WO2017130864A1 - Antifouling coating composition, coating film, and coating-film-attached base material - Google Patents

Abstract

The present invention is an antifouling coating composition comprising (A) a silyl acrylic copolymer that has a constituent unit (a1) derived from triisopropylsilyl (meth)acrylate and a constituent unit (a2) derived from a polymerizable monomer having a polymerizable double bond, (B) a lower alcohol that has 1 to 3 carbon atoms, (C) an antifouling agent that contains a copper component and a zinc component and (D) a monocarboxylic acid compound, wherein the content of the lower alcohol (B) in the antifouling coating composition is 0.1 to 3% by mass. The present invention provides: an antifouling coating composition for forming a coating film which is dissipated in a reduced amount under a condition where the coating film is in contact with water at ambient temperature of about 25ºC as well as a condition where the coating film is in contact with water at a higher temperature of about 30ºC and which can maintain the physical properties thereof for a long period; a coating film produced by curing the antifouling coating composition; a coating-film-attached base material which comprises a base material and the above-mentioned coating film formed on the base material; and a method for producing the coating-film-attached base material.

Description

Antifouling paint composition, coating film, and substrate with coating film

The present invention relates to an antifouling coating composition, a coating film formed using the same, and a substrate with a coating film having the coating film on the substrate.

Since underwater structures such as ships, harbor facilities, piping materials and bridges are exposed to the water inhabited by living organisms, microorganisms such as bacteria and animals and plants such as barnacles and diatoms adhere. When these microorganisms and animals and plants cover the surface of an underwater structure, problems such as corrosion occur and the frictional resistance against seawater or fresh water increases, resulting in a decrease in fuel efficiency of the ship.

As a method for solving such a problem, for example, an antifouling paint composition containing an antifouling agent such as cuprous oxide (Cu ₂ O) that can effectively prevent attachment of animals such as barnacles. And a method of forming an antifouling coating film on the surface of the underwater structure.
More specifically, Patent Document 1 discloses that 55 to 75 parts by weight of triisopropylsilyl (meth) acrylate (a), 2 to 20 parts by weight of methoxyethyl acrylate (b), and other polymerizable components in 100 parts by weight of the monomer component. An antifouling paint composition comprising a copolymer containing 43 to 5 parts by weight of monomer (c) and an antifouling agent such as cuprous oxide has been proposed.

JP 2001-226440 A

In the field of antifouling paint compositions, silyl polymers as described in Patent Document 1 are sometimes used as binder resins. However, the coating film formed with such an antifouling coating composition can reduce the consumption of the coating film under a condition where it is brought into contact with water at room temperature of about 25 ° C., but the temperature is about 30 ° C. Under the condition of contacting with water, there was a problem that the amount of consumption of the coating film increased and the coating film could not be maintained for a long time.

The present invention has been made in view of the above circumstances, and the consumption of the coating film is not only under the condition of contact with water at a normal temperature of about 25 ° C. but also under the condition of contact with water at a high temperature of about 30 ° C. It is an object of the present invention to provide an antifouling paint composition for forming a coating film capable of suppressing the amount small and maintaining the physical properties over a long period of time.
Moreover, this invention makes it a subject to provide the coating film which hardened the said antifouling coating composition, the base material with a coating film which has the said coating film on a base material, and this manufacturing method.

As a result of intensive studies by the inventors, in an antifouling coating composition containing a silyl polymer, a monobasic acid such as rosin used as an elution aid and an antifouling agent such as cuprous oxide or It has been found that zinc oxide forms a copper salt and a zinc salt, and the ratio between the copper salt and the zinc salt has a great influence on the water resistance and wear resistance of the coating film. And further examination, when the ratio of zinc salt increases, the consumption of the coating film under high temperature conditions increases, and conversely, when the ratio of copper salt increases, the consumption under high temperature conditions, It has been found that it can be suppressed to the same level as the amount of consumption below. Therefore, the present inventors conducted research on the control of the ratio between the copper salt and the zinc salt. By mixing a small amount of a lower alcohol in the antifouling coating composition, the copper salt in the antifouling coating composition was obtained. Thus, the present inventors have found that the amount of coating film consumed can be reduced not only under normal temperature conditions of about 25 ° C. but also under high temperature conditions of about 30 ° C., thereby completing the present invention. The gist of the present invention is as follows.

The present invention relates to the following [1] to [8].
[1] Silylacrylic copolymer (A) having a structural unit (a1) derived from triisopropylsilyl (meth) acrylate, and a structural unit (a2) derived from a polymerizable monomer having a polymerizable double bond, carbon number 1. An antifouling paint composition comprising 1 to 3 lower alcohol (B), an antifouling agent (C) containing a copper component and a zinc component, and a monocarboxylic acid compound (D), the antifouling coating composition An antifouling coating composition having a content of the lower alcohol (B) in the range of 0.1 to 3% by mass.
[2] The antifouling paint composition according to [1], wherein the mass ratio [(a1) / (a2)] of the structural unit (a1) to the structural unit (a2) is 40/60 to 95/5 object.
[3] The antifouling coating composition according to the above [1] or [2], wherein the content of the silylacrylic copolymer (A) in the antifouling coating composition is 5 to 40% by mass.
[4] The antifouling coating composition according to any one of [1] to [3], wherein the silylacrylic copolymer (A) has a weight average molecular weight (Mw) of 5,000 to 100,000. .
[5] A coating film obtained by curing the antifouling coating composition according to any one of [1] to [4].
[6] A substrate with a coating film having the coating film according to [5] on a substrate.
[7] The coated substrate according to [6], wherein the substrate is a ship.
[8] A step (1) of obtaining an applied body or an impregnated body by applying or impregnating a substrate with the antifouling coating composition according to any one of [1] to [4], and the applied body or The manufacturing method of the base material with a coating film which has the process (2) which hardens the said antifouling coating composition by drying an impregnation body.

According to the present invention, the amount of coating film consumed can be reduced not only under conditions of contact with water at room temperature of about 25 ° C. but also under conditions of contact with water of high temperature of about 30 ° C. It is possible to provide an antifouling paint composition for forming a coating film capable of maintaining the physical properties over a long period of time.
Moreover, according to this invention, the coating film which hardened the said antifouling coating composition, the base material with a coating film which has the said coating film on a base material, and this manufacturing method can be provided.

[Anti-fouling paint composition]
The antifouling coating composition of the present invention is a silylacrylic copolymer having a structural unit (a1) derived from triisopropylsilyl (meth) acrylate and a structural unit (a2) derived from a polymerizable monomer having a polymerizable double bond. An antifouling paint composition comprising a coalescence (A), a lower alcohol (B) having 1 to 3 carbon atoms, an antifouling agent (C) containing a copper component and a zinc component, and a monocarboxylic acid compound (D) The content of the lower alcohol (B) in the antifouling coating composition is 0.1 to 3% by mass.

<Silyacrylic copolymer (A)>
The antifouling coating composition of the present invention contains a silylacrylic copolymer (A) for the purpose of improving the antifouling property of the coating film, and the silylacrylic copolymer (A) is , A structural unit (a1) derived from triisopropylsilyl (meth) acrylate, and a structural unit (a2) derived from a polymerizable monomer having a polymerizable double bond.
In the present invention, the “polymerizable monomer having a polymerizable double bond” constituting the structural unit (a2) means “a polymerizable double bond other than triisopropylsilyl (meth) acrylate constituting the structural unit (a1)”. Means a polymerizable monomer. In the present invention, “(meth) acrylate” means “acrylate or methacrylate”, “(meth) acryl” means “acryl or methacryl”, and “(meth) acryloyl” means “acryloyl or It means “methacryloyl”.

[Constitutional unit derived from triisopropylsilyl (meth) acrylate (a1)]
The structural unit (a1) is a structural unit derived from triisopropylsilyl (meth) acrylate. The structural unit (a1) in the present invention may be a structural unit derived from any one of triisopropylsilyl acrylate (TIPSA) and triisopropylsilyl methacrylate (TIPSSMA), triisopropylsilyl acrylate, and Although it may be a structural unit derived from both of triisopropylsilyl methacrylate, from the viewpoint of improving the antifouling property of the coating film, a structural unit derived from any one of triisopropylsilyl acrylate and triisopropylsilyl methacrylate It is preferable that

[Constitutional unit derived from a polymerizable monomer having a polymerizable double bond (a2)]
The polymerizable monomer having a polymerizable double bond constituting the structural unit (a2) is not particularly limited as long as it is a polymerizable monomer having a polymerizable double bond other than triisopropylsilyl (meth) acrylate. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate, lauryl Meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, alkyl (meth) acrylates such as benzyl (meth) acrylate, aryl (meth) acrylate or aralkyl (meth) acrylate;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-propoxyethyl ( Alkoxyalkyl (meth) acrylates or aryloxyalkyl (meth) acrylates such as (meth) acrylate, 2-butoxyethyl (meth) acrylate, isobutoxybutyl diglycol (meth) acrylate, 2-phenoxyethyl (meth) acrylate;
Hydroxy such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate Alkyl (meth) acrylates;
Organosiloxane group-containing (meth) acrylate;
(Meth) acrylamide, polyethylene glycol mono (meth) acrylate, hydroxy group, amide group or ether group-containing (meth) acrylate such as methoxypolyethylene glycol mono (meth) acrylate;
And aromatic vinyl such as styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 4-tert-butylstyrene, 5-tert-butyl-2-methylstyrene, and the like. . These polymerizable monomers may be used alone or in combination of two or more.
In the present invention, “(meth) acrylamide” means “acrylamide or methacrylamide”.

Among the polymerizable monomers having a polymerizable double bond, alkyl (meth) acrylate and alkoxyalkyl (meth) acrylate are preferable, and methyl methacrylate (MMA), ethyl acrylate (EA), butyl acrylate (BA), 2-methoxy Ethyl acrylate (MEA) and 2-methoxyethyl methacrylate (MEMA) are preferred.

As the polymerizable monomer having a polymerizable double bond, an anionic unsaturated monomer or a cationic unsaturated monomer may be further used.
Anionic unsaturated monomers include carboxy group-containing unsaturated monomers such as (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, and crotonic acid, styrene sulfonic acid, and 3- (methacryloyloxy) Examples thereof include sulfonic acid group-containing unsaturated monomers such as propanesulfonic acid and acrylamidepropanesulfonic acid.
These anionic unsaturated monomers may be used partially or completely neutralized. The neutralization may be performed as a monomer, or may be neutralized after the polymer is formed.
Examples of the base used for neutralization include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and amine compounds such as ammonia, triethanolamine and trimethylamine.

Examples of the cationic unsaturated monomer include one or more selected from an amino group-containing unsaturated monomer and a quaternary ammonium base-containing unsaturated monomer.
Amino group-containing unsaturated monomers include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N- Diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) ) Acrylamide, 2-vinylpyridine, 4-vinylpyridine and structures obtained by neutralizing these with an acid represented by H ⁺ X ⁻ .
Further, as the quaternary ammonium base-containing unsaturated monomer, (meth) acryloyloxyethyltrimethylammonium, (meth) acryloyloxypropyltrimethylammonium, (meth) acryloylaminoethyltrimethylammonium having X ⁻ as a counter ion, ( And (meth) acryloylaminopropyltrimethylammonium, diallyldimethylammonium, 1-ethyl-4-vinylpyridinium, 1,2-dimethyl-5-vinylpyridinium, and the like.
X ⁻ represents an anion, preferably a halide ion, and more preferably a chloride ion.

[Method for Producing Silyl Acrylic Copolymer (A)]
The silylacrylic copolymer (A) can be produced, for example, by the following procedure.
First, a solvent is put in a reaction vessel and heated to about 80 to 120 ° C. to maintain the temperature, and the triisopropylsilyl (meth) acrylate, a polymerizable monomer having a polymerizable double bond, and polymerization start A silylacrylic copolymer (A) can be obtained by dropping a mixed solution of an agent, a chain transfer agent, a solvent, and the like and performing a polymerization reaction.
In addition, the ratio of each content (mass) of the structural unit derived from each monomer in the silylacrylic copolymer (A) is the ratio of the charged amount (mass) of each monomer used for the polymerization reaction. Can be regarded as the same.

There is no restriction | limiting in particular as a polymerization initiator which can be used for manufacture of a silyl acryl-type copolymer (A), Various radical polymerization initiators can be used. Specifically, benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, sodium persulfate, 2,2′-azobis (isobutyronitrile) [AIBN], 2,2 Examples include '-azobis (2-methylbutyronitrile) [AMBN], 2,2'-azobis (2,4-dimethylvaleronitrile) [ADVN], and tert-butyl peroxyoctate [TBPO]. These polymerization initiators may be used alone or in combination of two or more. These radical polymerization initiators may be added to the reaction system only at the start of the reaction, or may be added to the reaction system both at the start of the reaction and during the reaction.
The amount of the polymerization initiator used in the production of the silylacrylic copolymer (A) is preferably 0.5 to 20 parts by mass with respect to a total of 100 parts by mass of the respective monomers.

The chain transfer agent that can be used for the production of the silylacrylic copolymer (A) is not particularly limited, and examples thereof include α-methylstyrene dimer, thioglycolic acid, diterpene, terpinolene, γ-terpinene; tert-dodecyl; Mercaptans such as mercaptan and n-dodecyl mercaptan; halides such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane; secondary alcohols such as glycerin; and the like. These chain transfer agents may be used alone or in combination of two or more.
When a chain transfer agent is used in the production of the silylacrylic copolymer (A), the amount used is preferably 0.1 to 5 parts by mass with respect to a total of 100 parts by mass of the respective monomers.

Examples of the solvent that can be used in the production of the silylacrylic copolymer (A) include propylene glycol monomethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol mono Examples thereof include polyhydric alcohol monoalkyl ethers such as butyl ether; aromatic hydrocarbon solvents such as toluene, xylene and mesitylene; water and the like.
When a solvent is used in the production of the silylacrylic copolymer (A), the amount used is not particularly limited, but is preferably 5 to 150 parts by mass with respect to 100 parts by mass in total of the respective monomers.

The mass ratio [(a1) / (a2)] of the structural unit (a1) to the structural unit (a2) is preferably 40/60 to 95/5, more preferably 42/58 to 85/15, and even more preferably. Is 43/57 to 75/25, more preferably 44/56 to 70/30. In addition, the said mass ratio [(a1) / (a2)] can be computed from the preparation ratio of each monomer at the time of manufacturing a copolymer.

[Weight average molecular weight of silyl acrylic copolymer (A)]
The weight average molecular weight (Mw) of the silylacrylic copolymer (A) is preferably 5,000 to 100,000, more preferably 10,000 to 90,000, still more preferably 15,000 to 80,000, More preferably, it is 17,000 to 70,000, and still more preferably 18,000 to 60,000. When the weight average molecular weight (Mw) of the silylacrylic copolymer (A) is within the above range, the spray coating workability of the antifouling coating composition is improved and the physical properties of the coating film are also improved.
In addition, the weight average molecular weight (Mw) of a silyl acryl-type copolymer (A) points out the value of the gel permeation chromatography (GPC) measured by the method as described in an Example.

[Viscosity of Silyl Acrylic Copolymer (A)]
The viscosity of the silylacrylic copolymer (A) is preferably 500 to 10,000 mPa · s, more preferably 1,000 to 7,000 mPa · s, and still more preferably 1,500 to 6,000 mPa · s. More preferably, it is 1,800 to 5,000 mPa · s, and still more preferably 2,000 to 4,800 mPa · s. When the viscosity of the silylacrylic copolymer (A) is within the above range, the spray coating workability of the antifouling coating composition is improved.
The viscosity of the silylacrylic copolymer (A) can be measured by the method described in the examples below.

[Content of Silylacrylic Copolymer (A)]
The content of the silylacrylic copolymer (A) in the antifouling coating composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 13% by mass or more, and still more preferably 15% by mass. % Or more, more preferably 16% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, still more preferably 25% by mass or less, and still more. Preferably it is 23 mass% or less. When the content of the silylacrylic copolymer (A) is within the above range, a coating film exhibiting excellent antifouling properties can be obtained over a long period of time, and the strength of the coating film can be further increased over a long period of time. Can be maintained.

<Lower alcohol (B)>
The antifouling paint composition of the present invention is intended to suppress the amount of paint consumed not only under conditions of contact with water at room temperature of about 25 ° C. but also under conditions of contact with water of high temperature of about 30 ° C. As a lower alcohol (B) having 1 to 3 carbon atoms (hereinafter sometimes simply referred to as “lower alcohol (B)”). In addition, the lower alcohol (B) in this invention shall not be contained in the organic solvent (F) mentioned later.
Examples of the lower alcohol having 1 to 3 carbon atoms include methyl alcohol, ethyl alcohol, n-propyl alcohol, and isopropyl alcohol. Among these, ethyl alcohol is preferable from the viewpoint of reducing the amount of consumption under conditions of contact with high-temperature water at about 30 ° C.

[Content of lower alcohol (B)]
The content of the lower alcohol (B) in the antifouling coating composition is 0.1 to 3% by mass. When the content of the lower alcohol (B) is within the above range, the consumed amount of the coating film under the condition of contacting with high temperature water of about 30 ° C. can be suppressed. From the same viewpoint, the content of the lower alcohol (B) is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.4% by mass or more, and still more preferably 0.00%. 5% by mass or more, and preferably 2.5% by mass or less, more preferably 2.0% by mass or less, still more preferably 1.5% by mass or less, still more preferably 1.0% by mass or less, and more. More preferably, it is 0.9 mass% or less, More preferably, it is 0.8 mass% or less.

<Antifouling agent containing copper component and zinc component (C)>
In the present invention, an antifouling agent (C) containing a copper component and a zinc component (hereinafter, simply referred to as “antifouling agent (C)” may be used for the purpose of improving the antifouling property of the coating film. ) Is used.
The copper component in the antifouling agent (C) containing a copper component and a zinc component may be either organic or inorganic, such as cuprous oxide, rhodan copper, copper powder, copper pyrithione, and thiocyanic acid. Examples thereof include copper and cupronickel. Among these, cuprous oxide and copper pyrithione are preferable. On the other hand, the zinc component in the antifouling agent (C) containing a copper component and a zinc component may be either organic or inorganic, such as zinc oxide, zinc pyrithione, zinc dimethyldithiocarbamate, zinc ethylenebisdithio. Carbamate, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate and the like can be mentioned, and among these, zinc oxide is preferable. The copper component in the antifouling agent (C) may be used alone or in combination of two or more, and the zinc component in the antifouling agent (C) may be used alone or in combination of two or more. As the antifouling agent (C), it is preferable to use a combination of cuprous oxide, copper pyrithione, and zinc oxide.
The content of the antifouling agent (C) containing a copper component and a zinc component in the antifouling coating composition of the present invention is preferably 5 to 70% by mass from the viewpoint of improving the antifouling property of the coating film. Preferably, it is 10 to 60% by mass.
The antifouling agent (C) containing a copper component and a zinc component is a ratio between the copper component and the zinc component [copper from the viewpoint of reducing the consumption of the coating film even under conditions of contact with high-temperature water of about 30 ° C. Component / zinc component] (mass ratio) is preferably in the range of 99/1 to 40/60, more preferably in the range of 97/3 to 50/50, and 95/5 to 60/40. More preferably, it is in the range.

The antifouling coating composition of the present invention may be referred to as an antifouling agent other than the antifouling agent (C) containing a copper component and a zinc component (hereinafter simply referred to as “an antifouling agent other than the antifouling agent (C)”). .) May be contained.
Examples of the antifouling agent other than the antifouling agent (C) include medetomidine, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one, borane-nitrogen base adducts (pyridine triphenylborane, 4-isopropylpyridinediphenylmethylborane, etc.), (±) -4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole, N, N-dimethyl-N ′-(3,4-dichlorophenyl) urea, N- (2,4,6-trichlorophenyl) maleimide, 2-methylthio -4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine, 2,4,5,6-tetrachloroisophthalonitrile, bisdi Tildithiocarbamoyl zinc ethylene bisdithiocarbamate, chloromethyl-n-octyl disulfide, N ', N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, N', N'-dimethyl-N'- p-tolyl- (N-fluorodichloromethylthio) sulfamide, tetraalkylthiuram disulfide, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, 2,3-dichloro-N- (2 ′, 6′-diethylphenyl) maleimide, and Examples include 2,3-dichloro-N- (2′-ethyl-6′-methylphenyl) maleimide. Antifouling agents other than these antifouling agents (C) may be used alone or in combination of two or more.
The total content of the antifouling agent (C) in the antifouling coating composition of the present invention and the antifouling agent other than the antifouling agent (C) is preferably from the viewpoint of improving the antifouling property of the coating film. 5 to 70% by mass, more preferably 10 to 60% by mass.

<Monocarboxylic acid compound (D)>
In the present invention, the monocarboxylic acid compound (D) is used for the purpose of improving the surface renewability and water resistance of the coating film.
Examples of the monocarboxylic acid compound (D) include a compound in which one carboxy group is substituted for a saturated or unsaturated aliphatic hydrocarbon group having 10 to 40 carbon atoms, or a saturated or unsaturated group having 3 to 40 carbon atoms. A compound in which one carboxy group is substituted on a saturated alicyclic hydrocarbon group, or a compound in which one carboxy group is substituted on these substituents is preferable.
Among them, trimethylisobutenylcyclohexene carboxylic acid, versatic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, naphthenic acid, and these The metal salt is preferred. Also preferred are rosin and rosin derivatives mainly composed of rosin acid such as abietic acid, parastrinic acid, and isopimaric acid.
Examples of trimethylisobutenylcyclohexenecarboxylic acid include a reaction product of 2,6-dimethylocta-2,4,6-triene and methacrylic acid, which is 1,2,3-trimethyl-5- (2-Methylprop-1-en-1-yl) cyclohex-3-en-1-carboxylic acid and 1,4,5-trimethyl-2- (2-methylprop-1-en-1-yl) cyclohexa- The main component (85% by mass or more) is 3-ene-1-carboxylic acid.
Examples of rosin and rosin derivatives include rosins such as gum rosin, wood rosin and tall oil rosin, and rosin derivatives such as hydrogenated rosin and disproportionated rosin.
The content of the monocarboxylic acid compound (D) in the antifouling coating composition of the present invention is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, and further preferably 2 to 10% by mass.

<Optional component>
The antifouling paint composition of the present invention comprises a silylacrylic copolymer (A), a lower alcohol (B), an antifouling agent (C) containing a copper component and a zinc component, and a monocarboxylic acid compound (D). In addition, it contains a pigment (E), an organic solvent (F), a liquidity improver (anti-sagging, settling prevention) (G), a plasticizer (H), and a dehydrating agent (I) as necessary. It may be.

[Pigment (E)]
In the present invention, the pigment (E) may be used for the purpose of coloring the coating film or concealing the base, or for adjusting the coating film strength to an appropriate level and for further improving the antifouling property.
Examples of the pigment (E) include talc, mica, clay, potash feldspar, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, and zinc sulfide. Examples include extender pigments, petals, titanium white (titanium oxide), yellow iron oxide, carbon black, naphthol red, phthalocyanine blue, and the like, and talc and petals are preferred. These pigments can be used alone or in combination of two or more.
When the antifouling coating composition of the present invention contains the pigment (E), the content of the pigment (E) in the antifouling coating composition is preferably 1 to 30% by mass, more preferably 4 to 25% by mass. 7 to 20% by mass is more preferable.
In addition, although copper-based and zinc-based antifouling agents such as cuprous oxide, zinc oxide, copper pyrithione, and zinc pyrithione may have both a function as an antifouling agent and a function as a pigment, Is treated as an antifouling agent (C) containing a copper component and a zinc component.

[Organic solvent (F)]
In the present invention, an organic solvent (F) may be used for the purpose of keeping the viscosity of the antifouling coating composition small and improving spray atomization and spray coating workability.
As the organic solvent (F), aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ketones, esters, alcohols and the like can be used, preferably aromatic carbonization. It is a hydrogen-based organic solvent. These organic solvents can be used individually by 1 type or in combination of 2 or more types.
Examples of the aromatic hydrocarbon-based organic solvent include toluene, xylene, styrene, mesitylene and the like.
Examples of the aliphatic hydrocarbon organic solvent include pentane, hexane, heptane, and octane.
Examples of the alicyclic hydrocarbon-based organic solvent include cyclohexane, methylcyclohexane, ethylcyclohexane, and the like.
Examples of the ketone organic solvent include acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethyl carbonate.
Examples of the ester organic solvent include ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and the like.
Examples of the alcohol-based organic solvent include n-butanol and propylene glycol monomethyl ether.
When the antifouling coating composition of the present invention contains an organic solvent (F), the content of the organic solvent (F) in the antifouling coating composition is desired depending on the application form of the antifouling coating composition and the like. A preferable amount is determined depending on the viscosity, but usually 1 to 50% by mass is preferable. When there is too much content, malfunctions, such as a fall of sagging stop property, may generate | occur | produce.

[Liquidity improver (sagging prevention, settling prevention) (G)]
In the present invention, the liquidity improver (G) may be used for the purpose of adjusting the viscoelasticity of the antifouling coating composition and obtaining the effect of sagging and preventing sedimentation. Liquid improvers (G) include organic clay waxes (such as Al, Ca, Zn stearate salts, lecithin salts, alkyl sulfonates), organic waxes (polyethylene wax, polyethylene oxide wax, amide wax, poly Amide wax, hydrogenated castor oil wax, etc.), a mixture of organic clay wax and organic wax, synthetic fine powder silica and the like. These liquidity improvers can be used singly or in combination of two or more.
Commercially available products may be used as the liquidity improver (G), and examples thereof include “DISPARON 305”, “DISPARON 4200-20”, and “DISPARON A630-20X” manufactured by Enomoto Kasei Co., Ltd.
When the antifouling coating composition of the present invention contains a liquidity improving agent (G), the content of the liquidity improving agent (G) in the antifouling coating composition is usually preferably 0.01 to 10% by mass. 0.1 to 3% by mass is more preferable.

[Plasticizer (H)]
The antifouling coating composition of the present invention may use a plasticizer (H) for the purpose of improving crack resistance and water resistance of the coating film and suppressing discoloration.
Examples of the plasticizer (H) include n-paraffin, chlorinated paraffin, terpene phenol, tricresyl phosphate (TCP), and polyvinyl ethyl ether. Among these, chlorinated paraffin and terpene phenol are preferable, and chlorinated paraffin is more preferable. These plasticizers may be used alone or in combination of two or more.
As the plasticizer (H), a commercially available product may be used. For example, the n-paraffin is “n-paraffin” manufactured by Nippon Petrochemical Co., Ltd., and the chlorinated paraffin is Tosoh Corporation. “Toyoparax A-40 / A-50 / A-70 / A-145 / A-150” and the like can be mentioned.
When the antifouling coating composition of the present invention contains a plasticizer (H), the content of the plasticizer (H) in the antifouling coating composition is preferably 0.1 to 10% by mass.

[Dehydrating agent (I)]
In the present invention, the dehydrating agent (I) may be used for the purpose of improving the storage stability of the antifouling coating composition.
Examples of the dehydrating agent (I) include alkoxysilane, zeolite known by the general name of “molecular sieve”, orthoester such as alumina and alkyl orthoformate, orthoboric acid, isocyanates, gypsum, and ethyl silicate. be able to. These dehydrating agents may be used alone or in combination of two or more.
When the antifouling coating composition of the present invention contains a dehydrating agent (I), the content of the dehydrating agent (I) in the antifouling coating composition is preferably 0.1 to 10% by mass, preferably 0.2 to 2 mass% is more preferable. When the content of the dehydrating agent (I) is within the above range, the storage stability of the antifouling coating composition can be kept good.

<Method for producing antifouling paint composition>
The antifouling paint composition of the present invention can be prepared using the same apparatus, means, etc. as those of known general antifouling paints. Specifically, a solution of a silylacrylic copolymer (A) prepared in advance, an antifouling agent (C) containing a copper component and a zinc component, a monocarboxylic acid compound (D), and other as required While stirring the solution or dispersion obtained by mixing the additives and the like, the lower alcohol (B) is added thereto, and the mixture is further stirred and mixed.

[Coating film and substrate with coating film]
The coating film of the present invention is obtained by curing the antifouling coating composition of the present invention. Specifically, for example, a coating film can be obtained by applying the antifouling coating composition of the present invention to a substrate or the like and then curing it.
Examples of the method for applying the antifouling coating composition of the present invention include known methods such as a method using a brush, a roller, and a spray.
The antifouling coating composition applied by the above-described method can be cured, for example, by leaving it at 25 ° C. for about 0.5 to 14 days to form a coating film. The antifouling paint composition may be cured while blowing air under heating.
The thickness after curing of the coating film of the present invention is preferably about 30 to 1,000 μm, for example, from the viewpoint of improving the coating film strength. Examples of the method for producing a coating film having this thickness include a method in which the antifouling coating composition is applied at a thickness of usually 10 to 300 μm, preferably 30 to 200 μm, and applied once to a plurality of times per application. .

The substrate with a coating film of the present invention has the coating film on the substrate.
The method for producing the coated substrate of the present invention is not particularly limited. For example, a step of obtaining an applied body or an impregnated body by applying or impregnating the antifouling coating composition to the substrate, and By a method comprising a step of curing an antifouling paint composition applied to or impregnated on a material, or a method comprising a step of affixing a coating film obtained by curing an antifouling paint composition to a substrate. The substrate with a coating film of the invention can be produced.
As a method for obtaining an applied body or an impregnated body by applying or impregnating the antifouling paint composition to the substrate, specifically, after sufficiently stirring the antifouling paint composition, the substrate is sprayed or other The method of apply | coating or impregnating by a means is mentioned.
On the other hand, the method of curing the antifouling coating composition applied to or impregnated on the substrate is preferably a method of curing the coating composition by drying the coated body or impregnated body. Among them, a method of curing by leaving or heating forcedly for about 0.5 to 14 days can be mentioned. By such a method, the base material with a coating film of this invention which has the said coating film on a base material can be manufactured easily.

As a method for sticking the coating film obtained by curing the antifouling paint composition to the substrate, for example, by using a known technique described in JP2013-129724A, the antifouling paint composition is cured. The method of sticking the film containing the obtained coating film on a base material is mentioned. By this method, a substrate with a coating film in which the substrate is coated with a coating film can be produced.

The antifouling paint composition of the present invention provides a long-term antifouling function for a substrate in a wide range of industrial fields such as ships, fisheries, pipelines, water systems, diving equipment, underwater propulsion bodies, power generation, harbors and civil engineering construction. Can be used to maintain the Such base materials include, for example, ships (container ships, large steel ships such as tankers, fishing boats, FRP ships, wooden ships, yachts, etc. hull outer plates, new ships or repair ships), fishing materials (ropes, fishing nets) , Fishing gear, floats, buoys, etc.), oil pipelines, water conduits, circulating water pipes, diver suits, underwater glasses, oxygen cylinders, swimsuits, torpedoes, underwater structures such as water and water outlets of thermal and nuclear power plants, seawater Examples include equipment used (seawater pumps, etc.), mega floats, gulf roads, submarine tunnels, harbor facilities, sludge diffusion prevention membranes for various civil engineering works such as canals and waterways. Among these, as a base material, a ship is preferable.

The antifouling coating composition of the present invention may be applied or impregnated directly on the substrate. The antifouling paint composition of the present invention is also applied to a base material made of fiber reinforced plastic (FRP), steel, wood, aluminum alloy, etc., such as a water supply / drain port of a nuclear power plant, a mega float, and a ship. Can be adjusted so that the adhesion to the surface of these substrates (materials) is good.
Moreover, the base material to which the antifouling coating composition of the present invention is applied may have a coating film already formed on the surface. That is, the antifouling coating composition of the present invention may be applied to the surface of a substrate on which a base material (undercoat) such as a rust preventive or primer has been applied in advance. Furthermore, the antifouling paint composition of the present invention is overcoated on the surface of a substrate that has already been coated with a conventional paint or is coated with the antifouling paint composition of the present invention. May be. The kind of coating film which the antifouling paint composition of the present invention directly contacts is not particularly limited.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

<Production of Silylacrylic Copolymer (A)>
[Production Example 1: Production of silylacrylic copolymer (A1)]
A reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube and dropping funnel was charged with 53 parts by mass of xylene, and xylene in the reaction vessel under normal pressure while stirring the xylene with a stirrer in a nitrogen atmosphere. Was heated to 85 ° C. While maintaining the temperature of xylene in the reaction vessel at 85 ° C., 45 parts by mass of TIPSMA (triisopropylsilyl methacrylate), 35 parts by mass of MEMA (2-methoxyethyl methacrylate), 15 parts by mass of MMA (methyl methacrylate), BA (butyl) A monomer mixture consisting of 5 parts by weight of acrylate) and 1 part by weight of 2,2′-azobis (2-methylbutyronitrile) was added into the reaction vessel using a dropping funnel over 2 hours.
Next, 0.5 parts by mass of tert-butyl peroxyoctoate was further added to the reaction vessel, and stirring was continued with a stirrer for 2 hours while maintaining the liquid temperature in the reaction vessel at 85 ° C. under normal pressure. The liquid temperature in the container was raised from 85 ° C. to 110 ° C. and heated for 1 hour. Next, 14 parts by mass of xylene was added to the reaction vessel to lower the liquid temperature in the reaction vessel, and when the liquid temperature reached 40 ° C., stirring was stopped to prepare a silylacrylic copolymer (A1). . Table 1 shows characteristics of the silylacrylic copolymer (A1).

[Production Examples 2 to 4: Production of silylacrylic copolymers (A2) to (A4)]
Polymerization was conducted in the same manner as in Production Example 1 except that the amount of each monomer charged was changed according to the description in Table 1, and silylacrylic copolymers (A2) to (A4) were obtained. Table 1 shows the characteristics of the silylacrylic copolymers (A2) to (A4).

The measurement methods of the heating residue, weight average molecular weight (Mw), and viscosity of the obtained silylacrylic copolymers (A1) to (A4) are as follows.
<Calculation method of heating residue (mass NV)>
Weigh 1 g of silylacrylic copolymer (A) in a flat bottom pan, spread evenly using a wire with a known mass, dry at 125 ° C. for 1 hour, and then measure the mass of the residue and wire to obtain a heating residue ( Mass%) was calculated.

<Measurement of Weight Average Molecular Weight (Mw) of Silylacrylic Copolymer (A)>
The weight average molecular weight (Mw) of the silylacrylic copolymer (A) is “HLC-8120GPC” manufactured by Tosoh Corporation as a measuring device, and “TSK-gel α type” manufactured by Tosoh Corporation as a separation column (α- M) was used, and measurement was performed by gel permeation chromatography (GPC) using dimethylformamide (DMF) as an eluent. The weight average molecular weight (Mw) of the silylacrylic copolymer (A) was determined as polystyrene.

<Measurement conditions for viscosity>
The viscosity of the silylacrylic copolymer (A) was measured using a B-type viscometer [manufactured by Tokyo Keiki Co., Ltd.] at a liquid temperature of 25 ° C. (unit: mPa · s).

The abbreviations in Table 1 are as follows.
TIPSMA: triisopropylsilyl methacrylate TIPSA: triisopropylsilyl acrylate MEMA: 2-methoxyethyl methacrylate MEA: 2-methoxyethyl acrylate MMA: methyl methacrylate BA: butyl acrylate <Production of antifouling coating composition>
[Examples 1 to 14 and Comparative Examples 1 to 11]
-Blending ingredients Each blending ingredient used in the antifouling paint composition is shown in Table 2.

-Production of antifouling paint composition In the formulations (parts by mass) shown in Tables 3 to 6, the respective components were mixed and stirred to obtain an antifouling paint composition. Each antifouling paint composition was evaluated as follows. The results are shown in Tables 3-6.

[Evaluation of storage stability at 50 ° C.]
Each antifouling paint composition is left in a 50 ° C. incubator immediately after production, and the viscosity is measured every other week, and the viscosity immediately after production and the viscosity after storage (both adjusted to a paint temperature of 23 ° C.) And the increase in viscosity was confirmed. For the viscosity measurement, a Stormer viscometer was used (unit Ku). The measurement was performed up to 4 weeks later, and the difference in viscosity between 4 weeks and 1 week was taken as the thickening rate. It shows that it is excellent in storage stability, so that a viscosity increase rate is low.

[Evaluation of wear at 25 ° C]
Applying the antifouling paint compositions of Examples and Comparative Examples to a vinyl chloride plate (length 50 mm x width 50 mm) at room temperature using a film applicator with a gap of 0.7 mm so that the dry film thickness is 100 μm. Then, a test plate with a coating film was obtained by allowing it to stand at room temperature for 1 day.
The test plate with a coating film was immersed in seawater adjusted to 25 ° C. for 1 month under the condition that the water flow speed on the test coating film was calculated to be a speed corresponding to about 15 knots. After immersion for 1 month, the film thickness was measured using a non-contact type laser film thickness meter, and the difference between the film thickness before immersion and the film thickness after immersion was calculated to measure the consumption. Further, the amount of wear was measured in the same manner for the test plate after being immersed for 2 to 6 months under the above conditions.
In this evaluation, it shows that the amount of consumption is restrained small, so that a numerical value is small.

[Evaluation of wear at 30 ° C]
Except for immersing the test plate with a coating in seawater adjusted to 30 ° C., the amount of consumption was measured in the same manner as the consumable evaluation at 25 ° C.
In this evaluation as well, the smaller the numerical value, the smaller the consumption, and the closer the value of the ratio [consumption at 30 ° C./consumption at 25 ° C.] to 1, is more preferable.

As is clear from the results of Examples and Comparative Examples, according to the present invention, not only can the consumption of the coating film be kept small under conditions of contact with water at room temperature of about 25 ° C., but also about 30 ° C. Provided is an antifouling paint composition for forming a coating film that can reduce the consumption amount of the coating film under conditions of contact with high-temperature water and can maintain the physical properties over a long period of time. it can.

The antifouling coating composition of the present invention can not only reduce the consumption of the coating film under conditions of contact with water at room temperature of about 25 ° C., but also can be used under conditions of contact with water of high temperature of about 30 ° C. The consumption amount of the coating film can also be suppressed small. Therefore, maintain the physical properties of coatings formed on the surface of structures such as ships, underwater structures, surfaces of structures placed in water, and pipe structures such as pipelines over a long period of time. Is possible.

Claims (8)

Silylacrylic copolymer (A) having a structural unit (a1) derived from triisopropylsilyl (meth) acrylate and a structural unit (a2) derived from a polymerizable monomer having a polymerizable double bond, having 1 to 3 carbon atoms An antifouling agent composition comprising a lower alcohol (B), an antifouling agent (C) containing a copper component and a zinc component, and a monocarboxylic acid compound (D), wherein the antifouling coating composition comprises An antifouling paint composition having a content of the lower alcohol (B) of 0.1 to 3% by mass. The antifouling paint composition according to claim 1, wherein the mass ratio [(a1) / (a2)] of the structural unit (a1) to the structural unit (a2) is 40/60 to 95/5. 3. The antifouling paint composition according to claim 1 or 2, wherein the content of the silylacrylic copolymer (A) in the antifouling paint composition is 5 to 40% by mass. The antifouling paint composition according to any one of claims 1 to 3, wherein the silylacrylic copolymer (A) has a weight average molecular weight (Mw) of 5,000 to 100,000. A coating film obtained by curing the antifouling paint composition according to any one of claims 1 to 4. A base material with a coating film having the coating film according to claim 5 on the base material. The base material with a coating film according to claim 6, wherein the base material is a ship. A step (1) of obtaining an applied body or an impregnated body by applying or impregnating a substrate with the antifouling coating composition according to any one of claims 1 to 4, and drying the applied body or the impregnated body. The manufacturing method of the base material with a coating film which has the process (2) which hardens the said antifouling paint composition.