JP2001026621A - Silyl (meth)acrylate copolymer and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film, which is unlikely to suffer cracks, has good film adherence, is well controlled in hydrolytic speed, and has an excellent stain resistance performance and a long-term stain resistance, by constituting it of silyl (meth)acrylate having two different types of constituent units and other type of unsaturated monomer constituent unit wherein when the weight average molecular weight measured by GPC has a value not larger than a specified one. SOLUTION: The silyl (meth)acrylate copolymer is constituted of silyl (meth) acrylates of formulas I and II and an unsaturated monomer constituent unit different therefrom and has a weight average molecular weight of 200,000 or below. In the formulae, R represents H or methyl; R1 and R2 independently represents a 1-10C alkyl, phenyl or trimethylsilyloxy; R3 represents a 1-18C alkyl which may has a ring structure or may be a branched, 6-10C phenyl or trimethylsilyloxy; R4 and R5 independently represent a 3-10C branched alkyl or cycloalkyl; and R6 represents a 1-10C linear alkyl, or 3-10C branched alkyl or cycloalkyl, 6-10C phenyl or trimethylsilyloxy.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silyl (meth) acrylate copolymer and a method for producing the same, and more particularly to a coating film which is hardly cracked, has good coating adhesion, and does not easily peel off. Silyl (meth) which can produce an antifouling coating in which the hydrolysis rate of the coating film is well controlled and which has excellent antifouling performance (antifouling activity) and excellent long-term antifouling properties. The present invention relates to an acrylate copolymer and a method for producing the acrylate copolymer.

[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. JP-A-7-102193 discloses a compound represented by the formula: X-SiR ¹ R ² R ³ (where 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 or a fumaroyloxy group), and a monomer A represented by the 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 both a linear alkyl group-containing silyl (meth) acrylate component unit and a branched alkyl group-containing silyl (meth) acrylate component unit. above,
The paint described in this publication has a problem that the antifouling property is poor.

(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. Equation ^{_{(2) CH 2 = CR 4}} COOR 5 -NR 6 R 7
[R ⁴ represents H or CH ₃ , R ⁵ represents an alkylene group, and R ⁶ and R ⁷ are alkyl groups, 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. Show. 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 represents H and CH ₃ , and R ¹⁹ and R ²⁰ are alkyl groups which may be the same or different. (Meth) acrylic amide represented by the formula (7): CH ₂ ＣＲCR ²¹ CO
N⊂⊃Q [R ²¹ represents H and CH ₃ , and 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 2CR ²³ COOCH ₂ -T [R ²³
Represents H and CH ₃ , 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. Silyl (meta) that can be used to produce antifouling paints that are difficult to control and that have good control over the hydrolysis rate of the coating film and have excellent antifouling performance (antifouling activity) and long-term antifouling properties. It is an object of the present invention to provide an acrylate copolymer and a method for producing the acrylate copolymer.

[0024]

Silyl (meth) acrylate copolymer according to the present invention SUMMARY OF THE INVENTION, (a) Formula _{[I]: - CH 2 -CR} (COOSiR 1 R 2 R 3) - ····· [I] [ wherein [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 are each independently, a carbon number shows a branched alkyl or cycloalkyl group of 3 to 10, R ⁶ is 1 carbon atoms
A linear alkyl group having 10 to 10 carbon atoms, a branched or cycloalkyl group having 3 to 10 carbon atoms, or an optionally substituted phenyl group or trimethylsilyloxy group having 6 to 10 carbon atoms. Gel permeation chromatography comprising a silyl (meth) acrylate component unit represented by the formula: and (c) an unsaturated monomer component unit other than the (a) component unit and the (b) component unit. The weight average molecular weight (Mw) measured by (GPC) is 200,000 or less.

In the present invention, the above R ¹ , R ² and R
Preferably, each ³ is independently a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group or a trimethylsilyloxy group. In the present invention, R ⁴ , R ⁵ and R ⁶ each independently represent an isopropyl group, a sec-butyl group, a tert-
It is preferably either a butyl group or an isobutyl group.

In the present invention, the unsaturated monomer component unit (c) is one or more compounds selected from the group consisting of (meth) acrylic acid esters, styrene, 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, the silyl (meth) acrylate copolymer has a weight average molecular weight (Mw) of 30.
It is preferably from 100,000 to 100,000. The method for producing a silyl (meth) acrylate copolymer according to the present invention comprises the following steps: (a1) Formula [Ia]: CH ₂ ＣＲ CR (COOSiR ¹ R ² R ³ ) ··· [Ia] [Formula [Ia] Wherein R represents a hydrogen atom or a methyl group,
R ¹ and R ² each independently represent a straight-chain alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group or trimethylsilyloxy group, and R ³ has a ring structure or a branch. An alkyl group having 1 to 18 carbon atoms, an optionally substituted phenyl group having 6 to 10 carbon atoms, or a trimethylsilyloxy group. ]
(B1) Formula [II-a]: CH ₂ ＣＲCR (COOSiR ⁴ R ⁵ R ⁶ )... [II-a] [in the formula [II-a] , 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 or a cycloalkyl group having 3 to 10 carbon atoms, and 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 trimethylsilyloxy group having 6 to 10 carbon atoms which may be substituted. And (c1) another unsaturated monomer copolymerizable with the monomers (a1) and (b1) in the presence of a radical polymerization initiator. It is characterized in that the above silyl (meth) acrylate copolymer is obtained.

In the present invention, the above R ¹ , R ² and R
Preferably, each ³ is independently a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group or a trimethylsilyloxy group. In the present invention, R ⁴ , R ⁵ and R ⁶ each independently represent an isopropyl group, a sec-butyl group, a tert-
It is preferably either a butyl group or an isobutyl group.

In the present invention, the above unsaturated monomer (c
It is preferred that 1) is one or more compounds selected from (meth) acrylates, styrene, and vinyl organic carboxylate. In the present invention, the silyl (meth) acrylate (a1) contains 0.1%.
5 to 50% by weight of the silyl (meth) acrylate (b1)
Is 10 to 70% by weight, and the unsaturated monomer (c1) is 20% by weight.
Preferably, it is used in an amount of about 70% by weight ((a1) + (b1) + (c1) = 100% by weight).

In the present invention, the weight average molecular weight (Mw) of the obtained silyl (meth) acrylate copolymer is preferably 3,000 to 100,000 in any of the above production methods. ADVANTAGE OF THE INVENTION According to this invention, a crack is hard to generate | occur | produce in a coating film, coating film adhesion is favorable, coating film peeling does not occur easily, the hydrolysis rate of a coating film is controlled well, and antifouling performance (antifouling activity) and Disclosed is a silyl (meth) acrylate copolymer which is excellent in long-term antifouling property and can produce an antifouling paint capable of obtaining an antifouling coating film having a good balance of these properties, and a method for producing the same.

[0031]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the silyl (meth) acrylate copolymer according to the present invention and a method for producing the same will be specifically described. <Silyl (meth) acrylate copolymer> The silyl (meth) acrylate copolymer according to the present invention comprises a silyl (meth) acrylate component unit (a) represented by the following formula [I],
Acrylic unsaturated monomer component unit represented by the following formula [II]
(b) and an unsaturated monomer component unit (c) other than these component units (a) and (b).

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, in addition to 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.

Of these, R ¹ , R ² and R ³ may be the same or different from each other, but include 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 have 1 to 3 carbon atoms which may have a ring structure or a branch, similarly to R ³ in the above formula [I].
And represents an alkyl group of 18, 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 if 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) capable of deriving such a silyl (meth) acrylate component unit (b)
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 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, n-, is (meth) acrylate
hydrophobic (meth) acrylates such as o-, tert-butyl, 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2 -Hydroxypropyl, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methyl (meth) acrylate polyoxyethylene, methyl (meth) acrylate Hydrophilic (meth) acrylates such as polyoxypropylene; styrenes such as styrene, vinyltoluene and α-methylstyrene; vinyl acetate, vinyl benzoate,
Vinyl esters such as vinyl propionate and vinyl butyrate; organic carboxylic esters such as itaconic esters and maleic esters; and the like. Among these, (meth) acrylic esters, styrenes,
Organic carboxylic acid vinyl esters are preferable because an antifouling coating film having an appropriate coating film strength can be obtained.

The use of hydrophilic (meth) acrylic esters can increase the consumption of the coating film, and 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 according to the present invention, the silyl (meth) acrylate component unit (a) has a content of 0.5
In an amount of ５０50% by weight, preferably 0.5-25% by weight,
Silyl (meth) acrylate component unit (b) is 10 to 70
% By weight, preferably from 30 to 65% by weight,
And the unsaturated monomer component unit (c) other than (b) is 20 to 70% by weight, preferably 30 to 60% by weight ((a) + (b) + (c) =
(100% 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, peroxides and the like can be widely used.
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.

<Silyl (meth) acrylate copolymer
Use> The thus obtained silyl (meth) acrylate copolymer according to the present invention is suitably used as a coating film forming component for paints, especially for antifouling paints, 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 performance (antifouling activity), and is excellent in long-term antifouling properties is obtained.

<Other Components> Such an antifouling paint composition is also referred to as the above-mentioned silyl (meth) acrylate copolymer / silyl (meth) acrylate-based copolymer. ｝
In addition to this component, it promotes the dissolution of various antifouling agents such as copper and / or copper compounds, zinc oxide (zinc white), dehydrating agents, anti-sagging / anti-sedimentation agents, and rosin. Ingredients, plasticizers such as chlorinated paraffin, coloring pigments,
The following components, such as various pigments such as extender pigments, various resins such as acrylic resin and polyalkyl vinyl ether (vinyl ether (co) polymer), various additives such as antifoaming agent, anti-separation agent and leveling agent May be contained.

[Vinyl ether-based (co) polymer] The vinyl ether-based (co) polymer is represented by the formula [IV]: H ₂ C = CHO-R... [IV] Represents a hydrocarbon group.) (Co)
It is a polymer.

The above 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- fouling agent ] As the anti-fouling agent, copper and / or a copper compound is preferable.

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 and copper thiocyanate (copper thiocyanate). , Rodan copper), basic copper sulfate, copper chloride,
Examples of the organic copper compound include copper oxides such as basic copper acetate, copper oxine, copper nonylphenolsulfonate, copper bis (ethylenediamine) -bis (dodecylbenzenesulfonate), copper naphthenate, rosin copper, bis Copper (pentachlorophenolic acid) and the like are preferable, and inorganic cuprous oxide and copper thiocyanide (rhodan copper) are preferably 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 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,
A pyrithione-based compound represented by the following formula [IV] (that is, metal-pyrithiones) together with or instead of the copper and / or the copper compound, wherein R ^{1 to} R ⁴ are Each independently represents hydrogen, an alkyl group, an alkoxy group, or a halogenated alkyl group;
Represents Zn, Cu, Na, Mg, Ca, Ba, Pb, F
e represents a metal such as Al, and n represents a valence].

[0062]

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 may contain the following antifouling agent (other antifouling agent) together with or instead of the pyrithione compound. As the antifouling agent, various conventionally known antifouling agents can be used. Specifically, for example, tetramethylthiuram disulfide, carbamate-based poisons (eg, zinc dimethyldithiocarbamate,
Manganese-2-ethylenebisdithiocarbamate), 2,
4,5,6-tetrachloroisophthalonitrile, N, N
-Dimethyldichlorophenylurea, 4,5-dichloro-
2-n-octyl-4-isothiazolin-3-one, 2,4
Examples thereof include 6-trichlorophenylmaleimide, pyridine-triphenylborane, and amine-triphenylborane. In the present invention, such an antifouling agent is zinc pyrithione (in the above formula [IV], R ^{1 to} R ⁴ = H, M =
Zn, corresponding to n = 2), copper pyrithione (formula [I
V], R ^{1 to} R ⁴ = H, M = Cu, n = 2)
And the like, together with a pyrithione-based compound such as described above.

The content of various antifouling agents such as copper and / or a copper compound and a pyrithione compound contained in the antifouling coating composition depends on the amount of the antifouling agent used in preparing the antifouling coating composition and the amount of the film forming agent. Types such as water-soluble copolymers or types of ships on which such antifouling paint composition is applied (for ships, for ocean going-inland sea, for various seawater areas, wooden-FRP ships-steel ships, etc.) The 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. Is desirably contained.

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, further antifouling property cannot 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)] Such an antifouling paint 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. 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] 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, anhydrous gypsum and molecular sieve are preferably used. Such an inorganic dehydrating agent can be used alone or in combination of two or more.

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 an inorganic dehydrating agent is generally contained in the antifouling coating composition in a total amount of usually 0.01 to 10% by weight, preferably 0.1 to 10% by weight.
Desirably, it is contained in an amount of 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.

[ Anti-sagging / Anti-settling agent] As an anti- sagging / anti-settling agent, a known anti-sagging / anti-settling agent may be added in an optional amount. Such anti-sagging / anti-settling agents include Al, Ca, Zn stearate salts,
Salts such as lecithin salts and alkyl sulfonates, polyethylene waxes, amide waxes, hydrogenated castor oil waxes, polyamide waxes and mixtures thereof, synthetic finely powdered silica, polyethylene oxide waxes and the like are preferred. Castor oil wax, polyamide wax, synthetic finely divided silica, and polyethylene oxide wax are used. Examples of such anti-sagging and anti-settling agents include “DISPARON A-603-20X” manufactured by Kusumoto Kasei Co., Ltd.
Products marketed under the trade name such as "Dispalon 4200-20" can be mentioned.

[Elution-promoting component] The elution-promoting component has a function of promoting the self-polishing effect of the coating film in seawater. Such a dissolution-promoting component includes rosin (eg, trade name “Rosin WW”). And its derivatives, monocarboxylic acids and salts thereof. The rosin includes gum rosin, wood rosin, tall oil rosin and the like, and any of them can be used in the present invention. As rosin derivatives,
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), metal salts of rosin and rosin derivatives (Copper and zinc salts of rosin and rosin derivatives,
Magnesium salt), rosinamine and the like.
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.

[Pigment, Solvent ] As the pigment, various kinds of conventionally known 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 antifouling paints are used. . < Production of antifouling paint composition> Such an antifouling paint composition can be produced by appropriately using a conventionally known method. For example, the above silyl (meth) acrylate copolymer and 3 to 100 parts by weight of the copolymer
Copper and / or copper compound in an amount of 1400 parts by weight,
A pyrithione compound in an amount of 300 parts by weight (provided that the total amount of the antifouling agent is 25 to 1200 parts by weight), a vinyl ether (co) polymer in an amount of 0.3 to 200 parts by weight, and an amount of 2 to 700 parts by weight Zinc flower used as needed in 0.03 to
Add 200 parts by weight of a dehydrating agent (eg, anhydrous gypsum, molecular sieve) and an anti-sagging / anti-settling agent, pigment, solvent, etc. used in appropriate amounts at once or in any order, and stir / mix. What is necessary is just to disperse.

The antifouling paint composition is a one-part composition, has excellent storage stability, and satisfies various required performances such as adhesion, durability, and antifouling properties of the antifouling paint. The antifouling paint composition as described above is used for underwater structures (eg, water supply and drainage ports of nuclear power plants), gulf roads, submarine tunnels, harbor facilities, canal / waterway sludge diffusion prevention films for various marine civil engineering works, Ship,
If it is applied once to a plurality of times on the surface of various molded articles such as fishing gear (eg, ropes, fishing nets) according to an ordinary method, a hull or an underwater structure coated with an antifouling coating film having excellent crack resistance and antifouling properties can be obtained. can get. The antifouling paint composition may be applied directly to the surface of the hull or underwater structure or the like, or the surface of a hull or underwater 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, underwater 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, underwater structure or the like in this manner is not particularly limited, but is, for example, about 30 to 150 μm / time.

[0077]

According to the present invention, cracks do not easily occur in the coating film, the coating film has good adhesion to the coating film, and the coating film does not easily peel off.
It is possible to produce an antifouling paint in which the hydrolysis rate of the coating film is well controlled, the antifouling performance (antifouling activity) and the long-term antifouling property are excellent, and the antifouling coating film having a good balance of these properties is obtained. Such a silyl (meth) acrylate copolymer and a method for producing the same are provided.

[0078]

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".

[0079]

[Production Examples of Polymer] (Production of Copolymer S-1) Stirrer, condenser, thermometer, dropping device, nitrogen inlet tube,
Xylene 10 in a reaction vessel equipped with a heating / cooling jacket
0 parts were charged and heated and stirred at a temperature of 85 ° C. under a nitrogen stream. 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 conditions for measuring GPC and IR 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

[Examples and Comparative Examples of Production of Copolymers S-2 to S-11 and Copolymers H1 to H5 for Comparative Example] Except that the components were changed as shown in Tables 1 to 3, copolymers S-2 to S-11 and copolymers H1 to H5 for comparative examples were obtained in the same manner as above, and the same as above. The physical properties of these copolymers (solutions) were measured.

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.

[0084]

[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, the antifouling property 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 applied to this sandblasted steel sheet to a dry film thickness of 20 μm and 1 μm, respectively.
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. "Toyoparax 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. "Lutnal A-25" polyvinyl ethyl ether manufactured by BASF, viscosity: 2.5 to 6.0 Pa · s / 23
° C, specific gravity: 0.96 / 20 ° C. "Rosin solution" 50% xylene solution of WW rosin "Copper naphthenate solution" Xylene solution of copper naphthenate,
Copper content in solution: 8%. “Soluble anhydrous gypsum D-1” manufactured by Noritake Co., Ltd., IIICaSO ₄ , white powder, average particle size 15 μm
m. "Dispalon 4200-20" manufactured by Kusumoto Kasei Co., Ltd.
Polyethylene oxide 20% xylene paste "DISPARON A603-20X" Kusumoto Kasei Co., Ltd. fatty acid amide wax 20% xylene paste

[0092]

[Table 1]

[0093]

[Table 2]

[0094]

[Table 3]

[0095]

[Table 4]

[0096]

[Table 5]

[0097]

[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.

Continuation of the front page (72) Inventor Hidetaka Arimura, 1-7 Meiji Shinkai, Otake City, Hiroshima Prefecture, China Inside (72) Inventor Naoya Nakamura 7 China Coating, 1 Meiji Shinkai, Otake City, Hiroshima Prefecture F-term (reference) in Kyowa Co., Ltd.

Claims (12)

[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. 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). A silyl (meth) acrylate copolymer having a weight average molecular weight (Mw) measured by (GPC) of 200,000 or less. 2. The method according to claim ¹ , wherein R ¹ , R ² and R ³ are each independently any one of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group and a trimethylsilyloxy group. Item 7. The silyl (meth) acrylate copolymer according to Item 1. 3. The method according to claim 1, wherein R ⁴ , R ⁵ and R ⁶ are each independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl and isobutyl.
The silyl (meth) acrylate copolymer according to any one of the above. 4. The unsaturated monomer component unit (c) is derived from one or more compounds selected from (meth) acrylates, styrenes, and organic carboxylates. The silyl (meth) acrylate copolymer according to any one of claims 1 to 3, wherein 5. The silyl (meth) acrylate component unit
(a) is 0.5 to 50% by weight, the silyl (meth) acrylate component unit (b) is 10 to 70% by weight, and the unsaturated monomer component unit (c) is 20 to 70% by weight. ((A) + (b)
+ (C) = 100% by weight). The silyl (meth) acrylate copolymer according to any one of claims 1 to 4, wherein 6. The silyl (meth) acrylate copolymer according to claim 1, wherein the weight average molecular weight (Mw) of the silyl (meth) acrylate copolymer is 3000 to 100,000. 7. (a1) Formula [Ia]: CH ₂ ＣＲCR (COOSiR ¹ R ² R ³ )... [Ia] [In the formula [Ia], R represents a hydrogen atom or a methyl group. ,
R ¹ and R ² each independently represent a straight-chain alkyl group having 1 to 10 carbon atoms or an optionally substituted phenyl group or trimethylsilyloxy group, and R ³ has a ring structure or a branch. An alkyl group having 1 to 18 carbon atoms, an optionally substituted phenyl group having 6 to 10 carbon atoms, or a trimethylsilyloxy group. ]
(B1) Formula [II-a]: CH ₂ ＣＲCR (COOSiR ⁴ R ⁵ R ⁶ )... [II-a] [in the formula [II-a] , R represents a hydrogen atom or a methyl group,
R ⁴ and R ⁵ each independently represent a branched or cycloalkyl group having 3 to 10 carbon atoms, and R ⁶ represents a straight-chain alkyl group having 1 to 10 carbon atoms and a branched alkyl group having 3 to 10 carbon atoms. Or a cycloalkyl group, or an optionally substituted phenyl group or trimethylsilyloxy group having 6 to 10 carbon atoms. And (c1) another unsaturated monomer copolymerizable with the monomers (a1) and (b1) in the presence of a radical polymerization initiator. A method for producing a silyl (meth) acrylate copolymer, comprising obtaining the silyl (meth) acrylate copolymer according to claim 1. 8. The method according to claim ¹ , wherein R ¹ , R ² and R ³ are each independently any one of methyl, ethyl, n-propyl, n-butyl, n-hexyl and trimethylsilyloxy. Item 8. The method for producing a silyl (meth) acrylate copolymer according to Item 7. 9. The method according to claim 7, wherein R ⁴ , R ⁵ and R ⁶ are each independently any one of isopropyl, sec-butyl, tert-butyl and isobutyl.
The method for producing a silyl (meth) acrylate copolymer according to any one of the above. 10. The unsaturated monomer (c1) is one or more compounds selected from (meth) acrylic acid esters, styrene, and organic carboxylic acid vinyl esters. The silyl (meth) according to any one of items 1 to 9,
A method for producing an acrylate copolymer. 11. The silyl (meth) acrylate (a1)
Is 0.5 to 50% by weight, the silyl (meth) acrylate (b1) is 10 to 70% by weight, the unsaturated monomer (c1)
Is 20 to 70% by weight ((a) + (b) + (c) = 100% by weight). The silyl (meth) acrylate copolymer according to any one of claims 7 to 10, wherein Manufacturing method. 12. The production of the silyl (meth) acrylate copolymer according to claim 7, wherein the weight average molecular weight (Mw) of the silyl (meth) acrylate copolymer is 3000 to 100,000. Method.