CN113631378A

CN113631378A - Antifouling coating composition

Info

Publication number: CN113631378A
Application number: CN202080023781.XA
Authority: CN
Inventors: 仁井本顺治
Original assignee: Chugoku Marine Paints Ltd
Current assignee: Chugoku Marine Paints Ltd
Priority date: 2019-03-26
Filing date: 2020-03-12
Publication date: 2021-11-09
Anticipated expiration: 2040-03-12
Also published as: JP7153789B2; KR20210128472A; JPWO2020195907A1; WO2020195907A1; CN113631378B

Abstract

The present invention addresses the problem of providing an antifouling coating composition that can provide an antifouling coating film that has excellent discoloration resistance and can maintain high antifouling properties for a long period of time. The present invention also provides an antifouling coating film formed from the above antifouling coating composition, a substrate with the antifouling coating film, and a method for producing the substrate. The antifouling paint composition comprises a metal ester group-containing hydrolyzable polymer (A), zinc phosphate (B), and zinc oxide (C), wherein the mass ratio (B: C) of the zinc phosphate (B) to the zinc oxide (C) is 20: 80 to 75: 25.

Description

Antifouling coating composition

Technical Field

The present invention relates to an antifouling coating composition, an antifouling coating film using the antifouling coating composition, a substrate with the antifouling coating film, and a method for producing the substrate.

Background

In a substrate for a marine vessel, an underwater structure, a fishing net, or other fishery material, various aquatic organisms such as oyster, mussel, barnacle, and other animals, sea sedge, and bacteria are likely to adhere to the surface of the substrate exposed to water for a long period of time. In addition, the activity of marine organisms has been improved due to the recent rise in seawater temperature accompanying global warming, and countermeasures against these fouling organisms have been demanded.

As a countermeasure against this, an antifouling paint composition using a hydrolyzable resin having a property of being hydrolyzed in water to renew the surface of a coating film is widely used (see patent document 1).

For example, patent document 1 describes an antifouling coating composition using a combination of a metal salt bond-containing copolymer, a hydrolyzable copolymer such as a silyl ester copolymer, and medetomidine for the purpose of obtaining an antifouling coating film having a stable coating film wear degree and exhibiting excellent antifouling properties for a long period of time.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2011/118526

Disclosure of Invention

Problems to be solved by the invention

The conventional hydrolysis type antifouling paint composition may progress the hydrolysis reaction of the surface due to the influence of not only seawater but also rainfall and ultraviolet rays, and the surface of the coating film may be deteriorated. Due to the above-mentioned deterioration, discoloration of the coating film may occur in a long-term ship building process, which not only impairs the aesthetic appearance, but also requires countermeasures such as recoating, and therefore, there is a problem of a large economic loss.

Although the antifouling coating composition of patent document 1 achieves improvement in static antifouling property, no study has been made on both suppression of discoloration and antifouling property due to outdoor exposure in a long-term ship building process. The antifouling coating film formed from the composition has room for improvement in discoloration resistance.

An object of the present invention is to provide an antifouling coating composition that can provide an antifouling coating film that has excellent discoloration resistance and can maintain high antifouling properties for a long period of time. Further, an object of the present invention is to provide an antifouling coating film formed from the above antifouling coating composition, a substrate with the antifouling coating film, and a method for producing the substrate.

Means for solving the problems

The present inventors have conducted extensive studies and, as a result, have found that the above problems can be solved by using an antifouling paint composition shown below, and have completed the present invention.

The gist of the present invention is as follows.

The present invention relates to [ 1] to [ 14 ] below.

[ 1] an antifouling paint composition comprising: a metal ester group-containing hydrolyzable polymer (A), zinc phosphate (B), and zinc oxide (C), wherein the mass ratio (B: C) of the zinc phosphate (B) to the zinc oxide (C) is 20: 80 or more and 75: 25 or less.

[ 2 ] the antifouling paint composition according to [ 1], wherein the metal ester group is represented by the following formula (1).

[ solution 1]

(in the formula (1), M represents copper or zinc, and represents a bonding site.)

[ 3 ] the antifouling paint composition according to [ 1] or [ 2 ], wherein the hydrolyzable polymer (A) contains at least 1 selected from the group consisting of a polymer (A1) and a polymer (A2), the polymer (A1) has a structural unit derived from a polymerizable compound represented by the following formula (1-1), and the polymer (A2) has a structural unit derived from a polymerizable compound represented by the following formula (1-2).

[ solution 2]

(in the formula (1-1), R¹¹Each independently represents a 1-valent group containing a terminal ethylenically unsaturated group, and M represents copper or zinc. )

[ solution 3]

(in the formula (1-2), R²¹Represents a 1-valent radical containing a terminal ethylenically unsaturated group, R²²Represents a 1-valent organic group having 1 to 30 carbon atoms and containing no terminal ethylenically unsaturated group, and M represents copper or zinc. )

An antifouling paint composition according to any one of [ 1 ] to [ 3], wherein the hydrolyzable polymer (A) contains at least 1 selected from the group consisting of a polymer (A1 ') and a polymer (A2'), the polymer (A1 ') has a structural unit derived from a polymerizable compound represented by the following formula (1-1'), and the polymer (A2 ') has a structural unit derived from a polymerizable compound represented by the following formula (1-2').

[ solution 4]

(in the formula (1-1'), R¹²Each independently represents a hydrogen atom or a methyl group, and M represents copper or zinc. )

[ solution 5]

(in the formula (1-2'), R²³Represents a hydrogen atom or a methyl group, R²⁴Represents a 1-valent organic group having 1 to 30 carbon atoms and containing no terminal ethylenically unsaturated group, and M represents copper or zinc. )

[ 5] the antifouling paint composition according to any one of [ 1 ] to [ 4], wherein the content of the hydrolyzable polymer (A) in the hydrolyzable resin is 50% by mass or more.

[ 6 ] the antifouling paint composition according to any one of [ 1 ] to [ 5 ], wherein the total content of the zinc phosphate (B) and the zinc oxide (C) in the solid content of the antifouling paint composition is 30 to 70 mass%.

[ 7 ] the antifouling paint composition according to any one of [ 1 ] to [ 6 ], wherein the content of the monocarboxylic acid compound (D) in the solid content of the antifouling paint composition is 5% by mass or less.

The antifouling paint composition according to any one of [ 1 ] to [ 7 ], further comprising an organic antifouling agent (F).

[ 9 ] the antifouling paint composition according to any one of [ 1 ] to [ 8 ], wherein the content of the inorganic copper compound is 10% by mass or less in the solid content of the antifouling paint composition.

An antifouling coating film comprising the antifouling paint composition according to any one of [ 1 ] to [ 9 ].

[ 11 ] A substrate having an antifouling coating film, which is covered with the antifouling coating film according to [ 10 ].

[ 12 ] the substrate with an antifouling coating film according to [ 11 ], wherein the substrate is selected from the group consisting of ships, underwater structures, and fishery materials.

[ 13 ] A method for producing a substrate having an antifouling coating film, comprising: a step (I) of coating or impregnating a substrate with the antifouling paint composition described in any one of [ 1 ] to [ 9 ] to obtain a coated body or an impregnated body; and a step (II) of drying the coated body or the impregnated body.

[ 14 ] A method for producing a substrate having an antifouling coating film, comprising: a step (i) of drying the antifouling paint composition according to any one of [ 1 ] to [ 9 ] to form an antifouling coating film; and (ii) attaching the antifouling coating film to a substrate.

Effects of the invention

According to the present invention, an antifouling coating composition which can provide an antifouling coating film having excellent discoloration resistance and capable of maintaining high antifouling properties for a long period of time can be provided. Further, the present invention can provide an antifouling coating film formed from the above antifouling coating composition, a substrate with an antifouling coating film, and a method for producing the same.

Detailed Description

The antifouling coating composition, antifouling coating film, substrate with antifouling coating film and process for producing the same of the present invention will be described in detail below.

In the following description, "(meth) acryloyl", "(meth) acrylic acid", and "(meth) acrylate" mean "acryloyl or methacryloyl", "acrylic acid or methacrylic acid", and "acrylate or methacrylate", respectively.

[ antifouling paint composition ]

The antifouling paint composition of the present invention (hereinafter also referred to simply as "the present composition" or "paint composition") is characterized by comprising: a metal ester group-containing hydrolyzable polymer (A), zinc phosphate (B), and zinc oxide (C), wherein the mass ratio (B: C) of the zinc phosphate (B) to the zinc oxide (C) is 20: 80 or more and 75: 25 or less.

The antifouling coating composition described in patent document 1 has a problem in terms of discoloration due to outdoor exposure, and the coating film having such discoloration tends to have a reduced antifouling property. It was found that by making the present composition comprise: an antifouling coating film which comprises a metal ester-containing hydrolyzable polymer (A), zinc phosphate (B), and zinc oxide (C), and in which the mass ratio of zinc phosphate (B) to zinc oxide (C) is in a specific range, has excellent discoloration resistance, and can achieve both good appearance and high antifouling property even after a long-term ship building process.

In order to impart a coating film renewability to an antifouling coating composition, a coating composition containing a hydrolyzable resin is widely used, and examples of the hydrolyzable resin include the hydrolyzable polymer (a) containing a metal ester group and a copolymer containing a silyl ester group (silyl ester hydrolyzable polymer).

In an antifouling coating composition containing a silyl ester-based hydrolyzable resin as a main component among hydrolyzable resins, an elution assistant is substantially required to promote elution of an antifouling agent. A typical dissolution aid is rosin or its metal salt, which needs to be added in a certain amount. In the case where the antifouling paint composition contains rosin or a metal salt thereof, discoloration upon outdoor exposure tends to become remarkable. On the other hand, in the antifouling paint composition containing the metal ester group-containing hydrolyzable polymer (a), since the coating film wear-out property (antifouling agent elution property) is excellent and it is not necessarily required to use rosin and its metal salt, by using zinc phosphate (B) and zinc oxide (C) in combination and optimizing the ratio thereof, a composition that achieves both good discoloration resistance and long-term antifouling property can be realized.

In the antifouling paint composition containing the inorganic copper compound (F) such as cuprous oxide, although the resistance to discoloration is high, the selectivity of the color of the coating film is low. In the present invention, excellent antifouling properties can be obtained even in a composition containing no cuprous oxide, and therefore an antifouling paint composition having excellent color selectivity, which cannot be achieved by an antifouling paint composition containing cuprous oxide, can be provided.

Although the detailed mechanism of action for obtaining the above-described effects is not necessarily clear, it can be presumed that a part thereof is as follows. That is, it is considered that the inclusion of the metal ester group-containing hydrolyzable polymer (a) can impart appropriate water resistance and water renewability from the surface to the antifouling coating film, and the inclusion of the zinc phosphate (B) and the zinc oxide (C) in a specific mass ratio can provide an antifouling coating film which is excellent in discoloration resistance and can maintain high antifouling property even after long-term outdoor exposure such as in a ship building process due to the interaction in the obtained antifouling coating film.

The components contained in the antifouling paint composition of the present invention will be described in detail below.

< hydrolyzable Polymer (A) containing Metal ester group >

The present composition contains a hydrolyzable polymer (a) containing a metal ester group (hereinafter, may be simply referred to as hydrolyzable polymer (a)).

The "metal ester group" is a salt formed from a metal and an organic acid, and is preferably a group formed by bonding a metal and a carboxylic acid. The "polyvalent metal ester group" or "2-valent metal ester group" described later means a group formed by bonding a polyvalent metal or a 2-valent metal to an organic acid.

The metal ester group is preferably a polyvalent metal ester group, and more preferably a 2-valent metal ester group represented by the following formula (1).

[ solution 6]

(in the formula (1), M represents a metal and R represents a bonding site.)

Examples of the metal forming the metal ester group include magnesium, calcium, neodymium, titanium, zirconium, iron, ruthenium, cobalt, nickel, copper, zinc, and aluminum. The metal forming the metal ester group does not include a semimetal. Examples of the semimetal include boron, silicon, germanium, arsenic, antimony, and tellurium.

In the formula (1), M is a metal having a valence of 2, and a metal having a valence of 2 can be appropriately selected and used from the above metals. Among them, metals of groups 10 to 12 such as nickel, copper, and zinc are preferable, copper and zinc are more preferable, and zinc is further preferable.

In the formula (1), it represents a bonding site and is bonded to an arbitrary group, preferably an arbitrary organic group.

The hydrolyzable polymer (a) may have a group represented by the above formula (1) at the end of the main chain or side chain, and the main chains may be crosslinked with a group having a valence of 2, which includes the group represented by the formula (1). The hydrolyzable polymer (a) may be an addition polymerization type polymer obtained by polymerization of an ethylenically unsaturated compound, or a polycondensation type polymer obtained by polycondensation such as polyester and polyamide, and is not particularly limited. Among them, addition polymerization type polymers obtained by polymerization of an ethylenically unsaturated compound are preferable.

The hydrolyzable polymer (A) preferably contains at least 1 selected from the group consisting of a polymer (A1) having a structural unit derived from a polymerizable compound represented by the following formula (1-1) and a polymer (A2) having a structural unit derived from a polymerizable compound represented by the following formula (1-2). The hydrolyzable polymer (A) may have both a structural unit derived from the polymerizable compound represented by the following formula (1-1) and a structural unit derived from the polymerizable compound represented by the following formula (1-2), and in this case, it is considered to be the polymer (A1). That is, the polymer (A1) is a polymer having at least a structural unit derived from a polymerizable compound represented by the following formula (1-1), and the polymer (A2) has a structural unit derived from a polymerizable compound represented by the following formula (1-2) and does not have a structural unit derived from a polymerizable compound represented by the following formula (1-1).

When the hydrolyzable polymer (a) is a polymer (a1) having a structural unit derived from a polymerizable compound represented by the following formula (1-1), the polymerizable compound represented by the following formula (1-1) may be used as a monomer component to obtain the polymer (a1), or after a polymer having a carboxyl group is obtained, a crosslinked structure may be formed by metal esterification, and the polymer (a1) is preferably obtained using the polymerizable compound represented by the formula (1-1) as a monomer component from the viewpoint of ease of production.

Similarly, the polymer (a2) having a structural unit derived from the polymerizable compound represented by the following formula (1-2) can be obtained by using the polymerizable compound represented by the following formula (1-2) as a monomer component, or can be obtained by obtaining a polymer having a carboxyl group and then performing metal esterification, and is not particularly limited, but from the viewpoint of ease of production, it is preferable to obtain the polymer (a2) by using the polymerizable compound represented by the following formula (1-2) as a monomer component.

In the following description, the polymerizable compound represented by the following formula (1-1) is also referred to as a monomer (a1-1), and the polymerizable monomer having a group represented by the following formula (1-2) is referred to as a monomer (a 1-2). In addition, the monomer (a1-1) and the monomer (a1-2) are also collectively referred to as the monomer (a 1).

[ solution 7]

In the formula (1-1), R¹¹Represents a compound containing a terminal ethylenically unsaturated group (CH)₂1-valent radical of ═ C <), R¹¹The number of carbon atoms of (a) is preferably 2 or more and 50 or less, more preferably 2 or more and 30 or less, further preferably 2 or more and 10 or less, and further preferably 2 or more and 6 or less. R¹¹As long as it has a terminal ethylenically unsaturated group, it may have an ethylenically unsaturated group other than the terminal, however, it is more preferable to have an ethylenically unsaturated group only at the terminal.

As R¹¹The unsaturated aliphatic group preferably contains a terminal ethylenically unsaturated group, and the unsaturated aliphatic group may have an ester bond, an amide bond, or an ether bond in the carbon chain. As R¹¹Specifically, the carboxyl group of an unsaturated aliphatic monocarboxylic acid such as acrylic acid (2-acrylic acid), methacrylic acid (2-methyl-2-acrylic acid), 3-butenoic acid, 4-pentenoic acid, 10-undecenoic acid, 3- (meth) acryloyloxypropionic acid or 3- (meth) acryloyloxy-2-methylpropanoic acid can be removed. Further, a group obtained by removing 1 carboxyl group from an unsaturated aliphatic dicarboxylic acid having a terminal ethylenically unsaturated group such as itaconic acid can be exemplified.

Among them, as R¹¹The carboxyl group is preferably removed from an unsaturated aliphatic monocarboxylic acid having a terminal ethylenically unsaturated group, more preferably removed from acrylic acid, methacrylic acid, or a (meth) acryloyloxyalkylcarboxylic acid, and still more preferably removed from acrylic acid or methacrylic acid.

Examples of the polymerizable compound represented by the formula (1-1) (the monomer (a1-1)) include zinc diacrylate, zinc dimethacrylate, zinc acrylate (methacrylate), zinc bis (3-acryloyloxypropionate), zinc bis (3-methacryloyloxypropionate), zinc bis (3- (meth) acryloyloxy-2-methylpropionate), copper diacrylate, copper dimethacrylate, copper (methacrylate) acrylate, copper bis (3-acryloyloxypropionate), copper bis (3-methacryloyloxypropionate), and copper bis (3- (meth) acryloyloxy-2-methylpropionate).

[ solution 8]

In the formula (1-2), R²¹Represents a 1-valent group containing a terminal ethylenically unsaturated group. As R ²¹R in the formula (1-1) can be exemplified¹¹The same groups, preferences and the like.

In the formula (1-2), R²²Represents a 1-valent organic group having 1 to 30 carbon atoms and containing no terminal ethylenically unsaturated group. As R²²Examples thereof include an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 30 carbon atoms, which do not contain a terminal ethylenically unsaturated group. These groups optionally have a substituent. Examples of the substituent include a hydroxyl group.

The aliphatic hydrocarbon group may be either a straight-chain or branched-chain aliphatic hydrocarbon group, and may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. In addition, in R²²When it is an unsaturated aliphatic hydrocarbon group, R²²Contains no terminal ethylenically unsaturated groups. The aliphatic hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 28 carbon atoms, more preferably 1 to 26 carbon atoms, and still more preferably 1 to 24 carbon atoms. The aliphatic hydrocarbon group is optionally further defined by an esterCyclic hydrocarbon groups and aromatic hydrocarbon groups.

The alicyclic hydrocarbon group may be a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group. The alicyclic hydrocarbon group has 3 to 30 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 5 to 16 carbon atoms, and still more preferably 6 to 12 carbon atoms. The alicyclic hydrocarbon group is optionally further substituted with an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aromatic hydrocarbon group has 6 to 30 carbon atoms, preferably 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group is optionally further substituted with an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

Note that the whole R²²Has 1 to 30 carbon atoms.

R²²The organic acid residue is preferably formed of a monobasic acid, and specifically, a carboxyl group is removed from an organic acid selected from the group consisting of versatic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, and naphthenic acid.

Among them, preferred is a group obtained by removing a carboxyl group from an organic acid selected from abietic acid, versatic acid, and naphthenic acid, and more preferred is a group obtained by removing a carboxyl group from an organic acid selected from abietic acid and versatic acid.

The polymer (A2) having a structural unit derived from the polymerizable compound represented by the formula (1-2) is preferably a structural unit obtained by polymerizing only the terminal ethylenically unsaturated group in the polymerizable compound represented by the formula (1-2) (the monomer (a 1-2)). Examples of the monomer (a1-2) include polymerizable compounds selected from the group consisting of zinc 3- (meth) acryloyloxypropionate (abietic acid), zinc 3- (meth) acryloyloxypropionate (versatic acid), zinc (meth) acrylic acid (abietic acid), zinc (meth) acrylic acid (versatic acid), zinc (meth) acrylic acid (naphthenic acid), copper 3- (meth) acryloyloxypropionate (abietic acid), copper 3- (meth) acryloyloxypropionate (versatic acid), copper (meth) acrylate (abietic acid), copper (meth) acrylate (versatic acid), and copper (meth) acrylate (naphthenic acid).

In the formulae (1-1) and (1-2), M represents copper or zinc, preferably zinc.

The hydrolyzable polymer (a) more preferably contains at least 1 selected from the group consisting of a polymer (a1 ') having a structural unit derived from a polymerizable compound represented by the following formula (1-1') and a polymer (a2 ') having a structural unit derived from a polymerizable compound represented by the following formula (1-2'). The polymer (a1) is preferably the polymer (a1 '), and the polymer (a2) is preferably the polymer (a 2'). The hydrolyzable polymer (A) may have both a structural unit derived from the polymerizable compound represented by the following formula (1-1 ') and a structural unit derived from the polymerizable compound represented by the following formula (1-2').

[ solution 9]

Examples of the polymerizable compound represented by the formula (1-1') include zinc diacrylate, zinc dimethacrylate, zinc acrylate (methacrylic acid), copper diacrylate, copper dimethacrylate and copper acrylate (methacrylic acid).

[ solution 10]

In the formula (1-2'), as R²⁴R in the above formula (1-2) can be exemplified²²The same groups, preferablyThe same applies.

Examples of the polymerizable compound represented by the formula (1-2') include zinc (meth) acrylate (abietic acid), zinc (meth) acrylate (versatic acid), zinc (meth) acrylate (naphthenic acid), copper (meth) acrylate (abietic acid), copper (meth) acrylate (versatic acid), and copper (meth) acrylate (naphthenic acid).

In the formulae (1-1 ') and (1-2'), M represents copper or zinc, preferably zinc.

The total content of the structural units derived from the polymerizable compound represented by the formula (1-1), the polymerizable compound represented by the formula (1-1 '), the polymerizable compound represented by the formula (1-2) and the polymerizable compound represented by the formula (1-2'), that is, the total content of the structural units derived from the monomer (a1) in the hydrolyzable polymer (a) is preferably 1 mass% or more, more preferably 5 mass% or more, still more preferably 10 mass% or more, still more preferably 15 mass% or more, and furthermore preferably 60 mass% or less, still more preferably 50 mass% or less, still more preferably 40 mass% or less, still more preferably 35 mass% or less of all the structural units.

The ratio of the respective contents (mass) of the structural units derived from the respective monomers in the hydrolyzable polymer (a) can be regarded as the same value as the ratio of the charged amounts (mass) of the respective monomers used in the polymerization reaction.

The hydrolyzable polymer (a) preferably has a structural unit based on another monomer (a2) in addition to the structural unit containing a metal ester group.

The other monomer (a2) is preferably a monomer having an ethylenically unsaturated group, and specifically, examples thereof include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 3, 5, 5-trimethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and the like, or aryl (meth) acrylates;

Alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 3-methoxy-n-propyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, isobutoxybutyl diglycol (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, butoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, alkoxypolyalkylene glycol (meth) acrylate, aryloxyalkyl (meth) acrylate, alkoxypolyalkylene glycol (meth) acrylate, and the like, Or aryl polyalkylene glycol (meth) acrylates;

hydroxyalkyl (meth) acrylates or hydroxyaryloxyalkyl (meth) acrylates such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate;

glycidyl (meth) acrylate;

(meth) acrylate containing an organosiloxane group;

Vinyl compounds such as styrene, α -methylstyrene, vinyl acetate, vinyl benzoate, vinyl toluene, acrylonitrile, vinyl pyridine, vinyl pyrrolidone, and vinyl chloride. These monomers may be used alone or in combination of two or more.

Among them, an alkyl (meth) acrylate (the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, further preferably 1 or more and 6 or less, and still further preferably 1 or more and 4 or less), an alkoxyalkyl (meth) acrylate (the number of carbon atoms of the alkyl group and the alkyl group in the alkoxy group is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, further preferably 1 or more and 6 or less, further preferably 1 or more and 4 or less), and a hydroxyalkyl (meth) acrylate (the number of carbon atoms of the alkyl group is preferably 1 or more and 20 or less, more preferably 1 or more and 12 or less, further preferably 1 or more and 6 or less, and still further preferably 1 or more and 4 or less) are preferable.

From the viewpoint of good coating film physical properties and imparting appropriate water resistance to the antifouling coating film, the monomer (a2) preferably contains at least an alkyl (meth) acrylate, and the content of the alkyl (meth) acrylate in the monomer (a2) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more.

The content of the structural unit derived from the monomer (a2) in the hydrolyzable polymer (a) is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, further preferably 65% by mass or more, and further preferably 99% by mass or less, more preferably 95% by mass or less, further preferably 90% by mass or less, and further preferably 85% by mass or less in the entire structural units, from the viewpoints of durability of consumption of the antifouling coating film and water resistance.

The hydrolyzable polymer (a) can be produced, for example, by the following steps.

The monomer (a1) can be synthesized, for example, by a known method in which a metal compound (preferably an inorganic metal compound, specifically, an oxide, a hydroxide, a chloride, an organic acid salt (e.g., zinc acetate) or the like of copper or zinc) and an organic acid such as acrylic acid or methacrylic acid or an ester thereof are heated or stirred in the presence of an organic solvent and water at a temperature lower than the decomposition temperature of the metal salt.

More specifically, first, a mixed solution in which a solvent and a metal component such as zinc oxide are mixed is stirred while being heated to about 50 ℃ to 80 ℃, and a mixed solution of an organic acid such as acrylic acid or methacrylic acid or an ester thereof and water is added dropwise thereto and further stirred to prepare a metal ester group-containing monomer (a 1).

Then, a solvent is added to a newly prepared reaction vessel, and the mixture is heated to about 80 ℃ to 120 ℃ inclusive, and a mixed solution of the monomer (a1) containing a metal ester group, the other monomer (a2), a polymerization initiator, a chain transfer agent, a solvent, and the like is added dropwise thereto to carry out a polymerization reaction, whereby a hydrolyzable polymer (a) containing a metal ester group can be obtained.

The polymerization initiator that can be used for producing the hydrolyzable polymer (a) is not particularly limited, and various radical polymerization initiators can be used. Specifically, benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, sodium persulfate, 2 ' -azobisisobutyronitrile [ AIBN ], 2 ' -azobis (2-methylbutyronitrile) [ AMBN ], 2 ' -azobis (2, 4-dimethylvaleronitrile) [ ADVN ], tert-butyl peroctoate [ TBPO ] and the like can be mentioned. These polymerization initiators may be used alone, or two or more of them may be used in combination. 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 hydrolyzable polymer (a) is preferably 2 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the total of the monomers.

The chain transfer agent that can be used for the production of the hydrolyzable polymer (a) is not particularly limited, and examples thereof include α -methylstyrene dimer, thioglycolic acid, diterpene, terpinolene, γ -terpinene; mercaptans such as t-dodecyl mercaptan and n-dodecyl mercaptan; carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, and other halides; secondary alcohols such as isopropyl alcohol; 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 hydrolyzable polymer (a), the amount of the chain transfer agent used is preferably 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total of the monomers.

Examples of the solvent that can be used for producing the hydrolyzable polymer (a) include aromatic solvents such as toluene, xylene, and trimethylbenzene; alcohols such as propanol, butanol, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; esters such as ethyl acetate and butyl acetate; water, and the like. These solvents may be used alone in 1 kind, or two or more kinds may be used in combination.

When a solvent is used for producing the hydrolyzable polymer (a), the amount thereof is not particularly limited, but is preferably 5 parts by mass or more and 200 parts by mass or less, more preferably 50 parts by mass or more and 150 parts by mass or less, relative to 100 parts by mass of the total of the monomers.

The method for producing the hydrolyzable polymer (a) is not limited to this, and the hydrolyzable polymer (a) may be produced by a method in which a polymer (a3) having a carboxyl group, a monocarboxylic acid compound (D) described later, and a metal compound (preferably an inorganic metal compound, specifically, an oxide, a hydroxide, a chloride, an organic acid salt (e.g., zinc acetate) of copper or zinc) are reacted to introduce a metal ester group into the carboxyl group of the polymer (a 3); or reacting the polymer (a3) having a carboxyl group with a metal compound to introduce a metal ester crosslink into the polymer.

Examples of the polymer (a3) having a carboxyl group include a polyester polymer (a3-1) and an acrylic polymer (a3-2), and the polyester polymer (a3-1) is preferable.

As the polyester polymer (a3-1), a polyester resin having an acid group can be exemplified.

The solid acid value of the polyester polymer (a3-1) is preferably not less than 30mgKOH/g, more preferably not less than 50mgKOH/g, and further preferably not more than 250mgKOH/g, more preferably not more than 200 mgKOH/g.

The polyester polymer (a3-1) can be obtained by the reaction of 1 or more kinds of polyhydric alcohols with 1 or more kinds of polycarboxylic acids and/or anhydrides thereof, and any kind can be used in any amount, and the acid value and viscosity can be adjusted by the combination thereof.

As the polyester-based polymer (a3-1), a polymer obtained by reacting a 3-or more-membered alcohol (a3-11) with a dibasic acid and/or an acid anhydride thereof (a3-12) and a 2-membered alcohol (a3-13), and then reacting an alicyclic dibasic acid and/or an acid anhydride thereof (a3-14) as described in International publication No. 2014/010702 can be suitably exemplified.

As described above, the hydrolyzable polymer (A) can also be produced by a method of reacting the polyester polymer (a3-1) with the monocarboxylic acid compound (D) and the metal compound, or a method of reacting the polyester polymer (a3-1) with the metal compound.

As the monocarboxylic acid compound (D) to be reacted with the polyester polymer (a3-1), a monocarboxylic acid compound as described later can be used, and particularly, rosins are preferably used, and as the metal compound, for example, a metal oxide such as zinc oxide or copper oxide, and particularly, zinc oxide is preferably used.

Examples of the acrylic polymer (a3-2) include a carboxyl group-containing acrylic polymer (a3-2) obtained by radical polymerization using an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, 3- (meth) acryloyloxypropionic acid, 3- (meth) acryloyloxy-2-methylpropanoic acid, and other monomer (a2) used as necessary as a polymerizable compound (monomer).

The hydrolyzable polymer (A) can also be produced by a method of reacting the acrylic polymer (a3-2) with a monocarboxylic acid compound (D) and a metal compound (preferably an inorganic metal compound, specifically, an oxide, hydroxide, chloride, organic acid salt (e.g., zinc acetate) of copper or zinc, etc.) or a method of reacting the acrylic polymer (a3-2) with a metal compound, similarly to the polyester polymer (a 3-1).

The content of copper and/or zinc in the hydrolyzable polymer (a) is preferably 0.5% by mass or more and 25% by mass or less, more preferably 1% by mass or more and 20% by mass or less, further preferably 1% by mass or more and 10% by mass or less, and further preferably 1.5% by mass or more and 5% by mass or less, in view of forming an antifouling coating film excellent in coating film renewability and antifouling property. The content of copper and/or zinc can be measured by an X-ray diffraction apparatus or an ICP emission spectrometer, and can be adjusted as appropriate by the amount of the monomer used in synthesizing the hydrolyzable polymer (a).

The acid value of the hydrolyzable polymer (a) is preferably 30mgKOH/g or more and 250mgKOH/g or less from the viewpoint of setting the dissolution rate of the obtained antifouling coating film in water to a desired range.

An acid value of 30mgKOH/g or more is preferred because the metal content in the hydrolyzable polymer (A) is suitable and an antifouling coating film having excellent antifouling properties can be obtained. Further, an acid value of 250mgKOH/g or less is preferable in that an antifouling coating film having excellent long-term antifouling properties and coating film properties can be obtained.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolyzable polymer (a) are preferably appropriately adjusted in consideration of the viscosity and storage stability of the antifouling paint composition, the elution rate of the obtained antifouling coating film (film renewability), and the like.

The number average molecular weight (Mn) of the hydrolyzable polymer (a) is preferably 500 or more, more preferably 700 or more, and preferably 100000 or less, more preferably 10000 or less, and further preferably 3000 or less. The weight average molecular weight (Mw) of the hydrolyzable polymer (a) is preferably 1000 or more, more preferably 1500 or more, and is preferably 200000 or less, more preferably 50000 or less, and further preferably 10000 or less.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) can be determined by measuring with a gel permeation chromatography and converting with standard polystyrene.

The hydrolyzable polymer (A) may be used alone in 1 kind, or may be used in combination of two or more kinds.

The content of the hydrolyzable polymer (a) in the antifouling paint composition is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and further preferably 50% by mass or less, more preferably 35% by mass or less, further preferably 25% by mass or less in the antifouling paint composition, from the viewpoints of the workability of coating the composition, the durability of the formed antifouling paint film, and the obtainment of an antifouling paint film excellent in water resistance. The content of the hydrolyzable polymer (a) in the solid content of the antifouling paint composition is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 15% by mass or more, and is 50% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less.

In the present invention, when 2 or more types of the hydrolyzable polymer (a) are contained, the above content is a preferable range as the total content of the hydrolyzable polymer (a), and the same applies to each component described later.

In the present invention, the hydrolyzable resin may contain other hydrolyzable resins known in the art in addition to the hydrolyzable polymer (a). The other hydrolyzable resin is not particularly limited as long as it has a hydrolyzable group that undergoes a hydrolysis reaction in water and is a resin other than the hydrolyzable polymer (a), and examples thereof include a silyl ester hydrolyzable polymer.

In the present invention, the content of the hydrolyzable polymer (a) in the hydrolyzable resin is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass, even more preferably 100% by mass, from the viewpoint of excellent discoloration resistance and being able to maintain high antifouling property for a long period of time.

< Zinc phosphate (B) >

Examples of the zinc phosphate (B) include zinc phosphate, zinc polyphosphate, zinc pyrophosphate, zinc metaphosphate, and the like, and 1 kind may be used alone, or two or more kinds may be used in combination.

The zinc phosphate is generally present in the form of an anhydride or a tetrahydrate, and any of these compounds can be used as desired without affecting the properties, discoloration resistance and antifouling properties of the obtained antifouling coating film.

Among them, as the zinc phosphate (B), zinc phosphate (anhydride) or zinc phosphate tetrahydrate is preferable.

The average particle diameter (median diameter) of the zinc phosphate (B) is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.5 μm or more, even more preferably 1 μm or more, and furthermore preferably 40 μm or less, even more preferably 20 μm or less, even more preferably 10 μm or less, from the viewpoint of improving dispersibility in the present composition and from the viewpoint of improving antifouling properties of the obtained antifouling coating film.

In the present specification, the average particle diameter (median diameter) was measured by a laser diffraction scattering method using SALD-2200 (manufactured by Shimadzu corporation).

The shape of the particles of the zinc phosphate (B) is not particularly limited, and zinc phosphate (B) having various shapes such as a spherical shape, an elliptical shape, and an amorphous shape can be used.

< Zinc oxide (C) >

The composition contains zinc oxide (C).

The average particle diameter (median diameter) of the zinc oxide is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, further preferably 0.1 μm or more, and further preferably 30 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less, from the viewpoint of improving dispersibility in the present composition and from the viewpoint of improving the antifouling property of the obtained antifouling coating film.

The mass ratio (B: C) of the contents of the zinc phosphate (B) and the zinc oxide (C) in the present composition is 20: 80 or more, preferably 23: 77 or more, more preferably 25: 75 or more, further preferably 30: 70 or more, further preferably 35: 65 or more, and further 75: 25 or less, preferably 70: 30 or less, more preferably 65: 35 or less, further preferably 60: 40 or less, from the viewpoint of obtaining an antifouling coating film which is excellent in discoloration resistance, maintains high antifouling properties for a long period of time, and has good coating film physical properties. In the present invention, the content of zinc phosphate (B) refers to the content of zinc phosphate anhydride.

The above-mentioned effects are not a simple combination of the effects of the hydrolyzable polymer (a), zinc phosphate (B), and zinc oxide (C), but are first produced when they are used in combination.

The total content of the zinc phosphate (B) and the zinc oxide (C) in the solid content of the antifouling paint composition is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, and still more preferably 45% by mass or more, and is preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less, and still more preferably 55% by mass or less. The content of the zinc phosphate (B) is, as described above, the content based on the zinc phosphate anhydride.

When the total content of the zinc phosphate (B) and the zinc oxide (C) in the solid content of the coating composition is less than the above range, the dryness and the coating strength of the formed antifouling coating film tend to be lowered. On the other hand, if the viscosity is more than the above range, the workability tends to be lowered with an increase in the viscosity of the coating composition, and there may be a problem of poor coating film properties such as cracks occurring in the formed antifouling coating film.

< other optional ingredients >

The composition may further contain, in addition to the above components, a monocarboxylic acid compound (D), an organic antifouling agent (E), an inorganic copper compound (F), another binder component (G), a pigment (H), a solvent (I), an anti-sagging/anti-settling agent (J), a pigment dispersant (K), a plasticizer (L), a dehydrating agent (M), and the like, as required.

Other optional components will be described below.

[ monocarboxylic acid Compound (D) ]

The composition may contain the monocarboxylic acid compound (D), and 1 kind may be used alone, or two or more kinds may be used in combination.

In the present invention, the monocarboxylic acid compound (D) improves the renewability of the formed antifouling coating film in water from the surface, and when the antifouling coating film contains an antifouling agent, the release of the antifouling agent into water is promoted to improve the antifouling property, and the function of imparting appropriate water resistance to the antifouling coating film is also provided.

When the monocarboxylic acid compound (D) is represented by R-COOH, for example, R is preferably a saturated or unsaturated aliphatic hydrocarbon group having 10 to 40 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a substituent thereof.

Specific examples thereof include abietic acid, neoabietic acid, dehydroabietic acid, palustric acid, isopimaric acid, pimaric acid, trimethylmethacryloylcyclohexene carboxylic acid, versatic acid, stearic acid, naphthenic acid, salicylic acid and the like. Also, rosins containing abietic acid, palustric acid, isopimaric acid, and the like as a main component are preferable, and examples of the rosins include rosins such as gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, rosin derivatives such as rosin metal salts, pine tar, and the like.

Examples of trimethylisobutenylcyclohexene carboxylic acids include the reaction product of 2, 6-dimethyl-2, 2, 6-octatriene and methacrylic acid, the main component (85 mass% or more) of which is 1, 2, 3-trimethyl-5- (2-methyl-1-propen-1-yl) -3-cyclohexene-1-carboxylic acid.

The monocarboxylic acid compound (D) may form a metal ester in a part or all thereof. The metal ester may be formed in advance before the preparation of the coating composition, or may be formed by reaction with other components during the preparation of the coating composition.

The monocarboxylic acid compound (D) may correspond to the hydrolyzable polymer (a), and in such a case, it is considered to be the hydrolyzable polymer (a).

From the viewpoint of improving the coating workability and further improving the antifouling property, the monocarboxylic acid compound (D) is preferably contained, but a large content thereof causes problems such as a decrease in discoloration resistance of the formed coating film and an excessive consumption of the coating film, and therefore the content of the monocarboxylic acid compound (D) in the solid content of the present composition is preferably 5 mass% or less, more preferably 4 mass% or less, and still more preferably 3 mass% or less. The present composition may contain no monocarboxylic acid compound (D), preferably no monocarboxylic acid compound (D), but when the monocarboxylic acid compound (D) is contained, the content thereof is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5% by mass or more in the solid content of the coating composition.

[ organic antifouling agent (E) ]

In order to further improve the antifouling property of the antifouling coating film formed from the composition, the composition preferably further contains an organic antifouling agent (E). Examples of the organic antifouling agent (E) include metal pyrithione such as copper pyrithione and zinc pyrithione, (+/-) -4- [1- (2, 3-dimethylphenyl) ethyl ] -1H-imidazole (alias: medetomidine), 4, 5-dichloro-2-N-octyl-4-isothiazolin-3-one (alias: DCOIT), 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (alias: trobiparide), pyridine triphenylborane, 4-isopropylpyridine diphenylmethyl borane, N-dimethyl-N' - (3, 4-dichlorophenyl) urea (alias: diuron), and mixtures thereof, N- (2, 4, 6-trichlorophenyl) maleimide, 2, 4, 5, 6-tetrachloroisophthalonitrile, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1, 3, 5-triazine (alias: Cybutryne), bis (dimethyldithiocarbamoyl) zinc ethylenebis (dithiocarbamate) (alias: Furaz), chloromethyl-N-octyldisulfide, N '-dimethyl-N-phenyl- (N-fluorodichloromethylthio) sulfonamide (alias: dichlofluanid), tetraalkylthiuram disulfide (alias: TMTD), zinc dimethyldithiocarbamate (alias: Fumeizine), zinc ethylenebis (dithiocarbamate), 2, 3-dichloro-N- (2', 6 ' -diethylphenyl) maleimide, 2, 3-dichloro-N- (2 ' -ethyl-6 ' -methylphenyl) maleimide and the like. The organic antifouling agent (E) may be used alone in 1 kind, or two or more kinds may be used in combination.

The organic antifouling agent (E) in the present composition preferably contains at least 1 selected from the group consisting of copper pyrithione, zinc pyrithione, (+/-) -4- [1- (2, 3-dimethylphenyl) ethyl ] -1H-imidazole (alias: medetomidine), 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one (alias: DCOIT), and 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (alias: trobiparide), and more preferably contains at least 1 selected from the group consisting of copper pyrithione, zinc pyrithione, medetomidine, and trobiparide.

In addition, the organic antifouling agent (E) in the present composition preferably contains at least 1 selected from the group consisting of copper pyrithione and zinc pyrithione, and particularly preferably contains copper pyrithione. By containing at least 1 kind selected from the group consisting of copper pyrithione and zinc pyrithione, an antifouling coating film excellent in scratch resistance can be obtained. In particular, when the present composition contains copper pyrithione, the formed antifouling coating film has low wear-out properties and can provide an antifouling coating film having high antifouling properties, and as a result, the film thickness of the antifouling coating film can be set thin, and an antifouling coating film having further excellent scratch resistance can be obtained.

Copper pyrithione and zinc pyrithione are represented by the following formula (2).

[ solution 11]

(in the formula (2), R³Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group, an alkenyl group, an aryl group, an alkoxy group or a halogenated alkyl group, and M is Cu or Zn. )

In the formula (2), R³Preferably a hydrogen atom.

In addition, it is also preferable that the organic antifouling agent (E) in the present composition further contains an organic antifouling agent other than copper pyrithione and zinc pyrithione in addition to at least 1 selected from the group consisting of copper pyrithione and zinc pyrithione.

In the present composition, the content of the organic antifouling agent (E) is preferably 1 mass% or more and 50 mass% or less, more preferably 1.5 mass% or more and 45 mass% or less, and still more preferably 2 mass% or more and 40 mass% or less in the solid content of the antifouling paint composition of the present invention, from the viewpoint of the balance between the improvement of the long-term antifouling property of the formed antifouling coating film and the physical properties of the coating film.

[ inorganic copper Compound (F) ]

The present composition may contain the inorganic copper compound (F) for the purpose of further improving the antifouling property of the antifouling coating film. Examples of the inorganic copper compound include powdered copper (copper powder), cuprous oxide, copper thiocyanate (also known as Rhodane copper), and cupronickel (cupronickel).

The content of the inorganic copper compound (F) in the present composition is preferably 10% by mass or less, more preferably 3% by mass or less, further preferably 1% by mass or less, further preferably 0.1% by mass or less, and particularly preferably not contained in the solid content of the coating composition, from the viewpoint of excellent color selectivity of the formed antifouling coating film.

An antifouling paint composition containing no inorganic copper compound (F), particularly containing no cuprous oxide, tends to discolor early when exposed to the outside, and the discoloration is remarkable. On the other hand, the present composition can obtain sufficient antifouling property even if it does not contain the inorganic copper compound (F), and therefore, it can be suitably used as an antifouling paint composition containing no inorganic copper compound (F).

[ other Binder component (G) ]

The composition may contain a binder component (G) other than the hydrolyzable polymer (a) and other hydrolyzable resins for the purpose of imparting water resistance, crack resistance, and strength to the formed antifouling coating film. These may be used alone in 1 kind, or two or more kinds may be used.

Examples of the binder component include resins, and examples thereof include water-soluble resins such as chlorinated paraffin, acrylic resins containing no metal ester group, acrylic silicone resins, polyester resins, unsaturated polyester resins, fluorine resins, polybutene resins, silicone rubbers, polyurethane resins, epoxy resins, polyamide resins, vinyl resins (vinyl chloride copolymers, ethylene-vinyl acetate copolymers, and the like), polyvinyl alkyl ethers, chlorinated rubbers, styrene/butadiene copolymer resins, ketone resins, alkyd resins, cumarone resins, terpene phenolic resins, petroleum resins, and the like, which are not water-soluble or water-insoluble resins.

The chlorinated paraffin may have any linear or branched molecular structure, and may be liquid or solid (e.g., powder) at room temperature (e.g., 23 ℃).

The average carbon number of the chlorinated paraffin is preferably 8 or more and 30 or less, and more preferably 10 or more and 26 or less in one molecule. The antifouling paint composition containing the chlorinated paraffin can form an antifouling coating film with less cracks (cracks), peeling and the like. It is preferable that the average carbon number is 8 or more because the effect of suppressing the occurrence of cracks is high, and that the average carbon number is 30 or less because the antifouling property is not suppressed.

In addition, in the chlorinated paraffin, the viscosity (unit poise, measurement temperature 25 ℃) is preferably 1 or more, more preferably 1.2 or more, and the specific gravity (25 ℃) is preferably 1.05 to 1.80g/cm³More preferably 1.10 to 1.70g/cm³。

The chlorination rate (chlorine content) of the chlorinated paraffin is usually 35 to 70 parts by mass, preferably 35 to 65 parts by mass, when the chlorinated paraffin is 100 parts by mass. The antifouling paint composition containing the chlorinated paraffin having such a chlorination rate can form a coating film which is less likely to cause cracks (cracks), peeling, and the like. Specific examples of such chlorinated paraffins include "TOYOPARAX 150" and "TOYOPARAX A-70" (all available from Tosoh Corp.).

Further, examples of the petroleum resins include C5 series, C9 series, styrene series, dicyclopentadiene series, and hydrogenated products thereof. Specific examples of the petroleum resins include "Quintone 1500" and "Quintone 1700" (both manufactured by ZEON corporation, japan).

[ pigment (H) ])

The present composition may contain a pigment (H) other than the above-mentioned zinc phosphate (B) and zinc oxide (C). The antifouling paint composition of the present invention may contain a coloring pigment (H1) from the viewpoint of adjusting the color tone of the formed antifouling coating film and providing an arbitrary color tone, and may contain an extender pigment (H2) for the purpose of improving the coating film properties such as water resistance and crack resistance of the obtained antifouling coating film.

Examples of the coloring pigment (H1) include various known organic or inorganic coloring pigments. Examples of the organic coloring pigment include naphthol red and phthalocyanine blue. Examples of the inorganic coloring pigment include carbon black, red iron oxide (red iron oxide), barite powder, titanium white, and yellow iron oxide. The coloring pigment (H1) may be used alone in 1 kind, or two or more kinds may be used in combination.

The antifouling paint composition of the present invention may contain a coloring agent other than the coloring pigment such as a dye together with the coloring pigment (H1) or in place of the coloring pigment (H1).

Examples of the extender pigment (H2) include talc, silica, mica, clay, potash feldspar, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, condensed aluminum phosphate, magnesium carbonate, barium carbonate, and barium sulfate. Among them, talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, and potash feldspar are preferable. Calcium carbonate and white carbon are also used as a sagging/sedimentation inhibitor (J) and a matting agent, respectively, which will be described later. The extender pigment (H2) may be used alone in 1 kind, or may be used in combination of two or more kinds.

The content of the pigment (H) in the present composition is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and even more preferably 5 to 20% by mass in the solid content of the antifouling paint composition of the present invention, from the viewpoint of improving the appearance, masking property, discoloration resistance, antifouling property, water resistance, and mechanical properties of the obtained antifouling coating film.

[ solvent (I) ]

The present composition may contain a solvent (I) such as water or an organic solvent as necessary for the purpose of improving the dispersibility of the hydrolyzable polymer (a) or the like or adjusting the viscosity of the antifouling paint composition. The composition may contain a solvent used in the preparation of the hydrolyzable polymer (a) as the solvent (I), or may contain a solvent separately added when the hydrolyzable polymer (a) is mixed with other components used as needed. As the solvent (I), an organic solvent is preferable.

Examples of the organic solvent include aromatic organic solvents such as xylene, toluene, ethylbenzene, coal tar and naphtha; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic monohydric alcohols (having 1 to 10 carbon atoms, preferably about 2 to 5 carbon atoms) such as ethanol, isopropanol, n-butanol, isobutanol, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate and butyl acetate; and the like. The solvent (I) may be used alone in 1 kind, or two or more kinds may be used in combination.

When the present composition contains the solvent (I), the content thereof is preferably determined according to the desired viscosity according to the coating method of the coating composition, and is preferably 5 to 50% by mass, more preferably 10 to 40% by mass in the coating composition. If the content is too large, the sag resistance may be deteriorated.

[ anti-sagging/anti-settling agent (J) ]

When a substrate is coated with the present composition, the anti-sagging/anti-settling agent (J) may be contained from the viewpoints of reducing the occurrence of sagging caused by the coating composition, preventing the generation of precipitates during storage, and improving the stirring property.

The anti-sagging agent/anti-settling agent (J) may be exemplified by the anti-sagging agent and the anti-settling agent described in international publication No. 2018/003135, and the preferable ranges are the same including the content.

[ pigment dispersant (K) ]

When the present composition contains a pigment (H) such as a colored pigment (H1) or an extender pigment (H2), the antifouling paint composition of the present invention may contain a pigment dispersant (K) for the purpose of improving the pigment dispersibility.

Examples of the pigment dispersant (K) include the pigment dispersants described in international publication No. 2018/003135, and the preferable ranges are the same including the content.

[ plasticizer (L) ])

The present composition may contain a plasticizer (L) for the purpose of imparting plasticity to the antifouling coating film.

Examples of the plasticizer (L) include plasticizers described in international publication No. 2018/003135, and preferred ranges are the same including the content.

[ dehydrating agent (M) ]

The composition has excellent storage stability by using the hydrolyzable polymer (A) having excellent storage stability, and further excellent long-term storage stability can be obtained by containing the dehydrating agent (M) as required.

Examples of the dehydrating agent (M) include the dehydrating agents described in international publication No. 2018/003135, and the preferable ranges are the same including the content.

[ method for producing antifouling paint composition ]

The composition of the present invention can be prepared by the same apparatus and method as those of known general antifouling paints. For example, the water-soluble polymer (a) may be prepared in advance in a solvent, and then the solution of the water-soluble polymer (a), zinc phosphate (B), zinc oxide (C), and other components (D) to (M) used as needed may be added all at once or sequentially, and stirred and mixed to produce the water-soluble polymer (a).

[ antifouling coating film and substrate with antifouling coating film, method for producing same, and antifouling method ]

The antifouling coating film of the present invention is formed from the antifouling coating composition of the present invention, and is obtained by drying the antifouling coating composition. Specifically, for example, an antifouling coating film can be obtained by applying the antifouling coating composition of the present invention to a conventional coating film or substrate and then drying (curing) the coating film or substrate.

The method for applying the antifouling paint composition of the present invention includes known methods such as a method using a brush, a roller, and a spray.

The antifouling paint composition applied by the above-mentioned method can be dried by leaving it at 25 ℃ for about 0.5 to 7 days, preferably about 0.5 to 5 days, more preferably about 0.5 to 3 days, to obtain a coating film. In addition, the drying of the coating composition may be performed while blowing air under heating.

The thickness of the antifouling coating film after drying can be arbitrarily selected depending on the consumption rate of the antifouling coating film and the period of use, and is preferably about 30 to 1000 μm, for example. The method for producing a coating film having such a thickness includes a method of applying the coating composition 1 time to 1 time, preferably 1 to 300 μm, and more preferably 30 to 200 μm.

The substrate with an antifouling coating film of the present invention is covered with an antifouling coating film formed from the present composition, and the antifouling coating film is provided on the substrate.

The method for producing the substrate with an antifouling coating film of the present invention is not particularly limited, and for example, the method can be used by a method comprising the step (I) of applying or impregnating the antifouling coating composition of the present invention to a substrate to obtain a coated body or an impregnated body; and a step (II) of drying the coated body or impregnated body.

In the step (I), the coating method described above can be used as a method of applying the coating composition to a substrate. In addition, the method of impregnation is not particularly limited, and may be performed by immersing the base material in an amount sufficient for impregnation of the coating composition. The method for drying the coated body or impregnated body is not particularly limited, and the coated body or impregnated body can be dried by the same method as that used in the production of the antifouling coating film.

The substrate with an antifouling coating film of the present invention can also be obtained by a production method comprising the step (i) of drying the present composition to form a coating film and the step (ii) of attaching the coating film to the substrate.

The method for forming the coating film in the step (i) is not particularly limited, and the antifouling coating film can be produced by the same method as that for producing the antifouling coating film.

The method for attaching the coating film to the substrate in the step (ii) is not particularly limited, and for example, the attachment can be performed by the method described in japanese patent application laid-open No. 2013-129724.

The antifouling method of the present invention uses an antifouling coating film formed from the composition, and provides various substrates with the antifouling coating film, thereby inhibiting fouling of the substrates, specifically, inhibiting adhesion of aquatic organisms and the like.

The composition can be used for maintaining the antifouling property of a base material for a long period of time in a wide range of industrial fields such as ships, fisheries, underwater (marine) structures, and the like. Examples of such a base material include marine structures such as ships (large steel vessels such as container ships and tankers, outer hull plates of fishing boats, FRP boats, wooden vessels, yachts, and the like, newly-built ships, renovation ships, and the like), fishery materials (ropes, fishing nets, fishing gears, floats, buoys, and the like), and super-floating docks. Among them, the substrate is preferably selected from ships, underwater structures, and fishery materials, more preferably from ships and underwater structures, and further preferably from ships.

The substrate on which the present composition is formed may be a surface treated with another treating agent such as a rust inhibitor, a surface having formed thereon a certain coating film such as a primer, a surface having been coated with the present composition, or the like, and the type of the coating film with which the antifouling coating film of the present invention is in direct contact is not particularly limited.

Examples

The present invention will be further specifically described below with reference to examples, but the present invention is not limited to these examples. Hereinafter, "part" means part by mass unless specifically mentioned to be contrary to the gist.

[ production of hydrolyzable Polymer (A) ]

In the production of the hydrolyzable polymer (A), first, hydrolyzable group-containing monomers (a1-1) and (a1-2) were prepared as follows.

< preparation example 1: preparation of hydrolyzable group-containing monomer (Metal ester group-containing monomer) (a1-1)

To a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating/cooling jacket, 85.4 parts by mass of propylene glycol monomethyl ether and 40.7 parts by mass of zinc oxide were charged, and the temperature was raised to 75 ℃ while stirring. Next, a mixture containing 43.1 parts by mass of methacrylic acid, 36.1 parts by mass of acrylic acid, and 5.0 parts by mass of water was dropped from the dropping device at a constant rate for 3 hours. After the completion of the dropwise addition, the mixture was further stirred for 2 hours, and then 36.0 parts by mass of propylene glycol monomethyl ether was added to obtain a reaction solution containing a monomer having a hydrolyzable group (a metal ester group-containing monomer) (a 1-1).

< preparation example 2: preparation of hydrolyzable group-containing monomer (Metal ester group-containing monomer) (a1-2)

To a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating/cooling jacket, 72.4 parts by mass of propylene glycol monomethyl ether and 40.7 parts by mass of zinc oxide were charged, and the temperature was raised to 75 ℃ while stirring. Then, a mixture of 30.1 parts by mass of methacrylic acid, 25.2 parts by mass of acrylic acid, and 51.6 parts by mass of versatic acid was dropped from the dropping device at a constant rate over 3 hours. After the completion of the dropwise addition, the mixture was further stirred for 2 hours, and then 11.0 parts by mass of propylene glycol monomethyl ether was added to obtain a reaction solution containing a monomer having a hydrolyzable group (a metal ester group-containing monomer) (a 1-2).

< production example 1: production of hydrolyzable Polymer (copolymer containing Metal ester group) solution (A-1)

To a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating/cooling jacket, 15.0 parts by mass of propylene glycol monomethyl ether, 60.0 parts by mass of xylene, and 4.0 parts by mass of ethyl acrylate were charged, and the temperature was raised to 100. + -. 5 ℃ while stirring. 40.2 parts by mass of a reaction solution containing the metal ester group-containing monomer (a1-1) obtained in preparation example 1, 15.0 parts by mass of methyl methacrylate, 48.0 parts by mass of ethyl acrylate, 15.0 parts by mass of n-butyl acrylate, 2.5 parts by mass of a polymerization initiator 2, 2 '-azobisisobutyronitrile, 6.5 parts by mass of a polymerization initiator 2, 2' -azobis (2-methylbutyronitrile), 1.2 parts by mass of a chain transfer agent "Nofmer MSD" (a-methylstyrene dimer, manufactured by Nippon fat Co., Ltd.), and 10.0 parts by mass of xylene were added dropwise from a dropping device into the reaction vessel over 6 hours while keeping the same temperature. After completion of the dropwise addition, 0.5 part by mass of t-butyl peroctoate as a polymerization initiator and 7.0 parts by mass of xylene were added dropwise over 30 minutes, and after further stirring for 1 hour and 30 minutes, 8.0 parts by mass of xylene was added to prepare a pale yellow transparent hydrolyzable polymer solution (a-1) containing a hydrolyzable polymer (a copolymer containing a metal ester group).

The composition of the monomers used and the characteristic values of the hydrolyzable polymer solution (A-1) measured by the method described later are shown in Table 1. The theoretical amounts (parts by mass) of the monomers are shown in the table.

< production example 2: production of hydrolyzable Polymer (copolymer containing Metal ester group) solution (A-2)

To a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating/cooling jacket, 15.0 parts by mass of propylene glycol monomethyl ether, 57.0 parts by mass of xylene, and 4.0 parts by mass of ethyl acrylate were charged, and the temperature was raised to 100. + -. 5 ℃ while stirring. While maintaining the same temperature, 52.0 parts by mass of the reaction solution containing the metal ester group-containing monomer (a1-1) obtained in preparation example 1, 1.0 part by mass of methyl methacrylate, 66.2 parts by mass of ethyl acrylate, 5.4 parts by mass of 2-methoxyethyl acrylate, 2.5 parts by mass of a polymerization initiator 2, 2 '-azobisisobutyronitrile, 7.0 parts by mass of a polymerization initiator 2, 2' -azobis (2-methylbutyronitrile), 1.0 part by mass of a chain transfer agent "Nofmer MSD" (manufactured by Nippon fat Co., Ltd., α -methylstyrene dimer), and 10.0 parts by mass of xylene were dropped into the reaction vessel from a dropping device over 6 hours. After completion of the dropwise addition, 0.5 part by mass of tert-butyl peroctoate (TBPO) as a polymerization initiator and 7.0 parts by mass of xylene were added dropwise over 30 minutes, and after stirring for 1 hour and 30 minutes, 4.4 parts by mass of xylene was added to prepare a pale yellow transparent hydrolyzable polymer solution (a-2) containing a hydrolyzable polymer (a copolymer containing a metal ester group).

The constitution of the monomers used and the characteristic values of the hydrolyzable polymer solution (A-2) are shown in Table 1.

< production example 3: production of hydrolyzable Polymer (copolymer containing Metal ester group) solution (A-3)

To a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating/cooling jacket, 10.0 parts by mass of propylene glycol monomethyl ether, 63.0 parts by mass of xylene, and 3.0 parts by mass of ethyl acrylate were charged, and the temperature was raised to 100. + -. 5 ℃ while stirring. 50.3 parts by mass of a reaction solution containing the metal ester group-containing monomer (a1-2) obtained in production example 2, 9.0 parts by mass of methyl methacrylate, 58.0 parts by mass of ethyl acrylate, 5.0 parts by mass of a polymerization initiator 2, 2' -azobis (2-methylbutyronitrile), and 10.0 parts by mass of propylene glycol monomethyl ether were added dropwise from a dropping device into the reaction vessel over 4 hours while keeping the same temperature. After completion of the dropwise addition, 0.5 part by mass of t-butyl peroctoate as a polymerization initiator and 7.0 parts by mass of xylene were added dropwise over 30 minutes, and after further stirring for 1 hour and 30 minutes, 12.0 parts by mass of xylene was added to prepare a pale yellow transparent hydrolyzable polymer solution (a-3) containing a hydrolyzable polymer (a copolymer containing a metal ester group).

The composition of the monomers used and the characteristic values of the hydrolyzable polymer solution (A-3) measured by the method described later are shown in Table 1.

[ Table 1]

TABLE 1

< production example 4: production of hydrolyzable Polymer (silyl ester group-containing copolymer) solution (S-1)

53 parts of xylene were charged into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introduction tube and a dropping funnel, and the xylene was heated under normal pressure to 85 ℃ under a nitrogen atmosphere while stirring with the stirrer. While the temperature of xylene in the reaction vessel was maintained at 85 ℃, a monomer mixture composed of 50 parts by mass of tipma (triisopropylsilylmethacrylate), 30 parts by mass of MEMA (2-methoxyethyl methacrylate), 10 parts by mass of MMA (methyl methacrylate), 10 parts by mass of BA (butyl acrylate) and 1 part by mass of AMBN (2, 2' -azobis (2-methylbutyronitrile)) was added to the reaction vessel over 2 hours using a dropping funnel.

Then, 0.5 part by mass of t-butyl peroctoate was further added to the reaction vessel, and after the stirring was continued for 2 hours by a stirrer while the liquid temperature in the reaction vessel was kept at 85 ℃ under normal pressure, the liquid temperature in the reaction vessel was raised from 85 ℃ to 110 ℃ and heated for 1 hour, 14 parts by mass of xylene was added to the reaction vessel, and the liquid temperature in the reaction vessel was lowered, and the stirring was stopped when the liquid temperature reached 40 ℃ to prepare a polymer solution containing a hydrolyzable polymer (S-1). The composition of the monomers used and the characteristic values of the hydrolyzable polymer solution (S-1) measured by the method described later are shown in Table 2.

[ Table 2]

TABLE 2

The measurement methods of the characteristic values of the obtained hydrolyzable polymer solutions (A-1) to (A-3) and (S-1) are shown below.

< viscosity of Polymer solution >

The viscosity of the polymer solution at 25 ℃ was measured with an E-type viscometer (manufactured by Toyobo industries Co., Ltd.).

< weight average molecular weight (Mw) and number average molecular weight (Mn) of hydrolyzable Polymer >

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the hydrolyzable polymer were measured by GPC (gel permeation chromatography) under the following conditions.

GPC conditions

The device comprises the following steps: "HLC-8120 GPC" (manufactured by Tosoh corporation)

A chromatographic column: connecting "TSKgel SuperH 2000" and "TSKgel SuperH 4000" (both manufactured by Tosoh Co., Ltd., inner diameter of 6 mm/length of 15cm)

Eluent: tetrahydrofuran (THF)

Flow rate: 0.500ml/min

A detector: RI (Ri)

Temperature of chromatographic column thermostatic bath: 40 deg.C

Standard substance: polystyrene

The sample preparation method comprises the following steps: a small amount of calcium chloride was added to the polymer solution prepared in each production example to dehydrate the polymer solution, and then the polymer solution was filtered by a membrane filter, and the obtained filter residue was used as a GPC measurement sample.

< solid content >

In the present invention, the solid component refers to a heating residue obtained when a mixture or a composition containing a solvent or the like is dried in a hot air dryer at 108 ℃ for 3 hours and then the solvent or the like is volatilized.

Examples 1 to 9 and comparative examples 1 to 7: production of antifouling paint composition

Table 3 shows the components used in examples and comparative examples.

The hydrolyzable polymer composition obtained in the above production example, zinc oxide (B), zinc phosphate (C), and other components as shown in the following table 4 (note that the numerical values in the table indicate parts by mass) were uniformly mixed at normal temperature using a Paint Shaker (Paint Shaker), thereby producing an antifouling Paint composition.

The blending amounts of the respective components shown in table 4 indicate the blending amounts in terms of a solution or a dispersion for the components described as having solid components, and indicate the blending amounts in terms of solid components for the components described as not having solid components (excluding solvents).

[ Table 3]

TABLE 3

< evaluation >

The obtained antifouling paint composition was evaluated as follows.

[ outdoor exposure discoloration test ]

An epoxy-based rust preventive paint (trade name "BANNO 500", manufactured by China paint Co., Ltd.) was applied to a sandblasted plate of 70X 200X 3mm in such a manner that the dry film thickness was about 150 μm, and then an epoxy-based adhesive paint (trade name "BANNO 500N", manufactured by China paint Co., Ltd.) was applied thereto in such a manner that the dry film thickness was about 100 μm. Then, each test piece was prepared by applying 1 time the antifouling paint compositions of examples and comparative examples so that the dry film thickness was about 150 μm and drying the composition at room temperature for 7 days. The coating interval for each coating was set to 1day/1 coat.

An outdoor exposure platform (according to JIS K5600-7-6) installed in a field of chinese coating shoku located in the large bamboo city, kangaroo, kandao prefecture was installed at an angle of 45 ° with respect to the horizontal and the coated surface was exposed. The film was exposed to the outside for 3 months, and the color difference (Δ E value) between the initial coating film and the coating film after the outdoor exposure was measured every 1 month under a C light source and a field of view of 2 ℃ using a spectrophotometer "CM-3700A" (manufactured by Konika minolta K.K.). The Δ E value was calculated as an average value of 10 random measurements of a site 1cm or more away from the end of each test specimen.

In addition, Δ E is based on L obtained by a spectrocolorimeter^*、a^*、b^*The value of (d) is calculated by the following equation.

ΔE＝{(L^* ₁-L^* ₀)²+(a^* ₁-a^* ₀)²+(b^* ₁-b^* ₀)²}^1/2

Here, L^* ₁、a^* ₁、b^* ₁Respectively, L after outdoor exposure^*、a^*、b^*，L^* ₀、a^* ₀、b^*0 each represents L of the initial coating film^*、a^*、b^*。

[ standing antifouling test ]

An epoxy-based rust inhibitive paint (epoxy AC paint, trade name "BANNO 500", manufactured by China paint Co., Ltd.) was applied to a sand blast treated steel sheet (300 mm in length. times.100 mm in width. times.3.2 mm in thickness) so that the dry film thickness was about 150 μm, and then an epoxy-based adhesive paint (trade name "BANNO 500N", manufactured by China paint Co., Ltd.) was applied thereto so that the dry film thickness was about 100 μm. Further, the antifouling paint compositions of examples and comparative examples were applied 1 time to a dry film thickness of about 100 μm, and dried at room temperature for 7 days to prepare a test plate having a static antifouling coating film. The above-mentioned 3 times of coating were all set to 1daV/1 coat.

The test plate prepared as described above was vertically left standing and immersed for 6 months in the bay of Guangdong island, Guangdong prefecture so that the water depth was 1.5 m, and the area (%) of adhesion of marine organisms to the surface of the antifouling coating film was measured every 1 month during the immersion. Thereafter, the antifouling coating film was evaluated for static antifouling property according to the following evaluation criteria.

Evaluation criteria for static antifouling Properties based on the area of attachment of marine organisms-

0: without attachment of marine organisms

0.5: the attachment area of marine organisms is more than 0% and less than 10%

1: the attachment area of marine organisms is more than 10% and less than 20%

2: the attachment area of marine organisms is more than 20% and less than 30%

3: the attachment area of marine organisms is more than 30% and less than 40%

4: the attachment area of marine organisms is more than 40% and less than 50%

5: the attachment area of marine organisms is more than 50 percent

[ Table 4-1]

TABLE 4-1

[ tables 4-2]

TABLE 4-2

From the results in table 4, it is clear that all of examples 1 to 9 satisfying the requirements of the present invention are excellent in discoloration resistance and can obtain high antifouling property over a long period of time.

On the other hand, in comparative example 1 in which the mass ratio (B: C) of zinc phosphate (B) to zinc oxide (C) was more than 75: 25, zinc phosphate (B) and zinc oxide (C) were used in combination, but the long-term antifouling property was insufficient. On the other hand, in comparative example 2 in which the mass ratio (B: C) of zinc phosphate (B) to zinc oxide (C) is less than 20: 80, discoloration due to outdoor exposure is significant.

In comparative examples 3 to 5 containing no zinc phosphate, discoloration was significant, and sufficient long-term antifouling property could not be obtained.

In addition, in comparative examples 6 and 7 using a hydrolyzable polymer containing a silyl ester group as a hydrolyzable polymer, sufficient antifouling property and discoloration resistance cannot be obtained even if zinc phosphate (B) and zinc oxide (C) are contained at a mass ratio of 20: 80 to 75: 25.

Industrial applicability

The composition can provide an antifouling coating film which is excellent in discoloration resistance and maintains high antifouling properties. The antifouling paint of the present invention can be used in a wide range of industrial fields such as ships, fisheries, marine structures, and the like, and is particularly suitable as an antifouling paint composition for ships.

Claims

1. An antifouling coating composition comprising:

a hydrolyzable polymer A containing a metal ester group,

Zinc phosphate B, and

the zinc oxide C is added into the mixture of the zinc oxide C,

the mass ratio of the zinc phosphate B to the zinc oxide C, namely B to C, is 20: 80 to 75: 25.

2. The antifouling paint composition according to claim 1,

the metal ester group is represented by the following formula (1),

in the formula (1), M represents copper or zinc, and X represents a bonding site.

3. The antifouling paint composition according to claim 1 or 2,

The hydrolyzable polymer A contains at least one selected from the group consisting of polymer A1 and polymer A2,

the polymer A1 has a structural unit derived from a polymerizable compound represented by the following formula (1-1),

the polymer A2 has a structural unit derived from a polymerizable compound represented by the following formula (1-2),

in the formula (1-1), R¹¹Each independently represents a 1-valent group containing a terminal ethylenically unsaturated group, M represents copper or zinc,

in the formula (1-2), R²¹Represents a 1-valent radical containing a terminal ethylenically unsaturated group, R²²The compound is a C1-30 organic group containing no terminal ethylenic unsaturated group, and M is copper or zinc.

4. The antifouling paint composition according to any one of claims 1 to 3, wherein,

the hydrolyzable polymer A contains at least one selected from the group consisting of polymer A1 'and polymer A2',

the polymer A1 'has a structural unit derived from a polymerizable compound represented by the following formula (1-1'),

the polymer A2 'has a structural unit derived from a polymerizable compound represented by the following formula (1-2'),

in the formula (1-1'), R¹²Each independently represents a hydrogen atom or a methyl group, M represents copper or zinc,

in the formula (1-2'), R²³Represents a hydrogen atom Or methyl, R²⁴The compound is a C1-30 organic group containing no terminal ethylenic unsaturated group, and M is copper or zinc.

5. The antifouling paint composition according to any one of claims 1 to 4,

the content of the hydrolyzable polymer A in the hydrolyzable resin is 50% by mass or more.

6. The antifouling paint composition according to any one of claims 1 to 5,

the total content of zinc phosphate B and zinc oxide C in the solid content of the antifouling paint composition is 30 to 70 mass%.

7. The antifouling paint composition according to any one of claims 1 to 6,

the content of the monocarboxylic acid compound D in the solid content of the antifouling paint composition is 5% by mass or less.

8. The antifouling paint composition according to any one of claims 1 to 7,

also contains an organic antifouling agent E.

9. The antifouling paint composition according to any one of claims 1 to 8,

the content of the inorganic copper compound F is 10% by mass or less in the solid content of the antifouling paint composition.

10. An antifouling coating film formed from the antifouling paint composition according to any one of claims 1 to 9.

11. A substrate having an antifouling coating film, which is covered with the antifouling coating film according to claim 10.

12. The substrate with an antifouling coating film according to claim 11,

the substrate is selected from the group consisting of marine vessels, underwater structures, and fishery materials.

13. A method for producing a substrate having an antifouling coating film, comprising:

a step (I) of coating or impregnating a substrate with the antifouling paint composition according to any one of claims 1 to 9 to obtain a coated body or an impregnated body, and

and (II) drying the coated body or the impregnated body.

14. A method for producing a substrate having an antifouling coating film, comprising:

(ii) a step (i) of drying the antifouling paint composition according to any one of claims 1 to 9 to form an antifouling coating film, and

(ii) attaching the antifouling coating film to a substrate.