KR100891889B1 - High solid type antifouling coating - Google Patents

Abstract

(Problem) Provides high-solid anti-pollution paint with excellent anti-pollution and coating performance and in response to environmental and resource saving requests.

(Resolution) In the acrylic resin side chain, the formula (1)

로 표시되는 기, n 은 0 또는 1, Y 는 탄화수소, M 은 금속, m 은 금속 M 의 원자가-1 로 표시되는 정수, A 는 일염기산의 유기산 잔기를 나타냄)(Where X is

N is 0 or 1, Y is a hydrocarbon, M is a metal, m is an integer represented by the valence-1 of the metal M, A represents an organic acid residue of a monobasic acid)

An antifouling paint containing a metal-containing acrylic resin varnish having one or more groups represented by the above, wherein the metal-containing acrylic resin varnish has a solid content of 40% by weight or more, a viscosity at 25 ° C. of 18 poises or less, and the contamination prevention The paint is an antifouling paint, characterized in that the organic solvent content (VOC) is 400 g / l or less.

High Solid Antifouling Paint

Description

HI SOLID TYPE ANTIFOULING COATING

The present invention relates to an antifouling paint containing a metal-containing acrylic resin, and more particularly to a high solid antifouling paint containing a metal-containing acrylic resin.

Marine life such as barnacles, mussels, and algae tends to be attached to ships and other underwater structures, thereby causing problems such as disturbing efficient operation of ships and causing fuel waste. In order to prevent the adhesion of living organisms to these ships and other underwater structures, coating of the antifouling paint on the surface thereof is usually carried out. Representative antifouling paints conventionally used include matrix antifouling paints in which rosin is blended with vinyl resins, alkyd resins, and the like, which are insoluble in seawater. However, since the antifouling agent is eluted with rosin in seawater, this paint cannot be expected to have stable antifouling properties for a long time, and since the insoluble resin portion remaining in the coating film forms a skeleton structure, particularly in ships When applied, it has the drawback that the resistance of seawater and an application surface increases, and a speed fall etc. are caused.

In recent years, among the antifouling paints, hydrolytic antifouling paints have been widely used for their excellent advantages such as being able to exhibit antifouling properties over a long period of time, and as one of them, paints containing metal-containing resin compositions have been developed. Japanese Patent Laid-Open No. 62-101653, Japanese Patent Laid-Open No. 63-128008, Japanese Patent Laid-Open No. 63-128084 and Japanese Patent Laid-Open No. Hei 8-73536 of the present applicant have a pendant acidic monobasic organic acid. The metal containing resin which forms the salt with a metal atom together with its manufacturing method is disclosed. When this resin is used for an antifouling paint, the resin is gradually hydrolyzed in seawater to release metal ions with antifouling properties, at the same time, the resin itself is solubilized and starts to dissolve gradually, and exhibits a self-polishing effect.

By the way, since solvent type paints generally used as paints pollute the environment in terms of volatilizing a large amount of organic solvents in the air, they are regulated globally, and are high solid paints and water based paints as environmentally compatible paints. And powder coating materials have been developed. However, in the above-mentioned antifouling paint, there was no paint which reduced the content of the organic solvent and highly compatible both antifouling properties and coating performance.

An object of the present invention is to provide a high solids antifouling paint, which is excellent in antifouling and coating performance, and in response to requests for environmental and resource saving.

The present invention, in the acrylic resin side chain, the formula (1)                     

[Formula 1]

로 표시되는 기, n 은 0 또는 1, Y 는 탄화수소, M 은 금속, m 은 금속 M 의 원자가-1 로 표시되는 정수, A 는 일염기산의 유기산 잔기를 나타냄)(Where X is

N is 0 or 1, Y is a hydrocarbon, M is a metal, m is an integer represented by the valence-1 of the metal M, A represents an organic acid residue of a monobasic acid)

An antifouling paint containing a metal-containing acrylic resin varnish having one or more groups represented by the above, wherein the metal-containing acrylic resin varnish has a solid content of 40% by weight or more, a viscosity at 25 ° C. of 18 poises or less, and the contamination prevention The paint is an antifouling paint, characterized in that the organic solvent content (VOC) is 400 g / l or less.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The antifouling paint of the present invention has an organic solvent content (VOC) of 400 g / l or less. When it exceeds 400 g / L, it may not fall into the category of the high solid type paint in which the organic solvent content is regulated, and there exists a possibility that it may adversely affect an environment. Preferably, it is 350 g / l or less.

The antifouling paint of the present invention contains a metal-containing acrylic resin varnish.

In the present invention, in order to reduce the organic solvent content of the antifouling paint to 400 g / l or less, it is necessary to use the metal-containing acrylic resin varnish as having a solid content of 40% by weight or more and a viscosity at 25 ° C of 18 poises or less. have. If solid content is less than 40 weight%, the antifouling paint obtained cannot be made into a high solid type. When the solid content is 40% by weight or more, if the viscosity at 25 ° C exceeds 18 poises, in addition to poor handling and workability, the viscosity may be too high. There is a need and a high solid paint cannot be obtained.

The metal containing acrylic resin contained in the said metal containing acrylic resin varnish has one or more groups represented by the said Formula (1) in an acrylic resin side chain.

The said metal containing acrylic resin can be easily manufactured by any of the following methods, for example. That is, (1) a method of polymerizing an unsaturated organic acid monomer and other unsaturated monomers to react an acrylic resin obtained with a metal compound and a monobasic acid, or reacting a metal salt of the acrylic resin obtained with a monobasic acid, or ( 2) a method of polymerizing a metal-containing unsaturated monomer and other unsaturated monomers obtained by reacting an unsaturated organic acid monomer with a metal compound and a monobasic acid or by reacting an unsaturated organic acid monomer with a metal salt of a monobasic acid. . In view of the introduction rate of the metal salt of the monobasic acid and the yield of the resulting metal-containing acrylic resin, and the like, after polymerizing an unsaturated organic acid monomer and other unsaturated monomers to obtain an acrylic resin, the acrylic resin is reacted with a metal compound and a monobasic acid. Or the method of (1) which makes this acrylic resin and metal salt of monobasic acid react.

In addition, as in Japanese Unexamined Patent Publication No. 63-128008, a metal salt of a low boiling point organic basic acid having a boiling point of 20 ° C. or more lower than the boiling point of the monobasic acid and having a boiling point of 100 to 240 ° C. is used as the metal compound. It is also possible to manufacture by heating-reacting the metal salt of organic basic acid, the said acrylic resin, and the said monobasic acid, and removing the low boiling point organic basic acid out of a system.

As Y in the said Formula (1), if it is a hydrocarbon, it will not specifically limit, For example, the residue in the case of adding dibasic acids, such as a phthalic acid, succinic acid, maleic acid, to an unsaturated organic acid monomer is mentioned. That is, the metal containing acrylic resin of n = 1 can introduce X containing Y by adding the said dibasic acid to unsaturated monobasic hydroxyalkyl ester, copolymerizing this, and obtaining resin, or making resin into It can be obtained by introducing the dibasic acid in the production or after production.

As said unsaturated organic acid monomer, what contains 1 or more of carboxyl groups is mentioned, For example, Unsaturated monobasic acids, such as (meth) acrylic acid; Unsaturated dibasic acids such as maleic acid and monoalkyl esters thereof, itaconic acid and monoalkyl esters thereof, and monoalkyl esters thereof; Unsaturated monobasic hydroxy such as maleic acid adduct of 2-hydroxyethyl (meth) acrylate, phthalic acid adduct of 2-hydroxyethyl (meth) acrylate, and succinic acid adduct of 2-hydroxyethyl (meth) acrylate And dibasic acid adducts of alkyl esters. In addition, in this specification, (meth) acrylic acid means methacrylic acid and acrylic acid.

As said other unsaturated monomer, it is (meth) acrylic acid ester, for example, methyl (meth) acrylate, ethyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Alkyl (meth) acrylate having 1 to 20 carbon atoms in ester parts such as i-butyl acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate Ester; Hydroxyl-containing (meth) acrylic-acid alkylester whose C1-C20 ester part, such as 2-hydroxypropyl (meth) acrylic acid and 2-hydroxyethyl (meth) acrylic acid; (Meth) acrylic-acid cyclic hydrocarbon esters, such as phenyl (meth) acrylate and cyclohexyl (meth) acrylate; (Meth) acrylic acid polyalkylene glycol esters such as (poly) ethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate having a polymerization degree of 2 to 10; And (meth) acrylamides, in addition to alkoxyalkyl (meth) acrylates having 1 to 3 carbon atoms; Vinyl compounds such as styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl benzoate, vinyltoluene and acrylonitrile; And crotonic acid esters; And diesters of unsaturated dibasic acids such as maleic acid diesters and itaconic acid diesters. The ester portion of the acrylate esters is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Preferably, they are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate. The said unsaturated organic acid monomer and said other unsaturated monomer may respectively be used independently, and may use 2 or more types together.

It is preferable that the acrylic resin which comprises the said metal containing acrylic resin, ie, the acrylic resin obtained by superposing | polymerizing the said unsaturated organic acid monomer and the said other unsaturated monomer, has an acid value of 90-250 mgKOH / g. If it is less than 90 mg KOH / g, the amount of the metal salt which binds to a side chain will be small, and pollution prevention property may be inferior. If it exceeds 250 mg KOH / g, the elution rate will be too fast and antifouling effect will be expected over a long period of time. In addition to this, the viscosity of the resulting metal-containing acrylic resin varnish increases, which may not be a high solid antifouling paint.

It is preferable that the glass transition temperature of the acrylic resin which comprises the said metal containing acrylic resin is 5 degrees C or less. When it exceeds 5 degreeC, the viscosity of the metal containing acrylic resin varnish obtained may increase, and it may not be able to set it as a high solid antifouling paint. The acid value and the glass transition temperature are both design values and can be obtained from the monomer composition.

About the kind and compounding ratio of the said unsaturated organic acid monomer and the said other unsaturated monomer, it can select so that the acid value and glass transition temperature of the acrylic resin obtained from these monomers may become the said range. Preferably, it is a case where acrylic acid or its derivative is used as a main component as unsaturated organic acid monomer and other unsaturated monomer. The said main component means using acrylic acid or its derivative in the ratio of 60 weight% or more, Preferably it is 80 weight% or more, More preferably, it is 90 weight% or more with respect to the total amount of an unsaturated organic acid monomer and other unsaturated monomers.

Although it does not specifically limit as said metal compound, For example, metal oxide, hydroxide, chloride, a sulfide, basic carbonate, the metal salt of the said low boiling point organic basic acid, etc. are mentioned. The said metal compound may be used independently and may use 2 or more types together. As a metal in the said metal compound, it can select from 3A-7A, 8, 1B-7B group elements in a long-term periodic table. Especially, a bivalent metal is preferable, More preferably, they are copper and zinc.

It is preferable that the said metal is contained 0.3-20 weight% in the said acrylic resin solid content. If the amount of the metal salt is less than 0.3% by weight, elution in the resin is very slow. If it exceeds 20% by weight, the elution rate is too fast. More preferably, it is 0.5-15 weight%.

As said monobasic acid, a bulky monobasic acid is preferable, and it is preferable that an acid value is less than 200 mg KOH / g and 190 mg KOH / g or less. If it is 200 mg KOH / g or more, a high solid antifouling paint may not be obtained.

As said monobasic acid, if acid value is less than 200 mgKOH / g, it will not specifically limit, A monobasic cyclic organic acid is preferable from a viewpoint of long-term contamination prevention property and crack resistance of a coating film. It does not specifically limit as said monobasic cyclic organic acid, For example, there exists a thing which has cycloalkyl groups, such as naphthenic acid. Moreover, resin acids, such as tricyclic resin acid, and salts thereof are preferable, It does not specifically limit as such tricyclic resin acid, For example, the monobasic acid etc. which have a diterpene-type hydrocarbon backbone etc. are mentioned, Such a Examples of the compound include compounds having abiethane, pimaran, isopymaran, and Rabdan each skeleton, and for example, abietinic acid, neoabietinic acid, dehydroabietinic acid, hydrogenated abietinic acid, par Lastrin acid, fimaric acid, isopimaric acid, levopimaric acid, dextrosemaric acid, sandaracopimaric acid, etc. are mentioned. Among them, abietinic acid, hydrogenated abietinic acid, and salts thereof are preferable because hydrolysis is appropriately performed, and in addition to excellent long-term contamination prevention, as well as excellent crack resistance and availability of the coating film. .

The monobasic cyclic organic acid does not need to be highly purified, and for example, rosin, pine resin, etc. may be used, and for example, rosin, hydrogenated rosin, partial rosin, fire And equalized rosin. The rosin mentioned here is gum rosin, wood rosin, tall oil rosin and the like. Rosin, hydrogenated rosin, partial rosin, and disproportionated rosin are preferable because they are inexpensive, easy to obtain, have excellent handleability, and exhibit long-term contamination prevention.

The said monobasic acid may be used independently and may use 2 or more types together.

As a metal salt of the said monobasic acid, what is obtained by making the said metal compound and the said monobasic acid react beforehand is mentioned.

Although the reaction performed when manufacturing the said metal containing acrylic resin can be performed by a conventionally well-known method, It is preferable to perform heating, stirring, etc. at the decomposition temperature of a metal salt below.

It is preferable that the weight ratio based on solid content of the said monobasic acid and the acrylic resin which comprises a metal containing acrylic resin, ie, the acrylic resin obtained by superposing | polymerizing an unsaturated organic acid monomer and other unsaturated monomers, is 0.9: 1.1-1.2: 0.8. When the compounding quantity of the said monobasic acid is less than the said range, a metal ester bond may generate | occur | produce between resins, and a viscosity rise and gelation may occur, and even if it is too high than the said range, it will not change and it is not economical.

In addition, in the manufacturing method of the said metal containing acrylic resin, in the case of the said method (2), the weight based on solid content of an acrylic resin means the total weight of the unsaturated organic acid monomer and other unsaturated monomer which comprise an acrylic resin. It is.

It is preferable that the said metal containing acrylic resin is 20-60 in average polymerization degree. If it is less than 20, film-forming property may be inadequate, and a crack, peeling, etc. may be produced, and when it exceeds 60, the viscosity of a varnish may rise and a high solid antifouling paint may not be obtained.

The said average degree of polymerization can be calculated | required based on the degree of polymerization of polystyrene from the number average molecular weight obtained by polystyrene conversion by gel permeation chromatography.

The metal-containing acrylic resin thus obtained can be prepared with an antifouling paint by adding a conventional additive containing an antifouling agent. This antifouling paint is a hydrolysis antifouling paint having self-polishing property.

In order to adjust the physical property of a coating film and the consumption rate of a coating film, the antifouling paint of this invention can contain other binder resin other than the said metal containing acrylic resin. It is preferable that the said other binder resin contains the weight ratio [metal containing acrylic resin]: [other binder resin] based on resin solid content with respect to metal containing acrylic resin in 100: 0-30: 70. When the ratio of the said other binder resin exceeds the said range, it is unpreferable since it cannot maintain the outstanding long-term contamination prevention property and the crack resistance of a coating film.

As said other binder resin, for example, chlorinated paraffin, polyvinyl ether, polypropylene sebacate, partially hydrogenated terphenyl, polyvinyl acetate, poly (meth) acrylic acid alkyl ester, polyether polyol, alkyd resin, polyester resin, Polyvinyl chloride, silicone oil, wax, petrolatum, liquid paraffin, rosin, hydrogenated rosin, naphthenic acid, fatty acids, and divalent metal salts thereof.

Since the other binder resin can obtain a high solid antifouling paint easily, it is preferable that solid content which does not contain a solvent is 100 weight%.

When the said other binder resin contains a solvent, it is preferable that average polymerization degree is 60 or less. When it exceeds 60, a high solid antifouling paint may not be obtained.

The said antifouling paint can add the usual additives, such as an antifouling agent, a plasticizer, a pigment, a solvent, to the said metal containing acrylic resin varnish.

As said antifouling agent, a well-known thing can be used, For example, an inorganic compound, the organic compound containing a metal, the organic compound containing no metal can be used, For example, a cuprous oxide, a manganese ethylene bis dithio cover Mate, zinc dimethyl carbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea , Zinc ethylenebisdithiocarbamate, copper thiocyanide, 4,5-dichloro-2-n-octyl-3 (2H) isothiazolone, N- (fluorodichloromethylthio) phthalimide, N, N ' -Dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, 2-pyridinethiol-1-oxide zinc salt and copper salt, tetramethylthiuram disulfide, 2,4,6-trichloro Phenylmaleimide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3-iodo-2-propylbutylcarbamate, Diiodomethyl paratrisulfone, phenyl (bispyridyl) bismasdichloride, 2- (4-thiazolyl) -benzimidazole, and triphenyl boron pyridine salt. The said antifouling agent may be used independently and may use 2 or more types together.

As for the usage-amount of the said antifouling agent, 0.1-80 weight% is preferable in paint solid content. If it is less than 0.1 weight%, the antifouling effect cannot be expected, and when it exceeds 80 weight%, defects, such as a crack and peeling, may arise in a coating film. Preferably it is 1-60 weight%.

As said plasticizer, For example, Phthalic acid ester plasticizers, such as a dioctyl phthalate, a dimethyl phthalate, a dicyclohexyl phthalate; Aliphatic dibasic acid ester plasticizers such as isobutyl adipic acid and dibutyl sebacate; Glycol ester plasticizers such as diethylene glycol dibenzoate and pentaerythritol alkyl ester; Phosphate ester plasticizers, such as a triclinic diphosphate and a trichloroethyl phosphate; Epoxy plasticizers such as epoxy soybean oil and octyl epoxystearate; Organic tin plasticizers such as dioctyl tin laurate and dibutyl tin laurate; Trimellitic acid trioctyl, triacetylene and the like.

As said pigment, For example, extender pigments, such as precipitated barium, talc, clay, zinc white, silica white, alumina white, bentonite; And coloring pigments such as titanium oxide, zircon oxide, basic lead sulfate, tin oxide, carbon black, graphite, bengal, chrome yellow, phthalocyanine green, phthalocyanine blue and quinacridone.

As said solvent, For example, Hydrocarbons, such as toluene, xylene, ethylbenzene, cyclopentane, an octane, heptane, a cyclohexane, white spirit; Ethers such as dioxane, tetra hydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; Esters such as butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate; Ketones such as ethyl isobutyl ketone and methyl isobutyl ketone; Alcohol, such as n-butanol and propyl alcohol, is mentioned.

In addition to the above, other additives are not particularly limited, and examples thereof include monobasic acids such as monobutyl phthalate and monooctyl succinate, camphor and castor oil; Water binder, anti-spill agent; Color separation inhibitor; Sedimentation inhibitors; Antifoaming agents and the like.

In the antifouling paint of the present invention, for example, conventional additives such as antifouling agents, plasticizers, coating film consumption adjusters, pigments, and solvents are added to the metal-containing acrylic resin varnish, and ball mills, pebble mills, roll mills, and sand articles It can prepare by mixing using mixers, such as a line mill.

The said antifouling paint can be applied to the surface of a to-be-coated object according to a conventional method, and can form a dry coating film by volatilizing a solvent under normal temperature or heating.

As described above, the antifouling paint of the present invention contains a metal-containing acrylic resin varnish having a solid content of 40% by weight or more and a viscosity at 25 ° C of 18 poises or less, and an organic solvent content (VOC) of 400 g / l or less. to be. Such a high solid antifouling paint is, for example, (1) the average degree of polymerization of the metal-containing acrylic resin is 20 to 60, and (2) the acid value of the acrylic resin constituting the metal-containing acrylic resin is 90 to 250 mg KOH. / g, glass transition temperature is 5 degrees C or less, and the acid value of (3) monobasic acid can be obtained by one or more of things to be less than 200 mg KOH / g. The antifouling coating of the present invention is an environmentally friendly high solid type coating, and is also excellent in long-term contamination prevention and other coating film properties.

Therefore, the antifouling paint of the present invention can be suitably used for ships and underwater structures which have a strong demand for the development of high solid antifouling paints and require both coating film properties and antifouling properties. In addition, although the antifouling paint of the present invention can be used as a fishing net, the fish net is treated by immersion when the antifouling paint is applied. Therefore, in consideration of environmental aspects and in terms of coating properties, The requirements are different from ships or underwater structures.

Example

Although an Example is given to the following and this invention is demonstrated in more detail, this invention is not limited only to these Examples. Parts indicate parts by weight.

Preparation Example 1 Preparation of Acrylic Resin Varnish 1

70 g of xylene and 20 g of methyl isobutyl ketone were placed in a separate flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, and maintained at 120 ° C. To this, 12.5 g of n-butyl acrylate, 68.2 g of ethyl acrylate, 19.3 g of acrylic acid, and 2.5 g of t-butylperoxy 2-ethylhexanoate were added dropwise for 3 hours, followed by warming for 30 minutes, followed by 10 g of xylene, 0.3 g of t-butylperoxy 2-ethylhexanoate was added dropwise for 30 minutes, and then warmed for 90 minutes to give varnish 1 (number average molecular weight Mn = 3500 [average degree of polymerization 35]; solid content Tg of 50.1% by weight solid content concentration). = -12 deg. C: solid acid value = 150 mg KOH / g).

Preparation Example 2 Preparation of Acrylic Resin Varnish 2

70 g of xylene and 20 g of n-butanol were put into a separate flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, and maintained at 120 ° C. Here, 12 g of cyclohexyl acrylate, 58 g of ethyl acrylate, 26 g of acrylic acid, methacrylic acid methoxy polyethylene glycol ester (NK ester M-90G, the product made by Shin-Nakamura Chemical Co., Ltd.), and (alpha), (alpha) '-azobisiso 3.5 g of butyronitrile were added dropwise for 3 hours, kept warm for 30 minutes, then 10 g of xylene and 0.3 g of t-butylperoxy 2-ethylhexanoate were added dropwise for 30 minutes, and then warmed for 40 minutes, Varnish 2 (number average molecular weight Mn = 3000 [average degree of polymerization 30]; solid content Tg = -24 deg. C; solid acid value = 200 mg KOH / g) was obtained at a solid content concentration of 50.3% by weight.

Preparation Example 3 Preparation of Acrylic Resin Varnish 3

75 g of xylene and 15 g of n-butanol were put into a separate flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, and maintained at 115 ° C. 49.4 g of ethyl acrylate, 28.3 g of acrylic acid, 8.2 g of methoxyethyl acrylate, 14.1 g of cyclohexyl acrylate, and 2.5 g of α, α'-azobisisobutyronitrile were added dropwise thereto for 3 hours, followed by warming for 30 minutes. , 10 g of xylene, and 0.3 g of t-butylperoxy 2-ethylhexanoate were added dropwise for 30 minutes, and then warmed for 30 minutes to give varnish 3 (number average molecular weight Mn = 4500 [average of molecular weight 49.7% by weight). Polymerization degree 45], solid content Tg = -18 degreeC, solid content acid value = 220 mg KOH / g).

Preparation Example 4 Preparation of Acrylic Resin Varnish 4

75 g of xylene and 15 g of n-butanol were put into a separate flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, and maintained at 115 ° C. To this, 35 g of methyl methacrylate, 28 g of acrylic acid, 37 g of ethyl acrylate, 2.5 g of α, α'-azobisisobutyronitrile were added dropwise for 3 hours, and kept warm for 30 minutes, followed by 10 g of xylene, 0.3 g of t-butylperoxy 2-ethylhexanoate was added dropwise for 30 minutes, and then warmed for 30 minutes to prepare varnish 4 (number average molecular weight Mn = 4700 [average degree of polymerization 47]; solid content Tg) at a solid content concentration of 49.8% by weight. = + 40 ° C .: solid acid value = 220 mg KOH / g).

Preparation Example 5 Preparation of Acrylic Resin Varnish 5

50 g of xylene and 15 g of n-butanol were put into a separate flask equipped with a stirrer, a nitrogen inlet tube and a cooling tube, and maintained at 95 ° C. To this, 35 g of butyl acrylate, 28 g of acrylic acid, 37 g of ethyl acrylate, and 1.2 g of α, α'-azobisisobutyronitrile were added dropwise for 3 hours, and after being kept warm for 30 minutes, xylene 10 g, t- 0.3 g of butylperoxy 2-ethylhexanoate was added dropwise for 30 minutes, then warmed for 90 minutes, and then 25 g of xylene were added. Varnish 5 (number average molecular weight Mn = 11000 [average degree of polymerization 110]; solid content Tg = -14 ° C; solid acid value = 220 mg KOH / g) was obtained at a solid content concentration of 49.8% by weight.

Preparation Example 6 Preparation of Metal-Containing Acrylic Resin Varnish 6

In a separate flask equipped with a stirrer, a nitrogen inlet tube, a decanter and a cooling tube, 100 g of the varnish 1 obtained in Production Example 1, 47 g of WW rosin (acid value 160 mg KOH / g), 26.6 g of copper acetate monohydrate, 120 g of xylene was added to the mixture, the temperature was raised to the reflex temperature, and the mixed solvent of acetic acid, water and solvent flowing out was removed, and the reaction was carried out for 8 hours while replenishing the same amount of xylene, and 100 g of the solvent was further distilled off. Thereafter, 10 g of n-butanol and xylene were added to adjust the solid content concentration to 50% by weight. The viscosity at 25 degreeC was 12 poise. Let this be varnish 6.

Preparation Example 7 Preparation of Metal-Containing Acrylic Resin Varnish 7

100 g of varnish 2 obtained in Preparation Example 2 instead of varnish 1, 62 g of hydrogenated rosin (acid value 160 mg KOH / g) and 36 g of copper acetate monohydrate instead of WW rosin were used in the same manner as in Production Example 6. The varnish 7 was obtained. The viscosity in 25 degreeC was 15 poises.

Preparation Example 8 Preparation of Metal-Containing Acrylic Resin Varnish 8

100 g of varnish 3 obtained in Production Example 3 instead of varnish 1, 38 g of hydrogenated rosin instead of WW rosin and 30 g of NA-165 (naphthenic acid; acid value 165 mg KOH / g) manufactured by Daiwashi Kogyosha Co., Ltd. A varnish 8 was obtained in the same manner as in Production Example 6 except that 37 g of zinc acetate monohydrate was used instead. The viscosity at 25 degreeC was 17 poises.

Preparation Example 9 Preparation of Metal-Containing Acrylic Resin Varnish 9

Instead of the varnish 1, 100 g of varnish 4 obtained in Production Example 4, 68 g of WW rosin, 5 g of NA-200 (acid value 200 mg KOH / g) manufactured by Daiwa Yushi Kogyo Co., and 39 g of copper acetate monohydrate were used. A varnish 9 was obtained in the same manner as in Production Example 6 except that the solid content concentration was adjusted to 40 wt%. The viscosity in 25 degreeC was 24 poises.

Preparation Example 10 Preparation of Metal-Containing Acrylic Resin Varnish 10

The solid content concentration was the same as in Production Example 6, except that 100 g of the varnish 5 obtained in Production Example 5, 65 g of Daiwashi Kogyo Co., Ltd. NA-200 and 39 g of copper acetate monohydrate were used instead of the varnish 1. Varnish 10 was obtained by adjusting to 40 weight%. The viscosity at 25 degreeC was 26 poises.

Preparation Example 11 Preparation of Metal-Containing Acrylic Resin Varnish 11

Varnish 11 was obtained like Example 6 except having used 24 g of versatic acids (acid value 320 mg KOH / g) instead of WW rosin, and adjusting so that solid content concentration might be 40weight%. The viscosity at 25 degreeC was 30 poise.

Examples 1-6, Comparative Examples 1-3

Using varnishes 6-11 obtained in the manufacture examples 6-11 and the other components shown in Table 1, the coating material was prepared by mixing by high speed disper. In addition, the viscosity of the coating material was adjusted by adding xylene so that it became 80-90 KU using the Stormer viscometer (25 degreeC). In addition, although the viscosity of a coating material is 100 KU or less, coating is possible, but it set it as 80-90 KU which is a range more suitable for coating. VOC was calculated | required from the solvent amount and specific gravity in the obtained coating material. The results are shown in Table 1.

Example Comparative example One 2 3 4 5 6 One 2 3  Varnish 6 50 40  Varnish 7 55 46  Varnish 8 60 50  Varnish 9 40  Varnish 10 36  Varnish 11 40  Cuprous oxide 39 35 22 32 34 25 35  Zinc white 25 3 3 30  Triphenylboron 7 6  Zinc pyrithione 5 4 6 3 5 5 5  Copper pyrithione 3 4  rosin 10 4  Hydrogenated Rosin 5 10  Colloidal silica 2 2 2 2 2 2 2 2 2  Titanium oxide 2 2 2 3  Cyanine blue 3 4 4  Bengala 4 3 4 3 5 4  Chlorinated Paraffin 2 2 3  Xylene 20 16 14 100 100 100 100 100 100 100 100 100  importance 1.4 1.2 1.2 1.2 1.3 1.3 1.4 1.3 1.4  Solvent 25 27.5 30 25 23 20 44 39 38  VOC 350 330 360 300 299 260 616 489 532  Viscosity (KU) 80 85 85 80 90 90 90 85 90

Using the coating material obtained in Examples 1-6, the coating film state and long-term contamination prevention property were evaluated in accordance with the following evaluation method.

(evaluation)

Coating state

The said coating composition was apply | coated so that it might become a dry thickness of 300 micrometers on the blast board which apply | coated the antirust paint previously, and it left to stand indoors for 2 days and nights, and obtained the test board. The test plate was mounted on a cylindrical side surface having a diameter of 750 mm and a length of 1200 mm, and rotated continuously for six months at 15 knots in seawater. The state of the coating film of the test plate after 6 months was visually observed and the coating film state was evaluated.                     

Long-term pollution prevention

The test plate after observing the coating film state as described above was subjected to a biological adhesion test on a test raft installed at the Nippon Paintinsha Sea Research Institute in Tamano, Okayayama, to evaluate contamination resistance. For 24 months from the start of raft immersion, the proportion of the adherent organism's coating area was 0%, indicating good antifouling properties.

In Examples 1-6, the high solid type antifouling paint of 400g / L or less of VOC was obtained, and also long-term antifouling property and the outstanding coating film state were shown.

Since the coating material of the comparative example 1 had a high Tg of an acrylic resin, the viscosity of a metal containing acrylic resin varnish became high and it was not possible to make the antifouling coating high-solid. Since the coating material of the comparative example 2 had a high average polymerization degree of resin, the viscosity of a metal containing acrylic resin varnish became high and it was not possible to make the antifouling paint into a high solid form. Since the paint of the comparative example 3 used versatic acid with the high acid value of monobasic acid, the viscosity of a metal containing acrylic resin varnish became high and it was not possible to make a high solid type antifouling paint.

Since the antifouling paint of the present invention is of a high solid type, it is environmentally friendly and has excellent long-term antifouling property and coating film properties. Therefore, it can be used suitably for ships and underwater structures.

Claims (7)

In the acrylic resin side chain, the formula (1) [Formula 1]

(Where X is

N is 0 or 1, Y is a hydrocarbon, M is a divalent metal, m is an integer represented by the valence of metal M-1, A represents an organic acid residue of a monobasic acid) As antifouling paint containing metal-containing acrylic resin varnish which has one or more groups represented by The metal-containing acrylic resin varnish has a solid content of 40% by weight or more, a viscosity at 25 ° C of 18 poises or less, The antifouling paint is an antifouling paint, characterized in that the organic solvent content (VOC) is 400 g / ℓ or less. The antifouling paint according to claim 1, wherein the metal M is copper or zinc. The antifouling paint according to claim 1 or 2, wherein the metal-containing acrylic resin has an average degree of polymerization of 20 to 60. The antifouling paint according to claim 1 or 2, wherein the acrylic resin constituting the metal-containing acrylic resin has an acid value of 90 to 250 mg KOH / g and a glass transition temperature of 5 ° C or less. The antifouling paint according to claim 1 or 2, wherein the monobasic acid has an acid value of less than 200 mg KOH / g. The antifouling coating according to claim 1 or 2, wherein the weight ratio based on the solid content of the monobasic acid to the acrylic resin constituting the metal-containing acrylic resin is 0.9: 1.1 to 1.2: 0.8. The weight ratio based on the resin solid content with respect to a metal containing acrylic resin [Binder-containing acrylic resin]: [binder resin] is less than 100: more than 0:30:70 in any one of Claims 1-5. The antifouling paint to contain.