JP2001026729A - Antifouling coating material composition, antifouling coating film formed from the composition, antifouling using the composition and hull of ship or underwater structure coated with the coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antifouling coating film hardly cracking in the coating film, having improved adhesivity of the coating film and excellent antifouling performances. SOLUTION: This antifouling coating material composition comprises a copolymer which consists of (a) a silyl (meth)acrylate component unit of -CH2-CR (COOSiR1R2R3)- [R is a hydrogen atom or a methyl group; R1 and R2 are each a 1-10C straight-chain alkyl group, a phenyl group or trimethylsilyloxy group; and R3 is a 1-18C alkyl group, a 6-10C phenyl group or a trimethylsilyloxy group], (c) a silyl (meth)acrylate component unit of -CH2-CR(COOSiR4R5R6)- [R is a hydrogen atom or methyl group; R4 and R5 are each a cycloalkyl group; and R6 is a 1-10C straight-chain alkyl group, a 3-10C branched or cycloalkyl group or a 6-10C phenyl group or trimethylsilyloxy group] and another unsaturated monomer component unit and has <=200,000 Mw.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an antifouling paint composition, an antifouling coating film formed from the antifouling coating composition, an antifouling method using the antifouling coating composition, and coating with the coating film. More specifically, the obtained coating film is less likely to crack, the coating film adhesion is good, the coating film hardly peels off, and the hydrolysis rate of the coating film is well controlled. An antifouling paint composition that provides an antifouling coating having excellent antifouling properties and a long-term antifouling property under a particularly high fouling environment, an antifouling coating formed from the antifouling coating composition, and The present invention relates to an antifouling method using the antifouling coating composition and a hull or an underwater structure covered with the coating.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ship bottoms, underwater structures, fishing nets, etc.
When exposed to water for a long period of time, animals such as oysters, mussels and barnacles, plants such as seaweed (seaweed), and various aquatic organisms such as bacteria adhere and proliferate, impairing the appearance. , Its function may be impaired.

[0003] In particular, when such aquatic organisms attach to and propagate on the bottom of the ship, the surface roughness of the entire ship increases, which may lead to a decrease in ship speed, an increase in fuel efficiency, and the like. Also, removing such aquatic organisms from the ship bottom requires a great deal of labor and work time. In addition, bacteria attach to and propagate on underwater structures, and slime (sludge-like substances) adhere to them, causing decay. Furthermore, larger attached organisms form on underwater structures such as steel structures. If the coating or the like for preventing corrosion of the underwater structure is attached to and propagated on the surface and damaged, there is a possibility that the strength and function of the underwater structure are reduced, and the life of the underwater structure is significantly reduced.

Conventionally, in order to prevent such damage,
As antifouling paint with excellent antifouling properties on ship bottoms, for example,
A coating containing a copolymer of tributyltin methacrylate and methyl methacrylate and the like and cuprous oxide (Cu ₂ O) was applied. The copolymer in the antifouling paint is
Bistributyltin oxide (Tributyltin ether, Bu ₃ Sn-O-SnBu ₃ : B
u is a butyl group) or tributyltin halide (B
u ₃ SnX: X is with exert an antifouling effect by releasing organotin compounds halogen atom) or the like, "hydrolyzable going dissolving the copolymer itself hydrolysed be water-solubilizing seawater Because it is a “self-polishing paint,”
Resin residue does not remain, and an active surface can always be maintained.

However, such organotin compounds are highly toxic, and there are concerns about marine pollution, generation of malformed fish and malformed shellfish, and adverse effects on the ecosystem due to the food chain.
There is a need for the development of tin-free antifouling paints that can replace this. As such an antifouling paint containing no tin, for example, JP-A-4-264170,
JP-A-4-264169, JP-A-4-2641
No. 68, a silyl ester-based antifouling paint. However, these antifouling paints are inferior in antifouling properties, cracking and peeling, as taught in JP-A-6-157940 and JP-A-6-157940. There is.

JP-A-2-196869 discloses a carboxylic acid group obtained by copolymerizing trimethylsilyl methacrylate, ethyl methacrylate and methoxyethyl acrylate in the presence of an azo-based polymerization initiator. Antifouling coatings containing a blocked acid-functional copolymer (A) and a compound (B) of a polyvalent cation are taught. However, the coating film obtained from this antifouling paint has a problem that crack resistance is not sufficiently satisfactory.

Japanese Unexamined Patent Publication No. Sho 60-500452 and Japanese Unexamined Patent Publication No. Sho 63-215780 disclose a vinyl monomer having an organosilyl group such as a trialkylsilyl ester of (meth) acrylic acid. It is copolymerized with a monomer and has a number average molecular weight of 3,000 to 40,000.
Antifouling paint resin is described, and further, it is described that an organic water binder such as trimethyl orthoformate, an antifouling agent such as cuprous oxide, and a pigment such as red iron oxide can be blended. As described in Japanese Unexamined Patent Publication No. Hei 6-157940, this antifouling paint resin easily gels during storage, and the coating film formed from this antifouling paint has crack resistance and peel resistance. There is a problem that it is inferior.

Further, Japanese Patent Publication No. 5-32433 corresponding to the above-mentioned Japanese Patent Publication No. 60-500452 discloses a toxic substance (a),
Formula _{[(-CH 2 -CXCOOR) - (} B) -: X is H or CH _3, R is SiR _'3 or Si (OR') ₃ in R 'represents an an alkyl group, B is an ethylenically And a polymer binder (b) having a specific hydrolysis rate and the like. Pigment component,
Although it is described that an inert pigment, a filler, and a retarder may be contained, a coating film obtained from the antifouling paint described in this publication includes:
There is a problem that the crack resistance is poor.

Japanese Patent Application Laid-Open No. Hei 7-18216 discloses that (A) a compound of the formula (I): —COO—SiR ¹ R ² R ³ (where R ^{1 to} R ³ are alkyl groups having 1 to 18 carbon atoms, etc.) A) a coating composition comprising, as a main component, a polymer of an organosilicon-containing monomer A having a triorganosilicon ester group and (B) copper or a copper compound. As an essential component other than the component (B), the formula (C):

[0010]

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(In (C), R ^{4 to} R ^{6 each} represent a hydrogen atom, an alkoxy group having 1 to 18 carbon atoms, a cycloalkoxy group, and the like; R ⁷ represents an alkyl group having 1 to 18 carbon atoms;
and n represents an integer of 1 to 3). The publication also discloses a copolymer A of a monomer A having a group represented by the above formula (I) and a copolymerizable vinyl monomer B.
B may be contained, as monomer B,
(Meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate are mentioned.

However, the coating film obtained from the coating composition described in the publication has a problem that it is inferior in crack resistance and stain resistance. In addition, JP-A-7-102193 discloses a formula: X-
SiR ¹ R ² R ³ (wherein R ^{1 to} R ³ are all groups selected from an alkyl group and an aryl group, and may be the same or different from each other) .X is a monomer a represented by an acryloyloxy group, methacryloyloxy group, male alkanoyloxy group or fumaroyloxy group), the _{formula:. Y- (CH 2 CH 2} O) n -R 4 ( where R ⁴ is an alkyl group or an aryl group, Y is an acryloyloxy group or a methacryloyloxy group, and n is an integer of 1 to 25). A coating composition containing a polymer and an antifouling agent as essential components is disclosed. Examples of the antifouling agent include inorganic compounds such as copper compounds such as cuprous oxide and copper powder; zinc sulfate and zinc oxide; and organic copper-containing compounds such as oxine copper as organic compounds containing metals; And organic zinc-based compounds such as zinc pyrithione. However, this publication does not disclose any organic silyl ester group-containing polymer having both a linear alkyl group-containing silyl (meth) acrylate component unit and a branched alkyl group-containing silyl (meth) acrylate component unit. Above, there is a problem that the paint described in the publication is inferior in antifouling property.

(10) JP-A-8-199095 discloses that
Formula (1) described in JP-A-7-102193:
A monomer A represented by X-SiR ¹ R ² R ³ , and a formula (2): Y- (CH (R ⁴ ))-(OR ⁵ ) (where R ⁴
Is an alkyl group, and R ⁵ is an alkyl group or a cycloalkyl group. Y is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group or a fumaroyloxy group. ), A copolymer of a monomer mixture containing, if necessary, a vinyl monomer C copolymerizable with A and B, and an antifouling agent as essential components. Paint compositions are disclosed. Examples of the vinyl monomer C include acrylates, methacrylates, styrene, and vinyl acetate. Examples of the antifouling agent include inorganic compounds such as copper compounds such as cuprous oxide and copper powder; zinc sulfate and zinc oxide; and organic copper-containing compounds such as oxine copper as organic compounds containing metals; And organic zinc-based compounds such as zinc pyrithione.

(11) JP-A-8-269388 discloses that
Formula (1): X-SiR ¹ R ² R ³ (wherein, R ^{1 to} R ³ are all hydrocarbon groups having 1 to 20 carbon atoms, and are different groups even if they are the same group). And X is an acryloyloxy group, a methacryloyloxy group, a malenoyloxy group, a fumaroyloxy group or an itaconoyloxy group), and a monomer A represented by the formula (2): Y
— (CH ₂ CH ₂ O) _n —R ⁴ (where R ⁴ is an alkyl group or an aryl group, Y is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group, a fumaroyloxy group, or an itaconoyloxy group; n is 1
Is an integer of 〜25. A coating composition containing, as essential components, a copolymer of a monomer mixture containing a monomer B represented by the formula (1) and bis (2-pyridinethiol-1-oxide) copper salt (: copper pyrithione). Is disclosed. Further, as the monomer A, dimethyl-t-butylsilyl acrylate and the like can be mentioned. As the antifouling agent, an inorganic compound such as cuprous oxide, a copper compound such as copper powder, zinc sulfate,
Organic copper-based compounds such as oxine copper; organic nickel-based compounds;
Organozinc compounds such as zinc pyrithione; In addition, rosin as a dissolution rate regulator that can be added,
Rosin derivatives and the like are mentioned.

(12) JP-A-8-269389 discloses that
A copolymer of a monomer mixture containing an unsaturated monomer A having a triorganosilyl group and a monomer B represented by any of the following formulas (2) to (9); And a coating composition containing: Each monomer B is as follows. Formula (2) CH ₂ = CR ⁴ COOR ⁵ -NR ⁶ R ⁷ [R ⁴ is H
Or CH ₃ , R ⁵ represents an alkylene group, R ⁶ ,
R ⁷ is an alkyl group, which may be the same or different. Tertiary amino group-containing monomer represented by 'the formula ^{_{(3) CH 2 = CR 8}} COOR 9 -NR 10 R 11 R 12 (Y)
[R ⁸ represents H or CH ₃ , R ⁹ represents an alkylene group, R ^{10 to} R ¹² are alkyl groups, which may be the same or different, and Y represents a halogen atom. A quaternary ammonium salt-containing monomer represented by the formula: (4) CH ₂ ＣＨCH—Z [Z represents a group comprising an N-containing heterocyclic ring. A monomer containing a nitrogen-containing heterocycle represented by the formula: (5) CH ₂ ＣＲCR ¹³ COO (R ¹⁴ O) _m (R ¹⁵ O)
^{_{n (R 16 O) o -R}} 17 [R 1 3 is, H, indicates CH _3, R ¹⁴
Represents an ethylene group, R ¹⁵ represents an alkylene group having 3 carbon atoms, R ¹⁶ represents an alkylene group having 4 carbon atoms, and R ¹⁷ represents an alkyl group or an aryl group. m, n, and o are integers of 0 or more, and n and o are not simultaneously 0. A monomer having an alkoxy group or an aryloxyalkylene glycol group in the molecule represented by the formula: (6) CH ₂ ＣＲCR ¹⁸ CONR ¹⁹ R ²⁰ [R ¹⁸ is H, C
H ₃ is shown, and R ¹⁹ and R ²⁰ are alkyl groups which may be the same or different. (Meth) acrylic acid amide represented by the formula (7): CH ₂ ＣＲCR ²¹ CON⊂⊃Q [R ²¹ is H, CH ₃
Wherein N⊂⊃Q is an N-containing group, and Q may contain O, N, S and the like. (Meth) acrylamide containing a nitrogen-containing cyclic hydrocarbon group represented by the formula: (8) CH ₂ ＣＲCR ²³ COOCH ₂ -T [R ²³ is H,
CH ₃ is shown, and T represents a furan ring or a tetrahydrofuran ring. And a furan ring-containing (meth) acrylic acid ester represented by the formula (9): CH ₂ ＣＨCH—CN.

As optional components copolymerizable with the monomers A and B, various components such as acrylic acid, ethyl acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate can be used. Copolymerizable monomers are mentioned. Examples thereof include copolymers of tri-n-butylsilyl acrylate (TBSA), diethylaminoethyl methacrylate (DEAEMA) and methyl methacrylate (MMA), and tri-n-butylsilyl acrylate (TBSA) and N, N -Copolymers composed of dimethylacrylamide (DMAA) and methyl methacrylate (MMA) and the like are shown, but at least linear alkyl group-containing silyl (meth) acrylate and branched alkyl group-containing silyl (meth)
No copolymer using acrylate is disclosed.

Further, as a component which can be blended in the composition,
The same antifouling agent as the antifouling agent described in JP-A-8-269388 is mentioned. (13) JP-A-8-269390 discloses a formula (1): X
—SiR ¹ R ² R ³ (wherein, R ^{1 to} R ³ are all groups selected from an alkyl group and an aryl group, and may be the same or different groups. X is an acryloyloxy group, a methacryloyloxy group, a malenoyloxy group, a fumaroyloxy group or an itaconoyloxy group.) A polymer using the monomer A represented by the formula (2): Y- (CH ₂ CH ₂ O) _n -R ⁴ (where R ⁴ is an alkyl group or an aryl group, Y is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group, a fumaroyloxy group or an itaconoyloxy group, and n Is an integer of 1 to 25.) A coating composition containing a polymer using the monomer B represented by the formula (I) and an antifouling agent is disclosed. Examples of the antifouling agent include those described in JP-A-8-26.
The same antifouling agent as the antifouling agent described in No. 9388 is cited. In addition, resins that can be added include resins such as rosin, anti-settling agents, and the like.

(14) JP-A-8-277372 discloses that
The above (11): a monomer A represented by the formula (1): X-SiR ¹ R ² R ³ described in JP-A-8-269388, and a formula (2): Y also described in the same publication -(CH ₂ CH ₂ O) _n
Containing a copolymer of a monomer mixture containing a monomer B represented by -R ^4, and triphenyl boron pyridine complex,
A coating composition is disclosed in which the resin component and the marine organism adhesion inhibitor are composed only of a metal-free polymer and a metal-free organic inhibitor. In addition, rosin, rosin derivatives and the like are mentioned as dissolution rate regulators that can be added.

(15) JP-A-10-30071 discloses that
(A) one or more rosin compounds composed of rosin, rosin derivative or rosin metal salt, and (B) formula (1): X-SiR ¹ R ² R ³ (where R ^{1 to} R Each of ³ is a group selected from an alkyl group and an aryl group, and may be the same or different groups, and X is an acryloyloxy group, a methacryloyloxy group, a malenoyloxy group. , A fumaroyloxy group, an itaconoyloxy group, or a citraconoyloxy group.), And / or one or more polymers of the monomer M A coating composition comprising an organic silyl ester group-containing polymer composed of a polymer of two or more and one or two or more other polymerizable monomers, and (C) an antifouling agent is disclosed. I have. In addition, acrylic acid, methyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like as other monomers that can be copolymerized with the monomer M are exemplified. Are listed.

The antifouling agent is described in the above-mentioned JP-A-Hei-8.
The same antifouling agent as the antifouling agent described in JP-A-269388 is mentioned. In addition, pigments that can be added,
Chlorinated paraffins, anti-settling agents and the like are mentioned.
However, none of these publications (15) discloses copolymers using a combination of at least a linear alkyl group-containing silyl (meth) acrylate and a branched alkyl group-containing silyl (meth) acrylate. In the coating composition described in 1, the obtained coating film has poor crack resistance, or the obtained coating film has crack resistance, peeling resistance (coating adhesion), antifouling performance and long-term antifouling property, It is not sufficient in terms of balance such as abrasiveness.

Further, (16) Japanese Patent Publication No. 5-82865 discloses 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and the like as optional copolymerizable components. Also, (17) JP-A-9-48947
JP, (18) JP-A-9-48948, (19) JP-A-9-48949, (20) JP-A-9-48950, (21) JP-A-9-48951, (22) Tokuhei 5-
No. 32433, (23) US Pat. No. 4,593,055, (2
4) JP-A-2-196669, (25) WO91 / 1
No. 4743 describes a silyl (meth) acrylate copolymer. However, these publications (16)-
(25) has at least a linear alkyl group-containing silyl (meth) acrylate and a branched alkyl group-containing silyl (meth)
No copolymer using acrylate is disclosed.
In the antifouling paints using the copolymers described in these publications (16) to (25), the obtained coating film has poor crack resistance, or the obtained coating film has crack resistance and peel resistance. There is room for further improvement in terms of balance between (coating film adhesion), antifouling performance, long-term antifouling properties, and self-polishing properties.

(26) JP-A-63-215780 discloses that methyl methacrylate, n-
A copolymer using butyl methacrylate, acrylamide or the like is shown, and an antifouling paint in which the copolymer and cuprous oxide are blended is shown, but the same problem as the antifouling paint described in the above publication is shown. There is a point.

[0023]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above. It is an object of the present invention to provide an antifouling paint that is difficult to control, the hydrolysis rate of the coating film is well controlled, and an antifouling coating film having excellent antifouling property and long-term antifouling property under a high fouling environment.

Further, the present invention provides a method for antifouling a hull or an underwater structure (marine structure) using such an antifouling paint, and a hull or an underwater structure coated with an antifouling coating film having the above performance. It is intended to provide.

[0025]

Antifouling coating composition of the present invention SUMMARY OF THE INVENTION, (a) Formula _{[I]: - CH 2 -CR} (COOSiR 1 R 2 R 3) - ····· [I] [ Formula [I ], R represents a hydrogen atom or a methyl group, R ¹
And R ² each independently represent a linear alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group or trimethylsilyloxy group, and R ³ may have a ring structure or a branched structure. It represents a C1-C18 alkyl group, a C6-C10 optionally substituted phenyl group, or a trimethylsilyloxy group. Represented by a silyl (meth) acrylate component units], (b) formula _{[II]: - CH 2 -CR} (COOSiR 4 R 5 R 6) - ····· [II] [ Formula [II] in, R represents a hydrogen atom or a methyl group;
⁴ and R ⁵ each independently represent a branched alkyl group having 3 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, R ⁶ is a linear alkyl group having 1 to 10 carbon atoms, A branched or cycloalkyl group having 3 to 10 carbon atoms,
Or a phenyl group or a methylsilyloxy group having 6 to 10 carbon atoms which may be substituted. Gel permeation chromatography comprising a silyl (meth) acrylate component unit represented by the formula: and (c) an unsaturated monomer component unit other than the component units (a) and (b). It is characterized by containing a silyl (meth) acrylate copolymer [A] having a weight average molecular weight (Mw) measured by (GPC) of 200,000 or less, preferably 3000 to 100,000.

In the present invention, R ¹ and R in the above formula [I]
² and R ³ are each independently a methyl group, an ethyl group,
It is preferably any of an n-propyl group, an n-butyl group and an n-hexyl group. In the present invention, R ⁴ , R ⁵ and R ⁶ in the above formula [II] are preferably each independently any one of an isopropyl group, a sec-butyl group, a tert-butyl group and an isobutyl group.

In the present invention, the unsaturated monomer component unit (c) may be one or more compounds selected from (meth) acrylates, styrenes, and organic carboxylic acid vinyl esters. Is preferably derived from In the present invention, the silyl (meth) acrylate component unit (a) is 0.5 to 50% by weight, and the silyl (meth) acrylate component unit (b) is
10 to 70% by weight of the unsaturated monomer component unit (c)
Preferably, it is present at 20-70% by weight ((a) + (b) + (c) = 100% by weight).

In the present invention, it is preferable that the silyl (meth) acrylate copolymer [A] and the antifouling agent [B] are contained. In the present invention, the above silyl (meth)
It is preferable to contain the acrylate copolymer [A], [B] antifouling agent, and [C] zinc oxide. In the present invention,
The above silyl (meth) acrylate copolymer [A] and [B]
It preferably contains an antifouling agent and [D] an inorganic dehydrating agent.

In the present invention, it is preferable that the above-mentioned silyl (meth) acrylate copolymer [A], [B] antifouling agent, [C] zinc oxide, and [D] inorganic dehydrating agent are contained. . In the present invention, it is preferable to further contain [E] a dissolution promoting component. In the present invention, further derived from a vinyl ether represented by the formula [III]: H ₂ C ＝ CHO-R (III, wherein R represents a hydrocarbon group) It is preferable to contain a vinyl ether (co) polymer [F] containing the component unit to be obtained.

In the present invention, as the antifouling agent [B], copper and / or a copper compound (particularly, copper and / or inorganic copper compound [B-1]) and an organic antifouling agent [B-2] are used. It is preferable to use either one or both. In the present invention, the organic antifouling agent [B-2] is a metal pyrithione, pyridine-triphenylborane, amine-triphenylborane, N, N-dimethyldichlorophenylurea,
2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, 4,5-dichloro-2-
It is preferably at least one organic antifouling agent selected from the group consisting of n-octyl-4-isothiazolin-3-one and 2,4,5,6-tetrachloroisophthalonitrile.

In the present invention, the organic antifouling agent [B-2] is used.
Is preferably 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one. In the present invention, the organic antifouling agent [B-2] is N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropyl. Amino-s-triazine,
At least one organic antifouling agent selected from the group consisting of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and 2,4,5,6-tetrachloroisophthalonitrile; It is preferable to use a combination of pyrithiones.

In the present invention, the organic antifouling agent [B-2] is used.
Is copper pyrithione and / or zinc pyrithione;
It is preferable to use a combined system with 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one. In the present invention, the elution promoting component [E] is preferably at least one selected from rosin, a rosin derivative, naphthenic acid and a metal salt thereof.

In the present invention, the unsaturated monomer component unit (c) may be a (meth) acrylate, styrene,
1 selected from organic carboxylic acid vinyl esters
It is preferably derived from one or more compounds. The antifouling coating film according to the present invention is formed from the above antifouling coating composition. The antifouling method for a hull or a marine structure according to the present invention is characterized in that the antifouling paint composition is applied to the surface of a hull or a marine structure to cover the surface.

The hull or the marine structure according to the present invention is characterized in that the surface of the hull or the marine structure is coated with a coating film comprising the antifouling coating composition. According to the antifouling coating composition according to the present invention, cracks are hardly generated in the coating film, the coating film adhesion is good, the coating film is hardly peeled off, the hydrolysis rate of the coating film is well controlled, and the antifouling An antifouling coating film having excellent performance (antifouling activity), especially excellent antifouling property and long-term antifouling property in a high fouling environment, and having well-balanced excellent properties.

[0035]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the antifouling coating composition according to the present invention will be specifically described. The antifouling coating composition according to the present invention contains a silyl (meth) acrylate copolymer [A]. First, the silyl (meth) acrylate copolymer and a method for producing the same will be specifically described.

<Silyl (meth) acrylate copolymer>
This silyl (meth) acrylate copolymer has the following formula
Silyl (meth) acrylate component unit (a) represented by [I]
And an acrylic unsaturated monomer component unit (b) represented by the following formula [II], and an unsaturated monomer component unit (c) other than these component units (a) and (b): It is composed of

Hereinafter, the respective component units (a), (b) and (c) constituting the silyl (meth) acrylate copolymer will be sequentially described. [Silyl (meth) acrylate component unit (a)] The silyl (meth) acrylate component unit (a) is represented by the following formula [I]. Formula _{[I]: - CH 2 -CR} (COOSiR 1 R 2 R 3) - ····· [I] formula [I], R represents a hydrogen atom or a methyl group, R ¹ and R ² are And each independently represents a linear alkyl group having 1 to 10, preferably 1 to 8, more preferably 1 to 6 carbon atoms, or an optionally substituted phenyl group or trimethylsilyloxy group. Examples of the straight-chain alkyl group include a methyl group, an ethyl group, an n-propyl group, and n
-Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group.

Examples of the substituent capable of substituting a hydrogen atom in the phenyl group include alkyl, aryl, and halogen. R ³ is an alkyl group having 1 to 18, preferably 1 to 12, more preferably 1 to 9 carbon atoms which may have a ring structure or a branch, and 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. Optionally substituted phenyl group or trimethylsilyloxy group: “(CH ₃ ) ₃ SiO—”
It is.

Examples of such an alkyl group include the linear alkyl groups exemplified above;
branched alkyl groups such as o-butyl group, sec-butyl group, tert-butyl group and neo-pentyl group; alicyclic groups having an alicyclic structure (cyclohexane ring, norbornane ring) such as cyclohexyl group and ethylidene norbornyl group Alkyl group; and the like.

Among them, R ¹ , R ² and R ³ may be the same or different from each other, but may be a methyl group,
Ethyl, n-propyl, n-butyl, n-hexyl and trimethylsilyloxy are preferred, and methyl, n-propyl, n-butyl and n-hexyl are particularly preferred. Silyl (meth) acrylate capable of deriving such a silyl (meth) acrylate component unit (a)
(a1) is represented by the following formula [Ia].

CH ₂ ＣＲCR (COOSiR ¹ R ² R ³ ) [Ia] In the formula [Ia], R is the same as R in the above formula [I], and is a hydrogen atom Or a methyl group, and R ¹ and R ² also represent
It is the same as R ¹ and R ² in the above formula [I], and independently represents a linear alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group or a trimethylsilyloxy group. , R ³ also in the same manner as R ³ in the formula [I],
1 to 18 carbon atoms which may have a ring structure or a branch
An optionally substituted phenyl group having 6 to 10 carbon atoms, or a trimethylsilyloxy group.

Such a silyl (meth) acrylate [I
-a] is, for example, trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl (meth) acrylate, tri-n- (meth) acrylate Butylsilyl ester, tri-n-pentylsilyl (meth) acrylate, tri-n-hexylsilyl (meth) acrylate, tri-n-heptylsilyl (meth) acrylate, tri-n-octylsilyl (meth) acrylate Aliphatic silyl (meth) acrylates in which R ¹ , R ² and R ³ are the same, such as esters, tri-n-nonylsilyl (meth) acrylate, and tri-n-decylsilyl (meth) acrylate; In addition to triphenylsilyl (meth) acrylate, tris (meth) acrylate (trimethyl ^{Silyloxy) R 1, R 2, R} 3 are identical aromatic or siloxane type silyl (meth) acrylates such as silyl esters (meth) acrylic acid dimethyl n- propyl silyl ester, (meth) acrylic acid isopropyl dimethylsilyl Esters, di-n-butyl-iso-butylsilyl (meth) acrylate,
N-hexyl-dimethylsilyl (meth) acrylate, sec-butyl-dimethylsilyl (meth) acrylate, monomethyldi-n-propylsilyl (meth) acrylate, methylethyl n-propylsilyl (meth) acrylate , (Meth) acrylic acid ethylidene norbornyl-dimethylsilyl ester, (meth) acrylic acid trimethylsilyloxy-dimethylsilyl ester [CH ₂ ＣC (CH ₃ ) COOSi (CH ₃ ) ₂
(OSi (CH ₃ ) ₃ ), CH ₂ ＣＨCHCOOSi (C
_{H 3) 2 (OSi (CH} 3) 3)] R 1, silyl (meth) acrylates of a part or aliphatic in which all different from each other of R ² and R ³ as such; like can be mentioned Can be

In the present invention, the silyl (meth) acrylate [Ia] can be used alone or in combination of two or more. The silyl (meth) acrylate component unit (b) is represented by the following formula [II]. _{^{-CH 2 -CR (COOSiR 4 R 5}} R 6) - ····· [II] formula [II], R represents a hydrogen atom or a methyl group, R ⁴
And R ⁵ each independently represent a branched alkyl group having 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms, or 3 to 1 carbon atoms.
It represents 0, preferably 3 to 9 cycloalkyl groups.

As the above-mentioned branched alkyl group, the above-mentioned formula [I]
As in the above, iso-propyl, iso-butyl, sec-butyl, tert-butyl, iso-
And branched alkyl groups such as -butyl group and neo-pentyl group. Examples of the cycloalkyl group include a cyclohexyl group and an ethylidene norbornyl group.

R ⁶ has 1 to 10 carbon atoms, preferably 1 carbon atom.
To 8, more preferably 1 to 6 linear alkyl groups, 3 to 10 carbon atoms, preferably 3 to 9 branched or cycloalkyl groups, or 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms.
A phenyl group which may be substituted, or a trimethylsilyloxy group. A linear alkyl group in R ⁶ ,
Specific examples of the branched or cycloalkyl group and the phenyl group include the same groups as described above.

Of these, R ⁴ , R ⁵ , and R ⁶ may be the same or different from each other, but when they are the same, an isopropyl group, a sec-butyl group, an iso-butyl group,
-Butyl group is preferred, especially, iso-propyl group, s
An ec-butyl group is preferred. When some or all of R ⁴ , R ⁵ and R ⁶ are different, R ⁴ and R ⁵ may be the same or different from each other, but R ⁴ and R ⁵ are iso.
-Propyl group, iso-butyl group, sec-butyl group,
A tert-butyl group is preferred, and R ⁶ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, and a trimethylsilyloxy group.

The silyl (meth) acrylate (b) from which such a silyl (meth) acrylate component unit (b) can be derived
1) is represented by the following formula [II-a]. CH ₂ = CR (COOSiR ⁴ R ⁵ R ⁶ ) [II-a] In the formula [II-a], R is the same as R in the above formula [II] and is hydrogen. indicates an atom or a methyl group, there is R ⁴ and R ⁵ also similar to R ⁴ and R ⁵ in the formula [II], each independently, a branched alkyl group or carbon number of carbon atoms 3-10 there a cycloalkyl group having from 3 to 10, there is R ⁶ also similar to R ⁶ in the formula [II], 1 carbon atoms
A linear alkyl group having 10 to 10 carbon atoms, a branched or cycloalkyl group having 3 to 10 carbon atoms, an optionally substituted phenyl group having 6 to 10 carbon atoms, or a trimethylsilyloxy group.

Such a silyl (meth) acrylate [I
Specific examples of Ia] include, for example, triiso-propylsilyl (meth) acrylate, triiso-butylsilyl (meth) acrylate, and trisec-butylsilyl (meth) acrylate. R ⁴ , R ⁵ and R ⁶ are the same silyl (meth) acrylate, (meth) acrylic acid diiso-propyl-cyclohexylsilyl ester, (meth) acrylic acid diiso-
Propyl-phenylsilyl ester, diiso-propyl (meth) acrylate-trimethylsiloxysilyl ester, disec-butyl-methyl-silyl (meth) acrylate, disec-butyl (meth) acrylate-
Ethyl silyl ester, (meth) acrylic acid disec-
Silyl (meth) acrylate in which one or all of R ⁴ , R ⁵ and R ⁶ are different from each other, such as butyl-trimethylsilyloxysilyl ester and iso-propyl-sec-butyl-methylsilyl (meth) acrylate And the like.

In the present invention, such silyl (meth) acrylate [II-a] can be used alone or in combination of two or more. Such silyl (meta)
Among the acrylates, in particular, the ease of synthesizing the silyl (meth) acrylate copolymer, or the film-forming properties, storage stability, and polishing properties of the antifouling paint composition using such a silyl (meth) acrylate copolymer are improved. Considering the ease of controlling the scavenging property, of silyl (meth) acrylate [Ia], trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate,
(Meth) acrylic acid tri-n-propylsilyl ester,
(Meth) acrylic acid tri-n-butylsilyl ester,
N-hexyl-dimethylsilyl (meth) acrylate, n-octyl-dimethylsilyl (meth) acrylate, iso-propyl-dimethylsilyl (meth) acrylate, ethylidenenorbornyl-dimethyl (meth) acrylate Any one selected from silyl ester, trimethylsilyloxy- (meth) acrylate-dimethylsilyl ester, bis (trimethylsilyloxy) -methyl (meth) acrylate, and tris (trimethylsilyloxy) silyl (meth) acrylate Or two or more of tri (meth) acrylates of silyl (meth) acrylate [II-a]
So-propylsilyl ester, triiso-butylsilyl (meth) acrylate, trisec-butylsilyl (meth) acrylate, disec-butyl-methylsilyl (meth) acrylate, (meth)
It is preferable to use any one or more selected from diiso-propyl acrylate-trimethylsilyloxysilyl acrylate and disec-butyl-trimethylsilyloxysilyl (meth) acrylate in combination.

Further, silyl (meth) acrylate [I
-a], tri-n-butylsilyl (meth) acrylate and triiso-propylsilyl (meth) acrylate of silyl (meth) acrylate [II-a] are used in combination. Is preferred.

[Unsaturated monomer component unit (c)] The unsaturated monomer component unit (c) includes the component unit (a) and the component unit (c).
(b) constitutes the silyl (meth) acrylate copolymer, and is a component unit different from any of the above component units (a) and (b); Specific examples of the unsaturated monomer (c1) from which (c) can be derived include, for example, methyl (meth) acrylate, (meth)
Ethyl acrylate, n-, iso- (meth) acrylate,
hydrophobic (meth) acrylates such as tert-butyl, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate; (meth) acrylic acid 2
-Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methyl (meth) acrylate Hydrophilic (meth) acrylates such as polyoxyethylene and methyl (meth) acrylate polyoxypropylene; styrenes such as styrene, vinyltoluene and α-methylstyrene; vinyl acetate, vinyl benzoate, vinyl propionate; Vinyl esters such as vinyl butyrate; organic carboxylic esters such as itaconic esters and maleic esters; and the like. Among these, (meth) acrylic esters, styrenes, and organic vinyl carboxylate Esters provide antifouling coatings with moderate coating strength For preferred.

The use of hydrophilic (meth) acrylic esters can increase the consumption of the coating film. For this purpose, it is possible to use a hydrophilic comonomer such as an acrylamide derivative. These unsaturated monomers (c)
Are used alone or in combination of two or more. In the silyl (meth) acrylate copolymer, the silyl (meth) acrylate component unit (a) is used in an amount of 0.5 to 50% by weight, preferably 0.5 to 25% by weight. The acrylate component unit (b) is used in an amount of 10 to 70% by weight, preferably 30 to 65% by weight,
The unsaturated monomer component unit (c) other than (b) is 20 to 70% by weight, preferably 30 to 60% by weight ((a) + (b) + (c) = 1).
(00% by weight) is desirable in terms of preventing cracks in the coating film, peeling resistance of the coating film, strength of the coating film, and consumability.

The weight average molecular weight of such a silyl (meth) acrylate copolymer measured by gel permeation chromatography (GPC) is 200,000 or less.
Preferably 3000 to 100,000, particularly preferably 5000
-50,000, the ease of preparing an antifouling paint containing the silyl (meth) acrylate copolymer, the workability of coating the obtained antifouling paint, the consumption rate of the antifouling coating, and the crack resistance. It is desirable in such points.

<Silyl (meth) acrylate copolymer
Production> In order to obtain such a silyl (meth) acrylate copolymer, 0.5 to 50% by weight of the silyl (meth) acrylate (a1) represented by the above formula [Ia] and the above formula [II-a 10 to 70% by weight of the unsaturated monomer (b1) represented by the formula (I) and another unsaturated monomer (c1) copolymerizable with the monomers [Ia] and [II-a]: 70% by weight (however, (a1) + (b1) + (c1) = 10
0% by weight) in the presence of a radical polymerization initiator by random polymerization by various methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization.

As the radical polymerization initiator, conventionally known azo compounds and peroxides can be widely used, and specific examples of the azo compound include, for example, 2,2.
2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and the like. For example, benzoyl peroxide, tert
-Butyl peroxy acetate, tert-butyl peroxy octate, cumene hydroperoxide, t
tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, tert-butyl hydroperoxide, persulfate (potassium salt, ammonium salt) and the like.

When the above polymer is used in an antifouling paint,
Among the above various polymerization methods, a solution polymerization method or a bulk polymerization method in which polymerization is performed in an organic solvent is preferable. As the organic solvent used in the solution polymerization, aromatic hydrocarbons such as xylene and toluene; hexane, Aliphatic hydrocarbons such as heptane; esters such as ethyl acetate and butyl acetate; alcohols such as isopropyl alcohol and butyl alcohol; ethers such as dioxane and diethyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; No. These solvents are used alone or in combination of two or more.

<Antifouling paint composition> The antifouling paint composition according to the present invention includes the above silyl (meth) acrylate copolymer.
[A] is contained as a coating film forming component and a dissolution controlling component. According to the antifouling paint containing the silyl (meth) acrylate copolymer, a crack is not easily generated in the coating film, the adhesion of the coating film is good, the coating film is hardly peeled off, and the hydrolysis rate of the coating film is low. An antifouling coating film that is well controlled, has high antifouling properties, particularly high antifouling properties in a high fouling environment, and has excellent long-term antifouling properties can be obtained.

Such an antifouling paint composition is also referred to as the silyl (meth) acrylate copolymer [A] [(meth) acrylic acid silyl ester copolymer.必須 as an essential component, but in addition to the silyl (meth) acrylate copolymer [A] component, various antifouling agents [B] such as copper and / or inorganic copper compounds [B-1], and oxidizing agents Zinc (zinc flower)
[C], a dehydrating agent such as an inorganic dehydrating agent [D], an anti-sagging / anti-sedimentation agent, an elution-promoting component [E] such as rosin, a plasticizer such as chlorinated paraffin, various pigments such as coloring pigments and extenders, Contains the following components such as acrylic resin, various resins such as polyalkyl vinyl ether (vinyl ether (co) polymer [F]), various additives such as antifoaming agent, anti-separation agent, and leveling agent. You may.

[Antifouling Agent [B]] The antifouling agent [B] may be any of an organic type and an inorganic type, and conventionally known ones can be widely used. , Copper and / or a copper compound (particularly, copper and / or an inorganic copper compound [B-1]) or an organic antifouling agent [B-2] such as a metal pyrithione described later.

First, copper and / or copper compounds (excluding pyrithiones; the same applies hereinafter) will be described. The copper compound has a molecular weight of 63.5 to 2000,
Preferably 63.5 to 1000 are used. Such a copper compound may be any of an organic copper compound and an inorganic copper compound. Examples of the inorganic copper compound include cuprous oxide, copper thiocyanate (copper thiocyanate, and copper rhodan). ), Basic copper sulfate, copper chloride, copper oxide and the like. Examples of organic copper compounds include basic copper acetate, oxine copper, copper nonylphenol sulfonate, and copper bis (ethylenediamine) -bis (dodecylbenzenesulfonate). ), Copper naphthenate, rosin copper, bis (pentachlorophenolic acid) copper, and the like, and preferably an inorganic copper compound, for example, cuprous oxide or copper thiocyanate (rhodan copper).

Such a copper compound can be used in place of copper or in combination with copper, alone or in combination of two or more. Such copper and / or copper compound is usually contained in the antifouling coating composition in a total amount of 1 to 70% by weight,
Preferably, it is contained in an amount of 3 to 65% by weight. In addition, the total amount of the copper and / or copper compound is usually 3 to 1400 with respect to 100 parts by weight of the silyl (meth) acrylate copolymer contained in the antifouling coating composition.
It is desirable to include it in an amount of 10 parts by weight, preferably 10 to 1300 parts by weight.

When this copper and / or copper compound is in the above range in the antifouling coating composition, the antifouling property tends to be excellent. In the present invention, as an antifouling agent,
An organic antifouling agent [B-2] is preferably used together with the copper and / or copper compound (particularly copper and / or inorganic copper compound) or instead of the copper and / or copper compound.

As the organic antifouling agent [B-2], for example, a pyrithione compound represented by the following formula [IV] (that is, metal-pyrithiones) [wherein R ^{1 to} R ⁴ are each independently hydrogen , An alkyl group, an alkoxy group, or a halogenated alkyl group, and M represents Zn, Cu, Na, Mg, Ca, Ba,
Represents a metal such as Pb, Fe, or Al, and n represents a valence].

[0064]

Embedded image

Such a pyrithione compound is usually contained in the antifouling coating composition in a total amount of 0.1 to 15% by weight,
Preferably, it is contained in an amount of 0.5 to 10% by weight. Further, based on 100 parts by weight of the silyl (meth) acrylate copolymer contained in the antifouling coating composition,
The pyrithione compound is usually 0.3 to 300 in total.
It is desirable to include it in an amount of 2 parts by weight, preferably 2 to 200 parts by weight.

The antifouling coating composition of the present invention may contain the following organic antifouling agent (other organic antifouling agent) together with or instead of the pyrithione compound. Well, as such other organic antifouling agent, various conventionally known antifouling agents can be used. Specifically, for example, tetramethylthiuram disulfide, carbamate-based compound (eg, zinc) Dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate), 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, 2-methylthio-4-tert-butylamino-
6-cyclopropylamino-s-triazine, 4,5-
Examples thereof include dichloro-2-n-octyl-4-isothiazolin-3-one, 2,4,6-trichlorophenylmaleimide, pyridine-triphenylborane, and amine-triphenylborane. In the present invention, such an organic antifouling agent is used as zinc pyrithione (the above formula [IV]
And R ^{1 to} R ⁴ = H, M = Zn, and n = 2),
Copper pyrithione (in the above formula [IV], R ^{1 to} R ⁴ = H, M = C
These compounds can be used alone or in combination of two or more with a pyrithione compound (metal pyrithiones) such as u, n = 2. For example, copper pyrithione and / or zinc pyrithione and 4,5-dichloro-2
-N-octyl-4-isothiazolin-3-one can be used in combination.

The content of various antifouling agents such as copper and / or copper compounds and pyrithione compounds contained in the antifouling paint composition according to the present invention depends on the amount of the antifouling agent used in preparing the antifouling paint composition. , A type of a film-forming copolymer, or a type of a ship to which such an antifouling paint composition is applied and formed (for a ship, it is used for ocean-going, domestic, various seawater, and wooden-
Although it is not determined more unequivocally for steel ships, etc., the total amount of the antifouling agent is usually 10 to 1400 parts by weight, preferably 20 to 1300 parts by weight based on 100 parts by weight of the silyl (meth) acrylate copolymer. Desirably, it is contained in an amount of parts by weight.

When the total amount of the antifouling agent is less than 10 parts by weight, the antifouling property may be inferior. When the total amount exceeds 1400 parts by weight, no more antifouling property can be expected and crack resistance may be inferior. is there. For example, when copper pyrithione and cuprous oxide (Cu ₂ O) are used in combination as an antifouling agent, copper pyrithione is a silyl (meth) acrylate copolymer 1
The cuprous oxide is used in an amount of usually about 10 to 1300 parts by weight based on 100 parts by weight of the silyl (meth) acrylate copolymer. It may be contained in the coating composition.

[ Zinc oxide (zinc white) [C]] Such an antifouling coating composition may contain zinc oxide (zinc white). In the antifouling coating composition containing zinc oxide as described above, the strength of the obtained coating film is improved, and the abrasiveness of the coating film can be effectively controlled.

Such zinc oxide is usually added to the antifouling coating composition in an amount of 0.5 to 35% by weight, preferably 1 to 25% by weight, from the viewpoint of adjusting the degree of wear and the hardness of the coating film. It is desirable that it be contained in the amount of. [Dehydrating agent] The antifouling coating composition may contain an inorganic or organic dehydrating agent, preferably an inorganic dehydrating agent. The antifouling paint composition containing the dehydrating agent as described above can further improve the storage stability.

As the dehydrating agent, for example, anhydrous gypsum (Ca
SO ₄ ), synthetic zeolite-based adsorbents (trade name: molecular sieve, etc.), orthoesters such as methyl orthoformate, methyl orthoacetate, orthoborates, silicates and isocyanates (trade name: Additive T
1) and the like. In particular, as the inorganic dehydrating agent [D], anhydrous gypsum and molecular sieve are preferably used. Such an inorganic dehydrating agent [D] can be used alone or in combination of two or more.

Such a dehydrating agent, particularly the inorganic dehydrating agent [D],
It is preferable that the amount is usually 0.02 to 100 parts by weight, preferably 0.2 to 50 parts by weight, based on 100 parts by weight of the silyl (meth) acrylate copolymer. In addition, such an inorganic dehydrating agent is desirably contained in the antifouling coating composition in a total amount of usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight. .
When the inorganic dehydrating agent is contained in such an amount in the antifouling coating composition, storage stability tends to be improved.

[Elution Acceleration Component [E]] Elution Acceleration Component [E]
Has a function of accelerating the self-polishing action of a coating film in seawater. Examples of such an elution-promoting component include rosin (eg, trade name “Rosin WW”) and derivatives thereof, monocarboxylic acids and salts thereof, and the like. Is mentioned. The rosin includes gum rosin, wood rosin, tall oil rosin and the like, and any of them can be used in the present invention. Derivatives of rosin include, for example, disproportionated rosin, low melting point disproportionated rosin, hydrogenated rosin, polymerized rosin, maleated rosin, aldehyde-modified rosin, polyoxyalkylene ester of rosin, reduced rosin (rosin alcohol), rosin And metal salts of rosin derivatives (such as rosin and copper salts, zinc salts, and magnesium salts of rosin derivatives), and rosin amine. These rosins and their derivatives can be used alone or in combination of two or more.

Examples of the monocarboxylic acid include fatty acids having about 5 to 30 carbon atoms, synthetic fatty acids, and naphthenic acid. As salts of monocarboxylic acids, Cu salt, Zn
Salt, Mg salt, Ca salt and the like. Among these elution promoting components, rosin or a derivative thereof or a metal salt of naphthenic acid is preferred. These elution promoting components include 1
They can be used alone or in combination of two or more. These elution promoting components are contained in the antifouling coating composition in an amount of 0.1 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight in terms of solid content. Is desirably contained. It is desirable that the compounding ratio of the elution promoting component be in this range from the viewpoint of the antifouling performance and the water resistance of the coating film.

Further, based on 100 parts by weight of the silyl (meth) acrylate copolymer contained in the antifouling coating composition,
The dissolution promoting component is desirably contained in a total amount of usually 0.3 to 600 parts by weight, preferably 2 to 300 parts by weight. When the elution promoting component is in this range in the antifouling coating composition, the antifouling property and the consumable property of the coating film tend to be excellent.

[Vinyl ether (co) polymer [F]] This vinyl ether (co) polymer is represented by the formula [IV]: H ₂ C = CHO—R [IV] (formula [IV] Wherein R represents a hydrocarbon group.) (Co)
It is a polymer.

The vinyl ether [IV] is a vinyl ether
Tell bond (H_TwoVinyl ether having C = CH-O-)
And the hydrocarbon group R in the formula [IV] is usually a carbon
Aliphatic and aromatic hydrocarbon groups having a prime number of 1 to 25 are listed.
And may be linear or branched.
It has an alicyclic structure represented by a rohexyl ring,
Is also good. In addition, the hydrocarbon group (when the number of carbon atoms is 2 or more,
Carbon atom constituting C) ¹Is included in the alkyl group.
Carbon atom C¹Carbon atom C adjacent to^TwoAnd through the oxygen atom
To an ether bond (C¹-OC^Two) May be formed
And the hydrogen atoms that make up the hydrocarbon group
Group (-OH, -NH_TwoEtc.)
No.

More specifically, R in the above formula [IV] is 1
Represents a monovalent hydrocarbon group, and examples of the monovalent hydrocarbon group include an alkyl group and an optionally substituted phenyl group. The above vinyl ether (co) polymer has the above formula [I
V] or a vinyl ether copolymer containing the vinyl ether [IV] as a main component in an amount of 50% by weight or more (these are collectively referred to as “vinyl ether (co) polymer”). It is also desirable.).

Specific examples of the vinyl ether (co) polymer include polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl isopropyl ether, and polyvinyl isobutyl ether. Such a vinyl ether (co) polymer may be contained in the antifouling coating composition in a total amount of usually 0.1 to 10% by weight, preferably 0.2 to 5% by weight. desirable. The vinyl ether (co) polymer is usually added in an amount of 0.1 part by weight based on 100 parts by weight of the silyl (meth) acrylate (co) polymer contained in the antifouling coating composition.
It is desirably contained in an amount of 3 to 60 parts by weight, preferably 0.6 to 40 parts by weight.

When the vinyl ether (co) polymer is in this range in the antifouling coating composition, the resulting coating film has antifouling properties, crack resistance, peeling resistance, elution rate stability and the like. Tend to be better. [Anti-sagging / Anti-settling agent] As the anti- sagging / anti-settling agent, a known anti-sagging / anti-settling agent may be blended in any amount. Such anti-sagging / anti-settling agents include Al, Ca, Zn stearate salts, lecithin salts,
Salts such as alkyl sulfonates, polyethylene wax, amide wax, hydrogenated castor oil wax type, polyamide wax type and mixtures thereof, synthetic finely powdered silica, polyethylene oxide type wax, etc., preferably hydrogenated castor oil wax , A polyamide wax, a synthetic finely divided silica, and a polyethylene oxide wax. Examples of such anti-sagging and anti-settling agents include those marketed under the trade names such as "DISPARON A-603-20X" and "DISPARON 4200-20" manufactured by Kusumoto Kasei Co., Ltd.

[Pigment, Solvent ] Examples of pigments include various types of conventionally known organic and inorganic pigments (eg, titanium white, red iron,
Organic red pigment, talc, etc.). Note that various colorants such as dyes may be included. The crack resistance of the coating film can be further improved by using needle-like, flat-like, or scale-like pigments.

As the solvent, for example, various solvents such as an aliphatic type, an aromatic type (eg, xylene, toluene), a ketone type, an ester type, and an ether type which are usually blended in an antifouling paint are used. . < Production of antifouling paint composition> Such an antifouling paint composition can be produced by appropriately utilizing a conventionally known method. For example, the above silyl (meth) acrylate copolymer [A] And copper and / or copper compound (particularly copper and / or inorganic copper compound [B-1]) in an amount of 3 to 1400 parts by weight based on 100 parts by weight of the copolymer,
Organic antifouling agent such as pyrithione compound in an amount of 00 parts by weight
[B-2] (however, 25 to 1200 parts by weight in total of antifouling agent [B])
A vinyl ether (co) polymer [F] in an amount of 0.3 to 200 parts by weight, and zinc white (zinc oxide) [C] optionally used in an amount of 2 to 700 parts by weight; ~ 2
A dehydrating agent in an amount of 00 parts by weight, particularly an inorganic dehydrating agent (eg, anhydrous gypsum, molecular sieve), and an anti-sagging / anti-settling agent, a pigment, a solvent, and the like used in appropriate amounts are added all at once or in any order. What is necessary is just to stir, mix, and disperse.

This antifouling paint composition is a one-part composition, has excellent storage stability, and satisfies various required properties such as adhesion, durability, and antifouling properties of the antifouling paint. The above antifouling paint composition is applied to various marine civil engineering works such as underwater / overwater structures, that is, marine structures (eg, water supply / drainage ports of nuclear power plants), bay roads, submarine tunnels, port facilities, canals and waterways. Sludge diffusion prevention membranes, ships, fishing gear (eg ropes, fishing nets)
By applying it once to a plurality of times on the surface of various molded articles such as the above, a hull or marine structure coated with an antifouling coating film having excellent crack resistance and antifouling properties can be obtained. The antifouling paint composition may be applied directly to the surface of the hull or marine structure or the like, or the surface of a hull or marine structure or the like to which a base material such as a rust preventive or a primer has been applied in advance. May be applied. Further, hulls, marine structures, etc., which have already been coated with a conventional antifouling paint, or have been coated with the antifouling paint composition of the present invention containing the silyl (meth) acrylate copolymer described above. May be overcoated with the antifouling paint composition of the present invention for repair. The thickness of the antifouling coating film formed on the surface of the hull, marine structure, or the like in this manner is not particularly limited.
It is about 50 μm / time.

[0084]

According to the antifouling paint composition of the present invention,
The coating film is hardly cracked, the coating film adhesion is good, the coating film is hardly peeled off, the hydrolysis rate of the coating film is well controlled, the antifouling performance (antifouling activity), especially the antifouling under high fouling environment. It is possible to obtain an antifouling coating film which is excellent in stainability and long-term antifouling property and excellent in these properties in a well-balanced manner.

[0085]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following production examples and comparative examples of polymers, "parts" means "parts by weight".

[0086]

[Production Example of Polymer] (Production of Copolymer S-1) Xylene 100 was placed in a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating / cooling jacket.
The resulting mixture was heated and stirred under a nitrogen stream at a temperature of 85 ° C. While maintaining the same temperature, 50 parts of triisopropylsilyl acrylate, 5 parts of tri-n-butylsilyl methacrylate, 45 parts of methyl methacrylate, and 2,2′-azobisisobutyro as a polymerization initiator were introduced into the reactor from the dropping apparatus. A mixture of 1 part of nitrile was added dropwise over 2 hours. Then, after stirring at the same temperature for 4 hours, 2,2 ′
-Add 0.4 parts of azobisisobutyronitrile and further stir at the same temperature for 4 hours to obtain a colorless and transparent copolymer solution S-
1 was obtained.

The heating residue of the obtained copolymer solution S-1 (heating residue after drying in a thermostat at 105 ° C. for 3 hours) was 5%.
The viscosity at 25 ° C. is 264 cps, and the number average molecular weight (Mn) measured by GPC is 5%.
223, and the weight average molecular weight (Mw) was 19196. FIG. 1 shows a GPC chromatogram of copolymer S-1.
FIG. 4 shows a chart of the IR spectrum.

The measurement conditions of GPC and IR are as follows. [GPC Measurement Conditions] Apparatus: Tosoh HLC-8120 GPC Column: Tosoh Super H2000 + H4000 6 mm I.C. D. , 15 cm Eluent: THF flow rate: 0.500 ml / min Detector: RI column constant temperature bath temperature: 40 ° C. [IR measurement conditions] Apparatus: Hitachi Ltd. Model 270-30 Hitachi infrared spectrophotometer Measurement method: KBr Cell, Coating Method [Production Examples and Comparative Examples of Copolymers S-2 to S-11 and Copolymers 1 to H5 for Comparative Example] Drops were produced during the production of the copolymer S-1. Copolymer S-2 was prepared in the same manner as described above, except that the components were changed as shown in Tables 1 to 3.
~ Copolymer S-11 and copolymers H1 to H5 for comparative examples
Was obtained, and the physical property values of these copolymers (solutions) were measured in the same manner as described above.

The results are shown in Tables 1 to 3. GPC chromatograms of copolymer S-2 and copolymer S-3 are shown in FIGS. 2 and 3, respectively, and IR spectrum charts are shown in FIGS. 5 and 6, respectively.

[0090]

[Production Examples 1 to 23 of Antifouling Paint, Comparative Production Examples 1 to 5]
[Production example of antifouling paint composition] When producing antifouling paint compositions having the composition shown in Tables 4 to 6, these ingredients were shaken together for 2 hours in a paint shaker containing glass beads. After crushing, the mixture was filtered with a 100-mesh filter to obtain a desired antifouling paint composition.

The storage stability of the antifouling coating composition after storage at room temperature for 2 months is shown in Tables 4 to 6. The storage stability was evaluated immediately after the trial production of the paint and after storage for 2 months at room temperature (Ku at 25 ° C.
Value). (Evaluation criteria) 5: Increase in viscosity is less than 10 4: Increase in viscosity is 10 or more to less than 20 3: Increase in viscosity is 20 or more to less than 30 2: Increase in viscosity is 30 or more and poor fluidity 1: Flow No measurement and no Ku value.

Further, antifouling properties using the antifouling coating composition,
The degree of wear was evaluated as follows. Table 4 ~
6 is shown. (In the table, the production examples and comparative examples of the antifouling paint composition are simply referred to as examples and comparative examples.) [Evaluation of antifouling property] Side surface of rotating drum installed in seawater of Hiroshima Bay 70 × which is bent so that it can be attached to
A 200 × 3 mm sandblast steel plate was prepared.

An epoxy-based zinc-rich primer, an epoxy-based anticorrosive paint, and a vinyl-based binder coat were each applied to the sandblasted steel sheet to a dry film thickness of 20 μm.
After successively coating each day so as to be 50 μm and 50 μm, the test antifouling paint composition was dried to a film thickness of 2 μm.
The coating was applied to a thickness of 00 μm to obtain a test plate. This test plate was attached to a rotating drum, and a test was performed under a high-fouling environment condition for 12 months under a peripheral speed of 5 knots and 50% operating conditions (alternate operation of 12 hours of operation at night and 12 hours of stoppage during the day). An evaluation was performed.

The antifouling property was evaluated visually and the following criteria were used. (Evaluation criteria) 5: No deposits were found on the surface of the coating film 4: Thin slime was found on the surface of the coating film 3: Dark slime was found on the surface of the coating film 2: Slime was found on the surface of the coating film Adhesion of plants such as Shiono-mami is recognized 1: The entire surface of the coating film is covered with plants such as Shimi-no-mitsu, and the degree of wear was evaluated under the following conditions.

[Evaluation of Depletion Degree] Diameter 300 mm and thickness 3
mm disc-shaped sandblasted steel plate with epoxy-based zinc-rich primer, epoxy-based anticorrosion paint, and vinyl-based binder coat.
m and 50 μm were sequentially applied every day, and then dried in a room for 7 days. Thereafter, the test antifouling coating composition was radially applied from the center of the circle using an applicator having a gap of 500 μm to obtain a test plate. The test plate was mounted on a motor in a thermostat bath containing seawater at 25 ° C., and rotated at a peripheral speed of 15 knots for 2 months to measure the degree of wear (decrease in film thickness) around the circumference.

The evaluation results are shown in Tables 4 to 6. Further, the state of the coating film at the time of measuring the decrease in film thickness was visually observed and evaluated according to the following criteria. (Evaluation criteria) 5: No abnormality is observed in the coating film 4: Partially fine cracks are partially recognized 3: Fine cracks are entirely recognized 2: Partly noticeable cracks are partially recognized 1: Totally significant cracks are recognized Tables 4 to 6 also show the evaluation results in which cracks were observed.

The names of the components in the table are as follows. "Toyo Parax 150" chlorinated paraffin manufactured by Tosoh Corporation, average carbon number: 14.5, chlorine content: 50%, viscosity: 12 poise / 25 ° C, specific gravity: 1.25 / 25 ° C. "Lutinal A-25" polyvinyl ethyl ether manufactured by BASF, viscosity: 2.5 to 6.0 Pa · s / 23 ° C, specific gravity: 0.9
6/20 ° C. "Rosin solution" 50% xylene solution of WW rosin "Copper naphthenate solution" Xylene solution of copper naphthenate, Copper content in the solution: 8%. "Soluble anhydrous gypsum D-1" Ltd. Noritake made, IIICaSO _4, white powder, average particle size 15 [mu] m. "Dispalon 4200-20" manufactured by Kusumoto Kasei Co., Ltd., 20% xylene paste of polyethylene oxide wax "Disparon A603-20X" manufactured by Kusumoto Kasei Co., Ltd., 20% xylene paste of fatty acid amide wax

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

[Table 3]

[0101]

[Table 4]

[0102]

[Table 5]

[0103]

[Table 6]

[Brief description of the drawings]

FIG. 1 is a GPC chromatogram of copolymer S-1.

FIG. 2 is a GPC chromatogram of copolymer S-2.

FIG. 3 is a GPC chromatogram of copolymer S-3.

FIG. 4 is a chart of an IR spectrum of copolymer S-1.

FIG. 5 is a chart of an IR spectrum of copolymer S-2.

FIG. 6 is a chart of an IR spectrum of copolymer S-3.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Masaaki Oie 1 in Meiji Shinkai, Otake-shi, Hiroshima Prefecture 7 Inside China Paint Co., Ltd. (72) Inventor Yukio Kozono 1 in Meiji-Shinkai, Otake City, Hiroshima Prefecture 7 China Paint Co., Ltd. (72) Naoya Nakamura, Inventor Naoya Nakamura 1 Meiji-Shinkai, Otake City, Hiroshima Prefecture 7 China Paint Co., Ltd. F-term (reference) 4J038 BA231 CC021 CC071 CC081 CE052 CF021 CF091 CG141 CG151 CH031 CH041 CH071 CH121 CH131 CH141 CJ181 CL001 DF041 GA15 HA066 HA126 HA166 HA246 HA376 HA466 JA29 JA40 JB18 JB23 JB24 JB27 JB29 JB36 JC06 JC07 JC18 JC30 JC37 JC38 MA07 MA14 NA05 NA11 NA12 NA24 NA26 NA27 PA18 PB05 PC02 PC06 PC08

Claims (19)

[Claims] 1. (a) Formula [I]: —CH ₂ —CR (COOSiR ¹ R ² R ³ ) — .. [I] wherein R is a hydrogen atom or a methyl group And R ¹
And R ² each independently represent a linear alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group or trimethylsilyloxy group, and R ³ may have a ring structure or a branched structure. It represents a C1-C18 alkyl group, a C6-C10 optionally substituted phenyl group, or a trimethylsilyloxy group. Represented by a silyl (meth) acrylate component units], (b) formula _{[II]: - CH 2 -CR} (COOSiR 4 R 5 R 6) - ····· [II] [ Formula [II] in, R represents a hydrogen atom or a methyl group;
⁴ and R ⁵ each independently represent a branched or cycloalkyl group having 3 to 10 carbon atoms, R ⁶ is a linear alkyl group having 1 to 10 carbon atoms, a branched or cycloalkyl group having 3 to 10 carbon atoms or A cycloalkyl group, a phenyl group having 6 to 10 carbon atoms which may be substituted or a trimethylsilyloxy group is shown. And (c) an unsaturated monomer component unit other than the (a) component unit and the (b) component unit, and the gel permeation chromatography An antifouling paint composition comprising a silyl (meth) acrylate copolymer having a weight average molecular weight (Mw) measured by (GPC) of 200,000 or less. 2. [A] The silyl (meth) according to claim 1
An antifouling paint composition comprising an acrylate copolymer and [B] an antifouling agent. [3] The silyl (meth) according to the above [1].
An antifouling paint composition comprising an acrylate copolymer, [B] an antifouling agent, and [C] zinc oxide. [4] The silyl (meth) according to the above [1].
An antifouling paint composition comprising an acrylate copolymer, [B] an antifouling agent, and [D] an inorganic dehydrating agent. [5] The silyl (meth) according to the above [1].
An antifouling paint composition comprising an acrylate copolymer, [B] an antifouling agent, [C] zinc oxide, and [D] an inorganic dehydrating agent. 6. The antifouling coating composition according to any one of claims 1 to 5, further comprising [E] an elution promoting component. 7. A compound derived from a vinyl ether represented by the formula [III]: H ₂ C ＝ CHO—R (III) (wherein R represents a hydrocarbon group). The antifouling coating composition according to any one of claims 1 to 6, further comprising a vinyl ether (co) polymer [F] containing a component unit to be prepared. 8. The antifouling paint composition according to claim 2, wherein the antifouling agent [B] is a copper and / or inorganic copper compound [B-1]. 9. The antifouling coating composition according to claim 2, wherein the antifouling agent [B] is an organic antifouling agent [B-2]. 10. The method according to claim 2, wherein said antifouling agent [B] is a combination system of a copper and / or inorganic copper compound [B-1] and an organic antifouling agent [B-2]. An antifouling paint composition according to any one of the above. 11. The organic antifouling agent [B-2] is a metal pyrithione, pyridine-triphenylborane, amine-triphenylborane, N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide. , 2-
Methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, 4,5-dichloro-
11. The organic antifouling agent selected from the group consisting of 2-n-octyl-4-isothiazolin-3-one and 2,4,5,6-tetrachloroisophthalonitrile. An antifouling paint composition according to any one of the above. 12. The antifouling agent according to claim 9, wherein the organic antifouling agent [B-2] is 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one. Soil paint composition. 13. The organic antifouling agent [B-2] is pyridine-triphenylborane, amine-triphenylborane, N, N-dimethyldichlorophenylurea,
4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, 4,5-dichloro-2-n-
Octyl-4-isothiazolin-3-one and 2,
The antifouling agent according to any one of claims 9 to 10, wherein the antifouling agent is a combination of at least one organic antifouling agent selected from the group of 4,5,6-tetrachloroisophthalonitrile and a metal pyrithione. Paint composition. 14. The organic antifouling agent [B-2] is a combination system of copper pyrithione and / or zinc pyrithione and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one. The antifouling paint composition according to claim 9. 15. The antifouling paint according to claim 6, wherein the elution promoting component [E] is at least one selected from rosin, a rosin derivative, naphthenic acid and a metal salt thereof. Composition. 16. The unsaturated monomer component unit (c) is derived from one or more compounds selected from (meth) acrylates, styrenes, and organic carboxylates. The antifouling coating composition according to any one of claims 1 to 15, which is a coating composition. 17. An antifouling coating film formed from the antifouling coating composition according to any one of claims 1 to 16. 18. A hull or marine structure, wherein the antifouling coating composition according to claim 1 is applied to the surface of a hull or marine structure to cover the surface. Antifouling method. 19. A hull or marine structure, wherein the surface of the hull or marine structure is coated with a coating film comprising the antifouling coating composition according to any one of claims 1 to 16.