KR20200087820A - Antifouling composition - Google Patents

Abstract

The present invention (A) (i) 30 to 80% by weight of a silyl ester copolymer comprising a triisopropylsilyl methacrylate monomer; (ii) 20 to 55% by weight of a monocarboxylic acid or derivative thereof; And (iii) 5 to 20% by weight of an acrylic copolymer having a glass transition temperature (Tg) of less than 25° C., wherein component (i) and component (iii) are different; And (B) provides an antifouling coating composition comprising tralopyryl.

Description

Antifouling composition

The present invention relates to marine antifouling coating compositions, and more particularly to marine antifouling coating compositions comprising a silyl ester copolymer comprising triisopropylsilyl methacrylate as a monomer. The composition has a low Tg and preferably further contains an acrylic copolymer containing an acidic monomer, a monocarboxylic acid or derivative thereof and tralopyryl as a biocide. The present invention further relates to a method for protecting an object from contamination and an object coated with the antifouling composition of the present invention.

Surfaces that are submerged in seawater are contaminated by marine organisms, such as green algae, brown algae, barnacles, mussels, and tubeworms. In offshore structures such as ships, platforms for drilling oil, buoys, etc., such contamination is undesirable and has economic consequences. The contamination can lead to biological degradation of the surface, increased load and accelerated corrosion. Pollution in ships will increase frictional resistance, which will result in reduced speed and/or increased fuel consumption. In addition, this can reduce steering performance.

To prevent the settlement and growth of marine organisms, antifouling paint is used. Such paints generally include a film-forming binder together with various components, such as pigments, fillers, additives and solvents, along with biologically active substances (biocides). Biocides can be broadly divided into actives for soft attachments, such as green algae, brown algae, grass, mucus, and actives for hard attachments, such as barnacles, mussels, tubeworms, and the like.

The maintenance of objects in water is expensive, so the applied antifouling coating must be valid for the specified service life. Typical service life for commercial vessels ranges from 24 to 90 months. This requires controlled release of biocide from the coating over the entire service life to protect the object from contamination. This is best achieved using a self-polishing antifouling coating with a controlled polishing rate. In addition, too fast polishing will result in rapid consumption of the coating film, which prevents the surface from being protected. Too slow polishing will result in insufficient release of biocides essential for effective protection from contamination. Controlled deterioration over the lifespan will result in consistent release of biocides to provide good antifouling.

The most successful antifouling coating systems on the market today are based on silyl ester copolymers. The binder matrix often consists of a silyl ester copolymer with other binders, such as acrylates and rosin or rosin derivatives, to control the self-polishing and mechanical properties of the antifouling coating film.

Conventionally, the antifouling coating contains copper-based biocides, such as copper oxide, copper thiocyanate, and the like. In the past decade, new metal-free organic biocides have been commercially available. Its efficiency allows for a lower loading of biocide in the formulation. Tralopyryl is an organic biocide that has been shown to be very effective against a wide range of transgenic organisms, including barnacles, hydroids, mussels, oysters, and tubeworms. Antifouling coating compositions based on silyl ester copolymers using tralopyryl as biocide are disclosed, for example, in EP 3078715 and JP2016089167A.

However, it is difficult to develop an antifouling coating without inorganic copper biocide using a silyl (meth)acrylic binder that will last for a specified service life on the vessel. Replacing inorganic copper biocide with an organic biocide in an antifouling coating composition will alter the fine-tuned balance between the raw materials. This will affect the coating film properties and can often lead to uncontrolled or unpredictable deterioration of the coating film.

Controlled polishing of coatings and good mechanical properties, such as crack resistance and coating film hardness, can often be achieved by controlling the ratio of binder components. However, it is difficult to prepare an antifouling coating without inorganic copper biocide having the same controlled polishing and excellent mechanical properties as a conventional antifouling coating by merely changing the triisopropylsilyl methacrylate copolymer and rosin ratio. The antifouling coating composition comprising tralopyryl provides a solution that provides greater protection against marine pollution than other solutions that do not use commercially available inorganic copper biocides.

In order to provide consumers with an economically viable long-term antifouling solution, it is essential that the antifouling coating is polished at a constant rate over the entire life of the coating system to provide good antifouling protection. Insufficient antifouling will increase operating costs, such as fuel consumption and/or underwater hull cleaning costs. In addition, it is essential that the coating system can be applied with an acceptable film thickness. The thick film thickness would charge the consumer in relation to the cost of the paint being applied and the extended time at the pier resulting in increased porting costs and extended downtime. Other disadvantages of applying a thick film thickness are increased drying time due to sagging concerns during application and poor release of solvent during drying, and concerns about soft coating and/or coating failure, such as blistering and flaking when submerged in sea water. Is that

Therefore, there is a need for an antifouling coating composition comprising silyl methacrylate copolymer and tralopyryl having a controlled polishing and deterioration rate of the coating system.

We use triisopropylsilyl methacrylate copolymer and monocarboxylic acid with acrylic copolymer as the third component of the binder matrix, with controlled polishing and good mechanical properties, and then optimize the final binder mixture. I learned what can be achieved by doing. The inventors have demonstrated that the use of the binder in combination with tralopyryl can provide a self-polishing antifouling system with improved antifouling performance. In addition, the antifouling composition of the present invention has excellent crack resistance and very good self-polishing properties.

In one aspect, the present invention

(A) (i) 30 to 80% by weight of a silyl ester copolymer comprising a triisopropylsilyl methacrylate monomer;

(ii) 20 to 55% by weight of a monocarboxylic acid or derivative thereof; And

(iii) a binder comprising 5 to 20% by weight of an acrylic copolymer having a glass transition temperature (Tg) of less than 25°C, wherein component (i) and component (iii) are different; And

(B) Tralopyryl

It relates to an antifouling coating composition comprising a.

In another aspect, the present invention provides a method of protecting an object from contamination, comprising coating at least a portion of the object of contamination with an antifouling coating composition as defined herein.

The invention also relates to an object coated with an antifouling coating composition as defined herein.

In another aspect, the present invention relates to the use of a binder (A) as defined herein in an antifouling coating composition comprising tralopyryl, ie as a binder for said composition.

Justice

The terms "marine antifouling coating composition", "antifouling coating composition" or simply "coating composition" refer to a composition that, when applied to a surface, prevents or minimizes the growth of marine organisms on the surface.

The term "hydrocarbyl group" refers to any group containing only C and H atoms to include alkyl, alkenyl, aryl, cycloalkyl, arylalkyl groups, and the like.

The term "acrylic copolymer" refers to a copolymer comprising repeating units derived from (meth)acrylate monomers. Generally, the acrylic copolymer will contain at least 80% by weight of repeat units derived from (meth)acrylate monomers, ie acrylate and/or methacrylate monomers.

The term "(meth)acrylate" means methacrylate or acrylate.

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

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

The term “rosin” as used below is used to cover “rosin or derivatives thereof”.

The term “binder” defines a portion of a composition comprising a silyl ester copolymer and any other ingredients that together form a matrix that imparts material and strength to the composition. Typically, as used herein, the term “binder” refers to a silyl ester copolymer along with a monocarboxylic acid and acrylic copolymer, ie components (i), (ii) and (iii) as defined herein.

The term'Tg' refers to the glass transition temperature.

When the weight percent of a given monomer is given, the weight percent relates to the sum (weight) of each monomer present in the copolymer.

The term "% by weight based on the total weight of the composition" refers to the weight percent of the components present in the final, ready-to-use composition, unless otherwise specified.

Detailed description of the invention

The present invention is a silyl ester copolymer comprising a triisopropylsilyl methacrylate monomer in a specific weight ratio together with tralopyryl; (ii) monocarboxylic acids or derivatives thereof; And (iii) a binder containing a mixture of acrylic copolymers.

Silyl ester copolymer (i)

The silyl ester copolymer contains a monomer of triisopropylsilyl methacrylate. In one embodiment, the silyl ester copolymer comprises at least monomeric triisopropylsilyl methacrylate and hydrophilic (meth)acrylate. Typically, the weight percent of the triisopropylsilyl methacrylate monomer is in the range of 5 to 80% by weight, preferably 30 to 75% by weight, such as 40 to 70% by weight relative to the total weight of the silyl ester copolymer as a whole. to be. The hydrophilic (meth)acrylate monomer may be present in an amount of 2 to 50% by weight, such as 5 to 30% by weight, relative to the total weight of the silyl ester copolymer as a whole. Additional silyl ester (meth)acrylate monomers, hydrophilic (meth)acrylate monomers and/or non-hydrophilic (meth)acrylate monomers may additionally be present as described herein.

In a particularly preferred embodiment, the silyl ester copolymer comprises as monomer:

(a) triisopropylsilyl methacrylate;

(b) Compounds of formula (I):

Wherein R ¹ is hydrogen or methyl, R ² is a cyclic ether (such as an optionally alkyl substituted oxolane, oxane, dioxolane, dioxane) and X is C1-C4 alkylene; And/or a compound of formula (II):

Wherein R ³ is hydrogen or methyl, R ⁴ is a C3-C18 substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom; And in some cases

(c) one or more monomers of formula (III):

Wherein R ⁵ is hydrogen or methyl, and R ⁶ is C1-C8 hydrocarbyl.

Monomer

In one embodiment, the silyl ester copolymer comprises at least monomeric triisopropylsilyl methacrylate (a) and at least one hydrophilic monomer (b).

Given the weight percent of the monomers presented in the silyl ester copolymer, the weight percents are relative to the sum (weight) of each monomer present in the copolymer. Thus, when triisopropylsilyl methacrylate (a) and hydrophilic (meth)acrylate monomer (b) are the only monomers in the silyl ester copolymer, the weight percent of triisopropylsilyl methacrylate is [triisopropylsilyl Methacrylate (a) (weight)/(triisopropylsilyl methacrylate (a) (weight) + hydrophilic (meth)acrylate monomer (b) (weight))] x 100%. If only triisopropylsilyl methacrylate (a), hydrophilic (meth)acrylate monomer (b) and non-hydrophilic (meth)acrylate (c) are present, the weight percent of triisopropylsilyl methacrylate is [tri Isopropylsilyl methacrylate (a) (weight)/(triisopropylsilyl methacrylate (a) (weight) + hydrophilic (meth)acrylate monomer (b) (weight) + non-hydrophilic (meth)acrylate ( c)(weight))]×100%.

The copolymer is preferably >80% by weight, preferably >90% by weight, more preferably >95% by weight, particularly >98% by weight of triisopropylsilyl methacrylate (a), hydrophilic (meth)acrylic Rate monomer(s)(b) and non-hydrophilic (meth)acrylate monomer(s)(c).

Component (a) is preferably triisopropylsilyl methacrylate forming 5 to 80% by weight of the copolymer, preferably 30 to 75% by weight, in particular 40 to 70% by weight.

Component (b) (total) forms 2 to 50% by weight of the copolymer, preferably 3 to 40% by weight of the copolymer, especially 4 to 35% by weight of the copolymer, more particularly 5 to 30% by weight desirable. These weight percent values refer to the sum of the component (b) monomers present.

The ratio (a):(b) (weight/weight) is preferably in the range of 40:60 to 95:5, preferably in the range of 50:50 to 95:5, in particular in the range of 55:45 to 93:7 , Most preferably in the range of 60:40 to 90:10. It is preferable that the weight fraction of (a) in the copolymer is larger than that of component (b).

The amount of (a)+(b) in the copolymer is preferably 95% by weight or less, such as 90% by weight or less, particularly 85% by weight or less. The amount of (a)+(b) in the copolymer can be in the range of 30-95% by weight or 40-85% by weight.

Hydrophilic ( Met ) Acrylate Monomer(s) component (b)

In certain embodiments, the silyl ester copolymer contains at least one monomer of formula (I):

In the above formula, R ¹ is hydrogen or methyl, R ² is a cyclic ether (such as optionally alkyl substituted oxolane, oxane, dioxolane, dioxane), X is C1-C4 alkylene, preferably C1-C2 alkyl It's Ren.

The cyclic ether may contain 1 oxygen atom in the ring or 2 or 3 oxygen atoms in the ring. Cyclic ethers may contain rings containing 2 to 8 carbon atoms, such as 3 to 5 carbon atoms. The entire ring may contain 4 to 8 atoms, such as 5 or 6 atoms.

The cyclic ether ring may be substituted, for example, with one or more, such as one C1-C6 alkyl group. Such substituents can be present at any position on the ring, including those attached to the X group.

Suitable compounds of formula (I) include tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, isopropylideneglycerol methacrylate, glycerol formal methacrylate and cyclic trimethylolpropane formal acrylate.

Formula (I) most preferably represents tetrahydrofurfuryl acrylate having the structure:

In a further embodiment, the copolymer may include one or more monomers of formula (II):

In the above formula, R ³ is hydrogen or methyl, and R ⁴ is a C3-C18 substituent containing at least one oxygen or nitrogen atom, preferably at least one oxygen atom.

As indicated in the above formula, the term “hydrophilic (meth)acrylate” requires an R ⁴ group in formula (II) comprising at least one oxygen or nitrogen atom, preferably at least one oxygen atom. As described in detail below, additional non-hydrophilic (meth)acrylate monomers of formula (III) may also exist in which the R ⁶ units consist of only C and H atoms.

In one embodiment, the silyl ester copolymer contains at least one monomer of formula (II) above, wherein the R ⁴ group has the formula -(CH ₂ CH ₂ O) _m -R ⁷ , where R ⁷ is C1 -C10 hydrocarbyl substituent, preferably C1-C10 alkyl or C6-C10 aryl substituent, m is an integer in the range of 1 to 6, preferably 1 to 3. Preferably R ⁴ has the formula -(CH ₂ CH ₂ O) _m -R ⁷ , where R ⁷ is an alkyl substituent, preferably methyl or ethyl, m is in the range of 1 to 3, preferably 1 or It is an integer of 2.

In one embodiment, the silyl ester copolymer is 2-methoxyethyl methacrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate And 2-(2-ethoxyethoxy)ethyl acrylate.

Particularly preferred monomer(s) (b) are 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate.

In one embodiment, the silyl ester copolymer does not contain 2-(2-ethoxyethoxy)ethyl acrylate as a monomer.

As used herein, Formulas (I) and (II) define “polar” (meth)acrylate monomers or “hydrophilic” (meth)acrylate monomers. The use of this monomer together with triisopropylsilyl methacrylate ensures the formation of a binder with controlled degradation.

It is preferred when the silyl ester copolymer comprises a monomer of formula (I) or a monomer of formula (II). It is generally not desirable to have monomers from both of the above formulas present.

additional Non-hydrophilic ( Met ) Acrylate Monomer(s)(c)

The silyl ester copolymer may include one or more additional non-hydrophilic (meth)acrylate monomers of formula (III):

In the above formula, R ⁵ is hydrogen or methyl, and R ⁶ is a C1-C8 hydrocarbyl substituent, preferably a C1-C8 alkyl substituent, most preferably methyl, ethyl, n-butyl or 2-ethylhexyl. Monomers according to formula (III) are referred to herein as “non-hydrophilic” monomers.

In all embodiments of the invention, the silyl ester copolymer preferably comprises at least one additional non-hydrophilic methacrylate and/or non-hydrophilic acrylate monomer. When one or more non-hydrophilic (meth)acrylate monomers are present, the sum of the non-hydrophilic (meth)acrylate monomers in the silyl ester copolymer is preferably 60% by weight or less, preferably 55% by weight or less, such as 5 to 55 Within the weight percent range, in particular in the range of 10 to 50 weight percent.

In a preferred embodiment, the monomer triisopropylsilyl methacrylate (a), component (b) and any non-hydrophilic (meth)acrylate monomer(s) by formula (III) together are >80 in the silyl ester copolymer. It forms a monomer by weight, preferably >90% by weight, in particular >95% by weight.

In a preferred embodiment, the silyl ester copolymer comprises at least one of a non-hydrophilic monomer methyl methacrylate and/or n-butyl acrylate.

In all embodiments of the invention, it is preferred to include methyl methacrylate. When present, methyl methacrylate is preferably present in an amount of 2 to 60% by weight of the copolymer, preferably 5 to 50% by weight. In a preferred embodiment, the triisopropylsilyl methacrylate (a), component (b) and methyl methacrylate together are >50 wt%, preferably >55 wt%, especially >60 wt% in the silyl ester copolymer. To form a monomer.

When present, n-butyl acrylate is preferably present in an amount of 1 to 30% by weight, in particular 2 to 20% by weight.

The silyl ester copolymer can include additional ethylenically unsaturated monomers. Representative examples of suitable ethylenically unsaturated monomers are styrene, vinyl acetate, triisopropylsilyl acrylate, 2-(trimethylsiloxy)ethyl methacrylate, zinc (meth)acrylate, zinc acetate (meth)acrylate and zinc neo Decanoate (meth)acrylate. If present, any additional ethylenically unsaturated monomer preferably forms 20% by weight or less of the copolymer, preferably 10% by weight or less of the copolymer.

Characteristics of silyl ester copolymer

Silyl ester copolymers can be prepared using polymerization reactions known in the art. Silyl ester copolymers can be obtained in the presence of a polymerization initiator by polymerization of the monomer mixture in a conventional manner or by controlled polymerization techniques in any of a variety of ways, such as solution polymerization, bulk polymerization, emulsion polymerization, dispersion polymerization and suspension polymerization. have. In the preparation of the coating composition using the silyl ester copolymer, the copolymer is preferably diluted with an organic solvent to obtain a polymer solution having a suitable viscosity. From such a viewpoint, it is preferable to use solution polymerization.

Examples of suitable initiators for free radical polymerization are azo compounds such as dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 2,2' -Azobis (isobutyronitrile) and 1,1'-azobis (cyanocyclohexane); And peroxides such as tert-amyl peroxypivalate, tert-butyl peroxypivalate tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, 1,1, 3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethyl acetate, tert-butyl peroxyisobutyrate, tert-butyl peroxybenzoate, 1,1-di(tert-amyl Peroxy)cyclohexane, tert-amylperoxy 2-ethylhexyl carbonate, tert-butylperoxy isopropyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, polyether poly-tert-butyl Peroxy carbonate, di-tert-butyl peroxide and dibenzoyl peroxide. These compounds are used alone or as a mixture of two or more thereof.

Examples of organic solvents include aromatic hydrocarbons such as xylene, toluene, mesitylene; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone; Esters such as butyl acetate, tert-butyl acetate, amyl acetate, propyl propionate, n-butyl propionate, isobutyl isobutyrate, ethylene glycol methyl ether acetate; Ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, tetrahydrofuran, alcohols such as n-butanol, isobutanol, methyl isobutyl carbinol, benzyl alcohol; Ether alcohols, such as butoxyethanol, 1-methoxy-2-propanol; Aliphatic hydrocarbons, such as white spirit, limonene; And optionally a mixture of two or more solvents.

These compounds are used alone or as a mixture of two or more of them. The silyl ester copolymer can be a random copolymer, alternating copolymer, gradient copolymer or block copolymer. The copolymer is preferably a random copolymer.

The polymer containing the organosylyl ester group thus obtained preferably has a weight average molecular weight (Mw) of 5,000 to 100,000, preferably 15,000 to 80,000, more preferably 20,000 to 60,000. Mw is measured as described in the Examples section.

The copolymer preferably has a glass transition temperature (Tg) of at least 15°C, preferably at least 20°C, such as at least 25°C, and all values are measured according to the Tg test described in the Examples section. Values below 80°C are preferred, such as below 70°C, for example below 60°C.

The silyl ester copolymer can be provided as a polymer solution, such as a xylene solution. The polymer solution is preferably adjusted to have a solids content of 30 to 90% by weight, preferably 40 to 85% by weight, more preferably 45 to 75% by weight.

The amount of silyl ester copolymer present in the composition of the present invention is 30 to 80% by weight (dry solid), preferably 30 to 75% by weight, more preferably 35 to 70 based on the total weight of the binder (A). Weight percent (dry solid), more preferably 40 to 60 weight percent (dry solid).

The final antifouling coating composition of the present invention is 2 to 40% by weight (dry solids), such as 3 to 30% by weight (dry solids), especially 5 to 20% by weight (dry solids) of silyl ester copolymer based on the total coating composition. It is preferred to include coalescence.

Monocarboxylic acid (ii)

The antifouling coating composition of the present invention comprises a monocarboxylic acid or a derivative thereof.

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

The monocarboxylic acids present in the antifouling coating composition of the present invention include resin acids, derivatives of resin acids, C6-C20 cyclic monocarboxylic acids, C5-C24 acyclic aliphatic monocarboxylic acids, C7-C20 aromatic monocarboxylic acids and It is preferred to select from mixtures of these.

Derivatives of monocarboxylic acids include metal salts of monocarboxylic acids, such as alkali metal carboxylates, alkaline earth metal carboxylates (eg calcium carboxylate, magnesium carboxylate) and transition metal carboxylates (eg For example, zinc carboxylate, copper carboxylate). Preferably, the metal carboxylate is a transition metal carboxylate, particularly preferably the metal carboxylate is zinc carboxylate. Metal carboxylates can be produced in situ in antifouling coating compositions.

Representative examples of the resin acid are abietic acid, neoabietic acid, dehydroabietic acid, palustric acid, levopimaric acid, pimaric acid, isopicaric acid, sandaracopimaric acid, coric acid and mercuric acid , Secodehydroabietic acid. It will be understood that the resin acid can be derived from a natural source, and in that state can usually exist as a mixture of acids. Resin acids are also referred to as rosin acids. Representative examples of sources of resin acids are gum rosin, wood rosin and tall oil rosin. Particular preference is given to gum rosin, which is also referred to as colloponi and colloponium. Preferred rosins are those containing more than 85% resin acid, even more preferably more than 90% resin acid.

Commercial grades of rosin are often chromaticity XC (lightest), XB, XA, X, WW, WG, N, M, K, I, H, G, F, E, D (darkest) as specified in ASTM D509 It is classified according to his color by character designation. Preferred chromaticities for the compositions of the present invention are X, WW, WG, N, M, K, I, even more preferably WW. The commercial grade of rosin typically has an acid value of 155 to 180 mg KOH/g as specified in ASTM D465. Preferred rosin in the compositions of the present invention have an acid value of 155 to 180 mg KOH/g, more preferably 160 to 175 mg KOH/g, even more preferably 160 to 170 mg KOH/g. The commercial grade of rosin typically has a softening point (circulation method) between 70°C and 80°C as specified in ASTM E28. Preferred rosin for the composition of the present invention has a softening point of 70°C to 80°C, more preferably 75°C to 80°C.

Representative examples of resin acid derivatives include partially hydrogenated rosin, fully hydrogenated rosin, heterogeneous rosin, dihydroabietic acid, dihydropimaric acid, and tetrahydroabietic acid.

Representative examples of C6-C20 cyclic monocarboxylic acids are naphthenic acid, 1,4-dimethyl-5-(3-methyl-2-butenyl)-3-cyclohexen-1-yl-carboxylic acid, 1,3 -Dimethyl-2-(3-methyl-2-butenyl)-3-cyclohexen-1-yl-carboxylic acid, 1,2,3-trimethyl-5-(1-methyl-2-propenyl)- 3-cyclohexen-1-yl-carboxylic acid, 1,4,5-trimethyl-2-(2-methyl-2-propenyl)-3-cyclohexen-1-yl-carboxylic acid, 1,4 ,5-trimethyl-2-(2-methyl-1-propenyl)-3-cyclohexen-1-yl-carboxylic acid, 1,5,6-trimethyl-3-(2-methyl-1-propenyl )-4-cyclohexen-1-yl-carboxylic acid, 1-methyl-4-(4-methyl-3-pentenyl)-4-cyclohexen-1-yl-carboxylic acid, 1-methyl-3 -(4-methyl-3-pentenyl)-3-cyclohexen-1-yl-carboxylic acid, 2-methoxycarbonyl-3-(2-methyl-1-propenyl)-5,6-dimethyl -4-cyclohexen-1-yl-carboxylic acid, 1-isopropyl-4-methyl-bicyclo[2,2,2]2-octen-5-yl-carboxylic acid, 1-isopropyl-4 -Methyl-bicyclo[2,2,2]2-octene-6-yl-carboxylic acid, 6-isopropyl-3-methyl-bicyclo[2,2,2]2-octene-8-yl- Carboxylic acids and 6-isopropyl-3-methyl-bicyclo[2,2,2]2-octen-7-yl-carboxylic acid.

Representative examples of C5-C24 acyclic aliphatic monocarboxylic acids are versat™ acid, neodecanoic acid, 2,2,3,5-tetramethylhexanoic acid, 2,4-dimethyl-2-isopropylpentanoic acid, 2 ,5-dimethyl-2-ethylhexanoic acid, 2,2-dimethyloctanoic acid, 2,2-diethylhexanoic acid, pivalic acid, 2,2-dimethylpropionic acid, trimethylacetic acid, neopentanoic acid, 2-ethylhexanoic acid , Isononanoic acid, 3,5,5-trimethylhexanoic acid, isopalmitic acid, isostearic acid, 16-methylheptadecanoic acid and 12,15-dimethylhexadecanoic acid. The acyclic aliphatic monocarboxylic acid is preferably selected from liquid, acyclic C10-C24 monocarboxylic acid or liquid, branched C10-C24 monocarboxylic acid. It will be understood that many of the acyclic C10-C24 monocarboxylic acids can be derived from natural sources, and in isolated form they typically exist as mixtures of acids with different chain lengths in various branches.

Preferably the monocarboxylic acid is gum rosin, a derivative of gum rosin, acyclic C10-C24 monocarboxylic acid, C6-C20 cyclic monocarboxylic acid or mixtures thereof. The mixture of acids preferably contains at least one resin acid, gum rosin or derivatives of gum rosin. Gum rosin is most preferred.

In one embodiment, the derivative of the monocarboxylic acid is not a metal carboxylate.

The amount of monocarboxylic acid present in the composition of the present invention is 20 to 55% by weight (dry solid), preferably 25 to 51% by weight (dry solid), more preferably based on the total weight of binder (A). Is 30 to 50% by weight (dry solid).

The final antifouling coating composition of the present invention is preferably 2 to 30% by weight (dry solids), such as 4 to 25% by weight (dry solids), especially 5 to 20% by weight (dry solids), based on the total coating composition. Monocarboxylic acids.

Acrylic copolymer (iii)

In the context of the present invention, the term “acrylic copolymer” refers to a copolymer comprising at least one monomer based on acrylic acid, methacrylic acid, esters of acrylic acid and esters of methacrylic acid. The copolymer (iii) should be different from the copolymer (i) in the binder (A) of the present invention.

The acrylic copolymer has a Tg of less than 25°C, preferably less than 10°C, more preferably less than 0°C, and even more preferably less than -10°C, all values measured according to the Tg test described in the Examples section. do. The use of acrylic copolymers having a glass transition temperature (Tg) of less than 25° C. is expected to reduce the viscosity of the final antifouling coating composition to reduce the required solvent content.

Acrylic copolymers, except for monomers with acid functionality. It is preferred not to contain a hydrophilic monomer.

Preferably the acrylic copolymer more preferably has an acid value of less than 60 mg KOH/g polymer, more preferably less than 40 mg KOH/g polymer, even more preferably less than 25 mg KOH/g polymer (meth) Acrylic acid units. Preferably the acid value is greater than 2 mg KOH/g polymer, such as greater than 5 mg KOH/g polymer. The acid value is measured as described in the Examples section.

In one embodiment, the acrylic copolymer comprises 0.50-10% by weight of carboxylic acid containing monomer based on the total weight of the acrylic copolymer.

In certain preferred embodiments, the acrylic copolymer is a monomer

i. At least one (meth)acrylate of formula (IV):

Wherein R ⁸ is hydrogen or methyl, R ⁹ is a C1-C20 hydrocarbyl substituent;

ii. 0.5 to 10% by weight of at least one carboxylic acid-containing monomer based on the total weight of the acrylic copolymer

It includes.

i. And ii. The combination of monomers defined below may constitute at least 80% by weight of the acrylic copolymer, such as at least 85% by weight, preferably at least 90% by weight, more preferably at least 95% by weight. In another specific embodiment, i. And ii. The combination of monomers defined below represents up to 95% by weight of the acrylic copolymer, such as up to 99% by weight.

For clarity, "combination of monomers defined under i. and ii." includes the possibility of having two or more monomers of formula (IV) or two or more carboxylic acid-containing monomers. The acrylic copolymer is the i. And optionally less than 10% by weight, preferably less than 5% by weight, preferably less than 2% by weight of any monomer except monomers of formula (IV) and carboxylic acid-containing monomers as described in ii. . In certain embodiments, component i. And ii. constitute the entire monomer component of the acrylic copolymer.

In certain embodiments, the acrylic copolymer does not include hydrolysable monomers, such as silyl ester monomers. Preferably, the acrylic copolymer is non-hydrolyzable.

Preferably, the acrylic copolymer has a weight average molecular weight (Mw) of 10,000 to 50,000 g/mol, preferably 15,000 to 45,000.

The acrylic copolymer can have an acid value of 2 to 60 mg KOH/g polymer, such as 5 to 40 mg KOH/g polymer, as measured according to the acid value test described in the Examples section.

The binder (A) comprises 5 to 20% by weight (dry solid), preferably 7 to 15% by weight (dry solid), for example 10% by weight of acrylic copolymer.

In the present invention, the antifouling composition is 1.0 to 15% by weight (dry solid), preferably 1.2 to 10% by weight (dry solid), more preferably 1.5 to 8% by weight (dry solid) based on the total coating composition. It is preferred to include an acrylic copolymer of.

( Met ) Acrylate Monomer i.

It is preferred that the (meth)acrylate monomer used in the acrylic copolymer has the following formula (IV):

Wherein R ⁸ is hydrogen or methyl, R ⁹ is a C1-C20 hydrocarbyl, preferably a C1-8 alkyl substituent, most preferably methyl, ethyl, n-propyl, n-butyl or 2-ethylhexyl to be. Particularly preferred R ⁹ groups are methyl, n-butyl and 2-ethylhexyl.

Monomers according to formula (IV) are referred to herein as “non-hydrophilic” monomers.

In certain embodiments, the acrylic copolymer is selected from methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate ( IV) at least one (meth)acrylate monomer. In certain embodiments, the acrylic copolymer comprises at least two different monomers of formula (IV).

In certain embodiments, the acrylic copolymer comprises methyl methacrylate as one monomer and at least one other monomer of formula (IV). In a further specific embodiment, the acrylic copolymer comprises at least methyl methacrylate and n-butyl (meth)acrylate. When at least one (meth)acrylate monomer of the formula (IV) is present, the weight percentage of the sum of the (meth)acrylate monomers in the acrylic copolymer is preferably 99.5% by weight or less based on the total weight of the acrylic copolymer , For example 99.2% by weight or less, such as 99.0% by weight or less, such as 98.5% by weight or less, such as 98.0% by weight.

Furthermore, when one or more (meth)acrylate monomers of the formula (IV) are present, the weight percentage of the sum of the (meth)acrylate monomers in the acrylic copolymer is preferably at least 80 weight based on the total weight of the acrylic copolymer. %, such as at least 85% by weight, such as at least 90% by weight, such as at least 92% by weight.

When present, methyl methacrylate is preferably present in an amount of 1.0 to 50% by weight of the acrylic copolymer, preferably 1.5 to 30% by weight, more preferably 1.5 to 25% by weight.

When present, n-butyl acrylate is 50 to 99% by weight of the acrylic copolymer, preferably 55 to 98% by weight of the acrylic copolymer, more preferably 65 to 97% by weight of the acrylic copolymer, such as 70 to 95 It is preferred to be present in an amount by weight.

Carboxylic acid Containing monomers ii.

The carboxylic acid-containing monomer(s) used in the acrylic copolymer helps to provide improved compatibility of the acrylic copolymer in the coating film. The carboxylic acid-containing monomer(s) are referred to herein as alternating acidic monomer(s). It has been found that below the optimum range of the acidic monomer content, the acrylic copolymer tends to migrate in the coating film, while above the optimum range of the acidic monomer content, an acrylic copolymer having a high viscosity is obtained. A high viscosity acrylic copolymer means that a larger amount of solvent is required for the manufacture and application of the paint. This is undesirable due to strict VOC regulations.

Preferably, the acidic monomer is present in an amount of 0.5-10% by weight based on the weight of the acrylic copolymer. In a further specific embodiment, the carboxylic acid-containing monomer is 0.5-8.0% by weight, such as 0.7-8.6% by weight, such as 1.0-7.5% by weight, such as 1.2-7.0% by weight, such as 1.2-7.0% by weight, such as acrylic copolymer 1.3-6.5% by weight, such as 1.4-6.0% by weight.

Examples of the monomer-containing carboxylic acid are acrylic acid, methacrylic acid, 2-carboxyethyl acrylate, 2-carboxymethyl methacrylate, mono-2-(methacryloyloxy)ethyl maleate and mono-2- (Methacryloyloxy)ethyl succinate. Preferably, the carboxylic acid-containing monomer is acrylic acid or methacrylic acid, more preferably methacrylic acid. Combinations of both acrylic acid and methacrylic acid can be used. It is preferable that the carboxylic acid-containing acrylic copolymer is free of any N-vinyl lactam monomer. In particular, it is preferred that no N-vinyl pyrrolidone is present.

Preparation of acrylic copolymer

Acrylic copolymers can be prepared using polymerization reactions known in the art. Acrylic polymers are preferably prepared using addition polymerization or chain growth polymerization. The polymers are conventionally controlled or controlled by polymerization techniques, for example by any of a variety of methods, such as solution polymerization, bulk polymerization, emulsion polymerization, dispersion polymerization and suspension polymerization, in the presence of a polymerization initiator and optionally a chain transfer agent. It can be obtained by polymerizing the monomer mixture. In the preparation of the coating composition using the above polymer, it is preferred that the polymer is diluted with an organic solvent to obtain a polymer solution having an appropriate viscosity. From such a viewpoint, it is preferable to use solution polymerization.

Examples of suitable initiators for free radical polymerization are azo compounds such as dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 2,2' -Azobis (isobutyronitrile) and 1,1'-azobis (cyanocyclohexane); And peroxides such as tert-amyl peroxypivalate, tert-butyl peroxypivalate tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, 1,1, 3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethyl acetate, tert-butyl peroxyisobutyrate, tert-butyl peroxybenzoate, 1,1-di(tert-amyl Peroxy)cyclohexane, tert-amylperoxy 2-ethylhexyl carbonate, tert-butylperoxy isopropyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, polyether poly-tert-butyl Peroxy carbonate, di-tert-butyl peroxide and dibenzoyl peroxide. These compounds are used alone or as a mixture of two or more thereof.

Examples of organic solvents include aromatic hydrocarbons such as xylene, toluene, mesitylene; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone; Esters such as butyl acetate, tert-butyl acetate, amyl acetate, ethylene glycol methyl ether acetate, propyl propionate, n-butyl propionate, isobutyl isobutyrate; Ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, tetrahydrofuran, alcohols such as n-butanol, isobutanol, methyl isobutyl carbinol, benzyl alcohol; Ether alcohols, such as butoxyethanol, 1-methoxy-2-propanol; Terpenes such as limonene; Aliphatic hydrocarbons, such as white spirit; And optionally a mixture of two or more solvents. These compounds are used alone or as a mixture of two or more thereof. Preference is given to mixtures of aromatic hydrocarbons and one or more solvents selected from ketones, esters, ethers, alcohols and ether alcohols.

The acrylic copolymer can be a random copolymer, alternating copolymer, gradient copolymer or block copolymer. It is preferable that the acrylic copolymer is a random copolymer.

Other binder components

In addition to the components (i), (ii) and (iii) described above, additional binders can be used to control the properties of the antifouling coating film. Examples of binders that can be used include:

Hydrophilic copolymers such as poly(N-vinyl pyrrolidone) copolymers and poly(ethylene glycol) copolymers;

Vinyl ether polymers and copolymers, such as poly(methyl vinyl ether), poly(ethyl vinyl ether), poly(isobutyl vinyl ether), poly(vinyl chloride-co-isobutyl vinyl ether);

(Meth)acrylic homopolymers and copolymers, such as poly(n-butyl acrylate) and poly(n-butyl acrylate-co-isobutyl vinyl ether);

Polymer plasticizers from any of the polymer groups specified above. The term polymer plasticizer refers to polymers having a glass transition temperature (Tg) of less than 25°C.

Additional examples of other binders that may be present in the antifouling coating compositions of the present invention include:

Silyl ester (meth)acrylate copolymers, such as copolymers comprising triisopropylsilyl acrylate;

Metal (meth)acrylate copolymers, such as zinc (meth)acrylate, zinc hydroxide (meth)acrylate, zinc neodecanoate (meth)acrylate or a copolymer comprising zinc oleate (meth)acrylate;

Saturated aliphatic polyesters such as poly(lactic acid), poly(glycolic acid), poly(2-hydroxybutyric acid), poly(3-hydroxybutyric acid), poly(4-hydroxyvaleric acid), polycaprolactone, and , An aliphatic polyester copolymer containing two or more of the units selected from the above-mentioned units;

Polyoxalates as described in WO2009100908;

Esters of rosin and hydrogenated rosin, such as methyl esters, glycerol esters, poly(ethylene glycol) esters, pentaerythritol esters, preferably gum rosin and esters of hydrogenated gum rosin;

Dimerized and polymerized rosin;

Alkyd resins and modified alkyd resins;

Hydrocarbon resins, such as hydrocarbon resins formed only from polymerization of at least one monomer selected from C5 aliphatic monomers, C9 aromatic monomers, inden coumarone monomers or terpenes or mixtures thereof.

In addition to components (i), (ii) and (iii), if additional binder is present, the weight ratio of binder (A): binder is 70:30 to 99:1, preferably 75:25 to 95:5, in particular 80:20 to 90:10.

Biocide

The antifouling coating composition further comprises a compound that can prevent or eliminate marine pollution on or from the surface. In this regard, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile [tralopyryl] having the following structural formula should be present.

Examples of commercially available tralopyrils include Econea from Janssen PMP.

In addition to the biocide, other antifouling compounds may be present. The terms antifouling agents, antifouling agents, biocides, and toxic agents are used in the art to describe known compounds that act to prevent marine exploitation on the surface. The antifouling agent of the present invention is a marine antifouling agent.

Preferred additional biologically active agents are zinc pyrithione, copper pyrithione, zinc ethylenebis(dithiocarbamate)[Zineb], 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio )-1,3,5-triazine [cubbutrin], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], N-dichlorofluoromethylthio-N ',N'-Dimethyl-N-phenylsulfamide [diclofluanid], N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolylsulfamide [tolylfluanid], triphenyl Borane pyridine [TPBP] and 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine].

In one embodiment, the composition does not include 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole [medetomidine].

Mixtures of biocides can be used as a variety of biocides that act on a variety of marine organisms, as is known in the art.

Marine invertebrates, such as barnacles, tubular beetles, moss worms and hydroworms; Plants such as seaweed, algae and diatoms; And mixtures of biocides that are active against bacteria. In this regard, most preferred are biocides 1 selected from zinc pyrithione, copper pyrithione, zineb, diclofluanid and 4,5-dichloro-2-octyl-4-isothiazolin-3-one. It is a combination of species abnormality and tralopyryl.

In one embodiment, the composition as a whole is less than 0.5% by weight of inorganic copper biocide, preferably less than 0.2% by weight of inorganic copper biocide, more preferably less than 0.1% by weight relative to the total weight of the composition. Inorganic copper biocide. Most preferably, the composition does not contain an inorganic copper biocide.

In an alternative embodiment, the composition of the present invention comprises copper pyrithione, organometallic copper compounds.

In an alternative embodiment, the composition does not include any copper-based biocide.

The combined amount of biocide (including tralopyryl) can form up to 20% by weight of the coating composition, such as 0.5 to 15% by weight, such as 1.0 to 12% by weight. It will be understood that the amount of biocide varies depending on the end use and biocide used.

The amount of tralopyryl used is low. The usual amount in the composition is 0.5 to 10.0% by weight, such as 1.5 to 6.0% by weight, especially 2.0 to 4.5% by weight.

Some biocides can be encapsulated or adsorbed on an inert carrier for controlled release or can be bound to other materials. The percentages refer to the amount of active biocide present, and therefore not to any carrier used.

Other ingredients

In addition to the binder (A), tralopyryl (B) and any optional components described above, the antifouling coating composition according to the present invention is a component selected from other binders, inorganic or organic pigments, extenders and fillers, additives, solvents and diluents One or more may be additionally included in some cases.

The pigment can be an inorganic pigment, an organic pigment or a mixture thereof. Inorganic pigments are preferred. Examples of inorganic pigments include titanium dioxide, red iron oxide, yellow iron oxide, black iron oxide, zinc oxide, zinc sulfide, lithopone and graphite. Examples of organic pigments include carbon black, phthalocyanine blue, phthalocyanine green, naphthol red and diketopyrrolopyrrole red. Pigments may be surface treated, if desired, to be more readily dispersed in the paint composition.

Examples of extenders and fillers are minerals such as dolomite, plastorite, calcitic, quartz, barite, magnesite, silica, nepeline sienite, wollastonite, talc, chlorite, mica, kaolin, pyrophyllite and feldspar ; Synthetic inorganic compounds such as calcium carbonate, magnesium carbonate, barium sulfate, calcium silicate and silica; Polymer and inorganic microspheres such as uncoated or coated hollow and solid glass beads, uncoated or coated hollow and solid ceramic beads, polymeric materials such as poly(methyl methacrylate), poly(methyl methacrylate-co- Ethylene glycol dimethacrylate), poly(styrene-co-ethylene glycol dimethacrylate), poly(styrene-co-divinylbenzene), polystyrene, poly(vinyl chloride), porous and dense beads.

The total amount of extender and/or pigment present in the composition of the present invention is preferably 2-60% by weight, more preferably 5-50% by weight, even more preferably 7-45 based on the total weight of the composition. Weight percent. Those skilled in the art will understand that the bulking agent and pigment content varies depending on the particle size distribution, particle shape, surface morphology, particle surface-resin affinity, other components present, and end use of the coating composition.

Examples of additives that can be added to the antifouling coating composition are adjuvants, rheology modifiers, wetting and dispersing agents, antifoaming agents and plasticizers.

Examples of reinforcing agents are flakes and fibers. Fibers include natural and synthetic inorganic fibers and natural and synthetic organic fibers, such as those described in WO 00/77102. Typical examples of the fiber are mineral-glass fiber, wollastonite fiber, montmorillonite fiber, tobermorite fiber, attapulgite fiber, calcined bauxite fiber, volcanic rock fiber, bauxite fiber, rock wool fiber and mineral wool Processed mineral fibers from. Preferably, the fibers have an average length of 25 to 2,000 μm and an average thickness of 1 to 50 μm, a ratio between an average length of at least 5 and an average thickness. Preferably, the adjuvant is present in the composition of the present invention in an amount of 0-20% by weight, more preferably 0.5-15% by weight, even more preferably 1-10% by weight, based on the total weight of the composition.

Examples of rheology modifiers include thixotropic agents, thickeners and anti-settling agents. Representative examples of rheology modifiers are silica, such as fumed silica, organic modified clay, amide wax, polyamide wax, amide derivatives, polyethylene wax, oxidized polyethylene wax, hydrogenated castor oil wax, ethyl cellulose, aluminum stearate and mixtures thereof to be. The rheology control agent requiring activation can be added to the coating composition as it is, activated during the paint manufacturing process, or pre-activated in the coating composition, for example, as a solvent paste. Preferably the rheology modifier is in the amount of 0-5.0% by weight, more preferably 0.2-3.0% by weight, even more preferably 0.5-2.0% by weight, based on the total weight of the coating composition in the composition of the present invention. exist.

Examples of plasticizers are polymeric plasticizers, chlorinated paraffins, phthalates, phosphate esters, sulfonamides, adipates, epoxidized vegetable oils and sucrose acetate isobutyrate. Preferably, the plasticizer is present in the composition of the present invention in an amount of 0-10% by weight, more preferably 0.5-7% by weight, even more preferably 1-5% by weight, based on the total weight of the coating composition. .

Dehydrating and stabilizing agents improve the storage stability of the antifouling coating composition. The dehydrating agent is preferably a compound that removes moisture and water from the coating composition. It is also referred to as a water scavenger or desiccant. The dehydrating agent may be a hygroscopic material that absorbs water or binds water as crystalline water. This is often also referred to as desicant. Examples of the compound include anhydrous calcium sulfate, calcium sulfate hemihydrate, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous zinc sulfate, molecular sieves and zeolites. The dehydrating agent can also be a compound that chemically reacts with water. Examples of dehydrating agents that react with water include orthoesters such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, triisopropyl orthoformate, tributyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate Tributyl orthoacetate and triethyl orthopropionate; Ketal; Acetal; Enol ether; Orthoborates such as trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate and tri-tert-butyl borate; Organosilanes such as trimethoxymethylsilane, triethoxymethylsilane, tetraethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and ethyl polysilicate; And isocyanates, such as p-toluenesulfonyl isocyanate.

Preferred dehydrating agents are organosilanes, such as tetraethoxysilane and inorganic desiccants. The use of organosilanes is particularly preferred.

It is preferred that the stabilizer is an acid scavenger. Examples of stabilizers are carbodiimide compounds such as bis(2,6-diisopropylphenyl)carbodiimide, bis(2-methylphenyl)carbodiimide, 1,3-di-p-tolylcarbodiimide and WO2014064049 It is as described in.

The dehydrating agent and the stabilizing agent are preferably amounts of 0-5% by weight, more preferably 0.5-2.5% by weight, even more preferably 1.0-2.0% by weight, respectively, based on the total weight of the composition in the composition of the present invention. Exists as

It is particularly preferred that the antifouling composition contains a solvent. The solvent is preferably volatile, preferably organic. Examples of organic solvents and diluents include aromatic hydrocarbons such as xylene, toluene, mesitylene; Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone; Esters such as butyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, propyl propionate, n-butyl propionate, isobutyl isobutyrate; Ether esters such as ethylene glycol methyl ether acetate, ethyl 3-ethoxypropionate; Ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dibutyl ether, dioxane, tetrahydrofuran; Alcohols such as n-butanol, isobutanol, methyl isobutyl carbinol, benzyl alcohol; Ether alcohols, such as butoxyethanol, 1-methoxy-2-propanol; Terpenes such as limonene; Aliphatic hydrocarbons, such as white spirit; And optionally a mixture of two or more solvents and diluents.

Preferred solvents are aromatic solvents, especially xylenes and mixtures of aromatic hydrocarbons.

It is preferable that the amount of the solvent is as small as possible. The solvent content may be 45% by weight or less of the composition, preferably 40% by weight or less of the composition, such as 35% by weight or less, but may be as low as 15% by weight or less, for example, 10% by weight or less. Again, those skilled in the art will understand that some raw materials contain a solvent, contribute to the total solvent content as specified above, and that the solvent content will vary depending on the other components present and the end use of the coating composition.

Alternatively, the coating can be dispersed in a coating composition or in an organic non-solvent for the film forming component in an aqueous dispersion.

It is preferred that the antifouling coating composition of the present invention should have a solids content of greater than 40% by volume, for example greater than 45% by volume, such as greater than 50% by volume, preferably greater than 55% by volume.

More preferably the antifouling coating composition has a content of volatile organic compounds (VOCs) of less than 500 g/L, preferably less than 420 g/L, more preferably less than 400 g/L, for example less than 380 g/L. Should have The VOC content can be calculated (ASTM D5201-01) or measured as described in US EPA Method 24 or ISO 11890-2, preferably measured.

The antifouling coating composition of the present invention can be applied to all or part of the surface of any object that is prone to growth. The surface may be permanently or intermittently underwater (eg, by tidal movement, loading or expanding various cargoes). The surface of the object may typically be the surface of a ship's hull or a fixed marine object, such as a platform for oil rigs or buoys. The application of the coating composition can be accomplished by any convenient means, for example by painting the coating on an object (for example using a brush or roller) or spraying. Typically, the surface will have to be separated from seawater to allow coating. The application of the coating can be done as is commonly known in the art.

When an antifouling coating is applied to an object (eg a ship hull), the surface of the object is not protected only by a single coat of antifouling. Depending on the properties of the surface, antifouling coatings can be applied directly to existing coating systems. Such coating systems can include several layers of various common types of paint (eg, epoxy, polyester, vinyl or acrylic or mixtures thereof). Starting with an uncoated surface (e.g., steel, aluminum, plastic, composite, glass fiber or carbon fiber), the entire coating system is typically of an anti-corrosion coating (e.g. curable epoxy coating or curable modified epoxy coating). It will contain one or two layers, one layer of a tie-coat (eg, curable modified epoxy coating or physical dry vinyl coating) and one or two layers of antifouling paint. In the case of an exception, an additional layer of antifouling paint can be applied. If the surface is clean and is an intact antifouling coating from a previous application, the new antifouling paint is typically one or two coats, and in exceptional cases can be applied more directly.

In the following, the invention will be defined with reference to the following non-limiting examples.

Example

Materials and methods

Test

Measurement of polymer solution viscosity

The viscosity of the polymer was measured using a Brookfield DV-I viscometer with LV-2 or LV-4 spindle at 12 rpm according to ASTM D2196 Test Method A. The polymer solution was adjusted to 23.0°C±0.5°C before measurement.

Determination of non-volatile content in polymer solutions

The non-volatile content in the polymer solution was measured according to ISO 3251. A test sample of 0.5 g±0.1 g was taken and dried in a ventilated oven at 150° C. for 30 minutes. The weight of the residual material was considered to be non-volatile (NVM). Non-volatile content is expressed in weight percent. The values presented are the average of three parallel measurements.

Measurement of polymer molecular weight distribution

Polymers were characterized by gel permeation chromatography (GPC) measurements. The molecular weight distribution (MWD) is tetrahydrofuran as eluent using the Malvern Omnisec Resolve and Reveal system with two PLgel 5 μm mixed -D columns from Agilent in series. (THF) was measured with a refractive index (RI) detector at a constant flow rate of 1 ml/min. The column was calibrated using narrow polystyrene standards from Agilent polystyrene medium EasiVial (4 mL) red, yellow and green. The column oven temperature and detector oven temperature were 35°C. The sample injection volume was 100 μl. Data were processed using OmniSec 5.1 software from Malvern.

Samples were prepared by dissolving the polymer solution in an amount corresponding to 25 mg dry polymer in 5 ml THF. Samples were kept at room temperature for a minimum of 3 hours prior to sampling for GPC measurements. The sample before analysis was filtered through a 0.45 μm nylon filter. The weight-average molecular weight (Mw) and polydispersity index (PDI) are presented as Mw/Mn and reported in the table below.

Measurement of glass transition temperature

The glass transition temperature (Tg) was obtained by differential scanning calorimetry (DSC) measurement. DSC measurements were performed on a TA Instruments DSC Q200. The sample was transferred to an aluminum pan with a small amount of polymer solution corresponding to about 10 mg dry polymer material and dried in a ventilated heating cabinet at 50° C. for at least 16-20 hours and then 150° C. for 3 hours. Measurements were carried out by conducting a heating-cooling-heating procedure at a heating rate of 10°C/min and a cooling rate of 10°C/min and using an empty fan as a reference within a temperature range of -80°C to 120°C. Data were processed using Universal Analysis software from T Instruments. The inflection point of the glass transition temperature range of the second heating as defined in ASTM E1356-08 is reported as the Tg of the polymer.

By colorimetric titration Mountainous Measure

The acid value of the polymer was measured according to the procedure described in ISO 2114:2000 Method A. The metered amount of the polymer solution was dissolved in Jotun Thinner 17. Phenolphthalein was added as a colorimetric indicator, the solution was titrated with a 0.1 M KOH solution in ethanol until red discoloration appeared, and the solution was stable for 10-15 seconds while stirring. The acid value for the dry polymer was calculated based on the measured nonvolatiles of the polymer solution tested. The reported acid value is the average of three parallel measurements.

Preparation procedure of copolymer solution S1

60.0 parts of xylene was charged to a temperature controlled reaction vessel equipped with a stirrer, condenser, nitrogen inlet and feed inlet. The reaction vessel was heated and maintained at a reaction temperature of 85°C. 50.0 parts triisopropylsilyl methacrylate, 30.0 parts 2-methoxy methacrylate, 10.0 parts n-butyl acrylate, 10.0 parts methyl methacrylate and 0.8 parts 2,2'-azobis (2-methylbutyro Nitrile) was prepared. The premix was charged to the reaction vessel at a constant rate over a period of 2 hours under a nitrogen atmosphere. After a further 1 hour reaction, a post-addition of a boost initiator solution of 0.2 parts of 2,2'-azobis(2-methylbutyronitrile) and 7.5 parts of xylene was added. The reaction vessel was maintained at the reaction temperature for an additional 1.5 hours. Thereafter, the reactor was heated to 110° C. and maintained at this temperature for 1 hour. Finally, 33.5 parts of xylene were added and the reactor was cooled to room temperature. All parts shown are parts by weight.

Preparation procedure of copolymer solution S8

Copolymer solution S8 was prepared using the procedure described for copolymer solution S1 above with a reaction temperature of 95° C. and the amount of components shown in Table 1A below.

General preparation procedures for copolymer solutions S2-S7 and CS1-CS2

A predetermined amount of solvent was charged to a temperature controlled reaction vessel equipped with a stirrer, condenser, nitrogen inlet and feed inlet. The reaction vessel was heated and maintained at a temperature of 95°C. A premix of monomer, initiator and solvent was prepared. The premix was charged to the reaction vessel at a constant rate over a period of 2 hours under a nitrogen atmosphere. After an additional 1 hour reaction, post-addition of the boost initiator solution was added. The reaction vessel was maintained at the reaction temperature for an additional 1.5 hours. Thereafter, the reactor was heated to 105°C and maintained at this temperature for 1 hour. Finally, the reactor was cooled to room temperature.

Preparation procedure of copolymer solution A1

49.5 parts of xylene and 20.0 parts of 1-methoxy-2-propanol were charged to a temperature controlled reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet and feed inlet. The reaction vessel was heated and maintained at a reaction temperature of 85°C. A premix of 95.0 parts n-butyl acrylate, 4.2 parts methyl methacrylate, 2.8 parts methacrylic acid, 20.5 parts xylene and 1.60 parts 2,2'-azobis (2-methylbutyronitrile) was prepared. The premix was charged to the reaction vessel under a nitrogen atmosphere over 2.5 hours at a constant rate. After an additional 1 hour reaction, a post-addition of a boost initiator solution of 0.32 parts of 2,2'-azobis (2-methylbutyronitrile) and 10.0 parts of xylene was added. The reaction vessel was maintained at the reaction temperature for an additional hour, then cooled to room temperature. The amount of ingredients is given in parts by weight. The copolymer solution had the following properties:

NVM: 49.4 wt%; Mw 28,700; Tg -35°C; Acid value 19 mg KOH/g (dry polymer)

Preparation procedure of copolymer solutions A2 to A4

The copolymer solution was prepared using the procedure described for copolymer solution A1 with a reaction temperature of 95° C. and amounts of components in the reactor charge, feed charge and boost charge as shown in Table 1B below. Dilution of copolymer A3 was performed prior to cooling the polymer solution to room temperature.

zinc Rossinate Preparation of solution

Portuguese gum rosin (60% in xylene; acid value 109 mg KOH/g), a 1,400 g solution of 116.5 g zinc oxide and 57.5 g xylene 2 ℓ equipped with a stirrer, Dean-Stark trap and reflux condenser The temperature controlled reaction vessel was charged. The reaction mixture was heated to reflux. The reaction mixture was refluxed at 140-150° C. until no more water condensed in the Dean-Stark trap. The resulting solution of gum rosin zinc salt was filtered off and diluted with xylene. The zinc rosinate solution had 64.1% by weight of non-volatile material.

General manufacturing procedures for antifouling coating compositions

The ingredients were mixed in the proportions shown in Tables 3-4, 6-6 and 9 below. The mixture was dispersed in a 250 ml paint can in the presence of glass beads (about 2 mm diameter) using a vibratory shaker for 15 minutes. Glass beads were filtered off prior to testing.

Paint viscosity measurement using a cone-plate viscometer

The viscosity of the antifouling paint composition was measured by using a cone-plate viscometer setting according to ISO 2884-1:1999 at a temperature of 23° C. at a shear rate of 10,000 s ⁻¹ and providing a viscosity measuring range of 0-10 P. . Results are presented as the average of three measurements.

Volatile organic compounds of antifouling coating composition ( VOC ) Calculation of content

The volatile organic compound (VOC) content of the antifouling coating composition was calculated according to ASTM D5201.

Coated Mönig ( Koenig ) pendulum Measurement of hardness

The hardness of the coating film was measured using a pendulum hardness tester. The test was performed according to ISO 1522:2006. Each antifouling coating composition was applied to a transparent glass plate (100×200×2 mm) using a film coater having a gap size of 300 μm. The coating film was applied at 23° C. and 50% relative humidity for 1 week, and then dried in a ventilated heating cabinet at 50° C. for 72 hours. The coating film hardness of the dry coating film was measured using an Erichsen 299/300 pendulum hardness tester at a temperature of 23° C. and 50% relative humidity. Hardness is quantified as the number of pendulum motions that attenuates the amplitude from 6° to 3°. It indicates that the hardness of the coating is higher as the number of movements is larger. Results are reported as the average of three parallel measurements on the coating film after forced drying in a heating cabinet.

Coated Accelerated crack testing

The PVC panels were coated with Safeguard Plus (two-component polyamide cured vinyl epoxy-based coating, manufactured by Jokwang Yoton Co., Ltd. of Korea) using an airless spray. The panels were dried and cured according to the product application guide. The antifouling coating was applied on a cured precoated panel using a membrane applicator having a gap size of 800 μm. The coated coating film was dried at 52°C for 72 hours, and then immersed in seawater at 40°C. At regular intervals, after drying under ambient conditions for 24 hours and drying at 52° C. for 24 hours, the panel was taken out and evaluated. The panels were evaluated for cracks visually and at 10x magnification and graded as described in ISO 4628-4:2005. The density and size of cracks were reported. Thereafter, the panel was immersed again. Results after 6 months of exposure were reported.

Antifouling coating on rotating disks in seawater membranous Polishing rate measurement

The polishing rate was determined by measuring the decrease in film thickness of the coating film over time. For this test, PVC disks were used. The coating composition was applied on the disk to a gap size of 600 μm using a film applicator as a radial stripe. The thickness of the dry coating film was measured by a surface profiler. The initial dry film thickness will depend on the solids content and rate of application of the applied antifouling coating composition. The typical initial dry film thickness for the coating tested was 235±30 μm.

A PVC disk was mounted on the shaft and rotated in a vessel through which seawater flowed. Filtration and natural seawater temperature-controlled to 25°C±2°C were used. The speed of the axis of rotation provided an average simulated speed of 16 knots on the disk. PVC discs were taken at regular intervals for film thickness measurements. The disc was rinsed and dried overnight at room temperature, then the film thickness was measured. Results were presented as the film consumption, ie the difference between the initial film thickness and the thickness measured at a given time. The coating film was considered to be polished when a thin, non-abrasive leaching layer remained on the surface, typically at a thickness of 10-20 μm, or when the film was completely polished from the surface. This is indicated as PT in the result table. The polishing index is obtained by dividing the polishing rate between weeks 52 and 78 by the polishing rate between weeks 26 and 52. A coating film having a polishing index value of less than 2.0 is considered to exhibit controlled polishing.

Comparative Examples CPA-1 to CPA-4 in Table 5 indicate that polishing of the antifouling coating film was not controlled over a long time in the absence of component (iii) in the antifouling coating composition. The same applies when the amount of component (iii) is small as shown in Comparative Example CPA-5.

Comparative Examples CPA-6 to CPA-8 in Table 5 indicate that the antifouling coating film is soft and susceptible to mechanical damage when using a large amount of component (iii) in the antifouling coating composition. The polishing of CPA-6 to CPA-7 is not controlled as indicated by the high polishing index. The coating of CPA-8 also has poor crack resistance.

Comparative Example CPA-9 in Table 5 shows that the use of triisopropylsilyl acrylate copolymer provides uncontrolled polishing of the antifouling coating film.

Comparative Examples CPB-1 to CPB-5 in Table 8 indicate that the polishing of the antifouling coating film was not controlled over a long time in the absence of component (iii) in the antifouling coating composition.

The comparative examples CPB-6 to CPB-7 in Table 8 indicate that the use of component (i) without hydrophilic monomers was too slow to obtain sufficient release of the antifouling agent over time.

Comparative Examples CPB-8 to CPB-9 in Table 8 indicate that the use of triisopropylsilyl acrylate copolymer yields uncontrolled polishing of the antifouling coating film.

Claims (17)

(A) (i) 30 to 80% by weight of a silyl ester copolymer comprising a triisopropylsilyl methacrylate monomer;
(ii) 20 to 55% by weight of a monocarboxylic acid or derivative thereof; And
(iii) 5 to 20% by weight of an acrylic copolymer having a glass transition temperature (Tg) of less than 25°C.
A binder comprising a binder, wherein component (i) and component (iii) are different; And
(B) Tralopyryl
Antifouling coating composition comprising a. The antifouling coating composition according to claim 1, wherein the silyl ester copolymer (i) is present in an amount of 30 to 70% by weight. The antifouling coating composition according to claim 1 or 2, wherein the silyl ester copolymer (i) further comprises at least one hydrophilic monomer. The antifouling coating composition of claim 3, wherein the silyl ester copolymer comprises as monomer:
(a) triisopropylsilyl methacrylate;
(b) Compounds of formula (I):

Wherein R ¹ is hydrogen or methyl, R ² is a cyclic ether (such as an optionally alkyl substituted oxolane, oxane, dioxolane, dioxane), and X is C1-C4 alkylene; And/or
Compounds of formula (II):

Wherein R ³ is hydrogen or methyl, and R ⁴ is a C3-C18 substituent having at least one oxygen or nitrogen atom, preferably at least one oxygen atom; And in some cases
(c) one or more monomers of formula (III):

Wherein R ⁵ is hydrogen or methyl and R ⁶ is C1-C8 hydrocarbyl. 5. The compound of claim 4, wherein in Formula (II), R ⁴ is a group of the formula -(CH ₂ CH ₂ O) _m -R ⁷ , wherein R ⁷ is a C1-C10 alkyl or C6-C10 aryl substituent, m is An antifouling coating composition that is an integer in the range of 1 to 6, preferably 1 to 3. 6. The method of claim 5, wherein R ⁴ is a group of the formula -(CH ₂ CH ₂ O) _m -R ⁷ , wherein R ⁷ is a C1-C10 alkyl substituent, preferably methyl or ethyl, m is 1 to 3, The antifouling coating composition is preferably an integer in the range of 1 to 2. The component (b) according to any one of claims 4 to 6, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2- An antifouling coating composition comprising at least one of ethoxyethoxy)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate. The antifouling method according to any one of claims 1 to 7, wherein the acrylic copolymer (iii) comprises 0.5 to 10% by weight of a carboxylic acid-containing monomer, based on the total weight of the acrylic copolymer. Coating composition. The acrylic copolymer (iii) according to any one of claims 1 to 8, as a monomer.
a) at least one (meth)acrylate of formula (IV):

Wherein R ⁸ is hydrogen or methyl, R ⁹ is a C1-C20 hydrocarbyl substituent; And
b) 0.5 to 10% by weight of one or more carboxylic acid containing monomers based on the total weight of the acrylic copolymer
Antifouling coating composition comprising a. The antifouling coating composition according to any one of claims 1 to 9, wherein the monocarboxylic acid or derivative (ii) thereof is a gum rosin. The biocide according to any one of claims 1 to 10, selected from zinc pyrithione, copper pyrithione, zineb and 4,5-dichloro-2-octyl-4-isothiazolin-3-one. Antifouling coating composition further comprising one or more. The antifouling coating composition according to any one of claims 1 to 11, comprising 2 to 40% by weight (dry solid) of the silyl ester copolymer (i) based on the total weight of the antifouling coating composition. The antifouling coating composition according to any one of claims 1 to 12, comprising 2 to 30% by weight (dry solid) of monocarboxylic acid (ii) based on the total weight of the antifouling coating composition. The antifouling coating composition according to any one of claims 1 to 13, comprising 1.0 to 15% by weight (dry solid) of the acrylic copolymer (iii) based on the total weight of the antifouling coating composition. The antifouling coating composition according to any one of claims 1 to 14, which contains less than 0.2% by weight of an inorganic antifouling copper compound. A method for protecting an object from antifouling, comprising coating at least a part of the object to be antifouling with the antifouling coating composition according to any one of claims 1 to 15. An object coated with the antifouling coating composition according to any one of claims 1 to 15.