JP2784652B2 - Aqueous dispersion type antifouling paint - Google Patents

Description

The present invention relates to an aqueous dispersion-type antifouling paint for preventing marine organisms from adhering to fishing nets, ship bottoms, and marine structures.
It is particularly effective in preventing the adhesion of algae, can be used outdoors on beaches, fishing ports, fishing boats, etc., and is concerned with water-dispersed antifouling paints that are free from environmental pollution such as air pollution. The present invention relates to an aqueous dispersion type antifouling paint comprising a copolymer of a radical polymerizable monomer having a quaternary ammonium salt type cationic group.

[Conventional technology and its problems]

2. Description of the Related Art Conventionally, a solvent-type antifouling paint containing an antifouling substance such as an organotin-based antifouling substance has been used for preventing the adhesion of marine products to fishing nets, ship bottoms, and underwater structures. However, these antifouling substances are extremely harmful in the marine environment, and in recent years, the emergence of pollution-free antifouling paints has been expected.

Some proposals regarding such non-polluting antifouling paints are also known, for example, in Japanese Patent Application Laid-Open No. 62-84167,
(A) 1 to 55 mol% of an α, β-ethylenically unsaturated monomer containing a quaternary ammonium salt, (b) 5 to 25 mol of an α, β-ethylenically unsaturated monomer having a crosslinkable functional group %, (C)
Other α, β-ethylenically unsaturated monomer 20 to 94 mol%
(A) / (B) = Equivalent ratio of the amount of crosslinkable functional group (A) in the resin to the amount of functional group (B) in the curing agent, comprising a resin composition comprising a copolymer of 70/100 to 100/70 is disclosed.

However, the coating composition for preventing underwater fouling proposed above contains a large amount of an organic solvent solution such as xylol and methyl isobutyl ketone, and has a problem in terms of environmental hygiene.

In order to solve the above problems, an aqueous dispersion type antifouling paint has also been proposed. For example, Japanese Patent Application Laid-Open No. 232470/1987 discloses a component (A): an aqueous anionic resin emulsion having a solid content of 100% by weight. Part (B) component: General formula Cationic surfactants wherein shown in, R is -CH ₃ or -C ₂ H _5, it may be different even in the same,; R 'is alkyl of 8-18 carbon atoms X is a halogen atom selected from -Cl, -Br and -I] 10 to 40 parts by weight (C) Component: 20 to 50 parts by weight of nonionic surfactant and / or amphoteric surfactant Component (D): Plasticizer 0 to 15 parts by weight The above description relates to a coating composition for algae control comprising the above components (A), (B), (C) and (D) in the above proportions.

However, although the water-dispersed antifouling paint of the second proposal satisfies the marine environment conservation to some extent, it does not satisfy the point of preventing the adhesion of marine fouling organisms for a long time.

That is, the second proposal is to simply blend a cationic polymer, which is essentially water-soluble as an antifouling component, with a main polymer serving as a binder. A considerable amount of the cationic surfactant was eluted, and it was difficult to maintain the antifouling effect.

In view of this situation, the present inventors have conducted intensive studies to develop a non-polluting aqueous dispersion type antifouling paint having durability, and as a result, the copolymer containing a specific radical polymerizable monomer copolymer is contained. It has been found that the intended purpose can be achieved by using an aqueous dispersion of the present invention, and the present invention has been completed.

[Means for solving the problem]

 The present invention provides a quaternary ammonium salt type cationic group in the molecule.
An antifouling paint containing a copolymer having
The antifouling paint has the following monomers (a) to (c), (a) the following general formula,(Where R¹Is a linear or branched alkyl having 8 to 22 carbon atoms
Kill group or alkenyl group, R^TwoAnd R^ThreeRepresents 1 to 1 carbon atoms
An alkyl group of 3, R^FourRepresents a hydrogen atom or a methyl group;
Represents a monovalent anion).
Has a cationic surface activity with a ammonium salt type cationic group
Radical polymerizable monomer 8 to 20
% (Of all monomers), (b) the following general formula:(Where R^FiveIs a hydrogen atom or a methyl group, R⁶Is C≡N,And R⁷Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R⁸, R⁹Represents an alkyl group having 1 to 20 carbon atoms.
You. ) 60-92% by weight of ethylene monomer represented by
(C) amides of acrylic acid or methacrylic acid,
Methylolated products of phosphoric acid or methacrylamide and their
Derivative, having acrylic acid or methacrylic acid and epoxy group
Esters with alcohol, acrylic acid or methacrylic acid
Hydroxyalkyl esters of lylic acid and silane
Functional group-containing monomer selected from coupling agents (however,
Cross-linking monomers having two or more non-conjugated unsaturated groups
0 to 5% by weight (of all monomers), glass transition point obtained by emulsion copolymerization of -10 to + 15 ° C
Only the emulsion of the copolymer within the range
Moisture for preventing marine fouling organisms
The present invention relates to a dust-type antifouling paint.

 Hereinafter, the present invention will be described in detail.

 The quaternary ammonium salt type potassium used in the molecule used in the present invention
Has a thione group and acts as a cationic surfactant
Radical polymerizable monomer (a) (hereinafter referred to as cationic monomer)
May be abbreviated to) as the following general formula:(Where R¹Is a linear or branched alkyl having 8 to 22 carbon atoms
Kill group or alkenyl group, R^TwoAnd R^ThreeRepresents 1 to 1 carbon atoms
An alkyl group of 3, R^FourRepresents a hydrogen atom or a methyl group;
Represents a monovalent anion. ). Such a cationic unit
Specific examples of the monomer include 3-allyloxy-2-hydroxy
Cypropyl dimethyl stearyl ammonium chloride
, 3-allyloxy-2-hydroxypropyldimethyl
Lauryl ammonium chloride, 3-metaryloxy-
2-hydroxypropyldimethyl palmityl ammonium
Contains allyloxy group or metalloxy group such as muchloride
Cationic monomers; and the like. These cations
Monomer (a) may be used alone or in combination of two or more.
Can be used. The amount used is the total monomer
8-20% by weight, preferably more than 10% by weight,
% By weight or less. The amount used is too high exceeding the upper limit
As a result, the production of aqueous dispersion-type antifouling paint becomes difficult and
Storage stability and mechanical stability of paints
Is not preferred. In addition, too small below the lower limit
Is not preferable because the antifouling effect becomes insufficient.

In the present invention, together with the cationic monomer (a), an ethylene monomer (b) copolymerizable therewith and represented by the following general formula is used as a main component.

(Wherein, R ⁵ is a hydrogen atom or a methyl group, R ⁶ is C≡N, Wherein R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁸ and R ⁹ each represent an alkyl group having 1 to 20 carbon atoms. Examples of these monomers include acrylic acid such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, and stearyl acrylate. Alkyl ester monomers; for example, methyl methacrylate, ethyl methacrylate, n
Alkyl methacrylate monomers such as -butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate; aromatic vinyl monomers such as styrene, α-methyl styrene, vinyl toluene, and ethyl vinyl benzene; For example, saturated fatty acid vinyl monomers such as vinyl acetate, vinyl propionate, vinyl versatate, etc .; vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, etc. it can.

The amount of the ethylene-based monomer (b) represented by the above general formula is 60 to 92% by weight based on all monomers used to obtain the copolymer according to the present invention, and is preferably used. 70% by weight
More than 90% by weight.

It is also possible to copolymerize the functional group-containing monomer (c) for the purpose of improving the resulting copolymer, such as improving the adhesion to a coating object such as a fishing net and improving the film strength and water resistance.

Examples of the functional group-containing monomer (c) include amides of acrylic acid or methacrylic acid such as acrylamide, methacrylamide, and diacetone acrylamide; for example, N-methylolacrylamide,
Methylol methacrylamide, methylolated diacetone acrylamide, and etherified products of these monomers with alcohols having 1 to 8 carbon atoms (for example, N
Methylolates of acrylic acid or methacrylamide such as -isobutoxymethylacrylamide) and derivatives thereof; esters of acrylic acid or methacrylic acid such as glycidyl acrylate and glycidyl methacrylate with an alcohol having an epoxy group; Hydroxyalkyl esters of acrylic acid or methacrylic acid such as -hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 2-hydroxyethyl methacrylate; vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane,
Silane coupling agents such as 3-mercaptopropyltrimethoxysilane; monomer groups such as divinylbenzene, diallyl phthalate, triallyl cyanurate,
Excluding monomers having two or more non-conjugated unsaturated groups such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, allyl methacrylate, etc.) Can be mentioned.

The functional group-containing monomers (c) can be used alone or in combination of two or more, and the amount used is in the range of 0 to 5% by weight based on all the monomers. By copolymerizing the functional group-containing monomer (c) in an amount of 5% by weight or less, it is possible to obtain a copolymer having less problems in polymerization reaction and excellent film formability. Is suitably selected and used within the above range.

The copolymer according to the present invention comprises a cationic monomer (a) represented by the general formula, an ethylene monomer (b) represented by the general formula, and the functional group-containing monomer used as needed. It is obtained by copolymerizing the monomer (c).

As the above-mentioned copolymerization method, an emulsion polymerization method is adopted from the viewpoint of easy production of the aqueous dispersion type antifouling paint as the object of the present invention.

When the copolymer according to the present invention is produced by emulsion polymerization, the cationic monomer (a) of the above general formula acts as a cationic surfactant. Although not necessarily required, the polymerization reactivity is good, the amount of residue in the obtained copolymer emulsion is small (hereinafter, may be abbreviated as “appropriate emulsion polymerization reaction”), the mechanical stability of the emulsion, and the like. From the viewpoint of good storage stability and the like (hereinafter, may be abbreviated as emulsion stability), and good antifouling durability when the obtained antifouling paint is used, it is preferable to use the surfactant together with a surfactant. preferable.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl or alkenyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyalkylene oleyl ether; Polyoxyethylene octyl phenol ether,
Polyoxyalkylene alkylphenol ethers such as polyoxyethylene nonylphenol ether;
For example, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, and sorbitan trioleate; polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate; and polyoxyethylene monolau And polyoxyalkylene fatty acid esters such as polyoxyethylene monostearate;
For example, glycerin fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride;
For example, polyoxyethylene, polyoxypropylene,
Examples of the cationic surfactants include alkylamine salts such as laurylamine acetate; and quaternary ammonium salts such as uralyltrimethylammonium chloride and cetylbenzyldimethylammonium chloride. salt;
And amphoteric surfactants such as alkyl betaines such as lauryl betaine; N-alkyl amino acids such as N-lauryl glycine; N-alkylamino alcohol sulfate Esters; N-alkylamino alcohol phosphoric acid esters; N-alkyl amino alcohol sulfonic acid esters and the like. Further, those in which a part of the hydrogen of the alkyl group of these surfactants is substituted with fluorine can also be used.

As the amount of the surfactant used, monomers (a) to (c)
Is usually used in an amount of about 0.1 to about 10 parts by weight with respect to 100 parts by weight of the total amount, from about 0.5 to about 6 parts by weight in terms of emulsion polymerization reaction suitability, emulsion stability, and antifouling durability of the obtained antifouling paint. It is preferred to use about 0.5 to about 4 parts by weight.

In the emulsion polymerization, a protective colloid may be used in combination, if necessary. Examples of such protective colloids include, for example, polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol; for example, cellulose derivatives such as hydroxyethyl cellulose and hydroxypropyl cellulose; and, for example, And natural polysaccharides such as guar gum; and these can be used alone or in combination of two or more. The amount used can be appropriately selected and, for example, 0 to about 10 parts by weight based on 100 parts by weight of the total amount of the monomers (a) to (c) used can be exemplified.

The polymerization initiator used in the present invention may be a polymerization initiator used for ordinary cationic emulsion polymerization. Examples of such a polymerization initiator include organic peroxides such as tertiary butyl hydroperoxide, cumene hydroperoxide, and paramenthane hydroperoxide; hydrogen peroxide; azobisisobutyronitrile; Azobis compounds such as 2'-azobis (2-amidinopropane) dihydrochloride; and the like can be used. These polymerization initiators can be used either in one kind or in a combination of two or more kinds. The amount used can be appropriately selected, and the monomer (a) used
To (c) 100 parts by weight, for example, about 0.05 to
An example of the amount used is about 1 part by weight, more preferably about 0.1 to about 0.7 part by weight, particularly about 0.1 to about 0.5 part by weight.

In the emulsion polymerization, a reducing agent can be used in combination, if desired. Examples include ascorbic acid,
Examples thereof include reducing organic compounds such as tartaric acid, citric acid, and glucose; and reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. The amount used can be appropriately selected, for example, the monomer (a) used
The use amount of about 0.05 to about 1% with respect to 100 parts by weight of the total amount of (c) can be exemplified.

The polymerization temperature in the emulsion polymerization is generally 20 to 10
A temperature of about 0 ° C., preferably about 40 to 90 ° C., particularly preferably about 60 to 90 ° C. can be employed.

The solid content of the copolymer emulsion thus obtained is
Although not particularly limited, about 30 to more than productivity and ease of manufacture
Preferably it is about 65% by weight. The viscosity is 10,000cps. For the same reason (rotational viscometer, 25 ° C, 20R.PM)
The pH is preferably not more than pH 2 from the viewpoints of emulsion stability, excellent antifouling durability of the obtained antifouling paint, and the like.
It is preferably in the range of -8. Further, the average particle size of the dispersed particles of the copolymer in the emulsion is generally 0.02
From the viewpoint of the excellent antifouling durability of the obtained antifouling paint, it is preferably from 0.02 to 0.5 µ, particularly preferably from 0.02 to 0.2 µ.

In the present invention, the average particle diameter of the copolymer in the copolymer emulsion is a value measured and determined by the DLS method as described below.

Measurement method of average particle diameter: After diluting the copolymer emulsion 50,000 to 150,000 times with distilled water and mixing well by stirring, about 10 ml was collected in a 21 mmφ glass cell using a Pasteur pipette, and this was collected. It is set at a predetermined position of a dynamic light scattering photometer DLS-700 (manufactured by Otsuka Electronics Co., Ltd.) and measured under the following measurement conditions.

Measurement conditions Measurement temperature 25 ± 1 ℃ Clock rate 10μsec Correlation channel (Core.Channel) 512 Total number of measurements 200 times Light scattering angle 90 ° The above measurement results are processed by computer to determine the average particle diameter.

Furthermore, the glass transition point (hereinafter sometimes abbreviated as Tg) of the copolymer according to the present invention is preferably in the range of −15 to + 30 ° C., particularly, −10 to 15 ° C. When the Tg is equal to or more than the lower limit, the touch tack of the coating film of the obtained antifouling paint is relatively small, so that the coating workability on the object to be coated such as a fishing net is excellent, and the Tg is the upper limit. In the following, it is preferable to use a copolymer within the Tg range, since the coating film is less likely to crack, fall off, or the like during transportation or use of the obtained article.

In the present invention, the glass transition point (T
g) is a value measured and determined by the DSC method as described below.

Glass transition point measuring method: About 10 mg of a copolymer emulsion sample was weighed into a cell,
A sample dried at 0 ° C for 2 hours is used as a measurement sample. Shimadzu DT-30 Differential Scanning Calorimeter
Using a Calorimeter), the measurement is determined from -80 ° C at a heating rate of 20 ° C / min. The measurement is performed using nitrogen gas as a carrier gas at a flow rate of 20 cc / min.

In the present invention, for example, the copolymer emulsion obtained by emulsion copolymerization as described above alone as it is,
Or, if necessary, for example, a thickening agent such as polyvinyl alcohols, cellulose derivatives, special surfactants, and the like;
For example, an aqueous dispersion-type antifouling agent can be obtained by appropriately adding an ether ester solvent such as diethylene glycol monobutyl ether acetate, a film-forming auxiliary such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate; It can be a paint. The aqueous dispersion type antifouling paint of the present invention includes a pH of 2 to 9, a viscosity of 10 to 10,000 cps.
(25 ° C., 20 R.PM) and a minimum film forming temperature of about 10 ° C. or less (preferably, about 0 ° C.) are preferable from the viewpoint of workability of coating the object to be coated.

Further, the antifouling paint of the present invention, if necessary, for example,
Crosslinking agents such as amino resins, phenol resins, epoxy resins, urethane resins; for example, clay, talc,
Inorganic fillers such as calcium carbonate, silica, aluminum hydroxide and glass powder; organic or inorganic coloring agents such as titanium oxide, carbon black and phthalocyanine blue; phthalic acid esters such as dioctyl phthalate; A plasticizer such as a phosphate ester such as phosphate; an antioxidant; an ultraviolet absorber; a light stabilizer; a preservative;

The dried film of the aqueous dispersion type antifouling paint thus obtained is
Since the cationic monomer of the above general formula of the antifouling component is incorporated into the copolymer by copolymerization, the elution of the antifouling component when immersed in the sea is small and gradual, so it is essentially water-soluble. Unlike a simple blend of a cationic or amphoteric antifouling component, it is possible to prevent marine organisms from adhering to fishing nets for a long time.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

In addition, the various test methods in this example are as follows.

i) Film water immersion test Apply the aqueous dispersion type antifouling paint of the sample on release paper, 25 ℃
A film with a thickness of about 0.2μ was created by drying for 2 days, then immersed in tap water for a predetermined period, and then the film was taken out. From the loss on drying, the weight of the film after immersion was calculated when the weight of the film before immersion was 100. Was.

ii) Water resistance The aqueous dispersion type antifouling paint of the sample was applied to a glass plate so as to have a film thickness of about 50 μm, and dried at 25 ° C. × 1 day. Then, it was immersed in tap water for 24 hours to check the degree of whitening.

 The evaluation criteria are as follows.

○ → Slightly whitened △ → Slightly whitened × → Violently whitened iii) Underwater immersion test Apply dipping method so that the coating amount of the aqueous dispersion type antifouling paint of the sample is 4 to 6 parts by weight per 100 parts by weight of net. And applied.

Next, it was immersed in the sea for a predetermined time, and the state of algae generation was observed.

 The evaluation criteria are as follows.

○ → Slight algae generation △ → Slight algae generation × → Vigorous algae generation Example-1 56 parts by weight of deionized water was placed in a flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser, and The inside is replaced with nitrogen gas, and the temperature is raised to 75 ° C.

Next, 44 parts by weight of previously prepared 2-ethylhexyl acrylate, 45 parts by weight of styrene, and 3-allyloxy-
About 25% by weight aqueous solution of 2-hydroxypropyldimethylstearylammonium chloride [Latemul K-180
(Trade name): Kao Soap Co., Ltd.] 44 parts by weight, nonionic surfactant (polyoxyethylene alkylphenol ether) (HLB about 18) [Emulgen-950 (trade name): Kao Soap Co., Ltd.] 1.8 parts by weight A monomer emulsion consisting of 52 parts by weight of deionized water and 11 parts by weight of a 2% aqueous solution of 2,2'-azobis (2-amidinopropane) dihydrochloride were placed in a stirred flask for 2 hours. Sprinkle and drop.

The obtained copolymer emulsion had a solid content of about 40% by weight, a pH of 3.5, and a viscosity of 200 cps. (Rotational viscometer, 25 ° C., 20 R.P.
M .: The same applies hereinafter), and the emulsion stability was excellent. The average particle size of the copolymer in the emulsion is about
The Tg of the copolymer was about −6 ° C. Various tests were carried out using this copolymer emulsion as it was as an aqueous dispersion type antifouling paint. The results are shown in Table 1.

Examples 2 to 4 In Example 1, 2-ethylhexyl acrylate
A copolymer emulsion was obtained in the same manner except that the monomer (b) shown in Table 1 was used instead of 44 parts by weight and 45 parts by weight of styrene, and various tests were performed in the same manner. The results are shown in Table 1.

Examples 5 to 9 Copolymer emulsions were prepared in the same manner as in Example 1 except that the amount of styrene was changed to 43 parts by weight and the functional group-containing monomer (c) shown in Table 1 was used in an amount of 2 parts by weight. Then, various tests were carried out in the same manner. In Example 9, 3-methacryloxypropyltrimethoxysilane [KBM-503 (trade name): Shin-Etsu Chemical Co., Ltd.] was used as the functional group-containing monomer (c). The results are shown in Table 1.

Examples 10 and 11 Copolymer emulsions were obtained in the same manner as in Example 2 except that the amounts of methyl methacrylate and butyl acrylate were changed, and various tests were conducted. Table 1 shows the results.
Shown in

Comparative Example 1 In Example 1, the aqueous solution of the cationic monomer (a), Latemul K-180 (trade name), was not used, and the monomers used were 49 parts by weight of 2-ethylhexyl acrylate and 51 parts by weight of styrene. , A 62% by weight aqueous solution of a cationic surfactant stearyltrimethylammonium chloride [Coatamine 86P Conc (trade name): Kao Soap Co., Ltd.] 2
A monomer emulsion was prepared in the same manner except that 0 parts by weight was used and the amount of deionized water used was changed. Thereafter, a copolymer emulsion was obtained in the same manner, and various tests were performed. The results are shown in Table 1.

Comparative Example 2 In Comparative Example 1, the cationic surfactant Kotamine was used.
Instead of 20 parts by weight of 86P Conc (trade name), 1.8 parts by weight of nonionic surfactant (polyoxyethylene alkylphenol ether) (HLB about 13) [Emulgen 910 (trade name): Kao Soap Co., Ltd.] was used. A monomer emulsion was prepared in the same manner except that the amount of deionized water used was changed, and thereafter, a copolymer emulsion was obtained. This copolymer emulsion had a viscosity of 100 cps, a pH of 2.5, a solid content of about 45% by weight, and an average particle size of about 0.15 μm. 231 parts by weight of this copolymer emulsion was diluted with 29 parts by weight of water to a solid content of 40% by weight, and various tests were carried out in the same manner as in Example 1.
The results are shown in Table 1.

Comparative Examples 3 and 4 231 parts by weight of the copolymer emulsion obtained in Comparative Example 2 were then added to the cationic surfactant Cotamine, respectively.
20 parts by weight of 86P Conc (trade name) (approximately 11 parts by weight of the cationic surfactant in solids with respect to 100 parts by weight of the total solid content of the copolymer and the cationic surfactant) and 40 parts by weight of water Part, cationic monomer (a) aqueous solution latemul K-180
(Trade name) 49 parts by weight (cationic monomer is about 11 parts by weight with respect to the total of 100 parts by weight of the copolymer and the cationic monomer) and 10 parts by weight of water are added later to prevent stain. Various tests were carried out in the same manner as in Example 1 except that the paint was used. The results are shown in Table 1.

Claims (1)

(57) [Claims] 1. A quaternary ammonium salt type cationic group in a molecule.
An antifouling paint containing a copolymer having
The antifouling paint has the following monomers (a) to (c), (a) the following general formula,(Where R¹Is a linear or branched alkyl having 8 to 22 carbon atoms
Kill group or alkenyl group, R^TwoAnd R^ThreeRepresents 1 to 1 carbon atoms
An alkyl group of 3, R^FourRepresents a hydrogen atom or a methyl group;
Represents a monovalent anion).
Has a cationic surface activity with a ammonium salt type cationic group
Radical polymerizable monomer 8 to 20
% (Of all monomers), (b) the following general formula:(Where R^FiveIs a hydrogen atom or a methyl group, R⁶Is C≡N,And R⁷Is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R⁸, R⁹Represents an alkyl group having 1 to 20 carbon atoms.
You. ) 60-92% by weight of ethylene monomer represented by
(C) amides of acrylic acid or methacrylic acid,
Methylolated products of phosphoric acid or methacrylamide and their
Derivative, having acrylic acid or methacrylic acid and epoxy group
Esters with alcohol, acrylic acid or methacrylic acid
Hydroxyalkyl esters of lylic acid and silane
Functional group-containing monomer selected from coupling agents (however,
Cross-linking monomers having two or more non-conjugated unsaturated groups
0 to 5% by weight (of all monomers), glass transition point obtained by emulsion copolymerization of -10 to + 15 ° C
Only the emulsion of the copolymer within the range
Moisture for preventing marine fouling organisms
Stain-type antifouling paint.