KR101817486B1 - Antifouling coating composition, antifouling coating film, non-fouling base, process for producing non-fouling base, and method for storing antifouling coating composition - Google Patents

Abstract

으로 표시되는 단량체(a)로부터 유도되는 구조단위를 갖는다. The present invention relates to an antifouling paint composition used for preventing a substrate from being contaminated by aquatic organisms containing a silyl ester (co) polymer and medetomidine, and can form an antifouling coating film exhibiting excellent antifouling properties over a long period of time , An antifouling paint composition having good storage stability, and a use thereof.
In order to solve the above problems, the antifouling paint composition of the present invention comprises a silane ester (co) polymer (A), a medtomidine (B), a dehydrating agent (c1) and a rosin (C), wherein the silyl ester copolymer (A) is a copolymer of the general formula (I):

(A) represented by the following general formula (1).

Description

TECHNICAL FIELD [0001] The present invention relates to an antifouling coating composition, an antifouling coating film, a non-fouling base, a process for producing a non-fouling base, and a method for storing antifouling coating composition}

The present invention relates to an antifouling paint composition and its use, and more particularly to an antifouling paint composition which contains a silyl ester (co) polymer as a film-forming component and can be used to prevent fouling of a substrate by aquatic organisms, An antifouling base, a method for producing an antifouling base, and a method of storing the antifouling paint composition.

Currently, antifouling paints used for ships and underwater structures intended to prevent the aquatic organisms from being damaged by the aquatic environment are composed of a hydrolyzable resin for imparting paint film renewability to the antifouling coating film, And a method of combining the materials is widely used.

As the hydrolyzable resin, a silyl ester-based (co) polymer is widely used as a resin having particularly suitable renewability.

On the other hand, for example, Japanese Patent Application Laid-Open No. 2002-535255 (Patent Document 1) discloses that medetomidine is useful as an agent for inhibiting marine biological contamination on a solid surface.

International Patent Publication No. 2011/118526 (Patent Document 2) discloses an antifouling paint composition that exhibits excellent antifouling performance even in marine and navigational conditions and underwater structures exposed to a high pollution load by combining them, and specific examples thereof Discloses a coating composition comprising silyl ester-based copolymers having structural units derived from triisopropylsilyl acrylate, medetomidine, and calcined gypsum (Examples 10 and 11).

Japanese Patent Application Laid-Open No. 2002-535255 International Publication No. 2011/118526

However, in the antifouling coating composition disclosed in Patent Document 2, the silyl ester-based copolymer and the methadomidine coexist, resulting in an unusual increase in paint viscosity or solidification of the paint, which is presumably attributed to the decomposition of the silyl ester- It has been found that there is a problem that it is difficult to stably store the composition for a long period of time. More specifically, the storage life of the coating composition of Comparative Example 3 which will be described later including the silyl acrylate copolymer is 6 months or more, compared with that of the coating composition of Comparative Example 1 to which the medetomidine is added, The storage life was less than one month.

In view of such problems, the present invention provides an antifouling paint composition containing a silyl ester-based (co) polymer and medetomidine, which is used for preventing contamination of a substrate by aquatic organisms, To provide an antifouling paint composition capable of forming an antifouling coating film and having good storage stability, and a use thereof.

The inventors of the present invention have found that, even when an antifouling coating composition containing a silyl ester (co) polymer and a medothomidine is used, the storage stability can be enhanced by coexistence of specific components, and the present invention has been completed . The gist of the present invention is as follows.

[One]

(C) selected from the group consisting of silyl ester-based (co) polymer (A), medetomidine (B), dehydrating agent (c1) and rosin (c2)

When the silyl ester-based (co) polymer (A) is represented by the general formula (I):

[In the formula (I), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom,

R ¹ is a hydrogen atom or R ⁷ -OC = O (provided that R ⁷ is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom, or R ⁸ R ⁹ R ¹⁰ Si (provided that R ⁸ , R ⁹ and R ¹⁰ are each independently a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom)

n is 0 or an integer of 1 or more.]

And a structural unit derived from the monomer (a).

[2]

The method according to the above [1], wherein the component (C) comprises the dehydrating agent (c1) and the dehydrating agent (c1) comprises at least one component selected from the group consisting of organosilanes containing hydrolysable groups, zeolites and orthoesters Lt; / RTI >

[3]

The antifouling paint composition according to the above [2], wherein the dehydrating agent (c1) comprises the organosilane containing the hydrolyzable group.

[4]

The antifouling paint composition according to [2] or [3], wherein the dehydrating agent (c1) comprises the zeolite.

[5]

The antifouling paint composition according to any one of [2] to [4], wherein the dehydrating agent (c1) comprises the orthoester.

[6]

The antifouling paint composition according to any one of [1] to [5], wherein the component (C) comprises the rosin (c2).

[7]

The antifouling paint composition according to any one of [1] to [6], wherein the medetomidine (B) is contained in an amount of 0.001 to 10% by weight in 100% by weight of the solid content of the antifouling paint composition.

[8]

The antifouling paint composition according to any one of [1] to [7], wherein the dehydrating agent (c1) is contained in an amount of 0.01 to 200 parts by weight based on 100 parts by weight of the silyl ester-based (co) polymer (A).

[9]

The antifouling paint composition according to any one of [1] to [8], wherein the dehydrating agent (c1) is contained in an amount of 1 to 100,000 parts by weight based on 100 parts by weight of the medetomidine (B).

[10]

The antifouling paint composition according to any one of [1] to [9], wherein the rosin (c2) is contained in an amount of 0.01 to 500 parts by weight based on 100 parts by weight of the silyl ester-based (co) polymer (A).

[11]

The antifouling paint composition according to any one of [1] to [10], wherein the rosin (c2) is contained in an amount of 1 to 50,000 parts by weight based on 100 parts by weight of the medtomidine (B).

[12]

The antifouling paint composition according to any one of [1] to [11], wherein in the general formula (I), R ⁴ , R ⁵ and R ⁶ are both isopropyl groups.

[13]

The antifouling paint composition according to any one of [1] to [12], wherein the silyl ester-based (co) polymer (A) further has a structural unit derived from an unsaturated monomer (b) copolymerizable with the monomer (a) .

[14]

Wherein the unsaturated monomer (b) is at least one selected from the group consisting of alkyl (meth) acrylates, monomers represented by the following formula (II), alkoxyalkyl (meth) acrylates, hydroxyalkyl (meth) The antifouling paint composition according to the above-mentioned [13], wherein the antifouling paint composition comprises at least one unsaturated monomer selected from the group consisting of (meth) acrylate and (meth) acrylate having an organosiloxane group.

[In the formula (II), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom,

R ¹¹ is a hydrogen atom or R ¹⁷ -OC = O (provided that R ¹⁷ is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom, or R ¹⁸ R ¹⁹ R ²⁰ Si (provided that R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom)

n is 0 or an integer of 1 or more.]

[15]

Wherein the unsaturated monomer is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, triisopropylsilyl methacrylate, 2- methoxyethyl (meth) (Meth) acrylate. [14] The antifouling paint composition according to the above [14], wherein the antifouling coating composition is at least one unsaturated monomer selected from the group consisting of

[16]

The antifouling paint composition according to any one of [13] to [15], wherein the silyl ester-based (co) polymer (A) comprises 40 to 80% by weight of structural units derived from the monomer (a).

[17]

The antifouling paint according to any one of [1] to [16], wherein the medetomidine (B) is contained in an amount of 0.001 to 50 parts by weight based on 100 parts by weight of the silyl ester- Composition.

[18]

The antifouling paint composition according to any one of [1] to [17], further comprising an antifouling agent (E) other than the medetomidine (B).

[19]

Wherein the antifouling agent (E) other than the medetomidine (B) is at least one selected from the group consisting of copper oxide, copper fluoride, copper, copper pyrithione, zinc pyrithione, 4-bromo-2- (4-chlorophenyl) N-octyl-4-isothiazolin-3-one, borane-nitrogen base addition product, N, N-dimethyl-N (2,4,6-trichlorophenyl) maleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino- 5-triazine, 2,4,5,6-tetrachloroisophthalonitrile, bisdimethyldithiocarbamoylzinc ethylenebis dithiocarbamate, chloromethyln-octyl disulfide, N, N'-dimethyl- N, N'-diphenyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, tetraalkylthiuram disulfide, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, 2,3- , 6'-diethylphenyl) maleimide and 2,3-dichloro-N- (2'-ethyl-6'-methylphenyl) male Wherein the antifouling agent is at least one antioxidant selected from the group consisting of imides.

[20]

The antifouling paint composition according to any one of [1] to [19], further comprising a monocarboxylic acid compound (F).

[21]

The antifouling paint composition according to any one of the above [1] to [20], which is a one-pack type paint.

[22]

An antifouling coating film formed from the antifouling paint composition according to any one of [1] to [21].

[23]

An antifouling substrate having a substrate and an antifouling coating film according to the above [22], which is provided on the surface of the substrate.

[24]

An antifouling substrate according to the above [23], which is in contact with seawater or fresh water.

[25]

The antifouling substrate according to the above [24], wherein the substrate is an underwater structure, a ship exterior plate, or a fish.

[26]

A step of applying or impregnating the antifouling paint composition according to any one of [1] to [21] to the surface of the substrate, and a step of curing the antifouling paint applied or impregnated to the substrate by the step , or

A step of forming a coating film from the antifouling paint composition and curing the coating film to form an antifouling coating film, and a step of sticking the antifouling coating film to a substrate

A method for producing an antifouling substrate.

[27]

A method of storing an antifouling paint composition, wherein the antifouling paint composition according to the above [21] is filled in a container and stored.

By using the antifouling paint composition of the present invention, it is possible to form an antifouling coating film exhibiting excellent antifouling properties over a long period of time. Further, the antifouling paint composition of the present invention can be stably stored for a long period of time.

The antifouling paint composition or the like of the present invention will be described in more detail below.

In the present invention, when the component contains volatile components such as a solvent for dilution, the weight which is a standard for defining the content of the component in the present invention is a component capable of constituting a dry coating film excluding the volatile component, &Quot; The solid content refers to a residue of a component or composition containing a volatile component such as a solvent when the composition is dried at 105 캜 for 3 hours in a hot air dryer to volatilize the solvent or the like. The term "(co) polymer" is a generic term for polymer and copolymer, and "(meth) acrylate" is a generic term for acrylate and methacrylate.

[ Antifouling paint composition]

The antifouling paint composition of the present invention contains silyl ester (co) polymer (A), medtomidine (B) and specific component (C).

<Silylester-based (co) polymer (A)>

The silyl ester-based (co) polymer (A) is represented by the general formula (I):

(Also referred to as a "constituent unit", "constituent unit", "repeating unit", etc.) derived from the monomer (a) represented by the general formula (1) and optionally an unsaturated monomer (b) copolymerizable with the monomer (Co) polymers having structural units. Further, "component unit derived from X" means that when X is represented by A ¹ A ² C = CA ³ A ⁴ (C = C is a polymerizable carbon-carbon double bond), for example, It is a structural unit.

In the formula (I), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a monovalent organic group having 1 to 20 carbon atoms which may have a heteroatom, for example, Straight, branched or cyclic alkyl and aryl groups which may be interposed between carbon atoms and carbon atoms. R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are preferably a methyl group, an ethyl group, an iso-propyl group (isopropyl group), an isopropyl group Propyl group, sec-butyl group and the like, more preferably an isopropyl group.

R ¹ is a hydrogen atom or R ⁷ -OC = O (provided that R ⁷ is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom, or R ⁸ R ⁹ R ¹⁰ Si (provided that R ⁸ , R ⁹ and R ¹⁰ are each independently a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom), preferably a hydrogen atom.

As the monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom as R ⁷ , R ⁸ , R ⁹ and R ^10, a hetero atom such as an oxygen atom may be bonded to a carbon atom Branched, or cyclic alkyl and aryl groups, and isopropyl group is preferable.

n is 0 or an integer of 1 or more, preferably 0. The upper limit value of n may be, for example, 1,000.

Examples of the monomer (a) represented by the formula (I) include trimethylsilyl methacrylate, triethylsilyl acrylate, tri-n-propylsilyl acrylate, triisopropylsilyl acrylate, tri- Trialkylsilyl acrylates such as silyl acrylate, triisobutylsilyl acrylate, tri-sec-butylsilyl acrylate, tri-2-ethylhexylsilyl acrylate and butyldiisopropylsilyl acrylate, Nonylmethyltetrasiloxane. Of these, triisopropylsilyl acrylate is preferable in terms of the hydrolysis rate of the silyl ester-based (co) polymer (A) in the antifouling coating film of the present invention, the surface renewal persistency of the antifouling coating film of the present invention and It is preferable from the viewpoint of excellent water resistance.

Examples of the unsaturated monomer (b) that can be copolymerized with the monomer (a) include monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (Meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl Alkyl (meth) acrylates such as stearyl (meth) acrylate;

Phenyl (meth) acrylate;

Benzyl (meth) acrylate;

Acrylates such as methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, 2- ethoxyethyl (meth) , Methoxypropyl (meth) acrylate, ethoxypropyl (meth) acrylate, propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, isobutoxybutyl diglycol Alkoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate;

(Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyalkyl (meth) acrylates such as cyproxyl (meth) acrylate;

(Meth) acrylate containing a metal ester group such as zinc (meth) acrylate, zinc di (meth) acrylate, copper (meth) acrylate and copper di (meth) acrylate;

(Meth) acrylate containing an organosiloxane group, and

General formula (II):

In the formula (II), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a monovalent organic group having 1 to 20 carbon atoms which may have a heteroatom, for example, A straight chain, branched chain or cyclic alkyl group or aryl group which may be interposed between the atom and the carbon atom bond. Since the silyl ester-based (co) polymer (A) is hydrolyzed at a proper rate in the antifouling coating film of the present invention, it is preferably an alkyl group, more preferably an isopropyl group.

R ¹¹ is a hydrogen atom or R ¹⁷ -OC = O (provided that R ¹⁷ is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom, or R ¹⁸ R ¹⁹ R ²⁰ Si (provided that R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom), preferably a hydrogen atom.

Examples of the monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom as R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ include groups in which a hetero atom such as an oxygen atom may be interposed between a carbon atom and a carbon atom Chain, branched, cyclic alkyl group, aryl group, and the like, and isopropyl group is preferable.

n is 0 or an integer of 1 or more, preferably 0. The upper limit value of n may be 1,000, for example.]

(Meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-hydroxyethyl And triisopropylsilyl methacrylate are more preferable. (Silyl ester) (co) polymer (A) is more preferably an unsaturated monomer (b) derived from 2-methoxyethyl (meth) acrylate as the unsaturated monomer (b) Structural units derived from 2-methoxyethyl (meth) acrylate, and particularly preferably 1 to 30% by weight of structural units derived from 2-methoxyethyl (meth) acrylate, and the range may be 1 to 40% by weight.

The amount of the structural unit derived from the monomer (a) in the silyl ester-based (co) polymer (A) is usually from 10 to 100% by weight, preferably from 10 to 90% by weight, more preferably from 30 to 80% The amount of the structural unit derived from the unsaturated monomer (b) is usually 0 to 90% by weight, preferably 10 to 90% by weight, more preferably 20 to 70% by weight, based on the weight of the antifouling coating film of the present invention (The total amount of the structural units in the silyl ester-based (co) polymer (A) is 100% by weight).

The number average molecular weight Mn (polystyrene reduced value, measurement method is the method described in the following Examples or the equivalent method) of the silyl ester type (co) polymer (A) is usually 1,000 to 200,000, preferably 1,000 To 100,000 is preferable in terms of viscosity, storage stability, and physical properties of a coating film.

The content of the silyl ester-based (co) polymer (A) in the antifouling paint composition of the present invention is preferably 0.1 to 99% by weight, more preferably 5 to 90% by weight, particularly preferably 10 to 80% by weight.

The silyl ester-based (co) polymer (A) can be prepared by (co) polymerizing the monomer (a) and optionally the unsaturated monomer (b) by a known polymerization method.

(Weight) of the structural unit derived from the monomer (a) and the structural unit derived from the unsaturated monomer (b) contained in the silyl ester-based (co) polymer (A) (Weight) of the monomer (a) and the unsaturated monomer (b).

&Lt; Medetomidine (B) >

Medetomidine is (±) -4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole.

The content of medetomidine (B) in the antifouling paint composition of the present invention is preferably 0.001 to 10% by weight in 100% by weight of the antifouling paint composition (solid content). The content of medetomidine (B) in the antifouling paint composition of the present invention is preferably 0.01 to 50 parts by weight, more preferably 0.02 to 20 parts by weight, per 100 parts by weight of the silyl ester-based (co) polymer (A) By weight, more preferably 0.04 to 10 parts by weight. The antifouling coating film obtained from the antifouling paint composition of the present invention exhibits excellent antifouling property because the content of the medothomidine (B) falls within this range.

&Lt; Component (C) >

The antifouling paint composition of the present invention comprises at least one component (C) selected from the group consisting of a dehydrating agent (c1) and a rosin (c2).

The dehydrating agent (c1) may be either organic or inorganic, or a combination thereof.

Examples of the organic dehydrating agent include organosilanes containing a hydrolysable group, orthoesters such as alkyl orthoformates, orthoboric acid, isocyanates and the like, preferably hydrolyzable group-containing organosilanes or orthoformic acid alkyl esters, Hydrolyzable group-containing organosilane.

As the hydrolyzable group-containing organosilane, a compound represented by the following general formula (III) is preferable.

In the general formula (III), R ¹⁰ is independently a hydrocarbon group having 1 to 6 carbon atoms (for example, methyl group or ethyl group), Y is independently a hydrolyzable group (for example, methoxy group or ethoxy group) , and n is an integer of 0 to 3.

As the organosilane containing a hydrolyzable group, a commercially available organosilane can be used. For example, "ethyl silicate 28" (manufactured by Colcoat Co.) as tetraethyl orthosilicate, "KBM-13" (Manufactured by Chemical Co., Ltd.).

Examples of the inorganic dehydrating agent include zeolite, alumina and silica, and zeolite is preferable.

As such a zeolite, those marketed under the generic name of &quot; molecular zeolite &quot; can be used.

When they are contained as the dehydrating agent (cl), good paint storage stability is obtained.

When the component (C) is a dehydrating agent (c1) selected from an organosilane containing a hydrolysable group, a zeolite and an orthoester, the content of the dehydrating agent (c1) in the antifouling paint composition of the present invention is preferably not less than (B) is preferably from 1 to 100,000 parts by weight, more preferably from 1 to 50 parts by weight, and still more preferably from 1 to 100,000 parts by weight based on 100 parts by weight of the medtomidine (B) More preferably 10 to 10,000 parts by weight. When the blending amount of the dehydrating agent (c1) is in this range, good paint storage stability is obtained.

Examples of the rosin (c2) include rosin derivatives such as rosin, hydrogen rosin, disproportionated rosin, and rosin metal salts such as rosin, wood rosin and tolyrozine; and pine tar.

When the component (C) is the rosin (c2), the content of the rosin (c2) in the antifouling paint composition of the present invention is preferably from 0.01 to 500 parts by weight based on 100 parts by weight of the silyl ester- More preferably 1 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, and preferably 1 to 50,000 parts by weight based on 100 parts by weight of the medtomidine (B). When rosin (c2) is contained in this proportion, good storage stability of the antifouling paint composition is obtained, and antifouling performance with excellent antifouling coating film is obtained.

<Optional ingredients>

The antifouling paint composition of the present invention may contain, in addition to the above-mentioned components, an antifouling agent (E), a monocarboxylic acid compound (F), a coloring pigment (G), an extender pigment (H) (K) and a solvent (L) other than the silyl ester-based (co) polymer (A), the thixotropic agent (J), the silyl ester-based (co) polymer (A), and the like.

· Medetomidine (B) other than Antifouling agent (E)

When the antifouling paint composition of the present invention contains the antifouling agent (E) other than the medothomidine (B), the antifouling performance of the antifouling coating film obtained from the antifouling paint composition can be further improved.

Examples of the antifouling agent (E) other than the medethomidine may include inorganic and organic antifouling agents such as copper oxide, copper fluoride, copper, copper pyrithione, zinc pyrithione, 4-bromo-2- Dichloro-2-n-octyl-4-isothiazolin-3-one, borane-nitrogen based base moiety N, N-dimethyl-N '- (3,4-dichlorophenyl) urea, N- (2,4,6-trichlorophenyl) ) Maleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine, 2,4,5,6-tetrachloroisophthalonitrile, bisdimethyldithiocarb N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, tetraalkylthiuram disulfide, tetraalkyl thiuram disulfide, Zinc dimethyldithiocarbamate, zinc (2 ', 6'-diethylphenyl) maleimide, and 2,3-dichloro-N- (2'-ethyl-6'-methylphenyl) And a combination thereof may be used.

The blending amount of the antifouling agent (E) other than the medetomidine can be suitably adjusted and is, for example, 0.01 to 1,000 parts by weight based on 100 parts by weight of the silyl ester (co) polymer (A).

· Monocarboxylic acid  Compound (F)

By including the monocarboxylic acid compound (F) in the antifouling paint composition of the present invention, surface renewability and water resistance of the antifouling coating film obtained from the antifouling paint composition can be improved.

The monocarboxylic acid compound (F) is preferably a saturated or unsaturated aliphatic hydrocarbon group having 10 to 20 carbon atoms or a saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a substituent thereof. Among them, trimethyl isobutenyl cyclohexenecarboxylic acid compound, versatile acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12- Acid or naphthenic acids and salts thereof (e.g. metal salts) are preferred. Examples of the trimethylisobutylcyclohexenecarboxylic acid include the reaction products of 2,6-dimethylocta-2,4,6-triene and methacrylic acid, which include 1,2,3-trimethyl-5 -1-carboxylic acid and 1,4,5-trimethyl-2- (2-methylprop-1-en-1-yl) 1-yl) cyclohex-3-ene-1-carboxylic acid as the main component (85% or more).

The amount of the monocarboxylic acid compound (F) to be compounded can be appropriately adjusted and is, for example, 0.01 to 1,000 parts by weight, preferably 1 to 500 parts by weight, per 100 parts by weight of the silyl ester-based (co) polymer (A) .

· Coloring Pigment (G)

Examples of the coloring pigment (G) include inorganic pigments such as spinach, titanium white (titanium oxide) and yellow iron oxide, and organic pigments such as carbon black, naphthol red and phthalocyanine blue. These colored pigments may be used singly or in combination of two or more kinds. The coloring pigment may further contain various coloring agents such as a dye.

The blending amount of the coloring pigment (G) can be suitably adjusted, and is, for example, 0.05 to 125 parts by weight based on 100 parts by weight of the silyl ester-based (co) polymer (A).

· Extention pigments (H)

The extender pigment (H) is a pigment which has a low refractive index and is transparent when it is kneaded with oil or varnish and does not block the surface. Examples of the extender pigment H include talc, mica, clay, feldspar, zinc oxide, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, zinc sulfide Among them, zinc oxide, talc, mica, clay, calcium carbonate, kaolin, barium sulfate, calcium sulfate and potassium feldspar are preferable. These extender pigments may be used singly or in combination of two or more.

The blending amount of the extender pigment (H) can be suitably adjusted, and is, for example, 0.5 to 250 parts by weight based on 100 parts by weight of the silyl ester (co) polymer (A).

Plasticizers (I)

The plasticizer (I) is a component contributing to improvement of crack resistance, water resistance and discoloration of the antifouling coating film. Examples of the plasticizer (I) include n-paraffin, chlorinated paraffin, terpene phenol, tricresyl phosphate (TCP), polyvinyl ethyl ether and the like. Of these, chlorinated paraffin and terpene phenol are preferable, Particularly preferred. These plasticizers may be used alone or in combination of two or more. Paraffin &quot; manufactured by Nippon Petrochemical Co., Ltd. was used as the n-paraffin, and Toyoparax A-40 / A-50 / A-70 / A-145 / A-150 &quot; can be used.

The blending amount of the plasticizer (I) can be appropriately adjusted, and is, for example, 1 to 5% by weight based on the total solid content in the antifouling paint composition.

· Stool (J)

The thixotropic agent (J) is a component contributing to the prevention of sagging and sedimentation of the paint.

Examples of the thixotropic agent (J) include organic bentonite, stearate of Al, Ca or Zn, lecithin, alkyl sulfonate, polyethylene wax, oxidized polyethylene wax, amide wax, hydrogenated castor wax, amide wax / oxidized polyethylene wax Complex system. These thixotropic agents may be used singly or in combination of two or more.

The blending amount of the thixotropic agent (J) can be appropriately adjusted, and is, for example, 0.25 to 50 parts by weight based on 100 parts by weight of the silyl ester-based (co) polymer (A).

· Other resin Flow (K)

The antifouling paint composition of the present invention may contain one kind or two or more kinds of other resins (K), if necessary, in addition to the silyl ester type (co) polymer (A) described above.

For example, an acrylic resin containing no metal ester bond, an acrylic resin containing an ester group (other than silicon), an acrylic silicone resin, a polyester resin, an unsaturated polyester resin, a fluororesin, a polybutene resin, a silicone rubber, a polyurethane resin , An epoxy resin, a polyamide resin, a vinyl resin (a vinyl chloride copolymer, an ethylene · vinyl acetate copolymer and the like), a chlorinated rubber, a chlorinated olefin resin, a styrene · butadiene copolymer resin, a ketone resin, an alkyd resin, Phenol resin, petroleum resin, and other non-water-soluble or light-water-soluble resins.

The blending amount of the other resin streams (K) can be suitably adjusted and is, for example, 0.01 to 1,000 parts by weight based on 100 parts by weight of the silyl ester-based (co) polymer (A).

· Solvent (L)

The various components constituting the antifouling paint composition of the present invention are dissolved or dispersed in a solvent in the same manner as a conventional antifouling paint composition. In the present invention, an aliphatic solvent, an aromatic solvent (xylene, toluene etc.), a ketone solvent (MIBK, cyclohexanone and the like), an ester solvent, an ether solvent (propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate ), An alcohol-based solvent (isopropyl alcohol, etc.), and the like.

The blending amount of the solvent (L) can be suitably adjusted, for example, the proportion of the total solid content of the antifouling paint composition is 20 to 90% by weight, and may be added at the time of coating depending on workability.

(Method for producing antifouling paint composition)

The antifouling paint composition of the present invention can be prepared by using the same apparatus, means, and the like as the general antifouling paint known in the art. (A) ((co) polymer (A)) is prepared as a solution of the (co) polymer (A) , A solution obtained by preparing a polymer (A)), a medetomidine (B), a component (C) and, if necessary, other additives are added to the solvent at once or sequentially , Stirring, and mixing.

In addition, since the antifouling paint composition of the present invention has high storage stability, not only the components containing the silyl ester-based (co) polymer (A) and the component containing the medetomidine (B) Can also be stored as a one-pack type paint containing a system (co) polymer (A), a medtomidine (B) and a component (C).

[ Antifouling coating and antifouling equipment ]

The antifouling coating film of the present invention is composed of the solid content of the antifouling paint composition of the present invention. The antifouling coating film of the present invention is formed from the antifouling paint composition of the present invention. For example, when the antifouling paint composition contains the solvent (L), the antifouling paint composition of the present invention applied on the substrate may be, And dried or hardened by using a drying means such as a heater (that is, by removing the solvent L).

The antifouling substrate of the present invention comprises a substrate and an antifouling coating film of the present invention formed on the surface of the substrate. The antifouling coating composition of the present invention is applied to a substrate (the substrate is also an object of antifouling or an object to be coated) (That is, drying at a temperature of about room temperature), a heater (not shown), or the like by applying or impregnating a coating composition applied or impregnated on a substrate by using a coating means such as an air spray, an airless spray, a brush, Followed by drying and curing using a drying means such as a dryer to form an antifouling coating film on the substrate.

Alternatively, the antifouling substrate of the present invention can be produced by forming an antifouling coating film on the surface of the temporary substrate from the antifouling coating composition of the present invention, peeling the antifouling coating film from the temporary substrate, and attaching the antifouling coating film to the substrate. At this time, the antifouling coating film may be pasted on the substrate through the adhesive layer.

The base material is not particularly limited, but is preferably a base material which is in contact with seawater or fresh water. More specifically, the base material includes various kinds of materials such as water and wastewater for various power plants (thermal power, nuclear power), coast roads, submarine tunnels, harbor facilities, canals, Floors or buoys such as ropes, fishing nets, etc. (for example, ships, ships, etc.), underwater structures such as sludge diffusion barrier used in marine or river engineering works, ).

Examples of the material of the base material include steel, aluminum, wood, FRP and the like in the case of a shipboard shell, natural fibers or synthetic fibers in the case of fishing nets, And the material thereof is not particularly limited as long as it is described in the water which requires antifouling property and the like.

On the surface of these substrates, particularly when the substrate is in the bottom, etc., the surface of the primer treated substrate after priming such as a rust preventive paint is usually applied to the surface of the steel base material is coated with the antifouling paint composition (Antifouling paint) is coated and impregnated (the impregnation is carried out particularly when the substrate is a fishing nets, etc.), the antifouling coating composition is cured to form an antifouling coating film, (Antifouling property, particularly stiffness antifouling property) for preventing adhesion of aquatic organisms such as mosses, mosses, and worms for a long period of time, thereby allowing the antifouling component to be released for a long period of time.

In general, the surface of the substrate may be subjected to a primer treatment or may have a layer formed from various binder coatings. When the base material is a marine outer plate (particularly, its bottom), an underwater structure, etc., the antifouling paint composition is applied to the surface of the base material a plurality of times (also referred to as thick coat, the dried film thickness of the formed coating film is about 100 to 600 μm) The obtained antifouling base exhibits excellent antifouling property, moderate flexibility and excellent crack resistance.

When the substrate is a steel plate with a deteriorated antifouling coating film or a fishing net, etc., the antifouling paint composition of the present invention may be directly applied to the surface of the substrate, or when the substrate is a fishing net or the like, The base material may be impregnated with a coating composition and if the base material is a steel sheet raw material, a base material such as a rust preventive agent or a primer is previously applied to the surface of the base material to form a base layer, The antifouling paint composition of the present invention may be applied. The antifouling coating film of the present invention or the antifouling coating film of the present invention may be additionally formed on the surface of the substrate on which the antifouling coating film of the present invention is formed for the purpose of maintenance.

The thickness of the antifouling coating film of the present invention formed by a single coating operation is not particularly limited, but is about 30 to 250 占 퐉, for example, when the substrate is a shipboard shell or an underwater structure.

The underwater structure having the antifouling coating film of the present invention can maintain the function of an underwater structure for a long time due to the ability to prevent the attachment of aquatic organisms over a long period of time. Further, the fishing net having the antifouling coating film of the present invention is less likely to cause environmental pollution, and it is possible to prevent clogging of the mesh due to prevention of adhesion of aquatic organisms.

Example

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples at all.

<Viscosity of silyl ester-based (co) polymer solution>

The viscosity of the silyl ester-based (co) polymer solution at 25 캜 was measured by an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.)

<Solid content concentration of silyl ester-based (co) polymer solution>

The solid content refers to a heating residue when a reaction mixture containing a resin and a solvent, a paint or an uncured coating film is dried at 105 ° C for 3 hours in a hot air drier to volatilize a solvent or the like. The solid component usually contains a resin component, further, a pigment, and becomes a coating film forming component.

<Number-average molecular weight (Mn) and weight-average molecular weight (Mw) of silyl ester-based (co) polymer>

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the silyl ester type (co) polymer were measured using GPC (gel permeation chromatography) under the following conditions.

GPC  Condition

Apparatus: "HLC-8120GPC" (manufactured by Tosoh Corporation)

Column: &quot; Super H2000 + H4000 &quot; (manufactured by Tosoh Corporation, 6 mm (inner diameter), 15 cm (length)

Eluent: tetrahydrofuran (THF)

Flow rate: 0.500 ml / min

Detector: RI

Column thermostatic bath temperature: 40 ° C

Standard material: polystyrene

Preparation of samples: A small amount of calcium chloride was added to the polymer solution prepared in each Production Example, followed by dehydration, and then filtered with a membrane filter to obtain a GPC measurement sample.

[Preparation Example 1] (Preparation of silyl ester-based copolymer solution (A-1)) [

54 parts by weight of xylene was placed in a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction pipe and a heating and cooling jacket, and the mixture was heated under a nitrogen atmosphere at 85 캜 5 캜 and stirred. While maintaining the same temperature, a monomer mixture composed of 60 parts by weight of triisopropylsilyl acrylate and 40 parts by weight of methyl methacrylate and 0.75 parts by weight of 2,2'-azobisisobutyronitrile was added to the reaction vessel from the dropping apparatus into 2 Over a period of time. Thereafter, the mixture was stirred at the same temperature for 2 hours, 0.4 part by weight of 2,2'-azobisisobutyronitrile was added, and further stirred at the same temperature for 4 hours. Then, 44 parts by weight of xylene was added to obtain a colorless transparent silyl ester Based copolymer solution (A-1).

The amount of the raw materials used, the solution (A-1) and the properties of the silyl ester copolymer contained therein are shown in Table 1.

[Production Examples 2 to 4] (Preparation of silyl ester-based copolymer solutions (A-2) to (A-4)

Except that the monomer mixture having the composition shown in Table 1 was used in place of the monomer mixture used in Production Example 1 and the addition amount of xylene and 2,2'-azobisisobutyronitrile was appropriately adjusted. In the same manner, silyl ester-based copolymer solutions (A-2) to (A-4) containing a silyl ester-based copolymer were prepared.

The amounts of the raw materials used, the solutions (A-2) to (A-4) and the properties of the silyl ester copolymer contained therein are shown in Table 1.

[Examples 1 to 34 and Comparative Examples 1 to 6]

(Preparation of antifouling paint composition)

(A-1 to A-4), medetomidine (B), dehydrating agent (c1) and rosin (c2) containing the silyl ester copolymer obtained in Production Examples 1 to 4, 3 were uniformly mixed using a paint shaker with the ratios shown in Tables 2 and 3 (parts in the tables indicate parts by weight) to prepare an antifouling paint composition, and evaluation thereof was carried out by the following method.

<Storage stability>

The storage stability of the antifouling paint composition was evaluated in terms of the following shelf life and viscosity stability.

(Storage life)

The antifouling paint composition of the above example was stored at room temperature to check the paint condition every one month and the number of months to the month immediately before the paint became gel state or solidified was evaluated as the shelf life.

(Viscosity stability)

The antifouling paint compositions of the examples and comparative examples were stored at 50 占 폚 for 2 weeks and the viscosity immediately after storage was compared. The value obtained by dividing the viscosity difference before and after storage by the viscosity before storage was obtained as &quot; viscosity increase rate (%) &quot;, and the viscosity stability of the antifouling paint composition was evaluated based on this value. In Table 2, "-" indicates that the measurement was not performed because the storage life is very short.

The viscosities of the respective compositions were measured by a Stormer viscometer (manufactured by DAIUS Co., Ltd., product name: Sturmer Viscometer, Model: 691) under a temperature condition of 23 캜.

&Lt; Static antifouling property &

An epoxy-based anticorrosive paint (epoxy AC paint, trade name "Banano 500", manufactured by Chugoku Kogyo Co., Ltd.) was applied to a sandblast-treated steel sheet (300 mm in length × 100 mm in width × 3.2 mm in thickness) , And then a vinyl-based binder paint (Silvax SQ-K, manufactured by Jikkimyo Kogyo Co., Ltd.) was applied so as to have a dry film thickness of 40 탆. Subsequently, the antifouling paint composition prepared by the above example was applied once to a dry film thickness of 100 탆 and dried at room temperature for 7 days to prepare a test plate with an antifouling coating film. The above three paintings were performed at a single pace per day.

The test plate prepared as described above was immersed in Tokyo Bay for 3 months in summer so as to measure the area of the portion of the antifouling coating film to which the barnacle was adhered (hereinafter also referred to as "barnacle attachment area"). Then, the antifouling property of the antifouling coating film was evaluated according to the following (criteria for evaluation of static antifouling property according to the attached area of the barnacle). The results are shown in Tables 2 and 3.

[Criteria for evaluating the antifouling property according to the attachment area of the barnacle]

0: No attachment of barn cost

1: The barn is partly attached

2: The barn is attached to the front

Claims (27)

(C) selected from the group consisting of silyl ester-based (co) polymers (A), medetomidine (B), and dehydrating agents (c1) and rosins (c2)
When the silyl ester-based (co) polymer (A) is represented by the general formula (I):

[In the formula (I), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom,
R ¹ is A hydrogen atom or R ⁷ -OC = O (wherein R ⁷ represents a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom, or R ⁸ R ⁹ R ¹⁰ Si (provided that R ⁸ , R ⁹ , And R &lt; ¹⁰ &gt; each independently represents a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom)
n is 0 or an integer of 1 or more.]
And a structural unit derived from the monomer (a). The method according to claim 1,
Wherein the component (C) comprises the dehydrating agent (c1), and the dehydrating agent (c1) comprises at least one component selected from the group consisting of organosilane containing hydrolysable group, zeolite and orthoester. 3. The method of claim 2,
Wherein the dehydrating agent (c1) comprises the hydrolyzable group-containing organosilane. 3. The method of claim 2,
Wherein the dehydrating agent (c1) comprises the zeolite. 3. The method of claim 2,
Wherein the dehydrating agent (c1) comprises the orthoester. The method according to claim 1,
Wherein the component (C) comprises the rosin (c2). The method according to claim 1,
Wherein said medetomidine (B) is contained in an amount of 0.001 to 10% by weight in 100% by weight of a solid content of said antifouling paint composition. The method according to claim 1,
Wherein the dehydrating agent (c1) is contained in an amount of 0.01 to 200 parts by weight based on 100 parts by weight of the silyl ester-based (co) polymer (A). The method according to claim 1,
Wherein the dehydrating agent (c1) is contained in an amount of 1 to 100,000 parts by weight based on 100 parts by weight of the medetomidine (B). The method according to claim 1,
Wherein the rosin (c2) is contained in an amount of 0.01 to 500 parts by weight based on 100 parts by weight of the silyl ester-based copolymer (A). The method according to claim 1,
Wherein the rosin (c2) is contained in an amount of 1 to 50,000 parts by weight based on 100 parts by weight of the medetomidine (B). The method according to claim 1,
Wherein R ⁴ , R ⁵ and R ⁶ in the general formula (I) are all isopropyl groups. The method according to claim 1,
Wherein the silyl ester-based (co) polymer (A) further has a structural unit derived from an unsaturated monomer (b) copolymerizable with the monomer (a). 14. The method of claim 13,
Wherein the unsaturated monomer (b) is at least one selected from the group consisting of alkyl (meth) acrylates, monomers represented by the following formula (II), alkoxyalkyl (meth) acrylates, hydroxyalkyl (meth) (Meth) acrylate having an unsaturated group and a (meth) acrylate having an organosiloxane group.

[In the formula (II), R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom,
R ¹¹ is a hydrogen atom or R ¹⁷ -OC = O (provided that R ¹⁷ is a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom, or R ¹⁸ R ¹⁹ R ²⁰ Si (provided that R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a monovalent organic group having 1 to 20 carbon atoms which may have a hetero atom)
n is 0 or an integer of 1 or more.] 15. The method of claim 14,
Wherein the unsaturated monomer is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, triisopropylsilyl methacrylate, 2- methoxyethyl (meth) (Meth) acrylate. The antifouling paint composition according to claim 1, wherein the at least one unsaturated monomer is at least one selected from the group consisting of acrylic acid, methacrylic acid and methacrylic acid. 14. The method of claim 13,
Wherein the silyl ester-based (co) polymer (A) comprises 30 to 80% by weight of structural units derived from the monomer (a). The method according to claim 1,
Wherein the medetomidine (B) is contained in an amount of 0.001 to 50 parts by weight based on 100 parts by weight of the silyl ester-based (co) polymer (A). The method according to claim 1,
Further comprising an antifouling agent (E) other than the medetomidine (B). 19. The method of claim 18,
Wherein the antifouling agent (E) other than the medetomidine (B) is at least one selected from the group consisting of copper oxide, copper fluoride, copper, copper pyrithione, zinc pyrithione, 4-bromo-2- (4-chlorophenyl) N-octyl-4-isothiazolin-3-one, borane-nitrogen base addition product, N, N-dimethyl-N (2,4,6-trichlorophenyl) maleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino- 5-triazine, 2,4,5,6-tetrachloroisophthalonitrile, bisdimethyldithiocarbamoylzinc ethylenebis dithiocarbamate, chloromethyln-octyl disulfide, N, N'-dimethyl- N, N'-diphenyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, tetraalkylthiuram disulfide, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, 2,3- , 6'-diethylphenyl) maleimide and 2,3-dichloro-N- (2'-ethyl-6'-methylphenyl) male And at least one antioxidant selected from the group consisting of imides. The method according to claim 1,
Further comprising a monocarboxylic acid compound (F). The method according to claim 1,
Which is a one-pack type paint. An antifouling coating film formed from the antifouling paint composition according to any one of claims 1 to 21. An antifouling substrate having the substrate and the antifouling coating film according to claim 22 provided on the surface of the substrate. 24. The method of claim 23,
An antifouling substrate in contact with seawater or fresh water. 25. The method of claim 24,
Wherein said substrate is an underwater structure, shipboard plate, or fishing vessel. 21. A process for producing an antifouling paint composition comprising the steps of applying or impregnating the antifouling paint composition of any one of claims 1 to 21 to the surface of a substrate and curing the antifouling paint applied or impregnated to the substrate by the process , or
A step of forming a coating film from the antifouling paint composition and curing the coating film to form an antifouling coating film, and a step of sticking the antifouling coating film to a substrate
A method for producing an antifouling substrate. A storage method for storing an antifouling paint composition, wherein the antifouling paint composition according to claim 21 is filled in a container and stored.