JPS62283167A - Underwater antifouling coating agent - Google Patents

Abstract

PURPOSE:The titled coating agent, consisting essentially of a polymer having polydimethylsiloxane and trimethylsilyl groups in the side chain and further specific surface lubricating agent and having excellent storage stability to moisture and heat and remarkably improved antifouling property. CONSTITUTION:A coating agent consisting essentially of one or more polymers of (A) monomers expressed by the formula (X is H or CH3 n is 2-4; m is the average polymerization and 0-70), e.g. trimethylsilylethyl (meth)acrylate, etc., and/or a copolymer consisting of one or more of the above-mentioned monomers (A) and vinyl polymerizable monomers (B) copolymerizable therewith, e.g. methyl methacrylate, etc., and or or more surface lubricating agents capable of substantially sustaining a low surface tension held by coats formed from the polymers and/or copolymers. The surface lubricating agents are preferably petroleum wax, preferably paraffin wax, etc., specified by JIS K2235.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to an underwater antifouling coating agent containing a polymer having a polydimethylsiloxane group and/or a trimethylsilyl group in its side chain.

[Prior Art] Various problems occur on the surfaces of underwater objects immersed in seawater, such as ship bottoms, buoys, fishing nets, and various intake and drainage pipes for cooling, due to adhesion of Fujibo, Serpura, mussels, algae, and the like. It is well known that underwater antifouling coatings are often applied to the surfaces of objects immersed in seawater 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 organisms and are slightly soluble in seawater. has been done. However, in these cases, harmful substances may be eluted into the seawater, contributing to seawater pollution, and the effects on fish and shellfish may not be negligible.

Therefore, there has been a demand for an underwater antifouling coating that does not use such antifouling agents and does not dissolve in seawater. Examples include silicone rubber that is vulcanized or vulcanized by the action of both a catalyst and moisture to three-dimensionally crosslink and form a film. For example, Japanese Patent Publication No. 53-359'7'4 describes A method using sulfur/licone rubber as a coating agent is disclosed, and JP-A-51-96830 discloses a method using a mixture of an oligomeric silicone rubber having a hydroxyl end group and a silicone rubber. It is shown.

Furthermore, JP-A-53-79980 discloses a mixture of vulcanized silicone rubber and a fluid organic compound that does not contain metal or silicone.
Japanese Patent Publication No. 60-3433 describes 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. The paint used is indicated.

``Problem to be solved by the invention'' - These 11 underwater antifouling coatings have been applied to the surface by utilizing the bone θ properties of Noritsu/rubber coatings. The silicone rubber used to form the film has the following problem in that it is three-dimensionally crosslinked 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 occurs, hardening occurs from the surface of the coating that is about to come into contact with the humid atmosphere, and it progresses to the inside one after another.As the surface hardens first, subsequent moisture permeation is suppressed, resulting in a lack of moisture inside. As a result, deep curing is less likely to occur or the crosslinking density is lowered, making it difficult to obtain uniformity of the film.As a result, the film may peel off from the object to be coated or cause poor adhesion such as blistering. It turns out. Furthermore, since moisture penetrates into the interior slowly, the time required for curing becomes longer.

For example, when such an underwater antifouling coating is used in a high temperature and high humidity location, 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. In order to prevent this, catalysts such as tin compounds and platinum are sometimes used as curing accelerators.
In low-lying wetlands, their catalytic activity decreases, making it difficult for the condensation reaction by the crosslinking agent to occur, which inevitably slows down the curing of the film.

Second, there is the problem of overcoatability. Normally, the solvent of the topcoat coating material slightly soaks the undercoat surface and mixes at the interface, which improves interlayer adhesion. However, overcoatability to silicone rubber is improved because the base silicone rubber undergoes three-dimensional crosslinking and hardening. , the reapplied top coat does not soak 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 is that when the lid of the magnification variable lens is opened, moisture from the atmosphere enters and hardens and thickens the surface of the coating material, making it difficult to reuse it.

Therefore, the present inventors have made intensive studies to obtain an underwater antifouling coating agent that can avoid the various problems of the conventionally known underwater antifouling coating agents and have excellent antifouling performance. We have succeeded in obtaining an underwater antifouling coating using a specific solvent-volatile polymer having polydimethylsiloxane groups and/or trimethylsilyl groups, and have already proposed it in Japanese Patent Application No. 1983-298918.

The above-mentioned specific polymer according to this proposal differs from the conventionally known silicone rubber-based ones in that it is a solvent-volatile type, so it essentially suffers from the aforementioned problems such as curability, overcoatability, pot life, and storage stability. Moreover, the surface tension of clothing formed from this polymer is lower than that of conventionally known silicone rubber-based clothing, and because it exhibits excellent surface slipperiness, improved antifouling performance has also been observed. found.

The present invention is based on the above-mentioned prior invention and further improves this prior invention, that is, it can solve the problems of the above-mentioned conventionally known underwater antifouling coatings as well as the prior invention, and is further improved over the prior invention. The purpose of the present invention is to provide an industrially useful underwater antifouling coating material that can provide excellent antifouling performance.

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the present inventors have found that by using a specific surface lubricant together with the specific polymer according to the prior invention, the above object can be solved. The present invention was completed based on the knowledge that the antifouling performance can be further improved without losing the above-mentioned advantages based on polymers.

That is, the underwater antifouling coating agent of the present invention has the following general formula;
An integer of ~4, m represents an average degree of polymerization of O~70) and/or one or more of the above monomers A and these Substantially maintains the low surface tension of a copolymer consisting of one or more vinyl polymerizable monomers B that can be copolymerized with It contains one or more surface lubricants as an essential component.

[Structure and operation 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 +11, that is, a homopolymer or a copolymer (hereinafter, these (referred to as polymer A) and the specific surface lubricant, or one or more of the monomers A and one or two of the vinyl polymerizable monomers B copolymerizable therewith. copolymer with more than one species (hereinafter referred to as this)
(referred to as copolymer AB) and the above-mentioned specific surface lubricant are used together. Further, the above-mentioned polymer A and copolymer AB may be used in combination with the above-mentioned specific surface lubricant, if necessary.

Since both Polymer A and Copolymer AB have polydimethylsiloxane groups and/or trimethylsilyl groups derived from Monomer A in their side chains, the surface tension of the coating formed therefrom is low. This coating provides good slipperiness and effectively prevents the adhesion of aquatic organisms, but this adhesion prevention effect, that is, the antifouling performance, is not as good as the above polymer A.
By using the above-mentioned specific surface lubricating agent in combination with copolymer AB, the antifouling performance is further promoted, and the antifouling performance is maintained over a long period of time.

In addition, in the present invention, the use of the above-mentioned surface lubricant does not necessarily reduce the surface tension of the coating further. In other words, as a result of measuring the sliding angle of the coating surface, which indicates the degree of surface tension, using the method shown in the examples below, there was almost no major difference between when the above-mentioned surface lubricant was used and when it was not used. Ta. in spite of,
The fact that antifouling performance can be maintained over a long period of time by using the above-mentioned surface lubricating agent is completely unexpected and surprising from the above-mentioned conventionally known antifouling coatings.

The present inventors speculate that the above facts are due to the surface smoothing effect based on the use of the bone agent in Surface 1 and the deterioration prevention effect on the coating surface based on the interaction with polymer A and copolymer AB. This is thought to be due to the fact that the low surface tension of Polymer A and Copolymer AB is maintained under reinforcement over a long period of time.

Thus, in the present invention, by using the above-mentioned polymer A and/or copolymer AB in combination with the above-mentioned specific surface lubricant, the antifouling performance can be maintained for a long time due to their synergistic action. At the same time, as in the case of the prior invention, it is possible to solve all the problems of the conventionally known underwater antifouling coatings.

That is, since the above-mentioned polymer A and copolymer AB and the above-mentioned surface lubricant are all soluble in organic solvents,
A uniform film can be easily formed by applying this solvent S= to the surface of a cracked object soaked in seawater and drying it. Moreover, the above polymer A and copolymer AB
is essentially non-reactive, unlike the conventional reaction-curing type, so the underwater antifouling coating prepared by adding the above-mentioned surface lubricant is also stable, and therefore The above film formation is not affected by atmospheric humidity or temperature, and has excellent pot life and storage stability as a solution. Furthermore, when a similar or other coating is applied over this coating, the coating is immersed in the solvent of the topcoat, resulting in excellent glabellar adhesion with the topcoat.

Monomer A for obtaining polymer A and copolymer AB used in the present invention has a polydimethylsiloxane group (m=1 or more) or a trimethylsilyl group ( m = O). In formula +11, m = o to 70 because when m is larger than 70, the polymerizability or copolymerizability of monomer A decreases, and polymer A can be uniformly formed into a film.
Alternatively, this is because it becomes difficult to obtain copolymer AB. Also,
In the formula (+), n = 2 to 4 because when n is less than 2, the bonding property of the ester forming part of monomer A becomes weak, and the ester bond dissociates during the polymerization stage or when used as a coating material. This is because when n exceeds 4, the antifouling performance and its sustainability deteriorate, and when n exceeds 4, the polymer becomes soft, making it difficult to form a film with a low surface tension and no sticky feeling.

Specific compound groups of monomer A represented by the above general formula (1) include trinotylsilylethyl (meth)acrylate, trimethylsilylpropyl (meth)acrylate, and trimethylsilylpropyl (meth)acrylate as those having a trimethylsilyl group. ) Trimethylsilylbutyl acrylate containing polydimethylsiloxane groups (meta) up to m=70
Polydimethylsiloxane ethyl acrylate, (meth),
Polydimethylsiloxanepropyl acrylate, (meth)
There is polydimethylronoxanebutyl acrylate. Note that the above (meth) means that it may be either acrylic acid or methacrylic acid.

Such monomer A is easily available as a commercial product, but to give an example of its synthesis, an ester of (meth)acrylic acid and alkylene glycol is obtained, and a trimethylsilyl compound or polydimethylsiloxane is added to this. Examples include a method of subjecting compounds to a condensation reaction, and a method of obtaining an ester of sea lion (meth)acrylic acid and allyl alcohol and subjecting it to an addition reaction with a trimethylsilyl compound or a polydimethylsiloxane compound.

Examples of the vinyl polymerizable monomer B used together with the monomer A to obtain the copolymer AB include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and methacrylic acid. Methacrylic acid esters 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, diethyl maleate, fulleric esters such as dimethyl fumarate and diethyl fumarate, styrene, vinyltoluene, α -Methylstyrene, vinyl chloride, vinyl acetate, butadiene, acrylamide, acrylonitrino, methacrylic acid, acrylic acid, maleic acid, 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 weight of the polymer than monomer KA alone. It is also a convenient component for obtaining coalescence. The amount of monomer B used is set within an appropriate range, taking into consideration the above-mentioned performance and the antifouling effect based on monomer A. Generally, the proportion of monomer B in the total amount of monomer A is 90% by weight or less,
In particular, it is preferably 70% by weight or less. That is, if the proportion of monomer A constituting the copolymer AB is at least 10% by weight, in particular at least 30% by weight, then this monomer A
Since the antifouling effect based on the above can be sufficiently exhibited, the amount of monomer B to be 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. Examples of the vinyl polymerization initiator include azo compounds such as azobisisobutyronitrile and triphenylmethylazobenzene, benzoyl peroxide, diter
Peroxides such as L-butyl peroxide can be used.

The weight average molecular charge of Polymer A and Copolymer AB obtained by the above method is generally 1,000 to 150.00.
It is desirable that it be in the range of 0. If the molecular weight is too low, it will be difficult to form a film that can withstand use, and if the molecular weight is too high, the viscosity will be high when used as a coating varnish, and the resin solid content will be low, so only a thin film can be obtained with one application. First, there is the problem that several coats of paint are required to obtain a dry coating thickness greater than that of a window.

In the present invention, the surface lubricant used in combination with the above-mentioned polymer A and/or copolymer AB substantially maintains the low surface tension of the coating formed from polymer A and/or copolymer AB. Anything that can be used is fine. Here, "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 sustainability of the present invention is maintained. This means that the above-mentioned increase to some extent is acceptable as long as the improvement effect can still be maintained.

For example, the sliding angle of the coating surface measured by the method described below is 1
If the increase is as small as 100% or less, it can be used satisfactorily 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, "substantially maintaining a low surface tension" means that the surface lubricant of the present invention does not have such a smooth surface that its use considerably 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 JISK 2
Petroleum waxes defined in 235, fats and oils with a melting point of -5 to 60°C, waxes with a melting point of 30 to 95°C,
Liquid paraffin specified in JIS K 2231,
55 at 25°C. Examples include silicone oil having a kinematic viscosity of OOO Senna Stokes or less, aliphatic monocarboxylic acids having 8 or more carbon atoms or esters thereof, and glycerides having at least one ester bond formed from aliphatic monocarboxylic acids having 8 or more carbon atoms.

Examples of petroleum waxes specified in JIS K 2235 include paraffin wax, microcrystalline wax, and petrolatum.

As paraffin wax, JIS K 2235 120P% 12SP, 130P, 135P, 140P
Examples include products equivalent to 1145P, 150P, and 1'55P. Also, as a microcrystalline wax, J
IS K 2235 150M1.160M.

Examples include products equivalent to 170M, 180M, and 190M. Also, as petrolatum, JISK2235 1
Items corresponding to No., No. 2, No. 3, and No. 4 can be opened.

Examples of fats and oils having a melting point of -5 to 60°C include beef tallow, pig intestine, tallow, mutton tallow, cod liver oil, coconut oil, palm oil, wood wax,
Examples include kapok oil, cacao butter, China butter, and iritzpe butter. Note that oils and fats with a melting point of less than 15° C. have the drawback of reducing the adhesion of the underwater antifouling agent coating and further reducing the antifouling performance. In addition, since oils and fats with melting points exceeding 60°C are brittle, they make the resulting underwater antifouling agent coating brittle.
It has the disadvantage that it cannot keep up with slight shocks and may cause peeling.

Waxes having a melting point of 30 to 95°C include spermaceti;
Examples include mitsuro, carbaunaro, montanro, and mushiroro. Note that waxes with a melting point of less than 30°C have the disadvantage of poor adhesion and antifouling performance of the underwater antifouling agent coating, and waxes with a melting point of more than 95°C become brittle, so the resulting underwater antifouling It has the disadvantage that the agent coating film is fragile and cannot withstand slight shocks, causing peeling.

Liquid paraffin specified by JISK223F is l5OVGIO1I 5OVG 15, l5OVG3
2, 15OVG68, tsovc, and too equivalent products.

Examples of silicone oils having a kinematic viscosity of 55,000 centistokes or less at 25°C include, for example, KF96L-0,65, manufactured by Shin-Etsu Chemical Co., Ltd.;
KF96L-2,,01KF96-30,KF96)I
-, 50,000, KF96'5, KF50, KF54
, KF69, etc. This silicone oil is most commonly dimethyl silicone oil, but other types such as methylphenyl silicone oil may also be used. In addition, the kinematic viscosity at 25°C is 55.0
Silicone oils exceeding 0.00 centistokes have low fluidity and are inconvenient in the production of underwater antifouling agents, and also have the drawback of poor drying properties of coatings.

Examples of aliphatic monocarboxylic acids having 8 or more carbon atoms 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, and gadolein. Examples include whale oil acid, oil acid, and juniperic acid. In addition, esters of these carboxylic acids include stearyl stearate, butyl laurate, octyl palmitate, butyl stearate, isopropyl stearate, cetyl palmitate, ceryl cerotate,
Examples include myricyl palmitate and merisyl merisate. When the number of carbon atoms in the carboxylic acid is less than 8, both this acid and its ester have the disadvantage of lowering the antifouling performance of the underwater antifouling coating.

Examples of the glyceride having at least one ester bond consisting of an aliphatic monocarboxylic acid having 8 or more carbon atoms include tristearin, tripalmitin, triolein, myristodilaurin, caprylolauromyristin, and stearopalmitolein. It will be done. Incidentally, this glyceride includes mono-, di-, and triglycerides, and in short, it may be one in which an aliphatic monocarboxylic acid having the above carbon number is ester-bonded to at least one of the three hydroxyl groups of glycerin. Glycerides in which only aliphatic monocarboxylic acids having less than 8 carbon atoms are ester-bonded have the disadvantage of lowering the antifouling performance of underwater antifouling coatings.

In the present invention, the amount of the above-mentioned specific surface lubricant to be used is determined by taking into consideration the properties such as drying properties and adhesion properties based on the above-mentioned polymer A and/or copolymer AB, as well as the antifouling performance. , is set to an appropriate range. Generally, polymer A
and/or the proportion of the surface lubricant in the total amount of the copolymer AB and the surface lubricant is 1 to 70% by weight, especially 5 to 70% by weight.
Preferably, it is 50% by weight.

As is clear from the above description, the underwater antifouling coating of the present invention is usually prepared as a solution in which polymer A and/or copolymer AB and the above-mentioned specific surface lubricant are dissolved in an organic solvent. put to use. For this reason, it is particularly desirable to employ a solution polymerization method or a bulk polymerization method as the polymerization method for obtaining the polymer A and/or the copolymer AB. 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 to be used 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, and isoprohylalkonohbutyl alcohol. Alcohol solvents, dioxane, ether solvents such as diethyl ether, methyl ethyl ketone,
Examples include ketone solvents such as methyl isobutyl ketone alone or a mixture thereof.

The amount of organic solvent used is usually 5 to 80% by weight, especially 30 to 80% by weight, depending on the concentration of polymer A and/or copolymer AB during melting.
It is desirable that the content be in the range of 70% by weight. The viscosity of the solution at this time is generally 1 to 1, which facilitates the formation of a film.
It is preferable that the temperature be within the range of 0 voices/25°C.

The underwater antifouling coating of the present invention thus constructed may contain colorants such as pigments and dyes such as titanium dioxide, which is non-toxic and does not dissolve in seawater, if necessary. .

In addition, regular anti-sagging agents, anti-color separation agents, anti-settling agents,
It is okay to add antifoaming agents, etc.

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 mi agent as a solution to the surface of the object by an appropriate means, Simply dry at room temperature or under heat to volatilize and remove the solvent. As a result, an antifouling film with low surface tension and good slip properties is uniformly formed.

As described above, the underwater antifouling coating of the present invention solves the curability, which is the first problem with conventionally known underwater antifouling coatings, by eliminating the need for a chemical curing reaction and only by evaporating the solvent. The second problem, overcoatability, is solved by obtaining a tough coating, and since this coating is a solvent-volatilized drying type, the surface is re-dissolved by the solvent of the coating that is applied after the coating is formed. This problem is solved by improving interlayer adhesion.

Furthermore, the third problem, pot life, and the fourth problem, storage stability, are not limited by the pot life and are stable because this coating is one-component and non-reactive. resolved as a good thing.

More surprisingly, the surface tension of the dry film of the underwater antifouling coating of the present invention is shown in FIG. 1 (5), which will be described later.

When examining the slip angle by measuring the sliding angle by dripping seawater using the device shown in (2) above, it was found that the dry coatings of conventional underwater antifouling coatings using silicone rubber alone or in combination with silicone oil, liquid paraffin, petrolatum, etc. was in the range of 13 to 15 degrees on average, whereas the underwater antifouling coating according to the present invention had an average temperature in the range of 79 to 9.5 degrees, which was about 30% smaller at the minimum. This indicates that the dry film of the underwater antifouling coating of the present invention has a lower surface tension than that of the prior art and can be expected to have better efficacy against biofouling.

In addition, the underwater antifouling coating of the present invention may be because the effect of reducing the surface tension seen in the sliding angle as described above is sustained over a long period of time.
It has the advantage of having excellent sustainability of the bioadhesion prevention effect and further improving the antifouling performance compared to the above-mentioned previous invention, that is, the underwater antifouling coating material according to the present invention which does not use a specific surface lubricant.

[Effects of the Invention] As described above, in the present invention, by using the specific surface lubricant 2 in combination with the above-mentioned specific polymer, the present inventors, who did not use the above-mentioned surface lubricant, It is possible to provide an underwater antifouling coating agent that has even more improved antifouling performance than the previous invention.

Furthermore, like the underwater antifouling coating of the prior invention, this underwater antifouling coating is not of the type that undergoes a crosslinking reaction during film formation, and therefore is less susceptible to curing and drying due to humidity, temperature, etc. Therefore, no deterioration in antifouling properties due to peeling, blistering, etc. due to insufficient curing of the coating is observed. In addition, since a film is formed on the surface to be coated by only the volatilization of the solvent when applied, it dries quickly.
It is possible to shorten the time for recoating, and it is hoped that the coated object can be used in a short time. Furthermore, it is easy to handle because the coating work is not restricted by pot life, and it is possible to improve the interlayer adhesion with the top coat when applying the top coat.

In addition, since it has good storage stability against humidity and heat, it is not necessary to fill it with dry nitrogen gas during production, which helps reduce costs. Furthermore, even if there is leftover paint left over from painting, it can be stored in the usual way, such as simply plugging it, and it can be reused easily.

〔Example〕

Examples of the present invention will be described in more detail below in comparison with comparative examples. In addition, the polymer solutions (I)-(Vll) used in Examples 1 to 22 and Comparative Examples 1 to 5 below and the polymer solutions (Vllf)-(X
) were prepared according to Production Examples 1 to 10 below. In each production example, parts represent parts by weight, viscosity represents a Gardner viscosity measurement value at 25°C, and molecular weight represents a weight average molecular weight determined by GPC method.

Production Example 1 120 parts of butyl acetate was placed in a flask equipped with a stirrer,
Raise the temperature to 100°C and add methyl methacrylate 1 while stirring.
20 parts, polydimethylsiloxanepropyl methacrylate [as monomer A, in general formula (1), X is a methyl group, n
3, average degree of polymerization m is 10], and 1.2 parts of azobisisobutyronitrile were added dropwise over 2 hours, and after the addition was completed, the mixture was maintained at the same temperature for 30 minutes. Then, a mixed solution of 40 parts of butyl acetate and 0.6 parts of azobisisobutyronitrile was added dropwise over 15 minutes, and after the addition was completed, stirring was continued at the same temperature for 3 hours to complete the polymerization reaction. Finally, 80 parts of toluene was added and cooled to obtain a polymer solution.

The obtained polymer solution (I) was transparent, had a viscosity, and had a molecular weight of 89,000 for the U11 portion.

Production Example 2 180 parts of butyl acetate was placed in a flask equipped with a stirrer,
The temperature was raised to 115°C, and while stirring, 169.2 parts of methyl methacrylate, 10.8 parts of ethyl acrylate, and polydimethylsiloxanepropyl methacrylate [as monomer A, in the general formula fil, X is a methyl group, A mixed solution of 180 parts of polymer with n = 3 and average degree of polymerization m of 3 and 3.6 parts of azobisisobutyronitrile was added dropwise over 2 hours. Dripping completed 30
After 15 minutes, a mixed solution of 60 parts of butyl acetate and 1.8 parts of azobisinbutyronitrile was added dropwise over 15 minutes, and after the addition was completed, stirring was continued at the same temperature for 3 hours to complete the polymerization reaction.

Finally, 120 parts of xylene was added, cooled, and the polymer solution (
I got an ID.

The obtained polymer body size M (ID was transparent, viscosity was H11, and the molecular weight of the polymer was 54,000.

Production Example 3 In a heat-resistant and pressure-resistant container, 45 parts of methyl methacrylate, polydimethylsiloxane propyl methacrylate (as monomer A, in the general formula, X is a methyl group, n is 3, average degree of polymerization m
is 10] 55 parts, azobisisobutyronitrile 5
The reactor was completely sealed and heated to 130°C while shaking, and continued shaking at the same temperature for 2 hours to complete the polymerization reaction and obtain a solidified mass. Next, 100 parts of butyl acetate was added, and stirring was continued for 3 hours while maintaining the temperature at 130'C to dissolve the solidified material. After cooling, a polymer solution (a dish) was obtained.

The obtained polymer solution q0 was transparent, had a viscosity of A, and had a copolymer molecular weight of 9,000.

Production Example 4 50 parts of xylene was placed in a flask equipped with a stirrer, and 11
Raise the temperature to 0°C and add methyl methacrylate 85 while stirring.
15 parts of polydimethylsiloxane ethyl acrylate [monomer A, in the general formula (1), where X is a hydrogen atom, n is 2, and the average degree of polymerization m is 70], a mixture of 3 parts of benzoyl peroxide The solution was added dropwise over 3 hours. Dripping completed 3
After 0 minutes, add 20 parts of xylene and 1 part of benzoyl peroxide.
5 parts of the mixed solution was added dropwise over 20 minutes, and after the completion of the addition, stirring was continued for 5 hours at the same temperature to complete the polymerization reaction.

Finally, 30 parts of methyl isobutyl ketone was added and cooled.
A polymer solution (■) was obtained.

The resulting polymer solution was translucent, had a viscosity of P, and a copolymer molecular weight of 43,000.

Production Example 5 15 parts of xylene and 45 parts of ethylene glycol monoethyl ether were placed in a flask equipped with a stirrer, and heated to 120°C.
58 parts of methyl methacrylate, 2 parts of methacrylic acid, 5 parts of butyl acrylate, and 10 parts of styrene while stirring.
part, polydimethylsiloxane butyl methacrylate [as monomer A, in the general formula ill, X is a methyl group, n is 4,
A mixed solution of 25 parts of polymer having an average degree of polymerization m of 30 and 06 parts of azobisisobutyronitrile was added dropwise over 3 hours. 30 minutes after completion of the dropwise addition A mixed solution of 208 parts of Hc ethylene glycol mo/ethyl ether and 06 parts of azobisisobutyronitrile was added dropwise over 20 minutes. After the completion of the dropwise addition, stirring was continued at the same temperature for 4 hours to complete the polymerization reaction. Ta. Finally, 10 parts of butyl alcohol and 35 parts of methyl ethyl ketone were added and cooled to obtain a polymer solution (V).

The obtained polymer solution (V) was transparent, had a viscosity, and had a molecular weight of 27,000.

Production Example 6 In a flask with stirring a, 100f14 xylene, 100 parts of trimethylsilylpropyl methacrylate [as monomer A, in the general formula m, X is a methyl group, n is 3, and the average degree of polymerization m is O], benzoyl 15 parts of peroxide was charged, the temperature was raised to 140°C with stirring, and the temperature was raised to 140°C under reflux.
Continuing stirring for a certain period of time to complete the polymerization reaction, the polymer solution (
) was obtained.

The obtained polymer solution (material) was transparent, had a viscosity of A3, and a polymer molecular weight of 1,000.

Production Example 7 Place 30 parts of butyl acetate in a flask equipped with a stirrer, and add 8 parts of butyl acetate.
Raise the temperature to 0'C and add methyl methacrylate 72 while stirring.
parts, butyl methacrylate 12 parts, polydimethylsiloxanepropyl methacrylate [as monomer A, general formula (1
) A mixed solution of 36 parts of A, X is a methyl group, n is 3, and average degree of polymerization m is 20] and 0.6 part of benzoyl peroxide was added dropwise over 4 hours. Thirty minutes after the completion of the dropwise addition, a mixed solution of 20 parts of butyl acetate and 0.2 parts of benzoyl peroxide was added dropwise over 20 minutes, and after the completion of the dropwise addition, stirring was continued at the same temperature for 5 hours to complete the polymerization reaction. Finally, 1 toluene
30 parts were added and cooled to obtain a polymer solution.

The resulting polymer solution (VID) was transparent, had a viscosity of Z, and had a copolymer molecular weight of 150,000.

Production Example 8 Pour xylene 121 into a flask equipped with a stirrer,
Raise the temperature to 5°C and add methyl methacrylate 12 while stirring.
0 parts, polydimethylsiloxane methyl methacrylate [as monomer A, in the general formula +1+, X is a methyl group, n is 1
, with an average degree of polymerization m of 8] and 12 parts of azobisisobutyronitrile were added dropwise over 2 hours. After the dropwise addition was completed, the temperature was kept at the same temperature for 30 minutes, and then 40 parts of xylene was added.
A mixed solution of 06 parts of azobisisobutyronitrile was added dropwise over 15 minutes, and after the addition was completed, stirring was continued at the same temperature for 4 hours to complete the polymerization reaction. Finally, 80 parts of xylene was added and cooled to polymerize.

The resulting polymer solution (VIID) was cloudy, had a viscosity of W, and had a copolymer molecular weight of 72,000.

Production Example 9 180 parts of butyl acetate was placed in a flask equipped with a stirrer,
The temperature was raised to 110°C, and while stirring, 150 parts of methyl methacrylate, 30 parts of butyl methacrylate, polydimethylsiloxane pentyl methacrylate [as monomer A, in the general formula flll, X is a methyl group, n is 5, Average degree of polymerization m is 2
A mixed solution of 180 parts of azobisisobutyronitrile and 36 parts of azobisisobutyronitrile was added dropwise over 3 hours. 30 minutes after completion of dropping, 60 parts of butyl acetate, 1.81 parts of azobisisobutyronitrile
A mixed solution of was added dropwise over 15 minutes, and after the addition was completed, stirring was continued for 4 hours at the same temperature to complete the polymerization reaction.

Finally, 120 parts of xylene was added, cooled, and the polymer solution α
) was obtained.

The obtained polymer solution (IX) was transparent, had a viscosity of K, and a copolymer molecular weight of 65,000.

Production Example 10 In a heat-resistant and pressure-resistant container, 87 parts of methyl methacrylate, polydimethylsiloxane propyl methacrylate [as monomer A, in the general formula (1), X is a methyl group, n is 3, and the average degree of polymerization m is 75 13 parts] and 4 parts of benzoyl peroxide, sealed completely and raised the temperature to 120°C while shaking, continued shaking at the same temperature for 3 hours to complete the polymerization reaction, and turned into a cloudy viscous substance. Obtained. Then, butyl acetate 100
of the polymer solution (X
) was obtained.

The obtained polymer solution (X) was cloudy, had a viscosity of F, and had a copolymer molecular weight of 32,000.

Examples 1 to 22 Polymer solution (I) ~ (using VID, 2.00
Twenty-two types of underwater antifouling coatings were prepared by mixing and dispersing with a homomixer at 0 rpm. In addition, among the ingredients, paraffin wax 120P, 155P, microcrystalline wax 170M, petrolatum No. 1 and No. 4 are JIS
K 2235 petroleum wax, l5OVGIO
and 100 are JISK2231 liquid paraffin. Also, the product names are KF96L-10 and KF96H
-50,000 silicone oil is manufactured by Shin-Etsu Chemical Co., Ltd., and the product names are NAA-180 and NAA-8.
The aliphatic monocarboxylic acid No. 2 is manufactured by NOF ■, and the fatty acid ester whose trade name is Unistar M9676 is manufactured by NOF ■. In addition, Oil Blue 2N [Orient Chemical (product name made by Kiki)] is a dye, Disparon 6900-2.
0X [product name manufactured by Kusumoto Kasei ■] and Aeroseal 30
0 [trade name manufactured by Nippon Aeroseal ■] are all additives for sagging soil.

Comparative Examples 1 to 5 In the same manner as in Examples 1 to 22 using polymer solutions flll, (Illr), (V) and
An underwater antifouling coating having the composition shown in the table was prepared.

In addition, the product name in the ingredients is KF96H-60, Oo.
The silicone oil No. 0 is manufactured by Shin-Etsu Chemical Co., Ltd., and the caproic acid whose trade name is NAA-60 is manufactured by Nippon Oil & Fats Ichikawa. This silicone oil and caproic acid, together with camellia oil and methyl caproate, do not fall under the specific surface lubricant of the present invention.

Comparative Examples 6 to 8 Polymer solution (0 to 8 instead of 11 to (2))
Except for using (X), three kinds of underwater antifouling coatings having the compositions shown in Table 2 below were prepared in exactly the same manner as in Examples 1 to 22.

Comparative Examples 9-12 Polymer solution (11-(Vl[)Inia) Varini, KE
The formulation composition shown in Table 2 below was prepared in the same manner as in Examples 1 to 22, except that 45TS [trade name manufactured by Shin-Etsu Chemical Co., Ltd. (Kikusei; oligomeric cold-curing silicone rubber 50% by weight toluene solution] was used). Four types of underwater antifouling coatings were prepared.

Comparative Example 13 Underwater defense was prepared in the same manner as Examples 1 to 22, except that an organic tin copolymer solution was used instead of the polymer solutions (I) to (2). A soil coating 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 22 and Comparative Examples 1 to 13 described above was subjected to the following physical performance test, measurement of the sliding angle of the coating surface, and antifouling performance test to evaluate the performance.

<Physical Performance Test> The storage stability, drying properties, and adhesion of each coating material were measured by the following methods. The results were as shown in Table 3 below.

A) Storage stability of each coating material! 200 in a 250cc mayonnaise bottle
I put it in CC and sealed it with a lid. This was stored in a constant temperature and humidity 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 ○, 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 K 5400, 5.8.

That is, the measurement was performed on a glass plate coated with each coating material using a film applicator to a wet film thickness of 100 mm. 01 if the semi-cured 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 ×. 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 K 5400, 6.15. That is, each coating agent was applied to a polished steel plate (1
50x70x1) and kept at 20°C for 1 week.
The film, which had been dried in a thermostatic chamber with a humidity of 75%, was cut with a cutter knife in a 20 mm length in a cross pattern that reached the base layer. A 10 mm extrusion was performed from the back side of the test plate at the center using an Erichsen tester. At that time, on the surface of the coating,
Adhesion was determined by the length of peeling from the center of the crisscross cut. It was evaluated as ○ when the peeling rate was 0, △ when it was less than 5 days, and × when it was 5 days or more.

Table 3 As is clear from the results in Table 3 above, Examples 1 to 22 and Comparative Example 1 were good in terms of drying properties, adhesion, and storage stability. Comparative example 9 of silicone rubber type
-12 had poor drying properties, adhesion properties, and storage stability. Comparative Example 13 was slightly inferior only in storage stability. Moreover, Comparative Examples 2, 4, and 5 were slightly inferior only in drying properties, and Comparative Example 3 was inferior in drying properties and adhesion. In addition, in Comparative Examples 6 to 8, surface tackiness remained even after drying.

Measurement of sliding angle of coating surface> Figure 1 (5) for each test plate used in the drying test.
The slip angle of the film surface was measured in the following manner using the slip angle measuring device shown in (B). The above measuring machine has a transparent glass plate 1 and a fixing jig 2 on the glass plate I with one end on the A side.
The movable plate 4 is fixed by a support column 3 and has its other end B supported by a support column 3 so as to move upwardly along the support column 3.

First, as shown in FIG. 1 (2), a test plate 5 is placed on a transparent glass plate 1 with the coating side facing upward.
Place the test plate horizontally through the movable plate 4, and drop 2 cc of sterile filtered seawater using a syringe onto the test plate 5 at one end A of the movable plate 4, that is, at a distance T of 185 mm from the fixing jig 2. 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 slip angle of the coating surface.

The above measurements were performed in a constant temperature and humidity room at a temperature of 25° C. and a humidity of 7596°C, and each test plate was measured three times, and the average value was expressed. The results were as shown in Table 4 below.

Table 4 From the results in Table 4 above, for Examples 1 to 22, the surface slip angle was in the range of 7.9 to 9.5 degrees, and the average was 8.5. This corresponded to 8.5 degrees in Comparative Example 1, which did not. This means that the surface lubricant is a polymer solution (I
)-(Y[) shows that the resin coating obtained by the method retains good slipperiness.

In Comparative Examples 2 to 13, the surface slip angle was 10.5 to 25.
．． 0 degrees, which was a larger value than Examples 1-22.

Antifouling performance test> Each coating was applied to a painted plate (100X200X
A test plate was prepared by spray painting on both sides of 1 m) twice so that the dry film thickness was 120 μm on each side.

This test board was immersed in seawater for 36 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. The results were as shown in Table 5 below.

As is clear from the results in Table 5 above, Examples 1 to 22
The adhesion of organisms is 0% even after 36 months, but in Comparative Example 9 after 3 months, in Comparative Examples 6 to 8 and Comparative Examples 10 to 12 after 6 months, and in Comparative Examples 3 to 5
Adhesion of organisms was observed in Comparative Example 13 after 18 months, in Comparative Example 2 after 24 months, and in Comparative Example 1 after 30 months.

Comparative Example 1 achieved stain resistance for 24 months due to the small sliding angle of the coating film obtained by controlling the polymer solution, but in Examples 1 to 22, which were used in combination with a specific surface lubricant, it lasted an additional 36 months. This seems to indicate that the surface slip agent complements the sustainability of the surface sliding angle.

In addition, the poor antifouling property of Comparative Example 6 is due to the polymer solution used (
Since n in the general formula of monomer A in 2)) is 1, the bond in the ester forming part is weak, and the polydimethylsiloxane group is decoupled during the polymerization reaction, causing stickiness when formed into a film. In addition, this part was extracted from the membrane in seawater, and the combined effect of the surface lubricant used in combination was not exhibited, which is thought to be due to the fact that the antifouling durability could not be maintained.

In addition, in Comparative Example 7, since n in the general formula of monomer A in the polymer solution (ID) used was 5, the film formed from this softened and remained sticky even after drying. It is thought that even if a surface lubricant was used in combination, the increase in surface tension could not be prevented and the antifouling properties deteriorated.Furthermore, in Comparative Example 8, the concentration of monomer A in the polymer solution α) used was Because m in the general formula is as large as 75, the polymerization reactivity is extremely poor, unreacted monomer A separates from the membrane, and the uniformity of the membrane cannot be maintained.
It is thought that the antifouling durability could not be maintained even if a surface lubricant was used in combination.

In addition, in Comparative Examples 2 to 5, camellia oil, caproic acid,
It is thought that the antifouling properties deteriorated due to the presence of methyl caproate, etc., which left a sticky residue on the film and reduced the slipperiness of the surface.

[Brief explanation of the drawing]

FIGS. 1(5) and 1(B) are side views showing a method for measuring the surface slip angle of an antifouling film formed from an underwater antifouling coating agent.

Claims (11)

[Claims] (1) The following general formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) (However, in the formula, X is a hydrogen atom or a methyl group, and n is 2
an integer of ~4, m represents an average degree of polymerization of 0 to 70) and/or one or more of the above monomers A and these Substantially maintains the low surface tension of a copolymer consisting of one or more vinyl polymerizable monomers B that can be copolymerized with An underwater antifouling coating agent containing as an essential component one or more surface lubricating agents. (2) The underwater antifouling coating according to claim (1), wherein the surface lubricant is a petroleum wax specified in JIS K2235. (3) The underwater antifouling coating according to claim (2), wherein the petroleum wax is paraffin wax, microcrystalline wax, or petrolatum. (4) The underwater antifouling coating according to claim (1), wherein the surface lubricant is an oil or fat having a melting point of -5 to 60°C. (5) The underwater antifouling coating according to claim (1), wherein the surface lubricant is a wax having a melting point of 30 to 95°C. (6) The underwater antifouling coating according to claim (1), wherein the surface lubricant is liquid paraffin defined in JIS K2231. (7) The underwater antifouling coating according to claim (1), wherein the surface lubricant is a silicone oil having a kinematic viscosity of 55,000 centistokes or less at 25°C. (8) The underwater antifouling coating according to claim (7), wherein the silicone oil is dimethyl silicone oil. (9) The underwater antifouling coating according to claim 1, wherein the surface lubricant is an aliphatic monocarboxylic acid having 8 or more carbon atoms or an ester thereof. (10) The underwater antifouling coating according to claim (1), wherein the surface lubricant is a glyceride having at least one ester bond made of an aliphatic monocarboxylic acid having 8 or more carbon atoms. (11) The proportion of the surface lubricant in the total amount of the polymer and/or copolymer and the surface lubricant is 1 to 70% by weight.
An underwater antifouling coating according to any one of claims (1) to (10).