JPH011773A - Underwater antifouling coating - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

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

[Conventional technology]

Ship bottoms, buoys, fishing nets (aquaculture nets for yellowtail and scallops, fixed salmon nets, etc.) immersed in seawater? Various problems occur on the surfaces of underwater objects, such as roadside turbidity prevention sheets and various intake and drainage pipes for cooling, due to the adhesion of Fujibo, Serpura, mussels, algae, and the like. It is well known that an anti-ice coating is applied to the surface of objects immersed in seawater in order to prevent the formation of leta by these organisms.

As an underwater antifouling coating, it has an antifouling effect on living things and has an R? Many are used that use anti-Iη agents such as 8-decomposable organotin copolymers and cuprous oxide. However, in such cases, harmful substances may be eluted into the seawater, contributing to seawater pollution, and the negative impact on fish and shellfish may not be ignored.

So, without using such an antifouling agent? 'n5 There has been a demand for underwater antifouling coatings that do not dissolve in water.

Such non-toxic underwater antifouling coatings use silicone rubber that is vulcanized by the action of a catalyst or moisture, or vulcanized by the action of both a catalyst and moisture to three-dimensionally crosslink and form a film. Things can be given.

For example, Japanese Patent Publication No. 53-35974 discloses a coating using vulcanized silicone rubber, and Japanese Patent Publication No. 51-96830 discloses an oligomeric silicone rubber having a hydroxyl terminal group. A product using a 64 compound of rubber and silicone oil is shown. Further, JP-A-53-79980 discloses a mixture of vulcanized silicone rubber and a fluid organic compound that does not contain metal or silicone. Furthermore, Japanese Patent Publication No. 60-3433 discloses oligomeric room-temperature curing silicone rubbers (for example, Shin-Etsu Chemical Co., Ltd.'s trade names KE45TS, KE44 RTV, etc.);
Antifouling coatings for marine organisms are shown mixed with liquid paraffin or petrolatum.

[Problem that the invention seeks to solve]

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

The first is curing properties after painting. In other words, curing of silicone rubber occurs through a condensation reaction initiated by hydrolysis of the crosslinking agent by moisture in the atmosphere or by the action of a catalyst that is susceptible to temperature effects on the crosslinking agent. However, the curing speed and curing strength vary depending on the temperature, making it difficult to obtain uniformity of the film.For example, as shown in Japanese Patent Publication No. 60-3433, When an underwater antifouling coating agent made of oligomeric room-temperature-curing silicone rubber that forms a film is applied to the surface to be coated, curing occurs from the surface of the coating that is in contact with the humid atmosphere and gradually progresses to the inside. (This means that by first hardening the surface, subsequent moisture permeation is suppressed, and the lack of internal moisture makes it difficult for deep hardening to occur, or the crosslinking density becomes low, resulting in uniformity of the film. This will cause the film as a whole to peel off from the object to be coated, and will cause poor adhesion such as blistering.Also, the time required for curing will be longer as moisture penetrates into the interior more slowly. .

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. Become. Furthermore, in dry areas, since there is little moisture in the atmosphere, hydrolysis of the crosslinking agent is difficult to occur and the curing of the film is extremely slow. Therefore, a problem arises in that painted objects cannot be moved in a short period of time. Catalysts such as tin compounds and platinum are sometimes used as curing accelerators to prevent this, but their catalytic action decreases in low-temperature regions, making it difficult for the condensation reaction caused by the crosslinking agent to occur, making the curing of the film extremely slow. .

Second, there is the problem of overcoatability. Normally, the solvent of the topcoat coating material slightly invades the undercoat surface and heats up at the interface, improving interlayer adhesion, but overcoatability to silicone rubber is affected by three-dimensional crosslinking of the base silicone rubber, which hardens. Therefore, the reapplied top coat does not attack the silicone rubber surface, resulting in poor adhesion.

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

Fourth, there is the issue of storage stability. Anti-ice 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 will have short storage stability unless dry nitrogen gas is sealed during manufacture. .

Another problem was that when the lid of the magnification variable lens was opened, moisture from the atmosphere entered, hardening and thickening the surface of the coating material, making it difficult to reuse it.

[Means for solving problems]

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

That is, the present invention is based on the following general formula; is 2
an integer of ~5, m is a real number of 0 or more, R8-R2 are all groups selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxydyl group, or a substituted phenoxydyl group, and m of Ra, Rs and R
(1-R3 may be the same group or different groups, but at least one of them is a group other than a methyl group) , and/or an underwater antifouling agent containing as an essential component a copolymer consisting of one or more of the above monomers and one or more of vinyl polymerizable monomers B that can be copolymerized with these monomers. A first invention relating to a coating agent, together with the above polymer and/or copolymer, and one or more surface lubricants capable of substantially maintaining the low surface tension of the coating formed therefrom. and a second invention relating to an underwater antifouling coating agent containing as an essential component.

[Structure of the invention/#Z]

The underwater antifouling coating of the present invention contains as an essential component one or more polymers of monomer A represented by the above general formula, that is, a homopolymer or a copolymer (hereinafter referred to as these). or a copolymer of one or more of the above monomers and one or more vinyl polymerizable monomers B copolymerizable with these monomers (hereinafter referred to as these). (referred to as copolymer AB) is used.

Moreover, the above-mentioned polymer A and copolymer AB may be used in combination as necessary.

Such polymer A and copolymer AB both have organosilyl groups or organosiloxane groups derived from monomer A in their side chains, so they impart good slipperiness to the coating formed therefrom. This coating effectively prevents aquatic organisms from adhering to the surface of underwater objects. The present inventors have found that such adhesion prevention effect is more pronounced than that of the conventional underwater antifouling coating agent, as shown in the examples described below.

In addition, since the above-mentioned polymer A and copolymer AB are soluble in organic solvents, a uniform coating can be easily formed by applying a solution of the solvent to the surface of an object to be immersed in seawater and drying it. can be converted into Moreover, the above-mentioned polymer A and copolymer AB are essentially non-reactive, unlike the conventional reaction-curing type.
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 overcoated on this coating, the coating is immersed in the solvent of the topcoat, resulting in poor interlayer adhesion with the topcoat. That is, all of the drawbacks of the conventional underwater antifouling coatings are eliminated by using the polymer A and/or copolymer AB.

Polymer A and copolymer AB exhibiting such effects
Monomer A for obtaining is an unsaturated acid monoester having organosilyl 7J (m=Q) or organosiloxane 4 (m=1 or more) in the molecule represented by the above general formula.

In the general formula, m is the repeating number of organosiloxane groups, and can be a real number of 0 or more, but is usually up to about 5,000. In addition, since four organosiloxane groups are formed by an addition reaction as described below, monomer A is usually a mixture of different repeating numbers of organosiloxane groups. Therefore, the above-mentioned m stem should be expressed as the average value (seedlings) of these, and it is for this reason that it is expressed as the above-mentioned real number.

From this point of view, in the examples described later, the above-mentioned seedlings are used. In the general formula, n is an integer of 2 to 5, exactly 2.3.4 or 5.

Furthermore, in the general formula, R1-R3 are all alkyl groups,
It is a group selected from alkoxyl group, phenyl i, z-substituted phenyl group, phenoxydyl group or substituted phenoxyl group, and the number of carbon atoms in the above alkyl group and alkoxyl group is usually up to about 5, and the above Examples of the substituents of the substituted phenyl group and substituted phenoxyl group include alkyl groups, alkoxyl groups, and acyl groups having up to about 5 halogen carbon atoms.

Here, the m pieces of Ra, R1 and R, to R3 may be the same or different groups, but at least one of them needs to be a group other than a methyl group. That is, the use of a monomer in which all of the above groups are methyl groups has already been filed as Japanese Patent Application No. 298918/1982, and this is excluded in the present invention.

Such monomer A is easily available as a commercial product, and one example of its synthesis is acrylic acid or methacrylic acid, vinyl alcohol, allyl alcohol, etc. where n in the general formula is An ester with an unsaturated alcohol corresponding to the number of esters is obtained, and the above-mentioned R, ~
Organosilyl compounds having R3 or the above R1 in the molecule
There is a method in which an organosiloxane compound having ~r<s is subjected to an addition reaction.

In addition, in order to obtain copolymer AB, the above monomers, A
Examples of the vinyl polymerizable monomer B that can be used together include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate, and acrylic acid. ethyl, butyl acrylate,
Acrylic acid esters such as 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate, maleic acid esters such as dimethyl maleate and diethyl maleate, fumaric acid esters such as dimethyl fumarate and diethyl fumarate, styrene, vinyl Toluene, α-
Methylstyrene, vinyl chloride, vinyl acetate, butadiene, acrylamide, acrylonitrile, methacrylic acid,
Examples include acrylic acid and maleic acid.

Such vinyl polymerizable monomer B acts as a modifying component to impart various performances to the antifouling film depending on the purpose of use, and also has a higher molecular weight than monomer A alone. It is also a convenient component for obtaining coalescence. The amount of monomer B to be used is set within an appropriate range, taking into consideration the above performance and the anti-lη effect based on single L1 body A. - For boat fishing, it is preferable that the proportion of monomer B in the total weight of monomer A is 95 times or less, particularly 90% by weight or less. That is, if the R combination of the monomer A constituting the copolymer AB@ is at least 5% by weight, particularly preferably at least 10% 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 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 azu compounds such as azobisisobutyronitrile and triphenylmethylazohenzene, benzoyl peroxide, diter
Examples include peroxides such as t-butyl peroxide.

The weight average molecular weight of Polymer A and Copolymer AB obtained by the above method is 1,000 to 1°500.0 to -m.
It is desirable that it be in the range of 00. If the molecular weight is too low,
It is difficult to form a film that can withstand use, and if the temperature is too high, the viscosity will be high when used as a coating material, and the resin solid content will be low, so only a thin film can be obtained with one coating, and the dry film thickness will be too low for a given yield. The problem is that it takes several coats of paint to get the desired effect.

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

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

On the other hand, the above-mentioned maintenance does not mean intentionally eliminating cases where the surface tension of the coating is further reduced by the use of a surface lubricant. Even in such a case, the surface tension after addition is still low (and the above-mentioned sustainability improvement effect of the present invention can still be expected. After all, the surface lubricant of the present invention ``Able to substantially maintain a low surface tension'' means to exclude surface lubricants whose use would significantly increase the surface tension of the coating and cause a decrease in antifouling properties; Therefore, other surface lubricants can be widely used as the surface lubricant of the present invention.

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

Specific examples of the above (■) include paraffin wax, microcrystalline wax, petrolatum, etc.
Specific examples include l5OVGIO1l5OVG15,
I 5OVG3 2, I 5OVG6B, l5
As a specific example of the above (■), each equivalent product of OVGLOO is as follows.
Shin-Etsu Chemical Industry (naked product name KF96L-0,65, K
F96L-2,0, KF96-30, KF96H-50
,000,KF965,KF50,KF54,KF69
, Toshiba silicone (+Kiku product name TSF440..T
SF410, TSF4440, TSF431, TSF4
33, TSF404, TFA4200, YF3860,
YF3818, YF3841, YF3953, TSF4
51, Azuma silicone (structure product name S H200,5
1-T 510.5H3531, 5H230, FS12
65 etc.

The most common silicone oil mentioned above is dimethyl silicone oil, but other silicone oils include methylphenyl silicone oil, polyether silicone oil, cyclic polysiloxane oil, alkyl-modified silicone oil, methylchlorinated phenyl silicone oil, and higher fatty acid-modified silicone oil. Other materials such as oil, fluorosilicone oil, etc. may also be used.

Specific examples of the above (■) include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, cerotic acid, montanic acid, melisic acid, lauroleic acid, oleic acid, vaccenic acid, gadoleic acid, and whale oil. Examples include whale oil acid, juniperic acid, etc. In addition, esters of these carboxylic acids include stearyl stearate, butyl laurate, octyl palmitate, butyl stearate, isopropyl stearate, cetyl palmitate, seryl cerotate, myricyl palmitate, melysylmerisate, spermaceti, spermaceti Wax, carnauba wax, montan wax, mushi wax, tristearin, tolpalmitin, triolein, myristodilaurin, caprylolauromyristin, stearopalmitolein,
Monostearin, monopalmitin, distearin, civalmitin, beef tallow, pork fat, horse tallow, mutton tallow, cod liver oil, coconut oil,
Examples include palm oil, wood wax, kapok oil, cacao butter, China butter, and iris fat.

Further, specific examples of the above (■) include dodecylamine, tetradodecylamine, hexadecylamine, octadecylamine, oleylamine, beef tallow alkylamine, cocoalkylamine, soybean oil alkylamine, didodecylamine, di-tallow hydrogenated alkylamine, Specific examples of the above (■) include dodecyldimethylamine, cocoalkyldimethylamine, tetradecyldimethylamine, hexamethyldimethylamine, and octadecyldimethylamine.
Product name Nissan Bolibutene ON, 06N manufactured by NOF ■
, 015N, 3N, 5N, 1 ON.

3ON, 20ON, O5H, 06SH, 0155H, 3
Examples include SH15SH, 105H, 30SH, and 200SH.

In the present invention, one or more surface lubricants are selected from among the various surface lubricants described above, and the amount used is determined based on the drying properties based on the polymer A and/or copolymer AB. , is set within an appropriate range, taking into consideration performance such as adhesion and lη prevention performance. - For boat fishing, the proportion of the surface lubricant in the total amount of polymer A and/or copolymer AB and surface lubricant is 1 to 70%. It is preferable to have one.

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

Organic solvents used for the above purpose include aromatic hydrocarbon solvents such as xylene and toluene, aliphatic hydrocarbon solvents such as hexane and heptane, ester solvents such as ethyl acetate and butyl acetate, and isoflovir. Alcohol, alcohol solvents such as butyl alcohol, dioxane,
Examples include ether solvents such as diethyl ether, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, or a mixture thereof.

The amount of the organic solvent used is preferably such that the degree of polymer A and/or copolymer AB in the solution is usually 5 to 80% by weight, particularly preferably 30 to 70% by weight. The viscosity of the solution at this time is generally preferably 150 poise or less/25° C. to facilitate film formation.

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

In order to form an antifouling film on the surface of an object to be immersed in seawater using the underwater antifouling coating agent of the present invention, for example, after applying the coating agent as a solution to the surface of the object by an appropriate means, 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.

[For production]

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

Furthermore, by using the surface lubricant used in the second invention in combination with the above-mentioned Polymer A and/or Copolymer A I3, the antifouling performance can be further improved even in sea areas where marine organisms are actively breeding. This is important for long-term sustainability. The inventors' speculation regarding the above fact is that the surface slippage of the coating is due to the surface smoothing effect based on the use of a surface lubricant, the deterioration prevention effect of the coating made of polymer A and/or copolymer AB, etc. This is thought to be due to the fact that the condition is reinforced and maintained over a long period of time.

〔Effect of the invention〕

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

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

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

Therefore, the coating obtained by the present invention can be used in ship bottoms, underwater structures such as fishing nets and cooling water pipes that require prevention of marine biological fouling, and marine turbidity prevention membranes used to prevent sludge dispersion in marine civil engineering works. It exhibits a remarkable antifouling effect and can prevent biofouling of substrates submerged in the sea.

〔Example〕

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

Production Examples 1 to 7 Solvent a was charged in a flask equipped with a stirrer according to the formulations in Table 2 (1 and 2), the temperature was raised to a predetermined reaction temperature, and monomer A (A, ~A7), drop a mixed solution of monomer B and polymerization catalyst a into the flask over 6 hours,
After the dropwise addition was completed, the temperature was kept at the same temperature for 30 minutes. Then, a mixture of a solvent and a polymerization catalyst was added dropwise over 20 minutes, and stirring was continued for 5 hours at the same temperature to complete the polymerization reaction. Finally, a diluting solvent was added to dilute the solution to obtain each polymer solution (1) to (2).

Production Examples 8 and 9 In a heat-resistant and pressure-resistant container, monomer A (As, As>, monomer B, and polymerization catalyst a were added according to the formulations in Table 2 (1 and 2).
The reaction mixture was completely sealed and heated to a predetermined reaction temperature while shaking, and the reaction was further continued at the same temperature for 8 hours to complete the reaction. Next, a diluting solvent was added and dissolved by shaking for 3 hours to obtain polymer solutions (1) and (2).

Preparation Example 10 In a flask equipped with a stirrer, solvent a, monomer A (A I.) and polymerization catalyst a were charged according to the formulation in Table 2 (1.2), and the prescribed reaction was carried out while stirring. Raise the temperature to
Stirring was continued for 6 hours at the same temperature to obtain a polymer solution X.

In addition, monomer A (A +
~A+o) represents X, +1. rn
(seedling), R1-R6 have the structure as shown in Table 1 below.

Examples 1 to 18 Using polymer solutions (1) to (X), 2. Mixing and dispersion was performed using an OQQrpm homomixer to prepare 18 types of anti-ice coatings.

Among the ingredients, paraffin wax 120P and petrolatum No. 1 are JIS K2235 petroleum waxes, and 15OVCIO is JIS K2231 liquid paraffin. In addition, the silicone oil with the product name KF-69 is manufactured by Shin-Etsu Chemical Co., Ltd., and the product name is TS
The silicone oil for F433 is manufactured by Toshiba Silicone ■. Furthermore, Nissan Bolibutene 06N is a polybutene manufactured by NOF@.

In addition, Oil Blue 2N [trade name manufactured by Orient Kagaku A Zero] is a dye, Disparon 6900-20X [trade name manufactured by Kusunoki Kasei ■] and Aeroseal 300 [trade name manufactured by Nippon Aeroseal ■] are all anti-sagging agents. It is an additive for

Comparative Examples 1 to 4 Instead of polymer solutions (1) to (X), KE45TS (trade name, manufactured by Shin-Etsu Chemical Co., Ltd. 4m; oligomeric room temperature curing silicone rubber 50% by weight toluene solution) was used.
In the same manner as in Examples 1 to 18, four types of water intermediate lη coatings having the formulations shown in Table 3 below were prepared.

Each of the coating materials of Examples 1 to 18 and Comparative Examples 1 to 4 described above was subjected to the following physical performance test, measurement of the surface sliding angle of the coating, and antifouling performance test to evaluate the performance. The results were as shown in Table 4 below.

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

A) Storage stability: Pour each coating into a 250 cc mayonnaise bottle 2QQ.
I put it in a cc container and sealed it with a lid. This temperature is 70”C+
The storage stability was determined by the degree of viscosity increase of each sample after 2 weeks of storage in a thermostatic chamber with a humidity of 75%. 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 JTS K5400.5.8.

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

C) Adhesion The test was carried out in accordance with the JIS K5400.6.15 substrate test method. That is, each coating agent was applied to a polished steel plate (
150X70X1mm) and kept at a temperature of 20'' for one week.
The film was dried in a thermostatic chamber with a C2 humidity of 75%, and a cross-shaped cut reaching the base was made with a cutter knife at a length of 201 cm.

10 with an Erichsen tester from the back of the test plate at the center.
We pushed out the crane. At that time, adhesion was determined by the length of peeling from the center of the cross-cut uneven portion of the coating surface.

It was evaluated as ○ when the peeling was 0, △ when the peeling was less than 51 m, and × when the peeling was 5 dragons or more.

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

First, as shown in FIG. 1(A), a test plate 5 is placed on a transparent glass plate 1 with the coating side facing upward.
Place the movable plate horizontally via the movable plate 5 on the test plate 5 to one end of the movable plate 4, that is, the distance γ from the fixing jig 2 is 185.
A water droplet 6 is formed by dropping 0°2 mβ sterilized filtered seawater at the dragon position using a syringe. Thereafter, as shown in FIG. 1(B), the other end B side of the movable plate 4 is moved upward along the support 3 at a speed of 1/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 chamber at a temperature of 25° C. and a humidity of 75%, and each test plate was measured three times, and the average value was expressed.

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

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

/ As is clear from the results in Table 4 above, Example 11
-18 had good storage stability, drying properties, and adhesion. Moreover, the surface sliding angles are all in the range of 7.8 to 9.3 degrees.

In addition, in Examples 10 to 18 in which a surface lubricant was used in combination, the temperature was in the range of 7.9 to 9.3 degrees, which means that the film of the specific polymer of the present invention itself has strong surface slip properties. It also shows that the surface slipping agent maintains the strong surface slipping properties of the coating itself of the specific polymer of the present invention.

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

On the other hand, Comparative Examples 1 to 4 are silicone rubber-based coating materials, which have shortcomings in storage stability, drying properties, and adhesion. In addition, the lη resistance is also unsatisfactory, as evidenced by the high value of the surface slip angle.

[Brief explanation of drawings]

FIGS. 1A and 1B 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.▼ (However, in the formula, X is a hydrogen atom or a methyl group, and n is 2
an integer of ~5, m is a real number of 0 or more, R_1 to R_5 are all groups selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group, or a substituted phenoxyl group, and m R_4, R_5
and R_1 to R_3 may be the same group or different groups, but at least one of them is a group other than a methyl group). and/or a copolymer consisting of one or more of the above monomers A and one or more of the vinyl polymerizable monomers B that can be copolymerized with these, as an essential component. Soil coating agent. (2) The following general formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, X is a hydrogen atom or a methyl group, and n is 2
an integer of ~5, m is a real number of 0 or more, R_1 to R_5 are all groups selected from an alkyl group, an alkoxyl group, a phenyl group, a substituted phenyl group, a phenoxyl group, or a substituted phenoxyl group, and m R_4, R_5
and R_1 to R_3 may be the same group or different groups, but at least one of them is a group other than a methyl group). and/or a copolymer consisting of one or more of the above monomers A and one or more of the vinyl polymerizable monomers B that can be copolymerized therewith, and this polymer and/or An underwater antifouling coating agent containing as an essential component one or more surface lubricants capable of substantially maintaining the low surface tension of a coating formed from a copolymer.