JPS62232470A - Algicidal paint composition - Google Patents

Abstract

PURPOSE:To provide an algicidal paint which contains no harmful material and has excellent storage stability, by mixing an aq. emulsion of an anionic resin with a specified cationic surfactant and a nonionic surfactant or an ampholytic surfactant. CONSTITUTION:100pts.wt. (on a solid basis) aq. emulsion of an anionic resin (A) (e.g., an aq. emulsion of an ethyl acrylate/styrene copolymer resin) is mixed with 10-40pts.wt. algicidal agent (B) composed of a cationic surfactant of the formula (wherein R is methyl or ethyl; R<1> is an 8-18C alkyl; and X is Cl, Br or I) (e.g., dodecyl.trimethylammonium chloride), 20-50pts.wt. nonionic surfactant (e.g., polyoxyethylene alkyl ether) and/or ampholytic surfactant (C) and 0-15pts.wt. plasticizer (D) (e.g., dibutyl phthalate) to obtain the desired algicidal paint compsn.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applied to fibers of ships, water tanks, drainage ditches, joist ropes, filters, etc., buildings, etc., and is dried to coat these surfaces with algae-proofing agents. The present invention relates to a coating composition capable of forming a film.

[Prior art and problems]

BACKGROUND ART It has been conventionally known to prevent the growth of algae by forming a coating film containing the algae-preventing agent bistributyltin oxide (TBTO) on the surfaces of ships, fishing nets, and drainage ditches.

However, bitributyltin oxide is toxic to the human body.According to a chemical environmental survey report published by the Environment Agency in 1981, it was found to be found in wild fish in 14 out of 42 areas, including major ports and bays, at a maximum concentration of 0.48 ppm. The company is sounding the alarm because it contains organic tin.

Additionally, since fishing nets are impregnated with anti-algae paint every year, there was concern that the organic tin powder that was present in the nets during this process could be inhaled into the human body. .

[Purpose of the invention]

The present inventor has discovered that among cationic surfactants,
We have discovered that graded amines have a function as an algaecide.

However, when using an aqueous resin emulsion that poses no environmental health problems as a binder, the aqueous resin aqueous emulsion is usually obtained by emulsion polymerization of vinyl monomers in the presence of an anionic surfactant such as sodium dodecylbenzenesulfonate. Since it has anionic properties, if this cationic surfactant is added, it may cause gel formation or separation, resulting in poor storage stability.

The present invention provides an anti-algae coating composition with excellent storage stability.

[Failure to solve the problem]

That is, the present invention provides: Component (4): 100 parts by weight of the solid content of the anionic resin aqueous emulsion Component (B): A cationic surfactant represented by the general formula [wherein R is -CH3 or -C2Hs] and these may be the same or different: R' has 8 carbon atoms
~18 alkyl group; X is -α, -Br, -I
] 10 to 40 parts by weight (Component Q: nonionic surfactant and/or amphoteric surfactant
20-50 parts by weight 0 component: Plasticizer 0-15 parts by weight (4) above,
The present invention provides an anti-algae coating composition containing components (B), C) and 0 in the above proportions.

In the presence of an aqueous resin emulsion of component (4) as a binder, an anionic surfactant such as hinyl monomer, sodium tof-sylbenzenesulfonate, sulfuric half ester of p-nonylphenol, and calcium persulfate. It is preferably obtained by emulsion polymerization at a film-forming temperature of 20° C. or lower in terms of on-site drying properties.

The vinyl monomer is propyl methacrylate (Tg
81℃), styrene (100℃), acrylonitrile (
100℃), methyl methacrylate (105℃), methacrylic acid (130℃), itaconic acid (130℃), acrylamide (153℃), 2-ethylhexyl acrylate (Tg-85℃), n-butyl acrylate ( -54℃)
, ethyl acrylate (-22℃), isopropylacrylate/-(-5℃), 2-ethylhexyl methacrylate (
-5°C), n-propyl acrylate (8°C), n-butyl methacrylate (20°C), vinyl acetate (30°C), t-butyl acrylate (45°C), 2-hydroxyethyl methacrylate (55°C), °C), ethyl methacrylate (65 °C
), isobutylene methacrylate (67°C), vinyl chloride (79°C), vinylidene chloride (-18°C), ethylene, etc. can be used alone or in combination of two or more (the numbers in parentheses indicate these The glass transition point of a vinyl homopolymer is 61).

The type and amount of these monomers to be used are determined by considering the usage temperature of the resulting emulsion and using the glass transition point of the resulting resin as a guide. For example, when using an anti-algae coating composition at room temperature (20°C), the glass transition point of the emulsion resin is selected to be between -65°C and +30°C. When forced drying (60 to 200°C), the resulting aqueous emulsion resin may have a glass transition point of +40 to 180°C.

As a vinyl monomer component, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, etc.
Using 1 to 3 weight 70 is useful for increasing the adhesion of the anti-algae coating to the adherend (wood, concrete, metal). Preferred emulsions include (a) 40 to 80% by weight of lower alkyl acrylate (alkyl group has 1 to 6 carbon atoms) ester, (b) 20 to 50% by weight of styrene, and (c) unsaturated carboxylic acid θ~ An example is an emulsion polymerization solution with 3-weight polymer.

The emulsion resin has a particle size ranging from O.OS to 1 micron, and an emulsion resin having a concentration of 20 to 55% by weight is usually used.

(6) A cationic surfactant having an ingredient algaecide effect and represented by the following formula [wherein R is -CHa or -Ct Hs, which may be the same or different <:R ' is an alkyl group having 8 to 18 carbon atoms; X is -α, -Br, -
A halogen atom selected from I] includes decylφtrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, octadecenyltrimethylammonium chloride, Alkyl trimethyl ammonium chloride such as octadecagenyl trimethyl ammonium chloride [The product name is 1 Alucard from Lion Akzo ■, and the grade number is 12-50.16-50.18-50, C-50
, 5-50, T-50, etc.]; Part or all of the methyl groups of the alkyl trimethyl ammonium chloride are replaced with ethyl groups; The alkyl trimethyl ammonium chloride or the alkyl - Triethylammonium chloride in which the chloride is replaced with another halogen group such as bromine or iodine can be used.

Other cationic surfactants, such as dodecyl dimethyl benzylammonium chloride and dioctadecyl
Dimethylammonium chloride, didodecyl dimethylammonium chloride, dihexadecyl dimethylammonium chloride, polyoxyethylene tallow alkylamine, and the like have no algae-preventing effect or impair the storage stability of the coating composition.

The cationic surfactant of component 0 (6) is not compatible with anionic surfactants, and when sodium dodecylbenzenesulfonate, sodium stearate, etc. are added, it undergoes double decomposition and precipitates as an insoluble salt. do.

In order to prevent this double decomposition, nonionic surfactants or amphoteric surfactants are used.

As the nonionic surfactant, mineral oil, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, polyoxyethylene rubitan alkyl ester, etc. can be used.

As the amphoteric surfactant, betaine type surfactants with bactericidal properties are preferred, such as Lion's Enadicol CN.
S (product name) and Obazoline 552 from Toho Chemical Industry■,
662Y (all product names).

As a plasticizer for adjusting the texture of the film, heptatalic ester compounds such as dibutylbenzyl phthalate (BB
P), dibutyl phthalate) (DBP) and chlorinated paraffin can be used.

Other optional ingredients In addition to the above ingredients, (6), 0 and 0 ingredients, antifoaming agents, anti-settling agents, flow regulators, antifreeze agents, lower alcohols, pigments, dyes, fillers, wetting agents, water repellents A hand control agent, a crosslinking agent, a pI control agent, etc. may be added.

Composition The coating composition of the present invention is composed of 10 parts of the cationic surfactant as the component (6) and 2 parts per 100 parts by weight of the solid content of the resin emulsion as the component (4).
The plasticizer component (p) is used in an amount of 0 to 50 parts by weight and 0 to 15 parts by weight.

If the amount of component (B) used is less than 10 times, the anti-algae effect will be small. On the other hand, if the amount is 40 parts by weight, the strength of the film will be low and it is not practical. That is, in order to improve storage stability, C
It should be noted that the amount of nonionic surfactant used as component () also increases in proportion to the increase in cationic surfactant.

(If the amount of component (0) used is less than 20 parts by weight, the coating composition will lack storage stability. Conversely, if it exceeds 50 parts by weight, the strength of the film will be low and it is not practical. Preferably, component (6) 1 weight part Component (0) is used in an amount of 0.5 to 1 part by weight.

Component 0 is added as necessary. However, if more than 15 parts by weight is used, the film becomes sticky, which is not preferable.

To prepare the composition, add the cationic compound of component (B) directly to the resin emulsion of component (4), which will cause aggregation. After mixing the agent and water, the cationic compound (Component (2)) is added while stirring.

Application The coating composition of the present invention can be diluted with water if necessary and applied to adherends such as ropes, filters, nets, U-shaped grooves, ships, joists, etc. by dipping, roll coating, spray painting, etc. It dries and forms a film. The amount of paint is
It is used so that the solid content is 15 to 300 t/-.

Embodiments Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts and percentages in the examples are based on weight unless otherwise specified.

Examples 1 to 25, Comparative Examples 1 to 12, Reference Example 1 Room-temperature crosslinking type acrylic acid alkyl ester/styrene copolymer resin aqueous emulsion 1 Acronal YJ-2720D'' (product name, film forming temperature 6℃
, solid content concentration 50%) were blended with the nonionic surfactant, amphoteric surfactant, water, and plasticizer dibutyl phthalate shown in Table 1, and then mixed with Lion Akzo's alkyl trimethyl while stirring. Ammonium Chloride 1 Alucard 5-50" (trade name, alkyl group (R carbon number is hexadecyl (C16) is i.

%, 10% octadecyl (C1B), 35% octadecenyl (01B), and 45% octadecagenyl (exe)) were blended in the proportions shown in the table to prepare a coating composition.

This paint composition was applied to the inner surface of the U-shaped groove in a solid content of 509/W.
? After applying it so that it became like this, and letting it air dry, it was left for 3 days.

This U-shaped groove is installed in a place where treated wastewater discharged from factory wastewater treatment equipment is washed by seawater.
The presence or absence of algae growth was observed during the three months from October 2010 to January 1961.

Table 1 shows the storage stability of the coating composition and the presence or absence of algae growth.

Also, instead of Alucard 5-50, Alucard 12 which is alkyl trimethyl ammonium chloride
-50, Alucard 16-50, Alucard T-5
0 Nidialkyl dimethylammonium chloride Alucard 2C-75, Alucard 2I (T-7
5. Alucard S-2C-50:) "7" sildimethylbenzylammonium chloride; The same table also shows the results when the aliphatic amine polyoxy-14=ethylene ether was used.

The types of nonionic surfactants in the table are as follows.

Liponox: Polyoxyethylene alkyl ether emulsion manufactured by Lion■ Marken: Ethylene oxide adduct of nonylphenol manufactured by Kao ■Dopanox 25I Ethylene oxide adduct of higher alcohol manufactured by Nilion ■ (blank below)

Claims (1)

[Claims] 1), Component (A): 100 parts by weight of anionic resin aqueous emulsion solid content (B) Component: Cationic surfactant represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ agent [wherein R is -CH_3 or -C_2H_5,
These may be the same or different; R' is an alkyl group having 8 to 18 carbon atoms; X is 1Cl, -Br
, -I] 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 An anti-algae coating composition comprising the above components (A), (B), (C) and (D) in the above proportions. 2), the cationic surfactant of the component (B) is mixed with the nonionic and/or amphoteric surfactant of the component (C) at a weight ratio of 1:1 (0.5 to 0.5). 1) The anti-algae coating composition according to claim 1, characterized in that it is blended in the ratio of 1).