solution] were used, but in the same manner as in Examples 1 to 40, four types of underwater antifouling coatings having the formulations shown in Table 5 below were prepared.

Each of the coating materials of Examples 1 to 40 and Comparative Examples 1 to 4 described above 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 Tables 6 and 7 below.

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

A) Storage stability: Add 200 ml of each coating to a 250 cc mayonnaise jar.
I put it in a cc container and sealed it 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. When the increase rate was less than 10% from the initial viscosity, it was evaluated as Q, when it was 10% or more and less than 100%, it was evaluated as Δ, 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. ○ Half-curing drying time is less than 1 hour
, 1 hour or more but less than 3 hours was evaluated as Δ, 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 board test of JIS K5400.6.15. That is, each coating agent was applied to a polished steel plate (
150X70X1m++) and kept at a temperature of 20℃ for one week.
The film was dried in a thermostatic chamber at 75% humidity, and a 20 fl cross cut was made with a cutter knife, reaching the base layer.

10 with an Erichsen tester from the back of the test plate at the center.
We pushed out the crane. 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 rated as ◯ when the peeling was O, Δ when the peeling was less than 5f1, and × when the peeling was 5f1 or more.

<Measurement of surface sliding angle of coating> Figure 1 (A) for each test plate used in the drying test.
, (B) was used to measure the surface slip angle of the coating in the following manner. In addition, the above-mentioned measuring machine includes a transparent glass plate 1 and a fixing jig 2 on the glass plate 1 with one end on the A side.
The movable plate 4 is fixed by a support column 3, and the other end B side is supported by a support column 3, and is provided so as to be movable upward along the support column 3.

First, as shown in FIG. 1(A), a test plate 5 is placed on a transparent glass plate 1 with the coating side facing upward.
Place the test plate horizontally via the movable plate 4, and drop 1 ml of sterilized filtered warm water at 0°' with a syringe on the test plate 5 at one end A of the movable plate 4, that is, at a distance T from the fixing jig 2 of 185 mm. to form water droplets 6. Thereafter, as shown in FIG. 1(B), the other end B side of the movable plate 4 is moved upward along the support column 3 at a speed of 1 m/sec to tilt the test plate 5. Test board 5
The angle of inclination α at which the water droplets on the surface begin to slide was measured, and this was taken as the surface slip angle of the coating.

The above measurements were performed in a thermostatic chamber at a temperature of 25° C. and a humidity of 75%, and each test plate was measured three times, and the average value was expressed.

<Antifouling performance test> Each coating was applied to a painted plate (100X200X
A test plate was prepared by spraying two times on both sides of 1ml) so that the dry film thickness was 120 μm on one side.

This test board was immersed in seawater for 24 months in Yura Bay, Sumoto City, Hyogo Prefecture, and the area occupied by attached organisms on the test coating (
The percentage of adhesion area) was measured over time.

As is clear from the results in Tables 6 and 7 above, Examples 1-
Sample No. 40 had good storage stability, drying properties, and adhesion. Moreover, the surface sliding angles are all in the range of 7.8 to 9.3 degrees. In addition, in Examples 23 to 40 in which a surface lubricant was used in combination, the temperature was in the range of 8.0 to 9.1 degrees, which means that the coating itself of the specific polymer of the present invention has strong surface slip properties. Indicate that you have
Moreover, it is shown that the surface slipping agent maintains the strong surface slipping properties of the coating itself of the specific polymer of the present invention.

In the antifouling performance test, no biological adhesion was observed until at least 24 months had passed.

On the other hand, Comparative Examples 1 to 4 are silicone rubber-based coating materials, which have 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.

[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 in the cis form or It may be of any transformer type. 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 from 0 to 5, and m is a real number of 0 or more. be. 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 whether they are the same group or different groups, good. 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 A group selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group, a substituted phenoxyl group, or an organosiloxane group represented by formula (b), even if they are the same groups. The m R_4 and R_5 groups 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 agent containing a copolymer consisting of at least one species as an essential component. (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 or trans It can be of any type. 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 0 to 5, and m is a real number of 0 or more. . R_1 to R_3 are all groups selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group, or a substituted phenoxyl group, and may be the same group or different groups. good. 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) is a group selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group, a substituted phenoxyl group, or an organosiloxane group represented by formula (b), and is the same group as each other. 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. and one or more surface lubricants that can substantially maintain the low surface tension of the coating formed from this polymer and/or copolymer. Underwater antifouling coating agent containing as.