JP2021518475A - Composition - Google Patents

Abstract

The present invention reacts with (i) an acrylic acetal ester copolymer; (ii) either a zinc salt of a monocarboxylic acid or (ii) a monocarboxylic acid; and (iii) a monocarboxylic acid to form a monocarboxylic acid salt. The present invention relates to an antifouling coating composition containing a zinc compound.

Description

The present invention relates to an antifouling coating composition comprising an acrylic acetal ester copolymer and a zinc salt of a monocarboxylic acid. The present invention also relates to an antifouling coating composition comprising an acrylic acetal ester copolymer, a monocarboxylic acid and a zinc compound that reacts with the monocarboxylic acid to form a zinc salt of the monocarboxylic acid. The present invention also relates to a method for preparing the composition, a paint containing the composition, a paint container containing the composition, and a kit for preparing the paint. In addition, the present invention is to prevent fouling of the surface of an article, including coating at least a portion of the surface of the article with a coating, and coating at least a portion of the surface of the article with the composition. Regarding how to coat an article.

Surfaces submerged in seawater are polluted by marine organisms such as green and brown algae, barnacles, mussels and tubeworms. In marine structures such as ships (ships, tankers), oil platforms and buoys, such fouling is undesirable and of economic significance. Staining can lead to surface biodegradation, increased loading and accelerated corrosion. In ships, fouling increases frictional resistance, which causes reduced speed and / or increased fuel consumption.

Antifouling paints are used to prevent the sticking and growth of marine organisms. Currently, some of the most successful paints on the market are self-polishing antifouling paints based on hydrolyzable acrylic polymers as binders. There are two major self-polishing techniques, the silyl acrylate copolymer and the metal acrylate copolymer, of which the silyl acrylate copolymer is the most successful. When these copolymers are present in an antifouling coating composition with an antifouling agent, the composition efficiently dries to produce an antifouling coating or coating that produces a film with the desired hardness level. The coating also exhibits a constant rate of decomposition, once in contact with seawater, resulting in a controlled release of antifouling agent from the coating over time. Sometimes the controlled release is referred to as the controlled polishing rate over time.

A third type of copolymer that has been developed as a hydrolyzable binder is the (meth) acrylic acetal ester copolymer. These copolymers are of interest because they are cheaper than silyl ester copolymers and are made from sustainable monomers. However, a significant drawback facing the use of (meth) acrylic acetal ester copolymers in self-polishing antifouling coating compositions and coatings is that they tend to be bulk hydrolyzed. This is evident in slow and controlled initial polishing rates, followed by loss of coating integrity and relatively short-term disintegration. This severely limits the commercial use of this type of self-polishing paint, as antifouling paints need to last 1 to 10 years depending on the application.

A challenge faced by the paint industry is the production of antifouling coating compositions and paints that dry efficiently to produce the appropriate hardness of the coating or film. It is also highly desirable for coatings or films that exhibit a controlled degradation rate over a long period of time, eg, up to 5 years, once in contact with seawater. It is also clearly important that the compositions and paints can be applied by standard techniques, such as airless spraying, which has a constant viscosity level while minimizing the content of their volatile organic compounds. Means compositions and paints that further achieve good application properties.

From the first aspect, the present invention
Provided are an antifouling coating composition comprising (i) an acrylic acetal ester copolymer; and (ii) a zinc salt of a monocarboxylic acid.

From a further aspect, the present invention
(I) Acrylic acetal ester copolymer;
Provided are an antifouling coating composition comprising (ii) a monocarboxylic acid; and (iii) a zinc compound that reacts with the monocarboxylic acid to form a zinc salt of the monocarboxylic acid.

From a further aspect, the present invention
Provided are methods for preparing the compositions defined above, comprising (i) mixing an acrylic acetal ester copolymer; and (ii) a zinc salt of a monocarboxylic acid.

From a further aspect, the present invention
(I) Acrylic acetal ester copolymer;
A method for preparing the compositions defined above, comprising mixing (iii) a monocarboxylic acid; and (iii) a zinc compound that reacts with the monocarboxylic acid to form a zinc salt of the monocarboxylic acid. offer.

In view of a further aspect, the present invention provides paints comprising the compositions described above.

In a further aspect, the invention provides a paint container containing the compositions described above.

From a further aspect, the present invention
(I) A first container containing an acrylic acetal ester copolymer and optionally a stabilizer and / or dehydrating agent;
(Iii) A second container containing a zinc salt of monocarboxylic acid and optionally a dehydrating agent; and (iv) optionally an instruction to mix the contents of the first and second containers. , Provide kits for preparing the paints described above.

From a further aspect, the present invention
(I) A first container containing an acrylic acetal ester copolymer and optionally a stabilizer and / or dehydrating agent;
(Ii) A second container containing a monocarboxylic acid, a zinc compound that reacts with the monocarboxylic acid to form a zinc salt of the monocarboxylic acid, and optionally a dehydrating agent; and (iii) optionally the first. And a kit for preparing the paint described above, including instructions for mixing the contents of the second container.

In a further aspect, the invention provides an article comprising (eg, coated or coated) a coating containing the composition described above on at least a portion of the surface of the article.

From a further aspect, the present invention
A method of coating an article to prevent fouling of the article, including coating at least a portion of the surface of the article with the composition described above; and drying and / or curing the coating. offer.

In a further aspect, the invention provides the use of the compositions described above to coat at least a portion of the surface of an article to prevent its fouling.

Definitions As used herein, the term "antifouling coating composition" refers to a composition that, when applied to a surface, prevents or minimizes the growth of marine organisms on the surface.

As used herein, the term "paint" is a composition comprising an antifouling coating composition as described herein, and optionally a solvent ready for use, eg, spraying. Say something. Thus, the antifouling coating composition may itself be a paint, or the antifouling coating composition may be a concentrate to which a solvent is added to give rise to the paint.

As used herein, the term "acrylic acetal ester copolymer" refers to a polymer containing repeating units derived from the hemiacetal and hemicetal esters of (meth) acrylic acid. The repeating unit contains a − (CO) -OCR ″ R ″ O— group, where R ′ is H or alkyl and R ″ is alkyl. Thus, the term covers polymers containing repeating units derived from methacrylate acetal ester monomers and acrylate acetal ester monomers. As used herein, the term "acetal ester" includes both hemiacetal and hemicetal esters.

The term "acrylic polymer" refers to polymers and copolymers based on acrylic acids, methacrylic acids, esters of acrylic acids, esters of methacrylic acids, and mixtures thereof in the case of copolymers.

As used herein, the term "(meth) acrylate" refers to either acrylate or methacrylate; the term "(meth) acrylic" refers to either acrylic or methacrylic.

As used herein, the term "alkyl" refers to a saturated, linear, branched or cyclic group. The alkyl group may or may not be substituted.

As used herein, the term "cycloalkyl" refers to a saturated or partially saturated alkyl ring system containing 3 to 10 monocyclic or bicyclic carbon atoms. The cycloalkyl group may or may not be substituted.

As used herein, the term "alkylene" refers to a divalent alkyl group.

As used herein, the term "aryl" refers to a group containing at least one aromatic ring. The term aryl includes heteroaryls as well as fused ring systems in which one or more aromatic rings are fused to a cycloalkyl ring. Aryl groups may or may not be substituted. An example of an aryl group is phenyl, C ₆ H ₅ . The phenyl group may or may not be substituted.

As used herein, the term "heterocyclyl" refers to 3, 4, 5, 6, 7, 8, 9 or 10 rings of saturated (eg, heterocycloalkyl) or unsaturated (eg, heteroaryl). It has an atom and at least one of the ring atoms refers to a heterocyclic moiety selected from nitrogen, oxygen and sulfur.

As used herein, "substituted" means a hydrogen atom in one or more, eg, up to 6, more particularly 1, 2, 3, 4, 5 or 6 groups. , Independently of each other, refers to a group that has been replaced by a corresponding number of described substituents. The term "optionally replaced" means that, as used herein, it has been or has not been replaced.

As used herein, the term "monocarboxylic acid" refers to a compound containing one -COOH group.

As used herein, the term "resin acid" refers to a mixture of carboxylic acids present in a resin.

As used herein, the term "rosin" refers to rosin and derivatives of rosin.

As used herein, the term "reactive zinc compound" refers to a zinc-containing compound that reacts with a monocarboxylic acid to produce a zinc salt of the monocarboxylic acid. The reaction can be carried out during the production of the paint, during storage or during mixing prior to use.

As used herein, the term "zinc salt of monocarboxylic acid" refers to zinc carboxylate. Zinc salts of monocarboxylic acids, at least one, preferably two, zinc cations Zn ²⁺ binding or coordinating carboxylate - containing group ^(-COO).

As used herein, the term "stabilizer" refers to an acid scavenger. Stabilizers contribute to the storage stability of the compositions of the present invention.

As used herein, the term "carbodiimide" refers to a compound containing the functional group -N = C = N-.

As used herein, "dehydrating agent" refers to a water scavenger or desiccant that removes water from the composition.

As used herein, an "antifouling agent" prevents the adhesion of marine organisms to the surface, prevents the growth of marine organisms on the surface, and / or has marine presence from the surface. A compound or mixture of compounds that promotes the removal of the aircraft.

As used herein, the term "bulking agent" is used interchangeably with "filler" to refer to a compound that increases the volume or bulk of a coating composition.

As used herein, the term "molecular weight" refers to weight average molecular weight (Mw) unless otherwise stated.

As used herein, the term "PDI" or polydispersity index refers to Mw / Mn, where Mn refers to the number average molecular weight.

As used herein, the term "volatile organic compound (VOC)" refers to a compound having a boiling point of 250 ° C. or lower at an atmospheric pressure of 101.3 kPa.

As used herein, the term "wt% based on the total mass of the composition" refers to the wt% of the components present in the final ready-to-use composition, unless otherwise stated. say.

Detailed Description of the Invention The present invention
(I) Acrylic acetal ester copolymer; and (ii) Zinc salt of monocarboxylic acid; or (i) Acrylic acetal ester copolymer;
The present invention relates to an antifouling coating composition comprising (ii) a monocarboxylic acid; and (iii) a zinc compound that reacts with the monocarboxylic acid to form a zinc salt of the monocarboxylic acid.

Optionally, the composition is one or more (iv) antifouling agents; (v) pigments and / or bulking agents; (vi) cobinders; (vi) solvents; (viii) stabilizer compounds. It further comprises (ix) dehydrating agent and / or (x) additive.

In the antifouling coating composition of the present invention, the combination of the acrylic acetal ester copolymer with the zinc salt of the monocarboxylic acid advantageously provides a composition that dries relatively rapidly to form a hard coating or film. .. The zinc salt of a monocarboxylic acid can be in situ formed from a zinc compound that is present in the initial composition or reacts with the monocarboxylic acid and the monocarboxylic acid to form the zinc salt of the monocarboxylic acid. .. The coatings formed from the compositions of the present invention are also polished for long periods of time, eg 1-10 years, at a controlled, eg, substantially linear decomposition rate. This means that the coating provides a controlled release of antifouling agent for a long period of time, eg 1-10 years.

Acrylic acetal ester copolymer The acrylic acetal ester polymer present in the antifouling coating composition of the present invention is a copolymer. Acrylic acetal ester copolymers preferably contain at least two (eg, two, three or four) different monomers, more preferably two or three different monomers. The different monomers may be different (meth) acrylic acetal ester monomers or one type of (meth) acrylic acetal ester monomer, and another type of monomer, such as a (meth) acrylic acid ester monomer. Particularly preferred acrylic acetal ester copolymers present in the antifouling coating compositions of the present invention include at least one (meth) acrylic acetal ester monomer and at least one (meth) acrylic acid ester monomer.

の少なくとも１つのモノマーの残基を含み、式中、
Ｒ¹はＨ又はメチルであり；
Ｒ²はＨ又はＣ_1-4アルキル、好ましくはＨであり；
Ｒ³はＣ_1-4アルキルであり；及び
Ｒ⁴は任意選択で置換された直鎖又は分岐鎖のＣ_1-20アルキル、Ｃ_5-10シクロアルキル又はＣ_6-10アリールであるか；又は
Ｒ³及びＲ⁴は、それらが結合しているＯ原子とともに、任意選択で置換されたＣ_4-8員の環を形成している。 The preferred acrylic acetal ester copolymer present in the antifouling coating composition of the present invention is of formula (I):

Containing residues of at least one monomer of, in the formula,
R ¹ is H or methyl;
R ² is H or C _1-4 alkyl, preferably H;
R ³ is C _1-4 alkyl; and R ⁴ is optionally substituted linear or branched C _1-20 alkyl, C _5-10 cycloalkyl or C _6-10 aryl; or R ³ and R ⁴ _{form a C 4-8} membered ring optionally substituted with the O atom to which they are attached.

In the monomer of formula (I), when R ² is C _1-4 alkyl, R ² is preferably C _1-3 alkyl, more preferably C _1-2 alkyl. Even more preferably, when R ² is C _1-4 alkyl, R ² is selected from methyl, ethyl, n-propyl and i-propyl.

In the monomer of the preferred formula (I), R ² is methyl or H, particularly preferably H.

In some preferred monomers of formula (I), R ³ is C _1-4 alkyl, more preferably C _1-3 alkyl, even more preferably C _1-2 alkyl. Even more preferably, R ³ is selected from methyl, ethyl, n-propyl and i-propyl, and even more preferably from methyl and ethyl. In the monomer of the preferred formula (I), R ³ is methyl.

In some preferred monomers of formula (I), R ² is H and R ³ is methyl or ethyl, especially methyl.

In a more preferred monomer of formula (I), R ⁴ is an unsubstituted C _2-20 alkyl. When R ⁴ is an unsubstituted C _2-20 alkyl, the alkyl group is preferably 2 to 18 carbon atoms, more preferably 4 to 12 carbon atoms, such as 4, 5 or 6 carbon atoms. Contains atoms. Preferred alkyl groups contain 4-8 carbon atoms. The alkyl group may be straight or branched. When R ⁴ is an unsubstituted C _2-20 alkyl, the alkyl group is preferably selected from butyl, pentyl, hexyl, heptyl, octyl, dodecyl and octadecyl. When R ⁴ is butyl, R ⁴ is preferably n-butyl or isobutyl. When R ⁴ is octyl, R ⁴ is preferably 2-ethylhexyl.

In a more preferred monomer of formula (I), R ⁴ is a substituted C _1-20 alkyl. When R ⁴ is a substituted C _1-20 alkyl, the alkyl group is preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, such as 1, 2, 3, 4 or 6 Contains 1 carbon atom. The alkyl group is preferably linear. The alkyl group is preferably selected from methyl, ethyl, n-propyl, n-butyl, pentyl, hexyl, heptyl and octyl. When R ⁴ is a substituted C _1-20 alkyl, the substituent is selected from halogen, C _5-10 cycloalkyl, C _6-10 aryl, heterocyclyl or OR ⁵ , where R ⁵ is H, C _1-8. Alkyl, C _3-8 cycloalkyl and (CH ₂ CH _(2-m) (CH ₃ ) _m O) _n R ^{6 are} selected, R ⁶ is selected from H, C _1-4 alkyl and phenyl, m is It is 0 or 1, and n is an integer of 1 to 20, preferably 1 to 6. Optionally, the C _5-10 cycloalkyl substituent is itself substituted with an OH group. More preferably, the substituent is aryl (eg, phenyl), heterocyclyl or OR ⁵ , R ⁵ is selected from H, C _1-8 alkyl and (CH ₂ CH ₂ O) _n R ⁶ , where R ⁶ is H or It is C _1-4 alkyl, where n is an integer of 1-20, preferably 1-6.

When the alkyl group is substituted with a heterocyclyl, the heterocyclyl is preferably a 3- to 10-membered ring or ring system, more preferably a 5- or 6-membered ring, and may be saturated or unsaturated. Preferably, the heterocyclyl is saturated. Representative examples of possible heterocyclyl groups are tetrahydrofuryl or tetrahydropyranyl.

When the alkyl group is substituted with ^{OR 5 , R 5} is preferably H, C _1-8 alkyl (eg C _1-3 alkyl) and (CH ₂ CH _(2-m) (CH ₃ ) _m O). _n Selected from R ^{6 , R 6} is H, C _1-4 alkyl or phenyl, m is 0 or 1, and n is an integer of 1-20, preferably 1-6. Representative examples of R ⁵ include H, methyl, ethyl, (CH ₂ CH ₂ O) CH ₃ and (CH ₂ CH ₂ O) CH ₂ CH ₃ .

In a more preferred monomer of formula (I), R ⁴ is an unsubstituted C _5-10 cycloalkyl. Preferred cyclic alkyl groups contain 6-8 carbon atoms. The cycloalkyl group may be a crosslinked or polycyclic ring system. The preferred cycloalkyl group is monocyclic. When R ⁴ is an unsubstituted C _5-10 cycloalkyl, the cycloalkyl group is preferably cyclohexyl.

In a more preferred monomer of formula (I), R ⁴ is a substituted C _5-10 cycloalkyl. When R ⁴ is a substituted C _5-10 cycloalkyl, the alkyl group preferably contains 6-8 carbon atoms, eg 6 carbon atoms. The cycloalkyl group is preferably cyclohexyl. When R ⁴ is a substituted C _5-10 cycloalkyl, the substituent may be C _1-4 alkyl or OR ⁵ , and R ⁵ is selected from H or C _{1-8 alkyl.} More preferably, the substituent is C _1-4 alkyl or OR ⁵ , and R ⁵ is selected from H and C _{1-8 alkyl.}

When the cycloalkyl group is substituted with ^{OR 5 , R 5} is preferably selected from H and C _1-8 alkyl (eg C _1-3 alkyl). Representative examples of R ⁵ include H, methyl and ethyl.

In a more preferred monomer of formula (I), R ⁴ is an unsubstituted C _6-10 aryl. When R ⁴ is an unsubstituted C _6-10 aryl, the aryl group preferably contains 6 or 10 carbon atoms. Preferred aryl groups include phenyl.

In a more preferred monomer of formula (I), R ⁴ is a substituted C _6-10 aryl. When R ⁴ is a substituted C _6-10 aryl, it contains an aryl group, preferably 6 or 10 carbon atoms. Preferred aryl groups include phenyl. The substituent is preferably _{selected from halogen, C 1-8} alkyl and OR ⁵ , and R ⁵ is selected from H and C _{1-8 alkyl.}

In a more preferred monomer of formula (I), R ⁴ is an optionally substituted linear or branched C _4-18 alkyl or C _5-10 cycloalkyl. Even more preferably, R ⁴ is an unsubstituted C _4-18 alkyl or an unsubstituted C _5-10 cycloalkyl. Even more preferably, R ⁴ is selected from butyl, pentyl, hexyl, heptyl, octyl, dodecyl, octadecyl and cyclohexyl, particularly preferably butyl, octyl, dodecyl, octadecyl and cyclohexyl. When R ⁴ is butyl, R ⁴ is preferably n-butyl or isobutyl. When R ⁴ is octyl, R ⁴ is preferably 2-ethylhexyl.

In some preferred monomers of formula (I), R ² is H, R ³ is methyl or ethyl, especially methyl, and R ⁴ is from butyl, pentyl, hexyl, heptyl, octyl, dodecyl, octadecyl and cyclohexyl. Be selected. When R ⁴ is butyl, R ⁴ is preferably n-butyl or isobutyl. When R ⁴ is octyl, R ⁴ is preferably 2-ethylhexyl.

In other preferred monomers of formula (I), R ³ and R ⁴ _{form an optionally substituted C 4-8} membered ring with the O atom to which they are attached. When R ³ and R ⁴ _{form an unsubstituted C 4-8} member ring with the O atom to which they are attached, the ring preferably contains 4 or 5 carbon atoms, i.e., they. A 5- or 6-membered ring is formed with the O atom to which the is bonded. Preferably, R ³ and R ⁴ form an unsubstituted tetrahydrofuranyl or tetrahydropyranyl ring with the O atom to which they are attached. When R ³ and R ⁴ _{form a substituted C 4-8} member ring with the O atom to which they are attached, the ring preferably contains 4 or 5 carbon atoms, i.e. they are. A 5- or 6-membered ring is formed with the bonded O atom. Preferably, R ³ and R ⁴ form a substituted tetrahydrofuranyl or tetrahydropyranyl ring with the O atom to which they are attached. The substituent is preferably _{selected from halogen, C 1-8} alkyl and OR ⁵ , where R ⁵ is selected from H or C _{1-8 alkyl.}

In some preferred monomers of formula (I), R ² is H and R ³ and R ⁴ form an unsubstituted tetrahydrofuranyl or tetrahydropyranyl ring with the O atom to which they are attached. ..

Preferred monomers present in the antifouling coating composition of the present invention are 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1 -Dodecyloxyethyl methacrylate, 1-octadecyloxyethyl methacrylate, 2-tetrahydrofuranyl methacrylate, 2-tetrahydropyranyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1- (2-ethylhexyloxy) ethyl Includes acrylates, 1-cyclohexyloxyethyl acrylates, 1-dodecyloxyethyl acrylates, 1-octadecyloxyethyl acrylates, 2-tetrahydrofuranyl acrylates and 2-tetrahydropyranyl acrylates. 1-Isobutoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate and 2-tetrahydropyranyl methacrylate are particularly preferred monomers.

の少なくとも１つのモノマーの残基を含み、式中、
Ｒ⁷はＨ又はメチルであり；
Ｒ⁸は任意選択で置換されたＣ_1-18アルキル、任意選択で置換されたＣ_5-10シクロアルキル、任意選択で置換されたＣ_6-10アリール又は任意選択で置換されたヘテロシクリルであり、その置換基はＯＲ⁹及びヘテロシクリルから選択され；
Ｒ⁹はＨ、Ｃ_1-8アルキル及び（ＣＨ₂ＣＨ_2-p（ＣＨ₃）_pＯ）_qＲ¹⁰から選択され；
Ｒ¹⁰はＨ、Ｃ_1-4アルキル及びフェニルから選択され；
ｐは０又は１であり；及び
ｑは１〜２０、好ましくは１〜６の整数である。 Preferably, the acrylic acetal ester copolymer present in the antifouling coating composition of the present invention further comprises repeating units derived from the (meth) acrylic acid ester monomer. Particularly preferred acrylic acetal ester copolymers are of formula (II) :.

Containing residues of at least one monomer of, in the formula,
R ⁷ is H or methyl;
R ⁸ is optionally substituted C _1-18 alkyl, optionally substituted C _5-10 cycloalkyl, optionally substituted C _6-10 aryl or optionally substituted heterocyclyl. The substituent is ^{selected from OR 9} and heterocyclyl;
R ⁹ is selected from H, C _1-8 alkyl and (CH ₂ CH _2-p (CH ₃ ) _p O) _q R ¹⁰ ;
R ¹⁰ is selected from H, C _1-4 alkyl and phenyl;
p is 0 or 1; and q is an integer of 1-20, preferably 1-6.

In some preferred monomers of formula (II), R ⁸ is an unsubstituted C _1-18 alkyl. When R ⁸ is an unsubstituted C _1-18 alkyl, the alkyl group is preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, such as 1, 2, 3 or 4 carbon atoms. Contains carbon atoms of. Preferred alkyl groups contain 1 to 4 carbon atoms. The alkyl group may be a straight chain or a branched chain, but a straight chain alkyl group is preferable.

When R ⁸ is an unsubstituted C _1-18 alkyl, R ⁸ may be straight or branched. When R ⁸ is an unsubstituted C _1-18 alkyl, R ⁸ is preferably selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl and octadecyl. More preferred alkyl groups are methyl, ethyl, propyl, n-butyl and 2-ethylhexyl.

In some preferred monomers of formula (II), R ⁸ is a substituted C _1-18 alkyl. When R ⁸ is a substituted C _1-18 alkyl, the alkyl group is preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, such as 1, 2 or 3 carbon atoms. including. The alkyl group is preferably linear. Preferably, the alkyl group is methyl or ethyl.

When R ⁸ is a substituted C _1-18 alkyl, the substituents are heterocyclyl, OR ⁹ (R ⁹ is H, C _1-8 alkyl and (CH ₂ CH _2-p (CH ₃ ) _p O) _q R. is selected from ^10, R ¹⁰ is H or C _1-4 alkyl, p is 0 or 1, q is 1 to 20, preferably an integer of 1 to 6.) or N (R ¹¹⁾ ₂ (Each R ¹¹ may be independently H or C _1-6 alkyl.)

When the alkyl group is substituted with a heterocyclyl, the heterocyclyl is preferably a 3- to 10-membered ring or ring system, more preferably a 5- or 6-membered ring, and may be saturated or unsaturated. Preferably, the heterocyclyl is saturated. Representative examples of possible heterocyclyl groups are glycidyl, tetrahydrofuryl, pyrrolidonyl and morpholinyl.

When the alkyl group is substituted with ^{OR 9 , R 9} is preferably H, C _1-8 alkyl (eg C _1-3 alkyl) and (CH ₂ CH _2-p (CH ₃ ) _p O) _q R. ^{From 10} (R ¹⁰ is C _1-4 alkyl, p is 0 or 1, q is an integer of 1-20, preferably 1-6), even more preferably C _1-8 alkyl ( For example, C _1-3 alkyl) is selected. Representative examples of R ⁹ include H, methyl, ethyl, (CH ₂ CH ₂ O) CH ₃ and (CH ₂ CH ₂ O) CH ₂ CH ₃ .

When the alkyl group is substituted with ^{N (R 11} ) ₂ ^{, R 11} is preferably selected independently of H or C _1-6 alkyl, preferably C _{1-6 alkyl.} Representative examples of R ¹¹ include methyl and ethyl.

In a more preferred monomer of formula (II), R ⁸ is an unsubstituted C _5-10 cycloalkyl. Preferred cyclic alkyl groups contain 6-8 carbon atoms. The cycloalkyl group may be a crosslinked or polycyclic ring system. The preferred cycloalkyl group is monocyclic. When R ⁸ is an unsubstituted C _5-10 cycloalkyl, the cycloalkyl group is preferably selected from cyclopentyl, cyclohexyl, dicyclopentenyl and isobornyl. A more preferred cycloalkyl group is cyclohexyl.

In a more preferred monomer of formula (II), R ⁸ is a substituted C _5-10 cycloalkyl. When R ⁸ is a substituted C _5-10 cycloalkyl, the alkyl group preferably comprises 6-8 carbon atoms, eg 6 carbon atoms. The cycloalkyl group is preferably cyclohexyl. When R ⁸ is a substituted C _5-10 cycloalkyl, the substituent may be C _1-8 alkyl or OR ⁹ , and R ⁹ is selected from H and C _{1-8 alkyl.}

When the cycloalkyl group is substituted with ^{OR 9 , R 9} is preferably selected from H and C _1-8 alkyl (eg C _1-3 alkyl). Representative examples of R ⁹ include H, methyl and ethyl.

In a more preferred monomer of formula (II), R ⁸ is an unsubstituted C _6-10 aryl. When R ⁸ is an unsubstituted C _6-10 aryl, the aryl group preferably contains 6 or 10 carbon atoms. Preferred aryl groups include phenyl.

In a more preferred monomer of formula (II), R ⁸ is a substituted C _6-10 aryl. When R ⁸ is a substituted C _6-10 aryl, the aryl group preferably contains 6 or 10 carbon atoms. Preferred aryl groups include phenyl. When R ⁸ is a substituted C _6-10 aryl, the substituent may be halogen, C _1-8 alkyl or OR ⁹ , and R ⁹ is selected from H and C _{1-8 alkyl.} More preferably, the substituent is OR ⁹ and R ⁹ is selected from H and C _{1-8 alkyl.}

When the C _6-10 aryl group is substituted with ^{OR 9 , R 9} is preferably selected from H and C _1-8 alkyl (eg C _1-3 alkyl). Representative examples of R ¹⁰ include H, methyl and ethyl.

In a more preferred monomer of formula (II), R ⁸ is a C ₂ or C ₃ ^{alkyl substituted with OR 9} (eg ethyl or isopropyl) and R ⁹ is (CH ₂ CH _2-p (CH ₃ ) _p. O) _q R ¹⁰ , where R ¹⁰ is selected from H, C _1-4 alkyl and phenyl, p is 0 or 1, q is an integer of 1-20, preferably 1-6. Representative examples of R ¹⁰ include H, methyl and ethyl.

In a more preferred monomer of formula (II), R ⁸ is an unsubstituted or substituted C _1-18 alkyl, more preferably an unsubstituted or substituted C _1-8 alkyl. In a particularly preferred monomer of formula (II), R ⁸ is selected from methyl, ethyl, propyl, n-butyl, 2-ethylhexyl and tetrahydrofurfuryl. When R ⁸ is substituted, R ⁸ is preferably substituted by ^{OR 9 and R 9} is selected from methyl or (CH ₂ CH ₂ O) CH ₂ CH ₃ .

Preferred monomers present in the copolymer present in the antifouling coating composition of the present invention are methyl acrylate, ethyl acrylate, tert-butyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate. , Isooctyl acrylate, 2-propyl heptyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, tridecyl acrylate, octadecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, poly (ethylene glycol) ) Acrylate, Poly (propylene glycol) acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, methoxypoly (ethylene glycol) acrylate , Tetrahydrofurfuryl acrylate, 2-N-morpholinoethyl acrylate, N- (2- (acryloyloxy) ethyl) pyrrolidone, dimethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , Hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isooctyl methacrylate, 2-propyl heptyl methacrylate, decyl methacrylate, isodecyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, octadecyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate. , 4-Hydroxybutyl methacrylate, poly (ethylene glycol) methacrylate, poly (propylene glycol) methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxy) Includes ethoxy) ethyl methacrylate, methoxypoly (ethylene glycol) methacrylate, tetrahydrofurfuryl methacrylate, 2-N-morpholinoethyl methacrylate, N- (2- (methacryloyloxy) ethyl) pyrrolidone and dimethylaminoethyl methacrylate. Particularly preferably, the monomers present in the copolymer present in the antifouling coating composition of the present invention are ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-methoxyethyl acrylate, 2- (2-ethoxyethoxy). ) Ethyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, n-butyl methacrylate, 2-methoxyethyl methacrylate, and 2- (2-ethoxyethoxy) ethyl methacrylate. n-Butyl acrylate, tetrahydrofurfuryl acrylate, 2- (2-ethoxyethoxy) ethyl acrylate and methyl methacrylate are particularly preferred monomers.

In the preferred antifouling coating composition of the present invention, the acrylic acetal ester copolymer comprises at least two (eg, two, three or four) different (meth) acrylate monomers of formula (II), more preferably two or three formulas. Contains different (meth) acrylate monomers of (II). In some preferred compositions, the copolymer comprises ^{at least one monomer of formula (II) where R 7} is H and at least one monomer of formula (II) where R ⁷ is CH ₃ .

Preferably, the acrylic acetal ester copolymer present in the antifouling coating composition of the present invention does not contain repeating units derived from acrylic acid and / or methacrylic acid.

The preferred acrylic acetal ester copolymer present in the antifouling coating composition of the present invention further comprises repeating units derived from other ethylenically unsaturated monomers. Representative examples of suitable ethylenically unsaturated monomers are styrene, vinyl acetate, 1-vinyl-2-pyrrolidone, 1-vinylcaprolactam, 3-dimethylaminopropylmethacrylamide, triisopropylsilylacrylate, triisopropylsilylmethacrylate, 2 Includes- (trimethylsiloxy) ethyl methacrylate, zinc (meth) acrylate, zinc acetate (meth) acrylate, zinc neodecanoate (meth) acrylate.

The acrylic acetal ester copolymer present in the antifouling coating composition of the present invention preferably contains at least 15 wt% of the monomer of formula (I) based on the dry mass of the copolymer. The acrylic acetal ester copolymer contains a more preferably 15-70 wt%, even more preferably 20-60 wt%, even more preferably 25-55 wt% monomer of formula (II) based on the dry mass of the copolymer.

The acrylic acetal ester copolymer present in the antifouling coating composition of the present invention preferably contains at least 25 wt% of a monomer of formula (II) based on the dry mass of the copolymer. The acrylic acetal ester copolymer contains a more preferably 25-85 wt%, even more preferably 35-80 wt%, even more preferably 40-75 wt% monomer of formula (II) based on the dry mass of the copolymer.

The preferred acrylic acetal ester copolymer present in the antifouling coating composition of the present invention has a weight average molecular weight of 5,000 to 100,000, more preferably 1,500 to 60,000, even more preferably 2,000 to 50,000. The preferred acrylic acetal ester copolymer present in the antifouling coating composition of the present invention is preferably 10 to 70 ° C, more preferably 15 to 60 ° C, even more preferably when measured by the methods presented in the Examples. It has a glass transition point (Tg) of 20 to 50 ° C.

The antifouling coating composition may include one or more (1, 2, 3, 4 or 5) acrylic acetal ester copolymers described above. The preferred antifouling coating composition of the present invention comprises one, two, three or four acrylic acetal ester copolymers, and even more preferably one or two acrylic acetal ester copolymer polymers.

The total amount of acrylic acetal ester copolymers present in the compositions of the present invention is based on the total mass of the final composition (ie, if the composition is given in two packs, these values are final. It refers to the wt% present in the mixed composition), preferably 2 to 60 wt%, more preferably 5 to 40 wt%, and even more preferably 7 to 25 wt%.

Suitable acrylic acetal ester copolymers can be prepared using polymerization reactions known in the art. For example, acrylic acetal ester copolymers are suitable for initiation of polymerization by any variety of methods using conventional or controlled polymerization techniques, such as solution polymerization, bulk polymerization, emulsion polymerization, dispersion polymerization and suspension polymerization. It can be obtained by polymerizing at least one monomer of formula (I) and one or more monomers of formula (II) in the presence of the agent. The acrylic acetal copolymer may be a random copolymer, an alternating copolymer, a gradient copolymer or a block copolymer.

When preparing the coating composition using the acrylic acetal ester copolymers described above, the polymer is preferably diluted with an organic solvent to give a polymer solution with suitable viscosities. From the viewpoint, it is desirable to prepare a copolymer by adopting solution polymerization. Examples of suitable initiators for free radical polymerization are azo compounds such as dimethyl 2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 2, 2'-azobis (isobutyronitrile) and 1,1'-azobis (cyanocyclohexane), as well as peroxides such as tert-butylperoxypivalate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyocta Noate, tert-butylperoxydiethyl acetate, tert-butylperoxyisobutyrate, di-tert-butyl peroxide, tert-butylperoxybenzoate and tert-butylperoxyisopropyl carbonate, tert-amylperoxypivalate, tert-amylperoxy- Includes 2-ethylhexanoate, 1,1-di (tert-amylperoxy) cyclohexane and dibenzoyl peroxide. These compounds can be used alone or as a mixture of two or more of them.

Examples of suitable organic solvents are aromatic hydrocarbons such as xylene, toluene, mesitylen; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone; esters such as butyl. Acetate, tert-butyl acetate, amyl acetate, propyl propionate, n-butyl propionate, isobutyl isobutyrate, ethylene glycol methyl ether acetate; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, tetrahydrofuran; Alcohols such as n-butanol, isobutanol, benzyl alcohol; ether alcohols such as butoxyethanol, 1-methoxy-2-propanol, methylisobutylcarbinol; hydrocarbons such as white spirit, limonene; and optionally two or more. Contains a mixture of the solvents of. These compounds are used alone or as a mixture of two or more of them.

Alternatively, suitable acrylic acetal ester copolymers can be purchased commercially.

Monocarboxylic Acid The antifouling coating composition of the present invention may contain a monocarboxylic acid. In such compositions, the monocarboxylic acid reacts in situ with the zinc compound to give the zinc salt of the monocarboxylic acid. Preferably, the monocarboxylic acid is substantially completely converted to a zinc salt in the composition of the invention. In the form of zinc salts of monocarboxylic acids, improvements can be achieved with respect to the hardness of the film as well as the drying rate of the coating or film.

The monocarboxylic acid present in the antifouling coating composition of the present invention preferably contains 5 to 50 carbon atoms, more preferably 10 to 40 carbon atoms, and even more preferably 12 to 25 carbon atoms. include.

The monocarboxylic acids present in the antifouling coating composition of the present invention are preferably resin acids, derivatives of resin acids, C _6-20 cyclic monocarboxylic acids, C _5-24 acrylic aliphatic monocarboxylic acids, C _{7 -20} Selected from aromatic monocarboxylic acids and mixtures thereof.

Representative examples of resin acids include abietic acid, neoavietic acid, dehydroabietic acid, pulsetriic acid, levopimaric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, comnic acid, merxic acid, secodehydroabietic acid. It is understood that the resin acids are derived from natural sources and therefore typically exist as a mixture of acids. Resin acids are also referred to as rosin acids. Typical examples of raw materials for resin acids are rubber rosin, wood rosin and tar oil rosin. Rubber rosin, also known as colohoney and colophonium, is particularly preferred. Preferred rosins contain more than 85% resin acid, even more preferably more than 90% resin acid.

Often, the commercial grade of rosin is the designation of symbols for the color scale specified in ASTM D509, XC (brightest), XB, XA, X, WW, WG, N, M, K, I, H, G, F, E, D (darkest), classified by rosin color. Preferred color grades for the compositions of the present invention are X, WW, WG, N, M, K, I, and even more preferably WW. Typically, the commercial grade of rosin has an acid value of 155-180 mg KOH / g as defined in ASTM D465. Preferred rosins for the compositions of the present invention have an acid value of 155 to 180 mg KOH / g, more preferably 160 to 175 mg KOH / g, even more preferably 160 to 170 mg KOH / g. Typically, commercial grades of rosin have a softening point (ring-ball type) of 70-80 ° C. as defined in ASTM E28. Preferred rosins for the compositions of the present invention have a softening point of 70-80 ° C, more preferably 75-80 ° C.

Representative examples of derivatives of resin acids include partially hydrogenated rosins, fully hydrogenated rosins, disproportionated rosins, dihydroabietic acid, dihydropimal acid and tetrahydroabietic acid.

Typical examples of C _6-20 cyclic monocarboxylic acid are naphthalene acid, 1,4-dimethyl-5- (3-methyl-2-butenyl) -3-cyclohexene-1-yl-carboxylic acid, 1, 3-Dimethyl-2- (3-methyl-2-butenyl) -3-cyclohexene-1-yl-carboxylic acid, 1,2,3-trimethyl-5- (1-methyl-2-propenyl) -3-cyclohexene -1-yl-carboxylic acid, 1,4,5-trimethyl-2- (2-methyl-2-propenyl) -3-cyclohexene-1-yl-carboxylic acid, 1,4,5-trimethyl-2-( 2-Methyl-1-propenyl) -3-cyclohexene-1-yl-carboxylic acid, 1,5,6-trimethyl-3- (2-methyl-1-propenyl) -4-cyclohexene-1-yl-carboxylic acid , 1-Methyl-4- (4-methyl-3-pentenyl) -4-cyclohexene-1-yl-carboxylic acid, 1-methyl-3- (4-methyl-3-pentenyl) -3-cyclohexene-1- Il-carboxylic acid, 2-methoxycarbonyl-3- (2-methyl-1-propenyl) -5,6-dimethyl-4-cyclohexene-1-yl-carboxylic acid, 1-i-propyl-4-methyl-bicyclo [2,2,2] 2-octen-5-yl-carboxylic acid, 1-i-propyl-4-methyl-bicyclo [2,2,2] 2-octen-6-yl-carboxylic acid, 6-i -Propyl-3-methyl-bicyclo [2,2,2] 2-octene-8-yl-carboxylic acid and 6-i-propyl-3-methyl-bicyclo [2,2,2] 2-octene-7- Contains yl-carboxylic acid.

Typical examples of C _5-24 acrylic aliphatic monocarboxylic acids are Versatic ^TM acid, neodecanoic acid, 2,2,3,5-tetramethylhexanoic acid, 2,4-dimethyl-2-isopropylpentanoic acid, 2 , 5-Dimethyl-2-ethylhexanoic acid, 2,2-dimethyloctanoic acid, 2,2-dimethylhexanoic acid, pivalic acid, 2,2-dimethylpropionic acid, trimethylacetic acid, neopentanoic acid, 2-ethylhexanoic acid, Includes isononanoic acid, 3,5,5-trimethylhexanoic acid, isoparmitic acid, isostearic acid, 16-methylheptadecanoic acid, 12,15-dimethylhexadecanoic acid. The acrylic aliphatic monocarboxylic acid is preferably selected from liquid acrylic C _10-24 monocarboxylic acid or liquid branched chain C _10-24 monocarboxylic acid. Many of the acrylic C _10-24 monocarboxylic acids are derived from natural sources, typically in their free state, they are present as a mixture of acids of different chain lengths with varying degrees of branching. It is understood that it can be done.

Suitable monocarboxylic acids can be purchased commercially.

Preferably, the monocarboxylic acid is rubber rosin, a derivative of rubber rosin, acrylic C _10-24 monocarboxylic acid, C _6-20 cyclic monocarboxylic acid or a mixture thereof. The acid mixture preferably contains at least one resin acid, rubber rosin or a derivative of rubber rosin.

The total amount of monocarboxylic acids present in the composition of the present invention is preferably 1-30 wt%, more preferably 2-20 wt%, even more preferably 3-15 wt%, based on the total mass of the composition. %.

Zinc Compounds The antifouling coating composition of the present invention may also include zinc compounds and particularly reactive zinc compounds. In such compositions, the zinc compound reacts with the monocarboxylic acid to produce a zinc salt of the monocarboxylic acid in situ. The reaction between the monocarboxylic acid and the zinc compound preferably occurs during the production of the composition, during the storage of the composition and / or during the mixing of the paint prior to the application of the paint. The presence of a zinc salt of a monocarboxylic acid in the paint can be determined, for example, by Fourier transform infrared spectroscopy-total internal reflection spectroscopy. Zinc salts of monocarboxylic acids cause carbonyl expansion and contraction at ^{1580 cm -1.}

Zinc compounds provide Zn atoms or ions that interact with the monocarboxylic acids present in the composition. The interaction between zinc and the monocarboxylic acid improves the drying properties of the composition as well as the hardness of the film formed from the composition.

Typical examples of zinc compounds are inorganic zinc compounds such as zinc oxide, zinc sulfide, zinc carbonate, zinc carbonate hydroxide, basic zinc carbonate, lithopon, Sachtolith, zinc hydroxide soil, rhinozinc ore, zinc sulfate. Includes (zinc vitriol), white zinc sulfate (white vitriol), zinc white and zinc coordination compounds such as zinc pyrithione. The zinc compound is preferably selected from inorganic zinc compounds, more preferably from zinc oxide, zinc carbonate hydroxide, zinc sulfide, hydrozincite and lithopone. The coating composition may contain one or more zinc compounds.

The zinc compound has an average particle size distribution of d50, preferably less than 50 μm, more preferably less than 20 μm, even more preferably less than 5 μm. The zinc compound has an average particle size distribution of d50, preferably greater than 30 nm, more preferably greater than 100 nm, even more preferably greater than 300 nm. The zinc compound has an average particle size distribution of d50, preferably 30 nm to 50 μm, more preferably 300 nm to 20 μm, even more preferably 300 nm to 5 μm. The particle size and d50 are determined by the laser diffraction method described in ISO 13320: 2009.

Zinc compounds have a particle size of preferably less than 100 μm, more preferably less than 50 μm, even more preferably less than 10 μm, preferably with a mesh size of 45 μm with less than 0.05 wt% sieving residue. The sieving residue is determined as described in ISO 787-7: 2009.

Representative examples of commercial paint grade zinc compounds are EverZinc's Zinc oxide red seal; Hanil Chemical Ind. Co. , Ltd. Zinc oxide KS-1, Zinc oxide KS-2; S. Zinc Oxide grade 210 of Zinc, Zinc oxide grade AZO 66; Sachtleben Chemie GmbH of Sachtolith L, Sachtolith HD and Sactolith HD-S; Venator Materials PLC of Lithopone 30 DS, Lithopone 30 L, Lithopone 60 L; Bruggemann Chemical of Zinc Carbonate AC , Zinc Oxide Red Seal and Zinc Oxide White Seal; Lonza's Zinc Omade; Kolon Life Science Inc. CleanBio Zinc.

Examples of zinc compounds that do not provide reactive zinc, often present in antifouling coating compositions, include zineb, zinc phosphate and sulfate, and their hydrated forms.

The zinc compound is contained in the composition of the present invention in an amount of preferably 0.2 to 20 wt%, more preferably 0.5 to 15 wt%, even more preferably 1 to 10 wt% based on the total mass of the composition. Exists in. The molar ratio of zinc compound: monocarboxylic acid in the composition of the present invention is preferably 20: 1 to 1: 4, more preferably 15: 1 to 1: 3, and even more preferably 10: 1 to 1: 2. For example, 8: 1 to 1: 1.

Zinc Salt of Monocarboxylic Acid The antifouling composition of the present invention may contain a zinc salt of monocarboxylic acid. As explained above, the interaction between zinc and the monocarboxylic acid improves the drying properties of the composition as well as the hardness of the film formed from the composition.

In such compositions, the zinc salt is preferably formed from a monocarboxylic acid containing 5 to 50 carbon atoms, more preferably 10 to 40 carbon atoms, even more preferably 12 to 25 carbon atoms. Will be done.

More preferably, the zinc salt is a resin acid, a derivative of the resin acid, a C _6-20 cyclic monocarboxylic acid, a C _5-24 acrylic aliphatic monocarboxylic acid, a C _7-20 aromatic monocarboxylic acid and a mixture thereof. Formed from a monocarboxylic acid selected from.

Representative examples of resin acids include abietic acid, neoavietic acid, dehydroabietic acid, pulsetriic acid, levopipmaric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, comnic acid and merxic acid, secodehydroabietic acid. It is understood that the resin acids are derived from natural sources and therefore typically exist as a mixture of acids. Resin acids are also referred to as rosin acids. Typical examples of raw materials for resin acids are rubber rosin, wood rosin and tar oil rosin. Rubber rosin, also known as colohoney and colophonium, is particularly preferred. Preferred rosins contain more than 85% resin acid, even more preferably more than 90% resin acid.

Often, the commercial grade of rosin is the designation of symbols for the color scale specified in ASTM D509, XC (brightest), XB, XA, X, WW, WG, N, M, K, I, H, G, F, E, D (darkest), classified by rosin color. Preferred color grades for the compositions of the present invention are X, WW, WG, N, M, K, I, and even more preferably WW. Typically, the commercial grade of rosin has an acid value of 155-180 mg KOH / g as defined in ASTM D465. Preferred rosins for the compositions of the present invention have an acid value of 155 to 180 mg KOH / g, more preferably 160 to 175 mg KOH / g, even more preferably 160 to 170 mg KOH / g. Typically, commercial grades of rosin have a softening point (ring-ball type) of 70-80 ° C. as defined in ASTM E28. Preferred rosins for the compositions of the present invention have a softening point of 70-80 ° C, more preferably 75-80 ° C.

Representative examples of derivatives of resin acids include partially hydrogenated rosins, fully hydrogenated rosins, disproportionated rosins, dihydroabietic acid, dihydropimal acid and tetrahydroabietic acid.

Typical examples of C _6-20 cyclic monocarboxylic acid are naphthalene acid, 1,4-dimethyl-5- (3-methyl-2-butenyl) -3-cyclohexene-1-yl-carboxylic acid, 1, 3-Dimethyl-2- (3-methyl-2-butenyl) -3-cyclohexene-1-yl-carboxylic acid, 1,2,3-trimethyl-5- (1-methyl-2-propenyl) -3-cyclohexene -1-yl-carboxylic acid, 1,4,5-trimethyl-2- (2-methyl-2-propenyl) -3-cyclohexene-1-yl-carboxylic acid, 1,4,5-trimethyl-2-( 2-Methyl-1-propenyl) -3-cyclohexene-1-yl-carboxylic acid, 1,5,6-trimethyl-3- (2-methyl-1-propenyl) -4-cyclohexene-1-yl-carboxylic acid , 1-Methyl-4- (4-methyl-3-pentenyl) -4-cyclohexene-1-yl-carboxylic acid, 1-methyl-3- (4-methyl-3-pentenyl) -3-cyclohexene-1- Il-carboxylic acid, 2-methoxycarbonyl-3- (2-methyl-1-propenyl) -5,6-dimethyl-4-cyclohexene-1-yl-carboxylic acid, 1-i-propyl-4-methyl-bicyclo [2,2,2] 2-octen-5-yl-carboxylic acid, 1-i-propyl-4-methyl-bicyclo [2,2,2] 2-octen-6-yl-carboxylic acid, 6-i -Propyl-3-methyl-bicyclo [2,2,2] 2-octene-8-yl-carboxylic acid and 6-i-propyl-3-methyl-bicyclo [2,2,2] 2-octene-7- Contains yl-carboxylic acid.

Typical examples of C _5-24 acrylic aliphatic monocarboxylic acids are Versatic ^TM acid, neodecanoic acid, 2,2,3,5-tetramethylhexanoic acid, 2,4-dimethyl-2-isopropylpentanoic acid, 2 , 5-Dimethyl-2-ethylhexanoic acid, 2,2-dimethyloctanoic acid, 2,2-dimethylhexanoic acid, pivalic acid, 2,2-dimethylpropionic acid, trimethylacetic acid, neopentanoic acid, 2-ethylhexanoic acid, Includes isononanoic acid, 3,5,5-trimethylhexanoic acid, isoparmitic acid, isostearic acid, 16-methylheptadecanoic acid, 12,15-dimethylhexadecanoic acid. The acrylic aliphatic monocarboxylic acid is preferably selected from liquid acrylic C _10-24 monocarboxylic acid or liquid branched chain C _10-24 monocarboxylic acid. Many of the acrylic C _10-24 monocarboxylic acids can be derived from natural sources, typically in their free state, they are of different chain length acids with varying degrees of branching. It is understood that it exists as a mixture.

Suitable zinc salts of monocarboxylic acids can be purchased commercially.

Preferably, the zinc salt is formed from rubber rosin, a derivative of rubber rosin, a _{monocarboxylic acid selected from acrylic C 10-24} monocarboxylic acid, C _6-20 cyclic monocarboxylic acid or a mixture thereof. More preferably, the zinc salt is formed from a monocarboxylic acid selected from rubber rosin and derivatives of rubber rosin.

The zinc salt of the monocarboxylic acid is preferably in an amount of 1-30 wt%, more preferably 2-20 wt%, even more preferably 3-15 wt% in the composition of the present invention, based on the total mass of the composition. Exists in. The molar ratio of zinc cation: monocarboxylic acid in the composition of the present invention is preferably 20: 1 to 1: 4, more preferably 15: 1 to 1: 3, and even more preferably 10: 1 to 1: 2. For example, 8: 1 to 1: 1.

Antifouling Agent The antifouling coating composition of the present invention preferably contains an antifouling agent. The terms, antifouling agent, bioactive compounds, biocides, antifoulants, toxic agents are used to describe known compounds that act to prevent marine fouling on the surface in the industry. used. The antifouling agent present in the composition of the present invention is preferably a marine antifouling agent. The antifouling agent may be an inorganic substance, an organic metal or an organic substance. Suitable antifouling agents are commercially available.

Examples of inorganic antifouling agents include copper and copper compounds such as cuprous oxide, cupric oxide, copper sulfide, copper thiocyanate, copper powder and copper pieces.

Typically, cuprous oxide material grade commercial paints have a particle size distribution of 0.1 to 70 μm and an average particle size (d50) of 1 to 25 μm. Copper oxide materials may contain stabilizers (eg, to prevent surface oxidation and caking during storage and transport). Representative examples of commercially available cuprous oxide are Nordox Cuprose Oxide Red Paint Grade, Nordox XLT, Furukawa Chemicals Co., Ltd. of Nordox AS. , Ltd. Cuprous Oxide; American Chemet Corporation's Red Copp 97N, Purple Copp, Lolo Tint 97N, Chemet CDC, Chemet LD; Spies-Urania's Cuprous Oxide Red; , Ltd. Includes Cuprose oxide Roast and Cuprose oxide Electrical.

Examples of organic metal antifouling agents include zinc pyrithione, copper pyrithione, zinc bis (dimethyldithiocarbamate) [dilam] and zinc ethylenebis (dithiocarbamate) [zineb].

Examples of organic antifouling agents are 2- (tert-butylamino) -4- (cyclopropylamino) -6- (methylthio) -1,3,5-triazine [cibutrin], 4,5-dichloro-2-. n-octyl-4-isothiazolin-3-one [DCOIT], 2- (thiocyanatomethylthio) -1,3-benzothiazole [benziazole], 3- (3,4-dicyclophenyl) -1,1- Dimethylurea [diurone], N-dichlorofluoromethylthio-N', N'-dimethyl-N-phenylsulfamide [diclofluanide], N-dichlorofluoromethylthio-N', N'-dimethyl-N-p- Trillsulfamide [trilfluanide], N- (2,4,6-trichlorophenyl) maleimidepyridine triphenylborane [TPBP], 3-iodo-2-propynyl N-butylcarbamate [IPBC], 2,4 5,6-Tetrachloroisophthalonitrile [chlorotalonyl], p-((diiodomethyl) sulfonyl) toluene, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbo Includes nitrile [tralopyryl] and 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidin].

Other examples of antifouling agents include tetraalkylphosphonium halides, guanidine derivatives such as dodecylguanidine monohydrochloride; macrocyclic lactones such as avermectin and its derivatives such as ivermectin; spinosin and its derivatives. , For example spinosad; capsaicin and its derivatives such as phenylcapsaicin; and enzymes such as oxidase, proteolytic, semi-cellulose degradation, cellulose degradation, lipolytic and amylose degradation active enzymes.

Preferred antifouling agents are cuprous oxide, copper isothiocyanate, copper pyrithione, zinc pyrithione, zinc ethylenebis (dithiocarbamate) [geneb], 2- (tert-butylamino) -4- (cyclopropylamino) -6-. (Methylthio) -1,3,5-triazine [cibutrin], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], 4-bromo-2- (4-chlorophenyl)- 5- (Trifluoromethyl) -1H-pyrrole-3-carbonitrile [traropyryl] and 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole [medetomidin].

Particularly preferred antifouling agents are cuprous oxide, copper thiocyanate, zinc pyrithione, copper pyrithione, zinc ethylenebis (dithiocarbamate) [geneb], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-3. On [DCOIT], N-dichlorofluoromethylthio-N', N'-dimethyl-N-phenylsulfamide [diclofluanide], N-dichlorofluoromethylthio-N', N'-dimethyl-N-p-tolyl Sulfamide [trilfluanide], 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile [tralopyryl], 4- [1- (2,3) -Dimethylphenyl) Ethyl] -1H-imidazole [medetomidin] and phenylcapsaicin.

The antifouling agent can be used alone or in the form of a mixture in which different antifouling agents act on different marine fouling organisms. A mixture of antifouling agents is generally preferred. One preferred mixture of antifouling agents is active against marine invertebrates such as fujitsubo, lamellibrachia, bryozoa and hydroids; plants such as algae (seaweeds and diatoms); and bacteria.

Some preferred coating compositions of the present invention are essentially free of inorganic copper antifouling agents. Such compositions preferably consist of tralopyryl and one or more agents selected from zinc pyrithione, copper pyrithione, zineb, 4,5-dichloro-2-octyl-4-isothiazolin-3-one and medetomidine. Including combinations with.

Other preferred coating compositions are selected from cuprous oxide and / or copper thiocyanate and copper pyrithione, zineb, 4,5-dichloro-2-octyl-4-isothiazolin-3-one and medetomidine or one or the other. Contains multiple agents.

The combined amount of antifouling agent is up to 60 wt% of the total coating composition relative to the total amount of the composition (ie, based on both compositions when the composition is given in two packs). , For example 0.1 to 50 wt%, for example 0.2 to 45 wt% may be composed. Where the inorganic copper compound is present, a suitable amount of antifouling agent may be 5-60 wt% in the coating composition. Where less inorganic copper compounds are avoided, smaller amounts, such as 0.1 to 25 wt%, such as 0.2 to 10 wt%, may be used. It is understood that the amount of antifouling agent varies depending on the end use and the antifouling agent used. The use of these antifouling agents is known in antifouling coatings and their use is familiar to those skilled in the art. The antifouling agent may be encapsulated, adsorbed on an inert carrier, or bound to other materials for controlled release. These proportions relate to the amount of active antifouling agent present and therefore not to any carrier used.

Pigments and / or bulking agents The antifouling coating composition of the present invention preferably comprises one or more bulking agents and / or pigments.

The term, bulking agent is used herein to include bulking agents and fillers. These compounds increase the bulk of the composition. Examples of bulking agents and fillers are minerals such as dolomite, styrene, quartz, barite, magnesite, aragonite, silica, wollastonite, talc, green mudstone, mica, kaolin, pearlite and sulphate; synthetic inorganic compounds. , For example calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate, zinc phosphate and silica (including colloidal silica, fumed silica, etc.); polymer and inorganic microparticles such as uncoated or coated hollow and solid. Glass beads, uncoated or coated hollow and solid ceramic beads, polymer materials such as poly (methyl methacrylate), poly (methyl methacrylate-co-ethylene glycol dimethacrylate), poly (styrene-co-ethylene). Hollow, porous and dense beads of (glycol dimethacrylate), poly (styrene-cordivinylbenzene), polystyrene, poly (vinyl chloride).

The pigment may be an inorganic pigment, an organic pigment or a mixture thereof. Inorganic pigments are preferred. These compounds impart color and hiding power to the composition. Examples of inorganic pigments include titanium dioxide, red iron oxide, yellow iron oxide, black iron oxide, zinc oxide, zinc sulfide, lithopone and graphite. Examples of organic pigments include carbon black, phthalocyanine blue, phthalocyanine green, naphthol red, diketopyrrolopyrrole red. The pigment can be optionally surface treated so that it is more easily dispersed in the coating composition.

Preferred inorganic pigments include titanium dioxide and iron oxides.

The total amount of bulking agents, fillers and / or pigments present in the compositions of the present invention is preferably 0-40 wt%, more preferably 2-35 wt%, based on the total mass of the composition. More preferably, it is 5 to 30 wt%. Those skilled in the art will understand that the content of bulking agents and pigments will vary depending on the particle size distribution, particle shape, surface morphology, particle surface-resin affinity, other existing components and end use of the coating composition. do.

In addition to the cobinder acrylic acetal ester copolymer, additional binders can optionally be used to adjust the properties of the antifouling coating composition.

Examples of other polymeric binders that can be used are:
Acrylic resins such as methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate and isobutyl methacrylate homopolymers and copolymers;
(Meta) acrylate copolymers containing monomeric units of hydrophilic polymers such as hydroxyalkyl (meth) acrylates, alkoxyalkyl (meth) acrylates or alkylaminoalkyl (meth) acrylates; homopolymers and copolymers of (meth) acrylamides, and Homopolymers and copolymers of 1-vinyl-2-pyrrolidone and 1-vinylcaprolactam;
Polyethylene oxide and polypropylene oxide;
Vinyl ether homopolymers and copolymers such as poly (methyl vinyl ether), poly (ethyl vinyl ether), poly (isobutyl vinyl ether), poly (n-butyl acrylate-co-isobutyl vinyl ether), poly (vinyl chloride-co-isobutyl vinyl ether);
Includes polymer plasticizers from any of the polymer groups specified above. The term polymer plasticizer refers to a polymer having a glass transition point (Tg) below 25 ° C.

Additional examples of other binders that may be present in the antifouling coating composition of the present invention are:
Cyril ester (meth) acrylate copolymers, such as copolymers containing triisopropylsilyl (meth) acrylate;
Copolymers comprising metal (meth) acrylate copolymers such as zinc (meth) acrylate, zinc hydroxide (meth) acrylate, zinc neodecanoate (meth) acrylate or zinc oleate (meth) acrylate;
Saturated aliphatic polyesters such as poly (lactic acid), poly (glycolic acid), poly (2-hydroxybutyric acid), poly (3-hydroxybutyric acid), poly (4-hydroxyvaleric acid), polycaprolactone and described above. An aliphatic polyester copolymer containing two or more of the units selected from the units;
Polyoxalic acid as described in WO 2009/100908;
Alkyd resin and modified alkyd resin;
Esters of rubber rosin and hydrogenated rubber rosin, such as rosin methyl ester, rosin glycerol ester and rosin pentaerythritol ester;
Metals of rubber rosin and hydrogenated rubber rosin, such as alkaline earth metals of resin, such as magnesium resinate, calcium resinate, and transition metals of resin, such as zinc resinate, copper resinate; and hydrocarbon resins, for example. Includes hydrocarbon resins formed from the polymerization of at least one monomer selected from C5 aliphatic monomers, C9 aromatic monomers, indenkumaron monomers or terpenes or mixtures thereof.

Particularly suitable additional binders are acrylic resins, rubber rosin esters and polymeric plasticizers.

The cobinder is present in the compositions of the invention in an amount of preferably 0 to 15 wt%, more preferably 0.5 to 10 wt%, even more preferably 1 to 7 wt%, based on the total mass of the composition. do.

Solvent The antifouling coating composition of the present invention preferably contains a solvent. The solvent is preferably volatile. Preferably, the solvent is organic. The components of the antifouling coating composition can be dispersed in an organic non-solvent instead of the film-forming components (eg, polymers) in the coating composition or aqueous dispersion. Suitable solvents for use in the compositions of the present invention are commercially available.

Examples of suitable organic solvents and solvents are aromatic hydrocarbons such as xylene, toluene, mesitylane; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone; ester, For example butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, propyl propionate, n-butyl propionate, isobutyl isobutyrate; ether esters such as ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate, ethyl 3 -Ethoxypropionate; ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, tetrahydrofuran; ether alcohols such as butoxyethanol, 1-methoxy-2-propanol; alcohols such as n-butanol, isobutanol, methylisobutyl Carbinol, benzyl alcohol; hydrocarbons such as white spirit and limonene; and optionally a mixture of two or more solvents and solvents.

The total amount of solvent present in the antifouling coating composition of the present invention is preferably as low as possible to minimize the content of volatile organic compounds. The total solvent present in the composition of the present invention is preferably 0-40 wt%, more preferably 10-35 wt%, even more preferably 15-30 wt%, based on the total mass of the composition. Those skilled in the art will appreciate that some raw materials contain solvents and contribute to the total solvent content as specified above, and thus vary the added solvent content depending on the other components present. To understand the.

Dehydrating agents and stabilizers The antifouling coating composition of the present invention optionally contains a dehydrating agent, also referred to as a water scavenger or desiccant. Preferably, the dehydrating agent is a compound that removes water from the composition in which water is present. The dehydrating agent is water in the antifouling coating composition that results from raw materials such as pigments and solvents, or water that is formed by the reaction of a carboxylic acid compound with a metal oxide, metal hydroxide or metal carbonate compound. By removing it, the storage stability of the antifouling coating composition is improved. Dehydrating agents that can be used in antifouling coating compositions include organic and inorganic compounds.

The dehydrating agent may be a hygroscopic material that absorbs water or binds water as water of crystallization. These are often referred to as damp proofing agents. Examples of such compounds include calcium sulphate hemihydrate, calcium sulphate anhydrous, magnesium sulphate anhydrous, sodium sulphate anhydrous, zinc sulphate anhydrous, molecular sieves and zeolite.

The dehydrating agent may also be a compound that chemically reacts with water. Examples of dehydrating agents that chemically react with water include orthoesters such as trimethyl orthosilicate, triethyl orthosilicate, tripropyl orthosilicate, triisopropyl orthosilicate, tributyl orthosilicate, trimethyl orthoacetate, triethyl orthoacetate, tributyl orthoacetate. And triethyl orthopropionate; acetal; acetal; enol ether; orthosilicates such as trimethylboric acid, triethylboric acid, tripropylboric acid, triisopropylboric acid, tributylboric acid and tri-tert-butylboric acid; oxazolidine, eg. 3-Ethyl-2-methyl-2- (3-methylbutyl) -1,3-oxazolidine and 3-butyl-2- (1-ethylpentyl) -1,3-oxazolidine; monofunctional isocyanates such as p-toluene. Sulfonyl isocyanates; as well as organosilanes such as trimethoxymethylsilane, triethoxymethylsilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, tetraethoxysilane and ethylpolysilicates.

The stabilizer is preferably an acid supplement that contributes to the storage stability of the antifouling coating composition. Examples of stabilizers are carbodiimide compounds such as bis (2,6-diisopropylphenyl) carbodiimide and bis (2-methylphenyl) carbodiimide, as well as others described in Patent Application International Publication No. 2014/064049; amine compounds. Includes, for example, trihexylamine, triheptylamine, tris (2-ethylhexyl) amine, triisooctylamine, tribenzylamine and 1-methylimidazole.

The dehydrating agent and stabilizer are preferably 0-5 wt%, more preferably 0.5-2.5 wt%, even more preferably 1.0-2.0 wt% based on the total mass of the composition. Are present in the compositions of the present invention, respectively.

Additives The antifouling coating composition of the present invention preferably contains one or more other components. Examples of other ingredients that can be added to the antifouling coating composition are stiffeners, rheology modifiers, dispersants, wetting agents and plasticizers.

Examples of stiffeners are flakes and fibers. Fibers include natural and synthetic, inorganic and organic fibers, such as those described in WO 00/77102. Typical examples are mineral fibers, such as mineral glass fibers, urastonite fibers, montmorillonite fibers, tovamorite fibers, attapargite fibers, roasted bokisite fibers, volcanic rock fibers, bokisite fibers, litter fibers and minerals processed from mineral cotton. Contains fiber.

Preferably, the fibers have an average length of 25 to 2000 μm and an average thickness of 1 to 50 μm, with an average length / average thickness ratio of at least 5. The reinforcing agent is present in the composition of the present invention in an amount of preferably 0 to 20 wt%, more preferably 0.5 to 15 wt%, even more preferably 1 to 10 wt%, based on the total mass of the composition. do.

Examples of classes of rheology modifiers optionally present in the compositions of the invention include thixotropes, thickeners and anti-sedimentants. Typical examples of leology modifiers are silicas such as fumed silica, organic modified clay, amide wax, polyamide wax, amide derivatives, polyethylene wax, oxidized polyethylene wax, hydrogenated castor oil wax, ethyl cellulose, etc. Aluminum stearate and mixtures thereof. Tixotropes, thickeners and anti-settling agents that require activation can be added to the coating composition and can be activated during the paint manufacturing process, or they are preactive in the coating composition. It can be added in the form, for example in the form of a solvent paste.

The thixotrope, thickener and anti-settling agent are preferably 0-5.0 wt%, more preferably 0.2-3.0 wt%, even more preferably 0.5, based on the total mass of the composition. Each is present in the compositions of the present invention in an amount of ~ 2.0 wt%.

Examples of plasticizers are chlorinated paraffins, silicone oils (non-reactive polydimethylsiloxane), phthalates, phosphate esters, sulfonamides, adipates and epoxidized vegetable oils. The plasticizer is added in the composition of the present invention in an amount of preferably 0-10 wt%, more preferably 0.5-7 wt%, even more preferably 1-5 wt%, based on the total mass of the final composition. exist.

Compositions and Paints Some preferred antifouling coating compositions of the present invention are:
(I) 2-60 wt%, more preferably 5-40 wt% acrylic acetal ester copolymer;
(Ii) Contains 1 to 30 wt%, more preferably 2 to 20 wt% of zinc salt of monocarboxylic acid.

A more preferred antifouling coating composition of the present invention is
(I) 2-60 wt%, more preferably 5-40 wt% acrylic acetal ester copolymer;
(Ii) 1 to 30 wt%, more preferably 2 to 20 wt% zinc salt of monocarboxylic acid;
(Iv) 0.1 to 50 wt%, more preferably 0.2 to 45 wt% antifouling agent;
(V) 0-40 wt%, more preferably 2-35 wt% pigments and / or bulking agents;
(Vi) 0-15 wt%, more preferably 0.5-10 wt% cobinder;
(Vii) 0-35 wt%, more preferably 1-30 wt% solvent;
(Viii) 0-5 wt%, more preferably 0.5-2.5 wt% stabilizer;
It contains (ix) 0-5 wt%, more preferably 0.5-2.5 wt% dehydrating agent; and (x) 0-5 wt%, more preferably 0.2-3 wt% rheology modifier.

Other preferred antifouling coating compositions of the present invention are
(I) 2-60 wt%, more preferably 5-40 wt% acrylic acetal ester copolymer;
(Ii) contains 1-30 wt%, more preferably 2-20 wt% of monocarboxylic acid compounds; and (iii) 0.2-20 wt%, more preferably 0.5-15 wt% of zinc compounds.

A more preferred antifouling coating composition of the present invention is
(I) 2-60 wt%, more preferably 5-40 wt% acrylic acetal ester copolymer;
(Ii) 1 to 30 wt%, more preferably 2 to 20 wt% of monocarboxylic acid compound;
(Iii) 0.2 to 20 wt%, more preferably 0.5 to 15 wt% zinc compound;
(Iv) 0.1 to 50 wt%, more preferably 0.2 to 45 wt% antifouling agent;
(V) 0-40 wt%, more preferably 2-35 wt% pigments and / or bulking agents;
(Vi) 0-15 wt%, more preferably 0.5-10 wt% cobinder;
(Vii) 0-35 wt%, more preferably 1-30 wt% solvent; and (viii) 0-5 wt%, more preferably 0.5-2.5 wt% stabilizer;
It contains (ix) 0-5 wt%, more preferably 0.5-2.5 wt% dehydrating agent; and (x) 0-5 wt%, more preferably 0.2-3 wt% rheology modifier.

The present invention also relates to the method of preparing the composition described above, in which the components present in the composition are mixed. Any conventional manufacturing method can be used.

The compositions described herein can be prepared at suitable concentrations for use, eg spray coating. In this case, the composition is itself a paint. Alternatively, the composition may be a concentrate for the preparation of paints. In this case, a solvent is further added to the compositions described herein to form the coating. Preferred solvents are as described above in connection with the composition.

After mixing, and optionally after adding the solvent, the antifouling coating composition or paint is preferably filled in a container. Suitable containers include cans, drums and tanks.

The antifouling coating composition of the present invention can be given as one pack or multiple packs, for example two packs. Preferably, the composition is given as 2 packs.

When given as a pack, the composition is preferably in a form that is already mixed or ready for use. Optionally, one pack of product can be diluted with solvent prior to application. The composition preferably comprises an acrylic acetal ester copolymer and a zinc salt of a monocarboxylic acid.

When given as two packs, the first container preferably contains the acrylic acetal ester copolymer defined above and optionally a stabilizer, and the second container preferably contains a monocarboxylic acid and a zinc compound. do. The monocarboxylic acid and the zinc compound react in situ to generate the zinc salt of the monocarboxylic acid. When given as two packs, the contents of the first and second containers are preferably mixed immediately prior to use of the composition. Preferably, the conversion of the monocarboxylic acid to the zinc salt is completed in a second container prior to mixing. Optionally, an additional solvent is added to the composition to form the paint. Preferred solvents are as described above in connection with the composition.

Therefore, the present invention also relates to the kits for the preparation of the paints described above. The first kit for the preparation of the paint is a first container containing an acrylic acetal ester copolymer and optionally a stabilizer; a second container containing a zinc salt of a monocarboxylic acid and optionally a dehydrating agent; It also includes instructions for optionally mixing the contents of the first and second containers. Additional kits for the preparation of paints include a first container containing an acrylic acetal ester copolymer and optionally a stabilizer; a second container containing a monocarboxylic acid and a zinc compound; and optionally a first and first container. Includes instructions for mixing the contents of the second container. In both kits, preferably the first container also contains pigments and / or bulking agents. In both kits, pigments and / or bulking agents, antifouling agents, cobinders, solvents and additives are optionally present in the first container, the second container or both containers. Preferred acrylic acetal ester copolymers, monocarboxylic acids, zinc compounds, stabilizers, antifouling agents, pigments and / or bulking agents, cobinders, solvents and additives are described above in relation to the overall antifouling coating composition. As it was done. The preferred kit further includes instructions for mixing the contents of the first and second containers.

The antifouling coating composition and paint of the present invention preferably have a solid content of 40 to 80 vol%, more preferably 45 to 70 vol%, and even more preferably 50 to 65 vol%.

The antifouling coating composition and paint of the present invention preferably have a viscosity of 50 to 1500 cP, more preferably 100 to 1000 cP, and even more preferably 150 to 850 cP. Preferably, the viscosity is measured using a cone plate viscometer (ISO2884-1: 1999) as described in the examples.

Preferably, the antifouling coating compositions and paints of the present invention have a volatile organic compound (VOC) content of 50-500 g / L, preferably 100-420 g / L, for example 150-380 g / L. VOC content can be calculated, for example, as described in ASTM D5201-05 or IED 2010/75 / EU, or measured, for example, as described in US EPA Method 24 or ISO 11890-2. can.

The antifouling coating composition of the present invention can be produced by adopting a process well known to those skilled in the art. For example, an antifouling coating composition can be prepared by adding the components of the composition simultaneously or sequentially (in any order) and then stirring, mixing and / or dispersing the components in the composition. Any conventional mixing method can be employed that applies a high shear force to the mixture, including, for example, high speed dispersers, various mills and in-line mixers.

In the preferred process for preparing the compositions of the present invention, any pigment, extender and / or antifouling agent and rheology modifier requiring dispersion and / or activation may be combined with the solvent in the first step. It is preferably mixed using a high shear mixer. Sometimes this step is referred to as milling, grinding or dispersing. Optional other components such as acrylic acetal ester copolymers, zinc salts or zinc compounds of monocarboxylic acids and monocarboxylic acids, binders, stabilizers and / or dehydrators are also included in the grinding process. In one preferred process, the acrylic acetal ester copolymer, the zinc salt of the monocarboxylic acid, the antifouling agent, the optional stabilizer, the optional dehydrating agent and the optional solvent the pigment and / or the bulking agent, the antifouling agent. , Binder and / or mixed with a ground mixture of rheology modifiers. Various ingredients can be added simultaneously (in any order) or sequentially. Preferably, the resulting mixture is further mixed by stirring, mixing and / or dispersion. This method produces a one-component product.

In a preferred method for producing a two-component product, the first mixture is an acrylic acetal ester copolymer, optionally a stabilizer, optionally a rheologist and optionally any pigment and / or bulking agent, binder and activity. It is prepared by a rheology modifier that requires conversion and / or dispersion, and optionally by grinding the solvent. The second mixture requires a monocarboxylic acid and a zinc compound that reacts with the monocarboxylic acid to produce a zinc salt of the monocarboxylic acid, and optionally any pigment and / or bulking agent, binder and activation or dispersion. It is prepared separately by the rheology modifier, and optionally by grinding the solvent. Finally, the resulting compositions are mixed together to form an antifouling coating composition. This final mixing step is preferably carried out immediately prior to the use of the antifouling composition.

The antifouling coating compositions and paints of the present invention can be applied to all or part of the surface of any article exposed to fouling. The surface may be persistently or intermittently underwater (eg, through tide movements, cargo loading or waves). The article surface is typically the surface of a ship's hull or fixed marine object, such as an oil platform or buoy. Application of coating compositions and paints can be achieved by any conventional technique, eg, by painting (eg with a brush or roller), or more preferably by spraying the coating onto the article. Typically, the surface needs to be away from seawater to allow coating. The application of the coating can be achieved as conventionally known in the art. After the coating has been applied, the coating is preferably dried or cured.

When applying an antifouling coating to an object (eg, the hull of a ship), the surface 26 of the object is typically not alone protected by a single coat of antifouling composition. Depending on the surface properties, the antifouling coating can be applied directly to existing coating systems. Such coating systems may include several layers of paint in different general forms (eg, epoxy, polyester, vinyl or acrylic or mixtures thereof). If the surface is clean and the antifouling coating is intact from the previous application, a new antifouling paint, typically one or two coats, and in exceptional cases more coats. Can be applied directly with.

Alternatively, the applicant can start with an uncoated surface (eg, steel, aluminum, plastic, composite, glass transition or carbon fiber). To protect such surfaces, the overall coating system is typically one or more layers of corrosion resistant coatings (eg, curable or modified epoxy coatings). Includes one layer of tie coat (eg, curable modified epoxy coating or physically dry vinyl coating) and one or two layers of antifouling paint. Those skilled in the art are familiar with these coating layers.

Thus, some preferred articles of the invention include a coating on at least a portion of its surface, the coating comprising a corrosion resistant coating layer, such as a primer, a bonding layer and an antifouling coating composition defined herein.

The present invention is then defined in connection with the following non-limiting examples.

Methods for valuing polymers and determining polymer properties and polymer solution properties Determining the viscosity of polymer solutions According to ASTM D2196-15, LV-2 or LV-4 spindles using the Brookfield DV-I Prime digital viscometer. Was used to determine the viscosity of the polymer solution at 12 rpm. Prior to measurement, the polymer was adjusted to 23.0 ° C ± 0.5 ° C.

Determining the non-volatile substance content of the polymer solution As the non-volatile content, the solid content in the polymer solution was determined by mass according to ISO 3251: 2008. A 0.5 g ± 0.1 g test sample was transferred to a flat-bottomed metal dish and dried in a ventilator at 105 ° C. for 180 minutes. The mass of the residual material was considered as a non-volatile substance (NVM). The non-volatile substance content of the sample is expressed in mass percent. The value given is the average of the three parallel samples.

Determination of Average Molecular Weight Distribution of Polymers Polymers were characterized by gel permeation chromatography (GPC) measurements. The Malvern Omnisec Ressolve and Reveal system was used to determine the molecular weight distribution (MWD) using two PLgel 5 μm Mixed-D columns in series with Agilent. The column was calibrated using a narrow polystyrene standard by conventional calibration. The analysis conditions are presented in the table below.

Samples were prepared by dissolving the amount of polymer solution corresponding to 25 mg of dry polymer in 5 mL of THF. Samples were held at room temperature for a minimum of 3 hours prior to sampling for GPC measurements. Prior to analysis, samples were filtered through a 0.45 μm nylon filter. The weight average molecular weight (Mw) and the polydispersity index (PDI) given as Mw / Mn were reported.

Determination of Glass Transition Temperature The glass transition temperature (Tg) was obtained by differential scanning calorimetry (DSC) measurement. DSC measurements were performed on the TA Instruments DSC Q200. Samples can be prepared by drawing down the polymer solution using a coater with a gap size of 100 μm onto a glass plate. The glass plates were dried overnight in a ventilation heating chamber at room temperature, followed by 24 hours at 50 ° C. The dry polymer material was scraped from the glass plate and about 10 mg of the dry polymer material was transferred to an aluminum dish. The dish was closed with an unsealed lid. Measured by performing the heating-cooling-heating procedure using an empty dish as a reference at a heating rate of 10 ° C./min and a cooling rate of 10 ° C./min in the temperature range of -80 to 120 ° C. Was executed. Data recorded from temperature scans was processed using TA Instruments' Universal Analysis software. The inflection point of the glass transition range of the second heating as defined by ASTM E1356-08 as the Tg of the polymer was reported.

Determination of Acid Value by Colorimetric Titration The acid value of the carboxylic acid compound was determined by the procedure described in ISO 2114: 2000 Method A. About 1 g of the weighed amount of the carboxylic acid compound was added to about 50 mL of Jotun Thinner No. Dissolved in 17. Phenolphthalein was added as a color indicator and the solution was titrated in ethanol with 0.1 M KOH solution until red coloration appeared, the solution stirring the solution for 10 to 15 seconds. Nevertheless, it was stable. The reported acid value is the average of three parallel measurements. For carboxylic acid compounds in solution, the acid value for dry carboxylic acid compounds was calculated based on the measured non-volatiles in the tested carboxylic acid compound solution.

General Procedures for the Preparation of Copolymer Solutions A1 and A2 Reactors with stirrers, condensers, feed inlets and nitrogen inlets were filled with solvent. The contents of the reactor were heated to 85 ° C. and maintained at that temperature. A feed consisting of a mixture of monomers, solvent and initiator was added to the reactor at a constant rate for 2 hours. One hour after the feed addition was complete, a mixture of solvent and initiator was added. The reacted mixture was kept at 85 ° C. for an additional 2 hours before cooling the reactor.

The components for preparing the copolymer are listed in Table 1 below. All quantities are given in parts by mass.

General Procedures for Preparing Copolymer Solutions A3 to A12 Solvents were charged into reactors with stirrers, condensers, feed inlets and nitrogen inlets. The contents of the reactor were heated to 85 ° C. and maintained at that temperature. A feed consisting of a mixture of monomers and initiator was added to the reactor at a constant rate for 3 hours. One hour after the feed addition was complete, a mixture of solvent and initiator was added. The reacted mixture was kept at 85 ° C. for an additional 2 hours before the reactor was cooled by adding a fraction of the solvent.

The components for preparing the copolymer are listed in Table 1 below. All quantities are given in parts by mass.

Procedure for Preparation of Copolymer Solution CA1 Copolymer Solution CA1 was prepared by repeating Production Example B-2 of WO2016 / 167360.

Following the procedure of WO 2016/167360, 75 parts of xylene was filled into a temperature controlled reaction vessel with a stirrer, condenser, nitrogen inlet and supply inlet. The reaction vessel was heated and maintained at 85 ° C. while stirring the contents. A mixture of 10 parts of methyl methacrylate, 40 parts of 2-methoxyethyl methacrylate, 50 parts of 1-isobutoxyethyl methacrylate and 1.3 parts of 2,2'-azobis (isobutyronitrile) was prepared. The mixture was added to the reaction vessel at a constant rate for 4 hours under a nitrogen atmosphere. After the addition was complete, a mixture of 0.5 parts t-butylperoxyoctanoate and 2 parts xylene was added four times at 30 minute intervals. The contents of the reactor were further stirred at 85 ° C. for 1 hour. The reaction vessel was then cooled to room temperature with the addition of 7.1 parts of isobutyl vinyl ether, 6.7 parts of xylene and 3 parts of butyl acetate.

The copolymer solution A3 had a non-volatile substance content of 51.3 wt%, a solution viscosity of 307 cP, a Mw of 25200, a PDI of 2.34 and a measured Tg of 37 ° C.

Procedure for Preparation of Copolymer Solution A2 Copolymer solution CA2 was prepared by repeating Reference Example 5 (polymer a-4) of JP-A-04-103671.

Following the procedure of Japanese Patent Application Laid-Open No. 04-103671, 800 parts of xylene was filled in a temperature controlled reaction vessel having a stirrer, a condenser, a nitrogen inlet and a supply inlet. The reaction vessel was heated and maintained at 110 ° C. while stirring the contents. 200 parts xylene, 15 parts t-butylperoxyoctanoate, 5 parts 2,2'-azobis (isobutyronitrile), 300 parts methylmethacrylate, 200 parts n-butyl acrylate and 500 parts 1 -A mixture of isobutoxyethyl methacrylate was prepared. The mixture was added to the reaction vessel at a constant rate for 5 hours under a nitrogen atmosphere. After the addition was complete, the contents of the reactor were further stirred at 110 ° C. for 5 hours. The reaction vessel was cooled to room temperature.

The copolymer solution A4 had a non-volatile substance content of 50.1 wt%, a solution viscosity of 357 cP, a Mw of 11200, a PDI of 2.39 and a measured Tg of 31 ° C.

Procedure for Preparation of Acrylic Copolymer Solution X1 Temperature-controlled reaction of 48.0 parts of xylene and 20.0 parts of 1-methoxy-2-propanol with stirrer, condenser, feed inlet and nitrogen inlet The container was filled. The reaction content was heated to 85 ° C. and maintained at that temperature. 93.0 parts of n-butyl acrylate, 4.0 parts of methyl methacrylate, 3.0 parts of methacrylic acid, 1.58 parts of 2,2'-azobis (2-methylbutyronitrile) and 20.0 parts. A premix of xylene was prepared and added to the reactor at a constant rate for 2 hours and 30 minutes under a nitrogen atmosphere. One hour after the addition of the feed was completed, a mixture of 0.30 parts of 2,2'-azobis (2-methylbutyronitrile) and 10.0 parts of xylene was placed in the reaction vessel at a constant rate for 15 minutes. Added. The reacted mixture was kept at 85 ° C. for an additional hour before cooling the reactor to room temperature. The amount of component is given in parts by mass.

The acrylic copolymer solution had a non-volatile content of 49.9 wt% and a solution viscosity of 98 cP. The acrylic copolymer solution had an acid value of 28700 Mw, 3.12 PDI and a measured Tg at −35 ° C. and 18.6 mg KOH / g dry polymer.

Procedure for Preparation of Zinc Salt Z1 of Rubber Rosin 1400 g solution of Portuguese rubber rosin (60 wt% in xylene; acid value 109 mg KOH / g solution determined by the method described in the Examples section), 220 g zinc oxidation The product and 60 g of xylene were loaded into a 2 L temperature controlled reaction vessel with a stirrer, a Dean-Stark trap and a reflux condenser. The reaction mixture was refluxed at 140-160 ° C. until the water was no longer condensed in the Dean-Stark trap. Excess zinc oxide was settled before filtering the solution of rubber rosin zinc salt.

The filtered zinc rosinate solution had a non-volatile substance content of 66.9 wt%.

Procedure for Preparation of trimethylisobutenyl Cyclohexene Carboxylic Acid A trimethylisobutenyl cyclohexene carboxylic acid was prepared based on the procedure described in Chinese Patent No. 103980112.

54 parts of methacrylic acid, 102 parts of freshly distilled aloosimene and 0.1 parts of 4-methoxyphenol were added to a reaction flask with a stirrer, condenser and nitrogen inlet. The reaction mixture was placed under nitrogen before heating to 90 ° C. After the reaction for 72 hours, 103 parts of aloosimene was added and the reaction mixture was retained for 11 hours to complete the reaction. The product is purified by vacuum distillation, the first distillation for the crude product is 137-150 ° C., 3 mbar and the second distillation for the product is 140-147 ° C., 3 mbar.

The product was a pale yellow, clear, semi-solid material at room temperature. The product had an acid value of 246 mg KOH / g.

The product was a mixture of isomers of trimethylisobutenyl cyclohexenecarboxylic acid.

Other compounds used in the antifouling coating compositions exemplified herein are summarized in Tables 2a and 2b below. All of these compounds can be purchased from commercial sources.

Determining the properties of the antifouling coating composition and the properties of the coating formed from it Determining the viscosity of the paint using a cone plate viscometer REL digital cone plate viscometer according to ISO 2884-1: 1999 Was determined using, set to a temperature of 23 ° C. ^{, operated at a shear rate of 10000s -1} , and provided viscosity measurements in the range 0-10P. The results are given as the average of the three measurements.

VOC Determination The VOC (g / L) of the antifouling coating composition was calculated according to ASTM D5201-05.

Measurement of König Pendulum Hardness of Coating Film The hardness of the coating film was determined using a pendulum hardness tester. The test was performed according to ISO 1522: 2006.

Each of the antifouling coating compositions was applied to a transparent glass plate (100 x 200 x 3 mm) using a film coater with a gap size of 300 μm. The coating film was dried at 23 ° C. and 50% relative humidity for 1 week and then at 50 ° C. for 72 hours in a ventilation heating chamber. After 24 hours of drying and after 24 hours of forced drying, the coating film hardness of the dried coating film was measured at a temperature of 23 ° C. using an Ericssen 299/300 pendulum hardness tester. Hardness is quantified as the number of pendulum vibrations that reduce the amplitude from 6 ° to 3 °. A higher number of vibrations suggests a higher hardness of the coating.

Determining the polishing rate of the antifouling coating film on the rotating disk in seawater The polishing rate was determined by measuring the decrease in film thickness of the coating film over time. PVC discs were used for this test. The coating composition was applied as radial streaks on a disc using a film applicator with a gap size of 300 μm. The thickness of the dry coating film was measured with a surface profiler. A typical initial dry film depends on the solid content of the antifouling coating composition applied and the speed of application. A typical initial film thickness for the coating tested in the Examples section was 100 ± 15 μm. The PVC disc was mounted on the shaft and rotated in a container through which seawater passed. Natural seawater that had been filtered and temperature controlled to 25 ° C ± 2 ° C was used. The speed of the rotating shaft provided an average simulated speed of 16 knots on the disc. PVC discs were removed at regular intervals to measure film thickness. The disc was dried overnight at room temperature before measuring the film thickness. The result is given as film wear, i.e. the difference between the initial film thickness and the thickness measured at a given time. The coating film is polished when a thin, non-abrasive strained layer remains on the surface, typically to a thickness of 10-20 μm, or when the film is totally polished and removed from the surface. It is considered to be finished (polished through). Finishing polishing is called PT. Coating defects due to the separation of the coating film and flakes are called FL.

The ingredients were mixed in the proportions given in Tables 3, 5, 7-8, 10 and 12-13 below. The mixture was dispersed in a 250 mL paint can in the presence of glass beads (about 3-4 mm in diameter) using a vibrating shaker for 15 minutes. Prior to adding the remaining components to disperse the mixture, the solid resin was dissolved in a solvent to give a 50-60 wt% solid resin solution. The compositions described in Tables 3a, 3b, 5, 7, 10 and 13 were initially prepared as two components (component A and component B) in separate paint cans (250 mL each). Mixed slightly prior to application at a given ratio.

Results The patented examples exemplify the scope of the antifouling coating composition of the present invention. The examples demonstrate the improved film hardness achieved by the antifouling coating composition of the present invention.

The results in Table 4 show that when used in antifouling coating compositions tested for both different types and amounts of reactive zinc compounds, both 24 hours after application and on dried films. It shows that the pendulum hardness of the film formed by the composition is relatively high. These results can be compared with the results for Comparative Examples CPA1-CPA4, which produce significantly lower hardness 24 hours after application and after drying according to the sequence lacking the reactive zinc compound. The result is also that the coating formed from the comparative example is either polished and removed or the polishing rate is flat, while the coating formed from within the antifouling coating composition of the present invention is controlled. It is shown that it is polished at a high speed.

The results in Table 6 show that when used in antifouling coating compositions tested for both different types and amounts of different monocarboxylic acid compounds, both 24 hours after application and on dried films. It shows that the pendulum hardness of the film formed by the composition is relatively high. These results should be compared with the results for Comparative Examples CPB1 to CPB3, which contained significantly lower hardness 24 hours after application and after drying according to the sequence containing the same type of monocarboxylic acid compound but lacking the reactive zinc compound. Can be done. The results also show that the coating formed from Comparative Examples is ultimately defective, but the coating formed from within the antifouling coating composition of the present invention is polished at a controlled rate.

The results in Table 9 show different formulations used in the antifouling coating composition tested, such as different acetal ester copolymers, different cobinders, different biocides and different bulking agents, after application. The pendulum hardness of the films formed by the compositions of the present invention is relatively high, both in 24 hours and in dried films. The results also show that the coating formed from the antifouling coating composition of the present invention is polished at a controlled rate.

CPC2 and CPC3 replica compositions are disclosed in the prior art. Both of these compositions lack a reactive zinc compound. As shown in Table 9, all of these compositions produce significantly lower hardness levels (at 24 hours and after drying) than the compositions of the present invention. CPC1 is a further comparison that is the same as CPC but lacks the monocarboxylic acid compound. In addition, the coating formed from the comparative composition is either polished and removed or the polishing rate is flat.

The results in Table 11 show that in the case of copper-free antifouling coating compositions, the pendulum hardness of the films formed by the compositions of the present invention is relatively high, both 24 hours after application and on dried films. show. The results also show that the coating formed from the copper-free antifouling coating composition of the present invention is polished at a controlled rate. These results can be compared to comparative examples that produce fairly low hardness 24 hours after application and after drying. Furthermore, the composition formed from the comparative example is defective in the polishing test.

The results in Table 14 show that the range of acrylic acetal ester copolymers can be employed in the antifouling coating compositions of the present invention to produce films with relatively high pendulum hardness and controlled polishing rates. show. The illustrated compositions include 1-pack and 2-pack compositions.

Claims (26)

An antifouling coating composition comprising (i) an acrylic acetal ester copolymer; and (ii) a zinc salt of a monocarboxylic acid. (I) Acrylic acetal ester copolymer;
An antifouling coating composition comprising (ii) a monocarboxylic acid; and (iii) a zinc compound that reacts with the monocarboxylic acid to form a zinc salt of the monocarboxylic acid. The acrylic acetal ester copolymer is of formula (I):

Containing residues of at least one monomer of, in the formula,
R ¹ is H or methyl;
R ² is H or C _1-4 alkyl, preferably H;
R ³ is C _1-4 alkyl; and R ⁴ is optionally substituted linear or branched C _1-20 alkyl, C _5-10 cycloalkyl or C _6-10 aryl; or The composition according to claim 1 or 2, wherein R ³ and R ⁴ _{form an optionally substituted C 4- to 8-} membered ring with the O atom to which they are attached. The composition according to any one of claims 1 to 3, wherein the acrylic acetal ester copolymer further comprises a repeating unit derived from a (meth) acrylic acid ester monomer. Acrylic acetal ester copolymers have the formula (II):

Containing residues of at least one monomer of, in the formula,
R ⁷ is H or methyl;
R ⁸ is optionally substituted C _1-18 alkyl, optionally substituted C _5-10 cycloalkyl, optionally substituted C _6-10 aryl or optionally substituted heterocyclyl. The substituent is ^{selected from OR 9} and heterocyclyl;
R ⁹ is selected from hydrogen, C _1-8 alkyl and (CH ₂ CH _2-p (CH ₃ ) _p O) _q R ¹⁰ ;
R ¹⁰ is selected from hydrogen, C _1-4 alkyl and phenyl;
The composition according to any one of claims 1 to 4, wherein p is 0 or 1; and q is an integer of 1 to 20, preferably 1 to 6. The composition according to claim 5, wherein in formula (II), R ⁸ is an unsubstituted C _1-18 alkyl, more preferably an unsubstituted C _{1-8 alkyl.} The composition according to any one of claims 3 to 6, wherein the acrylic acetal ester copolymer contains at least 15 wt% of the monomer of the formula (I). The composition according to claim 5 or 6, wherein the acrylic acetal ester copolymer comprises at least 25 wt% of a monomer of formula (II). The composition according to any one of claims 1 to 8, wherein the amount of the acrylic acetal ester copolymer is 2 to 60 wt% based on the total mass of the composition. _{Zinc salts of monocarboxylic acids are resinic} acids, derivatives of resinous acids, C 6-20 cyclic monocarboxylic acids, C _5-24 acrylic aliphatic monocarboxylic acids, C _7-20 aromatic monocarboxylic acids and mixtures thereof. The composition according to any one of claims 1 to 9, which comprises a monocarboxylic acid selected from. The composition according to any one of claims 1 to 10, wherein the amount of the zinc salt of the monocarboxylic acid is 1 to 30 wt% based on the total mass of the composition. Claimed that the monocarboxylic acid is a resin acid, a derivative of a resin acid, a C _6-20 cyclic monocarboxylic acid, a C _5-24 acrylic aliphatic monocarboxylic acid, a C _7-20 aromatic monocarboxylic acid and mixtures thereof. The composition according to any one of claims 3 to 9 according to claim 2 or when subordinate to claim 2. The amount of the monocarboxylic acid is 1 to 30 wt% based on the total mass of the composition, according to claim 2, or any one of claims 3 to 9 when it is dependent on claim 2. The composition described. One of claims 3 to 9, wherein the zinc compound is selected from zinc oxide, zinc sulfide, zinc carbonate and zinc carbonate hydroxide, according to claim 2, or is dependent on claim 2. The composition according to. The amount of the zinc compound is 0.2 to 20 wt% based on the total mass of the composition, according to claim 2, or any one of claims 3 to 9 when it is dependent on claim 2. The composition according to. The composition according to any one of claims 1 to 15, further comprising a marine antifouling agent. The composition according to any one of claims 1 to 16, further comprising a stabilizer. 1 A method for preparing the composition according to the section. (I) Acrylic acetal ester copolymer;
The composition according to any one of claims 1 to 17, comprising mixing (iii) a monocarboxylic acid; and (iii) a zinc compound that reacts with the monocarboxylic acid to form a zinc salt of the monocarboxylic acid. A method for preparing things. A coating material containing the composition according to any one of claims 1 to 17. A paint container containing the composition according to any one of claims 1 to 17. (I) A first container containing an acrylic acetal ester copolymer and optionally a stabilizer and / or dehydrating agent;
(Ii) a second container containing a zinc salt of monocarboxylic acid and optionally a dehydrating agent; and (iii) optionally containing instructions for mixing the contents of the first and second containers. , A kit for preparing the paint according to claim 20. (I) A first container containing an acrylic acetal ester copolymer and optionally a stabilizer and / or dehydrating agent;
(Ii) A second container containing a monocarboxylic acid, a zinc compound that reacts with the monocarboxylic acid to form a zinc salt of the monocarboxylic acid, and optionally a dehydrating agent; and (iii) optionally the first. And a kit for preparing the paint according to claim 20, comprising instructions for mixing the contents of the second container. An article in which at least a portion of the surface of the article comprises a coating (eg, coated or coated) comprising the composition according to any one of claims 1-17. To prevent fouling of the article, including coating at least a portion of the surface of the article with the composition according to any one of claims 1-17; and drying and / or curing the coating. How to coat an article. Use of the composition according to any one of claims 1 to 17, for coating at least a part of the surface of the article to prevent its fouling.