JPH0264167A - Water-based dispersion type antifoul coating - Google Patents

Abstract

PURPOSE:To provide the title coating excellent in storage stability and mechanical stability and capable of preventing marine organisms from being stuck to fishnets, chip bottoms and marine structures, containing in the molecule a copolymer from radically polymerizable monomer having quaternary ammonium salt-type cationic group. CONSTITUTION:The objective coating containing a copolymer from (A) pref. 70-90wt.% of e.g., methyl (meth)acrylate and (B) a radically polymerizable monomer having in the molecule quaternary ammonium salt-type cationic group {e.g., a compound of the formula [R<1> is 8-22C alkyl or alkenyl; R<2> and R<3> are each 1-3C alkyl; R<4> is H or methyl; X is OC(O) or O-CH2; Y<-> is monovalent anion]}.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an aqueous dispersion antifouling paint for preventing marine fouling organisms from adhering to fishing nets, ship bottoms, and underwater structures, and in particular, to preventing the adhesion of algae. Regarding water-based dispersion antifouling paints that are effective in preventing pollution, can be used outdoors such as on beaches, fishing ports, and on fishing boats, and are free from concerns about environmental pollution such as air pollution.
The present invention relates to an aqueous dispersion type antifouling paint characterized by containing a copolymer of a radically polymerizable monomer having a quaternary ammonium salt type cationic group in the molecule.

[Conventional technology and its problems]

Conventionally, solvent-based antifouling paints containing antifouling poisons such as organotin-based substances have generally been used to prevent seafood from adhering to fishing nets, ship bottoms, and underwater structures. However, these antifouling poisons are extremely harmful to the marine environment, and in recent years, there has been great hope for the emergence of non-polluting antifouling paints.

Several proposals regarding such non-polluting antifouling paints are known. For example, Japanese Patent Application Laid-Open No. 62-84167 discloses (a) a quaternary ammonium salt-containing α,β-ethylenically unsaturated monomer; (b) α,β-ethylenically unsaturated monomer having a crosslinkable functional group 5 to 25 mol%
, (C) Other α, β-ethylenically unsaturated monomers 20
A resin composition consisting of ~94 mol% copolymer and a curing agent, the equivalent ratio of the amount of crosslinkable functional groups (A) in the resin to the amount of functional groups (B) in the curing agent is (A)/ (B)=70/1
A coating film-forming composition for preventing fouling in water is disclosed, which is characterized in that it has a coating composition of 00 to 100/70.

However, the above-proposed coating film forming composition for preventing underwater staining contains a large amount of an organic solvent solution such as pheasantol, methyl isobutyl ketone, etc., and thus remains a problem in terms of environmental hygiene.

In order to solve the above problems, water-based dispersion type antifouling paints have also been proposed. For example, in JP-A-62232470, component (A): 100 parts by weight of anionic resin aqueous emulsion solid content ( B) Component (2) A cationic surfactant represented by the general formula [wherein R is -CH or -CzHs, which may be the same or different; R' has 8 to 8 carbon atoms] 18 alkyl group; X is -C2, Br, -
10 to 40 parts by weight Component (C): nonionic surfactant and/or amphoteric surfactant
20-50 parts by weight Component (D): Plasticizer 0-15 parts by weight (A) above,
It describes an anti-algae coating composition in which components (B), (C) and (D) are blended in the above proportions.

However, although the water-based dispersion type antifouling paint of the second proposal satisfies the preservation of the marine environment to some extent, it is not satisfactory in terms of long-term prevention of adhesion of marine fouling organisms.

In other words, the second proposal simply blends a cationic surfactant, which is essentially water-soluble as an antifouling component, with the main polymer that serves as the binder. A considerable amount of the cationic surfactant was eluted, making it difficult to maintain the antifouling effect.

In view of the current situation, the present inventors have conducted intensive research to develop a long-lasting, non-polluting, water-based dispersion type antifouling paint. The present invention was completed based on the discovery that the desired object could be achieved by using an aqueous dispersion consisting of the following.

[Means for solving problems]

The present invention relates to an aqueous dispersion type antifouling paint characterized by containing a copolymer of a radically polymerizable monomer having a quaternary ammonium salt type cationic group in the molecule.

The present invention will be explained in detail below.

Examples of the radically polymerizable monomer (a) having a quaternary ammonium salt type cationic group in the molecule (hereinafter sometimes abbreviated as cationic monomer) that can be used in the present invention include the following - (In the formula, R1 is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, R2 and R3 are an alkyl group having 1 to 3 carbon atoms, R4 is a hydrogen atom or a methyl group, and X is a 0-C or 0-C11□, and Ye represents a monovalent anion). Specific examples of such cationic monomers include 3-allyloxy-2
-Cationic monomers containing an allyloxy group or a methazoloxy group such as hydroxypropyldimethylstearylammonium chloride, 3-allyloxy-2-hydroxypropyldimethyllauryl ammonium chloride, 3-methasoloxy-2hydroxypropyldimethylpalmityl chloride; 3-methacryloxy- 2-Hydroxypropyldimethylstearylammonium chloride, 3-
Acryloxy-2-hydroxypropyldimethyl lauryl ammonium chloride, 3-methacryloxy-2-
Examples include cationic monomers containing an acryloxy group or methacryloxy group such as hydroxyprobyl dimethyloleyl chloride. These cationic monomers (a
) can be used alone or in combination of two or more. Although the amount used is not particularly specified, it is preferably used in an amount of 2 to 30% by weight, more preferably 8 to 20% by weight, more than 10% by weight and less than 15% by weight. is preferable. By using less than this upper limit, the production of the aqueous dispersion type antifouling paint of the present invention is facilitated, and the resulting paint maintains excellent storage stability and mechanical stability, and by using more than this lower limit. Since the antifouling effect can be made more effective, it is preferable to use the cationic monomer (a) within the above usage range.

In the present invention, the cationic monomer (a) and an ethylene monomer copolymerizable therewith are used.

Among the above ethylene monomers, the main component (b) used is the following general formula (■), H2C= (-R6.
...■ (In the formula, R5 is a hydrogen atom or a methyl group, R6 is
7 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R
11 and R9 each represent an alkyl group having 1 to 20 carbon atoms. ) Monomers represented by these formulas can be preferably used. These monomers include, for example, acrylics such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, stearyl acrylate, etc. Acid alkyl ester monomers; for example, methacrylic acid alkyl ester monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate; for example, styrene , α-methylstyrene, vinyltoluene, ethylvinylbenzene, etc.; for example,
Examples include saturated fatty acid vinyl monomers such as vinyl acetate, vinyl propionate, and vinyl versatate; for example, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; and the like.

The amount of the monomer Φ) represented by the above-mentioned general input (3) occupies the main component amount in the ethylene monomer copolymerized with the cationic monomer (a), and for example, in the present invention. 50 to 98% by weight of the total monomers used to obtain such copolymers
, preferably 60 to 92% by weight, particularly preferably 70% or more and less than 90% by weight.

It is also possible to copolymerize a functional group-containing monomer (C) for the purpose of modifying the resulting copolymer, such as improving adhesion to objects to be coated such as fishing nets, film strength and water resistance.

Examples of such a functional group-containing monomer (C) include:
Amides of acrylic acid or methacrylic acid such as acrylamide, methacrylamide, diacetone acrylamide, etc.; etherified products with N-methylol acrylamide, N-methylol methacrylamide, etc.
Methylolated products of acrylic acid or methacrylic acid amides, such as N-isobutoxymethylacrylamide), and derivatives thereof; esters of acrylic acid or methacrylic acid with alcohols having an epoxy group, such as glycidyl acrylate, glycidyl methacrylate, etc.;
For example, hydroxyalkyl esters of acrylic acid or methacrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, etc.; Esters with alcohols having an amino group; for example, divinylbenzene, diallyl phthalate, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol acrylate, allyl methacrylate Monomers having two or more non-conjugated unsaturated groups such as vinyltrimethoxysilane, 3
- Silane coupling agents such as methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane;

The above functional group-containing monomers (C) can be used alone or in a mixture of two or more, and the amount used is, for example, 0 to 20% by weight, preferably 0 to 20% by weight based on the total monomers. ~
10% by weight, particularly preferably in the range from 0 to 5% by weight. By copolymerizing the functional group-containing monomer (C) in an amount below the upper limit, there are fewer problems in the polymerization reaction, and the resulting copolymer has excellent film-forming properties. It is preferable to appropriately select and use the amount within the range of .

The copolymer according to the present invention comprises the cationic monomer (a) shown in the above-mentioned -inclusion (1), the ethylene monomer shown in the -inclusion (1), etc.) and the above-mentioned functional group used as necessary. It is copolymerized with the group-containing monomer (C).

Although the method for the above copolymerization is not necessarily limited, it is desirable to employ an emulsion polymerization method from the viewpoint of ease of obtaining the aqueous dispersion type antifouling paint, which is the object of the present invention.

When producing the copolymer according to the present invention by emulsion polymerization, the cationic monomer (a) in (1) above acts as a cationic surfactant, so Although the agent is not necessarily required, it is important to have good polymerization reactivity, a small amount of residue in the resulting copolymer emulsion (hereinafter sometimes abbreviated as emulsion polymerization reaction suitability), and mechanical stability of the emulsion. It is used in combination with a surfactant from the viewpoint of good properties such as stability and storage stability (hereinafter sometimes referred to as emulsion stability), as well as good antifouling durability when using the resulting antifouling paint. is preferable.

Examples of the above-mentioned surfactants include nonionic surfactants such as alkyl or alkenyl ethers of polyoxyethylene such as polyoxyprolene lau;
For example, sorbitan fatty acid esters such as polyoxyethylene octylphenol ether, polyoxyethyl phenol ether, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, etc.; polyoxydialkylene turbicun fatty acids such as polyoxyethylene sorbitan monolaurate, etc. Esters; for example,
Polyoxyalkylene fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene monostearate; for example, oleic acid monoglyceride,
Examples include glycerin fatty acid esters such as stearic acid monoglyceride; for example, polyoxyethylene polyoxypropylene block copolymers; examples of cationic surfactants include alkyl amines such as laurylamine acetate; Salts; for example, quaternary ammonium salts such as uralyltrimethylammonium chloride and cetylbenzyldimethylammonium chloride; for example, pyridium bases such as cetylpyridium bromide; and amphoteric surfactants such as lauryl betaine. N-alkyl amino acids such as alkyl betaine, N-laurylglycine;
-Alkylamino alcohol sulfate; N-alkylamino alcohol phosphate; N-alkylamino alcohol sulfonic ester; and the like. Furthermore, surfactants in which some of the hydrogen atoms in the alkyl groups of these surfactants are replaced with fluorine can also be used.

The amount of surfactant to be used is usually about 0.5 to about 6 parts by weight based on a ratio of about 0.1 to about 10, based on 100 parts by weight of the total amount of monomers (a) to (C). Preferably about 0.5
It is particularly preferred to use up to about 4 parts by weight.

In addition, in the emulsion polymerization, a protective colloid can be used in combination, if necessary. Examples of such protective colloids include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and modified polyvinyl alcohol; for example, hydroxyethyl cellulose and hydroxypropyl cellulose; For example, natural multi-Fs such as guar gum; etc., and these can be used alone or in combination of multiple types. The amount used can be selected as appropriate, for example, based on 100 parts by weight of the total amount of monomers (a) to (C) used,
Amounts such as from 0 to about IO parts by weight may be exemplified.

The polymerization initiator used in the present invention may be a polymerization initiator used in ordinary cationic emulsion polymerization. Such polymerization initiators include, for example, organic peroxides such as tert-butyl high F rober oxide, cumene hydroperoxide, para-menthane hydroperoxide; hydrogen peroxide; azobisisobutyronitrile, 2 .Azobis-based compounds such as 2'-azobis(2-amidinopropane) dihydrochloride; etc. can be used. These polymerization initiators can be used either singly or in combination. The amount used can be selected as appropriate, and the monomers (a) to
For example, about 0.0 parts by weight per 100 parts by weight of (C)
Examples of usage amounts include 5 to about 1 part by weight, more preferably about 0.1 to about 0.7 part by weight, especially about 0.1 to about 0.5 part by weight.

Further, in the emulsion polymerization, a reducing agent can be used in combination, if desired. Examples include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, and glucose; reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. The amount used can be selected as appropriate, for example, monomers (a) to
About 0.05 to about 1 per 100 parts by weight of the total amount of (C)
For example, the amount used may be %.

The polymerization temperature in the emulsion polymerization is generally 20 to 1
A temperature of about 00°C, preferably 40 to 90°C, particularly preferably 60 to 90°C can be employed.

The solid content of the copolymer emulsion obtained by
Preferably it is about 65% by weight.

Also, its viscosity is 10,000 cps for the same reason,
(Rotational viscometer, 25°C 120R, P, M,
It is preferable that it is in the range of ~8. Furthermore, the average particle diameter of the copolymer dispersed particles in the emulsion is generally 0.
02 to 2μ, and from the viewpoint of excellent antifouling durability of the obtained antifouling paint, 0.02 to 0.5μ, particularly 0.0
The thickness is preferably 2 to 0.2μ.

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.

Measuring method of average particle diameter: The copolymer emulsion was diluted 50,000 to 50,000 times with distilled water, thoroughly stirred and mixed, and then diluted with about 10 ml of water using a 21 mmφ glass glass transition point pipette. The sample is placed in a predetermined position on a dynamic light scattering photometer [ILS-700 (manufactured by Otsuka Electronics)], and measured under the following measurement conditions.

Measurement conditions Measurement temperature 25±1°C Clock rate I Oμsec
Correlation Channel (Core, Channel
el) Cumulative number of measurements: 200 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 -15 to +30°C.
1. In particular, it is preferably within the range of -10 to 15°C. When Tg is above the lower limit, the tack to the touch of the resulting antifouling paint film is relatively small, resulting in excellent coating workability on m-coated objects such as fishing nets, and when Tg is above the upper limit, In the following, cracks in the coating film and
It is preferable to use a copolymer with a weight within this 7g range, since falling off is less likely to occur.

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

Glass transition point measurement method: Weigh out approximately 10 cm of copolymer emulsion sample in a cell,
A sample dried at 00°C for 2 hours is used as a measurement sample. Shimadzu DT-30 differential scanning calorimeter (Differe)
ntial Scanning Calorimete
r) at a heating rate of 20°C/min from -80°C.
, to determine the measurement. Note 1. The measurements are carried out using nitrogen gas as the carrier gas at a flow rate of 20 cc/ffl1n.

In the present invention, for example, the copolymer emulsion obtained by emulsion copolymerization as described above may be used alone as it is, or if necessary, for example, a copolymer emulsion such as polyvinyl alcohol, cellulose GI, special A surfactants, etc. may be used. By appropriately adding a thickener; for example, an ether ester solvent such as diethylene glycol monobutyl ether acetate, a membrane forming aid such as 2,2,4-)dimethyl-1,3-pentanediol monoisoptylate, etc. It can be made into an aqueous dispersion type antifouling paint. The aqueous dispersion type antifouling paint of the present invention has a pH of 2 to 9 and a viscosity of 10 to 10,000 cp.
s, (rotational viscometer, 25°C12OR, P, M,)
, minimum film forming temperature of 10°C or less (preferably about 0°C)
From the viewpoint of ease of coating onto objects, it is preferable that the amount of the coating is within a certain range.

Furthermore, the antifouling paint of the present invention may optionally contain crosslinking agents such as amino resins, phenol resins, epoxy resins, urethane resins, etc.; such as clay, talc, calcium carbonate, silica, and hydroxide. Inorganic fillers such as aluminum and glass powder; Organic or inorganic colorants such as titanium oxide, carbon black, and phthalocyanine blue; For example, phthalate esters such as dioctyl phthalate, and phosphate esters such as tricresyl phosphate. Plasticizers such as; anti-aging agents; ultraviolet absorbers; light stabilizers;
Preservatives; etc. may be added.

The dried film of the aqueous dispersion type antifouling paint obtained in this way has the antifouling component, the cationic monomer of the above-mentioned ship type (①), incorporated into the copolymer by copolymerization, so it has excellent protection when immersed in the sea. Since the elution of fouling components is small and gradual, unlike a simple blend of essentially water-soluble cationic or amphoteric antifouling components, it is possible to prevent marine fouling organisms from adhering to fishing nets etc. for a long period of time.

〔Example〕

The present invention will be explained in more detail below using Examples and Comparative Examples.

The various test methods used in this example are as follows.

i) Apply the aqueous dispersion type antifouling paint of the film water immersion test sample on the release paper, 25°C
A film with a thickness of approximately 0.2μ was created by drying for 2 days, then immersed in tap water for a predetermined period of time, the film was taken out, and the weight of the film after immersion was calculated based on the weight loss on drying, taking the weight of the film before immersion as 100. I asked for it.

ii) Water Resistance The aqueous dispersion type antifouling paint of the sample was applied to a glass plate to a film thickness of approximately 50 μm and dried at 25° C. for 1 day. Then, it was immersed in tap water for 24 hours, and the results were as follows: White O → Slight whitening Δ → Slight whitening × → Vigorous whitening iii) The amount of water-based dispersion antifouling paint for the underwater immersion test sample was 4 to 4 to 100 parts by weight of the net weight. It was coated by a dipping method so that the amount was 6 parts by weight.

Next, it is immersed in the sea for a predetermined period of time, and the state of algae growth ○ →
Slight algae growth △ → Slight algae growth × → Severe algae growth Example-1 Put 56 parts by weight of deionized water into a flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, and cool the system. Replace with nitrogen gas and raise the temperature to 75°C.

Next, 44 parts by weight of 2-ethylhexyl acrylate, 45 parts by weight of styrene, and about 25% by weight aqueous solution of 3-allyloxy-2-hydroxypropyldimethylstearylammonium chloride [lateml-1
80 (Product Name): Hanadama Soap ■] 44 parts by weight, nonionic surfactant (polyoxyethylene alkylphenol ether) (HLB approx. 18) [Emulgen-950 (
Product name): Kao soap ■] 1.8 parts by weight, deionized water 52
A monomer emulsion consisting of parts by weight and 2,2'-azobis(2
-amidinopropane) 11 parts by weight of a 2% aqueous solution of dihydrochloride are added dropwise into the flask under stirring over a period of 2 hours.

The resulting copolymer emulsion has a solids content of approximately 40% by weight.
, pH 3.5, viscosity 200 cps, (rotational viscometer, 2
5゛C520R,P,M: the same applies hereafter), and the emulsion stability was excellent. In addition, the average particle diameter of the copolymer in the emulsion is approximately 0.12μ, and the Tg of the copolymer
was approximately -6°C. Various tests were conducted 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 4
A copolymer emulsion was obtained in the same manner except that monomer (b) shown in Table 1 was used instead of 4 parts by weight and 45 parts by weight of styrene, and various tests were conducted in the same manner. The results are shown in Table-1.

Examples 5 to 9 A copolymer emulsion was prepared in the same manner as in Example 1, except that the amount of styrene used was 43 parts by weight, and 2 parts by weight of the functional group-containing monomer (C) shown in Table 1 was used. Various tests were conducted in the same manner. In addition, Example 9
Here, 3-methacryloxypropyltrimethoxysilane (KBM-503 (trade name): Shin-Etsu Chemical ■) was used as the functional group-containing monomer (C). The results are shown in Table-1.

Example 10.11 A copolymer emulsion was obtained in the same manner as in Example 2 except that the amounts of methyl methacrylate and butyl acrylate used were changed, and various tests were conducted. The results are shown in Table-1.

Example 12 A copolymer emulsion was prepared in the same manner as in Example 1 except that an approximately 25% by weight aqueous solution of 3-methacryloxy-2-hydroxypropyldimethylstearylammonium chloride was used instead of Latemul K-180 (trade name). Various tests were conducted. The results are shown in Table-1.

Comparative Example 1 In Example 1, -180 (trade name) was not used in the cationic monomer (a) aqueous solution of Latemul, and the monomers were 49 parts by weight of 2-ethylhexyl acrylate and 51 parts by weight of styrene. approximately 62% by weight of the cationic surfactant stearyltrimethylammonium chloride.
A monomer emulsion was prepared in the same manner except for using 20 parts by weight of an aqueous solution [Cortamino 86P Conc (trade name): Kao Soap ■] and changing the amount of deionized water. A polymer emulsion was obtained and various tests were conducted. The results are shown in Table-1.

Comparative Example 2 In Comparative Example 1, the cationic surfactant Cortamine 8
Instead of 20 parts by weight of 6P Conc (trade name), use a nonionic surfactant (polyoxyethylene alkylphenol ether) (IILB approx. 13) [Emulgen 910 (
A monomer emulsion was prepared in the same manner except for using 1.8 parts by weight of Kao Soap (trade name) and changing the amount of deionized water. 0. Irμ
Met.

231 parts by weight of this copolymer emulsion was diluted with 29 parts by weight of water to give a solid content of 40% by weight, and various tests were conducted in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 3 and 4 To 231 parts by weight of the copolymer emulsion obtained in Comparative Example 2, 20 parts by weight of the cationic surfactant Kotajin 86P Conc (trade name) (copolymer and the cationic surfactant) were added. For a total of 100 parts by weight of solid content, cationic surfactant (solid content of about 11 parts by weight), 40 parts by weight of water, cationic monomer (a) aqueous solution Latemul -180 (trade name) 49 Except for making an antifouling paint by adding parts by weight (approximately 11 parts by weight of the cationic monomer to a total of 100 parts by weight of the copolymer and the cationic monomer) and 10 parts by weight of water. Various tests were conducted in the same manner as in Example 1. The results are shown in Table-1.

Claims (1)

[Claims] (1) An aqueous dispersion type antifouling paint characterized by containing a copolymer of a radically polymerizable monomer having a quaternary ammonium salt type cationic group in the molecule.