WO2006006415A1

WO2006006415A1 - Hydrophilic resin composition for coating material and coating material containing the resin composition dispersed therein

Info

Publication number: WO2006006415A1
Application number: PCT/JP2005/012067
Authority: WO
Inventors: Takao Shimizu; Masakazu Nishiyama
Original assignee: Kuraray Co., Ltd
Priority date: 2004-07-08
Filing date: 2005-06-30
Publication date: 2006-01-19
Also published as: TW200606227A

Abstract

A hydrophilic resin composition which contains an isothiazoline antifouling agent and can prevent, over long, aquatic organisms from adhering. The hydrophilic resin composition preferably contains a fibrous ingredient comprising polyvinyl alcohol fibers at least 60 wt.% of which have a skin-core structure and which have a core proportion of 50% or higher, a fiber fineness of 0.1-30 dtex, and a fiber length of 3 mm or shorter, have the antifouling agent deposited thereon in an amount of 10 wt.% or larger based on the fibers, and have an antifouling-agent retention after cleaning with xylene of 80% or higher. Also provided are: a self-abrasivecoating fluid for underwater structures which contains the hydrophilic resin composition dispersed therein; and a coating film.

Description

Specification

Patent application title: Hydrophilic resin composition for coating material and coating material in which the resin composition is dispersed

TECHNICAL FIELD [0001] The present invention relates to a paint having an effect of preventing aquatic organisms from sticking to a ship bottom and an underwater structure used in contact with seawater or fresh water for a long period of time.

More preferably, it is a coating fiber that can carry a large amount of solvent-soluble antifouling agent and can be released slowly, especially for ship bottoms and underwater structures that are used in contact with seawater or fresh water for a long time. The present invention relates to a fiber useful for a paint having an effect of preventing adhesion of aquatic organisms over a long period of time.

Background art

[0002] As structures that are used in contact with seawater or fresh water for a long period of time, for example, ships, power plant cooling water intake channel facilities, subsea oil field drilling facilities, seaside industrial plants, port facilities, bridges, etc. There are fishery materials such as structures, fishery nets, fish nets for cultured fishery products, ship buoys, light buoys, mooring buoys, and civil engineering materials such as pollution prevention curtains. While these structures are in contact with seawater for a long period of time, they adhere to the surface of marine organisms, for example, algae such as guasa diatoms, coelenterates such as sea anemone, sponges such as isocaimen, annelids such as kuzumagokai, Tentacles such as bryozoans, molluscs such as mussels, arthropods such as barnacles, protozoa such as sea squirts, etc. are attached and inhabited, and the original functions of these structures cannot be fully achieved. A problem arises.

[0003] Conventionally used methods for preventing the attachment of aquatic organisms to structures that have been in contact with seawater or fresh water for a long period of time include triptyl tin oxide, triflate-rutin oxide. This is a method of treating materials and products with organic tin compounds such as oral oxide, triphenyltin acetate, and triphenyltin chloride. However, the method using these antifouling agents has a harmful effect accompanied by severe unpleasant odors and irritating odors during the processing operation, and these undesired drugs accumulate in the body of fish and shellfish and cause problems such as malformation and death. In recent years, it has been clarified that the adverse effects on the human body ingesting it are also significant, and it has been banned worldwide. Accordingly, there is a need for a new technology that can replace such organic tin compounds with such a great deal of harmful effects.

[0004] As one of such new technologies, a method of treating a product with a non-tin organic compound such as a urea compound, a benzimidazole compound, a benzothiazole compound, a thiophthalimide compound, or a sulfopyridine compound. (See, for example, Patent Documents 1 to 3.) o These organic compounds have been widely used as agricultural chemicals' bactericides and antifungal agents, and they are used against aquatic organisms. Is an attempt. However, it has been pointed out that all of them are not effective as an underwater antifouling agent, and are difficult to decompose in the environment, so that the same obstacles as organic tin compounds may be generated in the future.

[0005] By the way, it has been conventionally required that a medicinal component such as a fragrance, an antifouling agent, an insect repellent, a fungicide, a poultice, or the like is sustainedly released to maintain a certain effect over a long period of time. Countermeasures such as adjustment of the molecular weight of the component and introduction of functional groups, or loading a medicinal component into a microcapsule, have been made.

However, when medicinal ingredients are used in a solvent system, particularly in the case of paints, sufficient measures have not yet been taken.

[0006] Patent Document 2 has a description example regarding 4,5-dichloro-2-n-octylisothiazolin-3-one, which is one of the antifouling agents used in the present invention. The antifouling agent is extremely low toxic to the human body, which has a high antifouling effect on a variety of organisms attached to water tanks, and immediately after the antifouling action is completed, it is immediately decomposed into a completely nontoxic substance. It is clear to do. However, when an antifouling agent contained in a solvent-based paint is applied to an underwater structure and dried to form an antifouling coating film, it is effective when initially put into the sea. There is a problem that the antifouling component is eluted or removed from the coating film in a relatively short period of time, and the effect of preventing aquatic organism adhesion is lost. This is because the antifouling agent is easily soluble in organic solvents, so that the antifouling agent also moves to the surface of the coating film as the solvent moves to the surface when the coating film dries. This is because it is not uniform. As means for solving this problem, a sustained release composition according Porifueno one Louis匕合product has been proposed (e.g., see Patent Document 4.) ₀ teeth However, the organic solvent-based paints to be applied to underwater structures If used, the antifouling agent will migrate to the surface of the coating, and the problem that the effect of preventing the attachment of aquatic organisms will disappear in a short period of time can be solved. Not come.

As described above, paints using non-tin organic compounds, which have a high aquatic organism adhesion prevention effect and have sufficient sustainability, can be obtained in both fisheries and civil engineering fields. ,is the current situation.

[0007] Patent Document 1: Japanese Patent Laid-Open No. 5-139919

Patent Document 2: JP-A-7-69815

Patent Document 3: Japanese Patent Laid-Open No. 8-295829

Patent Document 4: Japanese Patent Laid-Open No. 11-12103

Disclosure of the invention

Problems to be solved by the invention

[0008] An object of the present invention is to provide a paint capable of preventing the adhesion of aquatic organisms over a long period of time when the antifouling agent is uniformly present in the coating film when applied to a structure used in contact with seawater or fresh water. More preferably, by providing a drug carrier suitable for a solvent-based paint having excellent chemical solution retention after xylene washing, that is, excellent sustained release of medicinal ingredients and long-term antifouling properties. is there.

Means for solving the problem

That is, the present invention relates to a hydrophilic resin composition containing a compound having an antifouling property, and preferably the compound having an antifouling property is a compound represented by the following general formula (1): The above-mentioned hydrophilic resin composition, which is a complex compound of a metal salt or an amine salt.

[0010] [Chemical 1]

In the general formula, Y represents a hydrogen atom, an alkyl group, a alkenyl group, or an aralkyl group, R represents a hydrogen atom, a halogen atom, or an alkyl group, and R ′ represents a hydrogen atom, a halogen atom, or an alkyl group. R and R 'may combine to form a benzene ring.

[0011] Further, the present invention is preferably the above-described hydrophilic rosin composition in which the hydrophilic resin is polybulal alcohol-based rosin, and more preferably, the hydrophilic resin has a fiber component of 60 wt% Z. It is a hydrophilic resin composition for paints, characterized by having a polybulal alcohol strength higher than that of fibers and satisfying all of the following 1) to 3).

1) The fiber has a skin core structure and the core ratio is 50% or more,

2) The fineness of the fiber is 0.1 to 30dtex, the fiber length is 3mm or less,

3) The antifouling agent component according to claim 2 is supported by 10% by weight Z fiber or more, and the antifouling agent retention rate after washing with xylene represented by the following formula is 80% or more,

Antifouling agent retention after xylene cleaning = (Antifouling agent retention after cleaning Z Antifouling agent retention before cleaning) X 100 (%)

[0012] And, the present invention relates to a method for producing a hydrophilic resin composition for paints, characterized by impregnating the fiber cut to 3 mm or less in a solution in which a drug component is dissolved in methanol. More preferably, a coating film-forming binder is contained, and the coating film-forming binder is the above-described coating liquid and coating film having self-polishing properties, and is formed by coating the above-described coating liquid with water. It relates to structures.

The invention's effect

[0013] When a paint in which the antifouling hydrophilic rosin composition of the present invention is dispersed is applied, migration of the antifouling agent to the solvent is prevented to prevent elution, for example, adhesion of aquatic organisms over a long period of time. It is possible to provide ships, underwater structures, fisheries and civil engineering materials that can be prevented. BEST MODE FOR CARRYING OUT THE INVENTION

[0014] The hydrophilic rosin composition of the present invention is obtained by solidifying and gelling a water-soluble polymer compound as a rosin component, and is obtained by polybulal alcohol (hereinafter abbreviated as PVA), sodium polytalylate. , Synthetic water-soluble polymer compounds such as polyethylene glycol and polyethyleneimine, and natural waters such as alkali metal alginate, carrageenan, mannan and chitosan Soluble polymer polysaccharides can be used, but they have many hydroxyl groups that are not only excellent in mechanical performance and chemical resistance, but other molecules due to intermolecular and intramolecular hydrogen bonding. PVA resin having a large barrier effect against water is preferably used. Since the PVA resin has a polymer structure as described above, it is excellent in sustained release of a substance incorporated in the polymer. Therefore, by dispersing the PVA resin composition containing the antifouling agent, a coating film having excellent antifouling effect can be obtained.

[0015] The PVA-based resin preferably used in the present invention is a resin containing a vinyl alcohol-based polymer. It does not matter if it contains other polymers or other components. However, in terms of the physical performance of the resin and the sustainability of the antifouling effect, the content of the butyl alcohol polymer is 60% by mass or more ZPVA, especially 80 to: LOO% by mass ZPVA. A preferred butyalcohol-based polymer constituting the hydrophilic resin of the present invention is not particularly limited as long as it has a butyal alcohol unit as a main component, and may have other constituent units. Examples of such comonomers include olefins such as ethylene, propylene, and butylene, acrylic acid and its salts and acrylic esters such as methyl acrylate, methacrylic acid and its salts, methacrylic esters such as methyl methacrylate, and acrylamide. , N Acrylamide derivatives such as methyl acrylamide, Methacrylamide, Methacrylamide derivatives such as N-methylol methacrylamide, N-Burpyrrolidone, N-Burformamide, N-Buramide such as N-Buracetoamide, Polyalkyleneoxide side chain Butyl ethers such as methyl butyl ether, -tolyls such as atari mouth nitrile, halogenated burs such as butyl chloride, maleic acid and salts thereof, anhydrides or esters thereof, and the like. The method for introducing the modified unit may be a copolymerization method or a post-reaction introduction method.

[0016] For example, when an ethylene butyl alcohol copolymer is used as the butyl alcohol-based polymer, the barrier properties of rosin can be further enhanced. When ethylene is copolymerized, the crystal form of the ethylene unit and the bull alcohol unit are similar, and the crystallinity of the PVA is unlikely to decrease, so the content of the bull alcohol unit is reduced. However, excellent performance is maintained.

However, point force sustained mechanical performance and antifouling effect of榭脂composition also includes bi - Ri force of alcohol units used Bulle alcohol polymer of 80-100 mole ^_0/0 preferred.

[0017] There are no particular limitations on the degree of hatching or degree of polymerization of the vinyl alcohol-based polymer constituting the hydrophilic resin composition, but from the viewpoint of ensuring the durability of water resistance, mechanical performance, antifouling performance, etc. It is preferable that the acidity is 90 mol% or more, particularly 95 mol% or more, more preferably 98 mol% or more, and more preferably 99 to 100 mol%, and the degree of polymerization is 500 or more, particularly 1000 or less. Furthermore, 1300 or more is preferable. If the degree of polymerization is 20000 or more, it is difficult to produce industrially with the current technology, so a degree of polymerization of 20000 or less is practically used.

[0018] The hydrophilic rosin composition of the present invention contains a compound having a basic structure represented by the following general formula (1) (hereinafter sometimes simply referred to as "antifouling agent"). Being good! In the general formula (1), Y represents a hydrogen atom, an alkyl group, an alkenyl group, or an aralkyl group. The alkyl group is preferably a methyl group, butyl group, hexyl group, octyl group, nor group, dodecyl group or the like. In addition, a alkenyl group having 2 to 18 carbon atoms such as a bur group and an isopropyl group is preferred. The aralkyl group is preferably an aralkyl group having 7 to 10 carbon atoms such as a benzyl group, a phenethyl group, or a 4-methoxybenzyl group. R represents a hydrogen atom, a halogen atom or an alkyl group, and R ′ represents a hydrogen atom, a halogen atom or an alkyl group. The halogen atom in R and R ′ is preferably chlorine, bromine, fluorine or the like. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group. R and R 'may combine to form a benzene ring.

[0019] [Chemical 2]

[0020] Specific examples of such compounds include 2-methyl-4 isothiazoline-3-one, 2-methyl-5chloro 4-isothiazoline-3-one, 1,2 benzoisothiazolin-3one, 2 --N—Octylisothiazoline-3one, 4,5 Dichloro 2-n—octylisothiazoline-3-one, etc. From the standpoint of preventing attachment of aquatic organisms, R and R 'are halogen atoms. It is desirable that Y is an alkyl group having 1 to 9 carbon atoms, and 4,5-di-2-n-oct-4-isothiazolin-3-one is the most preferred compound.

[0021] These compounds include zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc acetate, copper chloride, copper bromide, nickel chloride, calcium chloride, magnesium chloride, iron chloride, manga chloride. May be combined with metal salts such as sodium chloride, sodium chloride and barium chloride, and amine salts such as salt ammonium and other amine chlorides to form complex compounds. .

[0022] Polybulal alcohol (hereinafter abbreviated as PVA) that is suitably used as the hydrophilic resin composition of the present invention is not only excellent in various performances such as mechanical performance and chemical resistance, but also in hydroxy acid. It is suitable for the purpose of the present invention, which has a large number of groups and has a large noria effect on solvent molecules due to intermolecular and intramolecular hydrogen bonding. In particular, the component constituting the fiber that is preferably used as a fiber cannot obtain desired performance if it is mainly composed of strong PVA.

Specifically, it is preferably composed of PVA fibers of 60 wt% Z fibers or more, preferably 80 wt% Z fibers or more and 100 wt% Z fibers or less.

[0023] PVA fibers preferably used in the present invention preferably have a skin core structure and a core ratio of 50% or more. The antifouling agent supported on the fiber is a low crystalline In order to carry more antifouling agent, it is preferable that the ratio of the core portion is high.

Here, the core ratio is the ratio of the cross-sectional area of the core layer to the cross-sectional area of the fiber and is defined by the following equation.

Core ratio = (core layer cross-sectional area Z cross-sectional area of the entire fiber) X loo (%)

The cross-sectional area of the entire fiber includes both the skin layer and the core layer. Further, in the measurement, the cross section of the fiber is observed with an optical microscope, and the portion where the light is well transmitted and visible is defined as the skin layer, and the portion which is transmitted and appears dark is defined as the core layer. Depending on the manufacturing method, the difference in skin core structure may not be discernable, but in some cases it cannot be discriminated! / In this case, it is assumed that the core layer does not exist (core ratio 0%).

[0024] For the purpose of mixing the fibers into the paint, it is preferable that the fineness of the fibers is 0.1 to 30 dtex and the fiber length is 3 mm or less. Those having a fineness of less than 0. ldtex are difficult to disperse in the paint and it is difficult to produce fibers. When the fineness is 30dtex or more, the uniformity of the paint and coating film is poor. More preferably, it is 1 to 15 dtex. When the fiber length is 3 mm or more, it is difficult to mix into the paint, preferably 2 mm or less, more preferably 1 mm or less and 0.1 mm or more. Furthermore, since the penetration of the antifouling agent into the fiber also causes a cutting end face force, a shorter fiber length is advantageous in that the treatment can be performed in a shorter time.

[0025] On the other hand, the larger the amount of the antifouling agent supported, the smaller the amount of the fiber of the present invention can be used. In particular, in the case of a paint, the operability during coating and the coating film can be thinned. There is an advantage. Accordingly, the loading rate is preferably 10% by weight or more, more preferably 20% by weight or more, more preferably 25% by weight or more and 40% by weight or less.

[0026] Next, the chemical solution retention after xylene cleaning in the fiber of the present invention will be described. When PVA fibers that simply carry an antifouling agent are added to solvent-based paints, the antifouling component on the fiber surface is extracted into the solvent and migrates to the surface of the coating as the solvent dries. Arise.

The main purpose of the present invention is to prevent the extraction by the solvent, and the degree of the anti-extraction is expressed by the antifouling agent retention after the xylene cleaning. Specifically, an operation of positively extracting the fiber carrying the antifouling agent by immersing it in xylene at 65 ° C with a bath ratio of 100 for 5 hours is expressed by the following formula.

(Anti-fouling agent loading after washing Z Anti-fouling agent carrying rate before washing) X 100 (%) To suppress extraction of anti-fouling agent components with solvent, anti-fouling agent retention after xylene washing is 80% or more Preferably, it is 90% or more and 100% or less.

[0027] The fiber which is a preferred form of the present invention may contain a force PVA-based copolymer of PVA and other monomers or other components. However, it is preferable that the PVA content is 60% by weight, 7 fibers or more, especially from the viewpoint of the physical performance of the fat and the durability of the antifouling effect. 80 ~: L00% by weight Z fibers are preferred. Examples of the copolymerizable monomer include olefins such as ethylene, propylene, and butylene, acrylic acid and salts thereof and acrylic esters such as methyl acrylate, methacrylic acid and salts thereof, and methacrylic esters such as methyl methacrylate. Acrylamide derivatives such as acrylamide and N-methylacrylamide, methacrylamide such as methacrylamide and N-methylolmethacrylamide

Derivatives, N-Burpyrrolidone, N-Burformamide, N-Buramides such as N-Buracetoamide, Aryl ethers having polyalkyleneoxide in the side chain, Bul ethers such as methyl bull ether, Acrylonitrile, etc. Tolyls, halogenated butyls such as butyl chloride, maleic acid and its salts or anhydrides and their esters;

[0028] In addition to copolymerization, it is also possible to mix different components into the spinning dope and perform spinning. In order to increase the impregnation efficiency of the antifouling agent, that is, the degree of swelling with methanol, water-soluble polymers such as polyacrylic acid, starch, polybulurpyrrolidone, polyacrylamide or derivatives thereof, glycerin, ethylene glycol, sorbitol, pentaerythritol It is effective to add alcohols such as the above or derivatives such as ethylene oxide attached to the spinning dope.

On the other hand, it is also possible to promote the adsorption of the antifouling agent by adding a porous inorganic material such as silica, activated carbon or zeolite.

In addition, inorganic materials such as calcium carbonate, aluminum hydroxide and titanium oxide are used as the raw material for spinning. When mixed and spun into the liquid, fine voids are formed on the surface of the fiber, which facilitates the penetration of the phenol and, as a result, increases efficiency. This effect can also be expected for porous inorganic materials such as silica, activated carbon and zeolite.

[0029] For example, when an ethylene monobutyl alcohol copolymer is used as the butyl alcohol-based polymer, the barrier property of rosin can be further enhanced. When ethylene is copolymerized, the crystal morphology of the ethylene unit and the bull alcohol unit are similar, and the crystallinity of PVA is unlikely to deteriorate, so that even if the content of the bull alcohol unit is small, excellent performance is achieved. Retained.

However, the point forces sustained mechanical performance and antifouling effect of榭脂composition also includes bi - Ri force of alcohol units used Bulle alcohol polymer of 80-100 mole ^_0/0 preferred.

[0030] Although there is no particular limitation on the degree of polymerization and degree of polymerization of PVA, the degree of chaininess is 95 mol% or more from the viewpoint of ensuring water resistance, mechanical performance, durability of antifouling performance, etc. Furthermore, it is preferable that the degree of polymerization is 500 or more, particularly 1000 or more, more preferably 1300 or more and 5000 or less for the same reason that it is preferably 98 mol% or more, and further 99-: LOO mol%.

[0031] The fiber which is a preferred form in the present invention is advantageous in that it has a non-uniform structure in the cross-sectional direction, that is, a so-called skin core structure. A remarkable effect can be expected for fibers having a core ratio of 50% or more. It is estimated that the low crystallinity core portion swells easily with methanol, and the antifouling agent dissolved in methanol is infiltrated and adsorbed.

In addition, the fiber shape when immersed in a methanol bath of the drug is preferably cut short. This is because the antifouling agent easily penetrates from the cut end face. Specifically, as described above, the fiber length is preferably 3 mm or less, more preferably 2 mm or less, and even more preferably 1 mm or less and 0.1 mm or more. If it is 3mm or more, it will be difficult to mix in the paint.

[0032] The method for producing a fiber having a strong skin core structure is not particularly limited, but a general method, that is, a solution in which PVA is dissolved in water is used as a spinning dope and has a coagulating ability such as a nozzle cap. Extruded into a bath by wet or dry wet method, solidified, wet-stretched and dried according to a conventional method • Obtained by the method of dry heat stretching 'heat treatment. The concentration of the spinning dope may be adjusted as appropriate according to the polymerization of the PVA, but if it is a general one having a polymerization degree of 1500 to 2000, it is easy to adjust with 13 to 18% by weight Z fiber. The lower the concentration, the higher the core ratio at which a skin core structure can be easily formed.

As a bath having coagulation ability, a sodium sulfate bath is generally used, but ammonium sulfate, kenate or the like may be used. The closer these salts are to saturation, the better the coagulability.

Usually, the strength of the acetalization treatment is applied after the dry heat stretching 'heat treatment to supplement the water resistance. To facilitate the subsequent treatment with a methanol solution of the drug, a higher degree of swelling is preferred. If it is desirable to dissolve in water for the purpose of use, do not perform the acetalization process, but provide only the minimum required water resistance.

[0033] The above-mentioned minimum required water resistance means that the salt having a dehydrating ability attached to the fiber can withstand washing and drying. It is desirable that such salts be removed by washing in any of the steps before being immersed in the methanol solution of the drug.

Specifically, there are a method of passing through a washing tank before drying, or a method of washing and drying after dry heat stretching and heat treatment, but the latter is preferable because there is less concern about sticking and high production efficiency. .

Next, the method for applying the antifouling agent used in the present invention will be exemplified below.

A fiber having a fiber length of 3 mm or less as described above is immersed in a solution in which the antifouling agent is dissolved in methanol, and the fiber is swollen with methanol to allow the antifouling agent to penetrate into the fiber. The reason for using methanol is that methanol is a good solvent widely for various chemicals, and has a moderate affinity for PVA fibers, which involves destruction of fiber structures such as sticking and dissolution. This is because it is possible to swell the PVA fiber without any problems. The concentration and temperature of the solution may be appropriately adjusted according to the solubility of the antifouling agent and the target loading amount, but the treatment can be performed in a short time in the direction of high temperature and high concentration.

In order to more efficiently infiltrate the antifouling agent, it is also effective to use a component that swells the PVA fiber. In addition to water, liquid and methanol such as glycerin, ethylene glycol, sorbitol, and pentaerythritol Compatible polyhydric alcohols, boric acid and form Aldehydes and the like can also be used as swelling agents. The blending ratio of these components should be set as appropriate so long as it does not inhibit the solubility of the antifouling agent, and does not cause excessive swelling of the PVA fiber or dissolution! / 溶解.

[0035] In general, an antifouling agent that easily enters sebum tends to ooze out from sebum (in the present invention, PVA fiber), that is, tends to bleed out. Strength In the present invention, in particular, when a PVA fiber having a skin core structure is used, since the antifouling agent is adsorbed in the voids of the core layer, the bleed-out hardly occurs. It is also possible to enhance the bleed-out suppression effect by impregnating the antifouling agent and then drying or further applying heat treatment to crystallize the polymer.

[0036] After the above impregnation treatment, the antifouling agent adhering to the surface has no effect of sustained release, so it is economical to recover it by washing with a solvent. The solvent used here can be used as long as it dissolves the drug without causing the PVA fiber to swell so much, but it is the same type of solvent used for impregnation as the impregnation power, such as the recovery of antifouling agents. Methanol is preferred. At that time, it is desirable to carry out at a lower temperature than the impregnation treatment in order to prevent the extraction of the antifouling agent when the fiber swells.

[0037] The fiber of the present invention obtained in this way is suitable as an additive to a paint that expects a sustained release effect of an antifouling agent, and in particular, a ship bottom used in contact with seawater or fresh water for a long time, By applying to an underwater structure and forming a coating film, the intended effect of the present invention is exhibited.

[0038] The coating film-forming binder contained in the coating liquid of the present invention is preferably self-polishing. When the PVA fiber of the present invention containing an antifouling agent is dispersed in the coating film, the antifouling agent does not migrate to the coating surface over time, so that the antifouling agent can be stably immersed in water. In order to elute, it is preferable to use a self-polishing composition in which the film surface is slightly dissolved or disintegrated in water and always maintains a new surface in the film-forming binder.

When the self-abrasive binder is used for ship bottom paints, various rosin compositions have been proposed in order to elute cuprous oxide. For example, water-soluble rosin such as rosin-based rosin, methyl vinyl ether, N-bulurpyrrolidone, methoxyethylene glycol methacrylate, acrylamide, methyl triacetoxysilane 'methyl acrylate, 2-hydroxy acrylate copolymer, butyl triacet Such as xysilane 'methyl meta atallylate' butyl acetate copolymer Slightly hydrolyzable rosin, and copolymers and mixtures thereof are used. These binders are appropriately used as necessary, but are not particularly limited.

[0039] The organic solvent used in the coating liquid of the present invention includes aliphatic hydrocarbons such as hexane, heptane, rigging-in, and petroleum ether, and aromatic hydrocarbons such as benzene, toluene, and xylene. , Halogenated hydrocarbons such as chloroform, formaldehyde, carbon tetrachloride, dichloroethane, benzene, dichlorobenzene, ketones such as acetone, methylethylketone, methylisobutylketone, isophorone, cyclohexanone, formic acid , Fatty acids such as acetic acid and oleic acid, methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol, methylcelesolve, diethylene glycol, glycerin and other alcohols, ethyl formate, ethyl acetate, butyl acetate, jetyl carbonate, etc. -Trosation of esters, nitroethane, nitrobenzene, etc. -Tolyls such as acetonitrile, isobutyric-tolyl, pyridine, triethylamine, tertiary amines such as N, N-jetylaniline, tributylamine, N-methylmorpholine, formamide, N, N-dimethylformamide, Acid amides such as acetoamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, or mixtures thereof are used.

[0040] The thickness of the coating film formed from the paint of the present invention is not particularly limited, but in order to maintain the antifouling effect for a long time, it is preferably 10 µm or more, more preferably 50 µm or more.

[0041] In the present invention, the underwater structure means, for example, a structure, a fibrous material, a resin processed cloth, a rope, a woven fabric, a knitted fabric, a net, a non-woven structure in which at least a part of the above-mentioned coating film is coated or impregnated. Although it means a woven fabric, a film, etc., the form is not limited to these, and it is intended for all structures having various forms in which the effects of the present invention can be achieved depending on the use.

[0042] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples. In the examples of the present invention, the content of the antifouling agent in the hydrophilic rosin composition was measured by the following method.

[0043] [Anti-fouling agent content in hydrophilic rosin composition]

Take 0.1 lg of hydrophilic rosin composition sample, add 20 ml of dimethyl sulfoxide to dissolve, sample 30 ml of acetonitrile, standardize to 50 ml, and filter through a 0.45 φ filter. A sample solution was obtained. This was analyzed by high-performance liquid chromatography based on a calibration curve prepared with a standard solution for analysis prepared using 4,5-dichloro-1-n-octyl-4-isothiazolin-3-one standard substance. .

Measuring device: HPLC6A system unit (manufactured by Shimadzu Corporation)

Column: ODS column supelcosilLC—18150X

Column diameter 4.6 mm Column packing particle size 5 μm

Column temperature: 40 ° C

UV wavelength: 275nm

Mobile phase: Methanol Z distilled water (volZvol) = 80/20

Flow rate: 0.5 ml / min

Injection volume: 10 1

Holding time: 13.7 to 13.9min

[Example 1]

1) PVA with a degree of polymerization of 1700 and a degree of hatching of 99.9 mol% was dissolved in water at a concentration of 13 wt% Z fiber, and wet-spun into a 40 ° C saturated sodium sulfate bath through a 1000-hole spinning nozzle. It was taken out at a speed of / min, then stretched by 3.0 times, and further wet stretched by 1.5 times in a saturated sodium sulfate bath at 90 ° C and dried. The resulting fiber has a core ratio of 60% and a fineness of 2. Odtex.

2) Next, the salt cake adhering to this thread was washed and dried, and cut to a fiber length of 1 mm. Using this fiber as an antifouling agent, a methanol solution containing 50 wt. ⁰ / oZ fiber of 4,5 dichloro-2 n-octyl 4 isothiazoline 3-one (KATHON287T Rohm & Haas Co., Ltd.) at 60 ° C It was immersed in a bath at a bath ratio of 20 times for 6 hours, filtered and air-dried, and the antifouling agent adhering to the fiber surface was washed with methanol at 20 ° C and air-dried.

3) The antifouling agent loading of the fiber obtained in 2) above is 15% by weight Z fiber, and the antifouling agent loading measured after immersion for 5 hours in xylene at 65 ° C with a bath ratio of 100 13.8 wt% Z fiber, that is, the antifouling agent loading after xylene cleaning was 92%.

4) 30 parts by weight of water-soluble rosin methyl vinyl ether copolymer (Gardner viscosity R—S) as self-abrasive binder, dimethylacrylamide vinegar as slightly hydrolyzable rosin Disperse 60 parts by weight of the fiber obtained in 2) above in a self-polishing paint consisting of 25 parts by weight of an acid butyl methyl methacrylate copolymer, 5 parts by weight of a petiole pigment, and 60 parts by weight of xylene. It apply | coated to the acrylic board of 3mm X 50cm X 50cm. The coating thickness after drying was 200 μm.

This was submerged in the sea in Omeyama Bay, Omeyama Prefecture, and the state of aquatic organisms was regularly observed. For 24 months, organisms did not attach at all.

[Example 2]

1) PVA and DMSO with a polymerization degree of 1700 and an oxidation degree of 99.9 mol% were stirred and dissolved at 95 ° C for 10 hours to prepare a spinning dope with a PVA concentration of 20 wt%. This spinning dope was discharged through a nozzle with a hole diameter of 0.08 mmφ and a hole number of 1000 holes into a solidification bath having a methanol / DMSO ratio (weight ratio) of 70/30 and a temperature of 5 ° C. The obtained yarn was then subjected to DMSO extraction in a methanol bath substantially completely, and 4.0 times wet drawing, and a swollen yarn with an organic solvent (methanol) content of 140% by weight Z fiber. I got Shino.

2) Next, this shinoshino was used as an antifouling agent in a methanol solution containing 50% by weight of Z fiber. 4,5-Dichloro-1-n-octylu 4-isothiazoline-3-one ATHON287T manufactured by Rohm & Haas Co., Ltd. And then squeezed so that the pickup was 100% by weight / fiber and dried in hot air at 150 ° C. The dried yarn was cut into 3 mm to obtain a fiber having antifouling performance.

3) The antifouling agent loading after 3 mm cutting of the obtained fiber was 8 wt% Z fiber, and this was measured for the antifouling agent loading after dipping in 65 ° C xylene for 5 hours at a bath ratio of 100. Was 6.8 wt% Z fiber, that is, the antifouling agent loading after xylene cleaning was 85%.

4) 30 parts by weight of water-soluble rosin methylvinyl ether copolymer as a self-abrasive binder (Gardner viscosity R—S), 25 parts by weight of dimethylacrylamide butyl methyl methacrylate copolymer as a slightly hydrolyzable rosin In addition, 60 parts by weight of the fiber obtained in 2) above was dispersed in a self-polishing paint consisting of 5 parts by weight of petal pigment and 60 parts by weight of xylene, and applied to an acrylic plate having a thickness of 3 mm X 50 cm X 50 cm. . The coating thickness after drying was 200 μm.

This was submerged in the sea of Omeyama Bay in Mimei Bay, and the state of aquatic organism adhesion was regularly observed. For 15 months, the creatures did not adhere to it.

[Example 3]

1) Exactly the same treatment as in Example 1 was performed, except that 35% by weight of polyacrylic acid having a molecular weight of 5000 and 65% by weight of PVA were added to the spinning dope. The resulting fiber has an antifouling agent loading rate of 20% by weight 7 fibers, and the antifouling agent loading rate measured after immersion in xylene at 65 ° C for 65 hours at a bath ratio of 100 is 17% by weight Z fiber. That is, the antifouling agent loading after xylene cleaning was 85%.

2) In addition, 18 parts by weight of water-soluble rosin rosin as a self-abrasive binder, 35 parts by weight of N, N-dimethylacrylamide butyl methyl methacrylate copolymer as a slightly hydrolyzable resin, and 5 parts of petal pigment Disperse 60 parts by weight of the antifouling hydrophilic resin composition obtained in 2) above in a self-polishing paint consisting of 60 parts by weight of toluene and apply to an acrylic plate with a thickness of 3 mm X 50 cm x 50 cm. did. The coating thickness after drying was 200 μm.

[0047] [Example 4]

1) polymerization degree of 1750,鹼化degree 97 mole ^_0/0, 2 mol ^_0/0 both polymerized PVA and D MSO maleic anhydride for 10 hours dissolved with stirring at 90 ° C, the polymer concentration of 20 wt% of the spinning solution Was prepared. This spinning dope was discharged into a solidification bath having a methanol ZDMSO ratio (weight ratio) of 70Z30 and a temperature of 10 ° C through a nozzle having a hole diameter of 0.16 mmφ and a hole number of 1500 holes. Next, the obtained shinoshino was subjected to DMSO extraction in a methanol bath substantially completely, and 3.0 times wet stretching was performed to swell the organic solvent (methanol) content to 140 wt% Z fiber. I got Ishinoshino.

2) Then the Itoshino, 4 as an antifouling agent, 5-dichloro-one 2-n-Okuchiru 4 Isochia gelsolin one 3-one (methanol solution of KATHON287T Rohm & made Haas) containing 30 weight ^_0/0 It was soaked in a substitution bath consisting of the material, squeezed so that the pickup rate was 100% by weight Z fiber, and dried in hot air at 150 ° C. When the dried yarn was cut into lmm, a hydrophilic rosin composition having an antifouling agent holding ratio of 8% by weight Z fiber was obtained.

3) 18 parts by weight of water-soluble rosin rosin as a self-abrasive binder, slightly hydrolyzable cocoon A self-polishing paint consisting of 35 parts by weight of N, N-dimethylacrylamide butyl methyl methacrylate copolymer as fat, 5 parts by weight of petiole pigment, and 60 parts by weight of toluene was obtained in 2) above. 60 parts by weight of the antifouling hydrophilic rosin composition was dispersed and applied to an acrylic plate having a thickness of 3 mm × 50 cm × 50 cm. The coating thickness after drying was 200 μm.

This was submerged in the sea at Omeyama Bay in Okayama Prefecture, and the state of aquatic organisms was regularly observed, but for 12 months the organisms did not attach at all.

[0048] [Example 5]

1) polymerization degree of 1750,鹼化degree 97 mole ^_0/0, the PVA and D MSO polymerized 2 mole ^_0/0 both maleic anhydride and 10 hours dissolved with stirring at 90 ° C, the polymer concentration of 20 wt% stock solution Prepared. This stock solution was dropped into a solidification bath having a methanol ZDMSO ratio (weight ratio) of 70Z30 and a temperature of 10 ° C through a nozzle having a hole diameter of 0.16 mmφ and a hole number of 1500 holes. Subsequently, DMSO was substantially completely extracted from the obtained gel particles in a methanol bath to obtain gel particles having an organic solvent (methanol) content of 140 wt% / PVA polymer.

2) then this gel particle, 4 as an antifouling agent, 5-dichloro-one 2-n-Okuchinore one 4- Isochi Azorin one 3-one (methanol solution KATHON287T Rohm & made Haas) and containing 30 weight ^_0/0 After immersing in a replacement bath consisting of squeezed and squeezed, it was dried in hot air at 150 ° C. to obtain greaves particles. The resin particles were pulverized to obtain a hydrophilic resin composition having an antifouling performance with an average particle diameter of 20 m.

3) In addition, 18 parts by weight of water-soluble rosin rosin as a self-polishing binder, 35 parts by weight of N, N-dimethylacrylamide butyl methyl methacrylate copolymer as a slightly hydrolyzable resin, and 5 parts of petal pigment Disperse 60 parts by weight of the antifouling hydrophilic resin composition obtained in 2) above in a self-polishing paint consisting of 60 parts by weight of toluene and apply to an acrylic plate with a thickness of 3 mm X 50 cm x 50 cm. did. The coating thickness after drying was 200 μm.

This was submerged in the sea at Omeyama Bay in Okayama Prefecture, and the state of attachment of aquatic organisms was regularly observed. For 12 months, the organisms did not adhere at all.

[0049] [Comparative Example 1]

18 parts by weight of water-soluble rosin rosin as a self-polishing binder, 35 parts by weight of N, N-dimethylacrylamide butyl methyl methacrylate copolymer as a slightly hydrolyzable rosin, In addition, 5 parts by weight of petal pigment, 60 parts by weight of toluene, and 20 parts by weight of 4, 5 dichloro-2-noctyl 4 isothiazoline 3 on as a stain-proofing agent are contained in the hydrophilic resin composition. It melt | dissolved without making it and apply | coated to the acrylic board of thickness 3mm X 50cm X 50cm. The coating thickness after drying was 200 m.

This was submerged in the sea at Omeyama Bay in Okayama Prefecture, and the aquatic organisms were regularly observed for attachment, but the organisms did not attach at all for only 3 months.

[0050] [Comparative Example 2]

60 parts by weight of the antifouling hydrophilic resin composition of Example 2 is 40 parts by weight of bisphenol A type liquid resin having an epoxy equivalent of 184 to 194, 20 parts by weight of a curing agent, and 25 parts by weight of calcium carbonate. As an antifouling agent, 20 parts by weight of 4,5 dichloro-2 n-octyl 4 isothiazoline 3 -on was dispersed in the paint and applied to an acrylic plate having a thickness of 3 mm × 50 cm × 50 cm. The coating thickness after drying was 200 m.

This was submerged in the sea at Omeyama Bay in Okayama Prefecture, and the state of aquatic organisms was regularly observed, but the organisms did not attach at all for only one month.

[0051] [Comparative Example 3]

18 parts by weight of water-soluble rosin rosin as a self-abrasive binder, 35 parts by weight of N, N-dimethylacrylamide butyl methyl methacrylate copolymer as a slightly hydrolyzable rosin, and 5 parts by weight of petiole pigment, toluene A self-polishing paint with a weight of 60 parts by weight was applied to an acrylic plate having a thickness of 3 mm x 50 cm x 50 cm without any antifouling agent. The film thickness after drying is 200 μm and 7 pieces.

This was submerged in the sea at Omeyama Bay in Okayama Prefecture, and the state of aquatic organisms was regularly observed, but a large amount of organisms adhered within a month.

[0052] [Comparative Example 4]

Except for adding 45% by weight of polyacrylic acid having a molecular weight of 5000 and 55% by weight of PVA to the spinning dope, the same treatment as in Example 1 was performed. The obtained fiber had an antifouling agent loading rate of 24% by weight and 7 fibers, and the antifouling agent loading rate measured after immersion in xylene at 65 ° C for 65 hours at a bath ratio of 100 was 17.5% by weight. It was Z fiber, that is, the antifouling agent loading after washing with xylene was 73%. Using this fiber, a paint and a coating film were prepared in the same manner as in Example 1, and immersed in the sea in Omeyama Bay in Okayama Prefecture, and the state of aquatic organism adhesion was regularly observed, but no organisms adhered. It was only for 6 months.

[0053] [Comparative Example 5]

In Example 1, when the fiber length was 5 mm, the antifouling agent loading was 6%. When the fiber length was long, penetration of the antifouling agent occurred and was difficult. When the fiber length was 5 mm, it was difficult to add to the paint because the fiber length was too long.

[0054] [Comparative Examples 6-7]

The solvent of the antifouling agent in Example 1 was replaced with methanol, and methyl isobutyl ketone (Comparative Example 6) and xylene (Comparative Example 7) were used.

The anti-fouling agent loading ratio of the obtained fibers was 2% or less, both of which were very low. Both solvents hardly swell fibers that have no affinity with PVA. Methanol is suitable as a solvent that swells PVA moderately.

Industrial applicability

[0055] The structure coated with the antifouling coating liquid of the present invention prevents adhesion of aquatic organisms over a long period of time even when immersed in water, has excellent durability, and is environmentally friendly. Ships, power plant cooling water intake facilities, subsea oil field drilling facilities, coastal industrial plants, port facilities, large structures such as bridges, and fishery materials such as fishery nets Can be used for ship materials such as navigation buoys, light buoys and mooring buoys, and civil engineering materials such as pollution control curtains.

Claims

A hydrophilic rosin composition containing a compound having antifouling properties. 2. The hydrophilic resin composition according to claim 1, wherein the antifouling compound is a compound represented by the following general formula (1), a metal salt thereof, or a complex compound of an amine salt.

[Chemical 1]

[3] The hydrophilic resin composition according to claim 1 or 2, wherein the hydrophilic resin is polybulal alcohol-based resin.

[4] The hydrophilic resin for paint according to claim 3, wherein the hydrophilic resin according to claim 3 is a fiber whose fiber component has a polyvinyl alcohol strength of 60% by weight Z fiber or more and satisfies all of the following 1) to 3): Resin composition.

1) The fiber has a skin core structure and the core ratio is 50% or more,

2) The fineness of the fiber is 0.1 to 30dtex, the fiber length is 3mm or less,

3) The antifouling agent comprising the antifouling compound according to claim 2 is supported by 10% by weight or more of Z fibers, and the antifouling agent retention after xylene cleaning represented by the following formula is 80% or more. Antifouling agent retention after xylene cleaning = (Antifouling agent retention after cleaning Z Antifouling agent retention before cleaning) X 100 (%)

[5] Impregnated fiber cut to 3mm or less in a solution of antifouling agent dissolved in methanol 5. The method for producing a hydrophilic rosin composition for paints according to claim 4, wherein 6. The coating liquid and coating film according to any one of claims 1 to 5, wherein a coating film-forming binder is contained, and the coating film-forming binder has self-polishing properties.

An underwater structure obtained by coating the coating liquid according to any one of claims 1 to 6.