CN111712549A

CN111712549A - Controlled release antifouling coating composition via biocide interaction

Info

Publication number: CN111712549A
Application number: CN201880089261.1A
Authority: CN
Inventors: N·G·高马兹; E·A·马丁内兹
Original assignee: Hempel AS
Current assignee: Hempel AS
Priority date: 2017-12-14
Filing date: 2018-12-14
Publication date: 2020-09-25
Also published as: KR20200098579A; WO2019115747A1; EP3724278A1; SG11202004860RA

Abstract

A solvent borne antifouling coating composition comprising an erodible non-silicone based binder system, one or more metal-containing biocides such as cuprous oxide, copper pyrithione (copper pyrithione), zinc pyrithione (zinc pyrithione), and zinc ethylene bis (dithiocarbamate) (zineb), and one or more polyoxyalkylene modified alcohols.

Description

Controlled release antifouling coating composition via biocide interaction

Technical Field

The present invention relates to antifouling coating compositions comprising a metal-containing biocide and certain polyoxyalkylene modified alcohols; the invention also relates to a coating system comprising a coating comprising such a metal-containing biocide and an alcohol.

Background

Biocides and especially metal-containing biocides such as cuprous oxide and pyrithione salts are useful in erodible antifouling coating compositions, especially those based on erodible non-silicone based binder systems. An important challenge in designing such coating compositions is that the erodible antifouling coating forms a leaching layer that allows free diffusion of the biocide. Due to free diffusion through the leached layer, large amounts of biocide may be released from the coating too quickly, thus requiring higher amounts of biocide in order to maintain a sufficient level of antifouling activity over time.

JP2006-052284 discloses the preparation of aqueous dispersions of triorganosilyl containing resins. The aqueous dispersion may comprise a silicone oil and optionally a biocide. Wherein the silicone oil can be polyether modified silicone oil.

WO2011/076856 discloses a fouling control coating composition comprising a polysiloxane-based binder system, one or more hydrophilically modified polysiloxanes, and one or more biocides. Hydrophilically modified polysiloxanes are disclosed for facilitating the dissolution and delivery of biocides to coating surfaces.

Summary of The Invention

The present inventors have now found that by redesigning an erodible antifouling coating composition by including therein a polyoxyalkylene modified alcohol having the properties described herein, the free diffusion of the biocide along the leach layer can be delayed. This provides for a more efficient use of the metal-containing biocide to improve antifouling performance and/or reduce the amount of biocide needed to achieve the same antifouling performance by using the same level of biocide, as such controlled release will increase the bioavailability of the biocide to the fouling organism over a long period of time.

Without being bound by any particular theory, it is presently believed that the function of the polyoxyalkylene modified alcohol is to interact with the metal-containing biocide, which improves the antifouling performance and/or the durability of the antifouling effect. Means to control the leaching rate include the molecular size of the polyoxyalkylene modified alcohol, overall hydrophilicity, and miscibility with the binder.

Thus, in a first aspect, the present invention relates to a solvent borne antifouling coating composition, see claim 1.

A second aspect of the invention relates to an antifouling coating, see claim 17.

A third aspect of the invention relates to an antifouling coating system, see claim 18.

A fourth aspect of the invention relates to a ship structure, see claim 20.

A fifth aspect of the present invention relates to the use of a combination of one or more polyoxyalkylene modified alcohols and one or more metal containing biocides for improving the antifouling properties of a coating composition comprising an erodible non-silicone based binder system, see claim 21.

Detailed Description

Solvent-based antifouling coating composition

The present invention provides a solvent-based antifouling coating composition comprising:

a. a non-silicone based binder system that is susceptible to attack,

b. one or more metal-containing biocides, and

c. one or more polyoxyalkylene-modified alcohols,

wherein the total amount of the one or more polyoxyalkylene modified alcohols is from 0.05 to 15% by dry weight based on the coating composition.

Coating compositions (sometimes referred to as "paints" or "paint compositions") generally consist of a binder phase (which forms a paint film when dried and thus corresponds to the continuous phase of the final paint coat) and a pigment phase (corresponding to the discontinuous phase of the final paint coat). According to this simplified understanding, the one or more metal-containing biocides and the non-reactive polyoxyalkylene modified alcohol are not part of the continuous phase (binder phase) but form part of the "pigment phase".

In the context of the present invention, the term "solvent-borne" is understood to mean that the components of the binder system in the coating composition are dissolved in a non-aqueous solvent and wherein upon evaporation of the solvent, in some cases, upon further curing of the binder components, a coating layer corresponding to the coating composition is formed.

In a presently preferred embodiment, the solvent borne coating composition comprises a physically drying binder system, which is different from a chemically hardening binder system (see below) in that the binder component (i.e. the individual molecules) of the binder system in the dry coating is already present in the wet coating composition in the same form. The molecular structure or size of the binder composition or binder components is unchanged. The coating is formed entirely by evaporation of the solvent, leaving the binder molecules as chains wrapped and entangled in the coating.

In another embodiment, the solvent borne coating composition comprises a chemically curable binder system characterized in that the final binder molecules in the dried/cured paint film are not present in the wet film. In this case, relatively small molecules of the binder component (e.g., monomers) participate in the chemical reaction to form larger molecules, for example, by chain extension, and may involve crosslinking of the binder component.

In the context of the present invention, the term "non-silicone based binder system" is understood in the sense that the binder system in the antifouling coating composition is essentially free of silicone and polysiloxane moieties. In particular, any silicone portion in the coating composition preferably comprises less than 5% dry weight, such as less than 2% dry weight, or less than 1% dry weight, in particular about 0% dry weight of the binder system. It is also preferred that any such silicone-containing components (e.g., siloxanes and polysiloxanes) are not part of the binder backbone, but may represent pendant/side chains of the binder component backbone.

Binder system

The binder systems suitable for use in the present invention are non-silicone based binder systems that are susceptible to attack.

In most practical embodiments, the non-silicone based binder system comprises 25 to 80% by solids volume of the coating composition. In a preferred embodiment, the non-silicone based binder system comprises 20 to 70% solids volume of the coating composition, for example 18 to 55% solids volume.

The non-silicone based binder system typically comprises 18 to 75% by dry weight of the coating composition, when expressed as dry weight. In a preferred embodiment, the non-silicone based binder system comprises 16 to 60% dry weight, for example 15 to 40% dry weight of the coating composition.

The binder systems described herein are of the erodible type ("self-polishing").

As used herein, the term "erodible" (sometimes referred to as "self-polishing") is intended to mean that the lacquer coating (i.e., the dry film of the coating composition) should have a polishing rate of at least 1 μm per 10000 nautical miles (18520 km). In a preferred embodiment, the polishing rate is 1 to 50 μm, in particular 1 to 30 μm, per 10000 nautical miles (18520 km).

The binder phase of the coating composition forms a paint film when dried and thus corresponds to the continuous phase of the final (dried) paint coating.

It is envisaged that all erodible binder systems commonly used in "self-polishing" coating compositions may be used as binder systems for the coating compositions of the present invention. It has also been found that only minor modifications (optimizations) may be required for the relative amounts of binder system and pigment/filler/etc. in order to obtain a suitable polishing rate in relation to the marine environment to which the paint coating will be exposed.

To illustrate the scope of the invention with respect to the possible types of binder systems, a number of examples of binder systems for marine and yacht purposes are provided below.

The following types of components in the binder system are believed to be of particular interest: non-aqueous dispersion binder systems, silylated acrylate binder systems, metal acrylate binder systems, mixtures of silylated acrylate and metal acrylate binder systems, polyoxalate binder systems, zwitterionic binder systems, mixtures of silylated acrylates, polyester binder systems, (natural) rosins, rosin derivatives, disproportionated rosins, partially polymerized rosins, hydrogenated rosins, gum rosins, disproportionated gum rosins, acrylic resins, polyvinyl methyl ethers, and vinyl acetate-vinyl chloride-ethylene terpolymers.

Of particular interest in these systems are believed to be rosin binder systems, non-aqueous dispersion binder systems, silylated acrylate binder systems, metal acrylate binder systems, mixtures of silylated acrylate and metal acrylate binder systems, polyoxalate binder systems, zwitterionic binder systems, mixtures of silylated acrylates, and polyester binder systems.

Particularly preferred binder systems are non-silicone based binder systems comprising a component selected from the group consisting of rosin based binder systems, silyl acrylate binder systems, non-aqueous dispersion based binder systems, and metal acrylate based binder systems.

For purposes of illustration, some of these binder systems will be described in further detail below.

Non-aqueous dispersion binder system

The terms "non-aqueous dispersion resin", "NAD" and similar expressions refer to a shell-core structure, which includes resins obtained by stably dispersing a high-polarity high-molecular-weight resin microparticle component ("core component") into a non-aqueous liquid medium in a low-polarity solvent using a high-molecular-weight component ("shell component").

The nonaqueous dispersion resin can be prepared by a method in which a polymerizable ethylenically unsaturated monomer is dispersion-polymerized in a hydrocarbon solvent in the presence of a shell component (dispersion stabilizer) prepared from a polymer dissolved or swollen in the solvent according to a conventional method, wherein the polymerizable ethylenically unsaturated monomer is soluble in the hydrocarbon solvent and is polymerizable to form a polymer insoluble in the hydrocarbon solvent (core component).

The non-aqueous dispersion type resin used in the present invention may be a resin known per se, or may be produced as a known resin. Such non-aqueous dispersion type resins and a process for producing the same are described in, for example, US3,607,821, US4,147,688, US4,493,914 and US4,960,828, japanese patent laid-open No. 29,551/1973 and japanese laid-open patent publication No. 177,068/1982. Specifically, various high molecular substances soluble in a low-polarity solvent, which are described in, for example, US4,960,828 (japanese laid-open patent publication No. 43374/1989), can be used as the shell component constituting the non-aqueous dispersion type resin.

In view of the antifouling property of the final paint coating, a shell component such as an acrylic resin or a vinyl resin may be used.

Copolymers of ethylenically unsaturated monomers having high polarity can generally be employed as the core component. Preferably, the core component of the non-aqueous dispersion type resin has free acid groups or silyl ester groups convertible to acid groups by hydrolysis in seawater, or a combination thereof. Preferably, from 5 to 75% by weight, for example, from 5 to 60% by weight or from 7 to 50% by weight, of the monomers of the core polymer should bear free acid groups or silyl ester groups, or a combination thereof. It is presently preferred to have extra heavy free acid groups, since free acid groups will directly affect the properties of the coating formulation, whereas silyl ester groups only have an effect after hydrolysis in seawater.

Examples of silyl ester monomers are silyl acrylate or silyl methacrylate.

Minor proportions of free acid groups or silyl ester groups may also be included in the shell component, if desired.

The term "free acid group" is meant to encompass acid groups in their acid form. It will be appreciated that such acid groups may be temporarily present in salt form if a suitable counter ion is present in the composition or in the environment. As an illustrative example, it is contemplated that some free acid groups may be present in the form of sodium salts if such groups are exposed to saline.

Preferably, the resin acid value of the non-aqueous dispersion type resin is usually 15 to 400mg KOH/g, preferably 15 to 300mg KOH/g, for example 18 to 300mg KOH/g. If the total acid number of the NAD resin is below 15mg KOH/g, the polishing rate of the lacquer coating is too low and the antifouling properties are often not ideal. On the other hand, if the total acid value is higher than 400mg KOH/g, the polishing rate is too high, and thus a problem of water resistance (i.e., durability of the paint coating in seawater) may occur. (when the core component and/or the shell component comprises acid precursor groups, the resin acid value is the value obtained when said groups are converted to acid groups by hydrolysis). The "resin acid value" herein is the amount (mg) of KOH consumed for neutralizing 1g of resin (solid content), and indicates the content of acid groups (in the case of acid precursor groups, the content of acid groups formed by hydrolysis) of the resin (solid content).

It is recommended that the acid group and/or acid precursor group is contained in the core component so that the content thereof (as the resin acid value) is at least 80%, preferably at least 90%, more preferably at least 95% of the total resin acid value of the non-aqueous dispersion-type resin.

Therefore, hydrophobic shell components are generally preferred. The dry weight ratio of the core component to the shell component in the NAD resin is not particularly limited, but is generally in the range of 90/10-10/90, preferably 80/20-25/75, for example 60/40-25/75.

Silylated acrylate binder systems

In another interesting embodiment of the present invention, the binder system used in the coating composition of the present invention comprises a silylated acrylate copolymer comprising at least one side chain bearing at least one terminal group of formula (I):

wherein n is an integer of 0,1,2, etc., and X is-C (═ O) -, and R₁，R₂，R₃，R₄And R₅The definition is as follows:

when n is an integer of 0,1,2,3,4 or more, in these cases it is preferred that n is from 0 to 100, such as from 0 to 50, for example 0 or 1 or 2 to 15.

R₁-R₅Each being the same or different and selected from C_1-20Alkyl (e.g. methyl, ethyl, propyl, butyl, cycloalkyl such as cyclohexyl), optionally substituted aryl (e.g. substituted phenyl and substituted naphthyl). Examples of substituents for aryl are halogen, C_1-5Alkyl radical, C_1-10-alkylcarbonyl, sulfonyl, nitro or amino. In general, R₁-R₅Are each selected from C_1-8-alkyl and optionally substituted phenyl. It is generally preferred that each alkyl group has up to about 5 carbon atoms (C)_1-5-an alkyl group). As mentioned above, R₁-R₅May be the same or different groups.

Monomers containing terminal groups of the above general formula I can be synthesized as described in EP 0297505B 1.

Such monomers may be copolymerized with the vinyl polymerizable monomer (a) to obtain a copolymer. Examples of suitable vinyl polymerizable monomers (A) include methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate and methoxyethyl methacrylate; acrylic esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate; maleates such as dimethyl maleate and diethyl maleate; fumaric acid esters such as dimethyl fumarate and diethyl fumarate; styrene, vinyl toluene, alpha-methyl styrene, vinyl chloride, vinyl acetate, butadiene, acrylamide, acrylonitrile, methacrylic acid, acrylic acid, isobornyl methacrylate, and maleic acid.

The amount of the vinyl polymerizable monomer is not more than 95% by weight, preferably not more than 90% by weight, based on the total weight of the resulting copolymer. Thus, the amount of monomers comprising the terminal group of formula I above is at least 5% by weight, in particular at least 10% by weight.

The weight average molecular weight of the copolymer is preferably 1,000-1,500,000, such as 5,000-1,000,000, 5,000-500,000, 5,000-250,000 or 5,000-100,000.

In another interesting embodiment of the present invention, the binder system used in the coating composition of the present invention comprises a silylated acrylate copolymer comprising at least one side chain with at least one terminal group of formula II (i.e. formula I wherein n ═ 0):

wherein X, R₃，R₄And R₅As defined above.

Examples of monomers having a terminal group of formula II (as shown above) are acid functional vinyl polymerizable monomers such as monomers derived from acrylic acid, methacrylic acid, maleic acid (preferably in the form of a monoalkyl ester having 1 to 6 carbon atoms) or fumaric acid (preferably in the form of a monoalkyl ester having 1 to 6 carbon atoms).

Thus, suitable triorganosilyl groups of the formula I or II (i.e. -Si (R))₃)(R₄)(R₅) Specific examples of the group) includeTrimethylsilyl, triethylsilyl, tri-n-propylsilyl, tri-n-butylsilyl, triisopropylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tri-n-octylsilyl, tri-n-dodecylsilyl, triphenylsilyl, tri-p-methylphenylsilyl, tribenzylsilyl, tri-2-methylisopropylsilyl, tri-tert-butylsilyl, ethyldimethylsilyl, n-butyldimethylsilyl, diisopropyl n-butylsilyl, n-octyl di-n-butylsilyl, diisopropyl octadecylsilyl, dicyclohexylphenylsilyl, tert-butyldiphenylsilyl, dodecyl diphenylsilyl and diphenyl methylsilyl.

Specific examples of suitable methacrylic acid-derived monomers having at least one terminal group of formula I or II include trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl (meth) acrylate, triisopropylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tri-tert-butylsilyl (meth) acrylate, tri-n-pentylsilyl (meth) acrylate, tri-n-hexylsilyl (meth) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, tri-p-methylphenylsilyl (meth) acrylate, tribenzylsilyl (meth) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, tri-phenylsilyl (meth) acrylate, tri-n-pentylsilyl (meth), Ethyldimethylsilyl (meth) acrylate, n-butyldimethylsilyl (meth) acrylate, diisopropyl n-butylsilyl (meth) acrylate, n-octyldi-n-butylsilyl (meth) acrylate, diisopropyl stearyl silyl (meth) acrylate, dicyclohexylphenylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, and lauryl diphenylsilyl (meth) acrylate.

Specific examples of suitable maleic acid-derived monomers and fumaric acid-derived monomers having at least one terminal group of formula I or II include triisopropylsilylmethyl maleate, triisopropylsilylpentyl maleate, tri-n-butylsilyl n-butyl maleate, tert-butyldiphenylsilylmethyl maleate, tert-butyldiphenylsilyl n-butyl maleate, triisopropylsilylmethyl fumarate, triisopropylsilylpentyl fumarate, tri-n-butylsilyl n-butyl fumarate, tert-butyldiphenylsilylmethyl fumarate, and tert-butyldiphenylsilyl n-butyl fumarate.

In one interesting embodiment of the invention, the copolymer for the binder system comprises a combination of monomer units having terminal groups of general formulae I and II (as described above) and a second monomer B of general formula III:

Y-(CH(R_A)-CH(R_B)-O)_p-Z (III)

wherein Z is C_1-20An alkyl or aryl group; y is an acryloyloxy group, a methacryloyloxy group, a maleoyloxy group or a fumaroyloxy group; r_AAnd R_BIndependently selected from hydrogen, C_1-20-alkyl and aryl; p is an integer of 1 to 25. If p is>2, then R_AAnd R_BPreferably hydrogen or CH₃I.e. if p>2, the monomers B are preferably derived from polyoxyethylene or polyoxypropylene. If p is 1, then consider where R is_AAnd R_BIs a larger group such as C_1-20Monomers of-alkyl or aryl groups may also be used for the purposes described herein. As shown in the general formula III, the monomer B has an acryloyloxy group, a methacryloyloxy group, a maleyloxy group (preferably mono-C) in the molecule_1-6In the form of an alkyl ester), or fumaroyloxy groups (preferably mono-C)_1-6In the form of an alkyl ester) as unsaturated group (Y) and also has an alkoxypolyoxyethylene or aryloxypolyoxyethylene. In the alkoxypolyoxyethylene or aryloxyphenoxypolyoxyethylene group, the degree of polymerization (p) of polyoxyethylene is 1 to 25.

Specific examples of the monomer B having a (meth) acryloyloxy group in the molecule include methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, hexyloxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate and ethoxytriethylene glycol (meth) acrylate.

Specific examples of the monomer B having a maleyloxy group or a fumaroyloxy group in the molecule include methoxyethyl n-butyl maleate, ethoxydiglycol methyl maleate, ethoxytriglycol methyl maleate, propoxydiethylene glycol methyl maleate, butoxyethylmethyl maleate, hexyloxyethyl methyl maleate, methoxyethyl n-butyl fumarate, ethoxydiglycol methyl fumarate, ethoxytriglycol methyl fumarate, propoxydiethylene glycol methyl fumarate, butoxyethylmethyl fumarate and hexyloxyethyl methyl fumarate.

It will be appreciated by those skilled in the art that other vinyl monomers may be incorporated into the resulting copolymer comprising monomeric units having an end group of formula I or II (as shown above), or a combination of monomeric units having an end group of formula I or II (as shown above) and a second monomer B of formula III (as shown above).

As other monomers copolymerizable with the above monomers, various vinyl monomers can be used, for example, the vinyl polymerizable monomer (A) discussed above.

The proportion of monomers having terminal groups of the formula I or II is preferably from 1 to 95% by weight, the proportion of monomers B from 1 to 95% by weight and the proportion of further monomers copolymerizable therewith from 0 to 95% by weight, based on the total weight of the monomers.

Desirably, the molecular weight of the copolymer thus obtained is in the range of 1,000-150,000, for example, in the range of 3,000-100,000, for example, in the range of 5,000-100,000 in terms of weight average molecular weight.

In another interesting embodiment of the present invention, the binder system used in the coating composition of the present invention comprises a copolymer of a combination of monomeric units having a terminal group of formula I or II (as described above) and a second monomer C of formula IV:

wherein Y is an acryloyloxy group, a methacryloyloxy group, a maleoyloxy group or a fumaroyloxy group, R₆And R₇Are all C_1-12-an alkyl group.

As shown in the formula IV, the monomer C has an acryloyloxy group, a methacryloyloxy group, a maleyloxy group (preferably mono-C) in its molecule_1-6In the form of an alkyl ester) or fumaroyloxy groups (preferably mono-C)_1-6In the form of alkyl esters) as unsaturated group (Y) and also as hemiacetal group.

Monomer C can be prepared by conventional addition reaction of a carboxyl group-containing vinyl monomer selected from acrylic acid, methacrylic acid, maleic acid (or its monoester), and fumaric acid (or its monoester) with an alkyl vinyl ether (such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and 2-ethylhexyl vinyl ether) or a cycloalkyl vinyl ether (such as cyclohexyl vinyl ether).

It will be appreciated by those skilled in the art that other vinyl monomers may be incorporated into the resulting copolymer comprising a combination of monomer units having an end group of formula I or II (as shown above) and a second monomer C of formula IV (as shown above).

Preferably, the proportion of monomers having terminal groups of the formula I or II is from 1 to 95% by weight (preferably from 1 to 80% by weight), the proportion of monomers C is from 1 to 95% by weight (preferably from 1 to 80% by weight), and the proportion of further monomers copolymerizable therewith is up to 98% by weight, based on the total weight of the monomers.

Desirably, the molecular weight of the copolymer is in the range of 1,000-150,000, preferably in the range of 3,000-100,000, for example in the range of 5,000-100,000 in terms of weight average molecular weight.

Metal acrylate binder system

In one interesting embodiment of the present invention, the binder system used in the coating composition of the present invention comprises a metal acrylate copolymer comprising at least one side chain with at least one terminal group of formula V:

-X-O-M-(L)_n(V)

wherein X is-C (═ O) -, -S (═ O)₂-, -P (═ O) (OH) -; m is a metal having a valence of 2 or higher; n is an integer of 1 or more, provided that n +1 is equal to the valence of the metal; l is an organic acid residue, and each L is independently selected from:

-O-R₄，-S-R₄and

wherein R is₄Is a monovalent organic residue, or L is-OH or a combination thereof; r₃Is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.

Examples of monomers having terminal groups of the general formula V (as indicated above) are acid-functional vinyl polymerizable monomers, such as methacrylic acid, acrylic acid, p-styrenesulfonic acid, 2-methyl-2-acrylamidopropanesulfonic acid, phosphooxypropyl methacrylate 3-chloro-2-oate, phosphooxyethyl methacrylate, itaconic acid, maleic anhydride, monoalkyl itaconates (such as methyl, ethyl, butyl, 2-ethylhexyl), monoalkyl maleates (such as methyl, ethyl, butyl, 2-ethylhexyl); half esters of anhydrides with hydroxy-containing polymerizable unsaturated monomers (e.g., half esters of succinic, maleic or phthalic anhydride with 2-hydroxyethyl methacrylate). The above monomers may be copolymerized to obtain a copolymer having one or more vinyl polymerizable monomers. Examples of such vinyl polymerizable monomers are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, methoxyethyl methacrylate, styrene, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, vinyl acetate, acrylonitrile, methacrylonitrile, dimethyl itaconate, dibutyl itaconate, di-2-ethylhexyl itaconate, dimethyl maleate, di-2-ethylhexyl maleate, ethylene, propylene and vinyl chloride.

For the ligand (L), each individual ligand is preferably selected from:

-O-R₄，-S-R₄and

wherein R is₄Is a monovalent organic residue. Preferably, R₄Selected from:

-R₈-R₉and R₉，

Wherein R is₅Is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; r₆And R₇Each independently represents a hydrocarbon group having 1 to 12 carbon atoms; r₈Is a hydrocarbon group having 1 to 4 carbon atoms; r₉Is a cyclic hydrocarbon group having 5 to 20 carbon atoms, such as abietic acid, palustric acid, neoabietic acid, levopimaric acid, dehydroabietic acid, pimaric acid, isopimaric acid, sandaracopimaric acid and Δ 8, 9-isopimaric acid.

Examples of compounds that can be used as ligands are:

(1) a compound comprising the following group:

for example, aliphatic acids such as levulinic acid; alicyclic acids such as naphthenic acid, chaulmoogric acid, hydnocarpusic acid (hydnocarpusic acid), neoabietic acid, levopimaric acid, palustric acid, 2-methyl-bicyclo-2, 2, 1-heptane-2-carboxylic acid; aromatic carboxylic acids such as salicylic acid, methyl salicylic acid, alpha-naphthoic acid, beta-naphthoic acid, p-hydroxybenzoic acid; halogen-containing aliphatic acids such as monochloroacetic acid, monofluoroacetic acid; halogen-containing aromatic acids such as 2,4, 5-trichlorophenoxyacetic acid, 2, 4-dichlorophenoxyacetic acid, 3, 5-dichlorobenzoic acid; nitrogen-containing organic acids such as quinoline carboxylic acid, nitrobenzoic acid, dinitrobenzoic acid, nitronaphthalene carboxylic acid; lactone carboxylic acids such as occipital acid, occipital methyl ester; uracil derivatives such as uracil-4-carboxylic acid, 5-fluorouracil-4-carboxylic acid, uracil-5-carboxylic acid; carboxylic acids derived from penicillin, such as penicillin V, ampicillin, penicillin BT, penicillanic acid, penicillin G, penicillin 0; rifamycin B, rusomycin, Salcomycin, chloramphenicol, pseudopenicillin, Trypacidine; and various synthetic fatty acids.

(2) A compound comprising the following groups:

such as dimethyl dithiocarbamate and other dithiocarbamates.

(3) A compound comprising the following groups:

for example, sulfur-containing aromatic compounds such as 1-naphthol-4-sulfonic acid, p-phenylphenylsulfonic acid, β -naphthalenesulfonic acid, and quinolinesulfonic acid.

(4) A compound comprising an-S-group, such as a compound comprising:

(5) a compound comprising the following groups:

such as various thiocarboxylic compounds.

(6) Compounds containing-O-or-OH groups, such as phenol, cresol, xylenol, thymol, carvacrol, eugenol, isoeugenol, phenylphenol, benzylphenol, guaiacol, butylstilbene, (di) nitrophenol, nitrocresol, methyl salicylate, benzyl salicylate, monochlorophenol, dichlorophenol, trichlorophenol, tetrachlorophenol and pentachlorophenol, chlorocresol, chloroxylenol, chlorothymol, p-chloro-O-cyclohexylphenol, p-chloro-O-cyclopentylphenol, p-chloro-O-hexylphenol, p-chloro-O-benzylphenol, p-chloro-O-benzylm-cresol and other phenols, beta-naphthol, 8-hydroxyquinoline.

As the metal (M), any metal having a valence of 2 or more can be used. Specific examples of suitable metals include Ca, Mg, Zn, Cu, Ba, Te, Pb, Fe, Co, Ni, Bi, Si, Ti, Mn, Al and Sn. Preferred examples are Co, Ni, Cu, Zn, Mn and Te, particularly preferably Cu and Zn. In the synthesis of the metal-containing copolymer, the metal may be used in the form of an oxide, hydroxide or chloride. The copolymers used in the binder system of the coating compositions of the invention can be prepared, for example, as described in EP0471204B1, EP 0342276B1 or EP 0204456B 1. The monomers comprising the terminal group of formula V above may be copolymerized with other polymerizable unsaturated monomers (to obtain a copolymer), and any of the usual ethylenically unsaturated monomers may be used. Examples of such monomers are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, methoxyethyl methacrylate, styrene, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, vinyl acetate, acrylonitrile, methacrylonitrile, dimethyl itaconate, dibutyl itaconate, di-2-ethylhexyl itaconate, dimethyl maleate, di- (2-ethylhexyl) maleate, ethylene, propylene and vinyl chloride. One particular type of comonomer is an acrylate or methacrylate ester in which the alcohol residue comprises a large hydrocarbon group or a soft segment, for example a branched alkyl ester having 4 or more carbon atoms or a cyclic alkyl ester having 6 or more atoms, a polyalkylene glycol monoacrylate or monomethacrylate optionally having a terminal alkyl ether group or an adduct of 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate with caprolactone, as described in EP0779304a 1.

If desired, monomers containing hydroxyl groups such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate may also be used.

It should be noted that in the resulting copolymer, not all of the pendant organic acid groups need to contain a metal ester linkage; some of the pendant organic acid groups may remain unreacted in the free acid form, if desired.

The weight average molecular weight of the metal-containing copolymer is typically 1,000-150,000, for example 3,000-100,000, preferably 5,000-60,000.

In another interesting embodiment of the present invention, the coating composition further comprises an amount of organic ligands selected from the group consisting of aromatic nitro compounds, nitriles, urea compounds, alcohols, phenols, aldehydes, ketones, carboxylic acids and organic sulfur compounds such that the coordination ratio of ligands to metal is at least equal to 1:1, such that the copolymer defined above forms a polymer complex in situ with the organic ligands.

Examples of monobasic organic acids that can be used to form the hybrid salts include monobasic carboxylic acids such as acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, linoleic acid, oleic acid, naphthenic acid, chloroacetic acid, fluoroacetic acid, abietic acid, phenoxyacetic acid, valeric acid, dichlorophenoxyacetic acid, benzoic acid, or naphthoic acid; and monosulfonic acids, such as benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, or p-phenylbenzenesulfonic acid.

A preferred method for producing polymeric hybrid salts has been disclosed in Japanese patent Kokai No. 16809/1989.

Silyl-metal acrylate mixtures

Another interesting example of a binder of interest is a binder based on silyl acrylate monomers (such as those described further above) and metal acrylate monomers (such as those described further above). Such binders have backbone segments of the general formula:

and is described, for example, in KR 20140117986.

Polyoxalate binder

Another example of a binder of interest is a polyoxalate-based binder as disclosed in WO 2015/114091.

Zwitterionic binders and mixtures with silyl acrylates

Another example of binders of interest are polymer binders based on zwitterionic monomers with possible binding to silyl acrylate monomers as disclosed in WO2004/018533 and WO 2016/066567.

Polyester binder

Another example of a binder of interest is a polyester based binder as disclosed in WO 2014/010702.

Rosin-based binder system

Another binder system of interest may be a binder system based on rosin and/or rosin derivatives, which may be combined with any of the aforementioned binder systems.

Examples of components of such rosin-based binder systems are rosins, rosin derivatives, such as metal salts of rosins, i.e. resinates.

The terms "rosin", "resinate" and the like refer to gum rosin, wood rosin of grade B, C, D, E, F, FF, G, H, I, J, K, L, M, N, W-G, W-W (as defined by ASTM 0509 standard), virgin rosin, hard rosin, yellow impregnated rosin (yellow dip rosin), NF wood rosin, tall oil rosin, or rosin (colophony) or rosin (colophonium). The terms "rosin" and "resinate" and the like are also meant to include suitable types of modified rosins, particularly oligomerization, hydrogenation, dehydrohydrogenation/disproportionation, and the like that will reduce the amount of conjugated non-aromatic double bonds. It will be appreciated that further binder components of this group may include polymeric tougheners such as those specifically defined generally in WO97/44401, which is incorporated herein by reference.

When expressed on a dry weight basis, rosin-based binder systems typically constitute from 5 to 30% dry weight of the coating composition. In a preferred embodiment, the non-silicone based binder system comprises 8 to 25% by dry weight, for example 10 to 25% by dry weight, of the coating composition.

In most practical embodiments, the rosin-based binder system comprises 10 to 50% by solids volume of the coating composition. In a preferred embodiment, the non-silicone based binder system comprises 12 to 45% solids volume of the coating composition, for example 15 to 40% solids volume.

Other binder components

The above-described binder systems (e.g., non-aqueous dispersion binder systems, silylated acrylate binder systems, and various mixtures) may include (as part of the binder system) one or more other binder components therein. It should be understood that the binder components mentioned below may also constitute the binder system alone, see the general description of the binder system.

Examples of such other binder components are: oils, such as linseed oil and derivatives thereof, castor oil and derivatives thereof, soybean oil and derivatives thereof; and other polymeric binder components, such as saturated polyester resins; copolymers of polyvinyl acetate, polyvinyl butyrate, polyvinyl chloride-acetate, vinyl acetate and vinyl isobutyl ether; vinyl chloride; copolymers of vinyl chloride and vinyl isobutyl ether; alkyd resins or modified alkyd resins; hydrocarbon resins, such as petroleum distillate condensates; chlorinated polyolefins, such as chlorinated rubber, chlorinated polyethylene, chlorinated polypropylene; styrene copolymers, such as styrene/butadiene copolymers, styrene/methacrylate and styrene/acrylate copolymers; acrylic resins such as homopolymers and copolymers of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and isobutyl methacrylate; a hydroxy acrylate copolymer; polyamide resins, such as polyamides based on dimerized fatty acids (e.g., dimerized tall oil fatty acids); cyclized rubber; an epoxy ester; epoxy polyurethane; a polyurethane; an epoxy polymer; a hydroxy polyether resin; polyamine resins, etc.; and copolymers thereof.

These other binder components are typically present in an amount of 0-25% by wet weight, for example 5-20% by wet weight.

Metal-containing biocides

Another important component of the coating composition of the present invention is one or more metal-containing biocides.

In the context of the present invention, the term "biocide" refers to an active substance that is destroyed, prevented, rendered harmless by chemical or biological means, prevents its action, or otherwise exerts a controlling action on any pest.

Illustrative examples of metal-containing biocides are those selected from metal-containing organic biocides such as metal-dithiocarbamates (e.g., zinc bis (dimethyldithiocarbamate), zinc ethylene-bis (dithiocarbamate), manganese ethylene-bis (dithiocarbamate), zinc dimethyldithiocarbamate, and complexes between these); bis (1-hydroxy-2 (1H) -pyridinethiosulfuric acid-O, S) -copper (copper pyrithione); copper acrylate; bis (1-hydroxy-2 (1H) -pyridinethiosulfuric acid-O, S) -zinc (zinc pyrithione); phenyl (bispyridyl) -bismuth dichloride; and metal-containing inorganic biocides, for example metal biocides, such as copper (I) oxide, cuprous oxide and metallic copper, copper metal alloys, such as copper-nickel alloys, such as copper bronze; metal salts such as cuprous thiocyanate, basic copper carbonate, copper hydroxide, barium metaborate, copper chloride, silver nitrate, and copper sulfide; and N-cyclohexyl diazo dioxa bis copper.

Presently preferred examples thereof are copper-containing biocides and zinc-containing biocides, in particular cuprous oxide, copper pyrithione, zinc pyrithione and zinc ethylenebis (dithiocarbamate) (zineb).

Typically, the amount of metal-containing biocide is typically from 3 to 65%, such as from 5 to 60%, such as from 10 to 60%, or from 15 to 40%, or from 20 to 60% by dry weight of the coating composition. The amount of metal-containing biocide is typically from 3 to 45%, for example from 5 to 40%, for example from 7 to 38%, or from 10 to 35%, or from 15 to 35% by solids volume of the coating composition, expressed as solids volume.

In another embodiment of particular interest, the metal-containing biocide comprises a metal-containing inorganic biocide, particularly cuprous oxide. In this embodiment, the amount of biocide (especially cuprous oxide) is typically 3 to 65%, such as 5 to 60%, for example 10 to 60%, or 15 to 40%, or 20 to 60% dry weight of the coating composition. The amount of metal-containing inorganic biocide, particularly cuprous oxide, is typically from 3 to 45%, for example from 5 to 40%, for example from 7 to 38%, or from 10 to 35%, or from 15 to 35% by solids volume of the coating composition, expressed as solids volume.

In another embodiment of particular interest, the metal-containing biocide comprises only a metal-containing organic biocide. In this embodiment, the total amount of metal-containing organic biocide is typically from 0.25 to 30%, such as from 0.5 to 25%, for example from 0.75 to 20%, or from 1 to 15%, or even from 2 to 12% by dry weight of the coating composition. The amount of metal-containing organic biocide is typically from 0.5 to 15%, for example from 1 to 12%, for example from 2 to 10%, or from 4 to 9% by solids volume of the coating composition, expressed as solids volume.

In another embodiment of particular interest, the metal-containing biocide is copper pyrithione and/or zinc pyrithione. In this embodiment, the total amount of copper pyrithione and zinc pyrithione is generally from 0.25 to 30%, such as from 0.5 to 25%, such as from 0.75 to 20%, or from 1 to 15%, or even from 2 to 12% by dry weight of the coating composition. The total amount of copper pyrithione and zinc pyrithione, expressed as solid volume, is generally from 0.5 to 15%, such as from 1 to 12%, such as from 2 to 10%, or from 4 to 9% solid volume of the coating composition.

In this embodiment, the weight ratio between cuprous oxide and the total amount of copper pyrithione and/or zinc pyrithione is preferably in the range of 100:1 to 1:2, such as 50:1 to 1:1.5, or 30:1 to 1:1, such as 25:1 to 1:1, or 20:1 to 2: 1.

In this embodiment, the solid volume ratio between cuprous oxide and the total amount of copper pyrithione and/or zinc pyrithione is preferably in the range of 30:1 to 1:3, such as 25:1 to 1:2, or 20:1 to 1:1.5, such as 15:1 to 1:1.4, or 10:1 to 1: 1.2.

In another embodiment of particular interest, the metal-containing biocide is ethylene bis (dithiocarbamate) zinc (zineb). In this embodiment, the amount of ethylene bis (dithiocarbamate) zinc (zineb) is typically 1 to 30%, such as 2 to 20%, such as 3 to 15%, or 4 to 10%, or even 5 to 15% by dry weight of the coating composition. The total amount of zinc ethylenebis (dithiocarbamate) (zineb), expressed as solids volume, is typically 1-30%, such as 2-20%, such as 3-15%, or 4-10%, or 5-15% solids volume of the coating composition.

In some embodiments, where the metal-containing biocide is cuprous oxide in combination with one or more other metal-containing biocides, the total amount of biocide is typically 3-65%, such as 5-60%, for example 10-60%, or 15-60%, or even 20-60% dry weight of the coating composition. The amount of cuprous oxide combined with one or more other metal-containing biocides, expressed as solids volume, is typically 3-45%, such as 5-40%, for example 7-38%, or 10-35%, or 15-35% solids volume of the coating composition.

It will be appreciated that the metal-containing biocide may be combined with one or more non-metallic biocides such as heterocyclic nitrogen compounds, e.g. 3a,4,7,7 a-tetrahydro-2- ((trichloromethyl) -thio) -1H-isoindole-1, 3(2H) -dione, pyridine-triphenylborane, 1- (2,4, 6-trichlorophenyl) -1H-pyrrole-2, 5-dione, 2,3,5, 6-tetrachloro-4- (methylsulfonyl) -pyridine, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine and quinoline derivatives; heterocyclic sulfur compounds, e.g. 2- (4-thiazolyl) benzimidazole, 4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4, 5-dichloro-2-octyl-3 (2H) -isothiazolin (Sea-

-211N), 1, 2-benzisothiazolin-3-one and 2- (thiocyanomethylthio) -benzothiazole; (RS) -4- [1- (2, 3-dimethylphenyl) ethyl]-3H-imidazole (Medetomine,

) And 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (Tralopyril,

) (ii) a Urea derivatives such as N- (1, 3-bis (hydroxymethyl) -2, 5-dioxo-4-imidazolinyl) -N, N' -bis (hydroxymethyl) urea and N- (3, 4-dichlorophenyl) -N, N-dimethylurea, N-dimethylchlorophenylurea; amide or imide compounds of carboxylic, sulfonic and sulfenic acids, such as 2,4, 6-trichlorophenylmaleimide, 1-dichloro-N- ((dimethylamino) sulfonyl) -1-fluoro-N- (4-methylphenyl) -methylsulfinamide, 2-dibromo-3-nitrilo-propionamide, N- (fluorodichloromethylthio) -phthalimide, N-dimethyl-N '-phenyl-N' - (fluorodichloromethylthio) -sulfonamide and N-hydroxymethylformamide; carboxylates or carboxylates, such as 2- ((3-iodo-2-propargyl) oxy) -ethanolphenylcarbamate and ammonium N, N-didecyl-N-methyl-poly (oxyethyl) propionate; amines, such as dehydroabietylamine and dimethyl cocoamine; substituted methanes such as bis (2-hydroxy-ethoxy) methane, 5 '-dichloro-2, 2' -dihydroxydiphenylmethane and dithiocyano-methane; substituted benzenes, such as 2,4,5, 6-tetrachloro-1, 3-phthalonitrile, 1-dichloro-N- ((dimethylamino) -sulfonyl) -1-fluoro-N-phenylmethanesulfimide, and 1- ((diiodomethyl) sulfonyl) -4-methyl-benzene; tetraalkylphosphonium halides, such as tri-n-butyltetradecylphosphonium chloride; guanidine derivatives, such as n-dodecylguanidine hydrochloride; disulfides, such as bis- (dimethylthiocarbamoyl) -disulfide, tetramethylthiuram disulfide; imidazole-containing compounds, such as medetomidine (medetomidine); 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole; and mixtures thereof.

Polyoxyalkylene-modified alcohols

It has been found that functionalizing the hydroxyl groups of alcohols with polyalkylene oxides provides highly useful compounds in antifouling coatings for use in conjunction with biocides, particularly metal-containing biocides such as zinc pyrithione, copper pyrithione, cuprous oxide, and zineb. This is further illustrated below and in the "examples" section.

The coating comprises one or more polyoxyalkylene modified alcohols having the general formula (I):

(POA–O–)_X–R–(–O–FA)_Y(I)

wherein each POA represents a polyoxyalkylene moiety and each FA represents C_8-30Fatty acyl moiety, R represents an alcohol R (OH)_X+YThe organic residue of (a), the organic residue having 2 to 50 carbon atoms, and X is 1 to 5, Y is 0 to 10, and X + Y is 1 to 12.

In the above formula (I), the-O-related to POA-O-represents an ether oxygen covalently linking a polyoxyalkylene and an organic residue of an alcohol. The fatty acyl moiety FA is a long-chain acyl moiety forming an ester linkage (-O-C (═ O) -), wherein-O-associated with FA-O-represents an ester oxygen covalently linking the long-chain fatty acid and the organic residue of the alcohol.

The organic residue is typically of pure hydrocarbon origin, i.e., composed of straight, branched, cyclic, unsaturated and/or aromatic moieties, except that it may contain 1-5 ether linkages (-C-O-C-) either as part of the ring structure or directly attached to the ring structure. In some embodiments, the organic residue is a pure hydrocarbon source.

In one embodiment, the alcohol R (OH)_X+YHas 2 to 50 carbon atoms, for example 3 to 50 carbon atoms, and has only linear, branched and/or unsaturated moieties.

In another embodiment, the alcohol R (OH)_X+YHas 2 to 50 carbon atoms, for example 3 to 50 carbon atoms, and is selected from substituted phenols, sorbitan, lanolin or sterols. Preferably, the organic residue R is selected from lanolin or sterols.

The organic residue R such as in the preceding embodiments typically has from 2 to 50 carbon atoms, for example from 3 to 50 carbon atoms or from 6 to 50 carbon atoms, for example from 8 to 45 carbon atoms, for example from 9 to 40 carbon atoms or from 10 to 35 carbon atoms.

In embodiments where X + Y is 1, the organic residue typically has from 6 to 50 carbon atoms.

In general, the polyoxyalkylene moieties POA each represent R¹O-[R²-O]_n-R³-a moiety wherein R¹Selected from hydrogen, C_1-4-alkyl-C (═ O) -and C_1-4-an alkyl group; r²And R³Each selected from the group consisting of ethan-1, 2-ene and propan-1, 2-ene. n is an integer from 1 to 150.

The polyoxyalkylene moiety POA is typically a polyoxyalkylene moiety selected from the group consisting of polyoxyethylene, polyoxypropylene and poly (oxyethylene-co-oxypropylene).

In some embodiments of interest, n is from 4 to 150, such as from 5 to 100, for example from 6 to 75, especially from 6 to 30.

In one embodiment, the polyalkylene oxide is selected from polyoxyethylene and poly (oxyethylene-oxypropylene), preferably from those polyalkylene oxides having a number average molecular weight of, for example, 100-.

In one variant thereof, the polyalkylene oxide is selected from polyoxyethylene. Illustrative examples herein are PEG-30 and PEG-75.

In another variant thereof, the polyoxyalkylene is selected from poly (oxyethylene-co-oxypropylene). Illustrative examples thereof are PEG-5/PPG-5 and PEG-10/PPG-3.5.

In the alcohol R (OH)_X+YAfter partial esterification of (A), the fatty acid giving rise to the fatty acyl moiety FA is C_8-30Fatty acids, e.g. C_10-24A fatty acid. In some variations, the fatty acid may include one or more unsaturated bonds. Examples of fatty acids are stearic acid, lauric acid and oleic acid.

In the formula (I) (POA-O-)_X-R-(-O-FA)_YWherein X is 1-5, Y is 0-10 and X + Y is 1-12. Suitably, Y is 1 to 10. In some embodiments, X is 1-5 and Y is 0. In other embodiments, X is 1 and Y is 1 to 10. In other embodiments, X is 1-3 and Y is 1-5.

In one embodiment, the coating comprises 1-15%, such as 2-8%, in particular 3-7% by dry weight of the one or more polyoxyalkylene modified alcohols.

In another embodiment, the coating comprises 1 to 10%, such as 2 to 8%, in particular 3 to 7% by solid volume of said one or more polyoxyalkylene modified alcohols.

In yet another embodiment, the coating (or corresponding coating system)) Comprising 1 to 20, such as 2 to 18, in particular 3 to 16g/m²The one or more polyoxyalkylene-modified alcohols of (a).

In a particular embodiment, the coating comprises one or more polyoxyalkylene modified alcohols which comprise or consist of one or more polyoxyalkylene modified sterols.

Sterols are terpene-derived compounds having the general structure (II):

wherein the 3-position (in the A ring) is hydroxy-functional and wherein the 17-position (as in cholesterol) usually carries a branched aliphatic chain (the most typical structure is chain C)²⁰-C²⁷). Other positions, e.g. 4,14, etc. may also bear substituents (usually methyl), as may structures containing ethylenically unsaturated double bonds, such as between carbons 5 and 6 in cholesterol or between carbons 8 and 9 in lanolin. In addition, sterols may have one or more hydroxyl groups in addition to the 3-position hydroxyl group.

In some embodiments, the sterol represents an alcohol R — OH.

The hydroxyl group at the 3-position may be used for functionalization, such as ether modification (e.g., by polyalkylene oxide) to provide polyalkylene oxide modified sterols.

Polyoxyalkylene-modified sterols can be prepared by reacting a sterol alcohol with an alkylene oxide to polymerize a polyoxyalkylene by ring-opening polymerization initiated by the alcohol. Typical sources of such sterols are Aqualose from Croda, Generol from BASF and Lipolan from Lipo Chemicals. It has been found that functionalizing the 3-hydroxy group of sterols with a polyoxyalkylene provides a compound that is particularly useful in combination with biocides (particularly organic biocides such as zinc pyrithione, copper pyrithione, and zineb) in desmutting coatings.

In the context of the present invention, "polyoxyalkylene-modified sterols" are understood to be products which consist essentially of sterols of the general structure (II) which are polyoxyalkylene-functionalized in the 3-position with ethers (i.e., the-OH in the 3-position is substituted by POA-O-).

In the context of the present invention, the term "consisting essentially of means that at least 75% by weight of the solids of the" polyoxyalkylene modified sterol "consists of a sterol of the general structure (II) which is ether functionalized by a polyoxyalkylene at the 3-position. Preferably, at least 80%, for example at least 85 or at least 90% by weight of solids of the "polyoxyalkylene modified sterol" consists of this steroid. The content of ether functionalized sterols of general structure (II) of less than 100% is due to the fact that many commercial quality "sterols" contain small amounts of impurities.

In another specific embodiment, the alcohol R (OH)_X+YSelected from phenols.

Phenols are compounds of the general structure (III):

wherein the 1-position is hydroxy functional and wherein the hydrogen in the 2,3,4, 5 or 6-position may be substituted by a linear, branched, cyclic, unsaturated and/or aromatic moiety which may also carry a fatty acyl moiety of the formula-O-FA as further described above. In one variant of interest, the phenyl groups are substituted, in particular in the 2-, 4-and 6-positions each by, for example, styryl, nonyl and/or butyl. Thus, in the latter case, the alcohol may be selected from tristyrylphenol, nonylphenol and tributylphenol.

The hydroxyl group at the 1-position may be used as described above for functionalization by polyoxyalkylene to provide polyoxyalkylene modified phenols.

In another specific embodiment, the alcohol R (OH)_X+YIs sorbitan. Sorbitan is a compound of the general structure (IV):

and corresponds to the general formula R (OH)₄The alcohol of (1). Sorbitan can be modified by partial esterification of up to three of the four-OH groups with fatty acids,leaving one or more-OH groups unmodified and available for polyoxyalkylene modification. In the formula (I) (POA-O-)_X-R-(-O-FA)_YIn some embodiments, X is 1-3, Y is 1-3, and X + Y is 4, e.g., wherein X is 1-2, Y is 2-3, and X + Y is 4.

In a particular embodiment, the polyoxyalkylene modified sorbitan is based on sorbitan trioleate leaving only one-OH group available for functionalization by polyoxyalkylene as described above to provide a polyoxyalkylene modified sorbitan trioleate, i.e. X is 1 and Y is 3.

In another specific embodiment, the alcohol is selected from C_6-30Saturated linear or branched alcohols, such as saturated linear primary alcohols and saturated branched secondary or tertiary alcohols. The hydroxyl groups can be used for functionalization, e.g., ether modification (e.g., by polyoxyalkylene) to provide polyoxyalkylene modified C_6-30Alcohols, such as linear primary alcohols and polyoxyalkylene modified branched secondary and/or tertiary alcohols. In some embodiments, such alcohols have from 8 to 30 carbon atoms, for example from 10 to 24 carbon atoms.

A specific example of the above alcohol is C_8-30Alkyl alcohols, e.g. C_10-15Saturated linear primary alcohols, branched C₁₃Alcohols and oleyl alcohol.

It should be understood that the above embodiments may be considered independently or in combination. Thus, the one or more polyoxyalkylene modified alcohols may be represented by several variations of the same type or of different types specified above.

Solvents, additives, pigments and fillers

The coating composition may further comprise a solvent and additives.

The coating compositions described herein are solvent-borne and therefore comprise a solvent or solvent mixture. The solvent is non-aqueous. Examples of the solvent are aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons such as petroleum solvent, cyclohexane, methyl isobutyl ketone (MIBK), toluene, xylene and naphtha solvent, esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate, octamethyltrisiloxane, and mixtures thereof.

In one embodiment, the solvent is selected from the group consisting of aliphatic, alicyclic and aromatic hydrocarbons, such as petroleum solvents, cyclohexane, toluene, xylene and naphtha solvents, esters, such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate, octamethyltrisiloxane, and mixtures thereof, preferably those having a boiling point of 110 ℃ or higher.

The solvent typically comprises from 2 to 50% by volume of the coating composition, for example from 3 to 40%, or from 4 to 30%, or from 5 to 25% by volume of the coating composition.

Examples of additives are:

(i) a non-reactive fluid, such as an organopolysiloxane, for example, polydimethylsiloxane, methylphenylpolysiloxane, petroleum, and combinations thereof;

(ii) surfactants, such as propylene oxide or ethylene oxide derivatives, for example alkylphenol-ethylene oxide condensates (alkylphenol ethoxylates), ethoxylated monoethanolamides of unsaturated fatty acids, such as ethoxylated monoethanolamide of linoleic acid, sodium lauryl sulfate and soya lecithin;

(iii) wetting agents and dispersants, such as those described in M.Ash and I.Ash, "Handbook of Paint and coating raw materials, Vol.1",1996, Gower Publ.Ltd., Great Britain, pages 821-.

(iv) Thickeners and anti-settling agents (e.g., thixotropic agents) such as colloidal silica, aluminum silicate hydrate (bentonite), aluminum tristearate, aluminum monostearate, xanthan gum, chrysotile, fumed silica, hydrogenated castor oil, organically modified clays, polyamide waxes, and polyethylene waxes;

(v) dyes such as 1, 4-bis (butylamino) anthraquinone and other anthraquinone derivatives, toluidine dyes, and the like; and

(vi) antioxidants such as bis (tert-butyl) hydroquinone, 2, 6-bis (tert-butyl) phenol, resorcinol, 4-tert-butylcatechol, tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythritol tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate and the like.

The additives typically comprise 0-30% dry weight, such as 0-15% dry weight, of the coating composition.

Preferably, the coating composition comprises one or more thickeners and/or anti-settling agents (e.g. thixotropic agents), preferably in an amount of 0.2-10%, such as 0.5-5%, such as 0.6-4% by dry weight of the coating composition.

In addition, the coating composition for forming a coating layer may include a pigment and a filler.

In the context of the present invention, pigments and fillers are combined as components which can be added to the coating composition, with limited influence on the adhesion properties. "pigments" are generally characterized in that they render the final paint coating opaque and non-translucent, while "fillers" are generally characterized in that they do not render the paint non-translucent and therefore do not significantly hide any material underneath the coating.

Examples of pigments are titanium dioxide, red iron oxide, zinc oxide, carbon black, graphite, yellow iron oxide, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium silicoaluminate, quinacridone, phthalocyanine blue, phthalocyanine green, black iron oxide, indanthrone blue, cobalt aluminum oxide, carbazole dioxazine, chromium oxide, isoindole orange, bis-acetoacet-o-tolidiole, benzimidazolone, quinophthalone yellow, isoindolinone yellow, tetrachloroisoindolinone, quinophthalone yellow.

Examples of fillers are calcium carbonate, such as calcite, dolomite, talc, mica, feldspar, barium sulfate, kaolin, nephelin, silica, perlite, magnesium oxide, quartz powder and the like. Fillers (and pigments) may also be added in the form of nanotubes or fibers, and thus, in addition to the aforementioned examples of fillers, the coating composition may also comprise fibers, such as those specifically described generally in WO00/77102, which is incorporated herein by reference.

Any pigments and/or fillers typically constitute from 0 to 60% by dry weight of the coating composition, such as from 0 to 50%, preferably from 5 to 45%, such as from 5 to 40%, or from 5 to 35%, or from 0.5 to 25%, or from 1 to 20% by dry weight. These components typically constitute from 0.2 to 20%, for example from 0.5 to 15% by solids volume of the coating composition, taking into account the density of any pigments and/or fillers.

In order to make the coating composition easy to apply (e.g.by spraying, brushing or roller coating techniques), the viscosity of the coating composition is generally from 25 to 25000mPa.s, for example from 150 to 15000mPa.s, in particular from 200 to 4000 mPa.s.

Detailed description of the preferred embodiments

In one interesting embodiment, the present invention provides a solvent borne stain repellent coating composition comprising 18-40% by dry weight of a erodible non-silicone based binder system, 20-55% by dry weight of one or more metal containing biocides, and 0.05-15% by dry weight of one or more polyoxyalkylene modified alcohols.

In another interesting embodiment, the present invention provides a solvent borne stain repellent coating composition comprising 18-40% by dry weight of a erodible non-silicone based binder system, 0.25-30% by dry weight of one or more metal containing organic biocides, and 0.05-15% by dry weight of one or more polyoxyalkylene modified alcohols.

In another interesting embodiment, the present invention provides a solvent borne antifouling coating composition, wherein said coating composition comprises 1-15% by dry weight of said one or more polyoxyalkylene modified alcohols and 2-20% by dry weight of said one or more biocides.

Preferred binder systems for use in combination with the above embodiments are rosin-based binder systems, silyl acrylate binder systems, non-aqueous dispersion-based binder systems and metal acrylate-based binder systems.

Antifouling coating

Another aspect of the invention is an anti-fouling coating (sometimes referred to as a "lacquer coating" or "coating") comprising a non-silicone based binder matrix susceptible to attack, one or more metal-containing biocides, and one or more polyoxyalkylene modified alcohols. The components are as further defined above for the coating composition, and any description, preferences and variants also apply when allowed to dry, simply representing the coating of the coating composition.

Preferably, the antifouling coating comprises 1 to 40, such as 2 to 30, in particular 3 to 20g/m²And 10 to 500, such as 15 to 350, such as 20 to 250, such as 30 to 200, in particular 50 to 150g/m²The one or more metal-containing raw materials of (a)A pesticide.

Preparation of the coating composition

The corresponding antifouling coating was prepared using the antifouling coating composition.

The coating composition may be prepared by any suitable technique commonly used in the art of coating production. Thus, the various ingredients may be mixed together using a mixer, high speed disperser, ball mill, bead mill, three roll mill, and the like. Coating compositions are typically prepared and shipped as one-component or two-component systems that are combined and thoroughly mixed just prior to use. The paint according to the invention can be filtered using the following filters: bag filters, patron filters, line gap filters, wedge line filters, metal edge filters, EGLM turnoclean filters (e.g., Cuno), DELTA strain filters (e.g., Cuno), and jengag Strainer filters (e.g., jengag), or by vibration filtration. Examples of suitable preparation methods are described in the examples.

A first optional aspect of the invention-a coating system.

The invention also relates to an antifouling coating system comprising at least a first coating layer and a second coating layer,

a) the first coating layer comprises an erodible non-silicone based binder system, the first coating layer further comprising one or more polyoxyalkylene modified alcohols;

b) the second coating comprises a non-silicone based binder system that is susceptible to attack, and the second coating further comprises one or more metal-containing biocides.

In this alternative of the main aspect of the invention, the anti-fouling coating comprises 1 to 40, such as 2 to 30, in particular 3 to 20g/m²And 10 to 500, such as 15 to 350, such as 20 to 250, such as 30 to 200, in particular 50 to 150g/m²The one or more metal-containing biocides of (a).

It should be understood that the first and second coatings are prepared on the substrate as follows: a second coating is prepared over the first coating. Further, it is to be understood that the first coating can be prepared on an already existing coating (e.g., a corrosion resistant coating, or an aged anti-fouling or release coating, etc.) or directly on the natural substrate (see "application of coating composition" section below). Furthermore, although the second coating is preferably the outermost layer, the second coating may in principle be overcoated with a further coating (e.g. a top coat).

Without being bound by any particular theory, it is believed that the outermost coating (i.e. the second coating) comprises a metal-containing biocide and the first coating (the lower layer) comprises a polyoxyalkylene-modified alcohol, which then migrates to the outermost layer and provides an effect similar to that described for the main aspect of the invention.

Thus, the antifouling coating system comprises at least a first coating layer and a second coating layer. First, the "binder system", "polyoxyalkylene modified alcohol" (where appropriate), "solvent, additive, pigment and filler", "metal-containing biocide" (where appropriate), etc., sections above the first and second coatings (except that the binder systems are not necessarily the same) are described. The specific features of the first coating are described in the section "first coating.. and the specific features of the second coating are described further in the section" second coating.. below.

It should be understood that although the binder systems of the first and second coating layers are typically of the same or similar type (or even the same), the first and second coating layers are not identical. In particular, the first coating and the second coating differ at least in one of the following aspects: i) a content and/or type of metal-containing biocide, and ii) a content and/or type of polyoxyalkylene-modified alcohol.

Further embodiments of how to prepare the first and second coatings are outlined in the "application of the coating system" and "marine structure" sections below.

First coating of a coating System

The coating composition used to build the first coat of the coating system is essentially as described above for the "solvent-based antifouling coating composition" section above, except that the first coat does not (as a mandatory component) comprise a metal-containing biocide. Otherwise, the first coating is as described above, mutatis mutandis.

In one embodiment, the first coating comprises:

18-40% by dry weight of an erodible non-silicone-based binder system,

0.2-5% by dry weight of one or more polyoxyalkylene modified alcohols,

one or more additives, and

one or more pigments and fillers.

In one variation of the foregoing, the first coating further comprises one or more metal-containing biocides or other biocides, particularly biocides of the type and amount described further in the section "metal-containing biocides" above.

Second coat of the coating System

The coating composition used to build the second coat of the coating system is essentially as described above for the "solvent-borne antifouling coating composition" section, except that the second coat does not (as an obligatory ingredient) comprise a polyoxyalkylene-modified alcohol. Otherwise, the second coating is as described above, mutatis mutandis.

In one embodiment, the second coating comprises:

18-40% by dry weight of an erodible non-silicone-based binder system,

20-55% by dry weight of one or more metal-containing biocides,

one or more additives, and

one or more pigments and fillers.

In one variation of the above, the second coating further comprises one or more polyoxyalkylene modified alcohols, particularly alcohols of the type and amount described further in the section "polyoxyalkylene modified alcohols" above.

Application of coating compositions

The coating composition of the present invention is typically applied to at least a portion of the surface of a substrate.

The term "applying" is used in its usual meaning in the coatings industry. Thus, "applying" is by any conventional means, e.g., by painting, rolling, spraying, dipping, and the like. The most commercially interesting way to "apply" the coating composition is by spraying. Thus, the coating composition is preferably sprayable. The spraying is carried out using conventional spraying equipment known to those skilled in the art. The coating is typically applied at a dry film thickness of 50-600 μm, for example 50-500 μm, for example 75-400 μm, or 20-150 μm, or 30-100 μm.

Furthermore, the coating composition preferably has sag resistance for a wet film thickness of at least 70 μm, such as at least 200 μm, such as at least 300 μm, preferably at least 400 μm, especially at least 600 μm, in terms of sag resistance (see ASTM D4400-99, i.e. with respect to its ability to be applied to a vertical surface at an appropriate film thickness without sagging.

The term "at least a portion of the surface of the substrate" means that the coating composition can be applied to any portion of the surface. For many applications, the coating composition is applied to at least a portion of a substrate (e.g., a boat), where the surface (e.g., the hull) may be in contact with water, such as seawater.

The term "substrate" refers to a solid material onto which the coating composition is applied. The substrate typically comprises a metal such as steel, iron, aluminum or glass fiber reinforced polyester. In the most interesting embodiment, the substrate is a metal substrate, in particular a steel substrate. Alternatively, the substrate is a glass fiber reinforced polyester substrate. In some embodiments, the substrate is at least a portion of the outermost surface of the marine structure.

The term "surface" is used in its ordinary sense and refers to the outer boundary of an object. Specific examples of such surfaces are surfaces of marine structures, such as ships (including but not limited to boats, yachts, motorboats, ocean-going ships, tugboats, tankers, container ships and other cargo ships, submarines, and all types of naval vessels), pipelines, land and offshore machinery, surfaces of various types of buildings and objects (such as piers, piles, bridge understructures, flotation devices, hydraulic devices and structures), underwater oil well structures, fishing nets and other aquaculture facilities, cooling equipment and buoys, and the like, particularly suitable for hulls and ships, and pipelines.

The surface of the substrate may be a "natural" surface (e.g., a steel surface). However, the substrate is usually coated with, for example, an anticorrosive coating and/or an intermediate coating, so that the surface of the substrate is constituted by such a coating. When present, the (anti-corrosion and/or intermediate) coating is typically applied at a total dry film thickness of 100-. Alternatively, the substrate may carry a paint coating, such as a abraded antifouling paint coating or the like.

Preferably, the substrate is a metal substrate (e.g. steel substrate) coated with an anti-corrosive coating, such as an anti-corrosive epoxy based coating, e.g. a cured epoxy based coating, or a pre-coat primer layer, e.g. a zinc rich pre-coat primer layer. The substrate may also be a glass fiber reinforced polyester substrate coated with an epoxy primer coating.

The coating of the main aspect of the invention is typically used as the outermost coating (i.e. surface coating), i.e. the coating that is exposed to the environment (e.g. aquatic environment). However, it should be understood that the coating of the main aspect of the present invention may alternatively be applied as a layered system, wherein the coating of the main aspect of the present invention will be coated with one or more layers of one or more other coating compositions to enhance control of the leaching rate of the leachable components of the coating.

Prior to applying the coating composition to the marine structure, the marine structure may first be coated with a primer system, which may comprise several layers, and may be any conventional primer system used in conjunction with the coating composition applied to the marine structure. Thus, the primer system may include an anti-corrosive primer, optionally followed by an adhesion promoting primer.

The present invention therefore also relates to a process for the establishment of an antifouling coating system on a substrate surface, comprising the following sequential steps:

a) applying one or more layers of a primer composition to the surface of the substrate to form a primed substrate,

b) one or more layers of the solvent-based antifouling coating composition of the present invention are applied to the surface of the primed substrate, and the layers are dried/cured, thereby forming an antifouling coating as described above (main aspect).

In some variations of the above method, the anti-fouling coating may be further coated with a topcoat layer.

Thus, the present invention also relates to a method of establishing an antifouling coating system (according to the first alternative aspect) on a substrate surface, comprising the following sequential steps:

a) applying one or more layers of a solvent-borne antifouling coating composition to the surface of the substrate, which may be, for example, a natural substrate or a substrate already bearing one or more coating layers, as the case may be, and allowing the layers to dry/cure, thereby forming a first coating layer as defined above for the first optional aspect, and

b) applying one or more layers of the solvent-borne antifouling coating composition of the invention to the surface of the first coating layer, and drying/curing the layers to form a second coating layer as defined above for the first optional aspect.

The present invention also relates to a method of establishing an antifouling coating system (according to the first alternative aspect) on a substrate surface, comprising the following sequential steps:

a) applying one or more layers of a primer composition to the surface of the substrate and allowing the layers to dry/cure, thereby forming a primed substrate,

b) applying one or more layers of the solvent-borne antifouling coating composition of the invention to the surface of the primed substrate and allowing the layers to dry/cure, thereby forming a first coating layer as defined above for the first optional aspect, and

c) one or more layers of the solvent-borne antifouling coating composition of the invention are applied to the surface of the first coating layer and the layer is dried/cured to form a second coating layer as defined above for the first optional aspect.

The invention also relates to a method for building an antifouling coating system on the surface of an aged antifouling coating system, comprising the following sequential steps:

a) applying one or more layers of a sealer/midcoat composition to the surface of the substrate, allowing the layers to dry/cure, thereby forming a sealer-coated substrate,

b) applying one or more layers of the solvent-borne antifouling coating composition of the invention to the surface of the washcoat-coated substrate and allowing the layers to dry/cure, thereby forming a first coating layer as defined above for the first optional aspect, and

The invention further relates to a method of establishing an antifouling coating system on the surface of an aged antifouling coating system, comprising the following sequential steps:

a) applying one or more layers of a solvent-based antifouling coating composition to the surface of the aged antifouling coating system and allowing the layers to dry/cure, thereby forming a first coating layer as defined above for the first optional aspect, and

b) one or more layers of the solvent-borne antifouling coating composition of the invention are applied to the surface of the first coating layer and the layer is dried/cured to form a second coating layer as defined above for the first optional aspect.

Ship structure

The invention further provides a marine structure comprising on at least a part of its outer surface an outermost anti-fouling coating as defined in the "anti-fouling coating" section above. In particular, at least as part of the outer surface with the outermost coating is the submerged part of the structure.

The present invention also provides a marine structure comprising on at least a portion of its outer surface the outermost anti-fouling coating system as defined above in the section "first alternative aspect of the invention". In particular, at least as part of the outer surface with the outermost coating is the submerged part of the structure.

The coating composition, the method of establishing a coating on a substrate surface and the properties of the coating are as indicated above.

In one embodiment, the antifouling coating system of a marine structure may consist of an anticorrosive layer and an antifouling coating system as described herein.

In an alternative embodiment, the antifouling coating composition is applied on top of a used antifouling coating system, e.g. on top of a used antifouling coating.

In a specific embodiment of the above ship structure, the total dry film thickness of the anticorrosive layer is 100-; and the antifouling coating has a total dry film thickness of 20-500 μm, such as 20-400 μm, for example 50-300 μm.

Another embodiment of the marine structure is that at least a portion of the outermost surface of the structure is coated with an antifouling coating system comprising:

an anti-corrosive layer of epoxy-based paint, established by applying 1-4 layers, such as 2-4 layers, having a total dry film thickness of 150 and 400 μm; and

the antifouling coating (according to said main aspect) is built up by applying 1-2 layers, the total dry film thickness being 20-400 μm.

Another embodiment of the marine structure is one in which at least a portion of the outermost surface of the structure is coated with an antifouling coating system (first optional aspect) comprising:

an anti-corrosive layer of epoxy-based paint, established by applying 1-4 layers, such as 2-4 layers, having a total dry film thickness of 150 and 400 μm;

a first coating of the anti-fouling coating (see first alternative aspect) established by applying 1-2 layers, the total dry film thickness being 20-400 μm; and

a second coating of the anti-fouling coating (see first alternative aspect) which is established by applying 1-2 layers, the total dry film thickness being 20-400 μm.

Use of

Another aspect of the invention relates to the use of a combination of one or more polyoxyalkylene modified alcohols and one or more metal containing biocides to improve the antifouling properties of coating compositions comprising erodible non-silicone based binder systems.

The properties of the components are described in the sections "binder system", "polyoxyalkylene modified alcohols", "solvents, additives, pigments and fillers", "metal containing biocides", etc., above.

General description of the invention

Although the present description and claims are sometimes directed to binders, biocides, and the like, it should be understood that the coating compositions defined herein may comprise one, two, or more separate components. In such embodiments, the total amount of each component should correspond to the amount defined above for each component.

(s) "in the expression: compound(s), agent(s), etc. indicate that one, two or more separate components may be present.

On the other hand, when the expression "a" is used, only one of the respective components of (1) is present.

It should be understood that when referring to a coating composition, it is a hybrid coating composition. Further, all amounts expressed as% solids volume of the coating are understood to be% solids volume of the hybrid coating composition (or final coating) unless otherwise indicated.

It is to be understood that the expression "% by dry weight" refers to the percentage of the respective component based on the dry weight of the coating or coating composition (as the case may be). For most practical applications (and therefore, unless otherwise specified), "% dry weight" when referring to the final coating is the same as "% dry weight" of the coating composition.

Examples

Material

Material sticking:

chinese gum rosin, from Arawaka Chemical Industries (China), gum rosin Hypale CH, from Arakawa Chemical Industries (China) Foral AX-E, from Eastman Chemicals (Netherlands), hydrogenated rosin

Acronal 9020 from BASF (Germany), 60% by weight solution in xylene, acrylate co-binder

Synocryl 7013-SD50 from Archema (Spain), 50% by weight solution in butanol/petroleum (1:2), acrylic acid co-binder

NSP-100 from Nitto Kasei (Japan), 50% by weight solution in xylene/ethylbenzene (1:1), silanized acrylic copolymer cement solution

A plasticizer; 45% by weight solution in xylene.

The polyoxyalkylene-modified alcohol according to the present invention:

description of the invention	Trade name	Suppliers of goods
			PEG-15 lanolin	Polychol 15	Croda
PEG-20 lanolin	Polychol 20	Croda
			PEG-30 lanolin	Aqualose L30	Croda
PEG-75 lanolin	PEG 75Flake	NK Chemicals
			PEG-7 short alkyl	Serdox NES 7	Elementis
PEG-7 branched short alkyl	Serdox NRL 7E	Elementis
			PEG-5-PPG-5 short alkyl	Serdox NSBQ 5/5	Elementis
PEG-10 oleyl ether	Brij O10	Sigma Aldrich
			PEG-20 oleyl ether	Brij O20	Sigma Aldrich
PEG-12 stearate	PEG-12stearate	A.&E.Connock
			PEG-6 stearate	PEG-6stearate	A.&E.Connock
PEG-20 sorbitan trioleate	Tween 85	Sigma Aldrich
			PEG-20 sorbitan monostearate	Tween 60	Sigma Aldrich
Sorbitan trioleate	Span 85	Sigma Aldrich
			PEG-14 Tristyrylphenol	Serdox NSP 14	Elementis
PEG-9 nonyl phenol (phosphate end-capped)	Servoxyl VMNZ 9/100	Elementis
			PEG-8 tributylphenol	Sapogenat T 080	Clariant
PEG-13 tributylphenol	Sapogenat T 130	Clariant
			PEG-10 tert-octylphenyl ether	Triton X-100	Sigma Aldrich
PEG-12 nonylphenyl ether, branched	Igepal CO-720	Sigma Aldrich
			PEG-12	PEG550	Sigma Aldrich

Reference alcohol:

acetylated lanolin	ALAC	NK Chemicals
			Lanolin oil	Fluilan(NO BHT)-LQ-(RB)	Croda
Lanolin oil 2	Fluilan Pure Liquid Lanolin-LQ-(RB)	Croda
			Oleyl alcohol (Long alkyl)	Oleyl alcohol	Sigma Aldrich
1-dodecanol (short alkyl)	1-Dodecanol	Sigma Aldrich

A biocide:

nordox cuprous oxide paint grade, from Nordox (Norway), cuprous oxide

Copper Omadine, from Arch Chemicals (China), Copper pyrithione

Zineb Nautec from United phophorous (india) zinc ethylenebis (dithiocarbamate)

Solvent:

xylene

Additive agent

Thickening agent:

bentone 38 from Elementis Specialties (UK)

Wetting agent:

nuosperse 657RD from Elementis Specialties (the Netherlands)

Disperbyk 164 from BYK Chemie (Germany)

Antigelling agent:

DTBHQ from HangZhou Thomas (China), 2, 5-di-tert-butylhydroquinone

Thixotropic agent:

aditix M60, from Supercolori (Italy), modified polyethylene wax

Pigments and fillers:

zinc oxide Red Seal from Umicore (Netherlands)

Kronos 2310 from Kronos Titan A/S (Germany), titanium dioxide

An iron oxide pigment; micronox R01 from Promindsa (Spain)

Casiffux F75 from Ankerpoort, natural calcium silicate

MS603-

1000 from Lapinus fibers BV (Netherlands), synthetic glass fibers

Method of producing a composite material

Antifouling Property test

An acrylic test panel (15 × 20 cm) sandblasted on one side to promote coating adhesion²) 80 μm (DFT) of commercial vinyl tar primer (Hempanyl 16280 from Hempel' S Marine Paints A/S) was first applied by air spraying. After drying in the laboratory for a minimum of 24 hours at room temperature, the test coatings were applied using a knife coater having four gap dimensions with a film width of 80 mm. One coating was applied at a DFT of 90-100 μm. After drying for at least 72 hours, the test panels were mounted on racks and immersed in seawater.

Vilanova i la Geltr u-testing in northeast Spanish

At the test site, the panels were immersed in seawater with a salinity of 37-38% o and an average temperature of 17-18 ℃. Every 1-12 weeks, the plates were examined and evaluated for antifouling performance according to the rating shown in table 2. A score is given for total contamination of algae and animal types.

In Singapore testing

In the test site, the panels were immersed in sea water having a salinity of 29-31% o and a temperature of 29-31 ℃. Every 1-12 weeks, the plates were examined and evaluated for antifouling performance according to the rating shown in table 2. A score is given for total contamination of algae and animal types.

Preparation of coating compositions for test examples

The coating composition was prepared according to standard procedures. The binder is initially dispersed in an organic solvent, then some or all of the additives such as thixotropic agents and the like are added, and finally some or all of the pigments such as zinc oxide, fibers and the like are added and mixed on a Diaf dissolver equipped with an impeller disk. Subsequently, the remainder of the pigment, such as cuprous oxide, zinc ethylene bis (dithiocarbamate) (zineb), is added and temperature activation of any components that may require it, such as thixotropic agents, is initiated. Finally, the coating composition is mixed with the remaining additives and binders and its rheology is adjusted by the final addition of the remaining organic solvent.

Typically, the solid components of the coating composition are mixed and milled. Alternatively, the polyoxyalkylene-modified alcohol may be added in the initial or subsequent additive addition step.

The coating composition may be prepared as a one-component paint or by mixing two or more components, for example two premixes, one containing one or more resins and one containing one or more curing agents.

It is to be understood that the expression "% by dry weight" refers to the percentage of the respective component based on the dry weight of the coating or coating composition (as the case may be). For most practical applications (and therefore unless otherwise stated), the "% dry weight" when referring to the cured coating is the same as the "% dry weight" of the coating composition.

Test examples

Model paint

Table 1: the table illustrates the effect of different concentrations of polyoxyalkylene modified sterol (PEG-15 lanolin) with different biocides

The antifouling properties increase with increasing levels of polyoxyalkylene modified sterols.

Table 2: the table illustrates the effect of 2% by weight of different types of polyoxyalkylene modified sterols and lanolin oils

All polyoxyalkylene modified sterols performed better than the blank and better than pure lanolin. The performance of pure lanolin is superior to that of the blank.

Table 3: the table illustrates the effect of 2% by weight of a polyoxyalkylene-modified alcohol in the form of a short alkyl ether ethoxylate

Has a short (C) compared with the blank and the additive containing only short chain alkyl (reference example 17)_10-13) PEG-alkyl groups of the alkyl chain (examples 14-16) improved the properties of the CuO coatings. In the CuPt coating, the properties are the same.

Table 4: the table illustrates the effect of 2% by weight of a polyoxyalkylene-modified alcohol in the form of a long alkyl ether ethoxylate

PEG-alkyl with long alkyl chains (examples 18-21) improved the performance of CuPt and CuO coatings in Spain and Singapore compared to the blank and long alkyl chain additives.

Table 5: the table illustrates the effect of 2% by weight of a polyoxyalkylene-modified alcohol in the form of an alkyl ether-modified sorbitan

The poly (oxyalkylene) modified alcohols in the form of alkyl ether modified sorbitan (examples 23-25) improved the performance of the CuPt and CuO coatings in Spain and Singapore compared to the blank and PEG-free sorbitan.

Table 6: effect of polyoxyalkylene-modified alcohol in the form of polyoxyalkylene-modified phenol

The polyoxyalkylene modified phenols in Spain (examples 28-33) improved the performance of the CuPt coating compared to the blank. Examples 28-30 and 32 improved performance for singapore, while performance was at the same level as blank for examples 31 and 33. For CuO, the performance was improved in Singapore examples 28-30, while for examples 31-33, the performance was at the same level as the blank.

Table 7: effect of optional polyoxyalkylene-modified alcohols

PEG 12 is a polyoxyalkylene modified alcohol according to formula I, which is free of fatty acyl groups. When CuPt/zineb and CuO/zineb are used, the performance of the alloy is superior to that of the blank.

Claims

1. A solvent-borne antifouling coating composition comprising:

a. a non-silicone based binder system that is susceptible to attack,

b. one or more metal-containing biocides, and

c. one or more polyoxyalkylene modified alcohols wherein the one or more polyoxyalkylene modified alcohols has the general formula (I):

(POA-O-)_X-R-(-O-FA)_Y(I)

wherein each POA represents a polyoxyalkylene moiety and each FA represents C_8-30Fatty acyl moiety, R represents an alcohol R (OH)_X+YThe organic residue of (a), the organic residue having from 2 to 50 carbon atoms, and X is from 1 to 5, Y is from 0 to 10, X + Y is from 1 to 12;

the total amount of the one or more polyoxyalkylene modified alcohols is from 0.05 to 15% by dry weight based on the coating composition.

2. The coating composition of claim 1, wherein the polyoxyalkylene modified alcohol has a polyoxyalkylene chain selected from the group consisting of a polyoxyethylene chain, a polyoxypropylene chain, and a poly (oxyethylene-co-oxypropylene) chain.

3. The coating composition of any one of the preceding claims, wherein the coating composition comprises 1-20g/m²And 2 to 35g/m of the one or more polyoxyalkylene-modified alcohols of²The one or more biocides of (a).

4. The coating composition of any preceding claim, wherein the weight ratio of the one or more polyoxyalkylene modified alcohols to the one or more biocides is from 5:1 to 1: 10.

5. The coating composition according to any one of the preceding claims, wherein the organic residue R has 2-50 carbon atoms and only linear, branched and/or unsaturated moieties.

6. The coating composition according to any one of the preceding claims, wherein the organic residue R has 2-50 carbon atoms and is selected from substituted phenols, sorbitan, lanolin or sterols.

7. The coating composition according to any one of the preceding claims, wherein the organic residue R is selected from lanolin or sterol.

8. The coating composition according to any one of the preceding claims, wherein the polyoxyalkylene moieties POA each represent R¹O-[R²-O]_n-R³-a moiety wherein R¹Selected from hydrogen, C_1-4-alkyl-C (═ O) -and C_1-4-alkyl, R²And R³Each selected from the group consisting of ethan-1, 2-ene and propan-1, 2-ene, and n is an integer from 1 to 150.

9. The coating composition of any preceding claim, wherein the non-silicone based binder system comprises a component selected from the group consisting of a rosin based binder system, a silyl acrylate binder system, a non-aqueous dispersion based binder system, and a metal acrylate based binder system; preferably a component selected from the group consisting of rosin-based binder systems, silyl acrylate binder systems and metal acrylate-based binder systems; more preferably a component selected from the group consisting of rosin-based binder systems and silyl acrylate binder systems.

10. The coating composition according to any one of the preceding claims, wherein the total amount of the one or more metal-containing biocides is 3-65% dry weight, such as 5-60% dry weight, based on the coating composition.

11. The coating composition of any one of claims 1-9, wherein the metal-containing biocide comprises only a metal-containing organic biocide.

12. The coating composition of claim 11, wherein the total amount of metal-containing organic biocide is 0.25-30% dry weight of the coating composition, such as 0.5-25%, such as 0.75-20%, or 1-15%, or even 2-12% dry weight.

13. The coating composition of any preceding claim, wherein the one or more metal-containing biocides are selected from the group consisting of metal-dithiocarbamates, bis (1-hydroxy-2 (1H) -pyridinethiosulfuric acid-O, S) -copper (pyridinethione), copper acrylates, bis (1-hydroxy-2 (1H) -pyridinethiosulfuric acid-O, S) -zinc (pyridinethione), copper (I) oxide, cuprous oxide, metal copper, copper metal alloys, metal salts, and N-cyclohexyldiazo-dioxacopper bis.

14. The coating composition of any preceding claim, wherein the one or more metal-containing biocides are selected from cuprous oxide, copper pyrithione, and zinc pyrithione.

15. The coating composition of any preceding claim, wherein the one or more metal-containing biocides comprise cuprous oxide and at least one of copper pyrithione and zinc pyrithione.

16. The coating composition of claim 13, wherein the weight ratio of cuprous oxide to the total amount of copper pyrithione and/or zinc pyrithione is from 25:1 to 1:1.

17. The coating composition of any of the preceding claims, wherein Y is 1-10.

18. An antifouling coating comprising:

a. a non-silicone based binder matrix susceptible to erosion,

b. one or more metal-containing biocides, and

(POA-O-)_X-R-(-O-FA)_Y(I)

19. An antifouling coating system comprising at least a first coating layer and a second coating layer,

a. the first coating layer comprises an erodible non-silicone based binder system, the first coating layer further comprising one or more polyoxyalkylene modified alcohols; and

b. the second coating comprises a non-silicone based binder system that is susceptible to attack, and the second coating further comprises one or more metal-containing biocides.

20. An antifouling coating according to claim 18 or an antifouling coating system according to claim 19, wherein the coating system comprises 2-30g/m²20 to 250g/m of the one or more polyoxyalkylene-modified alcohols of²The one or more metal-containing biocides of (a).

21. A marine structure comprising on at least a portion of its outer surface an outermost anti-fouling coating according to any one of claims 18 or 20 or a coating system according to claim 19.