JPWO2018092668A1 - Antifouling paint composition and coated article having an antifouling coating film formed on the surface using the composition - Google Patents

Abstract

An antifouling paint composition comprising a triorganosilyl ester-containing copolymer that maintains a high coating film dissolution rate over a long period of time in seawater and maintains stable antifouling performance without causing coating film abnormalities such as cracks. Offer things. According to the present invention, (A) (a) general formula (1): (wherein R1 represents a hydrogen atom or a methyl group, R2, R3 and R4 are the same or different, 6 represents a branched alkyl group or phenyl group at the α-position) and (b) the (meth) acrylic triorganosilyl ester monomer. A triorganosilyl ester-containing copolymer obtained from a mixture with a polymerizable ethylenically unsaturated monomer, and (B) a siloxane compound having an alkoxy group having 1 to 4 carbon atoms and a siloxane skeleton (provided that the siloxane skeleton An antifouling paint composition containing 5 to 100 Si atoms therein is provided.

Description

The present invention relates to an antifouling coating composition and a coated article having an antifouling coating film formed using the composition on the surface.

Aquatic fouling organisms such as barnacles, cell plastics, blue mussels, scallops, sea squirts, blue sea breams, blue sea breams, slimes, etc., become submarine structures such as vessels (especially the bottom of the ship), fishing nets, fishing net accessories, etc. and power plant conduits. Adhering causes problems such as damage to the functions of the ship and the like, and the appearance.
Since the ban on the use of conventionally used organotin-containing copolymers, triorganosilyl group-containing copolymers with low toxicity and low environmental impact have been developed and used in antifouling paints (Patent Document 1). .
When the triorganosilyl ester copolymer is used, the coating film dissolves at a constant rate in seawater for a long period of time, but the coating film dissolution rate generally tends to be low. There is no problem when the ship is normally operated and has a navigation speed above a certain level, but in situations where the ship's berthing period is prolonged or the navigation speed is reduced due to the recent global economic downturn, The problem that the coating film dissolution rate became too low and the antifouling effect was not sufficiently exhibited came to arise.
Various proposals have been made to solve the above problems. For example, an antifouling paint containing a highly hydrophilic triorganosilyl ester-containing copolymer using a highly hydrophilic monomer as a constituent monomer of the triorganosilyl ester-containing copolymer (Patent Documents 2 to 4) Antifouling paints containing a large amount of dissolution aids such as rosin compounds have been proposed (Patent Documents 5 to 7).
However, the proposed antifouling paint cannot sufficiently improve the dissolution rate of the coating film, and as an adverse effect of excessively increasing the hydrophilicity, the coating film dissolves in a relatively short period of time after being immersed in seawater. Have stopped, or caused deterioration of coating film properties such as cracks.
Thus, including a triorganosilyl ester-containing copolymer that maintains a high coating film dissolution rate over a long period of time in seawater and can maintain stable antifouling performance without causing coating film abnormalities such as cracks. There has never been an antifouling paint composition.

JP-A-7-102193 JP 2000-17203 A JP 2000-248029 A WO2009 / 149919A1 Japanese Patent Laid-Open No. 10-30071 JP 2003-183567 A WO2015 / 156073A1

  The present invention includes a triorganosilyl ester-containing copolymer capable of maintaining a high coating film dissolution rate in seawater for a long period of time and maintaining stable antifouling performance without causing coating film abnormalities such as cracks. An object is to provide an antifouling paint composition.

According to the present invention, (A) (a) general formula (1):


(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² , R ^3, and R ⁴ are the same or different and each represents an alkyl group or a phenyl group branched from the α-position of 3 to 6 carbon atoms. (Meth) acrylic acid triorganosilyl ester monomer represented by
(B) a triorganosilyl ester-containing copolymer obtained from a mixture of the (meth) acrylic acid triorganosilyl ester monomer and a copolymerizable ethylenically unsaturated monomer, and (B) the number of carbon atoms Siloxane compound having 1 to 4 alkoxy groups and a siloxane skeleton (however, the number of Si atoms in the siloxane skeleton is 5 to 100)
An antifouling paint composition is provided.

  As a result of intensive studies, the present inventor added a siloxane compound (B) having a specific structure to the triorganosilyl ester-containing copolymer (A) having a specific structure, thereby providing physical properties of the coating film (particularly crack resistance). The present inventors have found that an unexpected effect of significantly improving the coating film dissolution rate, particularly the coating film dissolution rate from the initial stage, can be obtained without impairing the above. The siloxane compound (B) also has an advantageous characteristic that the coating film hardness is not lowered as compared with other coating film dissolution aids.

ADVANTAGE OF THE INVENTION According to this invention, the antifouling coating composition which can form the antifouling coating film which is excellent in storage stability and maintains high antifouling performance over a long period of time is provided.

  Hereinafter, the present invention will be described in detail.

Antifouling paint composition The antifouling paint composition of the present invention comprises the above triorganosilyl ester-containing copolymer (A) and the above siloxane compound (B).

<Copolymer (A)>
The copolymer (A) of the present invention is obtained by copolymerization of the monomer (a) and the monomer (b).
Hereinafter, a method for synthesizing the monomer (a), the monomer (b), the copolymer (A), and the like will be specifically described.

Monomer (a)
Examples of the alkyl group branched at the α-position having 3 to 6 carbon atoms include isopropyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1, Examples include 1-dimethylpropyl group, 1,1-dimethylbutyl group, texyl group and the like.
In particular, in the present invention, by selecting specific groups as R ² , R ^3, and R ⁴ , it is possible to form an antifouling coating film that hardly causes a coating film abnormality and has excellent water resistance. From such a viewpoint, R ² , R ³ and R ⁴ are the same or different and are preferably isopropyl, s-butyl, t-butyl and phenyl, and preferably isopropyl. More preferred.
Examples of the monomer (a) include triisopropylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, diisopropyl s-butylsilyl (meth) acrylate, (Meth) acrylic acid diisopropyl t-butylsilyl, (meth) acrylic acid diisopropyl texylsilyl, (meth) acrylic acid diisopropylphenylsilyl, (meth) acrylic acid isopropyl di-s-butylsilyl, (meth) acrylic acid isopropyl diphenylsilyl, ( Examples thereof include diphenyl hexylsilyl (meth) acrylate and t-butyldiphenylsilyl (meth) acrylate. In particular, trimethyacrylate (meth) acrylate, tris-butylsilyl (meth) acrylate, and (meth) acrylic acid are less likely to cause coating film abnormality and can form an antifouling coating film excellent in water resistance. t-Butyldiphenylsilyl is preferred, and triisopropylsilyl (meth) acrylate is more preferred. These (meth) acrylic acid triorganosilyl ester monomers are used alone or in combination of two or more.

Monomer (b)
The monomer (b) is an ethylenically unsaturated monomer copolymerizable with the monomer (a). For example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n-butyl, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl acrylate, 2-methoxy acrylate Propyl, 4-methoxybutyl acrylate, 2-methoxy (meth) acrylate, ethylene glycol monomethyl (meth) acrylate, propylene glycol monomethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acryl 2-hydroxypropyl acid, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) a (Meth) acrylic acid esters such as benzyl laurate and phenyl (meth) acrylate; vinyl compounds such as vinyl chloride, vinylidene chloride, (meth) acrylonitrile, vinyl acetate, butyl vinyl ether, lauryl vinyl ether, N-vinyl pyrrolidone; styrene , Aromatic compounds such as vinyltoluene and α-methylstyrene. Among these, (meth) acrylic acid ester is preferable, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) acrylic acid. 2-Ethylhexyl and 2-methoxyethyl acrylate are more preferred. The exemplified monomer (b) can be used alone or in combination of two or more as the monomer component of the copolymer (A).

Synthetic copolymer (A) of copolymer (A) is obtained by polymerizing a mixture of monomer (a) and monomer (b).
The content of the monomer (a) in the mixture is preferably about 20 to 70% by weight, and more preferably about 30 to 60% by weight. When the content of the monomer (a) is about 30 to 60% by weight, the coating film formed using the obtained antifouling coating composition exhibits stable coating film solubility, and is antifouling for a long time. Performance can be maintained.
The weight average molecular weight (Mw) of the copolymer (A) is preferably 10,000 to 100,000, and particularly preferably 20,000 to 70,000. When Mw is 10,000 to 100,000, the coating film does not become brittle and the coating film is moderately dissolved, so that a desired antifouling effect can be effectively exhibited. Examples of the method for measuring Mw include gel permeation chromatography (GPC).

The copolymer (A) is a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer of the monomer (a) and the monomer (b). It may be. The copolymer (A) can be obtained, for example, by polymerizing the monomer (a) and the monomer (b) in the presence of a polymerization initiator.

  Examples of the polymerization initiator used in the polymerization reaction include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis-2-methylbutyronitrile, dimethyl-2,2 ′. An azo compound such as azobisisobutyrate, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy 2-ethylhexanoate, Examples thereof include peroxides such as 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate and 1,1,3,3-tetramethylbutylperoxyneodecanoate. These polymerization initiators can be used alone or in combination of two or more. Examples of the polymerization initiator include AIBN, tert-butylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate or 1,1,3. 1,3-tetramethylbutylperoxyneodecanoate is preferred. The molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used. At this time, a chain transfer agent such as mercaptan or α-methylstyrene dimer can also be used.

Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like. Among these, solution polymerization is particularly preferable in that the copolymer (A) can be obtained easily and accurately.

  In the polymerization reaction, an organic solvent may be used as necessary. Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate; isopropyl Examples include alcohol solvents such as alcohol and butyl alcohol; ether solvents such as dioxane, diethyl ether, and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Among these, an aromatic hydrocarbon solvent is particularly preferable, and xylene is more preferable. These solvents can be used alone or in combination of two or more.

  What is necessary is just to set the reaction temperature in a polymerization reaction suitably according to the kind etc. of polymerization initiator, and it is 70-140 degreeC normally, Preferably it is 80-120 degreeC. What is necessary is just to set the reaction time in a polymerization reaction suitably according to reaction temperature etc., and is about 4 to 8 hours normally. The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas.

Although content in particular of the copolymer (A) in the composition of this invention is not restrict | limited, It is 2-50 mass% normally in solid content of the composition of this invention, Preferably it is 4-25 mass%. When the content of the copolymer (A) is 4% by mass to 25% by mass, an appropriate coating film dissolution rate and coating film properties in seawater can be obtained, and stable surface renewability can be maintained over a long period of time. A desired antifouling effect can be exhibited effectively. Moreover, the recoat performance which was excellent in the coating film can be exhibited.

<Siloxane compound (B)>
The siloxane compound (B) of the present invention is a siloxane compound having an alkoxy group having 1 to 4 carbon atoms and a siloxane skeleton, and the number of Si atoms in the siloxane skeleton is 5 to 100. Specifically, the number of Si atoms of the siloxane compound (B) is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85. , 90, 95, 100, and may be within a range between any two of the numerical values exemplified here. It is preferable that at least one alkoxy group having 1 to 4 carbon atoms is bonded to each Si in the siloxane skeleton.

Each Si in the siloxane skeleton has a plurality of substituents (terminal Si is three substituents, and other Si is two substituents). All of the plurality of substituents are preferably alkoxy groups having 1 to 4 carbon atoms. Two of the plurality of substituents may be an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an alkoxy group having 1 to 4 carbon atoms. The siloxane skeleton may be linear, branched or cyclic. The siloxane compound (B) may contain one kind of compound having a linear, branched or cyclic siloxane skeleton, or may be a mixture containing plural kinds.

Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy group, and preferably methoxy and ethoxy groups. Furthermore, an ethoxy group is preferable. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl and the like, preferably methyl, ethyl It is a group.

The siloxane compound (B) may include a compound represented by the following general formula (2).
The following general formula (2):

(Wherein R ⁵ is the same or different and each is an alkyl group having 1 to 4 carbon atoms, and R ⁶ is the same or different and each is an alkyl group having 1 to 6 carbon atoms, a phenyl group, or It is an alkoxy group having 1 to 4 carbon atoms, and n is 5 to 100).

Examples of R ⁵ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl group, and the like, preferably methyl and ethyl group. More preferably, it is an ethyl group.
R ⁶ includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, cyclohexyl, phenyl group, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy , T-butoxy group, and the like, preferably methyl, ethyl, phenyl, methoxy, and ethoxy groups.

The siloxane compound (B) of the present invention may be produced, for example, by partially hydrolytic condensation of an organosilicate, or a commercially available product may be used.
Specific examples of the organosilicate include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraisobutoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyl Tripropoxysilane, methyltriisopropoxysilane, methyltrin-butoxysilane, methyltriisobutoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, phenyltrin-butoxysilane, Trifunctional silanes such as phenyltriisobutoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane; dimethyldimethoxysilane, dimethyldiet Sisilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldiisobutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane, diphenyldin-butoxysilane , Bifunctional silanes such as diphenyldiisobutoxysilane, dihexyldimethoxysilane, and dihexyldiethoxysilane. These tetrafunctional, trifunctional or bifunctional silanes can be used alone or in combination of two or more.

Examples of commercially available siloxane compounds (B) include MKC silicate MS56, MKC silicate MS57, MKC silicate MS56S (all of which are trade names manufactured by Mitsubishi Chemical Corporation), methyl silicate 53A, ethyl silicate 40, and ethyl silicate. 48, EMS-485, SS-101 (all of which are manufactured by Colcoat Co., Ltd., trade names), silicate 40, silicate 45 (manufactured by Tama Chemical Industry Co., Ltd., trade names) KR-515, KR-500, KR -401N, KR-510 (all of which are manufactured by Shin-Etsu Chemical Co., Ltd., trade names), TES40WN (manufactured by Asahi Kasei Wacker Silicone), and the like.

The method for blending the siloxane compound (B) of the present invention into the coating composition is not particularly limited, and it may be blended at the coating dispersion step or at the final step. Alternatively, it may be added to the paint and mixed immediately before painting.

The siloxane compound (B) of the present invention is contained in an amount of 0.2 to 5% by mass, particularly preferably 0.5 to 2% by mass, in the solid content of the composition of the present invention. When the content of the siloxane compound (B) is within the above range, the effect of promoting the dissolution rate of the coating film in the initial stage (before immersion in seawater) is remarkable, and the antifouling coating film after being immersed in seawater for a certain period of time No coating film abnormalities (cracks, etc.) occur.

  When the content ratio of the copolymer (A) and the siloxane compound (B) is, in terms of solid content, a mass ratio (the copolymer (A) / the condensate (B)), 1 to 75, The effect of promoting the dissolution rate of the coating film in the initial stage (before immersion in seawater) is remarkably exhibited, and when the content ratio is 2.5 to 30, the effect is further exhibited.

  In addition to the copolymer (A) and the siloxane compound (B), an antifouling agent (C), an elution regulator (D), and a plasticizer (E ), Other resins (F) and the like can be blended. Thereby, the more outstanding antifouling effect can be exhibited.

<Anti-fouling agent (C)>
The antifouling agent (C) is not particularly limited as long as it is a substance having a killing or repelling action against marine fouling organisms. For example, inorganic chemicals and organic chemicals can be mentioned.
Examples of inorganic agents include cuprous oxide, copper thiocyanate (generic name: rhodan copper), cupronickel, copper powder, and the like. Of these, cuprous oxide and rhodan copper are particularly preferred.
Examples of organic agents include organic copper compounds such as 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylenebisdithiocarbamate. (Generic name: dinebu), bis (dimethyldithiocarbamate) zinc (generic name: diram), bis (dimethyldithiocarbamate) ethylenebis (dithiocarbamate) dizinc (generic name: polycarbamate) and other organic zinc compounds; Organic boron compounds such as triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, 4-phenylpyridyl-diphenylborane, triphenylboron-n-octadecylamine, triphenyl [3- (2-ethylhexyloxy) propylamine] boron ; Maleimide compounds such as 2,4,6-trichloromaleimide, N- (2,6diethylphenyl) 2,3-dichloromaleimide; and others, 4,5-dichloro-2-n-octyl-3-isothiazolone (generic name) : Sineine 211), 3,4-dichlorophenyl-N-N-dimethylurea (generic name: diuron), 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine (generic name: Irgarol 1051) ), 2,4,5,6-tetrachloroisophthalonitrile (generic name: chlorothalonil), N-dichlorofluoromethylthio-N ′, N′-dimethyl-Np-tolylsulfamide (generic name: trifluanide) N-dichloromethylthio-N ′, N′-dimethyl-N-phenylsulfamide (generic name: dichlorofluanide), 2- 4-thiazolyl) benzimidazole (generic name: thiabendazole), 3- (benzo [b] thien-2-yl) -5,6-dihydro-1,4,2-oxathiazine-4-oxide (generic name: Betoxazine), 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: ECONEA 028), and the like. Among these, zinc pyrithione, copper pyrithione, pyridine / triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, betoxazine, dineb, cineine 211 and irgarol 1051 are preferable, and copper pyrithione, zinc pyrithione, pyridine / triphenylborane and betoxazine are more preferable. preferable.

Antifouling agents (C) include cuprous oxide, rhodan copper, zinc pyrithione, copper pyrithione, pyridine / triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, betoxazine, dinebu, sineine 211 and irgarol 1051, trifluanid, diclofluaniani And cuprous oxide, copper pyrithione, zinc pyrithione, pyridine triphenylborane and betoxazine are more preferred.
These antifouling agents can be used alone or in combination of two or more.
The content of the antifouling agent (C) in the composition of the present invention is not particularly limited, but is usually 0.1 to 75% by mass, preferably 1 to 60% by mass in the solid content of the composition of the present invention. is there. When content of antifouling chemical | medical agent (C) is less than 0.1 mass%, there exists a possibility that sufficient antifouling effect may not be acquired. When the content of the antifouling agent (C) exceeds 75% by mass, the formed coating film is fragile, and further, the adhesion to the coating film formation is weak, and the function as an antifouling coating film is sufficient. I can't do it.

<Elution regulator (D)>
Examples of the elution regulator (D) include rosin, rosin derivatives and their metal salts, monocarboxylic acids and salts thereof, or alicyclic hydrocarbon resins.
Examples of the rosin include tall oil rosin, gum rosin, and wood rosin. Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin. As the metal salt of rosin and the metal salt of rosin derivative, a reaction product of a metal compound and rosin can be used. Examples of the metal salt of rosin include gum rosin zinc (or copper) salt, wood rosin zinc (or copper) salt, Examples include tall oil rosin zinc (or copper) salt. As metal salts of rosin derivatives, hydrogenated rosin zinc (or copper) salt, disproportionated rosin zinc (or copper) salt, maleated rosin zinc (or copper) salt, formylated rosin zinc (or copper) salt, polymerization Examples include rosin zinc (or copper) salt.
Examples of the monocarboxylic acid include fatty acids having about 5 to 30 carbon atoms, synthetic fatty acids, and naphthenic acids. Examples of the monocarboxylic acid salt include a copper salt, a zinc salt, a magnesium salt, and a calcium salt.
Examples of the alicyclic hydrocarbon resin include Quinton 1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon Co., Ltd.) and the like as commercially available products.

  In particular, the composition of the present invention is at least selected from the group consisting of rosin, rosin derivatives, and metal salts thereof, as an elution regulator (D) in that it can impart moderate elution promoting properties to the composition of the present invention. It is preferable to contain one, and it is particularly preferable to contain a copper salt or a zinc salt of rosin or a rosin derivative from the viewpoint of improving crack resistance and water resistance.

  Content of the elution regulator (D) in the composition of this invention is 1-80 mass parts normally with respect to 100 mass parts of copolymers (A), Preferably it is 10-50 mass parts. When the elution control agent (D) is less than 1 part by mass, the effect of preventing the adhesion of varicella-fouling organisms, particularly the effect of preventing the attachment of varicella-fouling organisms during the outfitting period cannot be expected. When the content of the elution regulator (D) exceeds 80 parts by mass, defects such as cracks and peeling are likely to occur in the coating film, and there is a possibility that the effect of preventing the adhesion of waterpox fouling organisms may not be exhibited sufficiently. The content of the elution regulator (D) is, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 with respect to 100 parts by mass of the copolymer (A). , 60, 65, 70, 75, 80 parts by mass, and may be within the range of any two numerical values exemplified here.

<Plasticizer (E)>
By including the plasticizer (E) in the antifouling coating composition of the present invention, the plasticity of the composition can be improved, and as a result, a tough coating film can be suitably formed.
Examples of the plasticizer (E) include phosphate esters such as tricresyl phosphate, trioctyl phosphate and triphenyl phosphate, phthalates such as dibutyl phthalate and dioctyl phthalate, dibutyl adipate, dioctyl adipate and the like. Adipic acid esters, sebacic acid esters such as dibutyl sebacate and dioctyl sebacate, epoxidized oils and fats such as epoxidized soybean oil and epoxidized linseed oil, alkyl vinyl ether polymers such as methyl vinyl ether polymer and ethyl vinyl ether polymer Polymers, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, t-nonyl pentasulfide, petrolatum, polybutene, trimellitic acid tris (2-ethylhexyl), liquid paraffin And chlorinated paraffin. These can be used alone or in combination of two or more.
Content of the plasticizer (E) in the composition of this invention is 0.1-20 mass parts normally with respect to 100 mass parts of copolymers (A), Preferably it is 0.5-10 mass parts.

<Other resins (F)>
By containing the other resin (F) in the antifouling coating composition of the present invention, the cost can be reduced without impairing the effects of the present invention, and a synergistic effect with the physical properties of the resin (F). Can be obtained.
Examples of the other resin (F) include (meth) acrylic resin, alkyd resin, polyester resin, chlorinated rubber resin, vinyl resin and the like.
Other resin (F) in the composition of this invention can be contained in the range by which the moderate coating-film dissolution rate and coating-film physical property in seawater are not impaired, The content is a copolymer ( A) It is 1-200 mass parts with respect to 100 mass parts, Preferably it is 20-100 mass parts.

<Other additives>
Furthermore, the antifouling coating composition of the present invention contains, as necessary, pigments, dyes, antifoaming agents, anti-sagging agents, dispersants, anti-settling agents, dehydrating agents, organic solvents, etc. It can be added within a range where the coating film dissolution rate and coating film physical properties are not impaired.

Process for producing antifouling paint composition The antifouling paint composition of the present invention is prepared, for example, by mixing and dispersing a mixed liquid containing a siloxysan compound (B) using a disperser or a siloxane compound (B). It can manufacture by adding and mixing a siloxane compound (B) at the last process, after mixing and dispersing the liquid mixture containing other than using a disperser. Or you may manufacture by adding and mixing a siloxysan compound (B) just before coating.
The contents of the copolymer (A) and the siloxane compound (B) in the mixed solution are the contents of the copolymer (A) and the siloxane compound (B) in the antifouling coating composition, and What is necessary is just to adjust suitably so that it may become a content rate.
As the disperser, for example, one that can be used as a fine pulverizer can be suitably used. For example, a commercially available homomixer, sand mill, bead mill or the like can be used. Alternatively, the mixed solution may be mixed and dispersed using a container provided with a stirrer to which glass beads for mixing and dispersing are added.

Antifouling treatment method, antifouling coating film , and coated article The antifouling treatment method of the present invention forms an antifouling coating film on the surface of a coating film-forming article using the antifouling coating composition. According to the antifouling treatment method of the present invention, the antifouling coating film gradually dissolves from the surface and the coating film surface is constantly renewed, thereby preventing the adhesion of chickenpox fouling organisms. Moreover, after dissolving a coating film, the antifouling effect can be exhibited continuously by overcoating the said composition.
Examples of the coating film formation include ships (particularly ship bottoms), fishing equipment, underwater structures, and the like. Examples of the fishery tools include aquaculture or stationary fishing nets, fishing net accessories such as floats and ropes used in the fishing nets, and the like. Examples of the underwater structure include a power plant conduit, a bridge, a port facility, and the like.
The antifouling coating film can be formed by applying the antifouling coating composition to the surface (entirely or partly) of the coating film forming article.
Examples of the application method include brush coating, spraying, dipping, flow coating, and spin coating. These may be used alone or in combination of two or more.
After application, dry. The drying temperature may be room temperature. What is necessary is just to set drying time suitably according to the thickness etc. of a coating film.
The antifouling coating film of the present invention formed using the antifouling coating composition exhibits an appropriate coating film dissolution rate and coating film properties in seawater, and can maintain a stable surface renewability over a long period of time. The desired antifouling effect can be effectively exhibited. Moreover, it has the advantage that the outstanding recoat performance of a coating film can be exhibited.
What is necessary is just to set the thickness of an antifouling coating film suitably according to the kind of coating-film formation thing, the navigation speed of a ship, seawater temperature, etc. For example, when the coating film formation is the bottom of a ship, the thickness of the antifouling coating is usually 50 to 500 μm, preferably 100 to 400 μm.
The antifouling coating film of the present invention has an appropriate hardness. That is, the antifouling coating film of the present invention has a hardness that does not cause coating film abnormality such as cold flow.
The coated article of the present invention has the antifouling coating film on the surface. The coated product of the present invention may have the antifouling coating film on the entire surface or a part thereof.
Since the coated product of the present invention has a coating film excellent in long-term stable surface renewability and recoatability by improving an appropriate coating film dissolution rate and coating film properties in seawater, the ship ( In particular, it can be suitably used as ship bottoms), fishing equipment, underwater structures and the like.
For example, when the antifouling coating film is formed on the ship bottom surface of the ship, the antifouling coating film gradually dissolves from the surface, and the coating film surface is constantly updated, thereby preventing adhesion of waterpox fouling organisms. it can.
Moreover, the hydrolysis rate of the antifouling coating film is suitably suppressed. Therefore, the ship can maintain antifouling performance for a long period of time. For example, even in a stationary state such as during anchoring or during the outfitting period, there is almost no adhesion and accumulation of Minamata fouling organisms, and the antifouling effect can be exhibited for a long period of time.
In addition, even after a long period of time, the antifouling coating on the surface is basically free from cracks or peeling. Therefore, it is not necessary to perform another operation such as forming a coating film after the coating film is completely removed. Therefore, an antifouling coating film can be suitably formed by directly overcoating the antifouling coating film composition. Thereby, it is possible to easily and continuously maintain the antifouling performance at a low cost.

Examples and the like are shown below to further clarify the features of the present invention. However, the present invention is not limited to these examples.
% In each production example, comparative production example, example and comparative example represents mass%. The viscosity is a measured value at 25 ° C., and is a value determined by a B-type viscometer. The weight average molecular weight (Mw) is a value (polystyrene conversion value) determined by GPC. The conditions of GPC are as follows.
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSKgel SuperHZM-M (Tosoh Corporation) 2 flow rate: 0.35 mL / min
Detector ... RI
Column thermostatic chamber temperature: 40 ° C
Eluent: THF
The heating residue is a value obtained by heating at 125 ° C. for 1 hour.
Moreover, the unit of the compounding quantity of each component in Table 1 is g.

Production Example 1 (Production of Copolymer Solution A-1)
A flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel was charged with 200 g of xylene and stirred at 85 ± 5 ° C. in a nitrogen atmosphere, 270 g of triisopropylsilyl methacrylate, 120 g of methyl methacrylate, acrylic acid A mixture of 20 g of 2-methoxyethyl, 20 g of n-butyl acrylate, 70 g of i-butyl methacrylate and 6 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate over 2 hours. It was dripped. Then, after stirring at the same temperature for 1 hour, 1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added three times every hour to complete the polymerization reaction, Triorganosilyl ester-containing copolymer solution A-1 was obtained by adding and dissolving 300 g of xylene. The viscosity of the obtained copolymer solution was 450 cps / 25 ° C., the heating residue was 49.8%, and the Mw was 51,000.

Production Example 2 (Production of copolymer solution A-2)
A flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel was charged with 170 g of xylene and stirred at 85 ± 5 ° C. in a nitrogen atmosphere, with 300 g of triisopropylsilyl acrylate, 130 g of methyl methacrylate, and mecrylic acid. A mixture of 20 g of 2-methoxyethyl, 20 g of n-butyl acrylate, 30 g of i-butyl methacrylate, and 4 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added over 2 hours. It was dripped. Then, after stirring at the same temperature for 1 hour, 1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added three times every hour to complete the polymerization reaction, Triorganosilyl ester-containing copolymer solution A-2 was obtained by adding and dissolving 330 g of xylene. The obtained copolymer solution had a viscosity of 490 cps / 25 ° C., a heating residue of 50.5%, and an Mw of 49,500.

Production Example 3 (Production of Copolymer Solution A-3)
A flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 200 g of xylene and stirred at 85 ± 5 ° C. in a nitrogen atmosphere, while 270 g of triisopropylsilyl methacrylate, 160 g of methyl methacrylate, acrylic acid A mixed solution of 20 g of n-butyl, 50 g of n-butyl methacrylate, and 6 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was dropped over 2 hours. Then, after stirring at the same temperature for 1 hour, 1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added three times every hour to complete the polymerization reaction, Triorganosilyl ester-containing copolymer solution A-3 was obtained by adding and dissolving 300 g of xylene. The viscosity of the obtained copolymer solution was 440 cps / 25 ° C., the heating residue was 50.3%, and the Mw was 50,500.

Production Example 4 (Production of Copolymer Solution A-4)
A flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel was charged with 350 g of xylene and stirred at 85 ± 5 ° C. in a nitrogen atmosphere, with 100 g of triisopropylsilyl methacrylate, 75 g of methyl methacrylate, acrylic acid 50 g of 2-methoxyethyl, 100 g of n-butyl acrylate, 100 g of i-butyl methacrylate, 75 g of 2-methoxyethyl methacrylate, and 5 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate Was added dropwise over 2 hours. Then, after stirring at the same temperature for 1 hour, 1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added three times every hour to complete the polymerization reaction, Triorganosilyl ester-containing copolymer solution A-4 was obtained by adding and dissolving 150 g of xylene. The viscosity of the obtained copolymer solution was 380 cps / 25 ° C., the heating residue was 49.5%, and the Mw was 48,000.

Examples 1 to 6 and Comparative Examples 1 to 7 (Manufacture of coating compositions)
The component shown in Table 1 was mix | blended in the ratio (mass%) shown in Table 1, and the coating composition was manufactured by mixing and dispersing with the glass bead of diameter 1.5-2.5mm. The details of each component in Table 1 are as follows.

Gum rosin zinc salt solution: used in Production Example 5 Gum rosin solution: Chinese gum rosin (WW) solid content about 60% xylene solution Cuprous oxide: Trade name “NC-301” (manufactured by Nisshin Chemco)
Copper pyrithione: Trade name “Copper Omagine” (manufactured by Arch Chemical Co., Ltd.)
Bengala: Trade name “TODA COLOR EP-13D” (manufactured by Toda Pigment Corporation)
Talc: Trade name “Crown Talc 3S” (Matsumura Sangyo Co., Ltd.)
Zinc oxide: Trade name “Zinc oxide 2 types” (manufactured by Shodo Chemical Co., Ltd.)
Titanium oxide: Trade name “FR-41” (Furukawa Machine Metal Co., Ltd.)
Fatty acid amide thixotropic agent: Trade name “Disparon A603-20X” (manufactured by Enomoto Kasei Co., Ltd.)
Siloxane compound (B):
Product name "Ethyl silicate 40" (manufactured by Colcoat Co., Ltd.)
Product name "Ethyl silicate 48" (manufactured by Colcoat Co., Ltd.)
Product name "MKC silicate MS56" (Mitsubishi Chemical Corporation)
Tetraethoxysilane: manufactured by Kishida Chemical Co., Ltd., special grade reagent tetramethoxysilane: manufactured by Kishida Chemical Co., Ltd., special grade reagent methyl silicate 51 (tetramer): manufactured by Colcoat Co., Ltd.

Production Example 5 (Production of gum rosin zinc salt solution)
In a 1 L flask equipped with a temperature system, a reflux condenser and a stirrer, 240 g of Chinese gum rosin (WW) and 240 g of xylene are placed in the flask, and zinc oxide is formed so that all resin acids in the gum rosin form a zinc salt. 120 g was added and reflux dehydrated under reduced pressure at 70-80 ° C. for 3 hours. Then, it cooled and filtered, and the xylene solution (dark brown transparent liquid, solid content about 60%) of the gum rosin zinc salt was obtained. The heating residue of the obtained xylene solution was 60.6%.

Test Example 1 (Rotary test)
A rotating drum having a diameter of 515 mm and a height of 440 mm was attached to the center of the water tank so that it could be rotated by a motor. In addition, a cooling device for keeping the temperature of the seawater constant and an automatic pH controller for keeping the pH of the seawater constant were attached.
A test plate was prepared according to the following method.
First, on a titanium plate (75 x 150 x 0.5 mm), a rust preventive paint (epoxy vinyl A / C) is applied so that the thickness after drying is about 100 μm and dried to form a rust preventive coating. did. Thereafter, the coating compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 7 were applied on the rust preventive coating so that the thickness after drying was about 300 μm. The obtained coated material was dried at 40 ° C. for 3 days to prepare a test plate having a dry coating film having a thickness of about 300 μm.
One of the produced test plates was fixed to the rotating drum of the rotating device of the apparatus so as to contact seawater, and the rotating drum was rotated at a speed of 20 knots. Meanwhile, the temperature of the seawater was maintained at 25 ° C. and the pH at 8.0 to 8.2, and the seawater was replaced every week.
The residual film thickness of each test plate is measured with a laser focus displacement meter at the initial stage and every 3 months after the start of the test, and the dissolved film thickness is calculated from the difference (μm / month ) In addition, the said measurement was performed for 24 months and the said coating-film melt | dissolution amount was computed for every 6-month progress.
Moreover, after drying the test plate after the end of the rotary test (after 24 months), the surface of each coating film was visually observed to evaluate the state of the coating film.
Evaluation was performed by the following method.
◎: When there is no abnormality ○: Slight hair cracks are observed △: Hair cracks are observed over the entire surface of the coating film ×: Large coatings such as blisters, blisters or peelings are observed

Test example 2 (antifouling test)
The coating compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 7 were applied on both sides of a hard PVC plate (100 × 200 × 2 mm) so that the thickness as a dry coating film was about 200 μm. The obtained coated material was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dry coating film having a thickness of about 200 μm. This test plate was immersed in 1.5 m below the sea surface in Owase City, Mie Prefecture, and the test plate was observed for contamination by deposits after 12 months and 24 months.
Evaluation was performed by visually observing the state of the coating film surface, and was judged according to the following criteria.
A: There is no adhesion of fouling organisms such as shellfish and algae, and there is almost no slime.
○: Level at which fouling organisms such as shellfish and algae do not adhere, and slime is thin (appreciable to the surface of the paint film) but can be gently wiped with a brush.
[Delta]: No fouling organisms such as shellfish and algae adhere, but the slime is so thick that the surface of the coating cannot be seen and cannot be removed even if wiped with a brush.
×: Level at which fouling organisms such as shellfish and algae adhere

The results are shown in Table 1.
From Table 1, the coating film formed using the coating composition of the present invention (Examples 1 to 6) is more submerged in seawater than the coating film formed using the coating composition of Comparative Examples 1 to 7. The dissolved amount is maintained high in any period, and the state of the dried coating film after the end of the rotary test (after 24 months) is generally good without causing large cracks. In the antifouling test, shellfish and algae It can be seen that there is no adhesion of fouling organisms such as, and there is almost no adhesion of slime.
On the other hand, the coating films formed using the coating compositions of Comparative Examples 1 to 7 have a low dissolution amount in seawater as a whole, and some of the dissolution amount disappears after the latter half. In some cases, cracks occur in the coating film or in the antifouling test, it is impossible to prevent the attachment of fouling organisms over a long period of time, and the performance cannot be balanced.

Claims (3)

(A) (a) General formula (1):


(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² , R ^3, and R ⁴ are the same or different and each represents an alkyl group or a phenyl group branched from the α-position of 3 to 6 carbon atoms. (Meth) acrylic acid triorganosilyl ester monomer represented by
(B) a triorganosilyl ester-containing copolymer obtained from a mixture of the (meth) acrylic acid triorganosilyl ester monomer and a copolymerizable ethylenically unsaturated monomer, and (B) the number of carbon atoms Siloxane compound having 1 to 4 alkoxy groups and a siloxane skeleton (however, the number of Si atoms in the siloxane skeleton is 5 to 100)
Antifouling paint composition containing The antifouling paint composition according to claim 1, wherein the siloxane compound includes a compound represented by the following general formula (2).
General formula (2):

(Wherein R ⁵ is the same or different and each is an alkyl group having 1 to 4 carbon atoms, and R ⁶ is the same or different and each is an alkyl group having 1 to 6 carbon atoms, a phenyl group, or (It is an alkoxy group having 1 to 4 carbon atoms, and n is 5 to 100) A coated product having an antifouling coating film formed on the surface thereof using the antifouling coating composition according to claim 1.