JP2001081147A - Silyl(meth)acrylate copolymer, antifouling coating composition containing the same, antifouling coating film formed of the composition and antifouling method using the composition and hull or marine structure coated with the coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer having a specified weight-a-verage molecular weight and excellent antifouling effect by designing itself to be composed of silyl(meth)acrylate component unit, polyoxyalkylene (meth)acrylate component unit and another unsaturated monomer component unit in specific proportions. SOLUTION: This copolymer is composed of a total of 100 wt.% of (A) 20-80 wt.% of a silyl(meth)acrylate component unit of formula I [R1 is H or methyl; R2 to R4 are each an alkyl, (substituted) cycloalkyl or the like], (B) 0.01-40 wt.% of a polyoxyalkylene (meth)acrylate component unit of formula II (R5 is H or methyl; R6 is an alkylene; R7 is an alkyl or the like; n is 26-100) and (C) 5-79.99 wt.% of another unsaturated monomer component unit, e.g. a (meth)acrylic ester, styrene, and has a weight-average molecular weight of <=200,000 determined by gel permeation chromatography(GPC).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silyl (meth) acrylate copolymer, an antifouling coating composition containing the copolymer, an antifouling coating film formed from the antifouling coating composition, and the antifouling coating. The present invention relates to an antifouling method using a coating composition and a hull or a marine structure covered with the coating film. More specifically, the obtained coating film is hardly cracked, has good adhesion to the coating film, and peels off the coating film. Is difficult to occur, the hydrolysis rate of the coating film is well controlled, and the antifouling coating composition for obtaining an antifouling coating film having excellent antifouling property, especially in a high fouling environment and long-term antifouling property. Novel silyl (meth) acrylate copolymer, antifouling coating composition containing the copolymer, antifouling coating film formed from this antifouling coating composition, and antifouling using the antifouling coating composition And a hull or marine structure coated 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.

JP-A-7-18216 discloses (A)
Formula (I): —COO—SiR ¹ R ² R ³ (R ^{1 to} R ³⁾
Represents an alkyl group having 1 to 18 carbon atoms, etc.) An organic silicon-containing monomer A having a triorganosilicon ester group represented by
In a coating composition comprising a polymer of (B) and copper or a copper compound as main components, as an essential component other than the above components (A) and (B), 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). Further, the publication states that a copolymer AB of the monomer A represented by the above formula (I) and the copolymerizable vinyl monomer B may be contained. As the body B, (meth) acrylates 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 antifouling property under a high fouling environment. In the highly polluted environment, the environment is eutrophic marine environment such as inland sea, or still in such marine area, or the ship is frequently operated or stopped repeatedly at a low speed of about 10 knots or less. Point.

JP-A-7-102193 discloses a compound represented by the 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). Wherein X is an acryloyloxy group, a methacryloyloxy group, a malenoyloxy group or a fumaroyloxy group.) , Formula: Y- (CH ₂ CH ₂
O) _n -R ⁴ (where R ⁴ is an alkyl group or an aryl group, Y is acryloyloxy group or methacryloyloxy group, the monomer n is represented by an integer from 1 to 25.) B A coating composition containing, as essential components, a copolymer of a monomer mixture containing the following and an antifouling agent 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 a polyoxyalkylene (meth) acrylate component unit in which one type of polyalkylene glycol group has a degree of polymerization (n) of 26 or more. However, there is a problem that the antifouling property is poor in a highly fouling environment.

(10) JP-A-8-199095 discloses a monomer A represented by the formula (1): X-SiR ¹ R ² R ³ described in JP-A-7-102193, Formula (2): Y— (CH (R ⁴ )) — (OR ⁵ ) (where R ⁴ is an alkyl group, R ⁵ is an alkyl group or a cycloalkyl group. Y is an acryloyloxy group, a methacryloyloxy group, and a male A copolymer of a monomer mixture containing a monomer B represented by a noyloxy group or a fumaroyloxy group) and, if necessary, a vinyl monomer C copolymerizable with A and B; A coating composition containing an antifouling agent as an essential component is disclosed. This vinyl monomer C
Examples include acrylic acid esters, methacrylic acid esters, styrene, vinyl acetate and the like. 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) Japanese Patent Application Laid-Open No. 8-269388 discloses a formula (1): X-SiR ¹ R ² R ³ (where R ^{1 to} R
Each of ³ is a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. 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 copolymer of a monomer mixture containing a monomer B represented by a group represented by the following general formula:, a maleinoyloxy group, a fumaroyloxy group, or an itaconoyloxy group, and n is an integer of 1 to 25. (2-pyridinethiol-1-oxide) copper salt (: copper pyrithione)
Are disclosed as essential components. Further, as the monomer A, dimethyl-t-butylsilyl acrylate and the like can be mentioned. As the antifouling agent, copper compounds such as cuprous oxide and copper powder as inorganic compounds,
Examples of the organic compound containing a metal include organic copper-based compounds such as oxine copper; organic nickel-based compounds; and organic zinc-based compounds such as zinc pyrithione. In addition, rosin, rosin derivatives and the like are mentioned as dissolution rate regulators that can be added.

(12) Japanese Patent Application Laid-Open No. 8-269389
Is an unsaturated monomer A having a triorganosilyl group,
A monomer B represented by any of the following formulas (2) to (9):
Containing a copolymer of a monomer mixture containing an antifouling agent
A composition is disclosed. Each monomer B is as follows
It is as follows. Formula (2) CH_Two= CR^FourCOOR^Five-NR⁶
R⁷[R^FourIs H or CH_ThreeAnd R^FiveIs an alkylene
A group represented by R⁶, R⁷Are alkyl groups,
It may be one or different. A tertiary amino group represented by
Containing monomer, formula (3) CH_Two= CR⁸COOR⁹-NR^TenR
¹¹R¹²(Y) [R⁸Is H or CH_ThreeAnd R⁹Is archi
Represents a len group;^Ten~ R¹²Is an alkyl group,
Y may be the same or different,
Show. A quaternary ammonium salt-containing monomer represented by the formula:
(4) CH_Two= CH-Z [Z is a group consisting of an N-containing heterocyclic ring
Show. A monomer containing a nitrogen-containing heterocyclic ring represented by the formula:
(5) CH_Two= CR¹³COO (R¹⁴O)_m(R^FifteenO)_n(R
¹⁶O)_o-R¹⁷ [R ¹³Is H, CH_ThreeAnd R¹⁴Is d
Represents a tylene group;^FifteenRepresents an alkylene group having 3 carbon atoms
Then R¹⁶Represents an alkylene group having 4 carbon atoms;¹⁷Is al
Represents a kill group or an aryl group. m, n, and o are integers of 0 or more
And n and o are not simultaneously 0. In the molecule shown by
Oxy group or aryloxyalkylene glycol group
Monomer having the formula (6) CH_Two= CR¹⁸CONR¹⁹R
²⁰[R¹⁸Is H, CH_ThreeAnd R¹⁹, R²⁰Is an alkyl
And may be the same or different from each other. ]
(Meth) acrylic acid amide, formula (7) CH_Two= CR^{twenty one}
CON () Q [R^{twenty one}Is H, CH_ThreeAnd N () Q is
In the N-containing group, Q may contain O, N, S and the like. ]so
(Meth) acryl containing nitrogen-containing cyclic hydrocarbon group shown
Luric amide, formula (8) CH_Two= CR^{twenty three}COOCH_Two-T
[R^{twenty three}Is H, CH_ThreeAnd T represents a furan ring, tetra
Shows a hydrofuran ring. ] Containing a furan ring (meth
(T) Acrylic ester, formula (9) CH_Two= CH-C
N.

Various optional components copolymerizable with the monomers A and B include acrylic acid, ethyl acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. 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 -A copolymer comprising dimethylacrylamide (DMAA) and methyl methacrylate (MMA) is shown, but the degree of polymerization (n) of one type of polyalkylene glycol group is 26 or more, polyoxyalkylene (meth)
No polymer containing an organic silyl ester group having an acrylate component unit 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) Japanese Patent Application Laid-Open No. 8-269390 discloses a formula (1):
X-SiR ¹ R ² R ³ (wherein, R ^{1 to} R ³ are groups selected from an alkyl group and an aryl group; 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 comprising a polymer using the monomer B represented by the formula (1) and an antifouling agent is disclosed. Examples of the antifouling agent include those described in
The same antifouling agent as the antifouling agent described in JP-A-269388 is mentioned. In addition, resins that can be added include resins such as rosin, anti-settling agents, and the like.

(14) JP-A-8-277372 discloses a compound represented by the formula (1): X-SiR ¹ R ² R ³ described in JP-A-8-269388. Body A,
Formula (2) also described in the same publication: Y- (CH ₂ CH ₂ O)
containing a copolymer of a monomer mixture containing a monomer B represented by _n -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-based compounds composed of rosin, a rosin derivative or a rosin metal salt, and (B) 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, an itaconoyloxy group, or a citraconoyloxy group.) A polymer, and / or an organic silyl ester group-containing polymer comprising a polymer of one or more of the monomers M and one or more of the other polymerizable monomers; (C) a coating composition containing an antifouling agent is disclosed. . 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. However, this publication discloses any organic silyl ester group-containing polymer having a polyoxyalkylene (meth) acrylate component unit in which one type of polyalkylene glycol group has a degree of polymerization (n) of 26 or more. Not.

The antifouling agent is described in Japanese Unexamined Patent Publication No.
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, these (15) include organic silyl esters using a polyoxyalkylene (meth) acrylate or the like having one kind of polyalkylene glycol group and having a degree of polymerization (n) of the polyalkylene glycol group of more than 25. No group-containing polymer is shown, and in the coating compositions described in these publications, the obtained coating film has poor crack resistance, or the obtained coating film has crack resistance,
It is not sufficient in terms of balance between peeling resistance (coating adhesion) and antifouling property, especially antifouling property in a high fouling environment, long-term antifouling property, and self-polishing property.

Further, (16) Japanese Patent Publication No. 5-82865 describes 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) Polyoxyalkylene (meth) having a degree of polymerization of one kind of polyalkylene glycol group (n) of 26 or more
There is no description of an organic silyl ester group-containing polymer using acrylate or the like. In addition, these publications (16) to
In the antifouling paint using the copolymer described in (25), the obtained coating film has poor crack resistance, or the obtained coating film has crack resistance, peeling resistance (coating film adhesion), There is room for further improvement in terms of the balance between the stain resistance, especially the stain resistance under a high stain environment, the long-term stain resistance, and the self-polishing property.

(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.

[0024]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above. A new type of antifouling paint for antifouling coatings that does not easily peel off, has good control over the hydrolysis rate of the coating film, and has excellent antifouling properties, especially in high fouling environments and long-term antifouling properties. It is an object of the present invention to provide a novel silyl (meth) acrylate copolymer and an antifouling paint composition containing the copolymer and having the above properties.

The present invention also relates to a coating film formed from such an antifouling coating composition, an antifouling method using the antifouling coating composition, and a hull or marine structure coated with the coating film. It is intended to provide.

[0026]

SUMMARY OF THE INVENTION The silyl (meth) acrylate copolymer of the present invention comprises (a) a compound represented by the formula [I]:

[0027]

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[In the formula [I], R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ and R ⁴ may be the same or different and have an alkyl group or a substituent. A cycloalkyl group which may be substituted, or a phenyl group which may have a substituent. 20 to 80% by weight of a silyl (meth) acrylate component unit represented by the formula (II):

[0029]

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[In the formula [II], R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an alkylene group, R ⁷ represents an alkyl group or a cycloalkyl group which may have a substituent. ,
A phenyl group which may have a substituent;
Shows the number from 6 to 100. 0.01 to 40% by weight of a polyoxyalkylene (meth) acrylate component unit represented by the formula: (c) an unsaturated monomer component unit 5 other than the component units (a) and (b) 79.99% by weight (however, (a)
+ (B) + (c) = 100% by weight), and is characterized by having a weight average molecular weight of 200,000 or less as measured by gel permeation chromatography (GPC).

In the present invention, the unsaturated monomer component unit (c) comprises at least one selected from (meth) acrylates, styrenes and vinyl esters.
Preferably it is a seed. In the present invention, R ⁶ in the formula [II] representing the polyoxyalkylene (meth) acrylate component unit (b) is an ethylene group (—CH ₂ —CH _2
2 -), propylene (-CH ₂ -CH ₂ -CH ₂ -, - C
It is preferably H ₂ —CH ₂ (CH ₃ ) —) or a butylene group, and n is preferably a number of 30 to 50.

The antifouling coating composition according to the present invention is characterized by containing the above silyl (meth) acrylate copolymer. The antifouling coating composition according to the present invention preferably contains the above silyl (meth) acrylate copolymer and [B] an antifouling agent. The antifouling coating composition according to the present invention preferably contains the above silyl (meth) acrylate copolymer, [B] an antifouling agent, and [C] zinc oxide.

The antifouling coating composition according to the present invention comprises the above silyl (meth) acrylate copolymer, [B] an antifouling agent,
[D] an inorganic dehydrating agent. The antifouling coating composition according to the present invention comprises the above silyl (meth) acrylate copolymer, [B] antifouling agent, [C] zinc oxide,
[D] an inorganic dehydrating agent.

The antifouling coating composition according to the present invention further comprises (c) a compound represented by the formula [III]:

[0035]

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(In the formula [III], R represents a hydrocarbon group.) It is preferable to include a vinyl ether (co) polymer [E] containing a vinyl ether component unit represented by the formula: It is preferable that the antifouling paint composition further contains an elution promoting component [F].

In the antifouling coating composition according to the present invention, the antifouling agent [B] may be copper and / or a copper compound (excluding copper pyrithiones; the same applies hereinafter) [B-1]. preferable.
In the present invention, the antifouling agent [B] includes copper and / or a copper compound (excluding copper pyrithiones) [B-1] and an organic antifouling agent (excluding copper compounds other than copper pyrithiones). ) [B-
2].

In the present invention, the organic antifouling agent [B-2] is used.
Are metal pyrithiones, N, N-dimethyldichlorophenylurea, pyridine-triphenylboron, 2,4,6
-Trichlorophenylmaleimide, 2-methylthio-4
-Tert-butylamino-6-cyclopropylamino-s
-Triazine, 4,5-dichloro-2-n-octyl-
It is preferably at least one selected from the group consisting of 4-isothiazolin-3-one and 2,4,5,6-tetrachloroisophthalonitrile.

In the present invention, the above organic antifouling agent [B-2]
Is N, N-dimethyldichlorophenylurea, pyridine-triphenylboron, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine,
At least one organic antifouling agent (b2) selected from the group consisting of 5-dichloro-2-n-octyl-4-isothiazolin-3-one and 2,4,5,6-tetrachloroisophthalonitrile; And a metal pyrithione (b1).

In the present invention, the above-mentioned metal pyrithiones
(b1) is preferably copper pyrithione. In the present invention, the elution promoting component [F] is preferably at least one selected from rosin, rosin derivatives, naphthenic acid and metal salts thereof.

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 described above is applied to a surface of a hull or a marine structure and the surface is coated. 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 composed of the antifouling paint composition described above.

The antifouling coating composition according to the present invention contains a novel silyl (meth) acrylate copolymer. According to such an antifouling coating composition, cracks are less likely to occur in the coating film. Good coating adhesion, less peeling of coating,
The hydrolysis rate of the coating film is well controlled, and an antifouling coating film having excellent antifouling properties, particularly in a high fouling environment and long-term antifouling properties, and having a good balance of these properties can be obtained.

[0043]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the silyl (meth) acrylate copolymer according to the present invention and an antifouling paint composition containing the copolymer will be described in detail. <Silyl (meth) acrylate copolymer [A]> The silyl (meth) acrylate copolymer according to the present invention has the following formula:
Silyl (meth) acrylate component unit (a) represented by [I]
And a polyoxyalkylene (meth) acrylate component unit (b) represented by the following formula [II] [also simply referred to as a (meth) acrylate component unit (b). And an unsaturated monomer component unit other than the component units (a) and (b) (c).
And is composed of

The component units (a), (b) and (c) constituting the silyl (meth) acrylate copolymer [A] will be described below in order. [Silyl (meth) acrylate component unit (a)] The silyl (meth) acrylate component unit (a) is represented by the following formula [I]. Formula [I]:

[0045]

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In the formula [I], R ¹ represents a hydrogen atom or a methyl group, and R ² , R ³ , and R ⁴ may be the same or different from each other, and each may be a linear or branched alkyl group. which may have a substituent cycloalkyl group, one of the phenyl group which may have a substituent, the carbon number of the alkyl group is preferably 1 to 18, more preferably 1 to And the carbon number of the cycloalkyl group is
It is preferably 3 to 10, more preferably 3 to 8.
Examples of the substituent that can be substituted for a hydrogen atom in the cycloalkyl group include halogen, and examples of the substituent that can be substituted for a hydrogen atom in the phenyl group include alkyl, aryl, and halogen.

The silyl (meth) acrylate capable of deriving such a silyl (meth) acrylate component unit is represented by the following formula [Ia]. Formula [Ia]:

[0048]

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[0049] In the formula [Ia], R ¹ is be similar to R ¹ in the formula [I], represents a hydrogen atom or a methyl radical, R
^2, R ^3, R ⁴ may be similar to R ^2, R ^3, R ⁴ in the formula [I], may be the same or different from each other, as with each of the above alkyl group, a substituted group Represents a cycloalkyl group which may have a phenyl group, or a phenyl group which may have a substituent.

Such a silyl (meth) acrylate [I
Specific examples of -a] include (meth) acrylic acid trimethylsilyl ester, (meth) acrylic acid triethylsilyl ester, (meth) acrylic acid tripropylsilyl ester, (meth) acrylic acid triisopropylsilyl ester, R ² , R ³ and R ⁴ are the same silyl (meth) such as tributylsilyl (meth) acrylate, trisec-butylsilyl (meth) acrylate, triiso-butylsilyl (meth) acrylate, etc. A) acrylate; (meth) acrylic acid dis
ec-butyl-methylsilyl ester, sec-butyl-dimethylsilyl (meth) acrylate, dimethylpropylsilyl (meth) acrylate, monomethyldipropylsilyl (meth) acrylate,
Examples thereof include silyl (meth) acrylates in which one or all of R ² , R ^3, and R ⁴ are different from each other, such as methylethylpropylsilyl (meth) acrylate.

In the present invention, such silyl (meth) acrylates can be used alone or in combination of two or more. In such a silyl (meth) acrylate, R ² , R ³ and R ⁴ each independently represent a methyl group, an ethyl group, an n-, iso-propyl group, a se
C-, tert-, iso-butyl and the like have 1 to 1 carbon atoms
And preferably has a 18 degree alkyl group, more preferably has a carbon number of at least one alkyl group of R ^2, R ³ and R ⁴ is 3 or more, R ^2,
It is preferable that R ³ and R ^{4 have} a total carbon number of about 5 to 21. Among such silyl (meth) acrylates, in particular, ease of synthesis of the silyl (meth) acrylate copolymer, or film formation of an antifouling coating composition using such a silyl (meth) acrylate copolymer In consideration of the properties, storage stability, and easy control of the cleaning properties, triiso-propylsilyl (meth) acrylate,
Triiso-butylsilyl (meth) acrylate, disec-butyl-methylsilyl (meth) acrylate, sec-butyl-dimethylsilyl (meth) acrylate, trisec- (meth) acrylate
Butylsilyl ester is most preferably used.

[ Polyoxyalkylene (meth) acryle
The salt component unit (b)] The polyoxyalkylene (meth) acrylate component unit (b) is represented by the following formula [II]. Formula [II]:

[0053]

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In the formula [II], R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents a linear, branched, or alicyclic alkylene group, and the degree of polymerization (n) is a number of 26 to 100, preferably 28 to 50, and more preferably 30 to 50. In the present invention, two or more kinds of polyoxyalkylene (meth) acrylate component units having different degrees of polymerization (n) may be present in the silyl (meth) acrylate copolymer [A]. In this case, n is an average value, and the polymerization degree (n) may not be an integer.

The alkylene group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms.
For example, a methylene group, an ethylene group (—CH ₂ —CH
₂ -), propylene (-CH ₂ -CH ₂ -CH ₂ -, - C
H ₂ —CH ₂ (CH ₃ ) —) and a butylene group. R ⁷ represents an alkyl group, a cycloalkyl group which may have a substituent, or a phenyl group which may have a substituent. Among them, the alkyl group may be linear or branched, and preferably has 1 to 1 carbon atoms.
2, more preferably 1 to 5 alkyl groups,
Specific examples include a methyl group, an ethyl group, an n-, iso-propyl group, an n-, tert-butyl group and the like. The carbon number of the cycloalkyl group is preferably 3 to 10, more preferably 3 to 6, and specific examples include a cyclopropyl group and a cyclohexyl group. Examples of the substituent that can be substituted for a hydrogen atom in the cycloalkyl group include halogen, and examples of the substituent that can be substituted for a hydrogen atom in the phenyl group include alkyl, aryl, and halogen. .

Such a polyoxyalkylene (meth)
The polyoxyalkylene (meth) acrylate (b1) capable of deriving the acrylate component unit (b) is represented by the following formula [II-a]. Formula [II-a]:

[0057]

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In the formula [II-a], R^Five, R⁶, R⁷, N is it
R in the above formula [II]^Five, R⁶, R⁷, N
Oh, R^FiveRepresents a hydrogen atom or a methyl group;⁶Is
An alkylene group;⁷Has an alkyl group and a substituent
Having an optionally substituted cycloalkyl group,
Phenyl group. Such a polio
As silalkylene (meth) acrylate [II-a],
Specifically, for example, in the formula [II-a], R^FiveIs H or CH_Threeso
Yes, R⁶Is "-(CH_Two) _Two-"And R⁷Is CH_Threeso
Certain methyl polyoxyethylene (meth) acrylates;
R^FiveIs H or CH_ThreeAnd R⁶Is "-(CH_Two)_Two-"
And R⁷Is -C₆H_FiveIs phenylpolyoxyethyl
Rene (meth) acrylate; R^FiveIs H or CH_ThreeIn
R⁶Is "-(CH_Two)_Three-Or -CH_TwoCH (C
H _Three)-] And R⁷Is -CH_ThreeIs methylpolyoxy
Cypropylene (meth) acrylate; R^FiveIs H or C
H_ThreeAnd R⁶Is "-(CH_Two)_Three-Or -CH_TwoCH
(CH _Three)-] And R⁷Is -C₆H_FivePhenylpo
Lioxypropylene (meth) acrylate; R^FiveBut H
Or CH_ThreeAnd R⁶Is "-(CH_Two)_Four-"And R
⁷Is -CH_ThreeMethyl polytetramethylene methacrylate
And the like.

In the present invention, these polyoxyalkylene (meth) acrylates [II-a] can be used alone or in combination of two or more. Among them, particularly, the ease of synthesizing the silyl (meth) acrylate copolymer, or the film-forming properties, storage stability, and stiffness of the antifouling coating composition using such a silyl (meth) acrylate copolymer are improved. Considering the ease of controlling the scavenging property, methylpolyoxyethylene (meth) acrylate is preferably used.

[Unsaturated monomer component unit (c)] The unsaturated monomer component unit (c) includes the above-mentioned component unit (a) and the above-mentioned component unit.
(b) constitutes the silyl (meth) acrylate copolymer of the present invention, and is a component unit different from any of the above-mentioned component units (a) and (b); As the unsaturated monomer (c1) capable of deriving the component unit (c),
Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid (n-, i
so-, tert-) butyl, 2- (meth) acrylate
Ethylhexyl, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth)
(Meth) acrylic esters such as hydroxybutyl acrylate; styrenes such as styrene, vinyltoluene and α-methylstyrene; vinyl esters such as vinyl acetate, vinyl benzoate, vinyl propionate and vinyl butyrate;
Crotonic esters, itaconic esters, fumaric esters, maleic esters, and the like. Of these, (meth) acrylic esters, styrenes, vinyl esters, and itaconic esters are preferable. Further, (meth) acrylic acid esters and styrenes are preferable because an antifouling coating film having an appropriate coating film strength can be obtained.

These unsaturated monomers are used alone or in combination of two or more. In the silyl (meth) acrylate copolymer according to the present invention, the silyl (meth) acrylate component unit (a) is used in an amount of 20 to 80% by weight, preferably 30 to 70% by weight, in a polyoxyalkylene (meth) ) The acrylate component unit (b) is in an amount of 0.01 to 40% by weight, preferably 0.1 to 20% by weight, and the unsaturated monomer component unit (c) is in an amount of 5 to 79.9% by weight, preferably 1
It is desirable that it is contained in an amount of 0 to 60% by weight ((a) + (b) + (c) = 100% by weight) in terms of coating film strength 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.
It is preferably 3000 to 100,000, which facilitates preparation of an antifouling paint containing the silyl (meth) acrylate copolymer, workability of coating the obtained antifouling paint, consumption rate of the antifouling coating film, It is desirable in terms of crack resistance and the like.

<Silyl (meth) acrylate copolymer
Production of [A]> In order to obtain such a silyl (meth) acrylate copolymer [A], 20 to 80% by weight of the silyl (meth) acrylate (a1) represented by the above formula [Ia] is added formula
0.01 to 40% by weight of the polyoxyalkylene (meth) acrylate (b1) represented by [II-a] and the monomer [Ia]
And another unsaturated monomer (c1) 5 copolymerizable with [II-a].
79.99% by weight (however, (a1) + (b1) + (c1) = 100% by weight) is used in various methods such as solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization in the presence of a radical polymerization initiator. Random copolymerization.

As the radical polymerization initiator, conventionally known azo compounds and peroxides can be widely used. As the azo compound, specifically, 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.

<Anti-fouling paint composition and its production> [Anti-fouling paint composition] The anti-fouling paint composition according to the present invention comprises the above-mentioned silyl (meth) acrylate as a film-forming component having self-polishing properties. The polymer [A] is contained as an essential component.

The silyl (meth) acrylate copolymer [A] is usually contained in the antifouling coating composition in an amount of 3 to 70% by weight, preferably 5 to 50% by weight. Is desirable. As described above, the antifouling paint composition according to the present invention contains the silyl (meth) acrylate copolymer [A] as an essential component. In addition to the copolymer [A], if necessary, the antifouling paint composition as described above may be used. Antifouling agent [B] represented by organic antifouling agents such as copper and / or copper compounds and pyrithiones, zinc oxide
[C], inorganic dehydrating agent [D], vinyl ether (co) polymer
[E], an elution promoting component [F], and the like. An antifouling paint composition containing such a component [A], and further a component
According to the antifouling coating composition containing [B] to [F], the coating film is hardly cracked, the coating film adhesion is good, the coating film is hardly peeled off, and the coating film has a good hydrolysis rate. Controlled by
An antifouling coating film having excellent antifouling properties, particularly in a high fouling environment and long-term antifouling properties, can be obtained.

The antifouling agent [B], zinc oxide [C], inorganic dehydrating agent [D], vinyl ether (co) polymer [E], elution promoting component [F] and the like will be described in detail below. [Antifouling agent [B]] As the antifouling agent [B], any of inorganic type and organic type may be used, and conventionally known ones can be widely used. And / or copper compound [B-1] is preferred. The copper compound has a molecular weight of usually 63.5 to 2000, preferably 63.000.
What is 5-1000 is used.

Such copper compounds (excluding copper pyrithiones) may be either organic or inorganic copper compounds. Examples of the inorganic copper compounds include cuprous oxide and thiocyanate. Copper oxide (cuprous thiocyanate, copper rhodan), basic copper sulfate, copper chloride, copper oxide, and the like. Examples of organic copper compounds include basic copper acetate, oxine copper, and nonylphenol sulfonate copper. , Copper bis (ethylenediamine) -bis (dodecylbenzenesulfonate), copper naphthenate, rosin copper, bis (pentachlorophenolic acid) copper and the like, preferably inorganic cuprous oxide and copper thiocyanide (rodan copper). Used.

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 the content of the copper and / or copper compound is within this range in the antifouling coating composition, the antifouling property tends to be excellent. In the present invention, as the antifouling agent [B], a pyrithione-based compound represented by the following formula [IV], together with the copper and / or copper compound [B-1] or instead of the copper and / or copper compound: Wherein R ^{1 to} R ⁴ each independently represent hydrogen, an alkyl group, an alkoxy group, or a halogenated alkyl group, and M represents Zn, Cu, Na, Mg, C
a, Ba, Pb, Fe, Al, etc., and n represents a valence].

[0072]

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The pyrithione is contained in the antifouling coating composition of the present invention in a total amount of usually 0.1 to 15% by weight, preferably 0.5 to 10% by weight. Is desirable. Further, based on 100 parts by weight of the silyl (meth) acrylate copolymer [A] contained in the antifouling coating composition,
It is desirable that the pyrithiones are contained in a total amount of usually 0.3 to 300 parts by weight, preferably 2 to 200 parts by weight.

In the present invention, the following organic antifouling agent (other antifouling agent) may be contained together with or in place of the pyrithiones. Can be used conventionally known various antifouling agents, specifically, for example, tetramethylthiuram disulfide, carbamate-based compounds (eg, zinc dimethyldithiocarbamate, manganese ethylenebisdithiocarbamate), , 4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, pyridine-triphenylboron, 4,5-
Dichloro-2-n-octyl-4-isothiazoline-3
-One, 2,4,6-trichlorophenylmaleimide,
2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine and the like can be mentioned.

Among these organic antifouling agents (excluding pyrithiones and organic copper compounds), 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, pyridine-triphenyl Boron, 4,
5-Dichloro-2-n-octyl-4-isothiazolin-3-one, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine is preferred. .

In the present invention, such an antifouling agent can be used alone or in combination of two or more with pyrithiones (b1) such as copper pyrithione and zinc pyrithione. Further, the content of various antifouling agents such as copper and / or copper compounds and pyrithiones contained in the antifouling coating composition depends on the antifouling agent and the film-forming copolymer used in preparing the antifouling coating composition. Or the type of ship or the like on which such an antifouling coating composition is applied (for ships, for ocean going-inland sea, for various seawater areas, wooden-FRP-steel ships, etc.). It is not determined, but based on 100 parts by weight of the silyl (meth) acrylate copolymer,
It is desirable that the antifouling agent is contained in an amount of usually 10 to 1400 parts by weight, preferably 20 to 1300 parts by weight as a total amount.

If the total amount of the antifouling agent is less than 10 parts by weight, the antifouling property may be inferior. If it exceeds 1400 parts by weight, no further antifouling property can be expected and crack resistance may be inferior. is there. For example, copper pyrithione as an antifouling agent,
Pyrithiones such as zinc pyrithione and cuprous oxide (Cu ₂
When used in combination with O), the pyrithione is used in an amount of 2 to 200 parts by weight based on 100 parts by weight of the silyl (meth) acrylate copolymer, and the cuprous oxide is used in combination with the silyl (meth) acrylate. It may be contained in the antifouling coating composition in an amount of usually about 10 to 1300 parts by weight based on 100 parts by weight of the copolymer. Even if the composition contains a pyrithione and cuprous oxide, the antifouling coating composition has excellent storage stability, unlike the antifouling coating according to the conventional example described above, and has an increased viscosity during storage. Does not gel.

[Zinc oxide (zinc white) [C]] Such an antifouling coating composition may contain zinc oxide (zinc white) [C]. 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. In addition, from the viewpoint of adjusting the degree of wear and adjusting the hardness of the coating film, such zinc oxide is usually contained in the antifouling coating composition in an amount of 0.5 to 35% by weight, preferably 1 to 25% by weight. It is desirable to be included.

[Dehydrating agent, especially inorganic dehydrating agent [D]] The antifouling coating composition contains an inorganic or organic dehydrating agent, preferably an inorganic dehydrating agent (inorganic dehydrating agent [D]). It may be. The antifouling paint composition containing the dehydrating agent as described above can further improve the storage stability.
As the dehydrating agent, specifically, 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
Among them, anhydrous gypsum and molecular sieve are preferably used as the inorganic dehydrating agent [D]. Such a dehydrating agent (inorganic dehydrating agent) may be one kind or two.
It can be used in combination of more than one kind.

The dehydrating agent, particularly the inorganic dehydrating agent, is used in an amount of usually 0.02 to 100 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the silyl (meth) acrylate copolymer.
It is preferable to mix in an amount of 2 to 50 parts by weight. Also,
Such a dehydrating agent, particularly an inorganic dehydrating agent, is 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. Is desirable. When the dehydrating agent, in particular, the inorganic dehydrating agent is contained in such an amount in the antifouling coating composition, the storage stability tends to be improved.

[Vinyl ether-based (co) polymer [E]] The vinyl ether-based (co) polymer has a vinyl ether component unit represented by the following formula [III]. It contributes to the improvement of releasability, dissolution rate stability, etc., and also functions as a coating film forming component.

[0082]

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In the formula [III], R represents a hydrocarbon group. Examples of the hydrocarbon group R in the formula [III] include an aliphatic or aromatic hydrocarbon group having 1 to 25 carbon atoms, and may be linear or branched. Further, it may have an alicyclic structure typified by a cyclohexyl ring. Further, the carbon atom C ¹ constituting the hydrocarbon group (when the number of carbon atoms is 2 or more) is linked to a carbon atom C ² contained in the alkyl group and adjacent to the carbon atom C ¹ via an oxygen atom. A bond (C ¹ -O-C ² ) may be formed, and a hydrogen atom constituting the hydrocarbon group is bonded to another functional group (-
OH, it may be substituted by -NH _2, etc.).

More specifically, R in the above formula [III] represents a monovalent hydrocarbon group, and as the monovalent hydrocarbon group,
Examples include the above-mentioned alkyl group, particularly an alkyl group having about 1 to 18 carbon atoms, and the above-mentioned phenyl group which may be substituted. The vinyl ether (co) polymer is a homopolymer of vinyl ether having only the vinyl ether component unit represented by the above formula [III], or 50% based on the vinyl ether component unit [III].
It is desirable that the vinyl ether copolymer is contained in an amount of not less than% by weight (these are collectively referred to simply as "vinyl ether (co) polymer").

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 [E] is
It is desirable that the antifouling coating composition is contained in a total amount of usually 0.1 to 10% by weight, preferably 0.2 to 5% by weight. Further, the vinyl ether (co) polymer is usually 0.3 to 60 parts by weight based on 100 parts by weight of the silyl ester (meth) acrylate (co) polymer contained in the antifouling coating composition. Preferably, it is contained in an amount of 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 tends to be excellent in crack resistance, peel resistance and elution rate stability. There is. The above vinyl ether component unit [II
I] is the following vinyl ether [III-a]: H ₂ C ＝ CHO
—R (wherein, in the formula [III-a], R represents the same hydrocarbon group as R in the formula [III]) is a component unit derived from vinyl ether.

Specific examples of such a vinyl ether [III-a] include, for example, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, and isobutyl vinyl ether. [Elution-promoting component [F]] The elution-promoting component [F] has a function of accelerating the self-polishing action of a coating film in seawater. And salts thereof.

The rosin includes gum rosin, wood rosin,
There are tall oil rosin and the like, and any of them can be used in the present invention. As the rosin derivative, for example, disproportionated rosin, low melting point disproportionated rosin, hydrogenated rosin,
Polymerized rosin, maleated rosin, aldehyde-modified rosin, rosin polyoxyalkylene ester, reduced rosin (rosin alcohol), metal salts of rosin (such as rosin copper, zinc and magnesium salts), 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 is preferable.
These elution promoting components can be used alone or in combination of two or more. These dissolution promoting components are contained in the antifouling coating composition in an amount of 0.1 to 30% by weight in terms of solid content,
Preferably, it is contained in an amount of 0.1 to 20% by weight, more preferably 0.5 to 15% by weight. 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.

<Other Components> In addition to the above components, the antifouling coating composition according to the present invention comprises various additives such as anti-sagging / anti-settling agents, plasticizers such as chlorinated paraffin, coloring pigments, extender pigments and the like. It may contain the following components such as various resins such as acrylic resin excluding vinyl ether (co) polymer, and various additives such as antifoaming agent, anti-separation agent and leveling agent.

[Anti-sagging / Anti-settling agent] As an anti-sagging / anti-settling agent, any conventionally known anti-sagging / anti-settling agent may be blended in any amount. Examples of such anti-sagging / anti-settling agents include salts such as stearate salts of Al, Ca and Zn, lecithin salts and alkyl sulfonates, polyethylene waxes, hydrogenated castor oil waxes, polyamide waxes and the like. Mixtures, synthetic finely divided silica, polyethylene oxide wax and the like, preferably hydrogenated castor oil wax, polyamide wax, synthetic finely divided silica,
Polyethylene oxide wax is used. Examples of such anti-sagging and anti-settling agents include "DISPARON A-603-20X" and "DISPARON 4200-20" manufactured by Kusumoto Kasei Co., Ltd.
And the like, which are marketed under the trade names such as

[Pigments, Solvents] As the pigments, conventionally known various organic and inorganic pigments (eg, titanium white, red iron oxide,
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] The antifouling paint composition according to the present invention can be produced by appropriately utilizing a conventionally known method. For example, the silyl (meth) acrylate copolymer [A] And copper and / or a copper compound in an amount of 3 to 1400 parts by weight based on 100 parts by weight of the copolymer [A], and a pyrithione such as copper pyrithione in an amount of 0 to 300 parts by weight; "Other organic antifouling agents" in parts by weight
(However, 10 to 1400 parts by weight of the total amount of the antifouling agent [B]) and 2
~ 700 parts by weight of zinc oxide [C], 0.03-20
0 parts by weight of a dehydrating agent (eg, anhydrous gypsum, molecular sieve) [D], 0.3 to 200 parts by weight of a vinyl ether (co) polymer [E], and 0 to 600 parts by weight The amount of the elution-promoting component [F] and the anti-sagging / anti-settling agent, pigment, solvent and the like used in appropriate amounts may be added all at once or in any order, followed by stirring, mixing and dispersion.

The 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, the surface of a hull, a marine structure, or the like, which has already been coated with a conventional antifouling paint or has been coated with the antifouling paint composition of the present invention, is used for repairing the antifouling paint of the present invention. The composition may be overcoated. 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.

[0096]

According to the present invention, a novel silyl (meth)
An acrylate copolymer is provided, which contains this copolymer as an essential coating film-forming component, further contains an antifouling agent [B], and further contains zinc oxide [C], an inorganic dehydrating agent [D], and vinyl ether. An antifouling coating composition containing a (co) polymer [E], an elution-promoting component [F], and the like is applied to the surface of an object to be coated such as a hull or a marine structure. Cracks are less likely to occur, coating adhesion is good, coating peeling is less likely to occur,
The hydrolysis rate of the coating film is well controlled, and an antifouling coating film having excellent antifouling properties, particularly in a high fouling environment and long-term antifouling properties, and having a good balance of these properties can be obtained.

Further, according to the present invention, there is provided a coating film having such excellent characteristics and a hull or marine structure covered with the coating film and having the above-mentioned characteristics. Further, according to the present invention, there is provided an antifouling method using such an antifouling coating composition and having extremely low risk of environmental pollution.

[0098]

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 Examples and Comparative Examples, “parts” means “parts by weight”. [Production Example of Polymer] (Production of Copolymer S-1) 100 parts of xylene was charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen introduction pipe, and a heating / cooling jacket, and under a nitrogen stream. Heating and stirring were performed at a temperature of 85 ° C. While maintaining the same temperature, 50 parts of triisopropylsilyl acrylate and 45 parts of methyl methacrylate were introduced into the reactor from the dropping device.
, A mixture of 5 parts of methyl polyoxyethylene (meth) acrylate (n = 30) and 1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours. Then, after stirring at the same temperature for 4 hours,
0.4 part of 2'-azobisisobutyronitrile was added, and the mixture was further stirred at the same temperature for 4 hours to obtain a colorless and transparent copolymer solution S-1.

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%.
0.6%, a viscosity at 25 ° C. of 263 cps, and a number average molecular weight (Mn) of 4 measured by GPC.
494, and the weight average molecular weight (Mw) was 18,340. FIG. 1 shows a GPC chromatogram of copolymer S-1.
FIG. 10 shows a chart of the IR spectrum.

The GPC and IR measurement conditions are as follows. [GPC measurement conditions] Apparatus: Tosoh HLC-8120GPC Column: Tosoh Super H2000 + H40
00 6 mmI. 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 of Copolymers S-2 to S-19 and Copolymers H1 to H6 for Comparative Example) Except for changing as shown in Tables 1 to 3, "Copolymer S-2" to "Copolymer S-19" and Comparative Example copolymers H1 to H6 were obtained in the same manner as above, The physical properties of these copolymers (solutions) were measured in the same manner as described above.

The results are shown in Tables 1 to 3.

[0102]

Examples 1 to 19 and Comparative Examples 1 to 6 [Production Examples of Antifouling Paint Compositions] When producing antifouling paint compositions having the composition shown in Tables 4 and 5, paint containing glass beads was used. After shaking for 2 hours together with these ingredients in a shaker, filter through a 100 mesh filter,
The desired antifouling coating composition was obtained.

The storage stability of the antifouling coating composition after storage at room temperature for 2 months is shown in Tables 4 and 5. The storage stability was evaluated immediately after the trial production of the paint and after storage for 2 months at room temperature (K at 25 ° C. measured with a Stormer viscometer).
(u value). (Evaluation criteria) 5: Increase in viscosity is less than 10 4: Increase in viscosity is less than 20 3: Increase in viscosity is less than 30 2: Increase in viscosity is 30 or more 1: Measurement of Ku value is impossible due to lack of fluidity.

Further, antifouling properties using the antifouling coating composition,
The degree of wear was evaluated as follows. Table 4 ~
The results are shown in Table 5. [Evaluation of antifouling property] 70 × which was bent so that it could be attached to the side of a rotating drum installed in the seawater of Hiroshima Bay
A 200 × 3 mm sandblast plate was prepared.

An epoxy-based zinc-rich primer, an epoxy-based anticorrosive paint, and a vinyl-based binder coat were applied to the sandblasted plate, each having a dry film thickness of 20 μm and a thickness of 15 μm.
0 μm and 50 μm were applied successively one by one every day, and then the test antifouling paint composition was dried to a thickness of 20 μm.
It was coated so as to have a thickness of 0 μm to obtain a test plate. Attach this test plate to a rotating drum and operate at 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)
For 12 months under high fouling environmental conditions to evaluate the antifouling property.

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 plate with epoxy zinc rich primer, epoxy anticorrosive paint, vinyl binder coat, each dry film thickness 20μm, 150μ
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 and 5. 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 and 5 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

[0110]

[Table 1]

[0111]

[Table 2]

[0112]

[Table 3]

[0113]

[Table 4]

[0114]

[Table 5]

[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 GPC chromatogram of copolymer S-4.

FIG. 5 is a GPC chromatogram of copolymer S-5.

FIG. 6 is a GPC chromatogram of Copolymer S-6.

FIG. 7 is a GPC chromatogram of Copolymer S-7.

FIG. 8 is a GPC chromatogram of Copolymer S-8.

FIG. 9 is a GPC chromatogram of Copolymer S-9.

FIG. 10 is a chart of an IR spectrum of copolymer S-1.

FIG. 11 is a chart of an IR spectrum of copolymer S-2.

FIG. 12 is a chart of an IR spectrum of copolymer S-3.

FIG. 13 is a chart of an IR spectrum of copolymer S-4.

FIG. 14 is a chart of an IR spectrum of copolymer S-5.

FIG. 15 is a chart of an IR spectrum of copolymer S-6.

FIG. 16 is a chart of an IR spectrum of copolymer S-7.

FIG. 17 is a chart of an IR spectrum of copolymer S-8.

FIG. 18 is a chart of an IR spectrum of copolymer S-9.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) // (C08F 230/08 220: 26 212: 08) (72) Inventor Hidetaka Arimura 1 Meiji Shinkai 1 Otake City, Hiroshima Prefecture No. 7 Inside China Paint Co., Ltd. (72) Inventor Yukio Kozono 1 in 7 China Paint Co., Ltd. (72) Inventor Naoya Nakamura Meiji Shinkai 1, Otake City, Hiroshima Prefecture Address 7 China Paint Co., Ltd. F-term (reference) 4J027 AC02 AC03 AC04 AC06 BA04 BA05 BA07 CD08 4J038 BA222 BA232 CC021 CE052 CF011 CF031 CG121 CG141 CH031 CH041 CH111 CH121 CJ031 CJ101 CJ131 CL001 GA02 GA15 HA066 HA356 HA166 HA216 JA55 JB18 JB24 JB27 JB35 JC06 JC07 JC18 JC37 JC38 MA14 NA05 PB05 PB07 PC02 PC04 PC10 4J100 AB02R AB03R AB04R AG02R AG04R AG08R AL03R AL04R AL08P AL08Q AL09R AL14R BA05Q BA08Q BA76R CA54A Copolymer, antifouling containing the copolymer Charge composition, the antifouling paint set forming composition antifouling coating film and-proof is formed from antifouling paint composition of the antifouling method and the hull or marine structure coated with the coating film using

Claims (20)

[Claims] (1) Formula (I): ## STR1 ## [In the formula [I], R ¹ represents a hydrogen atom or a methyl group;
² , R ³ and R ⁴ may be the same or different from each other;
It represents any of an alkyl group, a cycloalkyl group which may have a substituent, and a phenyl group which may have a substituent. 20 to 80% by weight of a silyl (meth) acrylate component unit represented by the formula: (b) Formula [II]: [In the formula [II], R ⁵ represents a hydrogen atom or a methyl group,
R ⁶ represents an alkylene group; R ⁷ represents any of an alkyl group, a cycloalkyl group which may have a substituent, and a phenyl group which may have a substituent; ~
Indicates the number of 100. 0.01 to 40% by weight of a polyoxyalkylene (meth) acrylate component unit represented by the formula: (c) an unsaturated monomer component unit 5 other than the component units (a) and (b) 79.99% by weight (however, (a) + (b)
+ (C) = 100% by weight) and having a weight average molecular weight of 200,000 or less as measured by gel permeation chromatography (GPC). 2. The unsaturated monomer component unit (c) is at least one selected from (meth) acrylates, styrenes and vinyl esters.
The silyl (meth) acrylate copolymer according to the above. 3. The polyoxyalkylene (meth) acrylate component unit (b) wherein R ⁶ in the formula [II] is an ethylene group, a propylene group or a butylene group.
The silyl (meth) acrylate copolymer according to any one of the above. 4. The polyoxyalkylene (meth) acrylate component unit (b) wherein n in the formula [II] represents 30 to 50.
The silyl (meth) acrylate copolymer according to any one of claims 1 to 3, wherein (A) An antifouling coating composition comprising the silyl (meth) acrylate copolymer according to any one of (1) to (4). 6. An antifouling paint composition comprising: [A] the silyl (meth) acrylate copolymer according to any one of claims 1 to 4, and [B] an antifouling agent. . 7. A method comprising: [A] the silyl (meth) acrylate copolymer according to any one of claims 1 to 4, [B] an antifouling agent, and [C] zinc oxide. Antifouling paint composition. 8. A method comprising: [A] the silyl (meth) acrylate copolymer according to any one of claims 1 to 4, [B] an antifouling agent, and [D] an inorganic dehydrating agent. Characteristic antifouling paint composition. 9. [A] The silyl (meth) acrylate copolymer according to any one of claims 1 to 4, [B] an antifouling agent, [C] zinc oxide, and [D] an inorganic dehydrating agent. And an antifouling paint composition comprising: 10. The method according to claim 1, further comprising the step of: 6. A vinyl ether (co) polymer [E] containing a vinyl ether component unit represented by the formula: [wherein R represents a hydrocarbon group in the formula [III]].
An antifouling paint composition according to any one of claims 1 to 9. 11. The antifouling paint composition according to claim 5, further comprising an elution promoting component [F]. 12. The antifouling coating composition according to claim 6, wherein the antifouling agent [B] is copper and / or a copper compound [B-1]. 13. The antifouling agent [B] includes copper and / or a copper compound (excluding copper pyrithiones) [B-1] and an organic antifouling agent (excluding copper compounds other than copper pyrithiones). The antifouling paint composition according to any one of claims 6 to 11, which is a combination system with (B-2). 14. The organic antifouling agent [B-2] is a metal pyrithione, N, N-dimethyldichlorophenylurea, pyridine-triphenylboron, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4. -Tert-butylamino-6-cyclopropylamino-s-triazine,
14. At least one selected from the group consisting of 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and 2,4,5,6-tetrachloroisophthalonitrile. Antifouling paint composition. 15. The organic antifouling agent [B-2] comprises N, N-dimethyldichlorophenylurea, pyridine-triphenylboron, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butyl. Amino-
6-cyclopropylamino-s-triazine, 4,5-
Dichloro-2-n-octyl-4-isothiazoline-3
A combination of at least one organic antifouling agent (b2) selected from the group consisting of -one, 2,4,5,6-tetrachloroisophthalonitrile and a metal pyrithione (b1). Item 14. An antifouling paint composition according to item 13. 16. The antifouling paint composition according to claim 14, wherein the metal pyrithione (b1) is copper pyrithione. 17. The antifouling paint according to claim 11, wherein the elution promoting component [F] is at least one selected from rosin, rosin derivatives, naphthenic acid and metal salts thereof. Composition. 18. An antifouling coating film formed from the antifouling coating composition according to any one of claims 5 to 17. 19. A hull or marine structure, comprising applying the antifouling coating composition according to any one of claims 5 to 17 to the surface of the hull or marine structure to cover the surface. Antifouling method. 20. 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 5 to 17.