CN109777178A - Antifouling composition - Google Patents

Antifouling composition Download PDF

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Publication number
CN109777178A
CN109777178A CN201811361666.4A CN201811361666A CN109777178A CN 109777178 A CN109777178 A CN 109777178A CN 201811361666 A CN201811361666 A CN 201811361666A CN 109777178 A CN109777178 A CN 109777178A
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weight
monomer
acid
formula
methyl
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CN109777178B (en
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谢默斯·迈克尔·杰克逊
亨宁·约翰森
马里特·达令
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Jordan AS
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Jordan AS
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
    • C09D193/04—Rosin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof

Abstract

The present invention provides a kind of antifouling compositions.The present invention also provides a kind of adhesives for antifouling paint compositions, include: the hydrophilic copolymers of (i) at least 0 DEG C of glass transition temperature, it includes the monomer of at least at least one formula (I) of 10 weight %,Wherein R1It is H or CH3, and R2It is C3-C18 substituent group or R with preferably at least one oxygen atom of at least one oxygen or nitrogen-atoms2It is poly- (aklylene glycol) chain；With the monomer of at least one formula (II),Wherein R1’It is H or CH3, and R2’It is C1-C20 alkyl, the hydrophilic copolymers include the comonomer other than formula (I) or (II) less than 15 weight %；(ii) cyclic monocarboxylic acid such as rosin or derivatives thereof；(iii) non-hydrophilic (methyl) acrylic polymer of the monomer comprising at least silyl ester copolymer of the silicyl ester monomer of 15 weight % and/or comprising the formula (I) less than 10 weight %.

Description

Antifouling composition
Technical field
The present invention relates to be used for marine antifouling coating compositions (marine antifouling coating Composition adhesive) relates more specifically to comprising based on hydrophily (methyl) acrylate copolymer, cyclic annular unitary The sea of three component adhesives of carboxylic acid and silyl ester (silicon substrate ester, silyl ester) or (methyl) acrylic polymer Foreign antifouling paint compositions.The invention further relates to protection objects from the method for dirt, and coated with of the invention antifouling group Close the object (object, object) of object.
Background technique
The surface immersed in seawater is subjected to the dirt of the marine organisms such as green alga and brown alga, barnacle, mussel, pipe worm.? On the marine structure of ship, oil platform, buoy etc., this dirt is undesirable and has economic consequences.It is dirty Dirt may cause the biodegrade on surface, load increase and accelerated corrosion.On ship, dirt will increase frictional resistance, this will Speed reduction and/or fuel consumption is caused to increase.It is also possible to that navigability is caused to reduce.
The sedimentation and growth of marine organisms in order to prevent uses antifouling paint (paint).These coating generally comprise film forming Adhesive and different components, such as pigment, filler, solvent and bioactive substance.
It is most successful currently on the market to be based on functionalized (methyl) acrylic compounds of silyl ester from polishing antifouling system Copolymer.Functionalized (methyl) acrylic copolymer of silyl ester usually with other adhesives such as acrylate and pine Fragrant or rosin derivative is used together, with adjust antifouling coat from polishing performance and mechanical performance.
Although marine antifouling coating designed for operating in the seawater, these coating operate also critically important in fresh water. Particularly, coating will not be important in fresh water by the absorption of excessive water.
Why the water in fresh water absorbs critically important for the coating on the ship of operation at sea, this may not be at once Clearly.However, many ships will pass through a period of time in fresh water.For example, the Panama Canal contains fresh water.In addition, in Many new buildings are equipped in the freshet of state.In these cases, excessive water, which absorbs, will lead to excessive expansion, and It will lead to film destruction in the worst case.
Resist the important indicator that the ability that the water in fresh water absorbs is also seawater operation.This is that coating has long-time stability Good index.In the seawater, film can absorb moisture, but since osmotic pressure is lower, and speed and amount can reduce.Mistake in fresh water The water absorption of amount shows that in the long run the water absorption in seawater will increase.
Antifouling paint is intended to the viability using up to 7.5 years.The smallest water is kept to absorb during the entire period It is an important factor for control discharges active component from coating.In the anti-soil technology of any given type, in property reliably and with long-term There are apparent relationships between energy and water absorption.Excessive water absorb will lead to the rate of release of active component than it is desired more Height, performance can reduce between the lifetime of coating.Depending on the type of used adhesive composition, increased water absorbs may It will lead to hydrolysis faster and excessive corrosion or the acceleration of active component leached, exhausted so as to cause thickness is formed to coating surface Layer (leaches layer, leached layer).In all cases, water absorb control design pollution resisting coating such as with It is crucial parameter in the coating of neotectonics and dry dock.
It was found by the inventors that the water unexpectedly reduced in antifouling paint using special adhesive in fresh water is inhaled It receives.Adhesive is the adhesive comprising three kinds of components, these three components are: the hydrophily (methyl) comprising some hydrophilic monomers Acrylate copolymer, cyclic monocarboxylic acid component and acrylic compounds/silyl ester copolymer component.When in antifouling paint group When being used together in conjunction object, adhesive reduces the amount of the water absorbed by film.Therefore, comprising the antifouling painting of adhesive of the invention Material provides extended task interval (service interval).
Document is containing there are many disclosures of the binder polymer for antifouling paint.Especially silyl ester copolymer Object and acrylic polymer are well-known.However, almost without adhesive comprising three kinds required in the present invention The disclosure of the blend of adhesive component.
In EP2128208, be prepared for antifouling paint compositions, it includes silyl ester copolymer, rosin components and The resin of plastification of extremely low glass transition temperature.As we have determined in embodiment, if hydrophily (methyl) third Olefine acid ester polymer has low Tg, then adhesive will suffer from high water absorption.
WO03070832 describes a kind of coating composition, and it includes copolymer As (silicyl copolymer), polymer B (usually non-hydrophobic property is total by (it is incompatible with copolymer A and may include hydrophilic co-monomer) and optional polymer C Polymers).Coating examples do not use cyclic monocarboxylic acid.Such as sour use is advantageous, because it reduce Coating material compositions The viscosity of object, therefore the coating composition with lower VOC can be prepared.
WO2014175246 describes a kind of antifouling paint compositions, and it includes based on following adhesives: being based on benzene second The copolymer and silyl ester copolymer of alkene and (methyl) glycidyl acrylate.Embodiment 15 uses rosin, but does not have Required copolymer (i) in the open present invention, because there are a large amount of excessive styrene.Copolymer therein such as A-13 tool There is the Tg far below 0 DEG C.
WO97/44401 describes rosin or rosin equivalent, fiber and polymer toughener in antifouling paint compositions Purposes.It does not include the coating examples of two kinds of (methyl) acrylic copolymer.
EP1288234 is described by the film forming polymer of the adhesive preparation with low hydrolyzable content of monomer.It enumerates Sole hydrophilic comonomer is vinyl pyrrolidone and methacrylic acid, and is based on acrylic copolymer without example Combination.
WO2005/005516 describes the silyl ester copolymer with low Mw and its purposes in antifouling paint. Embodiment 7 describes a kind of coating composition, contains based on unacknowledged silyl ester copolymer, rosin and Degalan The adhesive of LP 64/12 (non-hydrophilic BMA/MMA copolymer).Disclosed silicyl copolymer, which does not have, is higher than 10 The hydrophilic monomer content of weight % lacks hydrophilic adhesive component of the invention.
WO2011/131721 describes the coating prepared and adding different component (such as desiccant) with particular order Composition.In instances, rosin and Neocryl B725 (non-hydrophilic BMA/MMA copolymer) and Polyace NSP-100 (third Olefin(e) acid silyl ester) it is used together.Hydrophilic co-monomer is not used in Neocryl B725.
WO2014/175140 describes the silicyl copolymer with specified end group.
EP3078715 is related to a kind of antifouling paint compositions, and it includes silyl ester copolymer, bromo pyrrole carbonitrile are (bent Lip river Billy, tralopyril) and stabilizer.In instances, using methacrylic acid triisopropylsilyl ester copolymer, rouge Rosin (gum rosin) and acrylic polymer.The monomer composition or polymer performance of not specified acrylic copolymer.
WO2009/149919 patent is related to purposes of the comonomer of caprolactone modification in silicyl copolymer.Not yet Have and uses additional acrylic polymer.
EP2489710 illustrates antifouling paint, and illustrates two kinds of acrylic copolymers T3 and T4.They and rosin and chlorine Ethylene-isobutyl vinyl ether copolymer in combination.
In EP2161316 and relevant US2011/0166253, adhesive is based on rosin components and silyl ester group Point, that is, lack third adhesive component of the invention.
The combination of required component in the present invention is new and provides significant result.
Summary of the invention
In a first aspect, the present invention provides one kind for antifouling paint compositions (antifouling coating composition, Antifouling coating composition) adhesive, which includes:
(i) there are the hydrophilic copolymers of at least 0 DEG C of glass transition temperature, which includes at least 10 The monomer of at least one formula (I) of weight %
Wherein R1It is H or CH3, and R2It is the C3- at least one oxygen or nitrogen-atoms, preferably at least one oxygen atom C18 substituent group or R2It is poly- (aklylene glycol) chain (poly (alkylene glycol) chain)；
And the monomer of at least one formula (II),
Wherein R1’It is H or CH3, and R2’It is C1-C20 alkyl；
The hydrophilic copolymers include the copolymerization list other than those of formula (I) or (II) less than 15 weight % Body；
(ii) cyclic monocarboxylic acid (cyclic monocarboxylic acid), such as rosin or derivatives thereof be (such as Its salt)；And
(iii) silicyl comprising at least silicyl ester monomer of 15 weight % (silyl ester monomer) Ester copolymer, and/or the monomer according to formula (I) comprising being less than 10 weight %, preferably less than 5 weight %, most preferably 0 weight % Formula (I) monomer non-hydrophilic (methyl) acrylic polymer (non-hydrophilic (meth) acrylic polymer)。
The amount of component (i) is preferably in the range of 20 weight % to 60 weight % (dry solid) in adhesive.In adhesive The amount of component (ii) is preferably in the range of 10 weight % to 70 weight % (dry solid).The amount of component (iii) is excellent in adhesive It is selected in (dry solid) in the range of 5 weight % to 70 weight %.
The present invention also provides a kind of antifouling paint compositions, viscous in solvent it includes being preferably dispersed in as described herein Mixture.Antifouling paint can further include anti-fouling agent, preferably cuprous oxide, ethylenebis (aminodithioformic acid) zinc (sub- second Base is bis- (zinc dithiocarbamate), zinc ethylenebis (dithiocarbamate)) and/or copper pyrithione (pyrrole sulphur Copper, copper pyrithione).
The present invention also provides a kind of for protecting object from the method for dirt, and the method includes with defined herein Antifouling paint compositions coating is subjected at least part of the object of dirt.
The invention further relates to the objects for being coated with antifouling paint compositions defined herein, or are related to of the invention antifouling Composition is for protecting ocean surface (marine surface, marine surface) from the purposes of dirt.
Definition
Term " marine antifouling coating compositions ", " antifouling paint compositions " or abbreviation " coating composition ", which refer to, to be suitable for Composition in marine environment.Antifouling paint compositions preferably comprise anti-fouling agent, such as fungicide (antimicrobial, biocidal Agent, biocide).
Term " alkyl " refers to only any group containing C atom and H atom, therefore including alkyl, alkenyl, aryl, ring Alkyl, aralkyl etc..
Term " (methyl) acrylate " is methacrylate or acrylate.
Term " poly- (alkylene oxide) (poly- (alkylene oxide)) " refers to the chemical combination comprising-[alkylidene-O]-repetitive unit Object.In general, alkylidene is ethylidene or propylidene.
The term " rosin " being used below is for covering " rosin or derivatives thereof ".
Term " adhesive " defines the composition including copolymer and cyclic monocarboxylic acid and any other component A part, which, which is formed together, provides the matrix of substance and intensity for composition." adhesive " includes polymers compositions (i) and (iii) and cyclic monocarboxylic acid (ii).
Term " non-hydrophilic (methyl) acrylic polymer " defines following polymer, which includes at least one It plants (methyl) acrylic monomers or at least one (methyl) acrylate monomer (or both possible) but includes less than 10 weight % The monomer according to formula (I), preferably less than 5 weight %, most preferably 0 weight % formula (I) monomer.10 weights are less than when existing When measuring the monomer of the formula (I) of %, this is considered as non-hydrophilic.
In the case where providing weight % (wt%) to order body, weight % is relative to every kind of list present in copolymer The summation (weight) of body.Therefore, if acrylic acid 2- methoxy acrylate (MEA) and methyl methacrylate (MMA) are copolymers Only monomer in component (i), then the weight % of MEA be calculated as (MEA (weight)/(MEA (weight)+MMA (weight))) × 100%.
Specific embodiment
The present invention relates to a kind of new adhesive for marine antifouling coating compositions, presented in fresh water significantly compared with Low water absorbs.Therefore, these compositions provide extended service life.Antifouling paint compositions of the invention include containing extremely The adhesive of few three kinds of components.
Copolymer component (i)
The present invention is needed using some hydrophilies (methyl) acrylic acid esters co-polymer.Term used herein is " hydrophilic Property " to mean the monomer that there is at least at least one formula (I) of 10 weight %.Therefore, copolymer component (i) includes at least one The monomer of kind formula (I):
Wherein R1It is H or CH3, and R2It is the C3- containing at least one oxygen or nitrogen-atoms, preferably at least one oxygen atom C18 substituent group or R2Represent poly- (aklylene glycol) group.As used herein, which defines " hydrophily " (methyl) propylene Acid ester monomer.
As shown in above formula, term " hydrophily (methyl) acrylate " requires the R in formula (I)2Group includes at least one Oxygen or nitrogen-atoms, preferably at least an oxygen atom.As being explained in detail below, additional non-hydrophilic (methyl) acrylate list Body is also used as the monomer of formula (II) to be present in the component (i) of adhesive, wherein R2’Unit is only made of C and H atom.
In one embodiment, monomer of the binder copolymer component (i) containing at least one above-mentioned formula (I), wherein R2Group has formula (CH2CH2O)n-R3, wherein R3It is that C1-C10 hydrocarbyl substituent, preferably C1-C10 alkyl or C6-C10 aryl take Dai Ji, and n is the integer in 1 to 5, preferably 1 to 3 range.It is preferred that R2With formula (CH2CH2O)n-R3, wherein R3For C1-C10 Alkyl substituent, preferably CH3Or CH2CH3, and n is in 1 to 3 range, preferred an integer of 1 or 2.Such monomer can be third Olefin(e) acid 2- methoxy acrylate, acrylic acid 2- ethoxy ethyl ester, acrylic acid 2- butoxyethyl, acrylic acid 2- (2- methoxyl group ethoxy Base) ethyl ester, acrylic acid 2- (2- ethoxy ethoxy) ethyl ester, acrylic acid 2- (2- Butoxyethoxy) ethyl ester, acrylic acid 2- [2- (2- methoxy ethoxy) ethyoxyl] ethyl ester, acrylic acid 2- [2- (2- ethoxy ethoxy) ethyoxyl] ethyl ester, methacrylic acid 2- methoxy acrylate, methacrylic acid 2- ethoxy ethyl ester, methacrylic acid 2- butoxyethyl, methacrylic acid 2- (2- first Oxygroup ethyoxyl) ethyl ester, methacrylic acid 2- (2- ethoxy ethoxy) ethyl ester, methacrylic acid 2- (2- Butoxyethoxy) Ethyl ester, methacrylic acid 2- [2- (2- methoxy ethoxy) ethyoxyl] ethyl ester, methacrylic acid 2- [2- (2- ethoxy ethoxy Base) ethyoxyl] ethyl ester.
In one embodiment, copolymer component (i) includes 2 methoxy acrylate of acrylic acid (MEA), methacrylic acid 2- Methoxy acrylate (MEMA), methacrylic acid 2- ethoxy ethyl ester (EEMA), acrylic acid 2- (2- ethoxy ethoxy) ethyl ester (EDEGA) or one of methacrylic acid 2- (2- ethoxy ethoxy) ethyl ester (EDEGMA) or a variety of.
In another embodiment, copolymer component (i) contains the monomer of at least one above-mentioned formula (I), wherein R2Base Group is poly- (aklylene glycol) group, such as poly(ethylene glycol) group.Such group can have formula (CH2CH2O)m-R13Or (CH2CH(CH3)O)m-R13, wherein R13It is C1-C10 hydrocarbyl substituent, preferably C1-C10 alkyl or C6-C10 aryl substituent, And m is the integer in 5 to 100, preferably 5 to 20 ranges.Such monomer can be poly(ethylene glycol) methyl ether acetate, gather (ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) methyl ether methacrylate, poly(ethylene glycol) ethyl ether methacrylate.It is excellent This monomer of choosing has 300-4000, the number-average molecular weight (Mn) of more preferable 300-1000.
In one embodiment, copolymer component (i) contains the monomer of at least one above-mentioned formula (I), wherein R2Group It is saturated cyclic group, which contains at least one oxygen or nitrogen-atoms, preferably at least an oxygen atom.More preferably Ground, R2It is group W-R10, wherein R10Be cyclic ethers (such as tetrahydrofuran (butyl oxide link, oxolane), oxane (oxirane, Oxane), dioxolanes (dioxolane), dioxanes (dioxane), are optionally replaced by alkyl) and W be C1-C4 alkylene Base.Such monomer can be acrylic acid furfuryl group ester, tetrahydrofurfuryl acrylate (tetrahydrofurfuryl Acrylate), acrylic acid (1,3- dioxolanes -4- base) methyl esters, methacrylic acid furfuryl group ester, methacrylic acid tetrahydro furfuryl ester (tetrahydrofurfuryl methacrylate), methacrylic acid (2,2- dimethyl -1,3- dioxolanes -4- base) first Ester.Preferred cyclic ethers should contain at least four atom in ring.Most preferably, in this embodiment, the compound of formula (I) is Tetrahydrofurfuryl acrylate (THFA) and methacrylic acid tetrahydro furfuryl ester (THFMA).
In one embodiment, hydrophilic copolymers component (i) does not include glycidyl.
The monomer of formula (I) is preferably formed as at least 15 weight % of copolymer (i).Formula (I) is hydrophilic in adhesive component (i) Property (methyl) acrylate monomer particularly preferred amount be 15 weight % to 65 weight %, preferably 18 weight % to 62 weights Measure %, such as 20 weight % to 50 weight %.There are the monomer mixture of formula (I), this tittle is related to copolymer The combined weight fraction of the monomer of middle formula (I).
The monomer of formula (I) is preferably acrylic acid 2- methoxy acrylate (MEA), methacrylic acid 2- methoxy acrylate (MEMA), methacrylic acid 2- ethoxy ethyl ester (EEMA), tetrahydrofurfuryl acrylate (THFA), methacrylic acid tetrahydrofurfuryl Ester (THFMA), acrylic acid 2- (2- ethoxy ethoxy) ethyl ester (EDEGA) or methacrylic acid 2- (2- ethoxy ethoxy) second Ester (EDEGMA).
One or more non-hydrophilic (methyl) acrylate monomers
Copolymer component (i) of the invention further includes non-hydrophilic (methyl) acrylate list of one or more formulas (II) Body
Wherein R1’It is H or CH3, and R2’It is C1-C20 hydrocarbyl substituent, preferably C1-8 alkyl substituent, most preferably first Base, ethyl, n-propyl, normal-butyl or 2- ethylhexyl." non-hydrophilic " monomer is referred to herein as according to the monomer of formula (II).
In all of the embodiments of the present invention, copolymer component (i) includes at least one non-hydrophilic methacrylic acid Ester and/or non-hydrophilic acrylate monomer (II) and the monomer of at least one formula (I).The monomer of formula (II) is preferably formed to The component (i) of more 85 weight %, preferably 35 weight % are to 85 weight %, and such as 38 weight % are to 82 weight %, such as in 40 weights Measure the component (i) in the range of % to 80 weight %.There are the mixture of the monomer of formula (II), these are preferred Amount is related to the combined weight fraction of the monomer of formula (II) in copolymer.
In a preferred embodiment, copolymer component (i) is only by the monomer composition of formula (I) and (II).
In a preferred embodiment, the weight of the monomer of the weight ratio formula (I) of the monomer of formula (II) is more.
The monomer of formula (II) is preferably selected including methyl methacrylate (MMA), n-butyl acrylate (n-BA), methyl N-butyl acrylate (n-BMA), 2-EHA (2-EHA) or 2-Ethylhexyl Methacrylate (2-EHMA).? In all of the embodiments of the present invention, preferably methyl methacrylate (MMA) or n-butyl acrylate (n-BA) is included in copolymerization In object component (i).
In one embodiment, copolymer includes hydrophilic monomer MEA, EDEGA, EEMA, poly(ethylene glycol) methyl ether first One of base acrylate or THFA are a variety of, and at least one non-hydrophilic (methyl) acrylate monomer MMA or n- BA。
Copolymer component (i) contains any list other than the monomer of above-mentioned formula (I) and (II) less than 15 weight % Body.It is therefore desirable to which copolymer component (i) contains any silyl ester less than the formula (III) defined below 15 weight % Monomer, any silicyl ester monomer of the formula (III) defined below preferably less than 10 weight %.In some embodiments In, component (i) can be only by the monomer composition of formula (I) and (II).
Copolymer component (i) is preferably free of any (methyl) acrylic comonomers.
Copolymer component (i) is preferably free of the comonomer of any metal ion.
In a preferred embodiment, hydrophilic copolymers (i) include
(i) monomer of at least one formula (I) of 15 weight % to 65 weight %
Wherein R1It is H or CH3, and R2It is the C3- at least one oxygen or nitrogen-atoms, preferably at least one oxygen atom C18 substituent group or R2It is poly- (aklylene glycol) chain；
And 35 weight % to 85 weight % at least one formula (II) monomer,
Wherein R1’It is H or CH3, and R2’It is C1-C20 alkyl；
The hydrophilic copolymers include the copolymerization list other than those of formula (I) or (II) less than 15 weight % Body.
The performance of copolymer component (i)
Copolymer preferably has 5,000 to 70,000, preferably 10,000 to 60,000, especially 15,000 to 40,000 Weight average molecular weight (Mw).Mw described in embodiment part as measured.
Copolymer preferably has 1.5 to 5.0 polydispersity index (PDI).
Copolymer component (i) is preferably at least 0 DEG C of glass transition temperature (Tg).Copolymer preferably has at least 5 DEG C, preferably at least 10 DEG C, such as at least 15 DEG C of glass transition temperature (Tg), all values in embodiment part all in accordance with describing Tg test measure.Value lower than 80 DEG C is preferred, such as less than 75 DEG C, such as less than 50 DEG C.It is not intended to by theory Limitation, it is believed that higher Tg facilitates the reduction that the water that we observe in embodiment absorbs.The case where Tg is lower than 0 DEG C Under, water absorbs higher.
Copolymer component (i) is preferably partially or completely incompatible with the blend of other adhesive components.It is incompatible to refer to Adhesive component is incompatible according to the test method explained in following example part.
The amount of copolymer component (i) is preferably in 20 weight % to 60 weight %, such as 30 weight % to 50 weights in adhesive In the range of amount % (dry solid).
Final antifouling paint compositions of the invention preferably comprise 0.5 weight % to 45 weight %, such as 1.0 weight % extremely The copolymer component (i) of 30 weight %, especially 5.0 weight % to 25 weight % (dry solid).
Antifouling paint compositions of the invention optionally including copolymer component (i) of the invention mixture.
Polymers compositions (iii)
Adhesive of the invention additionally comprises polymers compositions (iii).The component is different from component (i).Component (iii) can Based on non-hydrophilic (methyl) acrylate copolymer, non-hydrophilic (methyl) acrylate polymer (iii-2) or comprising extremely The silyl ester copolymer (iii-1) of the silicyl ester monomer of few 15 weight %.Component (iii) can be non-hydrophilic (methyl) acrylic polymer (referred to herein as (iii-2)).Component (iii) is also possible to copolymer (iii-1) and gathers Close the mixture of object (iii-2).Therefore, component (iii) is different from component (i).
Silyl ester copolymer component (iii-1)
Component (iii-1) includes at least one silicyl (methyl) acrylate monomer.For the conjunction in component (iii) Suitable silicyl (methyl) acrylate monomer preferably has formula (III)
Wherein,
R4It is H or CH3；
R5It is each independently selected from the C of linear chain or branched chain1-4Alkyl；
R6It is each independently selected from by the C1-C20 alkyl of linear chain or branched chain, C3-C12 naphthenic base, the optionally C6- that replaces C20 aryl and-OSi (R7)3The group of group composition；
Each R7It is independently the C1-C4 alkyl of linear chain or branched chain,
P is 0 to 5 integer；
Term " alkyl " is intended to cover both alkyl of linear chain or branched chain, such as methyl, ethyl, isopropyl, propyl, butyl And tert-butyl.Particularly preferred naphthenic base includes cyclohexyl and substituted cyclohexyl.
The example of substituted aryl includes being selected from halogen, alkyl, acyl group with 1 to about 8 carbon atom by least one Or the aryl that the substituent group of nitro replaces.Particularly preferred aryl includes replacing and unsubstituted phenyl, benzyl, phenylalkyl (phenalkyl) or naphthalene.
It is desirable that preferred silicyl ester monomer is based on the compound of formula (III), wherein p is 0.
It is highly preferred that silicyl ester monomer has formula (IV)
Wherein R4It is H or CH3；With
R6It is each independently selected from the group being made of the C1-C10 alkyl of linear chain or branched chain.
The example of monomer containing silyl ester functional group is well-known.The monomer packet defined by leading to formula (III) It includes:
The silicyl ester monomer of acrylic acid and methacrylic acid, such as three n-propyl silicyl of (methyl) acrylic acid Ester, (methyl) acrylic acid triisopropylsilyl ester, three normal-butyl silyl ester of (methyl) acrylic acid, (methyl) acrylic acid Tri-iso-butylsilyl ester, (methyl) acrylic acid t-butyldimethylsilyl ester, the tertiary hexyl diformazan of (methyl) acrylic acid Base silyl ester (thexyldimethylsilyl (meth) acrylate), (methyl) acrylic acid tert-butyl diphenyl first silicon Arrcostab, nine methyl tetrasiloxane base ester of (methyl) acrylic acid, bis- (trimethylsiloxy) the methyl first of (methyl) acrylic acid Silane base ester (bis (trimethylsiloxy) methylsilyl (meth) acrylate), three (trimethyl of (methyl) acrylic acid Siloxy) silyl ester.
It is preferable to use acrylic acid triisopropylsilyl ester (TISA) or methacrylic acid triisopropylsilyl esters (TISMA)。
Preferably, component (iii-1) includes at least 15 weight %, preferably 15 weight % to 65 weight %, especially 35 weights Measure the silicyl ester monomer of % to 60 weight %.
Preferably, other than one or more silicyl ester monomers, silyl ester copolymer component (iii-1) packet Containing the second comonomer other than silicyl ester monomer.Second comonomer preferably has formula as hereinbefore defined (I) or (II).Silyl ester copolymer component (iii-1) also may include the monomer and formula of formula as hereinbefore defined (I) (II) monomer.
Monomer for formula (I) preferred in silyl ester copolymer component (iii) be EDEGA, THFA, MEA and MEMA, especially EDEGA and THFA.Preferred hydrophobic comonomer includes MMA, n-BA, n-BMA and 2-EHA.
Silyl ester copolymer preferably includes at least monomer (methyl) acrylic acid triisopropylsilyl ester, formula (I) Monomer and formula (II) monomer.Above-mentioned formula (I) and preferably selecting for formula (II) are applied independently for component (iii) embodiment party Formula.The monomer of formula (II) is preferably selected including methyl methacrylate (MMA), n-butyl acrylate (n-BA), metering system Sour N-butyl (n-BMA), 2-EHA (2-EHA) or 2-Ethylhexyl Methacrylate (2-EHMA).In this hair In bright all embodiments, preferably methyl methacrylate (MMA) or butyl acrylate (n-BA) is included in copolymer component (iii) in.
Preferably, silyl ester copolymer component (iii) includes at least 15 weight %, especially 15 weight % to 65 weights Measure the monomer component of the formula (II) of %.
Preferably, silyl ester copolymer component (iii) includes the monomer of the formula (I) of 5 weight % to 30 weight %.
Silyl ester copolymer preferably has the vitrifying turn of at least 15 DEG C, preferably at least 20 DEG C, such as at least 25 DEG C Temperature (Tg), all values are measured all in accordance with the test of Tg described in embodiment part.Preferably shorter than 80 DEG C, such as less than 75 DEG C, such as less than 50 DEG C of value.
Silyl ester copolymer component (iii) preferably has 5,000 to 70,000, preferably 10,000 to 60,000, spy It is not 20,000 to 50,000 weight average molecular weight.Mw described in embodiment part as measured.
Silyl ester copolymer preferably has 2 to 6 PDI.
The amount of silyl ester component (iii) is preferably in 10 weight % to 60 weight %, preferably 15 weight % in adhesive To 50 weight % (dry solid).
(methyl) acrylic polymer component (iii-2)
Alternatively or additionally, component (iii) includes non-hydrophilic (methyl) acrylic polymer, the non-hydrophilic (methyl) acrylic polymer includes at least one (methyl) acrylic monomers or at least one (methyl) acrylate monomer (or both), such as one kind of formula (II).Component (iii-2) can be homopolymer or copolymer, preferred copolymer.Particularly, In the case where there is (methyl) acrylic monomers, there is second comonomer preferably to form copolymer.In the embodiment Second comonomer is preferably the monomer of formula as herein defined (II).
Non-hydrophilic (methyl) acrylic polymer includes the monomer of any formula (I) less than 10 weight %, and excellent Choosing is free of the monomer of any formula (I).Further preferably be free of any silicyl ester monomer.
Preferably, there is (methyl) acrylic acid in non-hydrophilic (methyl) acrylic polymer component (iii-2).It is excellent There is (methyl) acrylic acid in selection of land, especially have formula in non-hydrophilic (methyl) acrylic copolymer component (iii-2) (II) the second comonomer.
The monomer including formula (II), such as MMA, n-BMA and n-BA are preferably selected with (methyl) acrylic acid combinations.
(methyl) acrylic acid content in copolymer component (iii-2) is preferably in 0.5 weight % to the range of 10 weight % It is interior.The monomer of formula (II) is preferably formed as at least 50 weight %, such as at least 75 weight %, especially 90 weight % to 99.5 weights Measure (methyl) acrylic copolymer of %.
Alternatively, non-hydrophilic (methyl) acrylic polymer component (iii-2) may include one or more formulas (II) monomer.Therefore, in one embodiment, non-hydrophilic (methyl) acrylic polymer component (iii-2) is (first Base) Voncoat R 3310, such as the monomer of formula (II).
In this embodiment, the monomer of formula (II) is preferably formed as at least 50 weight %, such as at least 75 weight %, especially It is 90 weight % to 100 weight % (methyl) acrylic polymer.Preferably selecting for formula (II) is above for component (i) It is those of described, such as methyl methacrylate (MMA), n-butyl acrylate (n-BA), n-BMA (n- BMA), 2-EHA (2-EHA) or 2-Ethylhexyl Methacrylate (2-EHMA).
In all of the embodiments of the present invention, preferably methyl methacrylate (MMA) or n-butyl acrylate (n-BA) It is included in polymers compositions (iii-2).
(methyl) acrylic polymer component (iii-2) preferably has less than 0 DEG C, preferably smaller than -20 DEG C, such as small In -22 DEG C of glass transition temperatures (Tg), all values are measured all in accordance with the test of the Tg described in embodiment part.It is excellent Choosing is more than -60 DEG C, such as the value more than -50 DEG C.
(methyl) acrylic polymer component (iii-2) preferably has 5,000 to 70,000, preferably 10,000 to 60, 000, especially 15,000 to 35,000 weight average molecular weight.Mw is measured as described in embodiment part.
(methyl) acrylic polymer component (iii-2) preferably has 1.5 to 5.0 PDI.
If it does, adhesive composition of the invention preferably comprises 0.5 weight % to 25 weight %, such as 1.0 weights Measure (methyl) acrylic polymer component of % to 22 weight %, especially 2.0 weight % to 18 weight % (dry solid) (iii-2)。
In general, in adhesive the amount (the combined amount of (iii-1)+(iii-2)) of component (iii) preferably 5 weight % extremely 70 weight %, preferably 10 weight % are to 60 weight %, preferably 10 weight % to 50 weight %, especially 15 weight % to 50 weights In the range of amount % (dry solid).
It is preferred that there is (methyl) acrylic polymer component (iii-2).If there is silyl ester copolymer component (iii-1), then further preferably there is (methyl) acrylic polymer component (iii-2).The weight ratio of these components can be (95-50): the component (iii-1) of (50-5), preferably (90-60): (40-10): (iii-2).Therefore, if there is (iii-1) , then preferably there is excessive component (iii-1) in both (iii-2).
Antifouling paint compositions of the invention preferably comprise at least 0.5 weight %, such as at least 1 weight %'s (dry solid) Component (iii).The upper limit of component (iii) can be 20 weight %, such as 15 weight %.
Prepare copolymer component (i) and polymers compositions (iii)
Polymerization reaction known in the art can be used and prepare polymer.It is preferable to use addition polymerizations for acrylic polymer The preparation of (addition polymerization) or chain growth polymerization.The example of suitable addition polymerization technology includes free radical Polymerization, anionic polymerisation and controlled polymerization technique appropriate.For example, can be by polymerization initiator and optional chain-transferring agent In the presence of by any one of various methods of such as polymerisation in solution, bulk polymerization, emulsion polymerization and suspension polymerisation with normal Rule mode makes monomer mixture polymerization obtain polymer by controlled polymerization technique.Coating group is being prepared using the polymer When closing object, organic solvent diluting polymer is used, preferably to obtain the polymer solution with proper viscosity.Go out from this viewpoint Hair, it is expected that using polymerisation in solution.
The example of polymerization initiator for free radical polymerization includes: azo-compound, bis- (the 2- first of such as 2,2'- azo Base propionic acid) dimethyl ester (2,2 '-azobis of dimethyl (2-methylpropionate)), bis- (the 2- methyl fourths of 2,2'- azo Nitrile), 2,2'- azo bis- (isobutyronitriles) and 1,1'- azo it is bis- (cyano cyclohexane)；And peroxide, such as peroxypivalic acid The tert-butyl ester, peroxide -2 ethyl hexanoic acid tert-butyl ester, the peroxide diethacetic acid tert-butyl ester, tert-butyl peroxyisobutyrate, two uncle of peroxidating Butyl (di-tert-butyl peroxide, di-tert-butyl peroxide), t-butyl peroxybenzoate and peroxy isopropyl base carbon Tert-butyl acrylate, t-amyl peroxypivalate, peroxide -2 ethyl hexanoic acid tert-pentyl ester, (t-amyl peroxy) hexamethylene of 1,1- bis- (1,1- Di (tert-amyl peroxy) cyclohexane) and dibenzoyl peroxide.It is used alone or with its two or more Mixture uses these compounds.
The example of organic solvent includes: aromatic hydrocarbon, such as dimethylbenzene, toluene, mesitylene；Ketone, such as methyl ethyl ketone, Methyl iso-butyl ketone (MIBK), methyl amyl ketone, methyl isoamyl ketone, cyclopentanone, cyclohexanone；Ester, such as butyl acetate, the tertiary fourth of acetic acid Ester, pentyl acetate, ethylene glycol monomethyl ether acetate (acetic acid glycol methyl ether ester, ethylene glycol methyl ether Acetate), butyl propionate, isobutyl isobutyrate；Ether, such as glycol dimethyl ether, diethylene glycol dimethyl ether, butyl oxide, two dislike Alkane (dioxane, dioxane), tetrahydrofuran；Alcohol, such as n-butanol, isobutanol, benzyl alcohol；Ether alcohol, such as butoxy second Alcohol, 1- methoxy-2-propanol；Cyclic terpene, such as (R)-4-isopropenyl-1-methyl-1-cyclohexene；Aliphatic hydrocarbon, such as white spirits (white spirit, White wine, rosin, white spirit)；And the mixture of two or more optional solvents.Be used alone or with its two The mixture of kind or more uses these compounds.Copolymer component (i) or (iii) are preferably random copolymer.
Cyclic monocarboxylic acid component (ii)
Adhesive of the invention includes at least one cyclic monocarboxylic acid.Cyclic monocarboxylic acid contains single carboxyl functional group (can be its salt form).Cyclic monocarboxylic acid can contain a ring or multiple rings (cyclic ring).Particularly, this ring It can be condensed ring.Cyclic monocarboxylic acid is preferably selected from resin acid (resin acid, resin acid), the derivative of resin acid, C6-20 Cyclic carboxylic acids and its mixture.Suitable monocarboxylic acid includes: resin acid, such as rosin acid, neoabietic acid (neoabietic Acid), dehydroabietic acid, dihydro rosin acid, tetrahydrogenated rosin acid, palustric acid (palustric acid), levopimaric acid are (left Resin acid, levopimaric acid), pimaric acid, isodextropimaric acid, sandaracopimaric acid (sandaracopimaric acid, Sandaracopimaric acid), elliotinoic acid (communic acid)；Aphthenic acids, methyl isohexenyl cyclohexene carboxylate Class such as 1- methyl -3- (4- methyl-3-pentenyl) -3- cyclohexene -1- base-carboxylic acid, 1- methyl -4- (4- methyl -3- amylene Base) -4- cyclohexene -1- base-carboxylic acid, trimethyl isobutenyl cyclohexene carboxylate class such as Isosorbide-5-Nitrae, 5- trimethyl -2- (2- methyl - 1- acrylic) -3- cyclohexene -1- base-carboxylic acid and 1,5,6- trimethyl -3- (2- methyl-1-propylene base) -4- cyclohexene -1- base - Carboxylic acid and its mixture.It is desirable that cyclic monocarboxylic acid is rosin or derivatives thereof.
Monocarboxylic acid can be used for adjusting antifouling coat from polishing performance and mechanical performance.The amount of component (ii) in adhesive It is preferred that in 10 weight % to 70 weight % (dry solid), in the range of preferably 20 weight % to 50 weight %.
It can be rosin or derivatives thereof for the rosin in the present invention, such as its salt, such as described below.Rosin The example of material includes: wood rosin (wood rosin), toll oil rosin (tall oil rosin) and gum rosin；Rosin derivative Object, such as hydrogenation and partially hydrogenated rosin, disproportionated rosin (disproportionated rosin), maleic acid modified pine Fragrant, fumaric acid modified rosin；The metal salt of rosin and rosin derivative, such as copper resinate (copper resinate), tree Resin acid zinc, calcium resinate, resin acid magnesium and such as the other materials described in WO97/44401.Preferably gum rosin and The derivative of gum rosin.
In the present invention, antifouling composition preferably comprises 0.5 weight % to 25 weight %, preferably 1 weight % to 20 weights Measure the cyclic monocarboxylic acid material of % (dry solid), the cyclic monocarboxylic acid material of preferably 3 weight % to 15 weight % (dry solid) Material.
Therefore, in an embodiment of invention adhesives, the 20 weight % to 60 of the amount of component (i) in adhesive In the range of weight % (dry solid)；
The amount of component (ii) is in the range of the 10 weight % to 70 weight % of adhesive (dry solid)；And
The amount of component (iii) is in the range of 10 weight % to 60 weight % (dry solid).
The performance of antifouling paint can be adjusted by changing the relative quantity of binder copolymer and rosin components.
Other adhesive components
Other than said components (i) to (iii), other adhesive component can be used to adjust the property of antifouling coat Energy.The example for the adhesive that can be used includes:
The ester of rosin and hydrogenated rosin, such as methyl esters, glyceride, poly(ethylene glycol) ester, pentaerythritol ester, preferably rouge The ester of rosin and hydrogenation gum rosin；
The rosin of dimerization and the rosin of polymerization；
Acid functional polymers (acid functional polymer), acidic group be bonded with monovalence organic residue two Valence metal or the divalent metal being bonded with OH residues sealing end；
Hydrophilic copolymers, such as (methyl) acrylate copolymer, such as poly- (n-vinyl pyrrolidone) copolymer With poly(ethylene glycol) copolymer；
Vinylic-ether polymer and copolymer, such as poly- (methyl vinyl ether), poly- (ethyl vinyl ether), poly- (isobutyl Base vinyl ethers), poly- (vinyl chloride -co- isobutyl vinyl ether)；
Aliphatic polyester, such as poly- (lactic acid), poly- (glycolic), poly- (3-hydroxybutyrate), gather poly- (2- hydroxybutyric acid) (4- hydroxypentanoic acid), polycaprolactone and containing selected from said units two or more units aliphatic polyester copolymer； And other condensation polymers, such as poly- oxalate (poly- oxalates, polyoxalate)；
Alkyd resin (alkyd resin) and modified alkyd resin；
Hydrocarbon resin, such as only by being selected from C5 aliphatic monomer, C9 aromatic monomer, indenes tonka-bean one monomers (indene Coumarone monomer) or terpenes or mixtures thereof at least one monomer the hydrocarbon resin that is formed of polymerization.
Acyclic monocarboxylic acid
In one embodiment, antifouling paint of the invention may include liquid C12-C24 monocarboxylic acid or its salt, that is, exist Intramolecular contains the acid or its salt of the single part-COOH.These acid " head groups " and nonpolar " tail portion base containing acid Group ", is preferably the branch of carbon atom.Monocarboxylic acid preferably only contains C, H and O atom.
Compared with the Comparative composition without acid constituents, can permit using this material improves the control leaching layer and being formed (thickness reduction).In addition, the composition containing acid constituents should show that similar polishing is horizontal, while keeping or even reducing coating Viscosity.
The component may include selected from liquid, acyclic, saturation C12-C24 monocarboxylic acid or liquid, acyclic, branching The monocarboxylic one or more monocarboxylic acids of C12-C24.Therefore, acid should not be straight chain unsaturated carboxylic acid.Preferred acid is saturation 's.
Monocarboxylic acid ideally has formula R11COOH, wherein R11For C11-23 is acyclic, alkyl or alkenyl of branching, or C11-23 is acyclic, the alkyl of saturation, straight chain or branching.It is preferred that R11It is that C11-23 is acyclic, alkyl of branching.
Most preferably, acyclic monocarboxylic acid is or mixtures thereof C12-24 fatty acid of branching.
Acid is liquid preferably under room temperature and normal pressure (23 DEG C and 1atm).
It is preferred that acid constituents is branching.The acid of branching must contain tertiary carbon atom or quaternary carbon atom in its tail groups.
It should be appreciated that many acid can be derived from natural origin, in this case, with unpack format, they are typically The mixture of acid as the different chain length with the different degrees of branching exists.The case where the acid used is the mixture of component Under, acid can have greater than 50%, preferably greater than 70%, greater than 80% or even greater than 90% the degree of branching.Here percentage Than being weight %.For example, the C18 acid constituents at least 50% degree of branching can contain the straight chain C 18 no more than 50 mass parts Sour (positive stearic acid, positive oleic acid, positive linoleic acid etc.), remaining is branch C18 acid (generally " isostearic acid ", " vaccenic acid ", " different Linoleic acid (isolinoleic acid) " etc.).
Acid is acyclic C14-C20 monocarboxylic acid in a preferred aspect, preferably acyclic C16-C20 monocarboxylic acid, Especially acyclic C16-18 monocarboxylic acid.It is preferred that carbochain contains even number of carbon atoms.Acid has low in a preferred aspect, In 350g/mol, especially less than 320g/mol, and the molecular weight of especially less than 300g/mol.
Acid, which has, in a preferred aspect, is lower than 310, especially less than 300, such as less than 290 or even lower than 280 Acid value." acid value " is well-known parameter, and is the quality (ISO of the KOH required for neutralizing one gram of acid in terms of milligram 660:2009)。
Acid, which has, in a preferred aspect, is lower than 50, such as less than 40, the iodine number lower than 30 or lower than 20.Some In embodiment, acid can be the saturated acid that iodine number is 0." iodine number " is well-known parameter, and is reacted with 100 grams of acid Iodine in gram quality (AOCS Tg1a-64).
The acid particularly preferably used includes being selected from one of group being made up of or a variety of: different palmitinic acid or different tristearin Or mixtures thereof acid.In each case, acid can be natural or synthesis.The blend of isostearic acid and different palmitinic acid can To be obtained with title Radiacid 0906, Radiacid 0907 and Radiacid 0909 from Oleon with the suitable degree of branching. The isostearic acid of special highly -branched grade is the product F ineoxocol isostearic acid N from Nissan Chemicals.
Particularly preferred acid is isostearic acid and different palmitinic acid, is had in each case greater than 70% degree of branching and low In 30 iodine number.Specially suitable component be product F ineoxocol isostearic acid N from Nissan Chemicals and Radiacid 0906, Radiacid 0907 or Radiacid 0909 from Oleon.
It should be appreciated that then any acid can be with forming salt if there is metal ion.Although inventor suggests in the form of its acid Acid is added, but acid can also be added with its salt form.Acid can also convert salifie form in the composition.It is added in composition The weight % of acid is it shall be assumed that acid is calculated in the form of its acid.
If there is other adhesive component, then this other adhesive component is desirably formed less than adhesive 10 weight % are ideally less than 5 weight % of adhesive.In a preferred embodiment, there is no other adhesive component, And adhesive is only made of component (i) to (iii).
In the preferred embodiment of adhesive, copolymer (i): the weight ratio (dry solid) of component (ii) can be In the range of 20:80 to 80:20, preferably from 30:70 to 70:30, more preferably from 40:60 to 60:40.
In the preferred embodiment of adhesive, polymer (i)+(iii): the weight ratio (dry solid) of component (ii) can With in the range of 35:65 to 85:15, preferably from 40:60 to 80:20, more preferably from 45:55 to 75:25.
In one embodiment, the component (i) of adhesive is partially or completely incompatible, i.e., it not with it is existing its Its adhesive component forms homogeneous mixture, and such as according to experimental section, (adhesive of measurement component (i), (ii) and (iii) is mixed The incompatibility of hydrophilic copolymers (i) in object) in method measured.
Adhesive composition of the invention is ideally added in antifouling paint compositions.Antifouling paint group of the invention Closing object may include adhesive of the 15 weight % to 50 weight %, and antifouling paint compositions especially of the invention include 15 weight % To the adhesive component (i) of 50 weight % to (iii).
Fungicide
Antifouling paint, which preferably additionally comprises, can prevent from being formed ocean dirt on the surface or remove ocean dirt from surface Compound.Term anti-fouling agent (antifouling agent), anti-staining agent (antifoulant), fungicide, toxic agent (toxicant) for the known compound in industry with description for preventing from forming ocean dirt on the surface.Of the invention is anti- Dirty agent is marine antifoulant.
Anti-fouling agent can be inorganic, organic metal or organic.Suitable anti-fouling agent is commercially available.
The example of inorganic anti-fouling agent includes copper and copper compound, such as: Cu oxide, such as cuprous oxide (copper (I) oxidation Object, copper (I) oxide) and copper oxide (copper (II) oxide, copper (II) oxide)；Copper alloy, such as copper-nickel close Gold；Mantoquita, such as cuprous sulfocyanide (cuprous sulfocyanide (I), copper (I) thiocyanate) and copper sulfide.Organic metal sea The example of foreign anti-fouling agent includes: 2- pyridine mercaptan -1- zinc oxide (zinc 2-pyridinethiol-1-oxide) [pyrithione Zinc]；Organocopper compound, such as 2- pyridine mercaptan -1- copper oxide [copper pyrithione], copper acetate, copper naphthenate, 8- hydroxyl quinoline Quinoline copper (copper 8-quinolinonate) [copper quinolinate (copper 8-hydroxyquinolinate, oxine-copper, oxine-copper)], nonyl benzene Copper phenolsulfonate, bis- (ethylenediamines) bis- (dodecyl benzene sulfonic acid) copper and bis- (pentachlorophenol) copper (copper bis (pentachlorophenolate))；Dithiocarbamate compound, such as bis- (dimethyl dithiocarbamic acid) zinc [ziram], ethylenebis (aminodithioformic acid) zinc [zineb], ethylenebis (aminodithioformic acid) manganese [Dai Sen Manganese] and the ethylenebis compound with zinc salt (aminodithioformic acid) manganese [Mancozeb].
The example of organic marine anti-fouling agent includes: heterocyclic compound, such as 2- (tert-butylamino) -4- (cyclopropyl ammonia Base) -6- (methyl mercapto) -1,3,5- triazine [cybutryne], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 1,2- benzene And isothiazoline -3- ketone [DCOIT], 2- (thiocyanomethylthio) -1,3- benzothiazole (2- (thiocyanato methyl mercapto) -1, 3- benzothiazole, 2- (thiocyanatomethylthio) -1,3-benzothiazole) [benzene thiophene bacterium it is clear (benthiozole, Benthiazole)], 3- benzo [b] thiophene -2- base -5,6- dihydro -1,4,2- oxa-thiazine 4- oxide [bethoxazin] With 2,3,5,6- tetra- chloro- 4- (methyl sulphonyl) pyridine；Urea derivative, such as 3- (3,4- dichlorophenyl) -1,1- dimethyl urea [diuron]；The amide and acid imide of carboxylic acid, sulfonic acid and sulfenic acids (sulphenic acids), such as N- (dichloro fluorine first sulphur Base) phthalimide, N- dichloro fluorine methyl mercapto-N', N'- dimethyl-N-phenyl sulfonamide [Euparen (dichlorofluanid)], N- dichloro fluorine methyl mercapto-N', N'- dimethyl-N-p-methylphenyl sulfonamide [tolyfluanid And N- (2,4,6- trichlorophenyl) maleimide (tolylfluanid)]；Other organic compounds, such as triphenylboron pyridine The iodo- 2-propynyl N- butyl carbamate of alkane, amine triphenylborane, 3- or salt [iodocarb], 2,4,5,6- tetrachloro isophthalic Dintrile (2,4,5,6-tetrachloroisophthalonitrile) [Bravo], p- ((diiodomethyl) sulfonyl) toluene With the bromo- 2- of 4- (4- chlorphenyl) -5- (trifluoromethyl) -1H- pyrroles -3- formonitrile HCN [bromo pyrrole carbonitrile (tralopyril)].
Other examples of marine antifoulant may is that Si Wan Ji Phosphonium halide (tetraalkylphosphonium Halogenides), guanidine derivatives；Compound containing imidazoles, such as 4- [1- (2,3- 3,5-dimethylphenyl) ethyl] -1H- imidazoles [dexmedetomidine (medetomidine)] and derivative；Macrolide, including avermectin (avermectins) and its derivative, it is all Such as ivermectin (ivermectine)；Multiple killing teichomycin (spinosyns) and derivative, such as pleocidin (spinosad)；It is peppery Green pepper element and derivative, such as phenylcapsaicin；And enzyme, such as oxidizing ferment, proteolytic activity enzyme, hemicellulose degradation activity Enzyme, cellulolytic activity enzyme, lipolysis activity enzyme and amylolytic activity enzyme.
Traditionally, antifouling paint compositions contain copper fungicide, such as metallic copper, cuprous oxide, cupric thiocyanate (thiocyanic acid It is cuprous, copper thiocyanate) etc..
Typical particle diameter distribution and 1-25 μm of average grain diameter (d50) of the cuprous oxide material with 0.1-70 μm.Oxidation is sub- Copper product can be containing stabilizer to prevent surface oxidation and agglomeration.The example of commercially available cuprous oxide includes: from Nordox The Nordox cuprous oxide paint grade (Nordox Cuprous Oxide Red Paint Grade) of AS, Nordox XLT are come From the cuprous oxide of Furukawa Chemicals Co., Ltd.；Red from American Chemet Corporation Copp 97N,Purple Copp,Lolo Tint 97N,Chemet CDC,Chemet LD；Oxygen from Spiess-Urania Change cuprous red (Cuprous Oxide Red)；From Taixing Smelting Plant Co., Ltd, (Taixing smeltery is limited Company) roasting oxidation cuprous (Cuprous oxide Roast), cuprous (the Cuprous oxide of electrolytic oxidation Electrolytic)。
A series of organic bactericides can be used instead of copper fungicide, such as 4- [1- (2,3- 3,5-dimethylphenyl) ethyl]- 1H- imidazoles [dexmedetomidine] and the bromo- 2- of 4- (4- chlorphenyl) -5- (trifluoromethyl) -1H- pyrroles -3- formonitrile HCN [bromo pyrrole carbonitrile]. Any of fungicide can be used in the present invention.
Preferred fungicide is cuprous oxide, cupric thiocyanate, zinc pyrithione, copper pyrithione, (two is thio for ethylenebis Carbamic acid) zinc [zineb], 2- (tert-butylamino) -4- (cyclopropylamino) -6- (methyl mercapto) -1,3,5- triazine [cybutryne], 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one [DCOIT], N- dichloro fluorine methyl mercapto-N', N'- bis- Methyl-N-phenyl sulfonamide [Euparen], N- dichloro fluorine methyl mercapto-N', N'- dimethyl-N-p-methylphenyl sulfonamide [press down first Bacterium spirit], 4- [1- (2,3- 3,5-dimethylphenyl) ethyl] -1H- imidazoles [dexmedetomidine], triphenylborane pyridine [TPBP] and 4- Bromo- 2- (4- chlorphenyl) -5- (trifluoromethyl) -1H- pyrroles -3- formonitrile HCN [bromo pyrrole carbonitrile].
As known in the art, the mixture of fungicide can be used, because different fungicide is dirty to different oceans Biological (marine fouling organism) is damaged to work.The mixture of generally preferable anti-fouling agent.
In one embodiment, antifouling paint compositions include cuprous oxide and/or cupric thiocyanate and one kind or more Kind selected from copper pyrithione, ethylenebis (aminodithioformic acid) zinc, the chloro- 2- octyl -4- isothiazoline -3- ketone of 4,5- bis- and The fungicide of dexmedetomidine.
In an alternative embodiment, antifouling paint is free of inorganic copper fungicide.In this embodiment it is preferred that Antimicrobial combination be related to bromo pyrrole carbonitrile with selected from zinc pyrithione, ethylenebis (aminodithioformic acid) zinc, 4,5- bis- One of chloro- 2- octyl -4- isothiazoline -3- ketone and dexmedetomidine or a variety of combinations.
In case of presence, the combined amount of fungicide can be formed coating composition up to 70 weight %, such as 4 Weight % to 60 weight %, such as 5 weight % to 60 weight %.It is depositing in a case of copper, is suitably being killed in coating composition The amount of microbial inoculum can be 20 weight % to 60 weight %.In the case where avoiding copper, lower amount, such as 0.1 weight can be used Measure % to 20 weight %, such as 0.2 weight % to 15 weight %.It should be appreciated that the amount of fungicide will be according to final use and institute Fungicide and change.
Some fungicide can be encapsulated or adsorb on a inert carrier or in conjunction with other materials to control release.These Percentage refers to the amount of existing active bactericide, therefore does not refer to any carrier used.
Other components
Other than adhesive described above and any optional component, antifouling paint compositions according to the present invention are also Optionally including it is one or more selected from other adhesives, inorganic or organic pigment, incremental agent (extender) and filler, add Add the component of agent, solvent and diluent.
Pigment, incremental agent and filler
Pigment can be or mixtures thereof inorganic pigment, organic pigment.Inorganic pigment is preferred.The example of inorganic pigment Including titanium dioxide and ferriferous oxide (iron oxide).The example of organic pigment includes phthalocyanine compound (phthalocyanine Compound), azo pigments and carbon black.
The example of incremental agent and filler is: mineral, such as dolomite, modeling stone (plastorite), calcite, quartz, again Spar, magnesite, aragonite (aragonite, aragonite), silica, wollastonite, talcum, chlorite (chlorite, chlorite), Mica, kaolin, grinding silica (ground silica) and feldspar；Synthesize inorganic compound, such as zinc oxide, trbasic zinc phosphate, Calcium carbonate, magnesium carbonate, barium sulfate, calcium silicates, the silica of grinding and precipitating silica；Polymerization and inorganic microsphere, it is such as uncoated Or the hollow and solid glass pearl of coating, uncoated or coating hollow and solid ceramic pearl, such as poly- (methyl of polymer material Methyl acrylate), poly- (methyl methacrylate -co- ethylene glycol dimethacrylate), poly- (styrene-co-ethylene glycol two Methacrylate), the porous and fine and close pearl of poly- (styrene-co-divinyl base benzene), polystyrene, poly- (vinyl chloride) (porous and compact bead)。
Preferably, there are the total amounts of incremental agent, filler and/or pigment in composition of the invention based on composition Total weight is 0 weight % to 70 weight %, more preferable 1 weight % to 60 weight %, even more preferably from 2 weight % to 50 weight %. The skilled person will understand that incremental agent and pigment content by according to the final use of existing other components and coating composition and Variation.
Dehydrating agent
Antifouling paint compositions of the invention optionally include dehydrating agent (dehydrating agent), and also referred to as water is removed Agent or desiccant.Preferably, dehydrating agent is the compound that water is removed from the composition that wherein there is water.By removing antifouling painting The moisture introduced in feed composition by raw material such as pigment and solvent, or by carboxylic acid compound and specific compound such as divalent gold Belong to the water that the reaction between oxide is formed, dehydrating agent is improved containing water reactive compounds such as silyl ester copolymer Antifouling paint compositions storage stability.The dehydrating agent and desiccant that can be used in antifouling paint compositions include it is organic and Inorganic compound.
Dehydrating agent can be the hygroscopic materials for absorbing water or water being combined into the crystallization water, commonly referred to as desiccant.It is dry The example of agent includes calcium sulfate hemihydrate, dead plaster, anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous zinc sulfate, molecular sieve And zeolite.
Dehydrating agent can be the compound chemically reacted with water.The example of the dehydrating agent reacted with water includes: ortho acid Ester, such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, three isopropyl ester of orthoformic acid, tributyl orthoformate, original 3-acetic acid methyl ester, triethly orthoacetate, ortho-acetic acid tributyl and triethyl orthopropionate；Ketal；Acetal (acetals)；Enol ether (enolethers)；Ortho-boric acid ester, such as trimethylborate, triethyl borate, triproylborate, triisopropyl borate ester, boric acid Three tert-butyl ester of tributyl and boric acid；Organosilan, such as trimethoxymethylsila,e, vinyltrimethoxysilane, phenyl three Methoxy silane, tetraethoxysilane and ethyl polysilicate.
Preferred dehydrating agent is that those of chemical reaction dehydrating agent occurs with water.Particularly preferred dehydrating agent is organosilicon Alkane.
Be preferably based on the total weight of composition, the amount of dehydrating agent in the present compositions be 0 weight % extremely 5 weight %, more preferable 0.5 weight % to 2.5 weight %, and even more preferably from 1.0 weight % to 2.0 weight %.
Solvent and diluent
It is highly preferred that antifouling composition contains solvent.The solvent is preferably volatile and preferably organic. The example of organic solvent and diluent is: aromatic hydrocarbon, such as dimethylbenzene, toluene, mesitylene；Ketone, such as methyl ethyl ketone, first Base isobutyl ketone, methyl isoamyl ketone, methyl amyl ketone, diisobutyl ketone, methyl propyl ketone, cyclopentanone, cyclohexanone；Ester, it is all As butyl acetate, tert-butyl acetate, pentyl acetate, isoamyl acetate, ethylene glycol monomethyl ether acetate, propyl propionate, butyl propionate, Isobutyl isobutyrate；Ether, such as glycol dimethyl ether, diethylene glycol dimethyl ether, butyl oxide, dioxanes, tetrahydrofuran；Alcohol, it is all Such as n-butanol, isobutanol, benzyl alcohol；Ether alcohol, such as butyl cellosolve, 1- methoxy-2-propanol；Cyclic terpene, such as d- lemon Lemon alkene；Aliphatic hydrocarbon, such as white spirits；And the mixture of optional two or more solvents and diluent.It is other The example of diluent includes water.
Preferred solvent is arsol and 1- methoxy-2-propanol, especially dimethylbenzene and aromatic hydrocarbon and 1- methoxy The mixture of base -2- propyl alcohol.
The amount of solvent is preferably as low as possible.Solvent content can be up to 50 weight % of composition, preferably of up to composition 45 weight %, such as up to 40 weight %, but can be down to 15 weight % or lower, such as 10 weight % or lower.Further It is secondary, the skilled person will understand that, solvent content will change according to the final use of existing other components and coating composition.
Alternatively, coating can be dispersed in for the organic non-of the film-forming components in coating composition or in aqueous dispersion In solvent.
Antifouling paint compositions of the invention, which should preferably have, is higher than 40 volume %, such as higher than by volume 45%, Such as higher than 50 volume %, the preferably higher than solid content of 55 volume %.
It is highly preferred that antifouling paint compositions should have lower than 500g/L, preferably shorter than 400g/L, such as less than Volatile organic compounds (VOC) content of 390g/L.(ASTM D5201-01) or measurement (US EPA method 24 can be calculated Or ISO 11890-1) VOC content.
Other additives
The example for the other additives that can be added in antifouling paint compositions is reinforcing agent, thixotropic agent, thickener, anti-settling Agent (antisettling agent, anti-settling agents), wetting agent and dispersing agent, plasticizer and stabilizer.
The example of reinforcing agent is thin slice (flakes) and fiber.Fiber includes: natural and synthesis inorfil, such as containing (phosphate is fine for silica fibre, carbon fiber, oxide fibre, carbide fibre, nitride fiber, sulphide fibres, phosphate fiber Dimension, phosphate fibres), mineral fibres；Metallic fiber；Natural and synthesis organic fiber, such as cellulose fibre, rubber Glue fiber, acrylic fiber, Fypro, polyimides, polyester fiber, polyhydrazide fiber, polyvinyl chloride fibre, poly- second Alkene fiber and other fibers described in WO 00/77102.Preferably, fiber has 25 to 2,000 μm of average length Degree and 1 to 50 μm of average thickness, wherein the ratio between average length and average thickness is at least 5.
The example of thixotropic agent, thickener and anti-settling agent is silica such as fumed silica (fumed silica), organically-modified Clay, amide waxe, polyamide wax, amide derivatives, polyethylene wax, the polyethylene wax of oxidation, hydrogenation castor oil wax, ethyl Cellulose, aluminum stearate and its mixture.
The example of plasticizer is chlorinated paraffin (chlorinated paraffins), phthalic acid ester (phthalic acid Salt, phthalates), phosphate, sulfanilamide (SN), adipate ester (adipate) and epoxidised vegetable oil.
The example for facilitating the stabilizer of the storage stability of antifouling paint compositions is carbodiimide compound, such as double (2,6- diisopropyl phenyl) carbodiimide and poly- (1,3,5- triisopropyl phenylene -2,4- carbodiimide) and in patent EP Other compounds described in 2725073.
In general, the amount of any one of these optional components can be in 0.1 weight % to 20 of antifouling composition Weight %, typically 0.5 weight % are to 20 weight %, in the range of preferably 0.75 weight % to 15 weight %.It should be understood that these The amount of optional components will change according to final use.
Antifouling paint compositions of the invention can coat (application) to the entirety on any object surface for being subjected to dirt or On part.It surface can be for good and all or intermittently in underwater (such as by tidal motion, different cargos loads or expansion). Body surface is usually the hull of ship (ship, vessel) or the surface of fixed ocean object such as oil platform or buoy. It can be by any convenient mode, such as by completing coating material (such as with brush or roller) or spray on object The coating of coating composition.In general, surface needs to be separated with seawater to allow to be coated.The coating of coating can be such as this field In conventionally known realize.
When being coated to antifouling paint on object (such as hull), the surface of object is not usually only individually to be prevented The protection of dirty coating.According to the characteristic on surface, antifouling paint can be coated directly in (application) to existing coating system.It is this Coating system may include several different types of coatings (such as epoxy resin, polyester, vinylite or acrylic acid or its mixing Object).If surface is can directly to coat new antifouling paint from the cleaning and complete nonpolluting coating previously coated, Usually as one or two coating, under special circumstances more.
Alternatively, technical staff can be from uncoated surface (such as steel, aluminium, plastics, composite material, glass fibre Or carbon fiber) start.In order to protect such surface, full coating system generally include one or two layers corrosion-inhibiting coating, one layer it is viscous Tie coating (tie-coat) and one or two layers nonpolluting coating (antifouling paint).It is familiar to those skilled in the art These coatings.
Under special circumstances, additional nonpolluting coating (paint layer, paint layer) can be coated.
Therefore, in another embodiment, the present invention provides a kind of substrates, are coated with corrosion-inhibiting coating thereon, such as Epoxy primer layer (epoxy primer), adhesive layer (tie layer) and herein definition in antifouling paint compositions.
The present invention is defined referring now to following non-limiting embodiment.
Material and method
Abbreviation Title
AMBN 2,2'- azo is bis- (2- methylbutyronitrile)
BDGMA Methacrylic acid 2- (2- Butoxyethoxy) ethyl ester
EDEGA Acrylic acid 2- (2- ethoxy ethoxy) ethyl ester
EEMA Methacrylic acid 2- ethoxy ethyl ester
MEA Acrylic acid 2- methoxy acrylate
MEMA Methacrylic acid 2- methoxy acrylate
MMA Methyl methacrylate
MPEG-MA 300 Poly(ethylene glycol) methyl ether methacrylate, Mn 300
n-BA N-butyl acrylate
PM 1- methoxy-2-propanol
THFA Tetrahydrofurfuryl acrylate
TISA Acrylic acid triisopropylsilyl ester
TISMA Methacrylic acid triisopropylsilyl ester
Solvesso 100 is purchased from Brenntag.
Measure the viscosity of polymer solution
According to ASTM D2196-15 test method A, using with LV-2 or LV-4 spindle (axis, spindle) Brookfield DV-I viscosimeter measures the viscosity of polymer at 12rpm.Before measuring by polymer temperature adjustment to 23.0 DEG C ±0.5℃。
Measure the Non-volatile content in polymer solution
The Non-volatile content in polymer solution is measured according to ISO 3251.Take out the sample of 0.5g ± 0.1g simultaneously It is 3 hours dry at 105 DEG C in ventilated drying oven.The weight of residual materials is considered as nonvolatile matter (NVM).It is non-volatile Property content of material is in terms of weight percentage.The value provided is three parallel average values.
Measure Polymer average molecular weights distribution
Pass through gel permeation chromatography (GPC) measurement & characterization polymer.Using Malvern Omnisec Resolve and Reveal system and concatenated two PLgel, 5 μm of Mixed-D columns from Agilent measure molecular weight distribution (MWD). Column is calibrated by normal calibration using narrow polystyrene standards.
Polymer solution by will be equivalent to the amount of 25mg dry polymeric, which is dissolved in 5mL THF, prepares sample.? Before sampling carries out gpc measurement, sample is kept at room temperature minimum 3 hours.Before analysis, sample passes through 0.45 μm of nylon Filter filtering.The polydispersity index (PDI) for having recorded weight average molecular weight (Mw) and being provided with Mw/Mn.
Analysis condition has been provided below:
Measure glass transition temperature
It is measured by differential scanning calorimetry (DSC) and obtains glass transition temperature (Tg).Dsc measurement is in TA It is carried out on Instruments DSC Q200.By in the applicator (spreader, applicator) with 100 μm of gap sizes Glass plate on blade coating (drawdown) prepare sample.By glass plate in air heat case (ventilated heating Cabinet 24 hours dry at 23 DEG C in) and 24 hours dry at 50 DEG C.About 10mg drying is collected from glass plate Polymer material is simultaneously transferred in aluminium dish with cover (aluminium pan).By heating-cooling-heating schedule, (- 80 DEG C extremely 120 DEG C) it measures, the rate of heat addition is 10 DEG C/min, and cooling rate is 10 DEG C/min.Blank panel is used as reference.Using coming from The Universal Analysis software data processing of TA Instruments.As defined in ASTM E1356-08, second The inflection point of the glass transition ranges of heating is recorded as the Tg of polymer.
Viscosity of the coating is measured using cone and plate viscometer
Antifouling paint is measured using the digital cone and plate viscometer at a temperature of being set in 23 DEG C according to ISO 2884-1:1999 The viscosity of composition, the viscosimeter is in 10000s-1Shear rate under work and the viscosity measurement range of 0-10P be provided.Knot Fruit is provided with the average value measured three times.
Result is shown into table 12 in table 8.
Weight measurement water absorbs in fresh water/deionized water
It is absorbed by the water in gravimetric detemination film.Coating is applied using the film applicator with 300 μm of gap sizes It overlays on the sand blasting glass plate (5.0 × 7.5cm) weighed and numbered in advance.Film is at least 1 day dry at ambient conditions, 50 It is dried overnight, is then dried under vacuum in drier 24 hours at DEG C.After drying, the glass plate for coating of weighing simultaneously is put into dress Have in the container of distilled water.In reading, compressed air rapid draing plate and coating surface are used.By plate weighing (mDirectly), then It dries 2 days at ambient conditions, then places 24 hours in vacuum desiccator, then weigh again (m to themIt is dry).It is dry The weight difference of front and back is expressed as water in percentage relative to film dry weight after exposure and absorbs.
Amount=(m that water absorbsDirectly-mIt is dry)/(mIt is dry-mHollow plate)
It is read after 34 days.Result is shown into table 12 in table 8.
Calculate the content of volatile organic compounds (VOC) in antifouling paint compositions
The content of the volatile organic compounds (VOC) of antifouling paint compositions is calculated according to ASTM D5201.
Measure the incompatibility of hydrophilic copolymers (i) in the binder combination of component (i), (ii) and (iii).
The mixture of adhesive component (i), (ii), (iii) and Irgazin Red L 3670HD is small in 10ml glass It is mixed in bottle.Ratio is given into table 7 in table 3.Bottle is mixed 3 minutes using Collomix Viba vibration and oscillation device.It will Sample places at least 24 hours at room temperature, then visual valuation incompatibility.If it is observed that the phase that at least two is different, then Think that copolymer (i) is incompatible.It is visually apparent with phases were separated that Irgazin Red L 3670HD is added.In table 3 provide result into table 7 with incompatible (I) or compatible (C).Binder combination should have consolidating for 52wt% to 57wt% Body.Dimethylbenzene: PM should be used with the weight ratio of 85:15 to 95:5.
Measure the polishing of antifouling coat in rotating disk in seawater
Reduction by measuring the film thickness of film polishes to determine.For the test, PVC disk is used.It is coated using film Coating composition is coated on disk by device with radial streak.The thickness of dry coating film is measured by surface profiler.PVC disk is installed It rotates on axis and in a reservoir, wherein seawater flows through the container.Using having already passed through filtering and temperature is adjusted to 25 DEG C ± 2 DEG C Natural sea-water.The speed of rotary shaft provides the averaging analog speed of 16 sections (in the sea/hour, knot) on disk.Take out PVC Disk is to measure film thickness.Rinsing disk simultaneously is dried at room temperature for overnight, then measuring film thickness.As a result it is given in the form of film reduction Out, i.e., the difference between initial film thickness and the thickness of given time measurement provides.
Prepare the general procedure of copolymer solution P1 to P12 and C1 to C8 (copolymer component (i))
By by 28.84 parts of dimethylbenzene and 6.75 parts of PM be added equipped with blender, reflux condenser, nitrogen inlet and into In the temperature control reaction vessel for expecting entrance, the polymer of all tests is produced in an identical manner.Reaction vessel is heated and kept At 95 DEG C.The premix of monomer, 6.57 parts of dimethylbenzene, 3.25 parts of PM and initiator are prepared, and it is small to continue 2 in a nitrogen atmosphere When 30 minutes with constant rate of speed be added reaction vessel in.After further reaction 1 hour, continue 15 minutes with constant rate of speed to anti- Answer the enhancing initiator solution of the initiator and 4.6 parts of dimethylbenzene that add after being added in container.By reaction vessel in reaction temperature Under keep again 1 hour, then cool to room temperature.Except that the reaction temperature of polymer P 4 and P6 are respectively 105 DEG C and 85 DEG C.
The general introduction of the different polymer of synthesis is given in Tables 1 and 2.The amount of ingredient is provided with parts by weight.
Prepare acrylic copolymer solution A -1 (polymers compositions (iii-2))
19.20 parts of dimethylbenzene and 7.70 parts of 1- methoxy-2-propanols are added equipped with blender, reflux condenser, nitrogen In gas entrance and the temperature control reaction vessel of feed entrance.Reaction vessel is heated and maintained at 85 DEG C.Prepare 53.80 parts of acrylic acid N-butyl, 3.40 parts of n-BMAs, 2.40 parts of methyl methacrylates, 0.40 part of methacrylic acid, 0.93 part 2, The pre-composition of bis- (the 2- methylbutyronitriles) of 2'- azo and 8.00 parts of dimethylbenzene simultaneously continues 30 minutes 2 hours under nitrogen atmosphere with constant Rate is added in reaction vessel.After further reaction 1 hour, continue 15 minutes after being added with constant rate of speed into reaction vessel The enhancing initiator solution of 0.20 part of 2,2'- azo bis- (the 2- methylbutyronitriles) and 4.00 parts of dimethylbenzene of addition.By reaction vessel It keeps 1 hour, then cools to room temperature again at the reaction temperatures.The amount of ingredient is provided with parts by weight.
The viscosity of copolymer solution A-1 is 327cP, and non-volatile content is that 61.7 weight %, Mw are that 36 200, PDI is 3.23 and Tg is -39 DEG C.
Prepare silyl ester acrylic copolymer solution A -2 (polymers compositions (iii-1))
35.00 parts of dimethylbenzene additions are anti-equipped with the temperature control of blender, reflux condenser, nitrogen inlet and feed entrance It answers in device.Reaction vessel is heated and maintained at 85 DEG C.Prepare 16.50 parts of methyl methacrylates, 3.50 parts of acrylic acid 2- first Oxygroup ethyl ester, 30.00 parts of acrylic acid triisopropylsilyl esters, 0.50 part of 2,2'- azo bis- (2- methylbutyronitriles) and 5.00 The pre-composition of part dimethylbenzene, and continue to be added in reaction vessel with constant rate of speed for 2 hours in a nitrogen atmosphere.Further reacting After 1 hour, continue bis- (the 2- methyl of 0.10 part of 2,2'- azo added after being added with constant rate of speed into reaction vessel 15 minutes Butyronitrile) and 5.00 parts of dimethylbenzene enhancing initiator solution.Reaction vessel is kept 2 hours again at the reaction temperatures.It will reaction The temperature of container rises to 120 DEG C and is kept for 30 minutes, then cools to room temperature.The amount of ingredient is provided with parts by weight.
The viscosity of copolymer solution A-2 is 152cP, and non-volatile content is 50.5 weight %, Mw 28000, and PDI is 3.61 and Tg is 35 DEG C.
Prepare silyl ester acrylic copolymer solution A -3 (polymers compositions (iii-1))
35.50 parts of dimethylbenzene additions are anti-equipped with the temperature control of blender, reflux condenser, nitrogen inlet and feed entrance It answers in device.Reaction vessel is heated and maintained at 85 DEG C.Prepare 11.83 parts of methyl methacrylates, 2.96 parts of positive fourths of acrylic acid Ester, 11.83 parts of tetrahydrofurfuryl acrylates, 32.54 parts of methacrylic acid triisopropylsilyl esters and 0.71 part of 2,2'- idol The pre-composition of nitrogen bis- (2- methylbutyronitriles), and continue to be added in reaction vessel with constant rate of speed for 2 hours in a nitrogen atmosphere.Into After single step reaction 0.5 hour, continue 0.12 part of 2, the 2'- azo added after being added with constant rate of speed into reaction vessel 20 minutes The enhancing initiator solution of bis- (2- methylbutyronitriles) and 4.50 parts of dimethylbenzene.Reaction vessel is kept to 2 small again at the reaction temperatures When.The temperature of reaction vessel is risen to 110 DEG C and is kept for 30 minutes, is then cooled to room temperature.The amount of ingredient is provided with parts by weight.
The viscosity of copolymer solution A-3 is 1275cP, and Non-volatile content 60.2w%, Mw 31000, PDI are 3.10, Tg be 46 DEG C.
Prepare the general procedure of antifouling paint compositions
Component is mixed with the ratio that table 8 is provided into table 12.It uses vibration and oscillation device (vibrational shaker) Mixture is dispersed 15 minutes in the presence of bead (diameter is about 2mm) in the paint can of 250ml.Before test by glass Glass pearl filters out.
2 comparative polymer of table is summarized
Table 4: the measurement (ingredient with gram provide) of incompatibility
Table 5: the measurement (ingredient with gram provide) of incompatibility
Table 6: the measurement (ingredient with gram provide) of incompatibility
Table 7: the measurement (ingredient with gram provide) of incompatibility
Table 9: comparison coating composition (ingredient is provided with wt%)
Table 10: coating composition (ingredient is provided with wt%)
Table 11: coating composition (ingredient is provided with wt%)
Table 12: comparison coating composition (ingredient is provided with wt%)
The combination of adhesive component (i), component (ii) and component (iii) is needed to finely tune the hydrophilic/hydrophobic balance of coating. Balance will affect coating performance, such as water absorption, polishing speed, crack resistance and viscosity of the coating.If very little (the ginseng of hydrophilic monomer See comparing embodiment C8), then polishing is slow.(implement referring to comparing in the case where component (i)+(ii) is used only in adhesive Example CP19), water absorbs higher.

Claims (20)

1. a kind of adhesive for antifouling paint compositions, includes:
(i) there are the hydrophilic copolymers of at least 0 DEG C of glass transition temperature, the hydrophilic copolymers include at least 10 weights The monomer of at least one formula (I) of % is measured,
Wherein R1It is H or CH3, and R2It is that the C3-C18 at least one oxygen or nitrogen-atoms, preferably at least one oxygen atom takes Dai Ji or R2It is poly- (aklylene glycol) chain,
With the monomer of at least one formula (II),
Wherein R1’It is H or CH3, and R2’It is C1-C20 alkyl,
The hydrophilic copolymers include the comonomer other than formula (I) or (II) less than 15 weight %；
(ii) cyclic monocarboxylic acid, such as rosin or derivatives thereof such as its salt；And
(iii) comprising at least silyl ester copolymer of the silicyl ester monomer of 15 weight % and/or comprising being less than 10 weights Measure non-hydrophilic (methyl) acrylic polymer of the monomer of the formula (I) of %.
2. adhesive according to claim 1, wherein component (iii) is three isopropyl of methacrylic acid comprising wherein monomer The silyl ester copolymer of base silyl ester or acrylic acid triisopropylsilyl ester.
3. adhesive according to claim 1 or 2, wherein the hydrophilic copolymers (i) include
(a) monomer of at least one formula (I) of 15 weight % to 65 weight %
Wherein R1It is H or CH3, and R2It is that the C3-C18 at least one oxygen or nitrogen-atoms, preferably at least one oxygen atom takes Dai Ji or R2It is poly- (aklylene glycol) chain；
(b) monomer of at least one formula (II) of 85 weight % to 35 weight %,
Wherein R1’It is H or CH3, and R2’It is C1-C8 alkyl；
The hydrophilic copolymers include the comonomer other than formula (I) or (II) less than 15 weight %.
4. adhesive according to claim 1 or 2, wherein with the amount of the component (ii) of dry solid in described adhesive In the range of 10 weight % to 70 weight %.
5. adhesive according to claim 1 or 2, wherein component (ii) is rosin or derivatives thereof such as its salt.
6. adhesive according to claim 1 or 2, wherein R2It is formula (CH2CH2O)n-R3Group, wherein R3It is C1- C10 alkyl or C6-C10 aryl substituent, and n is the integer in 1 to 6 range.
7. adhesive according to claim 1 or 2, wherein with the amount of the component (i) of dry solid the 20 of described adhesive In the range of weight % to 60 weight %.
8. adhesive according to claim 1 or 2, wherein the monomer of formula (I) be methacrylic acid 2- methoxy acrylate, Acrylic acid 2- methoxy acrylate, methacrylic acid 2- ethoxy ethyl ester, acrylic acid 2- (2- ethoxy ethoxy) ethyl ester and propylene Sour tetrahydro furfuryl ester.
9. adhesive according to claim 1 or 2, wherein the monomer of formula (II) is methyl methacrylate, metering system Sour N-butyl, 2-EHA and n-butyl acrylate.
10. adhesive according to claim 1 or 2 includes at least silicyl ester monomer of 15 weight % comprising (iii) Silyl ester copolymer and comprising less than 10 weight % formula (I) monomer non-hydrophilic (methyl) acrylic Object.
11. adhesive according to claim 1 or 2 includes non-hydrophilic (methyl) acrylic polymer (iii-2), Non-hydrophilic (methyl) acrylic polymer (iii-2) includes the monomer of the formula (I) less than 10 weight %.
12. adhesive according to claim 1 or 2 includes 10 weight % to the component with dry solid of 60 weight % (iii)。
13. adhesive according to claim 11, wherein non-hydrophilic (methyl) acrylic polymer (iii- 2) glass transition temperature is less than 0 DEG C.
14. a kind of antifouling paint compositions include adhesive according to any one of claim 1 to 13 and at least one Anti-fouling agent.
15. antifouling paint compositions according to claim 14, wherein the anti-fouling agent includes cuprous oxide and/or pyrrole Pyridine thioketones copper and/or ethylenebis (aminodithioformic acid) zinc.
16. antifouling paint compositions according to claim 14 or 15, wherein described adhesive accounts for the antifouling paint group Close the 15 weight % to 50 weight % of object.
17. a kind of for protecting object from the method for dirt, the method includes with any according to claim 14 to 16 Antifouling paint compositions coating described in is subjected at least part of the object of dirt.
18. a kind of object coated with antifouling paint compositions described according to claim 1 any one of 4 to 16.
19. object according to claim 18, wherein the object is coated with corrosion-inhibiting coating, adhesive layer and according to right It is required that antifouling paint compositions described in any one of 14 to 16.
20. object according to claim 18, wherein the object is coated with according to claim 1 any one of 4 to 16 The antifouling paint compositions, the antifouling paint compositions cover antifouling paint compositions pre-existing on substrate.
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JP7386603B2 (en) 2023-11-27
GB201718891D0 (en) 2017-12-27

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