JPS6381177A - Coating compound composition for preventing alga - Google Patents

Abstract

PURPOSE:To obtain the titled composition having improved compatibility and shelf stability, by blending a specific quaternary amine with a specific amount of an aqueous emulsion of an anionic resin having an amount of COOH group based on alpha,beta-unsaturated carboxylic acid limited to a specific range. CONSTITUTION:(A) 100pts.wt. aqueous emulsion of an anionic resin of a copoly mer containing 1.4X10<-3>-1.8X10<-2>mol COOH group based on alpha,beta-unsaturated carboxylic acid is blended with (B) 5-20pts.wt. cationic surface active agent shown by the formula (R is CH3 or C2H5; R' is 8-18C alkyl; X is Cl, Br or I) and (C) 0-15pts.wt. plasticizer (e.g. phthalic ester compound, etc.) to give the aimed composition. The component A, for example, is obtained by subjecting a mixture of 0.1-1.3wt% alpha,beta-unsaturated carboxylic acid, 40-55wt% 2-8C alkyl acrylate, 30-55wt% monomer such as methyl methacrylate, etc., and 1-10wt% vinyl monomer such as N-phenylmaleimide, etc., to emulsion polymeri zation.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to ships, water tanks, drainage ditches, joist ropes, filters and other fibers, buildings, etc. The present invention relates to a coating composition capable of forming a film of.

[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, bistributyltin oxide is toxic to the human body, and according to a chemical environmental survey report published by the Environment Agency in 1981, it was detected in natural 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.

Furthermore, since fishing nets are repeatedly impregnated with algae-proofing paint every year, there has been concern that the organic tin powder remaining on the nets during this process may 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 the function of algae-preventing agents.

However, when using an aqueous resin emulsion containing a carboxyl group that poses no environmental health problems and has good adhesion to adherends such as fishing nets as a binder, the aqueous resin emulsion is usually sodium dodecylbenzenesulfonate. It is obtained by emulsion polymerization of vinyl monomers in the presence of anionic surfactants such as, and because it has anionic properties, when this cationic surfactant is blended, there are problems such as formation of gel or separation. Yes, it has poor mixing stability and storage stability.

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

[Specific measures to solve the problem]

In the present invention, carboxyl groups (-C
OOH) abundance from 1.4 x 10-” to 1.8 x
By keeping the amount within the 10-" molar range, gelation does not occur even when an anionic resin aqueous emulsion is mixed with a cationic quaternary amine that has an anti-algae effect, and
To provide an anti-algae coating composition that does not cause viscosity change or gelation even during storage for one week in an atmosphere at .degree.

That is, the present invention provides (component A: carboxyl group based on α, β-unsaturated carboxylic acid (-
Anionic resin aqueous emulsion of a copolymer containing COOH) in a ratio of 1.4 x 10 = ~ 1.8 x 10 mol 100 parts by weight (solid content) of component (B) cationic interface represented by the general formula Activator [In the formula, R is -CH or -C2H, which may be the same or different]; R' is a carbon number of 8
~18 alkyl group: X is -C), -B'%
It is a halogen atom selected from I]
5 to 20 parts by weight Component (C): Plasticizer 0 to 15 parts by weight (4) above
, 03), and an anti-algae coating composition in which component (C) is blended in the above ratio.

(4) Component The aqueous anionic resin emulsion of component (4) as a binder has 1.4 carboxyl groups based on α,β-unsaturated carboxylic acid in the resulting copolymer, for example (a) α , β-unsaturated carboxylic acid 0.1 to 1.3% by weight (b) Acrylic acid alkyl ester (alkyl group has 2 to 8 carbon atoms) 40 to 55% by weight (C) From methyl methacrylate, styrene and acrylonitrile 30-55% by weight of selected monomers (d) N-phenylmaleimide, N-methylolacrylamide, acrylamide, methacrylamide, 2-
Vinyl monomer mixture 100 selected from hydroxyalkyl acrylate (alkyl group has 2 to 4 carbon atoms) and has a weight coefficient ratio of 1 to 10! The amounts are 0.1 to 5 parts by weight of anionic emulsifier and 0 to 5 parts by weight of nonionic emulsifier.
It is obtained by emulsion polymerization using a polymerization catalyst such as calcium persulfate in the presence of 5 parts by weight. This emulsion preferably has a film-forming temperature of 20° C. or lower in terms of on-site drying properties.

By the way, α, which improves adhesion to adherends such as fishing nets and U'$ grooves,! -Unsaturated carboxylic acids (including their anhydrides)
Examples of carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, etc., but as a result of the study in the present invention, the amount of carboxylic acid greatly affects miscibility and storage stability. The amount of carboxyl groups based on α, β-unsaturated carboxylic acid occupied is 1.4 × 10−3 to 1
．． 8 x 10-" moles.

Component (b), acrylic acid alkyl ester, is a soft monomer that provides readability to the film, and includes ethyl acrylate, inglovir acrylate, n-butyl acrylate, t-butyl acrylate, n-propyl acrylate, and 2-acrylic acid. Ethylhexyl etc. are used.

Component (C), methyl methacrylate, acrylonitrile, or styrene, is a hard monomer that imparts toughness to the film, and some of these may be replaced with ethyl methacrylate, inglovir methacrylate, or isobutyl methacrylate.

The component (d), a vinyl monomer having 10H groups, -00NH2 groups, and methylol groups, is used to impart adhesion to base materials such as fish nets and concrete.

The emulsion resin has a particle size of 0.05 to 1 micron, and an emulsion resin having a concentration of 20 to 55% by weight is usually used.

The stability of anionic resin aqueous emulsions usually decreases due to the mixing of cations and ions, but the invention of the previous application (Patent Application No. 61-75991) improves the stability of mixing with a cationic emulsifier, which is a cation and ion. Therefore, the objective was achieved by blending a large amount of a nonionic emulsifier or an amphoteric active agent, but the size and amount of the nonionic or amphoteric emulsifier and the mixing thereof are limited.

In the present invention, as a result of repeated studies on a method of directly mixing cations and ions without using additive stabilizers, we have found that by limiting the content of 1000H (carboxylic acid group) in the copolymer, You can achieve that purpose.

Furthermore, depending on the type of unsaturated acid, carboxyl groups are said to be mainly distributed inside the copolymer particles in the emulsion or on the surface of the particles, but depending on the amount, the miscibility stability at the time of addition differs, but it is accelerated by heating. As a result, it was confirmed that gelation occurred.

Also, in a previous report (Japanese Patent Application No. 1982-75991), there is an effect of using a nonionic emulsifier in combination, but since the amount of nonionic emulsifier used in a normal anionic emulsion is about 1/10 of this amount, the effect can be ignored. In the present invention, there is no need to add an amphoteric emulsifier.

This anionic resin aqueous emulsion needs to have a total amount of carboxyl groups in the copolymer of 1.8 x 10 moles or less in order to prevent gelation when mixed with the quaternary amine of component (1). By the way, depending on the type of acid, the particle surface &
Naturally, internal distribution should occur, but approximately 1
．． It has been observed that beyond 9 x 10 moles of carboxylic acid, the composition thickens and gels in an accelerated 50°C test, rendering it unusable, even though it does not exhibit gelation upon incorporation of the cationic emulsifier. Ta. Also, the carboxyl group is 1
．． 4 x 10-” moles or more (0.1 in terms of acrylic acid)
Morti] was selected in consideration of the balance of adhesion of the film to the substrate, mechanical stability, viscosity stability during acceleration, etc.

■) A cationic surfactant represented by the following formula having an ingredient algaecide effect [wherein R is -CH, or -C, H, which may be the same or different; R' has 8 carbon atoms
- is an alkyl group of engineering 8; X is -(J, -Br, -
A halogen atom selected from I] includes decyl trimethylammonium chloride, dodecyl trimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, octadecenyltrimethylammonium chloride, Alkyl, such as octadecadenyltrimethylammonium chloride,
Trimethylammonium chloride (as a free product, from Lion Akzo■, the product name is "Alucard", the grade number is 12-50.16-50.18-50, C-5)
0,5-50, 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 trimethyl ammonium chloride or It is possible to use triethylammonium chloride in which the chloride is replaced with another halogen group such as bromine or iodo.

This component CB) is present in an amount of 5 to 20 parts by weight (in terms of solid content) based on ioo parts by weight of resin solid content of the emulsion of the prisoner component. If it exceeds 20 parts by weight, it is not preferable because the water resistance of the film decreases and the amount of component (B) flows out at the beginning of use.

Do other cationic surfactants, such as dodecyl dimethyl-benzylammonium chloride, dioctadecyl dimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride, and polyoxyethylene tallow alkylamine, have no algae-preventing effect? , the storage stability of the coating composition is impaired.

(As a plasticizer for adjusting the texture of the Q component film, phthalate ester compounds such as dibutylbenzyl phthalate (BB
P), dibutyl heptalate (DBP) and chlorinated paraffin can be used.
Antifoaming agents, anti-settling agents, flow control agents, antifreeze agents, lower alcohols such as methanol, ethanol, and inglobil alcohol, pigments, dyes, fillers, wetting agents, water repellents, texture control agents, crosslinking agents, I) A H regulator, a drying accelerator, a base penetration enhancer, etc. may be added.

Composition The coating composition of the present invention contains 10 to 40 parts by weight, preferably 20 to 30 parts by weight of a cationic surfactant as component (B), based on 100 parts by weight of the solid content of the resin emulsion as the carrier component. (The plasticizer as component Q is used in a proportion of 0 to 15 parts by weight.

If the amount of component CB) used is less than 10 parts by weight, 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.

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

The composition may be prepared by adding the cationic compound of component (4) directly to the resin emulsion of component (4);
4) After mixing the components (Q component plasticizer and water), (
It is preferable to add the cationic compound of component B) with 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 3001/-.

It can also be used as an anti-mold coating material for indoor baths, etc.

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

Emulsion production example 1 Temperature controller, anchor stirrer, reflux condenser, supply container,
The following raw materials were charged into a reaction vessel equipped with a thermometer and a nitrogen introduction chamber.

200 parts of water 35% aqueous solution of the sodium salt of the sulfuric acid half ester of p-nonylphenol (anionic emulsifier) reacted with 20 moles of ethylene oxide 5 parts 20 parts of p-nonylphenol (nonionic emulsifier) reacted with 25 moles of ethylene oxide 20 parts of solution.

Next, after purging the inside of the reaction vessel with nitrogen gas, 10% of the following feed 1 was added, and the mixture was heated to 90°C.

Feed I Water 200 parts 35 parts aqueous solution of the anionic emulsifier 25 parts
Methyl methacrylate 195 parts n-butyl acrylate 189 parts Acrylic acid 8 parts Acrylamide 8 parts.

Additionally, after charging 10% of 2.5 parts of potassium persulfate dissolved in 85 parts of water (Feed ■) into the container, the remaining feed 1 and 40% of Feed ■ were added. The material was fed into the container over a period of 3.5 hours, and after the feeding was completed, the material was kept at the same temperature for 2 hours to polymerize the anionic resin aqueous emulsion.

Examples 2 to 9 Anionic resin aqueous emulsions were obtained in the same manner as in Example 1, except that the composition of the vinyl monomer was changed as shown in Table 1.

(Leaving space below) Examples 1 to 10, Comparative Examples 1 to 7 To 100 parts of the anionic resin aqueous emulsion (solid content concentration 50%) obtained in the above-mentioned artificial examples 1 to 9, the water and plasticizer shown in Table 2 were added. After blending dibutyl phthalate, with stirring, Lion Akzo's alkyl trimethyl ammonium chloride 1 Alucard S-50" (trade name, the number of carbon atoms in the alkyl group (R) is hexadecyl (CJ is 10
A coating composition was prepared by blending 10% of octadecyl (C1g), 35% of octadecenyl (C1,), and 45% of octadecagenyl (Cts) in the proportions shown in the table.

Apply this coating composition to the inner surface of the U-shaped groove at a solid content of 50y/y.
r? It was applied in a circular motion, allowed to dry naturally, and then 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 two-month period from June 2007 to August 1961. Storage stability of paint compositions (○: good, ×: poor) The presence or absence of algae growth is shown in Table 1.

Also, instead of Alucard 5-50, Alucard 12 which is alkyl trimethyl ammonium chloride
-50, Alucard 16-50° Alucard 'l'
-50; Alucard 2C-75, Alucard 2HT- which is dialkyl-dimethylammonium chloride
75, Alucard S-2C-50 Nidodecyldimethylbenzyl ammonium chloride; The results when using polyoxyethylene ether of aliphatic amine are also shown in the same table.

(Margin below)

Claims (1)

[Scope of Claims] 1), Component (A): 1.4×10^-^3 to 1 carboxyl group (-COOH) based on α,β-unsaturated carboxylic acid
．． Anionic resin aqueous emulsion of copolymer containing 8×10^-^2 mol 100 parts by weight of solid content Component (B): A cation represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ surfactant [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 a halogen atom selected from -Cl, -Br, and -I] 5 to 20 Parts by weight Component (C): Plasticizer 0 to 15 parts by weight An anti-algae coating composition comprising the above components (A), (B), and (C) in the above proportions. 2) The antialgal coating composition according to claim 1, wherein the α,β-unsaturated carboxylic acid is a compound selected from acrylic acid, methacrylic acid, and itaconic acid. 3), the copolymer of component (A) consists of (a) 0.1 to 1.3% by weight of α,β-unsaturated carboxylic acid (b) acrylic acid alkyl ester (the number of carbon atoms in the alkyl group is 2 to 8) ) 40-55% by weight (c) 30-55% by weight of a monomer selected from methyl methacrylate, styrene, acrylonitrile (d) N-phenylmaleimide, N-methylolacrylamide, acrylamide, methacrylamide, 2-hydroxy 100 parts by weight of a vinyl monomer mixture consisting of 1 to 10% by weight of vinyl monomers selected from alkyl acrylates (alkyl group has 2 to 4 carbon atoms), 0.1 to 5 parts by weight of an anionic emulsifier and a nonionic emulsifier. 0~
The anti-algae coating composition according to claim 1 obtained by emulsion polymerization in the presence of 5 parts by weight.