KR20200073248A - Self-polishing type anti-pollution coating composition comprising alkoxysilane - Google Patents

Abstract

The present invention relates to a self-polishing type anti-fouling coating composition comprising a non-silicone-based binder matrix, a metal compound and one or more alkoxysilanes, a coating layer formed of the composition and a marine structure coated with the composition.

Description

Self-polishing type anti-pollution coating composition comprising alkoxysilane

The present invention relates to a self-polishing type anti-fouling coating composition comprising an alkoxysilane. Specifically, it relates to a self-polishing type antifouling coating composition comprising a non-silicone-based binder matrix, a metal compound and one or more alkoxysilanes. In addition, the present invention relates to a marine structure coated with a self-polishing type anti-fouling coating composition and a coating layer formed on the structure.

In silyl-based paints based on silyl binder systems, alkoxysilanes such as tetraethoxysilane are used as water removers to prevent hydrolysis of silyl binders. In addition, the alkoxysilane is used as an inorganic capping agent, a crosslinking agent, a precursor of a silica gel network, a silicon oxide nanoparticle, and a catalyst support having controlled porosity.

European patent EP3078715 contains a silyl ester polymer, a rosin or a derivative of rosin, a trolopyril or a salt of trolopryl, and a carbodiimide, and a silane (tetraethoxysilane). It shows a marine pollution prevention coating composition comprising a binder containing a stabilizer comprising a. According to the European patent, the composition has improved storage stability and it is known that the viscosity of the paint is significantly reduced compared to when using a dehydrating agent such as CaSO ₄ or molecular sieves.

The present inventors have confirmed that the use of the alkoxysilane in the anti-fouling coating composition based on the non-silicone binder system improves physical properties. This has not been confirmed in a conventional silyl-based binder system, and prior art related thereto has not been disclosed.

The patent documents and references mentioned in this specification are incorporated herein by reference to the same extent that each document is individually and clearly specified by reference.

European patent EP 3078715 United States Patent US 3,607,821 United States Patent US 4,147,688 United States Patent US 4,493,914 United States Patent US 4,960,828 Japanese Patent Publication No. 29,551/1973 Japanese Patent Publication 177,068/1982

The present invention is a non-silicone-based binder matrix comprising a rosin-based binder system; A metal compound selected from the group consisting of a metal oxide, a metal hydroxide and a mixture of the metal oxide and the metal hydroxide; And at least one alkoxysilane (alkoxysilane) to prevent contamination by sea water and improve the drying characteristics and weathering characteristics of the self-polishing type anti-fouling coating composition, a coating layer formed by using the same, and to provide a marine structure to which the coating layer is applied There is this.

Other objects and technical features of the present invention are presented in more detail by the following detailed description of the invention, claims and drawings.

The present invention a) a non-silicone-based binder matrix comprising a rosin-based binder system; b) a metal compound selected from the group consisting of a metal oxide, a metal hydroxide and a mixture of the metal oxide and the metal hydroxide; And c) at least one alkoxysilane (alkoxysilane); provides a self-polishing type anti-fouling coating composition comprising a.

The rosin-based binder system comprises a rosin component selected from the group consisting of rosin, rosin derivatives, and rosin-modified polymers, and the metal oxide is Cu ₂ O, CuO, ZnO, CoO, CaO, MgO And Fe ₂ O _{3 It} is characterized in that any one selected from the group consisting of.

In the self-polishing type anti-fouling coating composition of the present invention, the non-silicone-based binder matrix is included in a solid content volume of 25 to 80% of the total solid content volume of the self-polishing type anti-pollution coating composition, and the metal compound is the self-polishing type contamination It is characterized in that it is included in a solids volume of 1 to 50% relative to the total solids volume of the anti-coating composition, and the alkoxysilane is included in a solids volume of 0.1 to 10% relative to the total solids volume of the self-polishing type anti-fouling coating composition. .

The present invention provides a marine structure in which the self-polishing type anti-pollution coating composition of the present invention is formed of one or more coating layers, the coating layer selected from the group consisting of ≡Si-OH chemical structure and ≡Si-O-Si≡ chemical structure Since it contains a siloxane network including any one or more chemical structures, it has an advantage of excellent drying and weathering characteristics.

The present invention relates to a self-polishing type anti-fouling coating composition comprising a non-silicone-based binder matrix, a metal compound and one or more alkoxysilanes, a coating layer formed of the composition, and a marine structure coated with the composition. In addition to the improvement, there is an advantage that the luster is maintained because it is not polluted even when exposed to sea water for a long time. In addition, the coating layer of the present invention includes a siloxane network including chemical structures such as ≡Si-OH and ≡Si-O-Si≡, and the siloxane network has an advantage of improving drying and weathering characteristics of the coating composition.

1 shows the difference in whitening effect of model paint samples based on a non-aqueous dispersion binder system in which the alkoxysilane (tetraethyl orthosilicate (TEOS)) of the present invention is added in various amounts.
FIG. 2 shows the difference in gloss of model paint samples based on the non-aqueous dispersion binder system in which the alkoxysilane (tetraethyl orthosilicate (TEOS)) of the present invention was added in various amounts.
FIG. 3 shows the whitening effect of model paint with or without 1 alkoxysilane of the present invention (tetraethyl orthosilicate (TEOS)) added at 1 VS%. Example 2b1 is a model paint based on the non-aqueous dispersion binder system not containing the alkoxysilane, and Example 2b2 is a model paint based on the non-aqueous dispersion binder system containing the alkoxysilane. Examples 2a1 and 2c1 are model paints based on the rosin binder system not containing the alkoxysilane, and examples 2a2 and 2c2 are model paints based on a rosin binder system containing the alkoxysilane.
Figure 4 shows the gloss effect of the model paint with or without the addition of 1 VS% alkoxysilane (tetraethyl orthosilicate (TEOS)) of the present invention. Example 2b is a model paint based on a non-aqueous dispersion binder system and Examples 2a and 2c are model paints based on a rosin binder system.
Figure 5 shows the results of a whitening change test (cosmetic property test) conducted for 7 months in Vilanova, Spain of the present invention.
6 shows the results of a whitening change test (cosmetic property test) conducted for 2 months in Busan, Korea of the present invention.
Figure 7 shows the drying characteristics (Beck Koller test) at room temperature of the non-aqueous dispersion binder-based paint with or without the alkoxysilane of the present invention.
Figure 8 shows the drying characteristics (Wood Block Setting test) at 5 ℃ of the non-aqueous dispersion binder-based paint with or without the alkoxysilane of the present invention.
9 shows that the whitening effect disappears when the alkoxysilane is included in the model paint based on the silylated acrylate binder of the present invention and when it is not.
FIG. 10 shows the whitening effect when alkoxysilane (tetrapropyl orthosilicate, (TPOS)) was added at 1 VS% or not added to the model paint based on the non-aqueous binder system of the present invention.
11 shows the degree of gloss retention when alkoxysilane (tetrapropyl orthosilicate, (TPOS)) is included or not included in various amounts in the model paint based on the non-aqueous binder system of the present invention.
FIG. 12 shows drying characteristics (Beck Koller test, room temperature) when the non-aqueous dispersant binder of the present invention contains or does not contain different alkoxysilanes.

The present invention will be described in detail below.

1. Anti-fouling coating composition

The present invention a) a non-silicone-based binder matrix comprising a rosin (rosin)-based binder system; b) a metal compound selected from the group consisting of metal oxides, metal hydroxides, and mixtures of the metal oxides and metal hydroxides; And c) one or two or more types of alkoxysilanes.

According to an embodiment of the present invention, the binder matrix is contained in 25 to 80% of the solid content of the coating composition, preferably 20 to 70% of the solid content, more preferably 18 to 55% in the solid content Is included.

When the content of the binder matrix is expressed as a dry weight, the binder matrix is included in an amount of 18 to 75% based on the dry weight of the coating composition, preferably 16 to 60% based on the dry weight. It is included, more preferably 15 to 40% based on the dry weight.

According to an embodiment of the present invention, the rosin-based binder system is included in 10 to 50% of the solid content of the coating composition, preferably 12 to 45% of the solid content, more preferably 15 in the solid content To 40%.

When the content of the rosin-based binder system is expressed as dry weight, the rosin-based binder system is included in an amount of 5 to 30% based on the dry weight of the coating composition, preferably based on the dry weight 8 to 25%, more preferably 10 to 25% based on the dry weight.

According to an embodiment of the present invention, the metal compound is contained in 1 to 50% of the solid content of the coating composition.

According to another embodiment of the present invention, the metal compound is included in 1 to 30% of the solid content of the coating composition, preferably 1 to 20%, more preferably 1 to 15%, more preferably 1 5%.

According to another embodiment of the present invention, the metal compound is included in 2 to 40% of the solid content of the coating composition, preferably 3 to 25%, more preferably 5 to 15%, and more preferably 8 To 12%.

According to an embodiment of the present invention, the alkoxysilane is included in 0.05 to 20% of the solid content of the coating composition, preferably 0.1 to 10%, more preferably 0.2 to 5%, more preferably 0.3 to 2 %.

According to another embodiment of the present invention, the alkoxysilane is included in 0.05 to 2% of the solid content of the coating composition, preferably 0.08 to 1.5%, more preferably 0.1 to 1%.

According to an embodiment of the present invention, the ratio of alkoxysilane and rosin (alkoxysilane: rosin) contained in the coating composition is 1:300 in solid content, preferably 1:150, more preferably 1:80, More preferably, it is 1:40.

According to an embodiment of the present invention, the binder matrix system further includes a non-aqueous dispersed binder system in addition to the rosin-based binder system. In this case, the non-aqueous dispersion binder system has a ratio of non-aqueous dispersion binder (NAD) and rosin (NAD: rosin) of 1:20 in the solid content of the coating composition, preferably 1:10. , More preferably, it is 1:5, More preferably, it is 2:3.

According to an embodiment of the present invention, the binder matrix system further includes an acrylic binder system in addition to the rosin-based binder system. In this case, the acrylic binder system has a ratio of acrylic binder to rosin (Acrylic: rosin) of 1:50 in the solid content of the coating composition, preferably 1:20, and more preferably 1:10. , More preferably 1:7.

According to an embodiment of the invention, the coating composition comprises a certain amount of biocide (biocide). In general, the biocide is contained in 3 to 45% of the solid content of the coating composition, preferably 5 to 40%, more preferably 7 to 38%, and more preferably 10 to 35%, more preferably 15 to 35%.

When the biocide is expressed in dry weight, the biocide is included in 3 to 65% based on the dry weight of the coating composition, preferably 5 to 60%, more preferably 10 to 60%, more preferably 15 to 60%, more preferably 15 to 40%, and more preferably 20 to 60%.

2. Binder matrix

The binder matrix of the coating composition is formed of a paint film by drying and curing. Therefore, the coating composition has a shape in which the final paint coating layer is continuously formed.

A binder system applicable to the non-silicone-based binder matrix is a self-polishing type non-silicone-based binder system.

The “self-polishing type” means a “polishing rate test” for a sample having a polishing rate of a paint coating layer, which means a film in which the coating composition is dried and cured, at least 10,000 nautical miles (Nautical miles, 1 nautical mile=18,520) per 1 km).

The “non-silicone-based binder matrix” means that at least 35% of the non-silicone-based binder is included based on the solid content of the binder matrix. According to an embodiment of the present invention, the non-silicone-based binder is 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, based on the solid content of the binder matrix, 90%, 95% or 100%.

Suitable examples of non-silicone-based binders include rosin binders, non-aqueous dispersion binders, metal acrylate binders, hybrids of silylated acrylate and metal acrylate binders, poly oxalate binders, amphoteric ion binders, silylated acrylate and amphoteric ions There are hybrids of binders, polyester binders and mixtures of these binders.

In particular, the amount of a silicone-based binder such as a silylated acrylate binder is included at a maximum of 10% based on the solid content of the non-silicone-based binder matrix.

According to an embodiment of the present invention, the silylated acrylate binder is included at a maximum of 8%, 6%, 4% or 2% based on the solid content of the binder matrix. According to another embodiment of the present invention, the silylated acrylate binder is included at a maximum of 1%, such as 0.75%, for example 0.5% or 2%, based on the binder matrix solids. According to another embodiment of the present invention, the silylated acrylate binder is not included in the binder matrix.

Preferably, the polishing rate corresponds to a range of 1 to 50 μm/10,000 dissociation, and in particular, 1 to 30 μm/10,000.

All the self-abrasive binder systems used in the self-abrasive coating composition may be a binder system for a generally available coating composition, but when using a silylated acrylate binder, it is preferable to use up to 10% based on the solid content of the binder matrix. Do.

In the relative amounts of the binder system, pigment, filler, etc., optimization through a small number of changes may be required to optimize the polishing rate, and the optimization of the polishing rate may relate to the marine environment where the paint coating layer is exposed.

In order to illustrate the scope of the available binder system of the present invention, the following examples are used for marine and yachting.

All of the applicable binder systems are self-polishing non-silicone-based binder systems. However, the coating composition of the present invention exhibits the best function when the rosin-based binder system is used as part of the binder matrix.

According to an embodiment of the present invention, the non-silicone-based binder matrix further includes an additional non-silicone-based binder system in addition to the rosin-based binder system. The additional non-silicone-based binder systems include, inter alia, hybrids of non-aqueous dispersion binders, metal acrylate binders, silylated acrylate and metal acrylate binder systems, polyoxalate binder systems, zwitterionic binder systems, silylated acrylates and both Hybrid and polyester binders of the sex ion binder system are preferred.

For marine use, non-aqueous dispersion binder systems and metal acrylate-based binder systems are preferred.

For the purpose of explanation, the binder system will be further described below.

The “rosin-based binder system” refers to all types of rosin-based binder systems, and a mixture in which an arbitrary component is further added to the rosin component will be further described below.

The “non-silicone-based binder system” refers to all types of non-silicone-based binder systems, and the binder system includes, for example, a rosin-based binder system, a non-aqueous dispersion binder system, a metal acrylate binder system, a silylated acrylate and a metal acrylate binder Hybrids of systems, polyoxalate binder systems, amphoteric ion binder systems, hybrids of silylated acrylate and amphoteric ion binder systems, and polyester binder systems. The “non-silicone-based binder system” may additionally be in the form of a mixture in which optional additives are added.

3. Rosin-based binder system

The rosin-based binder system is based on rosin or rosin derivatives. The components of the rosin-based binder system are rosin and rosin derivatives, and the rosin derivatives are metal salts of carboxylated rosin such as resinates.

The terms “rosin” and “resinate” include gum rosin; Wood grades of B, C, D, E, F, FF, G, H, I, J, K, L, M, N, W-G, and W-W grades according to ASTM 0509; Virgin rosin; Hard rosin; Yellow deep rosin; NF wood rosin; Tall oil rosin; Or it means a colony (colophony) or a colony (colophonium). The terms “rosin” and “resinate” refer to suitable types of modified rosin, and the denaturation may be, in particular, oligomerization, hydrogenation, dehydrogenation, hydrogenation, disproportionation or displacement, and the denaturation is a polymerization non-aromatic double It may be denaturation that reduces the amount of binding.

The additional binder component may further include a polymer softener and the polymer softener is specifically defined in WO 97/44401.

4. Non-aqueous dispersion binder system

“Non-aqueous dispersion resin”, “NAD” and similar terms mean a shell-core structure, wherein the shell-core structure has a high molecular weight of a high-polar material such as a resin fine particle component (core component) having a high molecular weight. And a resin obtained by stably dispersing in a non-aqueous liquid medium in a low-polarity solvent using a component (shell-component).

The non-aqueous dispersion resin can be prepared by the following method. The above method is conventional in that a polymerizable ethylenically unsaturated monomer (core component) soluble in a hydrocarbon solvent or insoluble in a hydrocarbon solvent and polymerizable with a polymer is dissolved in a solvent or a shell component (dispersion stabilizer) made of an expanded polymer. Disperse polymerization according to the method of.

The non-aqueous dispersion-type resin used in the present invention may be a resin known per se and may be prepared as a known resin.

The non-aqueous dispersion type resin and a method for manufacturing the same are disclosed in U.S. Pat.

In particular, as the shell component constituting the non-aqueous dispersion type resin, various polymer materials soluble in a low-polarity solvent may be used, which are disclosed in US Patent No. 4,960,828 or Japanese Patent Application Publication No. 43374/1989.

In terms of the anti-pollution properties of the final paint coating layer, a shell component such as acrylic resin or vinyl resin may be used.

The core component may be used without limitation as long as it is a copolymer of a highly polar ethylenically unsaturated monomer.

Preferably, the core component of the non-aqueous dispersion type resin may have a free acid group or a silyl ester group, and the free acid group or silyl ester group may be used as long as it can be converted into an acid group by hydrolyzing seawater or a mixture thereof. Do.

Preferably, 5 to 75% by mass of the monomer of the core polymer, such as 5 to 60% by mass or 7 to 50% by mass, should be a free acid group, a silyl ester group, or a combination thereof.

While the free acid group directly affects the properties of the paint formulation, the silyl ester group affects only after hydrolysis in sea water, and therefore it is preferable to have an excess of free acid group.

Examples of silyl ester monomers are silyl esters of acrylic or methacrylic acid.

If necessary, a smaller proportion of the free acid group or silyl ester group may be contained in the shell component.

The term "free acid group" is meant to include all acid groups in the acid form. When suitable counter ions are present in the composition or in the environment, the acid groups may be present in the form of temporary salts. For example, when the acid group is exposed to brine, some free acid groups may exist in the form of sodium salt. Preferably, the non-aqueous dispersed resin generally has a resin acid value of 15 to 400 mg KOH/g, more preferably a resin acid value of 15 to 300 mg KOH/g, and more preferably It has a resin acid value of 18 to 300 mg KOH/g.

When the total acid value of the NAD resin is less than 15 mg KOH/g, the polishing rate of the paint coating layer is too low, and the anti-pollution performance of the coating layer may be deteriorated. On the other hand, when the total acid value exceeds 400mg KOH/g, the polishing rate is too high, and the durability of the paint coating layer in seawater may deteriorate. For reference, when the core component or the shell component contains an acid precursor group, the resin acid value becomes a given value after the acid precursor group is converted to an acid group by hydrolysis.

The “resin acid value” means the amount of KOH consumed to neutralize 1 g of resin (mg) and can be expressed as the acid group content for the solid content of the resin. In the case of the acid precursor group, the acid group content formed by hydrolysis it means.

It is preferable that the acid group or acid precursor group is contained in the core component. The content may be at least 80% as a resin acid value relative to the total resin acid value of the non-aqueous dispersion resin, preferably at least 90%, more preferably at least 95%.

It is generally preferred that the shell component is hydrophobic.

The dry weight ratio (core/shell) of the core component and the shell component in the NAD resin is not particularly limited, but may generally fall within the range of 90/10 to 10/90, preferably 80/20 to 25/75. Range of, for example, 60/40 to 25/75.

5. Silylated acrylate binder system

According to an embodiment of the present invention, the binder matrix of the present invention may include a silylated acrylate binder system, and the silylated acrylate binder system may contain up to 10% based on solid content of the binder system.

The silylated acrylate binder system comprises a silylated acrylate copolymer having one or more side chains having one or more terminal groups described in Formula 1.

Wherein n means an integer, X means -C(=O)-, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are as defined below. The n may be an integer of 0, 1, 2, 3, 4 or more, but in this case, the n is preferably 0 to 100, for example, the n is an integer ranging from 0 to 50, 0, 1, 2, or 2 to 15 Can be

R ₁ -R ₅ are each C _1-20 -alkyl (eg, methyl, ethyl, propyl, butyl and cycloalkyl, such as cyclohexyl); An aryl group such as phenyl and naphthyl and a substituted aryl such as substituted phenyl and substituted naphthyl; independently selected from the group consisting of halogen, C _1-5 -alkyl, C _{1 -10} -alkylcarbonyl, sulfonyl, nitro and amino.

In general, R ₁ -R ₅ are each independently a group selected from C _1-8 -alkyl, phenyl and substituted phenyl. In general, each alkyl group preferably has about 5 or less carbon atoms (C _1-5 -alkyl). As indicated above, R ₁ -R ₅ may be the same or different groups.

The monomer containing the terminal group of Formula 1 may be synthesized as described in European Patent EP 0297505 B1.

The monomers used to obtain such copolymers can be copolymerized with vinyl polymerizable monomers. Examples of suitable vinyl polymerizable monomers include meta, including methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate and methoxyethylmethacrylate. Acrylate esters; Acrylate esters including ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate; Maleic acid esters, such as dimethyl maleate and diethyl maleate; Fumaric acid esters including dimethyl fumarate and diethyl fumarate; Styrene; Vinyl toluene; α-methylstyrene; Vinyl chloride; Vinyl acetate; butadiene; Acrylamide; Acrylonitrile; Methacrylic acid; Acrylic acid; Isobornyl methacrylate; And maleic acid.

The amount of the vinyl polymerizable monomer is 95% by weight or less, preferably 90% by weight or less, with respect to the total weight of the resulting copolymer.

Therefore, the amount of the monomer containing the end group of Formula 1 is 5% by weight or more, particularly 10% by weight or more.

Preferably, the copolymer may have an average molecular weight in the range of 1,000 to 1,500,000, for example, an average molecular weight in the range of 5,000 to 1,500,000, an average molecular weight in the range of 5,000 to 500,000, an average molecular weight in the range of 5,000 to 250,000, or an average in the range of 5,000 to 100,000 It can have a molecular weight.

The binder system used in the coating composition of the present invention comprises a silylated acrylate copolymer, wherein the acrylate copolymer is at least one side chain having one or more terminal groups represented by Formula 2 (ie, Formula 1 with n=0) ).

Where X, R ₃ , R ₄ and R ₅ are as defined above.

Examples of the monomer having a terminal group of the formula (2) is an acid functional vinyl polymerizable monomer, and the monomer is acrylic acid, methacrylic acid, maleic acid (preferably in the form of a monoalkyl ester having 1 to 6 carbon atoms) or fumaric acid ( It is preferably a monomer derived from a monoalkyl ester having 1-6 carbon atoms).

Thus, specific examples of suitable triorganosilyl groups represented by Formula 1 or 2 (the -Si(R ₃ )(R ₄ )(R ₅ ) groups) include trimethyl silyl, triethylsilyl, tri-n-propylsilyl, Tri-n-butylsilyl, tri-isopropylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tri-n-octylsilyl, tri-n-dodecylsilyl, triphenylsilyl, tri-p- Methylphenylsilyl, tribenzylsilyl, tri-2-methylisopropylsilyl, tri-tert-butyl-silyl, ethyldimethylsilyl, n-butyldimethylsilyl, di-isopropyl-n-butylsilyl, n-octyl-di- n-butylsilyl, di-iso-propyloctadecylsilyl, dicyclohexylphenylsilyl, tert-butyldiphenylsilyl, dodecyldiphenylsilyl and diphenylmethylsilyl.

Specific examples of suitable methacrylic acid-derived monomers having one or more terminal groups of formula 1 or 2 are trimethylsilyl (meth)acrylate, triethyl-silyl (meth)acrylate, tri-n-propylsilyl (meth)acrylic Rate, triisopropylsilyl(meth)acrylate, tri-n-butylsilyl(meth)acrylate, triisobutylsilyl(meth)acrylate, tri-tert-butylsilyl(meth)acrylate, tri-n- Amylsilyl (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, ethyldimethylsilyl(meth)acrylate, n-butyldimethylsilyl(meth)acrylate, diisopropyl- n-butylsilyl (meth)acrylate, n-octyldi-n-butylsilyl (meth)acrylate, diisopropylstearylsilyl (meth)acrylate, dicyclohexylphenylsilyl (meth)acrylate, t- Butyldiphenyl-silyl(meth)acrylate and lauryldiphenylsilyl(meth)acrylate.

Specific examples of suitable maleic acid-derived and fumaric acid-derived monomers having one or more terminal groups of Formula 1 or 2 are triisopropylsilylmethylmaleate, triisopropylsilylamylmaleate, tri-n-butylsilyln-butylmaleate , tert-butyldiphenylsilylmethylmaleate, t-butyldiphenylsilyl n-butylmaleate, triisopropylsilylmethylfumarate, triisopropylsilylamyl fumarate, tri-n-butylsilyln-butylfumarate , tert-butyl diphenylsilyl methyl fumarate and tert-butyl diphenyl silyl n-butyl fumarate.

The copolymers used in the binder system of the present invention include monomers in which the end groups of Formulas 1 and 2 are combined with the second monomer B of Formula 3:

Where Z is a C _1-20 -alkyl or aryl group; Y is an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group or a fumaroyloxy group; R _A and R _B are independently selected from the group consisting of hydrogen, C _1-20 -alkyl group and aryl group; p is an integer from 1 to 25.

If p> 2, R _A and R _B is preferably a hydrogen or methyl (CH _3), e.g., p> 2, if the monomer B is preferably derived from polyethylene glycol or polypropylene glycol.

When p = 1, monomers may also be useful for the purposes described herein, where R _A and R _B are larger groups, such as C _1-20 -alkyl or aryl.

As in the above formula (3), monomer B is an unsaturated group (Y) in the molecule, an acryloyloxy group, a methacryloyloxy group, a maleoyloxy group (preferably in the form of mono-C _1-6 -alkyl ester), or fumar It has a royloxy group (preferably in the form of mono-C _1-6 -alkyl ester) and alkoxypolyethylene glycol or aryloxypolyethylene glycol. In the alkoxypolyethylene glycol or aryloxypolyethylene glycol, the polymerization degree (p) of polyethylene glycol 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, and butoxyethyl (meth). Acrylate, hexyethylethyl (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 maleinoyloxy or fumaroyloxy group in the molecule include methoxyethyl-n-butyl maleate, ethoxydiethylene glycol methyl maleate, ethoxytriethylene glycol methyl maleate, and propoxydiethylene glycol Methyl maleate, butoxyethyl methyl maleate, hexoxyethyl methyl maleate, methoxyethyl-n-butyl fumarate, ethoxydiethylene glycol methyl fumarate, ethoxytriethylene glycol methyl fumarate, propoxydiethylene glycol Methyl fumarate, butoxyethyl methyl fumarate, and methyl fumarate.

As will be understood by those skilled in the art, other vinyl monomers can be incorporated into copolymers composed of one of the monomer units having end groups of Formula 1 or 2. In addition, other vinyl monomers may be incorporated into a copolymer composed of monomer units having terminal groups of Formula 1 or 2 combined with the second monomer B of Formula 3.

With respect to other monomers copolymerizable with the above-mentioned monomers, various vinyl monomers such as the vinyl polymerizable monomer (A) discussed above can be used.

Preferably, the proportion of the monomers having the end groups of Formula 1 or 2 is 1 to 95% by weight, based on the total weight of the monomers, monomer B is 1 to 95% by weight, and other copolymerizable monomers are 0 to 95% by weight

Preferably the molecular weight of the copolymer is in the range of 1,000 to 150,000 in terms of weight average molecular weight, for example in the range of 3,000 to 100,000 and for example in the range of 5,000 to 100,000.

The binder system used in the coating composition of the present invention includes a copolymer, and the coating composition includes a copolymer composed of monomer units having terminal groups of Formula 1 or 2 combined with the second monomer C of Formula 4.

Where Y is an acryloyloxy group, methacryloyloxy group, maleinoyloxy group or fumaroyloxy group, and R ₆ and R ₇ are both C _1-12 -alkyl.

As shown in the formula (IV), the monomer C is an unsaturated group (Y) in the molecule, an acryloyloxy group, a methacryloyloxy group, a maleanoyloxy group (preferably in the form of mono-C _1-6 alkyl ester) or fumaroylox Time (preferably in the form of mono-C _1-6 -alkyl ester).

Monomer C can be prepared by a conventional addition reaction of a carboxyl group-containing vinyl monomer, and the vinyl monomer is an alkyl vinyl ether (for example, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether and 2-ethylhexyl) ) Acrylic acid, methacrylic acid, maleic acid (or monoesters thereof) and fumaric acid (or monoesters thereof) vinyl ether; Or cycloalkyl vinyl ether (eg, cyclohexyl vinyl ether);

As will be understood by those skilled in the art, other vinyl monomers can be incorporated into the resulting copolymer comprising the monomer units, and the monomer units have end groups of Formula 1 or 2 combined with the second monomer C of Formula 4.

With respect to other monomers copolymerizable with the above-mentioned monomers, various vinyl monomers such as the vinyl polymerizable monomer (A) discussed above can be used.

Preferably, the proportion of monomers having a terminal group of Formula 1 or 2 is 1 to 95% by weight, more preferably 1 to 80% by weight, and more preferably 1 to 95% by weight of monomer C, more preferably Is 1 to 80% by weight, and other copolymerizable monomers are 98% by weight or less.

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

6. Metal acrylate binder system

The binder system used in the coating composition of the present invention comprises a metal acrylate copolymer having at least one terminal group of formula (5) with at least one side chain.

Phosphorus metal; N is an integer of 1 or more when n+1 is equal to a metal valence; L is an organic acid residue and L is independently selected from the following residues:

또는

이다. The residue

or

to be.

Where R ₄ is a monovalent organic residue; L is -OH or a combination thereof; R ₃ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.

Examples of the monomer having a terminal group of the formula (5) are methacrylic acid, acrylic acid, p-styrenesulfonic acid, 2-methyl-2-acrylamidepropanesulfonic acid, phosphoroxypropyl methacrylate, methacryl-3-chloro- Acid functional vinyl polymerizable monomers such as phosphooxypropyl 2-acid, methacrylic acid, phosphoethylethyl, itaconic acid, maleic acid, maleic anhydride, monoalkylitaconate (e.g. methyl, ethyl, butyl, 2 -Ethyl hexyl), monoalkylmaleates (eg, methyl, ethyl, butyl, 2-ethyl hexyl); And half esters of acid anhydrides with hydroxyl-containing polymerizable unsaturated monomers (eg, half esters of succinic anhydride, maleic anhydride or phthalic anhydride with 2-hydroxy ethylmethacrylate).

The above-mentioned monomers can be copolymerized to obtain copolymers with one or more vinyl polymerizable monomers. Examples of such vinyl polymerizable monomers are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and propyl acrylic Late, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, methoxyethyl methacrylate, styrene, vinyl Toluene vinylpyridine, vinylpyrrolidone, vinyl acetate, acrylonitrile, methacrylonitrile, dimethylitaconate, dibutylitaconate, di-2-ethylhexylitaconate, dimethylmaleate, di(2- Ethylhexyl)maleate, ethylene, propylene and vinyl chloride.

, 및

으로 구성되며, 상기 R₄는 1가 유기 잔기이다.With respect to the ligand (L), each individual ligand is preferably selected from the following groups of residues. The residue group

, And

R ₄ is a monovalent organic residue.

및 R₉로 구성된다.Preferably R ₄ is selected from the following group of residues. The residue group

And R ₉ .

R5 is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms; R7 is a hydrocarbon group each independently having 1 to 12 carbon atoms; R8 is a hydrocarbon group having 1 to 4 carbon atoms; R9 is 5 to 20 such as abietic acid, palletic acid, neoabietic acid, levopimaric acid, dehydroabietic acid, pimaric acid, isopicaric acid, sandaracopimaric acid and Δ8, 9-isopicaric acid. It is a cyclic hydrocarbon group having 2 carbon atoms.

Examples of compounds that can be used as ligands are;

잔기를 포함하는 화합물 (One)

Compounds containing residues

: The compound containing the residue is an aliphatic acid such as levulinic acid; Alicyclic acids such as naphthenic acid, chalmuic acid, hydronocarfuic acid, neoabietic acid, levopimaric acid, palletic acid, 2-methyl-bicyclo-2,2,1-heptan-2-carboxylic acid; Aromatic carboxylic acids such as salicylic acid, cresic acid, α-naphthoic acid, β-naphthoic acid, and p-oxybenzoic acid; Halogen-containing aliphatic acids such as monochloroacetic acid and 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 quinolinecarboxylic acid, nitrobenzoic acid, dinitrobenzoic acid, and nitronaphthalenecarboxylic acid; Lactonecarboxylic acids such as fulvic acid, fluoric acid; Uracil derivatives such as uracil-4-carboxylic acid, 5-fluorouracil-4-carboxylic acid, uracil-5-carboxylic acid; Penicillin-derived carboxylic acids such as penicillin V, ampicillin, penicillin BT, penicillic acid, penicillin G, penicillin O; Rifamycin B, leucomycin, salcomycin, chloroamphenicol, barizin, tripacidine; And various synthetic fatty acids.

잔기를 포함하는 화합물(2)

Compounds containing residues

: The compound containing the residue is dimethyldithiocarbamate and other dithiocarbamates.

잔기를 포함하는 화합물(3)

Compounds containing residues

: The compound containing the residue is a sulfur-containing aromatic compound such as 1-naphthol-4-sulfonic acid, p-phenylbenzenesulfonic acid, β-naphthalenesulfonic acid and quinolinesulfonic acid.

(4) Compound containing -S- residue

또는

을 포함하는 화합물이다.: The compound containing the residue

or

It is a compound containing.

잔기를 포함하는 화합물(5)

Compounds containing residues

: The compound containing the said residue is various thiocarboxylic acid compounds.

(6) Compounds containing -O- or -OH residues

Compounds containing the residue are phenol, cresol, xylenol, thymol, carbacol, eugenol, isoeugenol, phenylphenol, benzylphenol, confectionary call, butylstilbene, (di)nitrophenol, nitrocresol, methyl Salicylate, benzyl salicylate, mono-, di-, tri-, tetra- and penta-chlorophenol, chlorocresol, chlorosilenol, chlorothymol, p-chloro-o-cyclo-hexylphenol, p-chloro -o-cyclopentylphenol, p-chloro-on-hexylphenol, p-chloro-o-benzylphenol, p-chloro-o-benzyl-m-cresol and other phenols such as β-naphthol and 8-hydr It is Roxy Quinoline.

With respect to the metal (M), any metal having a valence of 2 or more can be used. Specific examples of the metal are Ca, Mg, Zn, Cu, Ba, Te, Pb, Fe, Co, Ni, Bi, Si, Ti, Mn, Al and Sn, and preferred examples are Co, Ni, Cu, Zn, Mn and Te, especially Cu and Zn. When synthesizing a metal-containing copolymer, the metal may be used in the form of an oxide, hydroxide or chloride. Copolymers used in the binder system in the coating composition of the present invention are known from EP 0471204 B1, EP 0342276 B1 or EP 0204456 B1.

The monomer containing the end group of Formula 5 may be copolymerized with another polymerizable unsaturated monomer to obtain a copolymer, and any commonly used ethylenically unsaturated monomer may be used. Examples of the 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, vinylpyridine, vinylpyrrolidone, vinyl acetate, acrylonitrile, methacrylonitrile, dimethyl itaco Nate, dibutylitaconate, di-2-ethylhexylitaconate, dimethylmaleate, di(2-ethylhexyl)maleate, ethylene, propylene and vinyl chloride.

If necessary, the monomer may also be a hydroxy-containing monomer such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. .

The synthesized copolymer does not need to contain a metal ester bond in all organic acid side groups, if necessary; Some of the organic acid side groups may remain unreacted in the form of free acid.

The weight average molecular weight of the metal-containing copolymer is generally in the range of 1,000 to 150,000, for example, in the range of 3,000 to 100,000, and preferably in the range of 5,000 to 60,000.

The coating composition of the present invention further comprises an organic ligand in an amount at least equal to a 1:1 ligand-to-metal co-ordination ratio. The organic ligand is selected from the group consisting of aromatic nitro compounds, nitriles, urea compounds, alcohols, phenols, aldehydes, ketones, carboxylic acids and organosulfur compounds, and the copolymers defined above are in situ with organic ligands. To form a polymer composite.

Monobasic organic acids that can be used to form hybrid salts include 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, dichloro Monocarboxylic acids such as phenoxyacetic 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 preparing the polymeric hybrid salt is disclosed in Japanese Patent Publication No. 16809/1989.

7. Hybridization of silylated acrylate and metal acrylate binder systems

Hybrids of the silylated acrylate and metal acrylate binder systems of the present invention are based on the silyl acrylate monomers and metal acrylate monomers described above, which are known from KR 20140117986.

8. Polyoxalate binder system

The polyoxalate binders of the present invention are based on polyoxalates known from WO 2015/114091. The polyoxalate may be a linear or branched polymer. The polyoxalate is a copolymer formed from three or more different monomers, and may be a random copolymer or a block copolymer. In addition, the polyoxalate contains sufficient repeating units to achieve a molecular weight of 4000 g/mol or higher.

The polyoxalate may be prepared through any of various methods known and used in the art such as condensation polymerization. The polyoxalate is preferably two or more polymers of oxalate monomers and the monomers are oxalic acid or diester derivatives thereof. Preferably, the second monomer is selected from the group consisting of cyclic diacids and cyclic diesters, and the third monomer is a diol.

The oxalate monomer used in the polymerization reaction is oxalic acid or a diester derivative thereof. The ester can be an alkyl ester, alkenyl ester, cycloalkyl ester or aryl ester. Preferably, the oxalate monomer is selected from the group consisting of oxalic acid and dialkyloxalate, and the dialkyloxalate may be dimethyloxalate, diethyloxalate, dipropyloxalate and dibutyloxalate.

In addition to the oxalate monomer, the polyoxalate includes a second monomer selected from the group consisting of cyclic diacids and cyclic diesters. For example, the cyclic diacid is a saturated, unsaturated or aromatic C ₃ -C ₈ ring including one or more hetero atoms selected from the group consisting of N, O and S, such as a C ₅ -C ₆ ring dicarboxylic acid to be.

The heterocyclic ring includes a furan, for example, the compound furan-2,5-dicarboxylic acid.

Examples of cyclic diesters are esterified rings of saturated, unsaturated or aromatic C ₃ -C ₈ rings, such as C ₅ -C ₆ rings, containing one or more hetero atoms selected from the group consisting of any N, O and S. It is a click dicarboxylic acid.

The poly oxalate also includes a third monomer that is a diol. The diol may be present as one diol monomer or one or more diol monomers, preferably two or three monomers are expected to be used. Examples of the diol include saturated aliphatic and saturated alicyclic diols, unsaturated aliphatic diols and aromatic diols, and saturated aliphatic and alicyclic diols may be preferable. Also mixtures of saturated aliphatic and saturated alicyclic diols can be used. Details of the polyoxalate binder system are known from WO 2015/114091.

9. Hybrid of zwitterionic binder system and silylated binder system and zwitterionic binder system

The binder of the present invention is based on an intermediate body comprising a polymer binder having zwitterionic monomers that can be combined with a silylated acrylate monomer, which binders are disclosed in WO 2004/018533 and WO 2016/066567, both suitable The ionic binder system is known from WO 2004/018533.

The different zwitterionic binder system comprises a polymer comprising a quaternary ammonium group or quaternary phosphonium group bound to the backbone of the polymer, said quaternary ammonium group or quaternary phosphonium group being neutralized by counter-ions, ie blocked or capped will be. The counter ions are composed of anionic residues of acids having aliphatic, aromatic or alkaline hydrocarbon groups containing 6 or more carbon atoms.

The polymer may be prepared by polymerization of a quaternary functional monomer capped with one or more types of long-chain acids, and contains a polymer containing a quaternary ammonium group or a quaternary phosphonium group and 6 or more carbon atoms. It can also be produced by reaction with an acid containing an aliphatic, aromatic or alkali hydrocarbon group. Details of the zwitterionic binder system are known from WO 2004/018533.

Suitable hybrids of silylated acrylate and zwitterionic binder systems are disclosed in WO 2016/066567. The hybrid comprises a polymer comprising a silyl ester group and a quaternary ammonium group or quaternary phosphonium group, the quaternary ammonium group or quaternary phosphonium group being neutralized by counter ions, the counter-ions being aliphatic, aromatic or It is composed of a conjugated base of an acid having an alkali hydrocarbyl group.

The polymer can be obtained by polymerizing a monomer containing a silyl ester group and a monomer containing a quaternary ammonium group or a quaternary phosphonium group, and the quaternary ammonium group or quaternary phosphonium group is neutralized by a counter ion, and the counter ion Is composed of a conjugated base of an acid having an aliphatic, aromatic or alkylhydrocarbyl group and any other monomers. The polymer may be a (meth)acrylic polymer.

Hybridization of silylated acrylates and amphoteric ion binder systems is described in detail in WO 2016/066567.

10. Polyester binder system

Polyester-based binder systems are disclosed in US 2015/0141562. The polyester resin can be obtained by the reaction of a trihydric or higher alcohol, dibasic acid or anhydride thereof and dihydric alcohol, and can also be obtained by further reacting an alicyclic dibasic acid or anhydride thereof.

The trivalent or higher alcohol may be an alcohol having three or more hydroxyl groups in the molecule, for example, polyfunctional polyhydrides such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol and pentaerythritol. Roxy compounds are included. Further, the number of carbon atoms is preferably 3 to 24, such as 3 to 8.

The dibasic acid or anhydride thereof is an acid having two or more ionizable hydrogen atoms in a molecule or anhydride thereof, such as aliphatic dibasic acid, alicyclic dibasic acid, aromatic dibasic acid, and anhydrides thereof. Specific examples of the aliphatic dibasic acid or anhydride thereof include malonic acid, maleic acid, fumaric acid, glutaric acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and 1,9-nonamethylenedicar Carboxylic acids, 1,10-decamethylenedicarboxylic acid, 1,11-undecamethylenedicarboxylic acid and 1,12-dodecamethylenedicarboxylic acid and their anhydrides, the alicyclic dibasic acids or Specific examples of the anhydride include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,4-decahydronaphthalenedicarboxylic acid , 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid and 2,7-deca hydronaphthalenedicarboxylic acid and their anhydrides. Further specific examples of aromatic dibasic acids or anhydrides thereof include orthophthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, anthracenedicarboxylic acid, dimer acid, hydrogenated dimer acid and phenanthrenedicarboxylic acid and their anhydrides It includes. They can naturally be used in various derivative forms (eg, dimethylcarboxylate ester or sodium-5-sulfoisophthalic acid), and two or more different ones can be used as a mixture.

The dihydric alcohol is an alcohol having two hydroxyl groups in the molecule, and examples of the alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, and 1,3-butanediol , 2-methyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2 ,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1, 12-octadecane diol. The alcohol is preferably a branched alkylene glycol considering the solubility of the synthetic ester.

The alicyclic dibasic acid or anhydride thereof means an acid having an alicyclic structure and two ionizable hydrogen atoms in a molecule or anhydride thereof. Examples of the alicyclic dibasic acid or anhydride thereof include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and 1,4-decahydro Naphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid and 2,7-decahydronaphthalenedicarboxylic acid, and acid anhydrides thereof. The polyester binder system is disclosed in detail in US 2015/0141562.

11. Additional binder composition

The rosin binder system, the non-aqueous dispersion binder system, the silylated acrylate binder system, and their hybrid system may include one or more additional binder components as part of the binder system, and the main binder component itself also comprises a binder system. Can be configured.

The additional binder component may include oil such as linseed oil and its derivatives, castor oil and its derivatives, soybean oil and its derivatives; And other polymer 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 resin or modified alkyd resin; Hydrocarbon resins such as castor fraction condensate; Chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene and chlorinated polypropylene; Styrene copolymers such as styrene-butadiene copolymer, styrene-methacrylate and styrene-acrylate copolymer; Acrylic resins such as homopolymers and copolymers of methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and isobutyl methacrylate; Hydroxy-acrylate copolymers; Polyamides based on dimerized fatty acids such as dimerized tall oil fatty acids and polyamide resins using the same; Cyclized rubber; Epoxy esters; Epoxy urethane; Polyurethane; Epoxy polymers; Hydroxy-polyether resins; Polyamine resins; Etc. There are copolymers of these.

The additional binder component is generally included from 0 to 25%, for example from 5 to 20% by weight, based on the coating composition.

12. Metal compounds

The coating composition of the present invention comprises a metal compound.

The metal compound may be any compound including metal ions. The metal ion may be any metal ion having a valence of 1, 2 or 3, and preferably, the metal ion is Cu(I) ion, Cu(II) ion, Zn ion, Co(II) ion, Ca ion, It may be Mg ion or Fe(III) ion.

The metal compounds are metal oxides, metal hydroxides or metal salts, such as metal chloride, metal fluoride, metal nitrate, metal acetate, metal sulfate, metal hydrogen sulfate, metal phosphate, metal hydrogen phosphate and metal dihydrogenphosphate. Preferably, the metal oxide is selected from the group consisting of metal oxides, metal hydroxides and mixtures thereof.

The metal compound is a metal oxide, and the metal oxide forms Cu(I) ion, Cu(II) ion, Zn ion, Co(II) ion, Ca ion, Mg ion and Fe(III). Including ions, Cu ₂ O, CuO, ZnO, CoO, CaO, MgO, and Fe ₂ O ₃ are obtained. Preferably, the metal compound is a mixture of ZnO and Fe ₂ O ₃ and more preferably ZnO.

The metal compound may be 1 to 50%, for example, 1 to 30%, 1 to 20%, 1 to 15%, or 1 to 5% based on the solid content of the coating composition, according to another embodiment The metal compound may be 2 to 40%, for example, 3 to 25%, 5 to 15%, or 8 to 12% based on the solid content of the coating composition.

13. Alkoxysilane

The coating composition of the present invention comprises one or more alkoxysilanes.

The alkoxysilane has a SiR _n (OR) _4-n composition. Wherein n = 0, 1, 2 or 3, each R can be an independent C _1-20 alkyl group and preferably R can be interrupted by an oxygen group. Preferably, the alkoxysilane has a relatively low molecular weight, for example, 400 g/mol or less. In addition, R is preferably an independent linear C _1-10 or branched C _3-10 alkyl group. More preferably, R is an independent C _1-6 alkyl group and the alkyl group is methyl, ethyl, n-propyl, isopropyl or n-butyl. Also, it is preferable that n is 0, 1 or 2, and the silane is preferably di-, tri-, or tetra-alkoxysilane. More preferably, n is 0 and the silane is tetra-alkoxysilane.

The alkoxysilanes of the present invention are known to those skilled in the art and are commercially available. Examples of the alkoxy silane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane and trimethylethoxysilane, preferably tetraethoxysilane and tetrapropoxysilane. Silane. The alkoxysilane of the present invention is comprised from 0.05 to 20% of the coating composition, such as 0.1 to 10%, preferably 0.2 to 5%, such as 0.3 to 2%.

14. Biocides

The coating composition of the present invention may include one or more autobiotics.

The “biocide” refers to an active substance that destroys harmful organisms by chemical or biological means, blocks harmful organisms, prevents the action of harmful organisms, or controls them. The biocide is a heterocyclic nitrogen compound and the heterocyclic nitrogen compound is 3a,4,7,7a-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-(methyl Sulfonyl)-pyridine, 2-methylthio-4-tert-butylamino-6-cyclopropylamine-s-triazine and quinoline derivatives; 2-(4-thiazolyl)benzimidazole, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-octyl-3(2H)-iso Heterocyclic sulfur compounds such as thiazolin (Sea-Nine ^® -211N), 1,2-benzisothiazolin-3-one, 2-(thiocyanatomethylthio)-benzothiazole, (RS)-4 -[1-(2,3-dimethyl phenyl)ethyl]-3H-imidazole (medetomidine, selecttope); and 4-brom-2-(4-chlorophenyl)-5-(trifluoro Lomethyl)-1H-pyrrole-3-carbonitrile (Tralopyril, Econea®); urea derivatives such as N-(1,3-bis(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl )-N,N'-bis(hydroxymethyl)urea and N-(3,4-dichlorophenyl)-N,N-dimethylurea, N,N-dimethylchlorophenylurea; amide or imide of carboxylic acid ; Sulfonic and sulfenic acids, for example 2,4,6-trichlorophenylmaleimide, 1,1-dichloro-N-((dimethylamino)sulfonyl)-1-fluoro-N-(4-methylphenyl )-Methanesulphenamide, 2,2-dibromo-3-nitrile-propionamide, N-(fluorodichloromethylthio)-phthalimide, N,N-dimethyl-N'-phenyl-N'-( Fluorodichloromethylthio)-sulfamide and N-methyl olformamide; salts or esters of carboxylic acids, such as 2-((3-iodo-2-propynyl)oxy)-ethanol phenyl carbamate and N , N-ddecyl-N-methyl-poly(oxyethyl)·ammonium propionate; amines such as dehydroabiethylamine and cocodidimethylamine; substituted methane such as di(2-hydroxy-ethoxy) Methane, 5,5'-dichloro-2,2'-dihydroxydiphenylmethane and methylene-bisthiocyanate; 2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile, 1,1 -Dichloro-N-((dimethylamino)-sulfonyl)-1-fluoro-N-phenylmethanesulfenamide and 1-(diaiodomethyl)sulfonyl)-4-methyl-benzene; Tetraalkylphosphonium halogenides such as tri-n-butyltetradecylphosphonium chloride; guanidine derivatives such as n-dodecylguanidine hydrochloride; Disulfides such as bis-(dimethylthiocarbamoyl)-disulfide, tetramethylthiuramdisulfide; Imidazole-containing compounds, such as medetomidine; 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole and mixtures thereof. Preferably, the heterocyclic nitrogen compound is 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-octyl-3(2H)-isothiazoline (Sea-Nine ^® -211N), (RS)-4-[1-(2,3-dimethylphenyl)ethyl]-3H-imidazole (Medetomidine, Selektope ^® ) or 4-brom-2-(4-chloro Phenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (Tralopyril, Econea ^® ).

The metal-containing biocide may be selected from metal-containing organic biocide, metal-containing inorganic biocide, metal salt, and copper bis(N-cyclohexyl-diazeniumdioxy). The metal-containing organic biocide is a metal-dithiocarbamate, for example, bis(dimethyldithiocarbamato)zinc, zinc-ethylenebis(dithiothiocarbamate) (Zineb, Zineb), ethylene- Bis(dithiocarbamato) manganese, dimethyldithiocarbamate zinc, and complexes thereof; Bis(1-hydroxy-2 (1H)-pyridine thionato-O, S)-copper (copper pyrithione); Bis(1-hydroxy-2 (1H)-pyridine thionato-O, S)-zinc (zinc pyrithione); Phenyl ­ (bispyridyl)-bismuth dichloride. The metal-containing inorganic biocide is a copper-nickel alloy such as copper (I) oxide, copper oxide and metal copper, and a copper metal alloy, for example, copper bronze. The metal salts are copper sulfite, basic copper carbonate, copper hydroxide, barium metaborate, copper chloride, silver chloride, silver nitrate and copper sulfide. Preferably the biocide can be a copper-containing biocide and a zinc-containing biocide, in particular copper oxide, copper pyrithione, zinc pyrithione and zinc-ethylene bis (dithiocarbamate) (Zenib) to be. Additionally, if a biocide is present in the composition, it is preferred not to contain tin.

The biocide is 2,4,5,6-tetrachloroisophthalonitrile (chlorohalonyl), copper thiocyanate (copper sulfocyanate), N-dichlorofluoromethylthio-N',N' -Dimethyl-N-phenylsulphamide (Dichlofluanid), 3-(3,4-dichlorophenyl)-1,1-dimethylurea (Diuron), N2-tert-butyl-N4-cyclopropyl-6-methylthio-1 ,3,5-triazine-2,4-diamine (Cybutryne), 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, ( 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole; trapyryl), N2-tert-butyl-N4-cyclopropyl-6-methylthio-1,3 ,5-triazine-2,4-diamine (cybutin), (RS)-4-[1-(2,3-dimethylphenyl)ethyl]-3H-imidazole (medetomidine), 4,5- Dichloro-2-n-octyl-4-isothiazolin-3-one (DCOIT, Sea-Nine ^® 211N), dichloro-N-((dimethylamino)sulfonyl)fluoro-N-(p-tolyl)methane Sulenamide (tolylfluanid), 2-(thiocyanomethylthio)-1,3-benzothiazole ((2-benzothiazolylthio)methylthiocyanate; TCMTB), triphenylboranepyridine (TPBP ); Bis(1-hydroxy-2(1H)-pyridinthionto-O,S)-(T-4)zinc (zinc pyridinthion; zinc pyrithione), bis(1-hydroxy-2(1H)-pyridine Thionto-O,S)-T-4) copper (copperpyridinion; copper pyrithione), zinc ethylene-1,2-bis-dithiocarbamate (zinc-ethylene-N-N'-dithiocar Barmate; zineb), copper(i) oxide, metal copper, 3-(3,4-dichlorophenyl)-1,1-dimethylurea (Diuron) and diiodomethyl-p-tolylsulfone; And from the group consisting of Amical 48. Preferably, the biocide is selected from biocides effective to prevent soft contamination such as mucus and algae, and the biocide is N2-tert-butyl-N4-cyclopropyl-6-methylthio-1,3, 5-triazine-2,4-diamine (cybutin), 4,5-dichloro-2-n-octyl-4-isothiazoline-3-1 (DCOIT, Sea-Nine ^® 211N), bis(1- Hydroxy-2(1H)-pyridinthionto-O,S)-(T-4)zinc (zinc pyridinthion; zinc pyrithione), bis(1-hydroxy-2(1H)-pyridinthionto-O ,S)-T-4) copper (copper pyridinion; copper pyrithione; copper omidine) and zinc ethylene-1,2-bis-dithiocarbamate (zinc-ethylene-N-N'-dithiocar Barmate); Geneve), copper(I) oxide, copper metal, copper thiocyanate, (sulfuric acid sulfocyanate), bis(1-hydroxy-2(1H)-pyridinthionato-O,S)-T-4) Copper (copper pyridinion; copper pyrithione; copper omadin).

The biocide comprises at least one organic biocide and the organic biocide is preferably a pyrithione complex such as zinc pyrithione or a pyrithione complex such as copper pyrithione. The organic biocide may be a complete organism or a part of it.

The biocide of the present invention is bis(1-hydroxy-2(1H)-pyridinthionato-O,S)-(T-4)zinc (zinc pyridinthion; zinc pyrithione), bis(1-hydroxy -2(1H)-pyridinethionato-O,S)-(T-4) copper (copperpyridinion; copper pyrithione) and zinc ethylene-1,2-bis-dithiocarbamate (zinc-ethylene -N-N'-dithiocarbamate; Zineb).

As detailed in US Pat. No. 7,377,968, when the biocide has high water solubility or is immiscible with the binder matrix and is rapidly depleted from the film, as a means of controlling the dosage of the biocide and extending the useful life of the film It is possible to add one or more biocides in encapsulated form. The encapsulated biocide of the present invention is 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (Sea-Nine CR2).

It is preferred that the biocide has a solubility in the range of 0-20 mg/L in water at 25°C, for example, a solubility in the range of 0.00001-20 mg/L.

The biocide of the present invention may include copper oxide, and the copper oxide is 3 to 65% based on the weight of the coating composition, for example, 5 to 60%, 10 to 60%, 15 to 60%, 15 to 40%, or 20 to 60%. Expressed in solids, the biocide may be included in 3 to 45%, for example 5 to 40%, 7 to 38%, 10 to 35%, or 15 to 35% based on the solids content of the coating composition. .

The biocide of the present invention can use only organic biocide, in which case the organic biocide is 0.25 to 30% based on the weight of the coating composition, for example, 0.5 to 25%, 0.75 to 20%, 1 to 15%, or 2 to 12%. If expressed in solids, the biocide may be included in 0.5 to 15%, for example, 1 to 12%, 2 to 10%, or 4 to 9% based on the solids content of the coating composition.

Example

According to an embodiment of the invention, the invention comprises a); b); And c) provides a self-polishing type anti-fouling coating composition comprising:

a) 25 to 80% solids of the non-silicone binder matrix comprising a rosin-based binder system;

b) 1 to 50% solids of any one metal compound selected from the group consisting of metal oxides, metal hydroxides and mixtures thereof; And

c) 0.1 to 10% solids of one or more alkoxysilanes.

According to another embodiment of the invention, the invention is a); b); And c) provides a self-polishing type anti-fouling coating composition comprising:

a) rosin-based binder system; And hybrids of non-aqueous dispersed binder systems, metal acrylate binder systems, silylated acrylate and metal acrylate binder systems, polyoxalate binder systems, amphoteric ion binder systems, and silylated acrylate and amphoteric ion binder systems. And 25 to 80% of the solid content of the non-silicone-based binder matrix comprising an additional non-silicone-based binder system selected from the group consisting of polyester binder systems;

b) 1 to 50% solids of any one metal compound selected from the group consisting of metal oxides, metal hydroxides and mixtures thereof; And

c) 0.1 to 10% solids of one or more alkoxysilanes.

According to another embodiment of the invention, the invention is a); b); And c) provides a self-polishing type anti-fouling coating composition comprising:

a) rosin-based binder system; And hybrids of non-aqueous dispersed binder systems, metal acrylate binder systems, silylated acrylate and metal acrylate binder systems, polyoxalate binder systems, amphoteric ion binder systems, and silylated acrylate and amphoteric ion binder systems. And a non-silicone-based binder matrix comprising an additional non-silicone-based binder system selected from the group consisting of polyester binder systems, wherein the binder matrix comprises up to 10% of a silylated acrylate binder system. 25 to 80%;

b) 1 to 50% solids of any one metal compound selected from the group consisting of metal oxides, metal hydroxides and mixtures thereof; And

c) 0.1 to 10% solids of one or more alkoxysilanes.

According to another embodiment of the invention, the invention is a); b); And c) provides a self-polishing type anti-fouling coating composition comprising:

a) rosin-based binder system; And hybrids of non-aqueous dispersed binder systems, metal acrylate binder systems, silylated acrylate and metal acrylate binder systems, polyoxalate binder systems, amphoteric ion binder systems, and silylated acrylate and amphoteric ion binder systems. And a non-silicone-based binder matrix comprising an additional non-silicone-based binder system selected from the group consisting of polyester binder systems, wherein the binder matrix comprises up to 10% of a silylated acrylate binder system. 20 to 70%;

b) 1 to 20% solids of any one metal compound selected from the group consisting of metal oxides, metal hydroxides and mixtures thereof; And

c) 0.3 to 2% solids of one or more alkoxysilanes.

According to another embodiment of the invention, the invention is a); b); c); And d) provides a self-polishing type anti-fouling coating composition comprising:

a) rosin-based binder system; And hybrids of non-aqueous dispersed binder systems, metal acrylate binder systems, silylated acrylate and metal acrylate binder systems, polyoxalate binder systems, amphoteric ion binder systems, and silylated acrylate and amphoteric ion binder systems. And a non-silicone-based binder matrix comprising an additional non-silicone-based binder system selected from the group consisting of polyester binder systems, wherein the binder matrix comprises up to 10% of a silylated acrylate binder system. 20 to 70%;

b) 1 to 20% solids of any one metal compound selected from the group consisting of metal oxides, metal hydroxides and mixtures thereof;

c) 0.3 to 2% solids of one or more alkoxysilanes; And

d) 3 to 45% of biocide solids

According to another embodiment of the invention, the invention is a); b); c); And d) provides a self-polishing type anti-fouling coating composition comprising:

a) rosin-based binder system; And hybrids of non-aqueous dispersed binder systems, metal acrylate binder systems, silylated acrylate and metal acrylate binder systems, polyoxalate binder systems, amphoteric ion binder systems, and silylated acrylate and amphoteric ion binder systems. And a non-silicone-based binder matrix comprising an additional non-silicone-based binder system selected from the group consisting of polyester binder systems, wherein the binder matrix comprises up to 10% of a silylated acrylate binder system. 50 to 55%;

b) 8 to 12% solids of any one metal compound selected from the group consisting of metal oxides, metal hydroxides and mixtures thereof;

c) 0.1 to 1% solids of one or more alkoxysilanes; And

d) 15-35% biocide solids.

1. Application of coating composition

The present invention relates to a marine structure, wherein the marine structure is coated by applying the self-polishing type anti-fouling coating composition of the present invention to a part of its surface. The marine structure may be formed of one or several coating layers with the coating composition of the present invention.

The coating composition according to the present invention can be applied to an offshore structure to be protected by one or several successive layers and can generally be formed of 1 to 4 ply coating layers, preferably 1 to 2 ply coating layers. The dried coating layer (film) may have a thickness of 10 to 600 mm per one coating layer, and preferably 20 to 500 mm, for example, 40 to 400 mm. Therefore, the thickness of the entire coating layer may be 10 to 1,800 mm, and preferably, 20 to 1,500 mm, 40 to 1,200 mm mm, or 80-800 mm.

Marine structures to which the coating composition of the present invention can be applied may be various types of solids that come into contact with water, and examples thereof include boats, yachts, all types of boats including motor boats, motor launches, submarine liners, Tugboats, tankers, container ships and other cargo ships, nuclear or conventional submarines and all types of naval vessels; pipe; All types of coastal and marine machinery, structures and objects, such as coastal and coastal machinery, bridge substructures, floating devices, underwater well structures, etc.; Nets and other marine facilities; Cooling equipment; buoy; And hulls and boat hulls and pipes.

Before the coating composition of the present invention is applied to a marine structure, the marine structure may be coated with a primer system. The primer system may be composed of several layers and may be a conventional primer system used for marine structures. Therefore, the primer system may include a corrosion-resistant primer, and may further be an adhesion promoting primer layer.

The primer system includes a combination of an epoxy resin having an epoxy equivalent of 60 to 600 as a binder system and a curing agent (eg, an amino type, a carboxylic acid type or an acid anhydride type), a combination of a polyol resin and a polyisocyanate type curing agent; Or a vinyl ester resin, or a coating material containing an unsaturated polyester resin, etc., and if necessary, a thermoplastic resin (such as a chloride rubber, an acrylic resin or a vinyl chloride resin), a curing accelerator, a rust preventive pigment, a coloring pigment, an extender pigment, A solvent, a tri alkoxy silane compound, a plasticizer, an additive (such as a rust inhibitor or anti-settling agent) or a tar epoxy resin-based coating material may be further added.

In addition, the present invention provides a method for coating a structure using the coating composition of the present invention. The coating method includes the step of applying the anti-pollution coating composition of the present invention to at least a portion of the structure as one layer, and the embodiment shows that it is extended to multiple layers.

2. Coating layer

The present invention provides one or more coating layers formed on the surface of a structure, such as an offshore structure, using the coating composition of the present invention, and the coating layer is formed by drying and curing after the coating composition is applied to the surface of the structure.

The coating layer of the present invention includes a siloxane network including chemical structures such as ≡Si-OH and ≡Si-O-Si≡, and the siloxane network has an advantage of improving drying and weathering characteristics of the coating composition.

The present invention also relates to a coating layer based on a non-silicone-based binder matrix, characterized in that it comprises a siloxane network comprising chemical structures such as ≡Si-OH and ≡Si-O-Si≡. According to an embodiment of the present invention, the non-silicone-based binder matrix does not include a silylated acrylate binder.

3. Materials

3-1. bookbinder

Chinese gum rosin: Arawaka Chemical Industries (China), gum rosin.

Hypale CH: Arakawa Chemical Industries (China).

Foral AX-E: Eastman Chemicals (Netherlands), hydrogenation rosin.

Acronal 9020: BASF (Germany), 60% by weight-xylene solvent, acrylate co-binder.

Synocryl 7013-SD50: Archema (Spain), 50% by weight-butanol/petroleum (1:2) solvent, acrylic co-binder.

NSP-100: Nitto Kasei (Japan), 50 wt%-xylene/ethylbenzene (1:1) solvent, silylated acrylic copolymer binder solution.

Plasticizer: 45% by weight-xylene solvent.

3-2. Biocide

Nordox Cuprous Oxide Paint Grade: Nordox (Norway), copper oxide.

Copper Omadine: Arch Chemicals (China), copper pyrithione.

Zineb Nautec: United Phosphorous (India), Zinc-Ethylenebis (Dibenzothiocarbamate).

DCOIT: The Dow Chemical company (USA), 4,5-dichloro-2-n-octyl-4-isothiazoline-3-1.

Medetomidine: I-Tech Abv (Sweden).

3-3. solvent

Xylene and methylisobutylketone.

3-4. additive

Thickener: Bentone 38, Elementis Specialties (UK).

Wetting agent: Nuosperse 657 RD, Elementis Specialties (Netherlands) and Disperbyk 164, BYKChemie (Germany).

Anti-gelling agent: DTBHQ, Hangzhou Thomas (China), 2,5-dibutyl butyl hydroquinone.

Thixotropic agent: Aditix M 60, Supercolori (Italy), modified polyethylene wax.

3.5 Metal compounds acting as pigments and fillers

Zinc Oxide Red Seal: Umicore (Netherlands).

Iron oxide pigment; Micronox R01-Promindsa (Spain).

3.6 Additional pigments and fillers

Dynasylan: A EVONIK (Germany), Tetraethoxysilane (TEOS).

Tetrapropyl orthosilicate: TCI Europe NV-division of TOKYO CHEMICAL INDUSTRY, Tetrapropoxysilane (TPOS).

4. Experimental Example

4-1. Salt Spray Test: SST

The salt spray test was performed according to ISO 9227. The method is performed to evaluate the corrosion resistance of the coating system by regenerating corrosion occurring in the atmosphere including salt spray or splash. In the present invention, the salt atmosphere surrounding the marine structure to which the coating composition is applied is reproduced, and it is evaluated whether a white precipitate is formed on the surface of the coating layer. The operating conditions of the salt spray test were constantly sprayed with a 5% NaCl solution at 35°C. The test panel was placed at an angle of 15° to 25° relative to the vertical. After the end of exposure (168 hours), the formation of a white precipitate was visually evaluated.

To quantify the improvement in whitening resistance, the gloss before and after the coating layer was exposed to SST was evaluated. Gloss retention was measured using BYK Gardner Gmbh's micro-TRI (Cat-No: 4430 and Serial No: 1001994). The measurements were made at 85 degrees on the panel surface. Three measurements were made for each panel and the average was calculated. To evaluate the paint, the difference between the values before and after exposure was plotted as a graph of the TEOS content of the paint.

4-2. Determination of drying time: Beck Koller test

Determination of the drying time was carried out using the Beck Koller drying time determination method according to ASTM D 5895-03. The coating layer was applied to a glass strip using a 400 micron clearance applicator and the applied test strip was immediately placed in a drying time recorder between brass studs. A needle carrier was drawn along the coating layer (I) set-to-touch (contact step), (II) tack free (non-viscosity step), (III) dry-hard (dry step) and (IV) dry-through ( It was recorded as a complete drying step).

4-3. Determination of drying and hardness: Wood block setting test

The drying degree and hardness of the coating layer (film) were evaluated. To this end, a 400 µm (DFT) thick acrylic panel (200x100x5.0mm) was coated with a doctor blade type applicator and dried at 5°C for 6 days. The drying time of 1, 2, 3, 6 days after placing a square piece of plastic (30x30mm) on the coating layer was measured by applying a pressure of 40Kg / Cm ² for 1 minute with a vise clamp device. Drying and hardness of the coating layer were evaluated according to the criteria in Table 1 below as a method of measuring the pressure traces remaining on the coating layer.

Performance Description Excellent
(Best) No serious deformation was observed
(No significant deformation is observed) Good
(good) Mounds observed
(Heap is observed) Fair
(usually) Large mound observed
(Large heap is observed) Poor
(Not good) Very large mound observed
(Very or large heap is observed)

4-4. Cosmetic property test: long term exposure in marine conditions

First, the acrylate test panel (15X20cm ² ) was sandblasted to ensure that the coating layer adhered well. A commercial vinyl tar primer (Hempanyl 16280: Hempel's Marine Paints A/S) was formed on the treated test panel by an air spray method to a thickness of 80 μm (DFT). The coated panel was dried for at least 24 hours at room temperature in the laboratory, and then mounted on a doctor blade applicator such that a 80 μm (DFT) thick film had a 4-gap size. The coating layer of 90-100 μm (DFT) was also measured in the same way. After drying for a minimum of 72 hours, the test panel was fixed and exposed to marine conditions.

에서 테스트 4-5. Vilanova i la Geltr in northeastern Spain

Tested in

Panel inspections were performed every 4 weeks and whitening of the coating layer was evaluated.

4-6. Testing in Busan, Korea

Panel inspections were performed every 4 weeks and whitening of the coating layer was evaluated.

4-7. Polishing rate test

Polishing and leaching characteristics were measured using a rotary setup similar to that described in Kiil et al. (Kiil, S, Weinell, CE, Yebra, DM, Dam-Johansen, K, “ Marine biofouling protection: design of controlled release antifouling paints. ” In: Ng, KM, Gani, R, Dam-Johansen, K (eds.) Chemical Product Design; Towards a Perspective Through Case Studies , 23 IDBN-13: 978-0-444-52217-7.Part II (7), Elsevier (2006).The measuring device consists of a rotatable rig and includes two concentric cylinders with a rotatable inner cylinder (rotor, 0.3 m in diameter, 0.17 m in height). It was immersed in a tank containing -500 liters of artificial sea water, the conditions of which are shown in Table 2 below.

Artificial seawater composition Salt Concentration in g/L NaCl 32 MgSO ₄ 7H ₂ O 14 NaHCO ₃ 0.2

The tank was equipped with a baffle to block the liquid flow. Therefore, the tank has the advantages of improving turbulence, improving the mixing rate of chemical species emitted from the coating layer, and improving the heat transfer of the temperature control system. The purpose of using the two cylinders is to make an approximation close to the couette flow (a flow between two parallel walls where one wall moves at a constant speed). The rotor was operated at 20 knots at 25° C. unless otherwise specified and the pH was adjusted to 8.2 using 1 M sodium hydroxide or 1 M hydrochloric acid. The sample was primed using a two-component paint (Hempadur 47182 ex Hempel) using an OHP film (3M PP2410) and using a doctor blade applicator with a gap size of 200 μm. The coating samples were applied adjacent to each other using a doctor blade applicator with a gap size of 250 μm. After drying for 1 day, the coated sample was cut into 2 cm strips to prepare 8 samples of 1.5 x 2 cm ² in a long strip (21 cm). The strip was then mounted on a rotor and dried for a week. The test started a week later and after 35, 65 and 140 days samples were removed to examine the depth of polishing and leaching. The sample was dried at room temperature for 3 days, cut in half and cast with paraffin. For the cross-section inspection of the coating, the inner front was peeled off before measuring the total thickness, and the thickness of the leaching layer was measured using an optical microscope.

Example 1: Testing the amount of alkoxysilane in a non-aqueous dispersion binder system

1 week for model paint based on non-aqueous dispersion binder system without alkoxysilane (Example 1a, Example 1a) and non-aqueous dispersion binder system with alkoxysilane (TEOS) (Example 1b, Example 1b) During the test it was conducted using the salt spray test (SST).

Table 3 and Figure 1 show the test results, all ratios are based on solids.

Model paints Top coat composition Top coat composition Example 1a: Non-aqueous dispersion binder Example 1b:
Non-aqueous dispersion binder+TEOS Wt-% VS-% Wt-% VS-% Binder system: Gum rosin 8.5 28.0 8.5 28.0 Non-aqueous dispersion binder (NAD) 11.0 19.0 11.0 19.0 Plastizicer 2.0 3.0 2.0 3.0 Biocides: Zineb --- --- --- --- Copper Pyrithione 3.0 6.0 3.0 6.0 Cuprous oxide 42.0 24.0 42.0 24.0 Other ingredients: Additives (thickeners, wetting agent, anti-gelling agent and thixotropic agent) 6.0 9.0 [6.2-6.1-6-5.9-5.7-5.5] [8.9-8.8-8.7-8.5-8.25-8] Fibers 1.0 1.0 1.0 1.0 Iron oxide 5.5 4.0 5.5 4.0 Zinc oxide 9.0 6.0 9.0 6.0 TEOS --- --- [0.3-0.5-0.8-1.3-2-2.7] [0.1-0.2-0.3-0.5-0.75-1.0] Solvents: MIBK 3.0 --- 3.0 Xylene 9.0 --- [8.5-8.4-8.2-7.8-7.3-6.8] --- Total 100 100 100 100 Ratios in solids volume NAD:ROSIN ratio 2:3 2:3 TEOS:ROSIN ratio --- [1:300, 1:140, 1:100, 1:60, 1:40, 1:30] ZnO:ROSIN ratio 1:5 1:5 Whitening after SST, 1 week Very High TEOS content (SV%):
[0-0.3]--> Whitening
[0.5-1.0] --> No Whitening

Additionally, the gloss difference was measured by exposing the panel to SST for 1 week. Figure 2 shows the results of the gloss measurement. The above Example 1 shows that the addition of 0.1% by volume of alkoxysilane (TEOS) is effective. The whitening gradually decreased and was found to have no whitening effect at 0.5% by volume or more. It was also found that the difference in gloss decreased linearly as a function of TEOS concentration.

Example 2: Alkoxysilane testing in different binder systems

Using the salt spray test, model paints based on three different binder systems were tested for a week.

Example 2a1 used a rosin-based binder system without alkoxysilane, and Example 2a2 used a rosin-based binder system with alkoxysilane (TEOS).

Example 2b1 used a non-aqueous dispersion binder system in which alkoxysilane was not present, and Example 2b2 used a non-aqueous dispersion binder system in which alkoxysilane (TEOS) was present.

Example 2c1 used a rosin-based binder system without alkoxysilane and Example 2c2 used a rosin-based binder system with alkoxysilane (TEOS).

Tables 4, 5, and 6 and Figure 3 below show the results of the above examples, all ratios are on a solids basis.

Model paints Top coat composition Example 2a1 Example 2a2 Wt-% VS-% Wt-% VS-% Binder system: Gum rosin 14.0 40.0 14.0 40.0 Acrylic cobinders 5.0 6.0 5.0 6.0 Plastizicer 3.0 5.0 3.0 5.0 Biocides: Zineb 9.0 14.0 9.0 14.0 Copper Pyrithione --- --- --- --- Cuprous oxide 28.0 14.0 28.0 14.0 Other ingredients: Additives (thickeners, wetting agent, anti-gelling agent and thixotropic agent) 5.0 7.0 4.0 6.0 Fibers 5.0 5.0 5.0 5.0 Zinc oxide 11.0 6.0 11.0 6.0 Iron oxide 5.0 3.0 5.0 3.0 TEOS 3.0 1.0 Solvents: MIBK 1.0 --- 1.0 --- Xylene 14.0 --- 12.0 --- Total 100 100 100 100 Ratios in solids volume Acrylic:ROSIN ratio 1:7 1:7 TEOS:ROSIN ratio --- 1:40 ZnO:ROSIN ratio 1:7 1:7 Whitening after SST, 1 week Very High Low

Model paints Top coat composition Example 2b1
: Non-aqueous dispersion binder Example 2b2
: Non-aqueous dispersion binder Wt-% VS-% Wt-% VS-% Binder system: Gum rosin 14.0 41.0 14.0 41.0 Non-aqueous dispersion binder (NAD) 1.0 2.0 1.0 2.0 Acrylic cobinders 5.0 7.0 5.0 7.0 Plastizicer 2.0 3.0 2.0 3.0 Biocides: Zineb --- --- --- --- Copper Pyrithione 2 4.5 2 4.5 Cuprous oxide 28 15.0 28 15.0 Other ingredients: Additives (thickeners, wetting agent, anti-gelling agent and thixotropic agent) 8.0 10.0 7.0 9.0 Fibers 5.0 5.0 5.0 5.0 Zinc oxide 10 6.0 10 6.0 Iron oxide 9.0 5.5 9.0 5.5 TEOS --- --- 3.0 1.0 Solvents: MIBK 1.0 --- 1.0 --- Xylene 15 --- 13 --- Total 100 100 100 100 Ratios in solids volume NAD:ROSIN ratio 1:20 1:20 TEOS:ROSIN ratio --- 1:41 ZnO:ROSIN ratio 1:7 1:7 Whitening improvement after SST, 1 week High No Whitening

Model paints Top coat composition Example 2c1
: Rosin based Example 2c2
: Rosin based+TEOS Wt-% VS-% Wt-% VS-% Binder system: Gum rosin 14.0 38.0 14.0 38.0 Acrylic cobinders 6.0 6.0 6.0 6.0 Plastizicer 5.0 8.0 5.0 8.0 Biocides: Zineb 7.0 11.0 7.0 11.0 Copper Pyrithione --- --- --- --- Cuprous oxide 22.0 11.0 22.0 11.0 Other ingredients: Additives (thickeners, wetting agent, anti-gelling agent and thixotropic agent) 7.0 9.0 6.0 8.0 Fibers 5.0 5.0 5.0 5.0 Zinc oxide 11.0 6.0 11.0 6.0 Iron oxide 7.0 5.0 7.0 5.0 TEOS --- --- 3.0 1.0 Solvents: MIBK 1.0 --- 1.0 --- Xylene 15.0 --- 13.0 --- Total 100 100 100 100 Ratios in solids volume Acrylic:ROSIN 1:6 1:6 TEOS:ROSIN ratio --- 1:38 ZnO:ROSIN ratio 1:6 1:6 Whitening after SST, 1 week Very high Few

As a result of the experiment, it was confirmed that the addition of the alkoxysilane improved the gloss retention even if all three binder systems were exposed to salt spray for a week.

Although all three binder systems were found to have good whitening even without alkoxysilane, it was confirmed that the whitening slightly decreased when alkoxysilane was present. In addition, when alkoxysilane was present, it was confirmed that the difference in gloss was significantly reduced in all three binder systems to show uniform gloss.

Example 3: Long time test in marine conditions

Test properties of non-aqueous dispersion binder system-based model paint containing alkoxysilane (Example 3a: 3 wt-% TEOS and Example 3b: 1.5 wt-% TEOS) Did. The test was conducted by exposure to marine conditions for several months and confirming that the degree of whitening was affected. The model paint of Example 1a was compared as a reference.

Tables 7 and 5 show the results for 7 months in Vilanova, Spain marine conditions, and Figure 6 shows the results for 2 months in Busan, Korea marine conditions.

Model paints Top coat composition Example 3a
: Non-aqueous dispersion binder Example 3b
:Non-aqueous dispersion binder Wt-% VS-% Wt-% VS-% Binder system: Gum rosin 9.0 28.0 9.0 28.0 Non-aqueous dispersion binder (NAD) 11.0 19.0 11.0 19.0 Plastizicer 2.0 3.0 2.0 3.0 Biocides: Isothiazolone algicide (DCOIT) 2.5 2.0 3.8 3.5 Medetomidine --- --- <1.0 <1.0 Zineb 3.5 6 --- --- Copper Pyrithione 3.0 6 3.0 6 Cuprous oxide 41.0 22.0 33.0 18.0 Other ingredients: Additives (thickeners, wetting agent, anti-gelling agent and thixotropic agent) 4.0 4.0 7.7 6.5 Fibers 1.0 1.0 3.0 3.0 Zinc oxide 5.0 3.0 5.0 3.0 Iron oxide 7.0 5.0 12.0 8.5 TEOS 3.0 1.0 1.5 0.5 Solvents: MIBK 3.0 --- 3.0 --- Xylene 5.0 --- 5.0 --- Total 100 100 100 100 Ratios in solids volume NAD:ROSIN 2:3 2:3 TEOS:ROSIN ratio 1:28 1:56 ZnO:ROSIN ratio 1:9 1:9 Whitening after 7 months exposed in sea Conditions Vilanova (Spain) No whitening Whitening after 2 months exposed in Sea conditions Busan (Korea) No whitening

Example 3 shows that the degree of whitening did not deteriorate despite exposure to marine conditions for 7 months. The whitening degree of Example 3 may be compared with the model paint used in the SST test in Example 1.

Example 4: Improvement of drying time in a non-aqueous dispersion binder system by addition of an alkoxysilane.

The improvement in drying time of the non-aqueous dispersion binder system by the addition of alkoxysilanes was confirmed through different drying tests as described above (Beck Koller and Wood Block Setting Test). The results from the Beck Koller, stage III (BKIII) test show that the drying time did not change significantly as the volume of TEOS increased from 0% to 0.1%. However, when adding 0.2 to 0.75 vol% of TEOS, the drying time was found to decrease steadily, and when adding 0.75 vol% or more of TEOS, it was confirmed that the drying time did not change any more. When the TOES contained 0.75% and the TOES was not included in the composition, the drying time was found to be 4 hours and 45 minutes, respectively. Figure 8 shows the properties of the coating with or without TEOS at 5° C., ie, the coating layer. The larger the heap left on the coating layer, the more drying time was required, which shows that the drying properties are improved as much as the paint containing TOES. As described above, the coating layer containing TEOS took only 3 days to dry, but the coating layer not containing TEOS took 6 days or more to dry. The results can be seen in FIG. 7 for the Beck Koller test and FIG. 8 for the wood block setting test.

Example 5: Effect of acrylate paint containing divalent metal oxide on alkoxysilane or silylated acrylate

Example 5 shows the results of testing the whitening of the paint coating layer composed of a silylated acrylate binder. The composition of the alkoxysilane and divalent metal oxide of each silylated paint is shown in Tables 8 and 9. The four paints of Tables 8 and 9 were applied to an acrylic test panel (DFT 150 micron), and then the salt spray test was performed.

All of these paints did not whiten after 1 week of exposure, which means that the main role of alkoxysilanes in the silylated acrylate based anti-pollution paints is a water remover to stabilize the silylated acrylate binders (Tables 8 and 9). And Figure 9).

Model paints Top coat composition Example 4a1
: silyl acrylate with ZnO Example 4a2
: s ilyl acrylate with ZnO +TEOS Wt-% VS-% Wt-% VS-% Binder system: Gum rosin 2.0 7.0 2.0 7.0 Silyl acrylate 37.0 57.0 36.0 57.0 Biocides: Cuprous oxide 50 28.0 49.0 28.0 Other ingredients: Additives (thickeners, wetting agent, anti-gelling agent and thixotropic agent) 4.0 6.6 4.0 6.0 Zinc oxide 2.0 1.4 2.0 1.4 TEOS --- --- 2.0 0.6 Solvents: Xylene 5.0 5.0 Total 100 100 100 100 Ratios in solids volume Silyl/ROSIN ratio 8:1 8:1 TEOS/ROSIN ratio 1:12 1:12 ZnO/ROSIN ratio 1:5 1:5 Whitening after SST, 1 week No whitening No whitening

Model paints Top coat composition Example 4b1
: silyl acrylate without ZnO Example 4b2
: s ilyl acrylate without ZnO +TEOS Wt-% VS-% Wt-% VS-% Binder system: Gum rosin 2.0 7.0 2.0 7.0 Silyl acrylate 37.0 57.0 36.0 57.0 Biocides: Cuprous oxide 52.0 29.5 51.0 29.4 Other ingredients: Additives (thickeners, wetting agent, anti-gelling agent and thixotropic agent) 4.0 6.5 4.0 6.0 TEOS --- --- 2.0 0.6 Solvents: Xylene 5.0 --- 5.0 --- Total 100 100 100 100 Ratios in solids volume Silyl:ROSIN ratio 8:1 8:1 TEOS:ROSIN ratio 1:12 1:12 ZnO:ROSIN ratio 1:5 1:5 Whitening after SST, 1 week No whitening No whitening

Example 6: Testing the amount of alkoxysilane in a non-aqueous binder system

Model paints based on a non-aqueous dispersion binder system without alkoxysilane (TPOS) (Example 6a) and model paints based on a non-aqueous dispersion binder system containing alkoxysilane (Example 6b) were sprayed with the brine described above for a week. Tests were conducted.

The results for this test are shown in Table 10 and Figure 10 below, and all ratios relate to solids volume.

Model paints Top coat composition Example 6a
: Non-aqueous dispersion binder Example 6b
: Non-aqueous dispersion binder + TPOS Wt-% VS-% Wt-% VS-% Binder system: Gum rosin 8.5 28.0 8.5 28.0 Non-aqueous dispersion binder (NAD) 11.0 19.0 11.0 19.0 Plastizicer 2.0 3.0 2.0 3.0 Biocides: Zineb --- --- --- --- Copper Pyrithione 3.0 6.0 3.0 6.0 Cuprous oxide 42.0 24.0 42.0 24.0 Other ingredients: Additives (thickeners, wetting agent, anti-gelling agent and thixotropic agent) 6.0 9.0 [5.7-5.4] [8.5-8] Fibers 1.0 1.0 1.0 1.0 Iron oxide 5.5 4.0 5.5 4.0 Zinc oxide 9.0 6.0 9.0 6.0 TPOS --- --- [1.3-2.6] [0.5-1.0] Solvents: MIBK 3.0 --- 3.0 Xylene 9.0 --- [8-7] --- Total 100 100 100 100 Ratios in solids volume NAD:ROSIN ratio 2:3 2:3 TPOS:ROSIN ratio --- [1:60, 1:30] ZnO:ROSIN ratio 1:5 1:5 Whitening after SST, 1 week Very High TPOS content (SV%)
: [0.5-1.0] --> Whitening improved

Additionally, the gloss difference between before and after the spray spray test was measured and the results are shown in FIG. 11. According to Example 6, it was confirmed that alkoxysilane (TPOS) had an effect even when 0.5 vol% was added. The paint added with 0.5 vol% of alkoxysilane (TPOS) was lowered in whitening, and the paint containing alkoxysilane (TPOS) in excess of 0.5 vol% was increased in whitening. Figure 12 shows the result of improving the drying characteristics as alkoxysilane is added to the non-aqueous binder system. In all cases where TEOS or TPOS was used as the alkoxysilane, drying time was found to be at a similar level.

The specific embodiments described herein are meant to represent preferred embodiments or examples of the present invention, and the scope of the present invention is not limited thereby. It is apparent to those skilled in the art that modifications and other uses of the present invention do not depart from the scope of the invention described in the claims of this specification.

Claims (15)

a) a non-silicone-based binder matrix comprising a rosin-based binder system;
b) a metal compound selected from the group consisting of a metal oxide, a metal hydroxide and a mixture of the metal oxide and the metal hydroxide; And
c) one or more alkoxysilanes;
Self-polishing type anti-fouling coating composition comprising a.
The method of claim 1, wherein the self-polishing type anti-fouling coating composition comprises a non-aqueous dispersion binder system, a metal acrylate binder system, a hybrid of silylated acrylate and metal acrylate binder systems, and a polyoxalate binder. Self-polishing, further comprising any one non-silicone-based binder system selected from the group consisting of a system, a zwitterion binder system, a hybrid of a silylated acetylate and a zwitterionic binder system, and a polyester binder system. Type anti-fouling coating composition.
The self-polishing type anti-fouling coating composition of claim 1, wherein the rosin-based binder system comprises a rosin component in which any one or two or more selected from the group consisting of rosin, rosin derivatives and rosin-modified polymers are mixed.
The metal oxide is Cu ₂ O, CuO, ZnO, CoO, CaO, MgO and Fe ₂ O ₃ Self-polishing type anti-fouling coating composition, characterized in that any one selected from the group consisting of.
The self-polishing type anti-fouling coating composition according to claim 1, wherein the at least one alkoxysilane is any one selected from the group consisting of tetraethoxysilane and tetrapropoxysilane.
The self-polishing type anti-fouling coating composition according to claim 1, wherein the non-silicone-based binder matrix is contained in a solids volume of 25 to 80% of the total solids volume of the self-polishing type anti-fouling coating composition.
The self-polishing type anti-fouling coating composition of claim 1, wherein the metal compound is contained in a solids volume of 1 to 50% of the total solids volume of the self-polishing type anti-fouling coating composition.
The self-polishing type anti-fouling coating composition according to claim 1, wherein the alkoxysilane is contained in a solids volume of 0.1 to 10% of the total solids volume of the self-polishing type anti-fouling coating composition.
The self-polishing type anti-fouling coating composition of claim 1, wherein the self-polishing type anti-fouling coating composition further comprises one or more biocide.
10. The self-polishing type antifouling coating composition of claim 9, wherein the one or more biocide is included in a solids volume of 3 to 45% relative to the total solids volume of the self-polishing type antifouling coating composition.
The method of claim 1, wherein the alkoxysilane and the rosin contained in the rosin-based binder system is a self-polishing type anti-fouling coating composition, characterized in that contained in a ratio of 1:300 (alkoxysilane: rosin) on a solids volume basis.
A method for coating a marine structure using a self-polishing type anti-fouling coating composition according to any one of claims 1 to 11 to form a coating layer on part or all of the marine structure.
A marine structure in which the self-polishing type anti-fouling coating composition of any one of claims 1 to 11 is formed of one or more coating layers.
The method according to claim 13, wherein the coating layer comprises a siloxane network comprising a chemical structure selected from the group consisting of ≡Si-OH chemical structure and ≡Si-O-Si≡ chemical structure. Marine structures characterized by.
The self-polishing type anti-fouling coating composition according to any one of claims 1 to 11, which is formed of one or more layers on part or all of the marine structure, and has a ≡Si-OH chemical structure and ≡Si-O-Si≡ chemistry. A coating layer of a marine structure including a siloxane network including any one or more chemical structures selected from the group consisting of structures.

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