JP2013234312A - High solid antifouling coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel low solvent antifouling coating composition based on an epoxy functional prepolymer having a hydrolyzable silyl group.SOLUTION: A self polishing antifouling coating composition comprises (a) a base component comprising a prepolymer and (b) a curing agent having at least one active hydrogen, for example, one selected from an amine, an amine epoxy adduct and a poly mercaptan; wherein the prepolymer has at least one epoxy functional group and a side chain having a terminal represented by formula I: -C(=O)-O-(SiRRO)-SiRRR( n is 0-5,000 and R, R, R, Rand Rare selected from 1-20C alkyl and optionally substituted phenyl groups ).

Description

  The present invention relates to a novel low solvent antifouling paint composition based on a prepolymer having hydrolyzable silyl groups.

  EP1641862 B1 discloses silyl ester copolymer compositions.

  International Publication No. 2009/100908 pamphlet discloses an antifouling composition containing polyoxalate as a binder.

  Japanese Unexamined Patent Application Publication No. 2010/235922 discloses an amino group curing agent having a hydrolyzable group. The hydrolyzable group is a group having a characteristic of hydrolyzing in seawater or fresh water. Ester groups and alkylsilyl groups are mentioned as examples of hydrolyzable groups.

  In view of the prior art, there remains a need for alternative antifouling compositions, especially high solids antifouling paint compositions.

The inventors of the present application have found that the above goals can be achieved with a self-polishing antifouling composition as defined herein.
Accordingly, in a first aspect, the present invention relates to a self-polishing antifouling composition as defined in claim 1. A second aspect of the invention relates to a kit as defined in claim 14 herein. A third aspect of the present invention relates to a kit as defined in claim 15 herein. A fourth aspect of the invention relates to a base component as defined in claim 16 herein. A fifth aspect of the invention relates to an offshore structure as defined in claim 17 herein. A sixth aspect of the present invention relates to a method for coating a structure as defined in claim 18 herein.

Antifouling paint composition As described above, the present invention relates to an antifouling paint composition. The coating composition comprises a base component comprising a prepolymer having at least one epoxy functional group and one or more curing agents each having at least one active hydrogen, such as amines and aliphatic polyamines such as diamines and polyamines. And selected from polymercaptans such as mercaptans, cycloaliphatic polymercaptans and aromatic polymercaptans. The coating composition may be present as two or more components, preferably as two components. Although not generally preferred from a practical point of view, the coating composition may contain additional components. The two or more components of the coating composition are typically combined and mixed immediately prior to application of the coating composition to the intended substrate, as described in more detail below.

（式中、Ｘはカルボニル基（＞Ｃ＝Ｏ）を表し、ｎは０〜５０００の整数であり、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅はそれぞれ独立してＣ_1-20アルキル及び任意で置換されたフェニルから選択される（例えばＣ_1-4−アルキル及びフェニル））の少なくとも１つの末端基を有する少なくとも１つの側鎖を有する。 The base component of the base component coating composition comprises a prepolymer having at least one epoxy functional group, the prepolymer having the general formula (I):

(In the formula, X represents a carbonyl group (> C═O), n is an integer of 0 to 5000, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently C _1-20. Having at least one side chain with at least one end group selected from alkyl and optionally substituted phenyl (eg C _1-4 -alkyl and phenyl).

を含む部分を意味することを意図する。 As used herein, the term “epoxy functional group” refers to an oxirane group:

Is intended to mean a part containing

  The prepolymer has at least one epoxy functional group and at least one side chain having at least one terminal group of general formula (I).

の末端基を有する少なくとも１つの側鎖を有するエポキシ官能性プレポリマーを含み、式中、Ｘはカルボニル基（＞Ｃ＝Ｏ）を表し、ｎは０〜５０００の整数であり、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄及びＲ₅はそれぞれ独立してＣ_1-20アルキル及び任意で置換されたフェニルから選択される。 In presently preferred embodiments, the base component of the coating composition comprises at least one general formula (I)

An epoxy-functional prepolymer having at least one side chain with a terminal group of: wherein X represents a carbonyl group (> C═O), n is an integer from 0 to 5000, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently selected from C _1-20 alkyl and optionally substituted phenyl.

  If the prepolymer is epoxy functional, the prepolymer must (on average) contain a sufficient number of epoxy groups to allow reaction with the curing agent. Typically, the prepolymer has an epoxy equivalent weight in the range of 450-10000, such as 500-7500 (such as 550-5000 or 550-3000). The epoxy equivalent is determined as described in the Example section.

  n is an integer of 0, 1, 2, 3, 4 or more. In this case, n is preferably at most about 5000, for example, 0 to 50 (0 to 10 or 1 to 15 or the like). In some special embodiments, n is 0, 1 or 2-5.

（式中、Ｘは上で定義された通りであり、Ｒ₃〜Ｒ₅はそれぞれ独立してＣ_1-20アルキル及び任意で置換されたフェニル（例えば、フェニル）から成る群から選択される基である）を有する。 In some embodiments, since n in general formula (I) is 0, the terminal group is in general formula (II):

Wherein X is as defined above, and R _{3 to} R ₅ are each independently a group selected from the group consisting of C _1-20 alkyl and optionally substituted phenyl (eg, phenyl). Is).

With respect to formulas (I) and (II) above, it is preferred that each alkyl group has up to about 6 carbon atoms (ie, C _1-6 alkyl). Illustrative examples of optionally substituted phenyl group substituents include halogen, nitro, amino, C _1-6 alkyl and C _1-10 alkylcarbonyl. As mentioned above, R _{1 to} R ₅ can be the same or different groups.

  Alkyl groups include linear, branched and cyclic hydrocarbon groups such as methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, isobutyl, tert-butyl, cyclohexyl, octadecyl and the like. Preferred alkyl groups are linear, branched and cyclic hydrocarbon groups having 1 to 6 carbon atoms.

  The groups of general formulas I and II represent hydrolyzable silyl esters in an aqueous medium (eg seawater).

  The acid value of the prepolymer after the silyl ester group has been completely hydrolyzed typically ranges from 5 to 500 mg KOH / g prepolymer (mg KOH / g (solids)), for example 30 to 350 mg KOH / g ( Solid content) (such as a range of 100 to 300 mg KOH / g (solid content)). The acid value is determined as described in the Example section.

  When the acid value of the prepolymer after complete hydrolysis is less than 5, the polishing rate determined according to the polishing rate test defined herein is typically less than 1 μm per 10,000 nautical miles. On the other hand, if the acid value exceeds 500, the polishing rate is typically too high.

  The prepolymer molecular weight is typically relatively low in order to facilitate obtaining desirable properties with respect to viscosity without the need for large amounts of solvent or diluent. For this reason, typically, the mass average molecular weight (Mw) of a prepolymer is 2000-100000 (2000-50000 etc.), for example, the range of 2000-15000.

In some interesting embodiments, the glass transition temperature T _g of the prepolymer ranges from −30 ° C. to 100 ° C., such as −20 ° C. to 100 ° C.

  In some interesting embodiments, the high shear viscosity of the prepolymer is in the range of up to 200 poise as measured according to ASTM standard D4287-00.

  A variety of suitable polymer backbones are believed to be associated with prepolymers having the above side chains. In presently preferred embodiments, the prepolymer backbone comprises an ethylenically unsaturated monomer (eg, (meth) acrylate type monomer, styrene type monomer, maleic acid type monomer, fumaric acid type monomer, vinyl acetate type monomer, vinyl alcohol type monomer. Etc.).

  For such prepolymers of ethylenically unsaturated monomers (eg having a (meth) acrylate skeleton), the monomers containing the end groups of general formula I above and general formula II below are described in EP 0 297 505 B1. It can be synthesized as described in the specification.

  Prepolymers are obtained by copolymerization of such monomers with other ethylenically unsaturated monomers. Examples of suitable ethylenically unsaturated monomers include methacrylate esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methoxyethyl methacrylate and isobornyl methacrylate. Acrylate esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate and methoxyethyl acrylate; maleate esters such as dimethyl maleate and diethyl maleate Fumarate esters such as dimethyl fumarate and diethyl fumarate Styrene, vinyl toluene, alpha-methyl styrene, vinyl chloride, vinyl acetate, butadiene, acrylamides and acrylonitrile.

  The amount of ethylenically unsaturated monomer is typically 95% by weight or less, preferably 90% by weight or less, for example 85% by weight or less, of the total weight of the resulting prepolymer. Accordingly, the amount of monomer containing the end group of general formula I above is at least 1% by weight of the prepolymer, such as at least 1-80% by weight, in particular at least 10% by weight (such as 10-65% by weight) or at least 15%. It is mass% (15-60 mass% etc.).

  Monomers containing terminal groups of general formula I above typically constitute 5-60 mol%, preferably 10-50 mol% (such as 15-45 mol%) of the prepolymer monomer composition.

  Monomers containing epoxy functional groups typically constitute 0.5 to 95 mol%, preferably 0.5 to 30 mol% (such as 2 to 20 mol%) of the monomer composition of the prepolymer.

（式中、Ｘ、Ｒ₃、Ｒ₄及びＲ₅は、上で定義された通りである）の末端基を有する少なくとも１つの側鎖を有するシリル化アクリレートコポリマーを含む。 In another interesting embodiment of the invention, the binder system used in the coating composition of the invention comprises at least one general formula II:

(Wherein X, R ₃ , R ₄ and R ₅ are as defined above) include silylated acrylate copolymers having at least one side chain having a terminal group.

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

With respect to the triorganosilyl group shown in Formula I or II above (ie, the —Si (R ₃ ) (R ₄ ) (R ₅ ) group), R ₃ , R ₄ and R ₅ can be the same or different. In one embodiment, these substituents are the same.

Thus, specific examples of suitable triorganosilyl groups represented by general formula I or II (ie, —Si (R ₃ ) (R ₄ ) (R ₅ ) groups) include trimethylsilyl, triethylsilyl, tri-n— Propylsilyl, tri-n-butylsilyl, tri-iso-propylsilyl, 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-iso-propyl-n-butylsilyl, n-octyl- Di-n-butylsilyl, di-iso-propyloctadecylsilyl, dicyclohexylpheny Silyl, tert- butyldiphenylsilyl, include dodecyl diphenyl silyl and diphenylmethylsilyl.

  Specific examples of suitable (meth) acrylic acid derived monomers having at least one terminal group of general formula I or II include trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl (meth) Acrylate, triisopropylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tri-tert-butylsilyl (meth) acrylate, tri-n-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-butyldiphenylsilyl (meth) acrylate and lauryl diphenylsilyl (meth) acrylate.

In an interesting embodiment of the present invention, the prepolymer used in the binder system comprises a monomer unit having a terminal group of general formula I or II (as described above) represented by general formula III:
_{Y- (CH (R A) -CH} (R B) -O) p -Z (III)
Wherein Z is a C _1-20 alkyl group or aryl group, Y is an acryloyloxy group, methacryloyloxy group, maleinoyloxy group or fumaroyloxy group, and R _A and R _B are independently hydrogen, C Selected from the group consisting of _1-20 alkyl and aryl, wherein p is an integer from 1 to 25) in combination with the second monomer B.

When p> 2, R _A and R _B are preferably hydrogen or CH ₃ , ie when p> 2, monomer B is preferably derived from polyethylene glycol or polypropylene glycol. When p = 1, monomers of groups with higher R _A and R _B (such as C _1-20 alkyl or aryl) are also considered useful for the purposes described herein.

As shown in Formula III, monomer B contains in its molecule an acryloyloxy group, a methacryloyloxy group, a maleinoyloxy group (preferably in the form of a mono-C _1-6 alkyl ester) or a fumaroyloxy group (preferably a mono- -C _1-6 alkyl ester form) as an unsaturated group (Y) and also has an alkoxy- or aryloxypolyethylene glycol. In the alkoxy or aryloxy polyethylene glycol group, the polymerization degree (p) of polyethylene glycol is 1-25.

  Specific examples of the monomer B having a (meth) acryloyloxy group in the molecule include methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, hexoxyethyl (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, propoxy diethylene 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 hexoxyethyl methyl fumarate Is included.

  As will be appreciated by those skilled in the art, other vinyl monomers can also be obtained from the resulting prepolymer comprising monomer units having terminal groups of general formula II (shown above) or second monomers B of general formula III (shown above). Can be incorporated into the resulting prepolymer comprising monomer units having end groups of general formula II (shown above).

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

  Specific examples of the monomer having an epoxy functional group in the molecule include glycidyl (meth) acrylate, allyl glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, and 1-vinyl-3,4-epoxycyclohexane.

The curing agent coating composition also includes one or more curing agents, each having at least one active hydrogen.

  The number of active hydrogens is defined as the number of hydrogen atoms bonded as epoxy-reactive hydrogens, ie typically N—H and S—H.

  Curing agents having at least one active hydrogen are typically amines (eg diamines, polyamines, polyamidoamines and their boron trifluoride complexes), amine adducts and polymercaptans (eg aliphatic polymercaptans, alicyclics). Polymercaptan, aromatic polymercaptan and thiol-terminated polymer).

  In one embodiment, the curing agent is selected from amines (amine type curing agents).

  Suitable amines include amines (such as diamines and polyamines) and amino functional polymers such as fatty amines and polyamines (such as alicyclic amines and alicyclic polyamines), diamines, polyamidoamines, polyoxyalkyleneamines (polyoxyalkylenes). Alkylene diamines, etc.), polyoxyalkylene diamines and polyamines (known as “Jeffamines”), alkylene amines (alkylene diamines, etc.), aralkyl amines, aromatic amines, imidazolines, Mannich bases, amino functional silicones or silanes, As well as those selected from ketimine and amine-modified thiolactic acid, and derivatives thereof.

Ketamine is seen as a potential amine (see below) that can be useful when formulating a one-component product. Upon application, the amine is liberated when exposed to moisture.

Another interesting type of curing agent is amine-modified thiolactic acid, which can be found as amine-modified thiourea.

Examples of suitable commercially available amine type curing agents are as follows:
Cardolite NC-541, Cardanol Chemicals (USA), Mannich Base Cardolite Lite 2001, Cardanol Chemicals (USA), Mannich Base Suntide CX-105X, Sanwa Chemical Ind. (Singapore), Mannich base Epikure 3140 curing agent, Resolution Performance Products (USA), polyamidoamine SIQ Amin 2030, SIQ Kunsartze (Germany), polyamidoamine Epikure 3115X-70 curing agent, Resolction Perfamine AUS SIQ Amin 2015, SIQ Kunsartze (Germany), Polyamidoamine Polypox VH 40309/12, Ulf Polymer Polymer-Chemie (Germany), Polyoxyalkyleneamine CeTepoxol Pendol 1490H, CTP Chemicals Measure Treg ymers (Germany), polyoxyalkyleneamine epoxy curing agent MXDA, Mitsubishi Gas Chemical Co. (USA), aralkylamine Diethylaminopropylamine, BASF (Germany), aliphatic amine Gaskamine 240, Mitsushi Gas AmChem ChemiCalChem ChemL , Cardanol Chemicals (USA), Mannich base Aradur 42 BD, Huntsman Advanced Materials (Germany), cycloaliphatic amines Isophorondiamin, BASF (Germany), cycloaliphatic amine metaxylenediamine, Mitsubi Gas Japan Aromatic diamine MDA-220, Mitsui Chemicals (Japan), aromatic diamine BAFL, JFE Chemical (Japan), aromatic diamine Wandamine HM, New Japan Chemical (Japan), alicyclic diamine hexamethylene diamine, Kisida Chemical (Japan), aliphatic diamine Adeka curing agent EH376-2, Asahi denka (Japan), cycloaliphatic polyamine Ancamide 506, Air Products Japan (Japan), aliphatic polyamine Aradur 424, Hutsman Advanced Mats (Switzerland) Amide Versamid 100, Cognis (USA), a reactive polyamine based on dimerized fatty acids and polyamines Resin Versamid 115, Cognis (USA), reactive polyamide resin Ancamide 220, Air Products (USA) based on dimerized fatty acids and polyamines, polyaminoamide Versamid 125, Cognis (USA), dimerized fatty acids and polyamines Reactive Polyamide Resin Based on Aradur 460, Hutsman Advanced Materials (Switzerland) Polyaminoamide Versamid 140, Cognis (USA), Reactive Polyamide Resin Based on Dimerized Fatty Acid and Polyamine

  In this particular embodiment, the amine is a boron trifluoride-amine complex, such as “Three Bond Technical News”, Issued Decemer 20, 1990, No. 1; 32, “Curing Agents for Epoxy Resin”.

  In other embodiments, the curing agent is selected from amines having at least two active hydrogens in one molecule. In some embodiments, the amine has 3 or more active hydrogens. In some cases, the number of active hydrogens is 2-20, such as 2-10 or 2-6 or 3-8. For commodities in the form of mixtures, it should be understood that the above numbers should be interpreted as the average number of active hydrogens in the population of amine molecules.

  In one interesting embodiment, the curing agent is selected from diamines and polyamines and includes aliphatic diamines, cycloaliphatic diamines, aromatic diamines, aliphatic polyamines, cycloaliphatic polyamines and aromatic polyamines.

  In another embodiment, the amine is an aliphatic or cycloaliphatic amine, such as an aliphatic or cycloaliphatic diamine or an aliphatic or cycloaliphatic polyamine.

  In another interesting embodiment, the curing agent is selected from polyamidoamines and imidazolines.

  The amine equivalent of the one or more amine type curing agents is typically in the range of 20 to 2000, such as 30 to 1200 (30 to 900, etc.). The amine equivalent is determined as described in the example section.

  The amine hydrogen equivalent weight (AHEW) of the one or more amine-type curing agents is typically in the range of 15-10000, such as 20-5000 (20-1000, etc.). The amine hydrogen equivalent (AHEW) is determined as described in the Example section.

  The ratio of amine of the amine-type curing agent to the epoxy functionality of the prepolymer and (amine: epoxy) (A / E) is typically 0.1: 1 to 4.0: 1, for example 0.2: 1. -4.0: 1 or 0.2: 1 to 3: 1 or 0.1: 1 to 3: 1.

  The ratio of active hydrogen of the amine type curing agent to the epoxy functionality of the prepolymer and (hydrogen: epoxy) (H / E) is typically 0.3: 1 to 3.5: 1, for example 0.5: 1 to 2.5: 1 (0.5: 1 to 1.5: 1 or 0.5: 1 to 1.2: 1 or 0.3: 1 to 1.2: 1 etc.) .

  In another embodiment, the curing agent is selected from amine epoxy adducts. An amine epoxy adduct is formed by mixing an epoxy resin or epoxy reactive diluent with an excess of amine that consumes all of the epoxy groups but not all of the reactive hydrogen in the amine. Is done. The resulting material can be used as a curing agent in epoxy paints.

Examples of suitable commercially available amine epoxy adduct type curing agents are as follows:
Epikure 3090 Curing Agent, Resolution Performance Products (USA), Polyamideamine Adduct with Epoxy Crayamid E260 E90, Cray Valley (Italy), Polyamideamine Adduct with Epoxy Aradur 943 CH, Huntsman Advanc Alkylene amine adduct Aradur 863XW 80 CH, Huntsman Advanced Materials (Switzerland), aromatic amine adduct with epoxy.

  The amine equivalent of the one or more amine epoxy adduct type curing agents typically ranges from 20 to 2000, such as 30 to 1200 (30 to 900, etc.). The amine equivalent is determined as explained in the example section.

  The amine hydrogen equivalent weight (AHEW) of the one or more amine epoxy adduct type curing agents is typically in the range of 15 to 10000, such as 20 to 5000 (such as 20 to 1000). The amine hydrogen equivalent (AHEW) is determined as described in the Examples section.

  The ratio of amine to epoxy functional group of the amine epoxy adduct type curing agent and the epoxy functional group of the prepolymer and (amine: epoxy) (A / E) is typically 0.1: 1 to 4.0: 1, for example 0. .2: 1 to 4.0: 1 or 0.2: 1 to 3: 1 or 0.1: 1 to 3: 1.

  The ratio of active hydrogen of the amine epoxy adduct type curing agent to the epoxy functionality of the prepolymer and (hydrogen: epoxy) (H / E) is typically from 0.3: 1 to 3.5: 1, for example 0.5: 1 to 2.5: 1 (0.5: 1 to 1.5: 1 or 0.5: 1 to 1.2: 1 or 0.3: 1 to 1.2: 1 etc.) It is a range.

  In yet another interesting embodiment, the curing agent is selected from polymercaptan. A polymercaptan has at least two mercaptan (-SH) groups in a single molecule. Examples of polymercaptans are aliphatic polymercaptans, alicyclic polymercaptans and aromatic polymercaptans. Other examples of polymercaptans are thiol-terminated polymers, such as linear polymers with terminal thiol groups.

  Specific examples of suitable polymercaptans are: pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3 -Mercaptobutyryloxyethyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptopropionate), 2,4,6-trimercapto -S-triazine monosodium salt, 2-dibutylamino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine, and 2,4,6-trimercapto-s-triazine .

Examples of suitable commercially available polymercaptan type curing agents are as follows:
Karenz MT PE1, Showa denko (Japan), aliphatic polymercaptan Daito Kral MR-94, Daito sangyo (Japan), aliphatic polymercaptan Sun thiol N-1, Sankyo kasei Chemical (Japan) Poly thiol QE-340M, Toray Industries (Japan), aliphatic polymercaptan Adeka curing agent EH316, Asahi denka (Japan), aliphatic polymercaptan Zisnet DB, Sankyo-Kasai (Japan), aromatic polymer 2 -Dibutylamino-4,6-dimercapto-s-triazine)
GPM-800, Gabriel Performance Products (US), mercaptan-terminated polymer Capcure 3-800, BASF (Germany), mercaptan-terminated polymer.

  The thiol hydrogen equivalent weight (THEW) of the one or more polymercaptan type curing agents is typically in the range of 15-10000, such as 20-5000 (20-1000). Thiol hydrogen equivalent weight (THEW) is determined as described in the Examples section.

  The ratio of polymercaptan type curing agent thiol hydrogen to prepolymer epoxy functionality and (hydrogen: epoxy) (H / E) is typically 0.3: 1 to 3.5: 1, for example 0.5 : 1 to 2.5: 1 (for example, 0.5: 1 to 1.5: 1 or 0.5: 1 to 1.2: 1 or 0.3: 1 to 1.2: 1.

  In some preferred embodiments, the coating composition includes one or more curing agents or a separate second component consisting of one or more curing agents.

  In other embodiments, such second component comprises some (but not all) of one or more curing agents. In that embodiment, any remaining curing agent (especially slow-reactive curing agent) can be included in the base component.

  In further embodiments, one or more curing agents are included in the base component and the second component includes or consists of one or more accelerators (see further below).

  Based on preliminary results, it appears that the polishing rate can be adjusted by appropriate selection of the curing agent. Thus, it has been observed that the choice of amine as the curing agent appears to give a relatively high polishing rate, but the choice of polymercaptan or amine adduct appears to give a relatively low polishing rate. This appears to be an important inventive feature in that the desired polishing rate is different for different applications. Polishing is a reduction in the thickness of the antifouling paint measured with a micrometer. Polishing is typically a combination of paint coat erosion and hydrolysis in seawater. Thus, for example, the biocide (if present) can be released in a controlled manner. The polishing rate of the paint coat is a parameter that can apply the antifouling paint to the sailing state of the ship. For ships with low activity and low speed, antifouling paints with a high polishing rate (for example, those using an amine curing agent) are preferred because they compensate for short distances where the thickness reduction per distance in the paint is greater. On the other hand, for ships with high activity and high speed, preferred paints are those having a low polishing rate (eg, those using amine adducts or polymercaptan curing agents).

Additional raw materials The base component may have included one or more other raw materials in addition to the prepolymer, and in some special embodiments, includes at least a portion of one or more curing agents. . However, desirably, some or all of such other ingredients may instead be presented as a separate (second or third) component in addition to the base component.

  Examples of further raw materials are binder components, such as rosin, rosin derivatives (metal salts of rosin, ie resinates, etc.), oils (linseed oil and derivatives thereof, castor oil and derivatives thereof, soybean oil and derivatives thereof), etc. Polymer binder component (saturated polyester resin, etc.); polyvinyl acetate, polyvinyl butyrate, polyvinyl chloride-acetate, copolymer of vinyl acetate and vinyl isobutyl ether; vinyl chloride; copolymer of vinyl chloride and vinyl isobutyl ether; alkyd resin or Modified alkyd resin; Hydrocarbon resin (petroleum fraction condensate, etc.); Chlorinated polyolefin (chlorinated rubber, chlorinated polyethylene, chlorinated polypropylene, etc.); Styrene copolymer (styrene / butadiene copolymer, styrene / metacrine) Acrylic resins (such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isobutyl methacrylate homopolymers and copolymers); hydroxy-acrylate copolymers; cyclized rubbers; epoxy esters; epoxy urethanes; Polyurethanes; epoxy polymers; and copolymers thereof.

  The terms “rosin”, “resinate” and the like are gum rosins; grades B, C, D, E, F, FF, G, H, I, 3, K, L, M, N, WG, WW (ASTM standard) 0509) wood rosin; virgin rosin; hard rosin; yellow dip rosin; NF wood rosin; tall oil rosin or colophony or colophonium. The terms “rosin”, “resinate” and the like are also intended to include appropriate types of modified rosins, which are specifically oligomerized, hydrogenated, dehydrogenated to reduce the amount of conjugated non-aromatic double bonds. / Disproportionation, dismutation, etc.

It should be understood that further binder component groups can include polymeric flexibility-imparting agents (such as those broadly and specifically defined in WO 97/44401), see this document. Is incorporated herein by reference.
Such additional dried binder components are typically 0-35% by weight of the coating composition, such as 0-20% by weight (such as 0-15% by weight) or 1-35% by weight. For example, it constitutes 1 to 20% by weight (1 to 15% by weight).

  The base component and / or one or more curing agents (or third component) are, of course, pigments, fillers, fibers, antifouling agents, dyes, additives, reactive diluents, accelerators and solvents and coating compositions. Other suitable components may also be included for inclusion in the product binder phase.

  However, such components (ie, pigments, fillers, fibers, antifouling agents, dyes, additives, reactive diluents, accelerators and solvents) are typically up to 85 of the coating composition in total. It is incorporated at solids volume%, such as up to 80 solids volume% or up to 60 solids volume% (such as up to 50 solids volume%), such as 20-50 solids volume% or 35-50 solids volume%. With respect to the moisture content of the entire coating composition (ie, base components, curing agents and other components), such components are typically up to 60% by weight of the coating composition in total (eg, up to 50% by weight etc.). ), For example, 0.1 to 40% by weight or 0.1 to 30% by weight. In certain high solids embodiments, such components are typically incorporated in a total amount of 60-85% by weight (such as 75-80% by weight) of the coating composition.

Examples of pigments are copper, copper alloys such as copper / nickel alloys, various metal oxides such as cuprous oxide (Cu ₂ O), cupric oxide (CuO), titanium dioxide, red iron oxide, zinc oxide , Carbon black, graphite, yellow iron oxide, red molybdate, yellow molybdate, zinc sulfide, antimony oxide, sodium aluminum sulfosilicate, quinacridone, phthalocyanine blue, phthalocyanine green, black iron oxide, indanthrone blue, cobalt aluminum oxide, carbazole Dioxazine, chromium oxide, isoindoline orange, bis-acetoaceto-o-tridiol, benzimidazolone, quinaphthalone yellow, isoindoline yellow, tetrachloroisoindolinone, and quinophthalone yellow. Such materials are characterized by making the final coating opaque and non-translucent. For example, even though copper, copper alloys, cuprous oxide and cupric oxide have antifouling characteristics, it is understood in this specification that such components are only considered “pigments”. .

When cuprous oxide is present in the coating composition, the Cu ₂ O content is preferably in the range of 1 to 40 solids volume%, for example 5 to 35 solids volume% of the coating composition. Expressed in terms of the moisture content of the coating composition, and when cuprous oxide is present, the Cu ₂ O content is preferably in the range of at least 5% by weight of the coating composition, eg, 10-75% by weight. In certain high solids embodiments, the Cu ₂ O content is preferably in the range of at least 5% by weight of the coating composition, such as 10-80% by weight.

  The pigment phase may further comprise pigment-like raw materials (such as fillers).

Examples of fillers include calcium carbonate, dolomite, talc, mica, barium sulfate, kaolin, silica (including pyrogenic silica, colloidal silica, fumed silica, etc.), perlite, magnesium oxide, calcite, quartz powder (quartz floor). ), Molecular sieve, synthetic zeolite, calcium silicophosphate, hydrated aluminum silicate (bentonite), organically modified clay, anhydrous gypsum and the like. Since these materials are characterized by not making the final coating non-translucent, they are not very useful in hiding the material under the final coating.

  Some fillers (and pigments) have certain advantageous properties of the type that binder phase additives (eg, stabilizers against water, dehydrating agents, water scavengers, thickeners, anti-settling agents, etc.) provide It is worth noting that it can be applied, but for the purposes of the present application with claims, such particulate material is considered to be part of the pigment phase.

  Examples of fibers are widely and specifically described, for example, in WO 00/77102, which is incorporated herein by reference.

  In order to consider a particular particle as a fiber herein, the maximum and minimum dimensions perpendicular to the length dimension (length dimension: longest dimension) at substantially all points along the longitudinal axis Ratio should not exceed 2.5: 1, preferably 2: 1. Furthermore, the ratio of the longest dimension to the average of the two shortest dimensions should be at least 5: 1. Thus, the fiber is characterized by having one long dimension and two short dimensions, where the long dimension is substantially longer than the two short dimensions (typically one digit or more), 2 The two short dimensions are substantially equal (same digit). For a perfectly standard fiber (ie a fiber having a cylindrical shape) it is clear how to determine the “length” (longest dimension) and the two (identical) shortest dimensions. In the case of more irregularly shaped fibers, it is believed that the relationship between dimensions can be evaluated by the following virtual experiment. That is, a standard right angle box is built around the fiber. The box is constructed to have a minimum volume that can fully accommodate the fiber. It is believed that the fiber is flexible (again virtually) to the extent that the fiber is curved, and the volume of the virtual box can be minimized by fiber “bending”. To recognize “fiber” in this specification, the ratio of the two smallest dimensions of the box is at most 2.5: 1 (preferably 2: 1), The ratio of the smallest dimension to the average should be at least 5: 1.

  Currently, particularly preferred fibers are mineral fibers such as mineral glass fibers, wollastonite fibers, montmorillonite fibers, tobermorite fibers, attapulgite fibers, calcined bauxite fibers, volcanic rock fibers, bauxite fibers, rock wool fibers and processed mineral fibers derived from mineral wool. is there.

  If present, the concentration of this fiber is usually in the range of 0.5-15 solids volume%, such as 1-10 solids volume% of the coating composition.

  If present, the fiber concentration is usually in the range of 0.1 to 20% by weight of the coating composition, for example 0.5 to 10% by weight, based on the total composition (wet amount). In certain high solids embodiments, the fiber concentration ranges from 0.1 to 25% by weight of the coating composition, such as from 0.5 to 15% by weight.

  Since the above range is the total amount of fibers, it should be understood that when two or more types of fibers are utilized, the total amount of the two types of fibers is within the above range.

The coating composition may also contain one or more antifouling agents as is conventional in the art. Examples of antifouling agents are metallo-dithiocarbamates such as bis (dimethyldithiocarbamato) zinc, ethylene-bis (dithiocarbamato) zinc (Zineb), ethylene-bis (dithiocarbamato) manganese and their complexes; bis (1-hydroxy -2 (1H) -pyridinethionato-O, S) copper (copper pyrithione; copper omadin); copper acrylate; bis (1-hydroxy-2 (1H) -pyridinethionato-O, S) -zinc (zinc pyrithione; zinc omadin) ); Phenyl (bispyridyl) bismuth dichloride; metal salts such as cuprous thiocyanate, basic copper carbonate, copper hydroxide, barium metaborate and copper sulfide; heterocyclic nitrogen compounds such as 3a, 4, 7, 7a- Tetrahydro-2-((trichloromethyl) -thio) -1H-isoindole-1,3 (2 ) -Dione, pyridine-triphenylborane (Borocide P), 1- (2,4,6-trichlorophenyl) -1H-pyrrole-2,5-dione, 2,3,5,6-tetrachloro-4- (Methylsulfonyl) -pyridine, 2-methylthio-4-tert-butylamino-6-cyclopropylamine-s-triazine (Irgarol 1051) and quinoline derivatives; heterocyclic sulfur compounds such as 2- (4-thiazolyl) benz Imidazole, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-octyl-3 (2H) -isothiazoline (Sea-Nine® 211N), 1 , 2-benzisothiazolin-3-one and 2- (thiocyanatomethylthio) -benzothiazole; urea derivative Conductors 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 and N, N-dimethylchlorophenylurea; amides or imides of carboxylic acids, sulfonic acids and sulfenic acids, such as 2,4,6-trichlorophenylmaleimide, 1,1-dichloro-N- ( (Dimethylamino) sulfonyl) -1-fluoro-N- (4-methylphenyl) -methanesulfenamide (Preventol A5F), 2,2-dibromo-3-nitrilo-propionamide, N- (fluorodichloromethylthio)- Phthalimide, N, N-dimethyl-N′-phenyl-N ′-(fluorodichloromethyl) Ruthio) -sulfamide and N-methylolformamide; salts or esters of carboxylic acids such as 2-((3-iodo-2-propynyl) oxy) -ethanolphenylcarbamate and N, N-didecyl-N-methyl-poly (oxyethyl) ) Ammonium propionate; amines such as dehydroabiethylamine and cocodimethylamine; substituted methanes such as di (2-hydroxy-ethoxy) methane, 5,5′-dichloro-2,2′-dihydroxydiphenylmethane and methylene-bisthiocyanate Substituted benzenes such as 2,4,5,6-tetrachloro-1,3-benzenedicarbonitrile, 1,1-dichloro-N-((dimethylamino) -sulfonyl) -1-fluoro-N-phenylmethane; Sulfenamide and 1-((diiodome ) Sulfonyl) -4-methyl-benzene; tetraalkylphosphonium halides such as tri-n-butyltetradecylphosphonium chloride; guanidine derivatives such as n-dodecylguanidine hydrochloride; disulfides such as bis- (dimethylthiocarbamoyl)- Disulfides, tetramethylthiuram disulfides; imidazole-containing compounds such as medetomidine; 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (Econea) and mixtures thereof.

  Currently, the antifouling agent is preferably an agent that does not contain tin.

  In one preferred embodiment, the coating composition comprises pyridine-triphenylborane (Boroside P), 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (Econea) and an imidazole-containing compound. An antifouling agent selected from the group consisting of (medetomidine, etc.).

  The total amount of antifouling agent (if present) is typically up to 30 solids volume% (such as 0.05 to 25 solids volume%) of the coating composition, such as 0.05 to 20 solids of the coating composition. The range is minute volume%.

  The total amount of antifouling agent, if present, relative to the total mass of the coating composition is typically from 0 to 40% by weight of the coating composition (such as 0.05 to 30% by weight), such as the coating It is in the range of 0.05 to 20% by weight of the composition. In certain high solids embodiments, the total amount of antifouling agent (if present) is usually in the range of 0-50% by weight of the coating composition, such as 0.05-25% by weight.

Examples of the dye include 1,4-bis (butylamino) anthraquinone, other anthraquinone derivatives; toluidine dye, and the like.

Examples of additives are (i) plasticizers such as chlorinated paraffins; phthalates such as dibutyl phthalate, benzyl butyl phthalate, dioctyl phthalate, diisononyl phthalate and diisodecyl phthalate; phosphate esters such as tricresyl phosphate, nonyl phenol phosphate, octyloxypoly (Ethyleneoxy) ethyl phosphate, tributoxyethyl phosphate, isooctyl phosphate and 2-ethylhexyl diphenyl phosphate; sulfonamides such as N-ethyl-p-toluenesulfonamide, alkyl-p-toluenesulfonamide; adipates such as bis (2 -Ethylhexyl) adipate), diisobutyl adipate and dioctyl adipate; phosphoric acid triethyl ester; butyl Sorbitan trifoliate; and epoxidized soybean oil; (ii) surfactants such as propylene oxide or derivatives of ethylene oxide (such as alkylphenol-ethylene oxide condensates); ethoxylated monoethanolamides of unsaturated fatty acids such as ethoxyl of linoleic acid Monoethanolamide; sodium dodecyl sulfate; alkylphenol ethoxylate; and soy lecithin; wetting and dispersing agents; (iii) antifoaming agents such as silicone oils; (iv) stabilizers such as light and heat stabilizers such as hindered amines Light stabilizer (HALS), 2-hydroxy-4-methoxybenzophenone, 2- (5-chloro- (2H) -benzotriazol-2-yl) -4-methyl-6- (tert-butyl) phenol and 2, Di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol; stabilizer or moisture scavenger, molecular sieve, oxazolidine, substituted silane and orthoformate triethyl ester; (v) stability to oxidation Agents such as butylated hydroxyanisole; butylated hydroxytoluene; propyl gallate; tocopherol; 2,5-di-tert-butyl-hydroquinone; L-ascorbyl palmitate; carotene; vitamin A; (vi) inhibitors against corrosion, such as Aminocarboxylates, ammonium benzoates, barium / calcium / zinc / magnesium salts of alkylnaphthalene sulfonates, zinc phosphates; zinc metaborate; (vii) fusion aids such as glycols, 2-butoxyethanol and 2,2 4-trimethyl-1,3-pentanediol monoisobutyrate; (viii) thickeners and anti-settling agents such as aluminum tristearate, aluminum monostearate, castor oil, xanthan gum, salicylic acid, hydrogenated castor oil, polyamide Waxes and polyethylene waxes; and (ix) dehydrating agents such as alkyl silicates such as orthopropionate, orthoformate, orthoacetate, alkoxysilane, tetraethylorthosilicate.

  The coating composition preferably contains 0-20 solids volume%, for example 1-20 solids volume%, of the coating composition in cumulative amounts of dyes and additives.

  It is preferable that the coating composition contains 0 to 10% by weight, for example, 1 to 10% by weight, of the coating composition in a cumulative amount with respect to the total mass of the coating composition. In certain high solids embodiments, the coating composition comprises 0 to 15%, such as 1 to 15%, by weight of the coating composition in cumulative amounts of dyes and additives.

  The base component (preferably not a component comprising one or more curing agents) can further comprise one or more reactive diluents.

Examples of reactive diluents included in the base component are butyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol diglycidyl ether, p-tert-pt-butylphenol glycidyl ether 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, resorcinol diglycidyl ether, trimethylolpropane triglycidyl ether and glycidyl neodeconoate (2,3-epoxypropyl neodecanoate) It is.

  It is preferred that the coating composition comprises 0 to 40 solids volume% of the coating composition, for example 0 to 20 solids volume% (0 to 10 solids volume%) of the reactive diluent in cumulative amount.

Examples of suitable commercially available reactive epoxy diluents are as follows:
2,3-epoxypropyl neodecanoate, NEO-S, NEO-Toto S, Nippon Steel Chemical (Japan)
1,6-hexanediol diglycidyl ether, HD, ADEKA GLYCIROL ED-503, Adeka (Japan)
Cardura E10P (Hexion)
Epodil 748 (Air Products)
Araldite DY-H / BD (Hunstman Advanced Materials)
Epodil 757 (Air Products)
Epikote Resin 493 (Hexion Specialty Chemicals)
Araldite DY-D / CH (Hunstman Advanced Materials)
Cardolite NC 513 (Cardolite)

  The composition may further comprise one or more accelerators. Such accelerators are preferably presented as a component separate from the base component and the one or more curing agents, or as part of the base component or as a component comprising one or more curing agents.

Examples of promoters include , for example, Live H. et al. Hare, Chapter 15, Technology Publishing, Pennsylvania 1994, “Protective Coatings. Fundamentals Chemistry and Compostion”, ISBN 0-934477-90-0, for example, diamines such as tertiary amines (e.g. Methyl) phenol, etc.), phosphorus compounds (triphenylphosphine, 1,2-bis (diphenylphosphino) ethane, diphenylphosphinas chloride, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine , Tris (p-methoxyphenyl) phosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine Tributylphosphine, tri-tert-butylphosphine, tri-n-octylphosphine, diphenylphosphinostyrene, 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane), alcohol (Such as phenol, alkylphenol and aliphatic alcohol), organic acids (such as sulfonic acid and salicylic acid), boron halides (such as boron trifluoride), inorganic acids (such as lithium chloride and calcium nitrate), and organic metal salts (stearic acid) Zinc).

  If present, the coating composition may contain an accelerator from 0.05 to 15 solids volume% of the coating composition, such as from 0.05 to 10 solids volume% (0.1 to 10 solids volume% or 0.2. -5.0 solids volume% or 0.3-4.5 solids volume%).

Examples of solvents are aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naphtha solvents; alcohols such as ethanol, n-butanol, 1-methoxy-2-propanol and 2-butoxy. -Ethanol); ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, methyl isoamyl ketone, diacetone alcohol and cyclohexanone; ethyl ether; esters such as ethyl acetate, propyl acetate, methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl Acetates; chlorinated hydrocarbons such as methylene chloride, tetrachloroethane and trichlorethylene; and mixtures thereof.

  It is preferable that the coating composition contains 0 to 30% by weight, for example, 0 to 20% by weight, of the coating composition in a cumulative amount with respect to the total mass of the coating composition. In certain high solids embodiments, the coating composition comprises one or more solvents in a cumulative amount of 0-10%, such as 0-5%, by weight of the coating composition.

  As used herein, the term “% by wet weight” is intended to mean the mass / mass% of the wet product of the coating composition. It should be understood that a solvent is included.

  As used herein, the term “% by solids volume” is intended to mean the volume / volume% of solids (ie, non-volatile materials) of the coating composition. It should be understood that the solvent (ie, volatile material) is ignored.

Preparation of Coating Composition The base component of the present invention is usually prepared by using the conventional components (ball mill, pearl mill, three roll mill, high speed disperser, etc.) for producing the coating composition (paint) once. Prepared by mixing and dispersing all or partly. The base components of the present invention (optionally including fiber) are bag filters, patron filters, wire gap filters, wedge wire filters, metal edge filters, EGLM turnnoclean filters (Cuno), DELTA strain filters (Cuno) ) And Jenag strainer filters (Jenag) or by vibration filtration. Prior to application, the base component is mixed with the second component, the third component, and the like.

  For example, airless spray coating, plural component airless coating, air spray coating, roller coating or brush on a ship or marine structure coated with a rust-preventive coating material, with the coating composition of the present invention as it is or after adjusting the viscosity with a diluent solvent. Can be coated by coating. Which technique is actually selected depends on the object to be protected, the particular composition (its viscosity, pot life, etc.) and the particular situation. Preferred application techniques are those using spray coating and brushes or rollers.

  The base component and the second component, eg, one or more curing agent components or one or more curing agent components and further components should be prepared and shipped separately and mixed thoroughly immediately before application. Should be understood.

  Accordingly, the present invention further provides a kit comprising an antifouling paint composition as defined herein, wherein component a (base component) is in the first container and 1 is in the second container. Contains more than a seed hardener. In this embodiment, the kit may contain one or more accelerators, eg, contained in a first container, contained in a second container, or contained in a separate container.

In another embodiment, the present invention provides a kit comprising an antifouling paint composition as defined herein, wherein the first container contains a base component and a curing agent, and the second container contains Contains one or more accelerators. In one variation of this embodiment, the curing agent is a polymercaptan curing agent and the one or more accelerators are preferably selected phosphines and tertiary amines.
In still further embodiments, all components can be formulated as a one-component coating composition. In this embodiment, the one or more curing agents are preferably of the ketamine type.

In addition, the present invention also provides specific embodiments of the base component as a separate product (ie, a base component for an antifouling paint composition), which component comprises at least one general formula I (see above). ) Comprising a base component comprising an epoxy functional prepolymer having at least one side chain having a terminal group, wherein X represents a carbonyl group (> C═O) and n is an integer from 0 to 5000 , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently selected from C _1-20 alkyl and optionally substituted phenyl, and the epoxy equivalent of the prepolymer is 450-10000, such as 500-7500 (550 to 5000 or 550 to 3000).

Application of coating composition The present invention further relates to an offshore structure having a coating of an antifouling coating composition as defined herein on at least a portion of its surface. This marine structure can be coated with one or several layers, in particular a continuous layer, of the coating composition.

  The coating composition of the present invention may be applied to a marine structure to be protected in one or several continuous layers, typically 1 to 4 layers, preferably 1 to 2 layers. The dry film thickness (DFT) of the coating film per layer is typically 10 to 600 μm, preferably 20 to 500 μm, for example 40 to 400 μm. For this reason, the total dry film thickness of the coating film is typically 10 to 1800 μm, preferably 20 to 1500 μm, particularly 40 to 1200 μm, for example 80 to 800 μm.

  The marine structure to which the coating composition of the present invention can be applied may be any of various solid objects that come into contact with water. For example, a ship (boat, yacht, motor boat, motor boat, ocean liner, tug boat, tanker) , Container ships, other cargo ships, submarines (including but not limited to nuclear submarines and conventional submarines); pipes; all types of machinery and structures used on the coast and in the ocean And objects such as piers, piles, bridge substructures, floating devices, subsurface oil well structures, etc .; nets and other underwater aquaculture equipment; cooling plants; and buoys, especially applicable to ships and boat hulls and pipes is there.

  Prior to applying the coating composition to the offshore structure, the offshore structure is first of all used in a primer system or a conventional system used in connection with the application of the coating composition to the offshore structure. The primer system can be coated. Thus, the primer system can include a rust-preventing primer, optionally overlying an adhesion enhancing primer layer.

  The above primer system is, for example, an epoxy resin having an epoxy equivalent of 160 to 600 and its curing agent (a combination of amino type, a combination of polyol resin and polyisocyanate type curing agent, vinyl ester resin, unsaturated as binder system Contains polyester resin, etc. If necessary, further thermoplastic resin (chlorinated rubber, acrylic resin, vinyl chloride resin, etc.), curing accelerator, rust-preventing pigment, colored pigment, extender pigment, solvent, silane compound, plasticizer, additive ( Coating materials containing anti-sagging agents, anti-settling agents, etc.) or, typically, tar epoxy resin type coating materials.

  In view of this specification, the present invention also provides a method of coating a structure, the method applying a layer of an antifouling paint composition as defined herein to at least a portion of the structure. Process. In some interesting embodiments, this layer is the final layer of the multilayer coating system.

Specific Embodiments of the Invention In a preferred embodiment, the total coating composition (ie, base component and further components) is at least 40%, such as at least 50%, such as 60-99% or 80-100%. Furthermore, it has a solid content mass ratio of 70 to 98% or 85 to 100%.

In a more specific embodiment, the entire coating composition has an essentially 100% solids mass ratio. The expression “essentially 100%” means that the composition is a solvent other than the trace amounts of volatile substances (solvents, residual monomers, etc.) that are inevitably present in the starting material of the coating composition. (Or other non-reactive volatiles) should be understood to mean free of any. For this reason, no solvent is added in this embodiment.

  The solids weight ratio (SWR) is a measurement according to ISO standard 3251: 2008.

  Regarding the self-polishing properties of the antifouling coating composition, the polishing rate measured according to the polishing rate test defined herein is preferably at least 1 μm per 10,000 nautical miles.

Determination of Acid Value “Acid Value” is defined as the number of milligrams (mg) of potassium hydroxide (KOH; Mw = 56.1 g / mol) required to neutralize one gram of polymer (eg, prepolymer). . For the purposes of the present invention, the acid value relates to a prepolymer in which the silyl groups have been removed by hydrolysis and have free acidic groups instead of silyl ester groups.

  The acid number can be determined based on the composition of the prepolymer (ie, information about the monomer components and their relative ratios).

  By way of example, the acid number for a prepolymer consisting of 50.0 g of triisopropylsilyl acrylate monomer (TIPSA; Mw = 228.4 g / mol) and 50.0 g of methyl methacrylate (MMA; Mw = 100.1 g / mol) Ask. As mentioned above, acrylic acid is used in the calculation instead of TIPSA because the calculation is based on the free acid analog. 50 g of TIPSA corresponds to 15.79 g of acrylic acid (Mw = 72.1 g / mol).

  The mass fraction of acrylic acid constitutes 24% of the prepolymer (15.8 g / (15.8 g + 50.0 g) × 100%).

  Methyl methacrylate monomer constitutes 76% (50.0 g / (15.8 g + 50.0 g) × 100%) of the prepolymer.

  One gram of prepolymer contains 3.33 mmol of free carboxyl groups (1 g × 24% / 72.1 g / mol).

  187 mg (3.33 mmol × 56.1 mg / mmol) of KOH is required to neutralize the free carboxyl groups of 1 g of prepolymer. This value is the acid value (AV).

Quantification of Epoxy Equivalent (EEW) “Epoxy equivalent” is defined as the amount (in grams) of a material containing 1 mole of epoxy groups (ie, the moiety containing the oxirane group).

  EEW can be measured based on the composition of the prepolymer (ie knowledge of the monomer components and their relative ratios) or by titration.

  As an example, EEW measured for a prepolymer made of 50.0 g glycidyl methacrylate monomer (GMA; MW = 142.2 g / mol) and 50.0 g methyl methacrylate (MMA; Mw = 100.1 g / mol). Can be done.

  The mass fraction of glycidyl methacrylate constitutes 50% of the prepolymer (50.0 g / (50.0 g + 50.0 g) × 100%).

  The methyl methacrylate monomer constitutes 50% of the prepolymer (50.0 g / (50.0 g + 50.0 g) × 100%).

  One gram of prepolymer contains 3.52 mmol (1 g × 50% / 142.2 g / mol) of epoxy groups.

  The amount (grams) of material containing 1 mole of epoxy groups is 284 g / mol (1 g / 3.52 mmol). This value is the epoxy equivalent (EEW).

Quantification of Amine Equivalent (AEW) “Amine equivalent” is defined as the amount of material (grams) containing 1 mole of (primary, secondary or tertiary) amine groups.

Amine equivalent weight can be measured according to the following protocol (based on ISO 9702-1996):
Accurately weigh "A" grams of amine-containing sample into a dry Erlenmeyer flask. Dissolve the sample in 25 mL of acetonitrile. If not completely dissolved, add a few mL of a standardized 0.1N perchloric acid solution in glacial acetic acid from the burette (the amount will be part of the “p” in the formula). As soon as the precipitate disappears, add 4 drops of crystal violet solution (1% in glacial acetic acid). The sample solution is titrated with the remaining portion of the standardized 0.1N perchloric acid solution from the burette until the blue color changes from blue-green to green and stabilizes for at least 30 seconds. The total amount of perchloric acid solution used is expressed as “p” mL.

  The blind test is performed using “q” mL of 0.1N perchloric acid solution.

  The sample and “blind” measurements are each repeated and should not deviate more than 3% from the mean value.

The amine equivalent (AEW) is the formula:
AEW = (A × 1000) / ((p−q) × N)
Where A is the mass of the sample, p is mL of perchloric acid solution used for the titration of the sample, q is mL of perchloric acid solution used for the blind test, N is the exact normality of the approximately 0.1N perchloric acid solution used for the titration.

Quantitative theoretical AHEW calculation of amine hydrogen equivalent (AHEW):
Based on the structure of the amine molecule, the number of hydrogen of the amine group that easily reacts with the epoxy group (active hydrogen) is confirmed as “y”, and the M _w of the amine molecule is known. AHEW is calculated as follows:
AHEW = M _w / y

Quantitative theoretical THEW calculation of thiol hydrogen equivalent (THEW):
Based on the structure of the mercaptan molecule, the number of hydrogens in the thiol group that easily reacts with the epoxy group is confirmed as “y”, and the M _w of the mercaptan molecule is known. THEW is calculated as follows:
THEW = M _w / y

Rotor test A stainless steel test plate (13.5 × 7 cm ² ) having a curvature corresponding to that of a cylindrical drum having a diameter of 1 m is first coated with a 150 μm (DFT) epoxy primer (Hempadur Primer 45141, Hemel A / S). To do. After 24 hours, the test plate is coated with a 100 μm (DFT) commercial epoxy tie coat (HEMPADUR 45182, Hempel A / S) by air spray painting.

  After a minimum of 24 hours of drying in a room temperature laboratory, the test paint is applied by air spray painting at a DFT of about 250 μm. The test plate is dried in a room temperature laboratory for at least one week prior to testing. The thickness at the start of the paint system is measured using a film thickness meter (Kett, LZ-200C).

  The rotor is rotated at a peripheral speed of 15 knots for a relative distance of at least 39000 nautical miles.

  The thickness is controlled by periodic inspection using a film thickness meter (Kett, LZ-200C). The starting inspection is performed before the rotor test. Polishing is the difference between the film thickness measured during a given inspection and the film thickness measured during the initial inspection.

Test on Naoshima A test plate is fixed to the convex surface of a cylindrical drum having a diameter of 1 m and rotated in seawater. The salinity of seawater ranges from 31 to 35 ppth at an average temperature of 24 ° C. at a test site in Naoshima, Japan located at 34 degrees north latitude and 134 degrees east longitude.

Test in Vilanova A test plate is fixed to the convex surface of a cylindrical drum with a diameter of 1 m and rotated in seawater. The salinity of the seawater is 37-38 ppth at an average temperature of 17-18 ° C. at the test site of Vilanova i la Geltru in northeastern Spain, located at 41.13 degrees north latitude and 1.43 degrees east longitude. Range.

Laboratory Rotor Test Polishing and leaching properties are measured using a rotating device similar to that described by Kiil et al. (Kil, S, Weinell, CE, Yebra, DM, Dam-Johansen, K, “Marine biofouling. protection: design of controlled release antifusing points. “In: Ng, KM, Gani, R, Dam-Johansen, K (eds.) Chemical Product Design 23; 52217-7.Part II (7), Elsevier. (2006)). This device consists of a rotary rig, has two concentric cylinders, and an inner cylinder (rotor, diameter 0.3 m, height 0.17 m) is rotatable. This cylinder pair is immersed in a tank containing about 400 to 500 liters of artificial seawater.

  The tank is fitted with a baffle that disrupts the flow of liquid, which promotes turbulence, enables faster mixing of the species released from the paint, and promotes heat transfer from the isothermal system. The purpose of using two cylinders is to create something close to the Couette flow (flow between two parallel walls. One wall moves at a constant speed). The rotor operates at 20 knots at 25 ° C. (unless otherwise specified) and the pH is frequently adjusted to 8.2 using 1M sodium hydroxide or 1M hydrochloric acid.

Samples are prepared using a transparent film for overhead projectors (3M PP2410) primed with a two-component paint (Hempadur 4518, Hempel A / S) with a Doctor Blade applicator (gap size: 200 μm). . Paint samples are applied adjacent to each other using a doctor blade applicator (gap: 250 μm). After drying for one day, the coated transparent film is cut into 2 cm strips to make 8 samples of 1.5 × 2 cm ² into long strips (21 cm). The strip is attached to the rotor and allowed to dry for 1 week.

  One week later, the study begins. During the experiment, at predetermined weeks (w) (see tables), samples are removed for polishing and leaching depth inspection. Samples are dried at ambient conditions for 3 days, then cut in half and embedded in paraffin. Before measuring the total film thickness and leached layer thickness with an optical microscope, the inner front of the sample is scraped off (inspection of the coating film cross section).

Antifouling property test Acrylic test plate (10 x 45 cm ² ) that was sandblasted on one side to promote adhesion of the coating film, first of all, a commercially available vinyl tar primer (Hemptex 46330 Hempel A / S) by air spray coating Is coated with 80 microns (DFT). After a minimum of 24 hours drying in a room temperature laboratory, the test paint is applied by air spray painting at DFT 90-100 microns. After drying for at least 72 hours, the test plate is fixed to a rack and immersed in seawater.

  The test site Toba is located on the Pacific coast of Japan. In this test site, the test plate is immersed in seawater. Alternatively, the test site is Villanova, Spain or Singapore (Singapore testing: seawater with a salinity in the range of 29-31 parts per thousand at a temperature in the range of 29-31 ° C, latitude 1 ° 23'38.8 " (North) and longitude 103 ° 58′33.32 ″ (east)). The panel is inspected every 4-8 weeks and the antifouling performance is evaluated according to the following scale.

Water absorption test A polycarbonate panel (5.7 × 10 × 0.4 cm) sanded to remove all moisture is dried at 60 ° C. for 2 weeks. Place the panel in a room temperature (RT) laboratory until ambient temperature is reached and weigh (Wp1). The polymer is applied to the panel using a doctor blade applicator with a 300 micron gap and dried in an RT laboratory for 24 hours and then in a 45 ° C. oven for 72 hours. After drying, the panel is weighed (Wp2), and the polymer mass is calculated as the difference between the panel mass and the coated and dried panel mass (Wp2-Wp1). The panel is fully immersed in artificial seawater (prepared in the same way as the laboratory rotor test) and placed in a 45 ° C. oven. After 21 days, the panel is removed from the immersion, the excess water is wiped off with soft paper, the panel is allowed to reach the laboratory RT and the water absorption is checked by weighing (Wpt).

  The water absorbed by the substrate of the coated panel is calculated using a bare sanded polycarbonate panel (5.7 × 10 × 0.4 cm) following the same procedure as the coated panels (Wb2 and Wbt).

Calculate the water absorbed by the polymer as follows:
((Wpt−Wp2) − (Wp1 × ((Wbt−Wb2) / Wb2)) / (Wp2−Wp1) × 100%

  In Table 10, the results are normalized to a sample without pre-curing agent (Prepolymer 1).

Preparation of coating composition Prepolymer synthesis procedure:
A premix of monomers (triisopropylsilyl acrylate, methyl methacrylate, butyl acrylate and glycidyl methacrylate), azobis-methylbutyronitrile and xylene was prepared at the specified ratio, and equipped with a stirrer, reflux condenser, and premix feed port An additional amount of xylene was charged to the temperature controlled reaction vessel. The reaction vessel was heated and maintained at 125 ° C., and the premix was charged to the reaction vessel at a constant rate for 4 hours under a nitrogen atmosphere. After another 30 minutes, the initiator and xylene premix were charged to the reactor at a constant rate for 1 hour. After another 30 minutes, the temperature of the reaction vessel was lowered.

Table 1-Prepolymer Composition and Properties The prepolymer contains silyl ester groups and epoxy functional groups.

  The properties of the polymer are measured by gel permeation chromatography (GPC). Molecular weight distribution (MWD) was determined by using a mechanical HLC-8220 (Tosoh) equipped with two TSK gel super multipore HZ-M columns and tetrahydrofuran (THF) as an eluent at a constant flow rate of 40 ° C. Determined using a refractive index (RI) detector at 0.350 mL / min. The column was calibrated using polystyrene standards. Samples were prepared by dissolving an amount of polymer solution corresponding to 40 mg dry polymer in 10 mL THF.

* 硬化剤７は、下記の方法に従って調製される：４０．７ｇの反応性希釈剤（Ｃａｒｄｏｌｉｔｅ ＮＣ ５１３）を５．５ｇのアミン（メタキシリレンジアミン）に添加し、３０分間撹拌する。２日後、１３．９ｇのキシレンを添加する。 Table 2-Curing agents

* Curing agent 7 is prepared according to the following method: Add 40.7 g of reactive diluent (Cardolite NC 513) to 5.5 g of amine (metaxylylenediamine) and stir for 30 minutes. After 2 days, 13.9 g of xylene is added.

Preparation of the coating composition In each case, the base component was prepared by grinding all the raw materials with glass beads for 30 minutes. The obtained particle size was 50 μm. As long as the zinc resinate was used (see table below), the zinc resinate was dissolved in the solvent before grinding.

  A model paint was prepared by simply mixing the components of the base component and the second component. The base component and the second component were mixed at 25 ° C. immediately before applying the coating composition according to the respective test (see further test description above).

  As long as the second component hardener was in solid form, the hardener was dissolved in a suitable solvent (see table below). For the second component with Zisnet DB, Zisnet DB and triphenylphosphine were added to the solvent and stirred until dissolved. For the second component with GPM800: Triphenylphosphine was dissolved in the solvent and stirred until dissolved, then added to GPM800 and stirred until mixed.

Table 3-6 Basic formulation of model paint

Table 7-Basic formulation of model paint

（^*)：Ｈｅｍｐｅｌ Ａ／Ｓ社製の市販の最上級自己研磨型防汚塗料組成物（参考）。＃：剥離のため、研磨率を求めることは不可能であった。これらの組成物の物理的性質は、ロジン（又はその誘導体）及び／又は可塑剤の添加によって改善され、繊維の添加によって更に改善されると考えられる。 result
Table 8

( ^* ): A commercially available superlative self-polishing antifouling paint composition manufactured by Hempel A / S (reference). #: It was impossible to determine the polishing rate due to peeling. It is believed that the physical properties of these compositions are improved by the addition of rosin (or derivatives thereof) and / or plasticizers and further improved by the addition of fibers.

Table 8 (continued)

コメント：同じ塗料中ＮＥＯ−ＳとＨＤのような２つの反応性希釈剤の使用は、ＨＤのみを使用する塗料と比較して研磨を増加させる（モデル塗料２６と２７、２５と２８、２９と３０を参照のこと）。 Table 9

Comment: The use of two reactive diluents such as NEO-S and HD in the same paint increases polishing compared to paint using only HD (model paints 26 and 27, 25 and 28, 29 and 30).

コメント：硬化後、未硬化プレポリマー１と比較して吸水が著しく減少することが認められる。吸水は、膨れ、亀裂、剥離のような機械的課題を最小にするためにできるだけ少なくしなければならない。 Table 10-Water absorption test

Comments: It can be seen that after curing, water absorption is significantly reduced compared to the uncured prepolymer 1. Water absorption should be as low as possible to minimize mechanical problems such as blistering, cracking and peeling.

Claims (18)

A self-polishing antifouling paint composition,
(A) at least one epoxy functional group and the general formula (I):

In the formula, X represents a carbonyl group (> C═O), n is an integer of 0 to 5000, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently C A base component comprising a prepolymer having at least one side chain with at least one end group selected from _1-20 alkyl and optionally substituted phenyl;
And (b) a curing agent having at least one active hydrogen.   2. A composition according to claim 1, wherein the curing agent is selected from amines such as diamines and polyamines.   The composition of claim 2 wherein the amine is in the form of a boron trifluoride complex.   The composition according to claim 1, wherein the curing agent is selected from amine epoxy adducts.   2. A composition according to claim 1, wherein the curing agent is selected from polymercaptans such as aliphatic polymercaptans, alicyclic polymercaptans, aromatic polymercaptans and thiol-terminated polymers.   Curing agents are pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryloxyethyl-1,3,5) -Triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptopropionate), 2,4,6-trimercapto-s-triazine-monosodium salt, 2-dibutyl 6. Composition according to claim 5, selected from amino-4,6-dimercapto-s-triazine, 2-anilino-4,6-dimercapto-s-triazine and 2,4,6-trimercapto-s-triazine. object.   7. A composition according to any of claims 1 and 5-6, further comprising one or more accelerators.   8. A composition according to claim 7, wherein the one or more accelerators are selected from tertiary amines, phosphorus compounds, alcohols and organic acids.   At least one promoter is a phosphorus compound such as triphenylphosphine, 1,2-bis (diphenylphosphino) ethane, diphenylphosphinas chloride, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p- Tolylphosphine, tris (p-methoxyphenyl) phosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine, tributylphosphine, tri-tert-butylphosphine, tri-n-octylphosphine, diphenylphosphinostyrene, 1,3-bis (diphenylphosphine) The composition according to claim 8, which is selected from fino) propane, 1,4-bis (diphenylphosphino) butane and the like. The terminal group of the general formula (I) is represented by the general formula (II):

Of an end group, wherein, X, R _3, R ₄ and R ₅ are as defined in claim 1, composition according to any one of claims 1 to 9.   The composition according to any of claims 1 to 10, wherein the epoxy equivalent of the prepolymer is in the range of 450 to 10,000.   The composition according to any one of claims 1 to 11, wherein the prepolymer has a mass average molecular weight of 2000 to 100,000.   13. A composition according to any one of the preceding claims, wherein the entire coating composition has a solids weight ratio of at least 40%.   A kit comprising the antifouling coating composition as defined in any one of claims 1 to 12, wherein the first container contains a base component and the second container contains a curing agent. Yes, a kit.   A kit comprising an antifouling paint composition as defined in any of claims 7 to 13, wherein the first container contains a base component and a curing agent, and the second container contains one or more accelerators. A kit characterized by being included. A base component for an antifouling paint composition having the general formula I:

In the formula, X represents a carbonyl group (> C═O), n is an integer of 0 to 5000, and R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently C A base component comprising an epoxy functional prepolymer having at least one side chain with at least one end group selected from _1-20 alkyl and optionally substituted phenyl;
The base component, wherein the epoxy equivalent of the prepolymer is in the range of 450 to 10,000.   The marine structure which has the coating film formed from the antifouling paint composition in any one of Claims 1-13 in at least one part of the surface.   A method for coating a structure comprising the step of applying a layer of an antifouling paint composition as defined in any of claims 1 to 13 to at least a part of the structure.