CN113631378B - Antifouling coating composition - Google Patents

Antifouling coating composition Download PDF

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Publication number
CN113631378B
CN113631378B CN202080023781.XA CN202080023781A CN113631378B CN 113631378 B CN113631378 B CN 113631378B CN 202080023781 A CN202080023781 A CN 202080023781A CN 113631378 B CN113631378 B CN 113631378B
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antifouling
mass
polymer
group
coating film
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CN113631378A (en
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仁井本顺治
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Chugoku Marine Paints Ltd
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Chugoku Marine Paints Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

Abstract

The invention aims to provide an antifouling coating composition which can obtain an antifouling coating film with excellent color change resistance and can maintain high antifouling performance for a long time. The present invention also provides an antifouling coating film formed from the above-mentioned antifouling coating composition, a substrate having the antifouling coating film, and a method for producing the substrate. The antifouling paint composition of the present invention comprises a metal ester group-containing hydrolyzable polymer (A), zinc phosphate (B) and zinc oxide (C), and the mass ratio (B: C) of zinc phosphate (B) to zinc oxide (C) is 20:80 to 75:25.

Description

Antifouling coating composition
Technical Field
The present invention relates to an antifouling paint composition, an antifouling coating film using the same, a substrate with an antifouling coating film, and a method for producing the same.
Background
In a substrate of a marine vessel, a water structure, a fishery material such as a fishing net, etc., various aquatic organisms such as oyster, mussel, barnacle, etc., sea weed, etc., and bacteria, etc., are easily attached to the surface of the substrate exposed to water for a long period of time. Further, in recent years, the activity of marine organisms has been increased due to the temperature rise of sea water associated with global warming, and countermeasures against these fouling organisms have been demanded.
As a countermeasure therefor, an antifouling paint composition using a hydrolyzable resin having a property of renewing the surface of a coating film by hydrolysis in water is widely used (see patent document 1).
For example, patent document 1 describes an antifouling paint composition in which a metal salt bond-containing copolymer, a hydrolyzable copolymer such as a silyl ester copolymer, and medetomidine are used in combination for the purpose of obtaining an antifouling paint film which has stable paint film consumption and exhibits excellent antifouling properties for a long period of time.
Prior art literature
Patent literature
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 cause hydrolysis reaction on the surface due to not only the influence of sea water but also rainfall and ultraviolet rays, and the surface of the coating film may be deteriorated. Due to the deterioration, discoloration of the coating film may occur in a long-term ship building process, and there are problems in that the appearance is impaired, countermeasures such as repainting are sometimes required, and thus economic loss is also large.
Although the antifouling paint composition of patent document 1 achieves improvement of static antifouling property, there has been no study on suppression of discoloration and compromise of antifouling property due to outdoor exposure in a long-term ship building process. An antifouling coating film formed using the composition has room for improvement in terms of its discoloration resistance.
The purpose of the present invention is to provide an antifouling coating composition which 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 using the above-described antifouling coating composition, a substrate having the antifouling coating film, and a method for producing the substrate.
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above problems can be solved by using an antifouling paint composition as shown below, and have completed the present invention.
The gist of the present invention is as follows.
The present invention relates to the following [1 ] to [ 14 ].
[1 ] An antifouling paint composition comprising: the metal ester group-containing hydrolyzable polymer (A), zinc phosphate (B), and zinc oxide (C), and the mass ratio (B: C) of zinc phosphate (B) to zinc oxide (C) is 20:80 or more and 75:25 or less.
The antifouling paint composition according to [2], wherein the metal ester group is represented by the following formula (1).
[ Chemical 1]
(In the formula (1), M represents copper or zinc, and X represents a bonding position.)
The antifouling paint composition according to any of [ 1 ] and [ 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) having a structural unit derived from a polymerizable compound represented by the following formula (1-1), and the polymer (A2) having a structural unit derived from a polymerizable compound represented by the following formula (1-2).
[ Chemical 2]
(In the formula (1-1), R 11 each independently represents a 1-valent group containing a terminal ethylenically unsaturated group, M represents copper or zinc.)
[ Chemical 3]
(In the formula (1-2), R 21 represents a 1-valent group containing a terminal ethylenically unsaturated group, R 22 represents a 1-valent organic group having 1 to 30 carbon atoms and not containing a terminal ethylenically unsaturated group, and M represents copper or zinc.)
The antifouling paint composition according to any 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 ') having a structural unit derived from a polymerizable compound represented by the following formula (1-1'), and the polymer (A2 ') having a structural unit derived from a polymerizable compound represented by the following formula (1-2').
[ Chemical 4]
(In the formula (1-1'), R 12 each independently represents a hydrogen atom or a methyl group, and M represents copper or zinc.)
[ Chemical 5]
(In the formula (1-2'), R 23 represents a hydrogen atom or a methyl group, R 24 represents a 1-valent organic group having 1 to 30 carbon atoms and containing no terminal ethylenically unsaturated group, and M represents copper or zinc.)
The antifouling paint composition according to any of [1] to [ 4 ], wherein the content of the hydrolyzable polymer (A) in the hydrolyzable resin is 50% by mass or more.
The antifouling paint composition according to any of [1 ] to [ 5 ], wherein the total content of zinc phosphate (B) and zinc oxide (C) in the solid content of the antifouling paint composition is 30% by mass or more and 70% by mass or less.
The antifouling paint composition according to any 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 of [1] to [ 7 ], wherein an organic antifouling agent (F) is further contained.
The antifouling paint composition according to any of [ 1] to [ 8 ], wherein the content of the inorganic copper compound in the solid content of the antifouling paint composition is 10% by mass or less.
[ 10 ] An antifouling coating film formed from the antifouling paint composition according to any of [ 1 ] to [ 9 ].
[ 11 ] A substrate having an antifouling coating film, which is covered with the antifouling coating film described in [ 10 ].
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 with an antifouling coating film, comprising: a step (I) of applying or impregnating the antifouling paint composition according to any of [1 ] to [ 9 ] to a substrate to obtain a coated body or an impregnated body; and (II) drying the coated body or impregnated body.
[ 14 ] A method for producing a substrate with an antifouling coating film, comprising: a step (i) of drying the antifouling paint composition according to any of [ 1] to [ 9 ] to form an antifouling coating film; and (ii) adhering the antifouling coating film to a substrate.
Effects of the invention
According to the present invention, an antifouling paint composition which can provide an antifouling paint film excellent in discoloration resistance and capable of maintaining high antifouling properties for a long period of time can be provided. Further, according to the present invention, an antifouling coating film formed using the above-described antifouling coating composition, a substrate with an antifouling coating film, and a method for producing the same can be provided.
Detailed Description
The antifouling paint composition, the antifouling paint film, the substrate with the antifouling paint film and the method for producing the same according to the present invention will be described in detail below.
In the following description, "(meth) acryl", "(meth) acrylic" and "(meth) acrylate" refer to "acryl or methacryl", "acrylic or methacrylic", and "acrylate or methacrylate", respectively.
[ Antifouling coating composition ]
The antifouling paint composition of the present invention (hereinafter also simply referred to as "the present composition" or "the paint composition") is characterized by comprising: the metal ester group-containing hydrolyzable polymer (A), zinc phosphate (B), and zinc oxide (C), and the mass ratio (B: C) of zinc phosphate (B) to zinc oxide (C) is 20:80 or more and 75:25 or less.
In the antifouling paint composition described in patent document 1, there is a problem in terms of discoloration due to outdoor exposure, and the coating film having such discoloration tends to be reduced in antifouling property. It was found that by having the present composition comprise: the metal ester group-containing hydrolyzable polymer (A), zinc phosphate (B) and zinc oxide (C), and the mass ratio of zinc phosphate (B) to zinc oxide (C) is in a specific range, whereby an antifouling coating film having excellent discoloration resistance and both of good appearance and high antifouling property can be formed even after a long-term ship building process.
In order to impart film-renewability to an antifouling paint composition, a paint composition containing a hydrolyzable resin is widely used, and examples of the hydrolyzable resin include a silyl ester group-containing copolymer (silyl ester-based hydrolyzable polymer) and the like in addition to the metal ester group-containing hydrolyzable polymer (a).
In an antifouling paint composition containing a silyl ester-based hydrolyzable resin as a main component among the hydrolyzable resins, a dissolution aid is essentially required to promote dissolution of an antifouling agent. A typical dissolution aid is rosin or a metal salt thereof, and a certain amount needs to be added. In the case where the antifouling paint composition contains rosin or a metal salt thereof, discoloration under outdoor exposure tends to become remarkable. On the other hand, in the antifouling paint composition comprising the metal ester group-containing hydrolyzable polymer (a), the coating film consumption (antifouling agent elution property) is excellent, and rosin and a metal salt thereof are not necessarily used, so that by using zinc phosphate (B) and zinc oxide (C) in combination, and optimizing the ratio thereof, a composition that combines both good discoloration resistance and long-term antifouling property can be achieved.
In the antifouling paint composition containing an inorganic copper compound (F) such as cuprous oxide, the film color selectivity is low although the resistance to discoloration is high. In the present invention, since excellent antifouling properties can be obtained even in a composition containing no cuprous oxide, it is possible to provide an antifouling paint composition excellent in color selectivity which cannot be achieved by an antifouling paint composition containing cuprous oxide.
Although the detailed mechanism of action to obtain the above effects is not necessarily clear, it can be presumed as follows for a part thereof. That is, it is considered that by containing the metal ester group-containing hydrolyzable polymer (a), proper water resistance and water renewability from the surface in water can be imparted to the antifouling coating film, and by containing zinc phosphate (B) and zinc oxide (C) in a specific mass ratio, an antifouling coating film excellent in discoloration resistance and capable of maintaining high antifouling property even after long-term outdoor exposure such as in the ship building process can be obtained due to interaction in the obtained antifouling coating film.
The components contained in the antifouling paint composition of the present invention are described in detail below.
< Metal ester group-containing hydrolyzable Polymer (A) >)
The present composition contains a metal ester group-containing hydrolyzable polymer (a) (hereinafter, sometimes simply referred to as hydrolyzable polymer (a)).
The term "metal ester group" as used herein refers to a salt of a metal and an organic acid, and is preferably a group formed by bonding a metal to a carboxylic acid. The term "polyvalent metal ester group" or "2-valent metal ester group" as used hereinafter refers to a group formed by bonding a polyvalent metal or 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).
[ Chemical 6]
(In the formula (1), M represents a metal, and X represents a bonding position.)
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 contain a half metal. Examples of the semi-metal 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 may be suitably selected 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 still more preferable.
The term "(1)" means a bonding position and means bonding 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 may be crosslinked between the main chains by a group having a valence of 2 containing the group represented by the formula (1). The hydrolyzable polymer (a) may be an addition-polymerizable polymer obtained by polymerizing an ethylenically unsaturated compound, or may be a polycondensation-type polymer obtained by polycondensation such as polyester or polyamide, and is not particularly limited. Among them, addition-polymerizable 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 a polymerizable compound represented by the following formula (1-1) and a structural unit derived from a polymerizable compound represented by the following formula (1-2), and in this case, 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).
In the case where 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 polymer (A1) can be obtained by using a polymerizable compound represented by the following formula (1-1) as a monomer component, or by obtaining a polymer having a carboxyl group and then carrying out metal esterification to form a crosslinked structure, but the polymer (A1) is not particularly limited, but from the viewpoint of ease of production, the polymer (A1) is preferably obtained by using a polymerizable compound represented by the formula (1-1) as a monomer component.
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 metal esterification after obtaining a polymer having a carboxyl group, but from the viewpoint of ease of production, the polymer (A2) is preferably obtained 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 (a 1-1), and the polymerizable monomer having a group represented by the following formula (1-2) is referred to as a monomer (a 1-2). The monomer (a 1-1) and the monomer (a 1-2) are also collectively referred to as the monomer (a 1).
[ Chemical 7]
(In the formula (1-1), R 11 each independently represents a 1-valent group containing a terminal ethylenically unsaturated group, M represents copper or zinc.)
In the formula (1-1), R 11 represents a group having a valence of 1 and containing a terminal ethylenically unsaturated group (CH 2 =c <), and the number of carbon atoms of R 11 is preferably 2 or more and 50 or less, more preferably 2 or more and 30 or less, still more preferably 2 or more and 10 or less, still more preferably 2 or more and 6 or less. R 11 may have a terminal ethylenically unsaturated group, or may have an ethylenically unsaturated group other than the terminal, but more preferably has an ethylenically unsaturated group only at the terminal.
R 11 is preferably an unsaturated aliphatic group containing 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. Specific examples of R 11 include a group obtained by removing a carboxyl group from 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-undecylenic acid, 3- (meth) acryloyloxy propionic acid, 3- (meth) acryloyloxy-2-methylpropanoic acid, and the like. Further, examples of the group obtained by removing 1 carboxyl group from an unsaturated aliphatic dicarboxylic acid having a terminal ethylenically unsaturated group such as itaconic acid are shown.
Among them, R 11 is preferably a group obtained by removing a carboxyl group from an unsaturated aliphatic monocarboxylic acid having a terminal ethylenically unsaturated group, more preferably a group obtained by removing a carboxyl group from acrylic acid, methacrylic acid or (meth) acryloyloxyalkyl carboxylic acid, and still more preferably a group obtained by removing a carboxyl group from acrylic acid or methacrylic acid.
Examples of the polymerizable compound (monomer (a 1-1)) represented by the formula (1-1) include zinc diacrylate, zinc dimethacrylate, zinc acrylate (methacrylic acid), zinc bis (3-acryloxypropionate), zinc bis (3-methacryloxypropionate), zinc bis (3- (meth) acryloxy2-methylpropionate), copper diacrylate, copper dimethacrylate, copper acrylate (methacrylic acid), copper bis (3-acryloxypropionate), copper bis (3-methacryloxypropionate), copper bis (3- (meth) acryloxy2-methylpropionate).
[ Chemical 8]
(In the formula (1-2), R 21 represents a 1-valent group containing a terminal ethylenically unsaturated group, R 22 represents a 1-valent organic group having 1 to 30 carbon atoms and not containing a terminal ethylenically unsaturated group, and M represents copper or zinc.)
In the formula (1-2), R 21 represents a 1-valent group containing a terminal ethylenically unsaturated group. R 21 is exemplified by the same group as R 11 in the formula (1-1), and the preferable embodiments are also the same.
In the formula (1-2), R 22 represents a 1-valent organic group having 1 to 30 carbon atoms and containing no terminal ethylenically unsaturated group. R 22 is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms, which does not contain a terminal ethylenically unsaturated group. These groups may optionally have a substituent. As the substituent, a hydroxyl group can be exemplified.
The aliphatic hydrocarbon group may be either a straight chain or branched chain, and may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. When R 22 is an unsaturated aliphatic hydrocarbon group, R 22 does not contain a terminal ethylenically unsaturated group. The aliphatic hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 28 carbon atoms, more preferably 1 to 26 carbon atoms, and even more preferably 1 to 24 carbon atoms. The aliphatic hydrocarbon group is optionally further substituted with an alicyclic hydrocarbon group or an aromatic hydrocarbon group.
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 even 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 even 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.
The number of carbon atoms of the whole R 22 is 1 to 30.
R 22 is preferably an organic acid residue formed from a monobasic acid, and specifically, examples thereof include groups obtained by removing carboxyl groups 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, a group having a carboxyl group removed from an organic acid selected from the group consisting of abietic acid, versatic acid, and naphthenic acid is preferable, and a group having a carboxyl group removed from an organic acid selected from the group consisting of abietic acid and versatic acid is more preferable.
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) (monomer (a 1-2)). Examples of the monomer (a 1-2) include polymerizable compounds selected from zinc 3- (meth) acryloyloxy propionate (abietic acid), zinc 3- (meth) acryloyloxy propionate (versatic acid), zinc (meth) acrylate (abietic acid), zinc (meth) acrylate (versatic acid), zinc (meth) acrylate (naphthenic acid), copper 3- (meth) acryloyloxy propionate (abietic acid), copper 3- (meth) acryloyloxy propionate (versatic acid), copper (meth) acrylate (abietic acid), copper (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 ') and a polymer (A2'), the polymer (A1 ') having a structural unit derived from a polymerizable compound represented by the following formula (1-1'), and the polymer (A2 ') having a structural unit derived from a polymerizable compound represented by the following formula (1-2'). The polymer (A1) is preferably a polymer (A1 '), and the polymer (A2) is preferably a polymer (A2'). The hydrolyzable polymer (A) may have both a structural unit derived from a polymerizable compound represented by the following formula (1-1 ') and a structural unit derived from a polymerizable compound represented by the following formula (1-2').
[ Chemical 9]
(In the formula (1-1'), R 12 each independently represents a hydrogen atom or a methyl group, and M represents copper or zinc.)
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).
[ Chemical 10]
(In the formula (1-2'), R 23 represents a hydrogen atom or a methyl group, R 24 represents a 1-valent organic group having 1 to 30 carbon atoms and containing no terminal ethylenically unsaturated group, and M represents copper or zinc.)
In the formula (1-2'), R 24 is exemplified as the same group as R 22 in the above formula (1-2), and the preferable embodiment is the same.
Examples of the polymerizable compound represented by the above 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 (a 1), in the total structural units in the hydrolyzable polymer (a) is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, still more preferably 35% by mass or less.
The ratio of the respective contents (masses) 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 amounts (masses) of the respective monomers used in the polymerization reaction.
The hydrolyzable polymer (a) preferably has a structural unit based on another monomer (a 2) in addition to the structural unit containing a metal ester group.
The other monomer (a 2) is preferably a monomer having an ethylenically unsaturated group, and specifically, examples thereof include (meth) alkyl acrylate or (meth) aryl acrylate 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-trimethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate and the like;
(meth) acrylic acid alkoxyalkyl esters 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, isobutoxybutyldiethylene glycol (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, or arylpolyalkylene glycol (meth) acrylate;
Hydroxy alkyl (meth) acrylates or hydroxy aryloxyalkyl (meth) acrylates such as hydroxy methyl (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) acrylic esters containing organosiloxane groups;
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 singly or in combination of two or more.
Among them, alkyl (meth) acrylates (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, still more preferably 1 or more and 6 or less, still more preferably 1 or more and 4 or less), alkoxyalkyl (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, still more preferably 1 or more and 6 or less, still more preferably 1 or more and 4 or less), and hydroxyalkyl (meth) acrylates (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, still more preferably 1 or more and 6 or less, still more preferably 1 or more and 4 or less).
From the viewpoints of good coating film physical properties and imparting moderate water resistance to the antifouling coating film, the monomer (a 2) preferably contains at least an alkyl (meth) acrylate, and the content of the alkyl (meth) acrylate in the monomer (a 2) is preferably 50 mass% or more, more preferably 70 mass% or more, and still more preferably 90 mass% or more.
The content of the structural unit derived from the monomer (a 2) in the hydrolyzable polymer (a) is preferably 40 mass% or more, more preferably 50 mass% or more, still more preferably 60 mass% or more, still more preferably 65 mass% or more, and further preferably 99 mass% or less, more preferably 95 mass% or less, still more preferably 90 mass% or less, and still more preferably 85 mass% or less, of all the structural units, from the viewpoints of the durability of the antifouling coating film to be consumed and the water resistance.
The hydrolyzable polymer (a) can be produced, for example, by the following steps.
The monomer (a 1) can be synthesized by a known method such as heating and stirring a metal compound (preferably an inorganic metal compound, specifically, an oxide, hydroxide, chloride, organic acid salt (for example, zinc acetate or the like) of copper or zinc), an organic acid such as acrylic acid or methacrylic acid, or an ester thereof in the presence of an organic solvent and water at a temperature of not higher than the decomposition temperature of the metal salt.
More specifically, first, a mixed solution of a solvent and a metal component such as zinc oxide is heated to about 50 ℃ to 80 ℃ and stirred, 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 stirred, thereby preparing a metal ester group-containing monomer (a 1).
Then, the solvent is added to a newly prepared reaction vessel, and then heated to 80℃or more and 120℃or less, and a mixture of the metal ester group-containing monomer (a 1), the other monomer (a 2), a polymerization initiator, a chain transfer agent, a solvent and the like is added dropwise thereto, whereby a metal ester group-containing hydrolyzable polymer (A) can be obtained.
The ratio of the respective contents (masses) 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 amounts (masses) of the respective monomers used in the polymerization reaction.
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, t-butyl hydroperoxide, potassium persulfate, sodium persulfate, 2' -azobisisobutyronitrile [ AIBN ], 2' -azobis (2-methylbutyronitrile) [ AMBN ], 2' -azobis (2, 4-dimethylvaleronitrile) [ ADVN ], t-butyl peroxyoctoate [ TBPO ] and the like can be mentioned. 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 hydrolyzable polymer (a) is preferably 2 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the total of the monomers.
The chain transfer agent that can be used for producing the hydrolyzable polymer (a) is not particularly limited, and examples thereof include α -methylstyrene dimer, thioglycolic acid, diterpene, terpinolene, and γ -terpinene; thiols such as t-dodecyl mercaptan and n-dodecyl mercaptan; halogenated compounds such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane and the like; secondary alcohols such as isopropyl alcohol; glycerol, and the like. These chain transfer agents may be used alone or in combination of two or more.
When the 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 relative 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, dipropylene glycol monomethyl ether, and the like; 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 singly or in combination of two or more.
In the case of using the solvent in the production of the hydrolyzable polymer (a), the amount of the solvent to be used 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 thereto, and a method may be employed in which the polymer (a 3) having a carboxyl group, a monocarboxylic acid compound (D) described later, and a metal compound (preferably an inorganic metal compound, specifically, an oxide, hydroxide, chloride, organic acid salt (for example, zinc acetate, etc.) of copper or zinc are reacted with each other to introduce a metal ester group into the carboxyl group of the polymer (a 3); or reacting the polymer (a 3) having a carboxyl group with a metal compound to introduce a metal ester crosslink into the polymer.
Examples of the polymer (a 3) having a carboxyl group include a polyester polymer (a 3-1) and an acrylic polymer (a 3-2), and the polyester polymer (a 3-1) is preferable.
As the polyester polymer (a 3-1), a polyester resin having an acid group can be exemplified.
The solid content acid value of the polyester polymer (a 3-1) is preferably 30mgKOH/g or more, more preferably 50mgKOH/g or more, and further preferably 250mgKOH/g or less, more preferably 200mgKOH/g or less.
The polyester polymer (a 3-1) can be obtained by the reaction of 1 or more polyhydric alcohols with 1 or more 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 using a combination thereof.
As the polyester polymer (a 3-1), there can be suitably exemplified a polymer obtained by reacting a 3-or more alcohol (a 3-11) with a dibasic acid and/or its acid anhydride (a 3-12) with a 2-membered alcohol (a 3-13) and then reacting an alicyclic dibasic acid and/or its acid anhydride (a 3-14) as described in International publication No. 2014/010702.
As described above, the hydrolyzable polymer (a) may be produced by a method in which the polyester polymer (a 3-1) is reacted with the monocarboxylic acid compound (D) and the metal compound, or by a method in which the polyester polymer (a 3-1) is reacted with the metal compound.
As the monocarboxylic acid compound (D) which reacts with the polyester polymer (a 3-1), a monocarboxylic acid compound described below can be used, and among them, rosin is preferably used, and as the metal compound, for example, a metal oxide such as zinc oxide or copper oxide can be used, and among them, zinc oxide is preferably used.
Examples of the acrylic polymer (a 3-2) include carboxyl group-containing acrylic polymers (a 3-2) obtained by radical polymerization using an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, 3- (meth) acryloxypropionic acid, 3- (meth) acryloxy2-methylpropanoic acid, and other monomers (a 2) as needed as polymerizable compounds (monomers).
The hydrolyzable polymer (a) may be produced by a method of reacting the acrylic polymer (a 3-2) with a monocarboxylic acid compound (D) and a metal compound (preferably an inorganic metal compound, specifically, an oxide, hydroxide, chloride, organic acid salt of copper or zinc (for example, zinc acetate or the like) or a method of reacting the acrylic polymer (a 3-2) with a metal compound, in the same manner as the polyester polymer (a 3-1).
The content of copper and/or zinc in the hydrolyzable polymer (a) is preferably 0.5 mass% or more and 25 mass% or less, more preferably 1 mass% or more and 20 mass% or less, still more preferably 1 mass% or more and 10 mass% or less, and still more preferably 1.5 mass% or more and 5 mass% or less, from the viewpoint of forming an antifouling coating film excellent in coating film renewability and antifouling property. The copper and/or zinc content can be measured by an X-ray diffraction apparatus or an ICP emission analyzer, and can be appropriately adjusted by the amount of the monomer to be blended 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 resulting antifouling coating film in water to a desired range.
When the acid value is 30mgKOH/g or more, the metal content in the hydrolyzable polymer (A) is suitable, and an antifouling coating film excellent in antifouling property can be obtained, which is preferable. In addition, when the acid value is 250mgKOH/g or less, an antifouling coating film excellent in long-term antifouling property and coating film physical properties can be obtained, and it is preferable from the viewpoint of being able to obtain an antifouling coating film.
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, storage stability, dissolution rate (film renewability) of the resulting antifouling coating film, and the like of the antifouling coating composition.
The number average molecular weight (Mn) of the hydrolyzable polymer (a) is preferably 500 or more, more preferably 700 or more, further preferably 100000 or less, more preferably 10000 or less, 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 obtained by measurement by gel permeation chromatography and conversion by standard polystyrene.
The hydrolyzable polymer (A) may be used alone or in combination of two or more.
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, still more preferably 10% by mass or more, and further preferably 50% by mass or less, more preferably 35% by mass or less, still more preferably 25% by mass or less, in view of the paint workability of the present composition, the durability of the formed antifouling coating film, and the excellent water resistance of the obtained antifouling coating film. 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, still more preferably 15% by mass or more, and further preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less.
In the present invention, when the content of the hydrolyzable polymer (a) is 2 or more, the content is a preferable range as the total content of the hydrolyzable polymer (a), and the same applies to the respective components described later.
In the present invention, the hydrolyzable resin may contain other conventionally known hydrolyzable resins in addition to the above-mentioned hydrolyzable polymer (a). The other hydrolyzable resin is not particularly limited as long as it is a resin other than the hydrolyzable polymer (a) having a hydrolyzable group that undergoes a hydrolysis reaction in water, and examples thereof include silyl ester-based hydrolyzable polymers.
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, further preferably 90% by mass or more, and may be 100% by mass, further preferably 100% by mass, from the viewpoint of excellent discoloration resistance and high antifouling property can be maintained for a long period of time.
< Zinc phosphate (B) >)
Examples of the zinc phosphate (B) include zinc phosphate, zinc polyphosphate, zinc pyrophosphate, and zinc metaphosphate, and 1 or two or more of them may be used singly.
The zinc phosphate is generally present in the form of an anhydride or tetrahydrate, and any of these can be used as desired without affecting the properties, discoloration resistance, and antifouling properties of the resulting antifouling coating film.
Among them, as the zinc phosphate (B), zinc phosphate (anhydrate) 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, still more preferably 1 μm or more, and further preferably 40 μm or less, more preferably 20 μm or less, still more preferably 10 μm or less, from the viewpoint of improving dispersibility in the present composition and improving the antifouling property of the resulting 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 zinc phosphate (B) is not particularly limited, and various shapes such as spherical, elliptical, and amorphous zinc phosphate (B) can be used.
< Zinc oxide (C) >)
The composition contains zinc oxide (C).
The average particle diameter (median diameter) of zinc oxide is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and further preferably 30 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, from the viewpoint of improving dispersibility in the present composition and improving the antifouling property of the resulting antifouling coating film.
The mass ratio (B: C) of the zinc phosphate (B) and zinc oxide (C) in the composition is 20:80 or more, preferably 23:77 or more, more preferably 25:75 or more, still more preferably 30:70 or more, still more preferably 35:65 or more, and further preferably 75:25 or less, preferably 70:30 or less, still more preferably 65:35 or less, and further preferably 60:40 or less, in terms of obtaining an antifouling coating film excellent in discoloration resistance, maintaining high antifouling property for a long period of time, and having good coating film properties. In the present invention, the content of zinc phosphate (B) refers to the content of zinc phosphate anhydride.
The above effects are not a simple combination of the effects of each of the hydrolyzable polymer (a), zinc phosphate (B), and zinc oxide (C), but the effects produced for the first time when they are used together.
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, still more preferably 45% by mass or more, and further preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less, still more preferably 55% by mass or less. The content of zinc phosphate (B) is as described above, and is the content in terms of zinc phosphate anhydride.
If the total content of zinc phosphate (B) and zinc oxide (C) in the solid content of the coating composition is less than the above range, the drying property and the coating film strength of the formed antifouling coating film tend to be lowered. On the other hand, if the content is larger than the above range, the workability tends to be lowered with an increase in the viscosity of the coating composition, and further, there is a case where a problem of poor coating physical properties such as cracks is generated in the formed antifouling coating film.
< Other optional ingredients >
The composition may further contain, in addition to the above-mentioned components, a monocarboxylic acid compound (D), an organic antifouling agent (E), an inorganic copper compound (F), other binder component (G), pigment (H), solvent (I), anti-sagging/anti-settling agent (J), pigment dispersant (K), plasticizer (L), dehydrating agent (M), and the like, as required.
The other optional components will be described below.
[ Monocarboxylic acid Compound (D) ]
The present composition may contain the monocarboxylic acid compound (D), and may be used alone or in combination of two or more.
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, thereby improving the antifouling property, and the antifouling coating film has a function of imparting moderate water resistance.
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 substituted product thereof.
Specifically, abietic acid, neoabietic acid, dehydroabietic acid, palustric acid, isopimaric acid, pimaric acid, trimethylisobutenyl cyclohexene carboxylic acid, versatic acid, stearic acid, naphthenic acid, salicylic acid, and the like can be mentioned. In addition, rosin containing abietic acid, palustric acid, isopimaric acid, and the like as main components is also preferable, and examples of the rosin include rosin such as gum rosin, wood rosin, and tall oil rosin, rosin derivatives such as hydrogenated rosin, disproportionated rosin, and rosin metal salt, and pine tar, and the like.
Examples of the trimethylisobutenyl cyclohexene carboxylic acid include a reaction product of 2, 6-dimethyl-2, 6-octatriene and methacrylic acid, wherein the main component (85 mass% or more) 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 part or in whole. Examples of the metal ester include zinc ester and copper ester, which may be formed in advance before the preparation of the coating composition, or may be formed by a reaction with other components during the preparation of the coating composition.
The monocarboxylic acid compound (D) is sometimes considered to be a hydrolyzable polymer (a) in some cases.
From the viewpoint of further improving the coating workability and the antifouling property, the monocarboxylic acid compound (D) is preferably contained, but if the content is large, there arises a problem that the discoloration resistance of the formed coating film is lowered and the coating film consumption becomes too high, so that 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 further preferably 3 mass% or less. The present composition may not contain the monocarboxylic acid compound (D), but in the case of containing the monocarboxylic acid compound (D), the content thereof is preferably 0.1 mass% or more, more preferably 0.3 mass% or more, and still more preferably 0.5 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 present composition, the present composition preferably further contains an organic antifouling agent (E). Examples of the organic stain-proofing agent (E) include pyrithione metals 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: trolby), pyridine triphenylborane, 4-isopropylpyridine diphenylmethylborane, N-dimethyl-N '- (3, 4-dichlorophenyl) urea (alias: diuron), N- (2, 4, 6-trichlorophenyl) maleimide, 2,4,5, 6-tetrachloro-m-phthalonitrile, 2-methylsulfanyl-4-tert-butylamino-6-cyclopropylamino-1, 3, 5-triazine (alias: cybutryne), bis (dimethyldithiocarbamate) zinc (N' -dicarboxyl) and N '-dicarboxyl-sulfamide (alias: N-methylsulfonylmethyl) sulfide (N' -dicarboxamide) and N '-dicarboxyl-sulfan-methylol (alias: N' -methylsulfonylmethyl) sulfide (N '-sulfan-methyl) sulfide (N' -sulfanyl) and N '-dicarboxyl sulfide (N' -methyl sulfide), zinc dimethyldithiocarbamate (alias: zinc feret), ethylene bis (zinc 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 or in combination of two or more.
The organic antifouling agent (E) in the present composition more preferably contains at least 1 selected from 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: trolbide), and still more preferably contains at least 1 selected from copper pyrithione, zinc pyrithione, medetomidine, trolbide.
The present composition further preferably contains at least 1 selected from copper pyrithione and zinc pyrithione, and particularly preferably contains copper pyrithione, as the organic antifouling agent (E). By containing at least 1 selected from copper pyrithione and zinc pyrithione, an antifouling coating film excellent in scratch resistance can be obtained. In particular, by containing copper pyrithione in the present composition, the formed antifouling coating film has low consumption 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 to be small, and an antifouling coating film having more excellent scratch resistance can be obtained, and therefore, copper pyrithione is preferably contained as the organic antifouling agent (E).
Copper pyrithione and zinc pyrithione are represented by the following formula (2).
[ Chemical 11]
(In the formula (2), R 3 each independently represents a hydrogen atom or an alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group, an alkoxy group or a halogenoalkyl group having 1 to 6 carbon atoms, and M is Cu or Zn.)
In formula (2), R 3 is preferably a hydrogen atom.
The organic antifouling agent (E) in the present composition preferably contains at least 1 selected from copper pyrithione and zinc pyrithione, and further contains an organic antifouling agent other than copper pyrithione and zinc pyrithione.
In the present composition, the content of the organic antifouling agent (E) is preferably 1% by mass or more and 50% by mass or less, more preferably 1.5% by mass or more and 45% by mass or less, and still more preferably 2% by mass or more and 40% by mass or less in terms of the balance between 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 an 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 (alias: rhodane copper), and copper nickel alloy (cupronickel).
In the present composition, the content of the inorganic copper compound (F) is preferably 10 mass% or less, more preferably 3 mass% or less, still more preferably 1 mass% or less, still more preferably 0.1 mass% or less, and particularly preferably no content 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 no cuprous oxide, tends to be discolored in advance by outdoor exposure, and the discoloration thereof is remarkable. On the other hand, the present composition can obtain sufficient antifouling properties even if it does not contain the inorganic copper compound (F), and thus can be suitably used as an antifouling paint composition containing no inorganic copper compound (F).
[ Other adhesive component (G) ]
The composition may contain a binder component (G) other than the hydrolyzable polymer (a) and the other hydrolyzable resin for the purpose of imparting water resistance, crack resistance, and strength to the formed antifouling coating film. These may be used singly or in combination of 1 kind or two or more kinds.
Examples of such binder components 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 rubber, polyurethane resins, epoxy resins, polyamide resins, vinyl resins (vinyl chloride-based copolymers, ethylene-vinyl acetate copolymers, etc.), polyvinyl alkyl ethers, chlorinated rubbers, styrene/butadiene copolymer resins, ketone resins, alkyd resins, indene resins, terpene phenolic resins, petroleum resins, and other water-insoluble or water-insoluble resins.
The chlorinated paraffin may have any molecular structure, linear or branched, and may be in a liquid state or a solid state (e.g., powder state) at room temperature (e.g., 23 ℃).
The average number of carbon atoms of the chlorinated paraffin is preferably 8 to 30, more preferably 10 to 26, in one molecule. The antifouling paint composition containing the chlorinated paraffin can form an antifouling coating film with less cracks (breakage), flaking 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 the average carbon number is 30 or less because the antifouling property is not suppressed.
In 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/cm 3, more preferably 1.10 to 1.70g/cm 3.
The chlorination rate (chlorine content) of the chlorinated paraffin is usually 35 to 70 parts by mass, preferably 35 to 65 parts by mass, based on 100 parts by mass of the chlorinated paraffin. An antifouling paint composition containing chlorinated paraffin having such a chlorination rate can form a coating film which is less likely to cause cracking (breakage), peeling, and the like. Specific examples of such chlorinated paraffin include "TOYOPARAX 150" and "TOYOPARAX A-70" (all manufactured by Tosoh Co., ltd.).
Further, examples of petroleum resins include C5-based, C9-based, styrene-based, dichloropentadiene-based, and hydrogenated products thereof. Specific examples of petroleum resins include "Quintone to 1500" and "Quintone to 1700" (all manufactured by ZEON corporation).
[ Pigment (H) ]
The present composition may contain a pigment (H) other than the above zinc phosphate (B) and zinc oxide (C). The antifouling paint composition of the present invention may contain a coloring pigment (H1) in terms of adjusting the color tone of the formed antifouling paint film and imparting an arbitrary color tone, and may contain an extender pigment (H2) for the purpose of improving the physical properties of the obtained antifouling paint film such as water resistance and crack resistance.
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, iron oxide red (red iron oxide), barite powder, titanium white, and yellow iron oxide. The coloring pigment (H1) may be used alone or in combination of two or more.
In addition, the antifouling paint composition of the present invention may contain a coloring agent other than a coloring pigment such as a dye together with the coloring pigment (H1) or in place of the coloring pigment (H1).
Examples of extender pigments (H2) include talc, silica, mica, clay, potassium feldspar, calcium carbonate, kaolin, alumina white, white carbon black, aluminum hydroxide, condensed aluminum phosphate, magnesium carbonate, barium carbonate, and barium sulfate. Among them, talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, potassium feldspar are preferable. The calcium carbonate and the white carbon black are also used as an anti-sagging agent, an anti-settling agent (J) and a matting agent, respectively, which will be described later. The extender pigment (H2) may be used alone or in combination of two or more.
In the present composition, the content of the pigment (H) 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 terms of improving the appearance, masking property, discoloration resistance, stain resistance, water resistance, and mechanical properties of the resulting stain-proofing coating film.
[ Solvent (I) ]
The composition may contain a solvent (I) such as water or an organic solvent as needed 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 present composition may contain, as the solvent (I), a solvent used in the preparation of the hydrolyzable polymer (a), or may contain a solvent which is 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 (about 2 to 5 carbon atoms) monohydric alcohols such as ethanol, isopropanol, n-butanol, isobutanol, propylene glycol monomethyl ether, and the like; ester solvents such as ethyl acetate and butyl acetate; etc. The solvent (I) may be used alone or in combination of two or more.
When the present composition contains the solvent (I), the content thereof can be determined in a preferable amount according to the desired viscosity corresponding to the application mode of the coating composition, and in the coating composition, it is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. If the content is too large, there are some cases where the sagging resistance is lowered.
[ Anti-sagging/anti-settling agent (J) ]
When the present composition is used to coat a substrate, an anti-sagging agent/anti-settling agent (J) may be contained from the viewpoints of reducing the occurrence of sagging caused by the coating composition, preventing the occurrence of precipitates during storage, and improving the stirring property.
Examples of the anti-sagging agent/anti-settling agent (J) include anti-sagging agents and anti-settling agents described in International publication No. 2018/003135, and the preferable ranges are the same, inclusive of the content.
[ Pigment dispersant (K) ]
When the present composition contains a pigment (H) such as a coloring 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 pigment dispersibility.
As the pigment dispersant (K), pigment dispersants described in International publication No. 2018/003135 are exemplified, and 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.
As the plasticizer (L), plasticizers described in International publication No. 2018/003135 can be exemplified, and preferable 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.
As the dehydrating agent (M), the dehydrating agent described in International publication No. 2018/003135 can be exemplified, and preferable ranges are the same, including the content.
[ Method for producing antifouling paint composition ]
The composition of the present invention can be prepared by using the same apparatus and method as those of the known general antifouling paint. For example, the aqueous dispersion can be produced by preparing the hydrolyzable polymer (a) in a solvent in advance, then adding the solution of the hydrolyzable polymer (a), zinc phosphate (B), zinc oxide (C), and other components (D) to (M) if necessary, and the like, at once or sequentially, and stirring and mixing them.
[ Antifouling coating film and substrate with antifouling coating film, process for producing the 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.
As a method of applying the antifouling paint composition of the present invention, known methods such as a method using a brush, a roller, and spraying can be mentioned.
The antifouling paint composition applied by the method described above is allowed to stand at 25℃for about 0.5 to 7 days, preferably about 0.5 to 5 days, more preferably about 0.5 to 3 days, and dried, for example, to obtain a coating film. In the drying of the coating composition, the air may be blown under heating.
The thickness of the dried antifouling coating film 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. Mu.m. As a method for producing a coating film of such thickness, there is a method of applying the coating composition 1 to more times, preferably 10 to 300 μm, more preferably 30 to 200 μm, per 1 application.
The substrate with an antifouling coating film of the present invention is covered with an antifouling coating film formed by the present composition, and the above-mentioned 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 may be used which has a 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 composition may be applied to the substrate by the coating method described above. In addition, the method of impregnation is not particularly limited, and may be performed by immersing the substrate in a coating composition in an amount sufficient for impregnation. The method for drying the coated body or the impregnated body is not particularly limited, and the coated body or the impregnated body may 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 forming a coating film by drying the present composition and the step (ii) of adhering the coating film to a substrate.
The method for forming the coating film in the step (i) is not particularly limited, and the coating film can be produced by the same method as that used in producing an antifouling coating film.
The method of attaching the coating film to the substrate in the step (ii) is not particularly limited, and for example, the method described in JP-A2013-129724 may be used for the attachment.
The antifouling method of the present invention uses an antifouling coating film formed by the present composition, and provides an antifouling coating film to various substrates to inhibit fouling of the substrates, specifically, to inhibit 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, fishery and underwater (marine) structures. Examples of such a base material include ships (large steel vessels such as container ships and tankers, fishing vessels, FRP vessels, wooden vessels, hull plates of yachts, new ships and repair vessels), fishery materials (ropes, nets, fishing gear, floats, buoys, etc.), and marine structures such as super-floating docks. Among them, the substrate is preferably selected from ships, underwater structures, and fishery materials, more preferably selected from ships and underwater structures, and still more preferably ships.
The substrate on which the present composition is formed may be a surface treated with another treating agent such as an anticorrosive agent, a surface on which some coating film such as a primer has been formed, a surface on which the present composition has been applied, or the like, and the type of coating film with which the antifouling coating film of the present invention is in direct contact is not particularly limited.
Examples
Hereinafter, the present invention will be described in further detail with reference to examples, but the present invention is not limited to the examples. Hereinafter, "parts" means parts by mass unless the gist is specifically violated.
[ Production of hydrolyzable Polymer (A) ]
In the production of the hydrolyzable polymer (A), first, the hydrolyzable group-containing monomers (a 1-1) and (a 1-2) are prepared as follows.
< Preparation example 1: preparation of hydrolyzable group-containing monomer (Metal ester group-containing monomer) (a 1-1)
85.4 Parts by mass of propylene glycol monomethyl ether and 40.7 parts by mass of zinc oxide were charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating/cooling jacket, 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 added dropwise from the dropping device at a constant rate of 3 hours. After the completion of the dropwise addition, the mixture was stirred for 2 hours, and then 36.0 parts by mass of propylene glycol monomethyl ether was added thereto to obtain a reaction solution containing a monomer having a hydrolyzable group (a monomer having a metal ester group) (a 1-1).
< Preparation example 2: preparation of hydrolyzable group-containing monomer (Metal ester group-containing monomer) (a 1-2)
72.4 Parts by mass of propylene glycol monomethyl ether and 40.7 parts by mass of zinc oxide were charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating/cooling jacket, and the temperature was raised to 75℃while stirring. Next, 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 added dropwise from the dropping apparatus at a constant rate of 3 hours. After the completion of the dropwise addition, the mixture was stirred for 2 hours, and then 11.0 parts by mass of propylene glycol monomethyl ether was added thereto to obtain a reaction solution containing a monomer having a hydrolyzable group (a monomer having a metal ester group) (a 1-2).
< Production example 1: production of solution (A-1) of hydrolyzable Polymer (copolymer containing Metal ester group)
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 into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating/cooling jacket, and the mixture was stirred and heated to 100.+ -. 5 ℃. 40.2 parts by mass of the reaction solution containing the metal ester group-containing monomer (a 1-1) 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 polymerization initiator 2,2 '-azobisisobutyronitrile, 6.5 parts by mass of polymerization initiator 2,2' -azobis (2-methylbutyronitrile), 1.2 parts by mass of chain transfer agent "Nofmer MSD" (manufactured by Japanese fat and oil Co., ltd.,. Alpha. -methylstyrene dimer), and 10.0 parts by mass of xylene were added dropwise from a dropping device into the reaction vessel over 6 hours while maintaining the same temperature. After completion of the dropwise addition, 0.5 part by mass of t-butyl peroctoate and 7.0 parts by mass of xylene as polymerization initiators were added dropwise over 30 minutes, followed by stirring for 1 hour and 30 minutes, and then 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 constitution 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 solution (A-2) of hydrolyzable Polymer (copolymer containing Metal ester group)
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 into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating/cooling jacket, and the mixture was stirred and heated to 100.+ -. 5 ℃. 52.0 parts by mass of the reaction solution containing the metal ester group-containing monomer (a 1-1) obtained in preparation example 1, 1.0 parts 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 polymerization initiator 2,2 '-azobisisobutyronitrile, 7.0 parts by mass of polymerization initiator 2,2' -azobis (2-methylbutyronitrile), 1.0 parts by mass of chain transfer agent "Nofmer MSD" (manufactured by Japanese fat and oil Co., ltd.,. Alpha. -methylstyrene dimer), and 10.0 parts by mass of xylene were added dropwise from a dropping device to the reaction vessel over 6 hours while maintaining the same temperature. After completion of the dropwise addition, 0.5 part by mass of t-butyl peroctoate (TBPO) and 7.0 parts by mass of xylene as polymerization initiators were added dropwise over 30 minutes, followed by stirring for 1 hour and 30 minutes, and then 4.4 parts by mass of xylene was added to prepare a pale yellow transparent hydrolyzable polymer solution (A-2) containing a hydrolyzable polymer (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.
< Manufacturing example 3: production of solution (A-3) of hydrolyzable Polymer (copolymer containing Metal ester group)
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 into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating/cooling jacket, and the mixture was stirred and heated to 100.+ -. 5 ℃. While maintaining the same temperature, 50.3 parts by mass of the reaction solution containing the metal ester group-containing monomer (a 1-2) obtained in preparation example 2, 9.0 parts by mass of methyl methacrylate, 58.0 parts by mass of ethyl acrylate, 5.0 parts by mass of 2,2' -azobis (2-methylbutyronitrile) as a polymerization initiator, and 10.0 parts by mass of propylene glycol monomethyl ether were added dropwise to the reaction vessel from a dropping device over 4 hours. After completion of the dropwise addition, 0.5 part by mass of t-butyl peroctoate and 7.0 parts by mass of xylene as polymerization initiators were added dropwise over 30 minutes, followed by stirring for 1 hour and 30 minutes, and then 12.0 parts by mass of xylene was added to prepare a pale yellow transparent hydrolyzable polymer solution (A-3) containing a hydrolyzable polymer (copolymer containing a metal ester group).
The constitution 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: preparation of solution (S-1) of hydrolyzable Polymer (silyl ester group-containing copolymer)
53 Parts of xylene was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube and a dropping funnel, and the xylene was stirred with the stirrer under a nitrogen atmosphere and heated at normal pressure until the temperature of the xylene in the reaction vessel became 85 ℃. While maintaining the temperature of xylene in the reaction vessel at 85 ℃, a monomer mixture formed of 50 parts by mass of tigma (triisopropylsilyl methacrylate), 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 into the reaction vessel using a dropping funnel for 2 hours.
Then, 0.5 parts by mass of t-butyl peroxyoctoate was further added to the reaction vessel, and the temperature of the liquid in the reaction vessel was kept at 85℃under normal pressure, and after stirring was continued for 2 hours with a stirrer, the temperature of the liquid in the reaction vessel was increased from 85℃to 110℃and heated for 1 hour, and then 14 parts by mass of xylene was added to the reaction vessel, and the temperature of the liquid in the reaction vessel was lowered, and stirring was stopped at a point when the temperature of the liquid reached 40℃to prepare a polymer solution containing a hydrolyzable polymer (S-1). The constitution 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 by an E-type viscometer (manufactured by DONGMACHINE Co., ltd.).
< Weight average molecular weight (Mw) and number average molecular weight (Mn) of hydrolyzable Polymer >
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the hydrolyzable polymer were measured using GPC (gel permeation chromatography) under the following conditions.
GPC conditions
The device comprises: "HLC-8120GPC" (manufactured by Tosoh Co., ltd.)
Chromatographic column: connection "TSKgeL SuperH2000" and "TSKgeL SuperH4000" (both manufactured by Tosoh Co., ltd., inner diameter 6 mm/length 15 cm)
Eluent: tetrahydrofuran (THF)
Flow rate: 0.500ml/min
A detector: RI (RI)
Chromatographic column oven temperature: 40 DEG C
Standard substance: polystyrene
Sample preparation method: a small amount of calcium chloride was added to the polymer solutions prepared in the respective production examples, and the polymer solutions were dehydrated, and then, the polymer solutions were filtered by a membrane filter, and the obtained filter residues were used as GPC measurement samples.
< Solid content >
In the present invention, the solid component refers to a heated residue obtained when a mixture, composition, or the like 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
The components used in examples and comparative examples are shown in Table 3.
The hydrolyzable polymer composition obtained in the above production example, zinc oxide (B), zinc phosphate (C), and other components were uniformly mixed at normal temperature using a paint stirrer (PAINT SHAKER) as shown in table 4 below (the numerical values in the table indicate parts by mass).
The amounts of the components shown in table 4 are amounts of the components in terms of a solution or a dispersion for the components having solid contents, and amounts of the components (excluding a solvent) having no solid contents are amounts of the components in terms of solid contents.
TABLE 3
TABLE 3 Table 3
< Evaluation >
The following evaluation was performed on the obtained antifouling paint composition.
[ Outdoor exposure discoloration test ]
An epoxy anticorrosive paint (trade name "BANNO" manufactured by chinese paint co., ltd.) was coated on a 70×200×3mm sand blast plate so that the dry film thickness was about 150 μm, and then an epoxy adhesive paint (trade name "BANNO 500N", manufactured by chinese paint co., ltd.) was coated thereon so that the dry film thickness was about 100 μm. The antifouling paint compositions of the examples and comparative examples were further applied 1 time so that the dry film thickness was about 150. Mu.m, and dried at room temperature for 7 days, to prepare respective test pieces. The coating interval of each coating was set to 1day/1coat.
An outdoor exposure stand (according to JIS K5600-7-6) provided in a place of China coating corporation in Daphne, guangshi county was provided so as to be 45℃to the horizontal and so as to expose the coated surface. The outdoor exposure was carried out for 3 months, and the color difference (ΔE value) between the initial coating film and the coating film after the outdoor exposure was measured under the conditions of a C light source and a field of view of 2℃every 1 month using a spectrocolorimeter "CM-3700A" (manufactured by Konikoku Mida Co., ltd.). The Δe value was calculated as an average value of 10 points randomly measured at a position separated by 1cm or more from the end of each test piece.
The Δe is calculated from the value of L *、a*、b* obtained by a spectrocolorimeter using the following formula.
ΔE＝{(L* 1-L* 0)2+(a* 1-a* 0)2+(b* 1-b* 0)2}1/2
Here, L * 1、a* 1、b* 1 represents L *、a*、b*,L* 0、a* 0、b* 0 after outdoor exposure, respectively, and L *、a*、b* of the initial coating film, respectively.
[ Test of stain resistance by standing ]
An epoxy anticorrosive paint (epoxy AC paint, trade name "BANNO 500", manufactured by chinese paint co., ltd.) was coated on the sand blast treated steel sheet (vertical 300mm x horizontal 100mm x thickness 3.2 mm) so that the dry film thickness was about 150 μm, and then an epoxy adhesive paint (trade name "BANNO 500N", manufactured by chinese paint co., ltd.) was coated thereon so that the dry film thickness was about 100 μm. The antifouling paint compositions of the above examples and comparative examples were further applied thereto 1 time so that the dry film thickness thereof was about 100. Mu.m, and dried at room temperature for 7 days, thereby producing a test plate with a stationary antifouling coating film. The number of the above-mentioned 3 applications was 1daV/1coat.
The test plate prepared as described above was immersed in the Guangdong of Guangdong county for 6 months while standing vertically so that the water depth became 1.5 m, and the adhesion area (%) of marine organisms to the surface of the antifouling coating film was measured every 1 month. Thereafter, the static antifouling property of the antifouling coating film was evaluated in accordance with the following evaluation criteria.
Evaluation criterion for static antifouling properties based on the adhesion area 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%
[ Table 4-1]
TABLE 4-1
[ Table 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 for 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 greater than 75:25, although zinc phosphate (B) and zinc oxide (C) were used in combination, 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) was less than 20:80, discoloration by outdoor exposure was remarkable.
In comparative examples 3 to 5, which did not contain zinc phosphate, discoloration was remarkable, and sufficient long-term antifouling properties could not be obtained.
In comparative examples 6 and 7 in which a silyl ester group-containing hydrolyzable polymer was used as the hydrolyzable polymer, sufficient antifouling property and discoloration resistance could not be obtained even when zinc (B) phosphate and zinc (C) oxide were contained in a mass ratio of 20:80 to 75:25.
Industrial applicability
According to the present composition, an antifouling coating film having excellent discoloration resistance and maintaining high antifouling properties can be obtained. The antifouling paint of the present invention can be used in a wide range of industrial fields such as ships, fishery, marine structures, etc., and is particularly suitable for use as an antifouling paint composition for ships.

Claims (11)

1. An antifouling coating composition comprising:
a metal ester group-containing hydrolyzable polymer A,
Zinc phosphate B, and
The zinc oxide C is added to the mixture,
The content of the hydrolyzable polymer A in the hydrolyzable resin is 90% by mass or more,
The mass ratio of the zinc phosphate B to the zinc oxide C is as follows: c is 20: 80-75: 25,
The total content of zinc phosphate B and zinc oxide C in the solid component of the antifouling paint composition is 30% by mass or more and 55% by mass or less,
The content of the monocarboxylic acid compound D in the solid content of the antifouling paint composition is 5% by mass or less.
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 position.
3. An antifouling paint composition according to claim 1, wherein,
The hydrolyzable polymer A contains at least one 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),
The polymer A2 has a structural unit derived from a polymerizable compound represented by the following formula (1-2),
In the formula (1-1), R 11 each independently represents a 1-valent group containing a terminal ethylenically unsaturated group, M represents copper or zinc,
In the formula (1-2), R 21 represents a 1-valent group containing a terminal ethylenically unsaturated group, R 22 represents a 1-valent organic group having 1 to 30 carbon atoms and containing no terminal ethylenically unsaturated group, and M represents copper or zinc.
4. An antifouling paint composition according to claim 1, wherein,
The hydrolyzable polymer A contains at least one 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'),
The polymer A2 'has a structural unit derived from a polymerizable compound represented by the following formula (1-2'),
In the formula (1-1'), R 12 each independently represents a hydrogen atom or a methyl group, M represents copper or zinc,
In the formula (1-2'), R 23 represents a hydrogen atom or a methyl group, R 24 represents a 1-valent organic group having 1 to 30 carbon atoms and not containing a terminal ethylenically unsaturated group, and M represents copper or zinc.
5. An antifouling paint composition according to claim 1, wherein,
And also contains an organic antifouling agent E.
6. An antifouling paint composition according to claim 1, wherein,
The content of the inorganic copper compound F in the solid content of the antifouling paint composition is 10% by mass or less.
7. An antifouling coating film formed from the antifouling paint composition according to any one of claims 1 to 6.
8. A substrate with an antifouling coating film, which is covered with the antifouling coating film of claim 7.
9. The substrate with an antifouling coating film as claimed in claim 8, wherein,
The substrate is selected from the group consisting of ships, underwater structures, and fishery materials.
10. A method for producing a substrate with an antifouling coating film, comprising:
A step (I) of applying or impregnating the antifouling paint composition according to any of claims 1 to 6 to a substrate to obtain a coated body or an impregnated body, and
And (II) drying the coated body or impregnated body.
11. A method for producing a substrate with an antifouling coating film, comprising:
A step (i) of drying the antifouling paint composition according to any of claims 1 to 6 to form an antifouling coating film, and
And (ii) a step of adhering the antifouling coating film to a substrate.
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