JPS63168476A - Underwater antifouling coating agent - Google Patents

Abstract

PURPOSE:To provide an underwater antifouling coating agent which is quick- drying, has a long pot life and excellent interlaminar adhesion and can keep an antifouling performance over a long period of time, consisting of a specified copolymer and an antifouling agent. CONSTITUTION:10-100wt.% monomer of the formula (wherein X is H or methyl; n is 2-4; m is 0-70 at an average degree of polymn.) is (co)polymerized with 90-0wt.% polymerizable vinyl monomer copolymerizable therewith (e.g., methyl methacrylate) in the presence of a vinyl polymn. initiator to obtain a (co)polymer having a weight-average MW of 1,000-150,000. 5-80wt.% compsn. obtd. by blending the (co)polymer with 0.1-65wt.% antifouling agent (e.g., triphenyltin hydroxide) and optionally 1-70wt.% external lubricant (e.g., paraffin wax) is diluted with an org. solvent (e.g., xylene) to obtain an underwater antifouling coating agent having a viscosity not higher than 25P at 25 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an underwater antifouling coating 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 antifouling paints are applied to the surfaces of objects immersed in seawater in order to prevent the attachment of these organisms. There are two types of antifouling coatings: 42 types as shown below.

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

For example, regarding paints using organic tin compounds as antifouling agents, Japanese Patent Publication No. 40-21426 and Publication No. 44 of
-9579 Publication, Japanese Patent Publication No. 13392/1972, Japanese Patent Publication No. 20491/1972, Japanese Patent Publication No. 11647/1977
It is disclosed in Japanese Patent Publication No. 52-48170.

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

For example, Japanese Patent Publication No. 53-35974 discloses a coating using vulcanized silicone rubber, and Japanese Patent Application Publication No. 51-96830 discloses a coating using vulcanized silicone rubber as a coating material. A mixture with 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 paint for preventing the adhesion of marine organisms, 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. It is shown.

[Problem to be solved by the invention 1 These conventionally known antifouling paints can exhibit performance depending on their type, so they are used depending on the purpose of use, but all of them have the following drawbacks. has,
Improvements in this are desired.

First of all, there are two more types of antifouling paint of type A above.One is that the resin that forms the paint film does not dissolve in water, but only the antifouling agent dissolves in seawater. This is a type of antifouling paint that prevents the adhesion of marine organisms. This type of antifouling coating has a good initial antifouling effect. However, after the antifouling agent on the surface of the paint film is eluted and lost, the antifouling agent in the deeper part of the paint film gradually elutes. Because it is slow, it has the disadvantage that the prevention effect becomes insufficient in the long term.

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

In addition, the antifouling paints for the mouth are all made to take advantage of the slipperiness of the silicone rubber coated surface to prevent aquatic organisms from adhering to the surface, and like the paint in A above, Although it has the advantage of not containing eluted components that may cause water pollution, the silicone rubber used to form the film has the following problems in that it undergoes three-dimensional crosslinking to form a film during use. .

First, there is the problem of curing properties after painting. For example, when an antifouling paint using an oligomeric room-temperature curing silicone rubber that hardens under the action of moisture in the air to form a film, as shown in Japanese Patent Publication No. 60-3433, is applied to the surface to be coated. The cross-linking agent that controls the curing and condensation reaction of silicone rubber is activated by moisture and temperature in the air, and as a result, 1) the surface of the coating film hardens quickly, which actually prevents the deep part of the coating from curing, resulting in insufficient curing; As a result, there is a great risk that the paint film will peel off from the surface to be coated and blistering will occur. Also,
Since moisture penetrates slowly, the time required for curing becomes longer. In addition, 11) When such an antifouling paint is used in a high temperature and high humidity location, only the hydrolysis of the crosslinking agent takes priority, and the crosslinking density does not increase, resulting in a decrease in the physical properties of the paint film. become. Furthermore, II) In dry areas, there is little moisture in the atmosphere, so hydrolysis of the crosslinking agent is difficult to occur and the curing of the film is extremely slow. To prevent this, catalysts such as tin compounds and platinum are sometimes used as curing accelerators.
In low-lying wetlands, their catalytic effects tend to be insufficient.

Second, there is the problem of overcoatability. Normally, the solvent in the top coat slightly soaks the surface of the undercoat, improving interlayer adhesion, but because the underlying silicone rubber cures through three-dimensional crosslinking, the solvent in the top coat does not soak the silicone rubber surface. Poor adhesion.

Thirdly, there is the issue of pot life. In actual painting work, painting may take a long time or be interrupted due to factors such as the size of the object to be painted, the complexity of the structure, and rainfall during painting. In such cases, antifouling paints with a short pot life are extremely inconvenient in painting operations.

Fourth, there is the issue of storage stability. Antifouling paints may be stored for a long time from the time they are manufactured until they are used, but those that harden due to moisture need to be filled with dry nitrogen gas during manufacture, and - when the lid of the variable magnification lens is opened, atmospheric air is released. There is a problem in that moisture gets inside and causes the surface of the paint to harden and thicken, making it difficult to reuse it.

Therefore, the present inventors conducted intensive studies to obtain an underwater antifouling coating that can avoid the various problems mentioned above and has excellent antifouling performance. We have succeeded in obtaining an underwater antifouling coating using a specific solvent-volatile polymer, and have already proposed it in Japanese Patent Application No. 60-298918.

Unlike the conventionally known silicone rubber-based materials, the above-mentioned specific polymer is essentially free from the aforementioned problems such as curability, overcoatability, pot life, and storage stability because it is a solvent-volatile type. Moreover, it has been found that the coating film formed from this polymer has improved antifouling performance because it exhibits surface slipperiness.

In addition, the present inventors have found that when a surface lubricant such as petroleum wax, silicone oil, or oil is added to the specific polymer proposed above, the antifouling performance is further improved. I learned of this and have already proposed it in Japanese Patent Application No. 126988/1983.

The present invention further improves the prior invention based on these prior inventions, that is, it solves the problems of the conventionally known antifouling paints as well as the prior invention, and
It is an object of the present invention to provide an industrially more useful underwater antifouling coating that provides even more improved antifouling performance than the previous invention.

[Means for solving problems]

As a result of intensive studies to achieve the above object, the present inventors have found that by using an antifouling agent together with the specific polymer according to the prior invention, and by using the above antifouling agent and a surface lubricating agent. The present invention was completed based on the knowledge that the antifouling performance can be further improved compared to the prior invention without losing the aforementioned advantages based on the polymer.

That is, the present invention is based on the following general formula;
An integer of ~4, m represents an average degree of polymerization of 0 to 70) (hereinafter referred to as polymer A).
), and/or a copolymer consisting of one or more of the above monomers A and one or more vinyl polymerizable monomers B that can be copolymerized with these monomers (hereinafter referred to as copolymerizable monomers). A first invention relating to an underwater antifouling coating agent containing a copolymer AB) and an antifouling agent as essential components; This invention consists of a second invention relating to an underwater waterproof T15 coating material.

Polymer A and copolymer A B used in the present invention
The single ijt compound A represented by the general formula (1) for obtaining the formula (1) has a polydimethylsiloxane group (m=1) in its molecule.
above) or an unsaturated carboxylic acid monoester having a trimethylsilyl group (m=0). In the formula fil, m=
The reason why it is set as o~70 is that if it is larger than m or 70,
This is because the polymerizability or copolymerizability of monomer A decreases, making it difficult to obtain polymer A or copolymer AB that can be formed into a uniform film.

Also, in the formula tll, n = 2 to 4 is n
If it is less than 2, the bonding strength of the ester-forming moiety of monomer A will be weakened, and the ester bond will be dissolved during the polymerization stage or when used as a 'fgl covering agent, resulting in a decrease in the antifouling performance and its sustainability. However, if n exceeds 4, the polymer will soften, which is not preferable.

Specific compound cores of such monomer A include trimethylsilylethyl (meth)acrylate, trimethylsilylpropyl (meth)acrylate, and trimethylsilylbutyl (meth)acrylate as those having a trimethylsilyl group. Those having a dimethylsiloxane group include polydimethylsiloxaneethyl (meth)acrylate, polydimethylsiloxanepropyl (meth)acrylate, and polydimethylsiloxanebutyl (meth)acrylate in which m is up to 70. 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 (meth)acrylic acid and allyl alcohol, and subjecting it to an addition reaction with a trimethylsilyl compound or a polydimethylsiloxane compound.

In addition, examples of the vinyl polymerizable small bottle B used together with the above-mentioned monomer A to obtain the copolymer AB include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic Iv2-ethylhexyl, methacrylic acid 24 Methacrylic esters such as droxyethyl, ethyl acrylate, butinope acrylate, acrylic esters such as 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, maleic esters such as dimethyl maleate, diethyl maleate, dimethyl fumarate , fumaric acid esters such as diethyl fumarate, styrene, vinyltoluene, α-methylstyrene, vinyl chloride, vinyl acetate, butadiene, acrylamide, acrylonitrile, methacrylic acid, acrylic acid, maleic acid, and the like.

The amount of n1mer B to be used is set within an appropriate range in consideration of the antifouling effect based on monomer A. Generally, the proportion of monomer B in the total amount of monomer A is preferably 90% by weight or less, particularly 70% by weight or less. That is, if the proportion of the monomer A constituting the copolymer AB is at least 10% by weight, especially at least 30% by weight,
Since the antifouling effect based on monomer A 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 thereof in the presence of a vinyl polymerization initiator.
It can be obtained from polymerization by 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, and peroxides such as benzoyl peroxide and di[-butyl peroxide].

The weight average molecular weight of polymer A and copolymer AB obtained by the above method is generally 1,000 to 150.000.
It is desirable that it be within the range of . If the molecular weight is too low, it will be difficult to form a film that can withstand use, and if it 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 formed with one application. However, the problem arises that several coats of paint are required to obtain a dry film thickness above a certain level.

The antifouling agents used in the present invention include a wide range of conventionally known antifouling agents. Broadly divided, organic compounds containing metals,
There are organic and inorganic compounds that do not contain metals.

Examples of organic compounds containing metals include organotin compounds, organocopper compounds, organic nickel compounds, and organozinc compounds, and examples thereof include maneb, manseb, propineb, and the like. Organic compounds that do not contain gold 1.4 include 1,4-naphthoquinone, N-trihalomethylthiophthalimide, dithiocarbamine H1N-arylmaleimide, 3-substituted amine-3-tinsyridine-2,4
- Diones, dithiocyano compounds, etc. moreover,
Examples of inorganic compounds include cuprous oxide, copper powder, copper thiocyanate, copper carbonate, copper chloride, copper compounds such as sulfur, zinc sulfate, zinc oxide, nickel sulfate, and the like.

Among the organic compounds containing the above metals, organotin compounds include triphenyltin halides such as triphenyltin chloride and triphenyltin fluoride, and tricyclohexyltin halides such as tricyclohexyltin chloride and tricyclohexyltin fluoride. , tributyltin chloride, tributyltin fluoride and other tributyl halides, triphenyltin hydroxide, tricyclohexyltin hydroxide, bis(triphenyltin 8
)-α・α′-dibromosuccinate, bis(tricyclohexyltin)-α・α′-dibromosuccinate, bis(tributyltin)-α・α′-dibromosuccinate, bis-(triphenyltin) oxide , bis-(tricyclohexyltin) oxide, bis-(tributyltin) oxide, triphenyltin acetate, tricyclohexyltin acetate, tributyltin acetate, triphenyltin monochloroacetate, triphenyltin versatate, triphenyltin dimethyldithio These include carbamates and triphenyltin nicotinic acid esters.

In addition, organic copper compounds include oxine copper, nonylphenol sulfone gradation, kappa bis(3-chloro-1
・4-naphthoquinone-2-oleate), Kappabis(1,4-naphthoquinone-2-oleate), Kappabis(ethylenediamine)-bis(dodecylbenzenesulfonate), Copper acetate, Copper naphthenate, Bis(pentachlorophenolic acid) ) Copper, etc. Furthermore, examples of organic nickel compounds include nickel acetate and nickel dimethyldithiocarbamate, and examples of organic zinc compounds include zinc acetate, zinc carbazate, and zinc dimethyldithiocarbamate.

Furthermore, one of the above metal-free organic compounds
・4-naphthoquinone includes 2-ami/-3-chloro-1,4-naphthoquinone, 2,3-cycloroto-4-naphthoquinone, 5,10-dihydro-5,10-dioxanaphtho [2,3-bl-1・4-dithiin-2,3-dicarbonitrile, etc., N-trihalomethylthiophthalimide such as N-trichloromethylthiophthalimide, N-fluorodichloromethylthiophthalimide, etc., and dithiocarbamic acid such as bis(dimethylthiocarbamoyl) disulfide. , ammonium N-methyldithiocarbamate, ammonium ethylenebis(dithiocarbamate), milneb, and the like.

In addition, as N-arylmaleimide, N-(2.4
・64 Licro-phenyl)maleimide, N-4-1-'
J lumaleimide, N-3-chlorophenylmaleimide)'
, N-(4-n-butylphenyl)maleimide, N-(
anilinophenyl)maleimide, N-(2,3-xylyl)maleimide, etc., and 3-substituted amino 3-thiazolidine-2,4-dione such as 3-benzylidene amide 7-1, 3-thiazolidine-2,4 -dione, 3-(
4-methylbenzylideneami/)-1,3-thiazolidine-2,4-dione, 3-(2-hydroxybenzylideneami/)-1,3-thiazolidine-2,4-dione,
3-(4-dimethylaminobenzylideneamino)-1.
3-Thiazoline-2,4-dione, 3-(2,4-dichlorobenzylideneamino)-1,3-thiazolidine-2
・4-dione etc. are dithiocya/based compounds,
Examples include dithiocyanomethane, dithiocyanoethane, 2,5-dithiocya/thiophene, and the like.

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

The surface lubricant used in the present invention may be vaguely referred to as surface lubricant. There are a number of substances that are known to impart P1 properties, and representative examples include ■JISK2
Petroleum wax specified in 235, ■JIS K 22
Liquid paraffin defined by 31, silicone oil having a kinematic viscosity of 55,000 centistokes or less at 025°C, ■ carbon number 8 having a melting point of -5°C or more
The above fatty acids and their esters, 0 carbon atoms 12-20
Examples include organic amines having an alkyl group or an alkenyl group.

Specific examples of the above (■) include paraffin wax, microcrystalline wax, petrolatum, etc.
As a specific example, l5OVGIO1ISOVG15,
Specific examples of the above (■) include products equivalent to l5OVG32, l5OVG68, and l5OVG100, such as the product names KF96L-0,85 and KF manufactured by Shin-Etsu Chemical Co., Ltd.
96L-2,0, KF96-30, KF96H-50,
000, KF965, KF50, KF54, KF69, etc., respectively.

The silicone oil mentioned in (2) above is most commonly dimethyl silicone oil, but other types such as methylphenyl silicone oil may also be used.

Further, as specific examples of the above (■), for example, caprylic acid,
Examples include capric acid, lauric acid, myristic acid, valmitic acid, stearic acid, cerotic acid, montanic acid, mellisic acid, lauroleic acid, oleic acid, vaccenic acid, gadoleic acid, whale oil acid, whale 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, seryl cerotate, myricyl palmitate, melysylmerisate, spermaceti, spermaceti Wax, carnauba wax, montan wax, wax wax, tristearin, tolpalmitin, triolein, myristodilaurin, caprylolauromyristin, stearopalmitolein, monostearin, monopalmitin, distearin, civalmitin, beef tallow, pork fat , horse tallow, mutton tallow, cod liver oil,
Examples include palm oil, palm oil, wood wax, kapok oil, cacao butter, China butter, and iritsupe butter.

Furthermore, as specific examples of the above (1), for example, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, beef tallow alkylamine, cocoalkylamine, soybean oil alkylamine, didodecylamine, di-tallow hydrogenated alkylamine. , dodecyldimethylamine, cocoalkyldimethylamine, tetradecyldimethylamine, hexamethyldimethylamine, octadecyldimethylamine, and the like.

In the present invention, one or more of the above-mentioned surface lubricants are selected and used, and the amount used is determined by the amount of the above-mentioned polymer A and/or copolymer AB and the antifouling agent. Drying properties based on

It is set within an appropriate range, taking into consideration performance such as adhesion and antifouling performance. Generally, the proportion of the surface lubricant in the total amount of the polymer A and/or copolymer AB and the surface lubricant is 1 to 70% by weight, particularly 5 to 50% by weight.
It is preferable that

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. 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.

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. Alcohol solvents such as Nato, ether solvents such as dioxane and diethyl ether, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be used alone or as a mixed solvent.

The amount of organic solvent used is such that the concentration of polymer A and/or copolymer AB in the solution is usually 5 to 80% by weight, particularly 30 to 80% by weight.
It is desirable that the content be in the range of 70% by weight. The viscosity of the solution at this time is generally preferably in the range of 25 poise or less/25°C, which facilitates the coating ratio.

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

In order to form an anti-teta film on the surface of an object to be immersed in seawater using the underwater anti-Tll agent of the present invention, the above-mentioned wave agent, which is a dispersion containing a solvent, is applied to the surface of the object by appropriate means. After coating, all you need to do is dry it for 6 minutes or under heat to volatilize and remove the solvent.

As a result, an antifouling film with good surface slipperiness and a synergistic effect with the antifouling agent is uniformly formed.

[Effect]

The above-mentioned polymer A and/or copolymer AB used in the present invention both have polydimethylsiloxane groups and/or trimethylsilyl groups derived from monomer A, so the coating film formed has a strong surface. It imparts slipperiness. Therefore, the coating film itself has the function of physically preventing marine life and proboscis attachment.

In addition, vinyl polymerizable monomer B is used in order to impart appropriate surface slipperiness to the coating film of copolymer AB, and to obtain a polymer with a higher molecular weight than monomer A alone. It acts as a convenient regulatory component.

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

As described above, when using the polymer A and/or copolymer AB in combination with an antifouling agent in the first invention, the polymer A and/or copolymer AB prevents excessive elution and insufficient elution of the antifouling agent. It has the ability to adjust appropriately, and it is thought that the antifouling performance of the paint film is maintained stably over a long period of time.

Furthermore, by using the surface lubricant used in the second invention in combination with the above-mentioned polymer A and/or copolymer AB and an antifouling agent, the antifouling agent can be used in combination with the above-mentioned polymer A and/or copolymer AB and an antifouling agent. This is important in achieving further long-term sustainability. According to the inventors' speculation regarding the above facts, the surface smoothening effect based on the use of the surface lubricant, the coating film made of the polymer A and/or copolymer AB and the antifouling agent, This is thought to be due to the fact that the surface slipperiness of the coating film is reinforced and maintained over a long period of time due to the deterioration prevention effect.

〔Effect of the invention〕

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

During the production of paint, there is no risk of deterioration due to antifouling agents and it is stable. Furthermore, 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 paint film or by humidity or temperature during drying, so blistering and peeling are less likely to occur.

When the same type of paint or another paint is applied over the paint film, it has excellent adhesion to living rooms.

Since the paint film does not wear out even when it comes into contact with seawater, it can maintain its antifouling performance over a long period of time. Also,
Compared to the surface slipperiness of conventional cross-linked silicone-based antifouling paints, this value is clearly lower, confirming the excellent antifouling effect.

[Example 1] The present invention will be specifically explained below with reference to polymer production examples, examples, and comparative examples. In the examples, parts are parts by weight, viscosity is a foam viscosity measurement value at 25°C, and molecular weight is a weight average molecular weight measured by GPC method.

Production Examples 1, 2, 4.5 and 7 iQ Add solvent a according to the formulation in Table 1 to a flask with 4 holes, raise the temperature to the reaction temperature, and add monomer A1 monomer B and A mixed solution of polymerization catalyst a was dropped into the flask over a period of 2 to 3 hours, and after the dropwise addition was completed, the mixture was maintained at the same temperature for 30 minutes. Then, add 2 mixtures of solvent and polymerization catalyst.
The mixture was added dropwise over 0 minutes, and stirring was continued for 3 to 5 hours at the same temperature to complete the polymerization reaction. Finally, a diluting solvent was added to dilute to obtain each polymer (He I, II, IV, V and vII. In Table 1, the structural formula of 'JAM substance A is X in the general formula + 1). The structure of and n+ I
Expressed as a numerical value of n.

Production Example 3 In a heat-resistant and pressure-resistant container, monomer A, monomer B, and polymerization catalyst a were charged according to the formulation shown in Table 1, the container was completely sealed, and the temperature was raised to the reaction temperature while shaking. Further shaking was continued at the same temperature for 2 hours to complete the reaction. Next, a diluting solvent was added and dissolved by shaking for 3 hours to obtain a polymer solution Ill.

Production Example 6 In a flask equipped with a stirrer, add solvent a, according to the formulation in Table 1.
Monomer A and polymerization catalyst a were charged, the temperature was raised to the reaction temperature while stirring, and stirring was continued at the same temperature for 3 hours to obtain polymer solution 1.

Examples 1 to 56 Using polymer solutions (I) to (Vll),
According to the formulation shown in Table 4 (values in the table are weight%), 2
．． Mix and disperse with a homo mixer of 00 Orpm to 56
An underwater antifouling coating for seeds was prepared. In addition, among the ingredients, paraffin wax 120P and petrolatum No. 1 are J
ISK2235 petroleum wax, l5OVGIO
is JISK2231 liquid paraffin. The silicone oil whose trade name is KF-69 is manufactured by Shin-Etsu Chemical Co., Ltd.

In addition, Oil Blue 2N [trade name of Orient Chemical ["J] is a dye, and Disparon 6900-20X [trade name of Kusumoto Kasei ■] and Aeroseal 300 [trade name of Nippon Aeroseal ■] are anti-sagging products. It is an additive for

Comparative Examples 1 to 4 In the same manner as in Examples 1 to 56, using polymer solutions (I) to ([), underwater protective coatings having the compositions shown in Table 5 below were prepared.

Comparative Examples 5 to 8 Instead of polymer solutions (I) to (■1), KE45TS
[Product name manufactured by Shin-Etsu Chemical Co., Ltd. (a); Oligomeric room-temperature curing silicone rubber 50 M% toluene solution] was used in the same manner as in Examples 1 to 56, from the formulation shown in Table 5 below. Four types of underwater anti-TL reversible agents were prepared.

Example 9 to 13 Same as Examples 1 to 56 except that organic tin copolymer solution was used instead of polymer solutions (I) to (Vll).
An underwater antifouling coating having a composition shown in Table 5 below 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 56 and Comparative Examples 1 to 13 was subjected to the following physical performance test, measurement of the surface slip angle of the coating, and antifouling performance test to evaluate the performance. The results were as shown in Table 6.7 below.

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

A) Storage stability 200 pieces of each coating agent were placed in a mayonnaise bottle with a capacity of 250 cc, and the bottle was sealed with a lid. Temperature 70°C 1 Humidity 7
Storage stability was determined by the degree of viscosity increase of each sample after 2 weeks of storage in a 5% constant temperature and humidity chamber.

When the increase rate was less than 10% from the initial viscosity, it was evaluated as 0, 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 Drying 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 agent to a wet film thickness of 100 μm using a film applicator. 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 ×. Note that each test plate was dried in a constant temperature and humidity room at a temperature of 20° C. and a humidity of 75%.

C) Adhesion The test was carried out according to the method of the substrate test of JIS K 5400.6.15. That is, each coating agent was applied to a polished steel plate (1
50 x 70 x 1 fl) for one week at a temperature of 20°C.
The coating was dried in a constant temperature room with a humidity of 75%, and a cut was made in a cross pattern reaching the base layer with a length of 20 tx using a cutter knife. Ten eggs were extruded from the back of the test plate at the center using an Erichsen tester. At that time, adhesion was determined by the length of peeling from the center of the cross-cut uneven portion of the coating surface. ○ when peeling is 0, △ when less than 5f1, 5f
When it was 1 or more, it was evaluated as ×.

<Measurement of surface sliding angle of coating> For each test plate used in the drying test, see Figure 1 (5).
The surface slip angle of the coating was measured in the following manner using the slip angle measuring device shown in (13). The above-mentioned measuring device consists of a transparent glass plate 1, one end A side is fixed to the glass plate 1 by a fixing jig 2, the other end B side is supported by a column 3, and is moved upward along this column 3. It is composed of a movable plate 4 provided in a hanging manner.

First, as shown in the first position, the test plate 5 is placed horizontally on the transparent glass plate 1 with the film forming side facing upward, and the test plate 5 is movable on the test plate 5. A water droplet 6 is formed by dropping 0.2 me of sterilized filtered seawater using a syringe at one end A of the plate 4, that is, at a position where the distance γ from the fixing jig 2 is 185 degrees. After that, as shown in Figure 1 CB),
The other end B side of the movable plate 4 is moved upward along the support column 3 at a speed of 1 fl/sec to tilt the test plate 5. The inclination angle α at which the water droplets on the test plate 5 begin to slide was measured, and this was taken as the surface slip angle of the coating.

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

<Antifouling performance test> Each coating was applied to a sandblasted steel plate coated with tarvinyl anticorrosive paint (100 x 200
A test plate was prepared by spray painting on both sides of the sample (X 1 rm) twice so that the dry film thickness was 120 tones on one side.

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

As is clear from the results in Tables 6 and 7 above, Examples 1-
Sample No. 56 had good storage stability, drying properties, and adhesion. In addition, the surface sliding angle is 7 to 11
range of degrees. Example 1 without using a surface lubricant
-40 is also in the range of 11 degrees or less, which indicates that the coating itself of the specific polymer of the present invention has strong surface slipping properties. Further, in the antifouling performance test, no biological attachment was observed at all until at least 24 months had passed.

On the other hand, Comparative Examples 1 to 4 were paints that did not contain the antifouling agent, which is an essential component of the present invention, and adhesion of living organisms was observed after 18 to 24 months. Moreover, Comparative Examples 5 to 8 are silicone rubber-based paints and have shortcomings in storage stability, drying properties, and adhesion. The antifouling properties are also unsatisfactory, as evidenced by the high value of the surface sliding angle. Furthermore, Comparative Examples 9 to 1
3 is an organic tin copolymer-based antifouling paint. Slightly inferior in storage stability and stain resistance. The coating surface was more hydrophilic and the surface slip angle showed a high value.

[Brief explanation of the drawing]

FIGS. 1(4) 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 (2)

[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 An underwater antifouling coating agent containing as essential components a copolymer consisting of one or more types of vinyl polymerizable monomer B that can be copolymerized with B, and an antifouling agent. (2) 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 An underwater antifouling coating agent containing as essential components a copolymer consisting of one or more vinyl polymerizable monomers B that can be copolymerized with B, an antifouling agent, and a surface lubricant.