CN109803533A

CN109803533A - Pass through the antifouling paint compositions of biocide interaction controlled release

Info

Publication number: CN109803533A
Application number: CN201780045298.XA
Authority: CN
Inventors: E·安德莱斯玛蒂奈兹; M·霍夫曼
Original assignee: Hempel AS
Current assignee: Hempel AS
Priority date: 2016-06-22
Filing date: 2017-06-22
Publication date: 2019-05-24
Also published as: WO2017220097A1; SG11201811257SA; EP3474668A4; EP3474668A1; KR20190021273A

Abstract

This application discloses a kind of solvent type antifouling paint compositions, it includes erodible non-silicone base sizing systems, one or more metalliferous biocide (such as cuprous oxide, copper pyrithione (pyrrole sulphur copper), zinc pyrithione (zinc pyrithione) and ethylenebis (zinc dithiocarbamate) (zineb), with one or more non-reacted polyoxyalkylene-modified silicone oil, especially PEG/PPG modified silicone oil, such as hydrophile-lipophile balance (HLB) value are those of 9-18.Disclosed herein as well is a kind of Ship Structures, comprising outermost from polishing antifouling coating or coating system at least part of its outer surface.

Description

Pass through the antifouling paint compositions of biocide interaction controlled release

Technical field

The present invention relates to antifouling paint compositions comprising metalliferous biocide and certain polyoxyalkylene-modified Silicone oil；The invention further relates to the coating systems for including the coating containing such metalliferous biocide and silicone oil.

Background technique

Biocide and especially metalliferous biocide such as cuprous oxide and pyrithione are commonly used in easy In the antifouling paint compositions to weather, it is based particularly on those of erodible non-silicone base sizing system.Design this One significant challenge of the coating composition of sample is that erodible nonpolluting coating forms leaching layer, which allows biology to kill Go out the free diffusing of agent.Due to the free diffusing by leaching layer, a large amount of biocide may discharge too from coating Fastly, the biocide of higher amount is thus needed to keep the antifouling activity of enough levels so as to passage at any time.

JP 2006-052284 discloses the aqueous dispersion of resin of the preparation containing three Organosilyls.The aqueous dispersion It may include silicone oil and optional biocide.Wherein silicone oil can be polyether-modified silicone oil.It is understood to water-based microemulsion It polymerize (as described in Japanese patent application), that is, polymerize the method carried out in emulsified oil droplet (50-500nm) in water.In this way Oil droplet contain it is monomer to be polymerized, and with low HLB oil in water surfactant (such as KF-945) stablize, the surfactant will Encapsulating monomer simultaneously stablizes oil-in-water emulsion.Such polymerizable aqueous will limit the size of polymer by the size of encapsulating.Moreover, Polymer will not re-form uniform film in the aqueous systems for wherein polymerizeing and preparing by it, this is molten in solvent type preparaton The feature of agent polymer, polymer.But water-based microemulsion polymer will be as by the surfactant encirclement of their emulsion polymerization Zone of dispersion and be non-uniformly distributed.

WO2015/150249A1 discloses a kind of erodible antifouling paint compositions, and it includes erodible viscous Material system, one or more anti-fouling agents and at least one silicone oil.Applied silicone oil is conventional straight chain and branched alkyl/aryl Polysiloxanes.

WO2011/076856 discloses a kind of pollution control coating composition, it includes based on polysiloxanes sizing system, one Kind or a variety of hydrophilic modifying polysiloxanes and one or more biocides.Hydrophilic modifying polysiloxanes is disclosed for promoting Into biocide dissolution and be transported to coating surface.

KR2014/0117922 discloses a kind of anti-fouling paint composition, comprising metal ester sizing, polyether-modified silicone oil and Fumed silica.

Summary of the invention

Inventor now discovered that by wherein including the polyoxyalkylene-modified silicone oil of performance described herein, again Erodible antifouling paint compositions are designed, biocide can be postponed along the free diffusing for leaching layer.This, which is provided, more has Effect ground use metalliferous biocide, thus improved by using the biocide of phase same level anti-pollution and/ Or the amount of biocide needed for reducing the identical anti-pollution of acquisition, because this controlled release will improve biocide pair for a long time The bioavilability of fouling organism.

It is without being bound to any particular theory, it is now recognized that the function of non-reacted polyoxyalkylene-modified silicone oil be with Metalliferous biocide generates interaction, and which improve anti-pollution and/or the durabilities of anti-fouling effect.Control is leached The means of rate include molecular size, total hydrophily and the compatibility with sizing of polyoxyalkylene-modified silicone oil.The latter Ke Tong Cross so-called HLB value (hydrophilic-lipophilic balance) expression.Very small molecule tends to diffusion and leaching from film and comes out, and does not reach To expected effect, and excessive molecule can change the interaction of film and water and change the leaching of required biocide.

Therefore, in a first aspect, the present invention relates to a kind of solvent type antifouling paint compositions, referring to claim 1.

The second aspect of the present invention is related to a kind of nonpolluting coating, referring to claim 11.

The third aspect of the present invention is related to a kind of nonpolluting coating system, referring to claim 12.

The fourth aspect of the present invention is related to a kind of Ship Structure, referring to claim 14.

The fifth aspect of the present invention is related to one or more non-reacted polyoxyalkylene-modified silicone oil and one or more The combined purposes of metalliferous biocide, for improving the coating comprising erodible non-silicone base sizing system The anti-pollution of composition, referring to claim 15.

Detailed description of the invention

Solvent type antifouling paint compositions

The present invention provides a kind of solvent type antifouling paint compositions, it includes:

A. erodible non-silicone base sizing system,

B. one or more metalliferous biocides, and

C. one or more non-reacted polyoxyalkylene-modified silicone oil,

Wherein, it is based on coating composition, the total amount of one or more non-reacted polyoxyalkylene-modified silicone oil is 0.05- 10% dry weight.

Usually by sizing phase, (it forms paint when dry to coating composition (sometimes referred to as " paint " or " paint composite ") Film, and therefore correspond to the continuous phase of final lacquer coat) and pigment phase (discontinuous phase corresponding to final lacquer coat).According to this The simplified understanding of kind, one or more metalliferous biocides and non-reacted polyoxyalkylene-modified silicone oil are not to connect The a part of continuous phase (sizing phase), but form a part of " pigment phase ".

In the context of the present invention, term " solvent type " is interpreted as coating composition, and wherein the component of sizing system is molten Solution in some cases, in further solidification sizing group timesharing, is formed in nonaqueous solvents, and wherein when evaporating solvent Coating corresponding to coating composition.

In a presently preferred embodiment, solvent-borne coating composition includes physics drying property sizing system, different In chemicosolidifying sizing system (seeing below) be the sizing component (i.e. individual molecule) of sizing system in dry coating with Identical form is present in wet coating composition.The molecular structure or size of sizing composition or sizing component do not change. The evaporation that coating passes through solvent completely is formed, to leave the chain of sizing molecule in the coating as winding and winding.

In another embodiment, solvent-borne coating composition includes chemicosolidifying sizing system, it is characterised in that Final sizing molecule in the paint film of dried/cured is not present in wet film.In this case, relatively small sizing component Molecule (such as monomer) participates in chemical reaction and forms biggish molecule, for example, passing through chain extension, thereby increases and it is possible to be related to handing over sizing component Connection.

In the context of the present invention, term " non-silicone base sizing system " is interpreted as antifouling paint group for meaning The sizing system in object is closed substantially free of siloxanes and polysiloxane fraction.Particularly, any organic in coating composition Silicon part (when ignoring the silicyl of any ester linkage of polyoxyalkylene-modified silicone oil and sizing) preferably accounts for sizing system Less than 5% dry weight, be, for example, less than 2% dry weight, or less than 1% dry weight, especially about 0% dry weight.It is also preferred that it is any it is such containing The component (such as siloxanes and polysiloxanes) of machine silicon is not a part of sizing main chain, but can indicate the side of sizing component main chain Base/side chain.

Sizing system

Being suitable for the invention sizing system is erodible non-silicone base sizing system.

In most of actual embodiments, non-silicone base sizing system accounts for the 25-80% solid of coating composition Volume.In preferred embodiments, non-silicone base sizing system accounts for the 20-70% solid volume of coating composition, such as 18-55% solid volume.

When being indicated with dry weight, non-silicone base sizing system usually accounts for the 18-75% dry weight of coating composition.Preferred Embodiment in, non-silicone base sizing system accounts for the 16-60% dry weight of coating composition, such as 15-40% dry weight.

Sizing system as described herein is erodible type (" from polishing ").

As used herein, term " erodible " (sometimes referred to as " from polishing ") is intended to indicate that lacquer coat (i.e. The dry film of coating composition) there should be the polishing speed of at least 1 μm of every 10000 nautical miles (18520km), according to embodiment portion " polishing speed test " specified in point determines.In preferred embodiments, polishing speed is every 10000 nautical miles 1-50 μm of (18520km), especially 1-30 μm.

The sizing of coating composition mutually forms paint film when dry, therefore corresponds to the continuous of final (drying) lacquer coat Phase.

It is contemplated that can be used as this commonly used in all erodible sizing systems in " from polishing " coating composition The sizing system of invention coating composition.It has also been found that for the relative quantity for sizing system and pigment/filler/wait, in order to obtain Will be exposed to the related appropriate polishing speed of marine environment therein with lacquer coat, may only need small improvement (optimization).

In order to illustrate the scope of the present invention of the possibility type about sizing system, it is provided below for ship and yacht Many examples of the sizing system of purposes.

Think, the following kind of component in sizing system is of special interest: nonaqueous dispersion sizing system, first silicon Alkanisation acrylate sizing system, metal acrylate salt sizing system, silylation acrylate and metal acrylate salt sizing The mixture of system, poly- oxalate sizing system, amphoteric ion sizing system, silylation acrylate, amphoteric ion sizing The mixture of system and polyester sizing system, (natural) rosin, rosin derivative, disproportionated rosin, partially polymerized rosin, hydrogenation Rosin, gum rosin are disproportionated gum rosin, acrylic resin, polyvinyl methyl ether and vinyl acetate-vinyl chloride-ethylene ternary Copolymer.

In these systems, it is believed that it is particularly interesting that rosin sizing system, nonaqueous dispersion sizing system, monosilane Change acrylate sizing system, metal acrylate salt sizing system, silylation acrylate and metal acrylate salt sizing body The mixture of system, poly- oxalate sizing system, amphoteric ion sizing system, silylation acrylate, amphoteric ion sizing body The mixture of system and polyester sizing system.

Particularly preferred sizing system is non-silicone base sizing system, and it includes be selected from abietyl sizing system, first silicon The component of alkyl acrylate sizing system, nonaqueous dispersion base sizing system and metal acrylate alkali sizing system.

For purposes of illustration, these some sizing systems are detailed further below.

Nonaqueous dispersion sizing system

Term " nonaqueous dispersion resin ", " NAD " and similar statement refer to shell-core structure comprising utilize high molecular weight Component (" shell component "), by highly polar high molecular weight resin particulate constituent (" core component ") stable dispersion in low polar solvent Non-aqueous liquid media in and obtain resin.

Nonaqueous dispersion resin can be prepared via a method which, in the method, according to conventional methods, by polymerizable alkene Belong to unsaturated monomer in the presence of shell component (dispersion stabilizer), dispersin polymerization is carried out in hydrocarbon solvent, wherein polymerizable Ethylenically unsaturated monomer dissolves in the polymer (core component) of hydrocarbon solvent and polymerizable formation insoluble in the hydrocarbon solvent, the shell Component is by the polymer that is dissolved in or swells in the solvent.

Non-aqueous dispersion figure resin used in the present invention can be resin known per se, or can be according to known tree The resin of rouge production.This non-aqueous dispersion figure resin and preparation method thereof is described in ,=for example, US 3,607,821, US 4, 147,688, US4,493,914 and US 4,960,828, Japanese patent application publication No. 29,551/1973 and Japanese Laid-Open Patent Publication In number 177,068/1982.Specifically, it can be used the various polymer substances for being dissolved in low polar solvent as composition non-aqueous dispersion The shell component of figure resin, wherein the polymer substance is described in such as 4,960,828 (Japanese Laid-Open Patent Publication number of US 43374/1989) in.

In view of the soil resistance of final lacquer coat, the shell component of such as acrylic resin or vinyl can be used.

The copolymer with highly polar ethylenically unsaturated monomer usually can be used as core component.Preferably, non-moisture The core component of granular media type resin has free acidic-group or can be by hydrolysis in the seawater at the first silicon of acidic-group Alkyl group, or combinations thereof.It is preferred that 5-75wt%, for example, the monomer of the nuclear polymer of 5-60wt% or 7-50wt% should band There are free acidic-group or silicyl ester group, or combinations thereof.Match since free acidic-group will directly affect coating Preparation, and silicyl ester group has an impact after only hydrolyzing in the seawater, therefore currently preferably has overweight free acid Property group.

The example of silicyl ester monomer is acrylic acid monosilane ester or methyl methacrylate silicon ester.

If desired, also may include the free acid groups or silicyl ester group of small percentage in shell component.

Term " free acid " group " refers to the acidic-group for covering acid form.If should be appreciated that composition in or There are suitable counter ion in environment, such acidic-group can temporarily exist in the form of salts.As illustrative example, it is contemplated that such as The such group of fruit is exposed in salt water, and some free acid groups can exist with sodium-salt form.

Preferably, the resinous acid value of non-aqueous dispersion figure resin is usually 15-400mg KOH/g, preferably 15-300mg KOH/g, such as 18-300mg KOH/g.If the total acid number of NAD resin is lower than 15mg KOH/g, the polishing speed of lacquer coat It is too low, and anti-pollution is usually undesirable.On the other hand, if total acid number is higher than 400mg KOH/g, polishing speed is too high, And thus it is likely to occur water resistance (that is, the durability of lacquer coat in the seawater) problem.(when core component and/or shell group subpackage When group containing acidic precursor, resinous acid value is the value obtained when converting acidic-group for the group by hydrolyzing).Herein " resinous acid value " be neutralize 1g resin (solid content) consumed by KOH amount (mg), indicate the resin (solid content) Acidic-group content (in the case where acidic precursor group, to pass through the content of the acidic-group hydrolyzed to form).

Recommend acidic-group and/or acidic precursor group to be included in core component, so that its content (as resinous acid value) It is at least the 80% of total resinous acid value of non-aqueous dispersion figure resin, preferably at least 90%, more preferably at least 95%.

Therefore it is usually preferred to hydrophobic shell component.In NAD resin, core component and the dry weight ratio of shell component be not special Limitation, but usually in the range of 90/10-10/90, preferably 80/20-25/75, such as 60/40-25/75.

Silylation acrylate sizing system

In another interested embodiment of the invention, the sizing system for coating composition of the present invention includes Silylation acrylate copolymer, it includes at least one side chains of the end group at least one logical formula (I):

Wherein n is 0,1,2 equal integer, and X is-C (=O)-, and R₁, R₂, R₃, R₄And R₅It is defined as follows:

When n is 0,1,2,3,4 or bigger integer, in these cases it is preferred to which n is 0-100, such as 0-50, such as 0 Or 1 or 2 or 2-15.

R₁-R₅Respectively it is identical or different group, is selected from C_1-20Alkyl (such as methyl, ethyl, propyl, butyl, naphthenic base Such as cyclohexyl), the aryl (such as substituted phenyl and substituted naphthalene) optionally replaced.The example of the substituent group of aryl is halogen Element, C_1-5Alkyl, C_1-10Alkyl-carbonyl, sulfonyl, nitro or amino.In general, R₁-R₅Respectively it is selected from C_1-8Alkyl and optionally substitution Phenyl.It is usually preferable that each alkyl has most about 5 carbon atom (C_1-5Alkyl).As described above, R₁-R₅It can be phase Same or different group.

It can be according to the monomer of end group of the description synthesis comprising formula above I in 0297505 B1 of EP.

Such monomer can with vinyl polymerizable monomers (A) combined polymerization, to obtain copolymer.Suitable vinyl polymerisable The example of monomer (A) includes methacrylate, as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-Ethylhexyl Methacrylate, 2-Hydroxyethyl methacrylate and methoxyethyl methacrylate；Acrylate, such as propylene Acetoacetic ester, butyl acrylate, 2-EHA and acrylic acid 2- hydroxyl ethyl ester；Maleate, such as dimethyl maleate and Diethyl maleate；Fumarate, such as dimethyl fumarate and diethyl fumarate；Styrene, vinyltoluene, Alpha-Methyl benzene Ethylene, vinyl chloride, vinyl acetate, butadiene, acrylamide, acrylonitrile, methacrylic acid, acrylic acid, methacrylic acid are different Norbornene ester and maleic acid.

The amount of vinyl polymerizable monomers is not higher than the 95wt%, preferably more than 90wt% of gained copolymer total weight. Therefore, the amount of the monomer of the end group comprising formula above I is at least 5wt%, particularly, at least 10wt%.

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

In another interested embodiment of the invention, the sizing system for coating composition of the present invention includes Silylation acrylate copolymer, it includes at least one side chain of the end group at least one general formula II (i.e. its The general formula I of middle n=0):

Wherein X, R₃, R₄And R₅As defined above.

The example of the monomer of end group (as shown above) with general formula II is the vinyl polymerizable monomers of sour function, As derived from propylene acid, methacrylic acid, maleic acid (preferably with single alkyl ester form of 1-6 carbon atom) or fumaric acid are (excellent Select have 1-6 carbon atom single alkyl ester form) monomer.

Therefore, suitable three organosilicon alkyls group (i.e.-Si (R shown in general formula I or II₃)(R₄)(R₅) group) and tool Body example includes trimethylsilyl, triethyl silyl, three n-propyl silylation, three normal-butyl silylation, triisopropyl silicon Alkyl, three n-pentyl silylation, three n-hexyl silylation, three n-octyl silylation, three dodecyl silylation, triphenyl silicon Alkyl, three p-methylphenyl silylation, tribenzyl silylation, three -2- isopropyl methyl silylation, tri-tert silylation, second Base dimethylsilyl, normal-butyl dimethylsilyl, diisopropyl normal-butyl silylation, n-octyl di-n-butyl silylation, Diisopropyl octadecylsilane base, dicyclohexylphenylbismuthine silylation, tert-butyldiphenylsilanyl, dodecyl diphenyl silicon Alkyl and diphenylmethylsilane base.

The specific reality of suitable methacrylic acid derivative monomer comprising the end group at least one general formula I or II Example includes (methyl) acrylic acid trimethylsilyl ester, (methyl) acrylic acid triethylsilane ester, three n-propyl of (methyl) acrylic acid Silicon ester, (methyl) acrylic acid tri isopropyl silane ester, three normal-butyl silicon ester of (methyl) acrylic acid, (methyl) acrylic acid three are different Butylsilane ester, (methyl) acrylic acid tri-tert silicon ester, three n-pentyl silicon ester of (methyl) acrylic acid, (methyl) acrylic acid Three n-hexyl silicon esters, three n-octyl silicon ester of (methyl) acrylic acid, three dodecyl silicon ester of (methyl) acrylic acid, (first Base) acrylic acid tri-phenyl-silane ester, three p-methylphenyl silicon ester of (methyl) acrylic acid, (methyl) acrylic acid tribenzyl silane Ester, (methyl) acrylic acid ethyl dimethyl-silicon alkyl ester, (methyl) acrylic acid normal-butyl dimethyl-silicon alkyl ester, (methyl) acrylic acid two Isopropyl normal-butyl silicon ester, (methyl) acrylic acid n-octyl di-n-butyl silicon ester, (methyl) acrylic acid diisopropyl are stearic Base silane ester, (methyl) acrylic acid dicyclohexylphenylbismuthine silicon ester, (methyl) acrylic acid t-butyl diphenylsilane ester and (first Base) lauryl base diphenyl silane ester.

The suitable maleic acid derivative monomer and fumarate derivative monomer of end group at least one general formula I or II Specific example include maleic acid tri isopropyl silane base methyl esters, maleic acid tri isopropyl silane base pentyl ester, the positive fourth of maleic acid three Base silane base N-butyl, maleic acid tert-butyldiphenylsilanyl methyl esters, maleic acid tert-butyldiphenylsilanyl N-butyl, richness Horse acid tri isopropyl silane base methyl esters, fumaric acid tri isopropyl silane base pentyl ester, three normal-butyl silylation N-butyl of fumaric acid, richness Horse acid tert-butyldiphenylsilanyl methyl esters and fumaric acid tert-butyldiphenylsilanyl N-butyl.

In an interested embodiment of the invention, for sizing system copolymer include have general formula I and The combination of the second comonomer B of the monomeric unit and general formula III of the end group (as described above) of II:

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

Wherein, Z is C_1-20Alkyl or aryl；Y is acryloxy group, methacryloyloxy group, Malaysia acyl-oxygen Base group or fumaroyl oxygroup group；R_AAnd R_BIndependently selected from hydrogen, C_1-20Alkyl and aryl；P is the integer of 1-25.If p > 2, then R_AAnd R_BPreferably hydrogen or CH₃, i.e., if p > 2, monomer B is preferably derived from polyoxyethylene or polyoxypropylene.If p= 1, then consider the R in monomer_AAnd R_BFor compared with macoradical, such as C_1-20Alkyl or aryl, it can also be used to purpose as described herein.As led to Shown in formula III, there is acryloxy group, methacryloyloxy group, Malaysia acyloxy group in the molecule of monomer B (preferably mono- C_1-6The form of Arrcostab) or fumaroyl oxygroup group (preferably mono- C_1-6The form of Arrcostab) as unsaturated Base (Y), and also there is alkoxy-polyoxyethylene or aryloxy group polyoxyethylene.In alkoxy-polyoxyethylene or aryloxy group polyoxy second In alkenyl group, the polyoxyethylated degree of polymerization (p) is 1-25.

The specific example of monomer B in molecule with (methyl) acryloxy group includes (methyl) methoxyethyl Ethyl ester, (methyl) ethoxyethyl acrylate, (methyl) acrylic acid propoxy ethyl, (methyl) acrylate, butoxy ethyl, (first Base) acrylic acid hexyloxy ethyl ester, methoxyl group diethylene glycol (methyl) acrylate, methoxy triethylene (methyl) acrylic acid Ester, ethoxydiglycol (methyl) acrylate and ethoxytriglycol (methyl) acrylate.

The specific example of monomer B with Malaysia acyl-oxygen group or fumaroyl oxygen groups in molecule includes maleic acid methoxyl group Ethyl N-butyl, maleic acid ethoxydiglycol methyl esters, maleic acid ethoxytriglycol methyl esters, maleic acid propoxyl group diethyl Glycol methyl esters, maleic acid butoxyethyl group methyl esters, maleic acid hexyloxyehtyl methyl esters, fumaric acid methoxy ethyl N-butyl, richness Horse acid ethoxydiglycol methyl esters, fumaric acid ethoxytriglycol methyl esters, fumaric acid butoxy diethylene glycol methyl esters, rich horse Sour butoxyethyl group methyl esters and fumaric acid hexyloxyehtyl methyl esters.

It will be understood by those skilled in the art that other vinyl monomers can be introduced into comprising there is general formula I or II (such as Shown on) end group monomeric unit gained copolymer in, or include the end with general formula I or II (as shown above) In the combined gained copolymer of the second comonomer B of the monomeric unit and general formula III (as shown above) of end group group.

For the other monomers that can be copolymerized with above-mentioned monomer, various vinyl monomers can be used, it is as discussed above Vinyl polymerizable monomers (A).

Total weight based on monomer, the preferably ratio of the monomer of the end group with general formula I or II are 1-95wt%, single The ratio of body B is 1-95wt%, and the ratio for the other monomers that can be copolymerized with it is 0-95wt%.

It is desirable that range of the molecular weight of thus obtained copolymer with Weight-average molecular meter 1,000-150,000, example Such as 3,000-100,000 range, such as in 5,000-100,000 range.

In another interested embodiment of the invention, the sizing system for coating composition of the present invention includes The combined copolymer of the second comonomer C of the monomeric unit and general formula IV of end group with general formula I or II (as described above):

Wherein, Y is acryloxy group, methacryloyloxy group, Malaysia acyloxy group or fumaroyl oxygroup Group, R₆And R₇It is C_1-12Alkyl.

As shown in formula IV, monomer C has acryloxy group, the methyl as unsaturated group (Y) in the molecule thereof Acryloxy group, Malaysia acyloxy group (preferably mono- C_1-6The form of Arrcostab) or fumaroyl oxygroup group is (preferably Mono- C_1-6The form of Arrcostab), also there is hemiacetal group.

It can be by the inclusion of vinyl monomer and alkyl vinyl ether (such as ethyl vinyl ether, propyl ethylene of carboxylic group Base ether, butyl vinyl ether, hexylvinyl ether and 2- ethylhexyl vinyl ether) or cycloalkyl vinyl ethers (such as hexamethylene Base vinyl ethers) conventional addition reaction prepare monomer C, wherein the vinyl monomer comprising carboxylic group be selected from propylene Acid, methacrylic acid, maleic acid (or its monoesters) and fumaric acid (or its monoesters).

It will be understood by those skilled in the art that other vinyl monomers can be introduced into comprising there is general formula I or II (such as Shown on) end group monomeric unit and formula IV (as shown above) second comonomer C combined gained copolymer in.

Total weight based on monomer, the preferably ratio of the monomer of the end group with general formula I or II are that 1-95wt% is (excellent Select 1-80wt%), the ratio of monomer C is 1-95wt% (preferably 1-80wt%), and the ratio for the other monomers that can be copolymerized with it is most Mostly 98wt%.

It is desirable that range of the molecular weight of copolymer with Weight-average molecular meter 1,000-150,000, preferably 3,000- 100,000 range, such as in 5,000-100,000 range.

Metal acrylate salt sizing system

In an interested embodiment of the invention, the sizing system for coating composition of the present invention includes gold Belong to acrylate copolymer, it includes at least one side chains of the end group at least one general formula V:

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

Wherein, X is-C (=O)-,-S (=O)₂,-P (=O) (OH)-；M is that chemical valence is 2 or higher metal；N is 1 Or bigger integer, condition are that n+1 is equal to metal compound valence；L is organic acid residue, and each L independently selected from:

Wherein, R₄It is monovalence organic residue or L is-OH or combinations thereof；R₃It is hydrogen or the hydrocarbon with 1-10 carbon atom Base.

The example of the monomer of end group with general formula V (as shown above) is the vinyl polymerizable monomers of sour function, Such as methacrylic acid, acrylic acid, p styrene sulfonic acid, 2- methyl -2- acrylamide propane sulfonic acid, methacrylic acid phosphorus oxygen base third The chloro- 2- acid phosphorus oxygen base propyl of base, methylacryloyl 3-, methacrylic acid phosphorus oxygen base ethyl, itaconic acid, maleic acid, maleic acid Acid anhydride, itaconic acid monoalkyl ester (such as methyl, ethyl, butyl, 2- ethylhexyl), maleic acid mono alkyl ester (such as methyl, ethyl, Butyl, 2- ethylhexyl)；Half ester (such as succinic anhydride, maleic anhydride of acid anhydrides and the polymerizable unsaturated monomer comprising hydroxyl Or the half ester of phthalic anhydride and methacrylic acid 2- hydroxyethyl ester).The above monomer copolymerizable can be obtained has one The copolymer of kind or a variety of vinyl polymerizable monomers.The example of such vinyl polymerizable monomers is methyl acrylate, methyl Methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, first Base butyl acrylate, 2-ethyl hexyl acrylate, 2-Propenoic acid, 2-methyl-, octyl ester, 2-EHA, 2-Ethylhexyl Methacrylate, Methoxyethyl methacrylate, styrene, vinyltoluene, vinylpyridine, vinyl pyrrolidone, vinyl acetate, Acrylonitrile, methacrylonitrile, dimethyl itaconate, dibutyl itaconate, two -2- ethylhexyl of itaconic acid, dimethyl maleate, Maleic acid two (2- ethylhexyl) ester, ethylene, propylene and vinyl chloride.

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

Wherein, R₄It is monovalent organic residue.Preferably, R₄It is selected from:

Wherein, R₅For hydrogen or the hydrocarbyl group with 1-20 carbon atom；R₆And R₇It each independently represents with 1-12 carbon The hydrocarbyl group of atom；R₈For the hydrocarbyl group with 1-4 carbon atom；R₉For the cyclic hydrocarbon group with 5-20 carbon atom, such as rosin Acid, palustric acid (pallustric acid), neoabietic acid, levopimaric acid, dehydroabietic acid, pimaric acid, isodextropimaric acid, Sandaracopimaric acid and Δ 8,9- isodextropimaric acid.

It can be used as the example of the compound of ligand are as follows:

(1) comprising the compound of following group:

Such as aliphatic acid, such as levulic acid；Alicyclic acid, such as aphthenic acids, chaulmoogric acid, hydnocarpic acid (hydnocarpusic acid), neoabietic acid, levopimaric acid, palustric acid,-two ring -2,2,1- heptane -2- carboxylic of 2- methyl Acid；Aromatic carboxylic acid, such as salicylic acid, cresotinic acid, α-naphthoicacid, β-naphthoic acid, p-hydroxybenzoic acid；Halogen-containing aliphatic series Acid, such as monochloro acetic acid, single fluoroacetic acid；Halogen-containing aromatic acid, such as 2,4,5- trichlorophenoxyacetic acids, 2,4- Dichlorophenoxy Guanidine-acetic acid, 3,5- dichlorobenzoic acid；Nitrogenous organic acid, such as quinoline carboxylic acid, nitrobenzoic acid, dinitrobenzoic acid, nitro Naphthalene-carboxylic acid；Lactone carboxylic acid, such as pulvinic acid, vulpinic acid；Uracil derivative, such as uracil -4- carboxylic acid, 5 FU 5 fluorouracil - 4- carboxylic acid, uracil -5- carboxylic acid；The carboxylic acid as derived from penicillin, such as ospen, ampicillin, penicillin BT, penam Acid, benzyl penicillin, penicillin 0；Rifamycin B, lucimycin, Salcormycin, chloramphenicol, variotin, Trypacidine；With the fatty acid of various synthesis.

(2) comprising the compound of following group:

Such as aminodithioformic acid dimethyl ester and other dithiocarbamates.

(3) comprising the compound of following group

Such as the aromatic compounds of sulfur-bearing, such as Neville acid, to phenyl benzene sulphonic acid, beta-naphthalenesulfonic-acid and quinoline sulphonic acid.

(4) comprising the compound of-S- group, such as compound comprising following group

(5) comprising the compound of following group

Such as various thiocarboxylic acid compounds.

(6) comprising the compound of-O- or-OH group, such as phenol, cresols, dimethlbenzene, thymol, carvacrol, Ding Zi Fragrant phenol, isoeugenol, phenylphenol, benzylphenol, guaiacol, butyl stilbene, (two) nitrophenol, nitrocresol, bigcatkin willow Sour methyl esters, benzyl salicylate, monochloro phenol, chlorophenesic acid, trichlorophenol, 2,4,6,-T, tetrachlorophenol and pentachlorophenol, chloreresol, chlorine diformazan Phenol, chlorothymol, to chlorine o cyclohexyl phenol, to chlorine neighbour's cyclopentylphenol, to chlorine neighbour's n-hexyl phenol, to chlorine neighbour's benzyl Phenol, to chlorine neighbour's benzyl metacresol and other phenols, betanaphthol, 8-hydroxyquinoline.

About metal (M), it is 2 or higher metal that any chemical valence, which can be used,.The specific example packet of suitable metal Include Ca, Mg, Zn, Cu, Ba, Te, Pb, Fe, Co, Ni, Bi, Si, Ti, Mn, Al and Sn.Preferred embodiment be Co, Ni, Cu, Zn, Mn and Te, particularly preferred Cu and Zn.When synthesizing the metalliferous copolymer, oxide, hydroxide or chloride can be used The metal of form.The copolymer used in the sizing system of coating composition of the present invention can be according to such as EP It is prepared by the description of 0471204B1, EP 0342276B1 or EP 0204456B1.The monomer of end group comprising formula above V It can be copolymerized (obtain copolymer) with other polymerizable unsaturated monomers, it is unsaturated single that any commonly employed olefinic can be used Body.The example of such monomer is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid Propyl ester, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethyl hexyl acrylate, 2-Propenoic acid, 2-methyl-, octyl ester, propylene Sour 2- ethylhexyl, 2-Ethylhexyl Methacrylate, methoxyethyl methacrylate, styrene, vinyltoluene, ethylene Yl pyridines, vinyl pyrrolidone, vinyl acetate, acrylonitrile, methacrylonitrile, dimethyl itaconate, dibutyl itaconate, Two -2- ethylhexyl of itaconic acid, dimethyl maleate, maleic acid two (2- ethylhexyl) ester, ethylene, propylene and vinyl chloride.Such as Described in EP 0779304A1, a kind of particular type of comonomer is acrylate or methacrylate, wherein alcohol residue Branch alkyl ester including large volume alkyl or soft chain segment, such as with 4 or more carbon atoms has 6 or more originals The cycloalkanes ester of son, optionally with the polyalkylene glycol mono acrylate or monomethacrylates or third of end alkyl ether group The adduct of olefin(e) acid 2- hydroxyl ethyl ester or 2-Hydroxyethyl methacrylate and caprolactone.

If desired, the monomer comprising hydroxyl can also be used, such as acrylic acid 2- hydroxy methacrylate, methacrylic acid 2- hydroxyl Ethyl ester, acrylic acid 2- hydroxy propyl ester, methacrylic acid 2- hydroxy propyl ester.

It should be noted that in generated copolymer, and not all organic acid side group is required comprising metal ester bond；If It needs, some organic acid side groups can keep unreacted free acid form.

The weight average molecular weight of metalliferous copolymer is usually 1,000-150,000, such as 3,000-100,000, preferably 5,000-60,000。

In another interested embodiment of the invention, the coating composition, which further includes, a certain amount of to be had Machine ligand, so that the match ratio of ligand and metal, at least equal to 1:1, the organic ligand is selected from aromatic nitro compound, nitrile, urea Compound, alcohol, phenol, aldehyde, ketone, carboxylic acid and organosulfur compound, to make copolymer defined above and organic ligand original position shape At oligometric comples.

The example that can be used to form the unitary organic acid of the heterozygosis salt includes monocarboxylic acid, as acetic acid, propionic acid, butyric acid, Lauric acid, stearic acid, linoleic acid, oleic acid, aphthenic acids, monoxone, fluoroacetic acid, rosin acid, phenoxy acetic acid, valeric acid, Dichlorophenoxy Acetic acid, benzoic acid or naphthoic acid；With single sulfonic acid, such as benzene sulfonic acid, p-methyl benzenesulfonic acid, dodecyl benzene sulfonic acid, naphthalene sulfonic acids or to benzene Base benzene sulfonic acid.

Preferred method for producing polymerization heterozygosis salt is had been disclosed in Japan Patent Kokai No.16809/1989.

Silicyl-metal acrylate salt mixture

Another interested example of interested sizing is based on acrylic acid monosilane ester monomer (as further above Those of description) and metal acrylate salt monomer those of (as further described above) sizing.Such sizing have with The backbone segments of lower general formula:

And it is described in such as KR 20140117986.

Poly- oxalate sizing

Another example of interested sizing is viscous based on poly- oxalate as disclosed in WO 2015/114091 Material.

Amphoteric ion sizing and mixture with acrylic acid monosilane ester

The example of another interested sizing is as disclosed in WO 2004/018533 and WO 2016/066567 It may be with the polymer binder of the zwitterionic monomer in conjunction with acrylic acid monosilane ester monomer based on having.

Polyester sizing

Another example of interested sizing is the sizing based on polyester as disclosed in WO 2014/010702.

Abietyl sizing system

Another interested sizing system may be based on the sizing system of rosin and/or rosin derivative, may be with Any aforementioned sizing system combinations.

The example of the component of such abietyl sizing system is rosin, rosin derivative, such as the metal salt of rosin, i.e. resin Acid esters.

Term " rosin ", " resinate " etc. refer to gum rosin, B, C, D, E, F, FF, G, H, I, J, K, L, M, N, W-G, W- W grades of wood rosins (defining by 0509 standard of ASTM), former rosin, hard pine is fragrant, Huang leaching rosin (yellow dip rosin), NF wood Rosin, toll oil rosin or rosin (colophony) or rosin (colophonium).Term " rosin " and " resinate " etc. Also refer to the rosin of the modification including suitable type, will especially reduce the oligomeric of the amount for being conjugated non-aromatic double bond；Hydrogenation, dehydrogenation add Hydrogen/disproportionation/disproportionation etc..It should be appreciated that the further sizing component of the group may include polymer toughener, in WO97/44401 Those of be usually specifically defined, the document is incorporated herein by reference.

When being indicated with dry weight, usual abietyl sizing system accounts for the 5-30% dry weight of coating composition.Preferred real It applies in scheme, non-silicone base sizing system accounts for coating composition 8-25%, such as 10-25% dry weight.

In most of actual embodiments, abietyl sizing system accounts for the 10-50% solid volume of coating composition. In preferred embodiments, non-silicone base sizing system accounts for the 12-45% solid volume of coating composition, such as 15- 40% solid volume.

Other sizing components

Above-mentioned sizing system (such as nonaqueous dispersion sizing system, silylation acrylate sizing system and various mixed Close object) it can wherein include (a part as sizing system) one or more other sizing components.It should be appreciated that mentioning below To sizing component can also be separately formed sizing system, referring to the general introduction of sizing system.

The example of these other sizing components are as follows: oil, such as linseed oil and its derivative, castor oil and its derivative, Soybean oil and its derivative；With other polymers sizing component, such as saturated polyester resin；Polyvinyl acetate, polyvinyl alcohol Butyrate, polyvinyl chloride-acetic acid esters, the copolymer of vinyl acetate and vinyl isobutyl ether；Vinyl chloride；Vinyl chloride and ethylene The copolymer of base isobutyl ether；Alkyd resin or the alkyd resin of modification；Hydrocarbon resins, such as petroleum distillate condensate；Chlorination Polyolefin, such as chlorinated rubber, haloflex, chlorinated polypropylene；Styrol copolymer, such as phenylethylene/butadiene copolymerization Object, styrene/methacrylic acid ester and phenylethylene ethylene/propenoic acid ester copolymer；Acrylic resin, such as methyl methacrylate, The homopolymer of ethyl methacrylate, n-BMA, Isobutyl methacrylate and Isobutyl methacrylate and Copolymer；Hydroxy acrylate copolymer；Polyamide, it is such as poly- based on dimer (fatty acid) yl (such as dimerization ready denier oil acid) Amide；Thermoprene；Epoxy-ester；Epoxy polyurethane；Polyurethane；Epoxy polymer；Hydroxy polyethers resin；Polyamines resin etc., with And their copolymer.

These other sizing components usually account for 0-25% weight in wet base, such as 5-20% weight in wet base.

Metalliferous biocide

Another important component of coating composition of the present invention is one or more metalliferous biocides.

In the context of the present invention, term " biocide ", which refers to, is destroyed by chemistry or biological means, is prevented, made Its active material that is harmless, preventing its effect or otherwise apply control action to any harmful organism.

The illustrative example of metalliferous biocide be selected from metalliferous organic-biological agent for killing those, such as gold Category-dithiocar-bamate (such as bis- (aminodithioformic acid) zinc of bis- (dimethyl dithiocarbamic acid) zinc, ethylene- Complex compound between bis- (aminodithioformic acid) manganese of (zineb), ethylene-and these substances)；Bis- (1- hydroxyls -2 (1H) - Pyridine thiosulfuric acid-O, S)-copper (copper pyrithione)；Acrylic acid copper；Bis- (1- hydroxyl -2 (1H)-pyridine thiosulfuric acid-O, S) - Zinc (zinc pyrithione)；Phenyl (double pyridyl groups)-bismuth dichloride；It is raw with metalliferous lithotroph agent for killing, such as metal Object agent for killing, such as copper oxide (I), cuprous oxide and metallic copper, copper metal alloy, such as copper-nickel alloy, such as copper bronze；Metal salt, Such as cuprous sulfocyanide, basic copper carbonate, Kocide SD, barium metaborate, copper chloride, silver chlorate, silver nitrate and copper sulfide；With N- ring Hexyl diazonium two dislikes pairing copper.

Its currently preferred example is that the biocide comprising copper and the biocide comprising zinc, especially oxidation are sub- Copper, copper pyrithione, zinc pyrithione and zinc ethylene bisdithiocarbamate (zineb).

In general, the amount of metalliferous biocide is usually the 3-65% of coating composition, such as 5-60%, such as 10-60% or 15-60% or 15-40% or 20-60% dry weight.It is indicated with solid volume, metalliferous biocide Amount is usually the 3-45% of coating composition, such as 5-40%, such as 7-38% or 10-35% or 15-35% solid volume.

In another embodiment of special interest, metalliferous biocide includes metalliferous lithotroph Agent for killing, especially cuprous oxide.In this embodiment, the amount of the biocide (especially cuprous oxide) is usually to apply The 3-65% of feed composition, such as 5-60%, such as 10-60% or 15-60% or 15-40% or 20-60% dry weight.With Solid volume indicates that the amount of the biocide (especially cuprous oxide) comprising inorganic metal is usually the 3- of coating composition 45%, such as 5-40%, such as 7-38% or 10-35% or 15-35% solid volume.

In another embodiment of special interest, metalliferous biocide only includes metalliferous organic life Object agent for killing.In this embodiment, the total amount of metalliferous organic-biological agent for killing is usually the 0.25- of coating composition 30%, such as 0.5-25%, such as 0.75-20% or 1-15%, or even 2-12% dry weight.It is indicated with solid volume, containing gold The amount of the organic-biological agent for killing of category is usually coating composition 0.5-15%, such as 1-12%, such as 2-10% or 4-9% Solid volume.

In another embodiment of special interest, metalliferous biocide is copper pyrithione and/or pyrrole Pyridine thioketones zinc.In this embodiment, the total amount of copper pyrithione and zinc pyrithione is usually the 0.25- of coating composition 30%, such as 0.5-25%, such as 0.75-20% or 1-15%, or even 2-12% dry weight.It is indicated with solid volume, pyridine The total amount of thioketones copper and zinc pyrithione is usually the 0.5-15% of coating composition, such as 1-12%, such as 2-10% or 4- 9% solid volume.

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

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

In another embodiment of special interest, metalliferous biocide is ethylenebis dithiocarbamates Zinc formate (zineb).In this embodiment, the amount of zinc ethylene bisdithiocarbamate (zineb) is usually coating The 1-30% of composition, such as 2-20%, such as 3-15% or 4-10%, or even 5-15% dry weight.With solid volume table To show, the total amount of zinc ethylene bisdithiocarbamate (zineb) is usually the 1-30% of coating composition, such as 2-20%, Such as 3-15% or 4-10% or 5-15% solid volume.

In some embodiments, wherein metalliferous biocide be cuprous oxide and it is one or more it is other containing gold The combination of the biocide of category, the total amount of biocide are usually the 3-65% of coating composition, such as 5-60%, such as 10-60% or 15-60%, or even 20-60% dry weight.It is indicated with solid volume, cuprous oxide other contains with one or more The amount of the biocide combination of metal is usually the 3-45% of coating composition, such as 5-40%, such as 7-38% or 10- 35% or 15-35% solid volume.

It should be appreciated that metalliferous biocide can be combined with one or more nonmetallic biocides, it is described Nonmetallic biocide such as heterocyclic nitrogen compounds, such as 3a, the different Yin of 4,7,7a- tetrahydro -2- ((trichloromethyl)-is thio) -1H- Diindyl -1,3 (2H)-diketone, pyridine-triphenylborane, 1- (2,4,6- trichlorophenyl) -1H- pyrroles -2,5- diketone, 2,3,5,6- Four chloro- 4- (methyl sulphonyl)-pyridines, 2- methyl thio -4- tert-butylamino -6- cyclopropylamino-s-triazine and quinoline spread out Biology；Heterocyclic sulfur compounds, such as 2- (4- thiazolyl) benzimidazole, the chloro- Kathon of 4,5- bis-, 4, Chloro- -3 (the 2H)-isothiazoline of 2- octyl of 5- bis-, 1,2-benzisothiazolin-3-one and 2- (sulphur Cyano methyl is thio)-benzothiazole；(RS) -4- [1- (2,3- 3,5-dimethylphenyl) ethyl] -3H- imidazoles (Medetomidine,) and the bromo- 2- of 4- (4- chlorphenyl) -5- (trifluoromethyl) -1H- pyrroles's -3- carbon nitrile (Tralopyril,)；Urea derivative, such as N- (1,3- bis- (methylol) -2,5- dioxo -4- imidazolinyls)-N, bis- (the hydroxyl first of N ' - Base) urea and N- (3,4- dichlorophenyl)-N, N- dimethyl urea, N, N- dimethyl chloride phenyl urea；The acyl of carboxylic acid, sulfonic acid and sulfenic acids Amine compounds or imide compound, such as 2,4,6- trichlorophenyl maleimides, chloro- N- ((dimethylamino) sulphur of 1,1- bis- Acyl group) the fluoro- N- of -1- (4- aminomethyl phenyl)-methyl sulfenamide, the bromo- 3- nitrilo--propionamide of 2,2- bis-, N- (fluorine dichloromethyl It is thio)-phthalimide, N, N- dimethyl-N '-phenyl-N '-(fluorine dichloromethyl is thio)-sulfonamide and N- hydroxymethyl formamide；Carboxylic Hydrochlorate or carboxylate, such as 2- ((the iodo- 2- propargyl of 3-) oxygroup)-ethyl alcohol carbanilate (salt) and N, N- didecyl-N- Poly- (oxygen ethyl) the propionic acid ammonium of methyl-；Amine, such as dehydroabietylamine and dimethylcocoamine；Substituted methane, such as two (2- hydroxyls-second Oxygroup) methane, 5,5 '-two chloro- 2,2 '-dihydroxydiphenyl methane and dithiocyano-methane；Substituted benzene, such as 2,4,5,6- tetra- Chloro- 1,3- benzene dicarbonitrile, the fluoro- N- phenyl first sulfenamide of 1,1- bis- chloro- N- ((dimethylamino)-sulfonyl) -1- and 1- ((two iodomethyl) sulfonyl) -4- methyl-benzene；Tetra-alkyl-phosphonium halide phosphine, such as three normal-butyl myristyl phosphonium chlorides；Guanidine is derivative Object, such as dodecyl guanidine hydrochloride；Disulphide, such as double-(dimethyl thio carbamyl)-disulphide, tetramethyl autumn Blue nurse disulphide；Compound containing imidazoles, such as dexmedetomidine (medetomidine)；2- (rubigan) -3- cyano -4- Bromo- 5- trifluoromethyl pyrpole；And its mixture.

Non-reacted polyoxyalkylene-modified silicone oil

The main component of coating composition of the present invention is one or more non-reacted polyoxyalkylene-modified silicone oil.

Term " polyoxyalkylene-modified silicone oil " refers to non-reactive silicone oil.Polyoxyalkylene-modified silicone oil is due to same point Surfactant and emulsifier are widely used as containing hydrophilic group and lipophilic group in son.By being obtained with polyalkylene oxide groups are modified Hydrophily.

Polyoxyalkylene-modified silicone oil is non-reactive, that is, select the oil make they without containing can with sizing or appoint The group of what individual sizing component reaction.Therefore, polyoxyalkylene-modified silicone oil refers to non-reacted, especially for sizing Component is non-reactive, so that polyoxyalkylene-modified silicone oil will not be covalently attached with sizing, but is freely embedded in sizing In film, wherein these silicone oil can more or less free migration in principle.Particularly, according to silicone oil further below (A), (B) and the illustrative description of the example of (C), polyoxyalkylene-modified silicone oil do not have any reactive group to sizing component.It can With receiving, silicone oil can have " function " base, for example, C-OH group, as long as they are not with any significant at room temperature Mode and surrounding air form any chemical reaction with any sizing component contained in coating composition or any additive.

The water-wet behavior of silicone oil is usually obtained by including side chain and/or terminal polyoxyalkylene chain, below will be more detailed Description.Non-reacted polyoxyalkylene-modified silicone oil is the silicone oil with polyoxyalkylene chain.

Polyoxyalkylene chain is generally selected from polyoxyethylene chain, polyoxypropylene chains and poly- (ethylene oxide -co- oxypropylene) chain.The latter Example be polyoxyethylene-block-polyoxypropylene, polyoxyethylene-block-polyoxypropylene-block-polyoxyethylene, polyoxypropylene- Block-polyoxyethylene, polyoxypropylene-block-polyoxyethylene-block-polyoxypropylene and polyoxyethylene-be random-polyoxypropylene.

It has been found that polyoxyalkylene-modified silicone oil of special interest usually has the HLB value of 4-19.5 (by embodiment Description measurement in part), especially 5-19 perhaps 6-19 or 7-19, for example, more preferable 9-18, such as 11-17.

In order to obtain suitable HLB value, preferably polyoxyalkylene chain is selected from polyoxyethylene chain, poly- (ethylene oxide -co- oxypropylene) Chain, wherein ethylene oxide (PEG) and the weight ratio of oxypropylene (PPG) are greater than 25:75, such as in the range of 95:5-25:75, example Such as 90:10-30:70, preferably 75:25-35:65, more preferable 60:40-40:60.

In a variant of the invention, polyoxyalkylene-modified silicone oil is with the polyoxyalkylene chain being grafted to thereon Siloxanes.The illustrated examples of the structure of this polyoxyalkylene-modified silicone oil are general formula (A):

Wherein

Each R¹Independently selected from C_1-5Alkyl (including linear chain or branched chain alkyl) and aryl (such as phenyl (- C₆H₅)), Especially methyl；

Each R²Independently selected from-H, C_1-4Alkyl (such as-CH₃,-CH₂CH₃,-CH₂CH₂CH₃,-CH (CH₃)₂,- CH₂CH₂CH₂CH₃), phenyl (- C₆H₅) and C_1-4Alkyl-carbonyl is (for example,-C (=O) CH₃,-C (=O) CH₂CH₃With-C (=O) CH₂CH₂CH₃), especially-H and methyl；

Each R³Independently selected from-CH₂CH₂And-CH₂CH(CH₃)-；

Each R⁴Selected from-(CH₂)_2-6-；

- x is 0-2500, and y is 1-100 and x+y is 1-2000；

- n is 0-50, and m is 0-50 and m+n is 1-70.

In the embodiment of general formula (A) above, n+m includes 3-60 repetitive unit, such as 3-50 repetitive unit, Such as 3-30 or even 4-20 repetitive unit.In another interested embodiment, n+m includes 6-40 and repeats list Member, such as 8-30 or 10-25 repetitive unit.

In a specific embodiment of general formula (A) above, it is, for example, less than 20, or less than 15 that x+y, which is less than 25,. In another embodiment, x+y includes 3-30 repetitive unit, such as 3-20 repetitive unit, for example, 3-15 or Even 4-12 repetitive unit.In another interested embodiment, x+y includes 6-20 repetitive unit, such as 8-15 A repetitive unit.

In another variant of the present invention, polyoxyalkylene-modified silicone oil is the silicon oxygen with terminal polyoxyalkylene chain Alkane.The illustrated examples of the structure of this polyoxyalkylene-modified silicone oil are general formula (B):

(B) wherein

Each R³Independently selected from-CH₂CH₂And-CH₂CH(CH₃)-；

Each R⁴Selected from-(CH₂)_2-6-；

- x is 1-2500；With

- n is 0-50, and m is 0-50 and m+n is 1-70.

In the embodiment of general formula (B) above, n+m includes 3-60 repetitive unit, such as 3-50 repetitive unit, Such as 3-30 or even 4-20 repetitive unit.In another interested embodiment, n+m includes 6-40 and repeats list Member, such as 8-30 or 10-25 repetitive unit.

In the embodiment of general formula (B) above, x includes 3-1000 repetitive unit, such as 3-200 or 5-150, Or 5-100 repetitive unit, such as 1-50 recurring unit.In another interested embodiment, x includes 3-30 weight Multiple unit, such as 3-20 repetitive unit, such as 3-15, or even 4-12 repetitive unit.In another interested reality It applies in scheme, x includes 6-20 repetitive unit, such as 8-15 repetitive unit.

In the embodiment of general formula (B) above, n+m+x includes 3-120 repetitive unit, such as 3-100 repetition Unit, such as 3-80, or even 4-50 repetitive unit.In another interested embodiment, n+m+x includes 6-40 Repetitive unit, such as 8-35 repetitive unit, such as 8-30 repetitive unit.

In another variant of the present invention, polyoxyalkylene-modified silicone oil be with terminal polyoxyalkylene chain and have connect Siloxanes of the branch to polyoxyalkylene chain thereon.The illustrative example of the structure of this polyoxyalkylene-modified silicone oil is general formula (C):

Wherein:

Each R³Independently selected from-CH₂CH₂And-CH₂CH(CH₃)-；

Each R⁴Selected from-(CH₂)_2-6-；

- x is 0-2500, and y is 1-100 and x+y is 1-2000；

- k is 0-50, and l is 0-50 and k+l is 1-50；With

- n is 0-50, and m is 0-50 and m+n is 1-50.

In the embodiment of general formula (C) above, n+m includes 3-60 repetitive unit, such as 3-50 repetitive unit, Such as 3-30 or even 4-20 repetitive unit.In another interested embodiment, n+m includes 6-40 and repeats list Member, such as 8-30 or 10-25 repetitive unit.

In the embodiment of general formula (C) above, k+l includes 3-60 repetitive unit, such as 3-50 repetitive unit, Such as 3-30 or even 4-20 repetitive unit.In another interested embodiment, k+l includes 6-40 and repeats list Member, such as 8-30 or 10-25 repetitive unit.

In the embodiment of general formula (C) above, x includes 3-1000 repetitive unit, such as 3-200 or 5-150, Or 5-100 repetitive unit, such as 1-50 recurring unit.In another interested embodiment, x includes 3-30 weight Multiple unit, such as 3-20 repetitive unit, such as 3-15, or even 4-12 repetitive unit.In another interested reality It applies in scheme, x includes 6-20 repetitive unit, such as 8-15 repetitive unit.

In the embodiment of general formula (C) above, y includes 3-1000 repetitive unit, such as 3-200 or 5-150, Or 5-100 repetitive unit, such as 1-50 recurring unit.In another interested embodiment, y includes 3-30 weight Multiple unit, such as 3-20 repetitive unit, such as 3-15, or even 4-12 repetitive unit.In another interested implementation In scheme, y includes 6-20 repetitive unit, such as 8-15 repetitive unit.

In above structure (A), (B) and (C) ,-CH₂CH(CH₃)-group can be in two kinds of possible directions Any one exists.Similarly, it should be understood that x and y times of segment random distribution or conduct usually in siloxane structure is presented Block distributed.Furthermore, it is to be understood that l and k and m and n times of group is presented usually as block distributed, but can randomly divide Cloth.

In these embodiments and variant, the polyoxyalkylene chain is preferably selected from polyoxyethylene and polyoxyethylene polyoxy third Alkene copolymer.Therefore, in above structure (A), (B) and (C), each R of two oxygen atoms is connected³Selected from-CH₂CH₂And- CH₂CH(CH₃)-。

It should be appreciated that one or more non-reacted polyoxyalkylene-modified silicone oil (if present) can be difference Type, for example, above two or more type.

Preferably, each above-mentioned polyoxyalkylene chain includes at least three repetitive unit, for example, at least 5 repetitive units.Permitted In mostly interested embodiment, the polyoxyalkylene chain includes 3-200 repetitive unit, such as 3-150 or 5-100 or 5- 80 repetitive units.In another interested embodiment, the polyoxyalkylene chain includes 3-30 repetitive unit, such as 3-20 repetitive unit, such as 3-15 or even 4-12 repetitive unit.In another interested embodiment, polyoxy Changing alkene chain includes 6-20 repetitive unit, such as 8-15 repetitive unit.

In some preferred embodiments, the number-average molecular weight (M of the polyoxyalkylene chain_n) it is 100-20000g/ Mol, such as 100-15000g/mol, especially 200-10000g/mol or 200-8000g/mol.

In other interested embodiments, the number-average molecular weight (M of the polyoxyalkylene chain_n) it is 50-2000g/ Mol, such as 50-700g/mol or even 100-700g/mol.

It is particularly interesting that those polyoxyalkylene-modified silicone oil, wherein the relative weight of polyoxyalkylene chain is polyoxygenated 1% or more (such as 1-90%) of the modified silicone oil total weight of alkene, such as 5% or more (such as 5-80%), especially 10% or more (such as 10-70%).In one embodiment, the relative weight of polyoxyalkylene chain is polyoxyalkylene-modified The 25-60% of silicone oil total weight, such as 30-50%.

In a preferred embodiment, the number-average molecular weight (M of polyoxyalkylene-modified silicone oil_n) it is 200- 100000g/mol, such as 250-75000g/mol, especially 500-50000g/mol.

In another preferred embodiment, the number-average molecular weight (M of polyoxyalkylene-modified silicone oil_n) it is 500- 20000g/mol, such as 1000-10000g/mol or 1000-7500g/mol or even 1500-5000g/mol.

It is also preferred that the viscosity of polyoxyalkylene-modified silicone oil is within the scope of 10-20000mPas, such as in 20- Within the scope of 10000mPas, especially within the scope of 40-5000mPas.

Interested commercially available non-reacted polyoxyalkylene-modified silicone oil is OFX-5103, OFX-190, OFX-5103, OFX QC2-5211, OFX-Q2-5097, OFX-Q4-3669, OFX-Q4-3667, OFX-2-86 and OFX-193 (are all from Xiameter), from BYK-331, the DBE-621 of BYK, the CMS-222 from Gelest, CoatOSil 3501, SilSurf Di 1010, Silwet 7280, CoatOSil 7210, CoatOSil 7200, CoatOSil 7602, CoatOSil 1220 (being all from Momentive), the TEGO Glide 410 from Evonik industries, the Pluronic from BASF L64, the KF945 from Shin-Etsu, and the MB30X-8 from Sekisui Plastics.

One or more non-reacted polyoxyalkylene-modified silicone oil include in the coating composition (and in final coating) Amount be 0.05-10% dry weight.In certain embodiments, one or more non-reacted polyoxyalkylene-modified silicone oil account for painting Feed composition/final coating 0.05-10% dry weight, 0.05-7% dry weight, such as 0.1-6% dry weight, especially 0.15-5% Dry weight or 0.15-4% or 0.2-3.5% or 0.1-3.2%.In certain other embodiments, one or more non-reactions The polyoxyalkylene-modified silicone oil of property accounts for the 1-10% dry weight of coating composition or final coating, such as 2-9% dry weight, especially 2- 7% dry weight or 3-7% dry weight or 3-5% dry weight or 4-8% dry weight.

If non-reacted polyoxyalkylene-modified silicone oil is present in coating composition with higher usage amount, coating will It cannot suitably dry, and tend to become liquid or wax-like, and is very rapidly erodible in water.Include The Qi Buneng of the 15% dry weight oil is dry and hardening, and just simply eats away in several weeks after plate immerses seawater.

One or more non-reacted polyoxyalkylene-modified silicone oil are usually with 0.01-40%, such as 0.05-30% solid Volume includes in the coating composition (and in final coating).In certain embodiments, one or more non-reacted polyoxies Change the modified silicone oil of alkene and account for coating composition/final coating 0.05-25% solid volume, such as 0.1-20% solid volume, Especially 0.15-15% solid volume, or be 0.15-14% or 0.2-12% or 0.5-10%.In other certain embodiment party In case, one or more non-reacted polyoxyalkylene-modified silicone oil account for coating composition or the 0.05-25% of final coating is solid Body volume, such as 0.1-20% solid volume, especially 0.15-15% solid volume, or be 0.15-14% solid volume, or 0.2-12% solid volume or 0.5-10% solid volume.

Solvent, additive, pigment and filler

The coating composition can further include solvent and additive.

Coating composition as described herein is solvent type, therefore includes solvent or solvent mixture.Solvent is non-aqueous. The example of solvent is aliphatic hydrocarbon, clicyclic hydrocarbon and aromatic hydrocarbon, such as petroleum solvent, hexamethylene, methyl iso-butyl ketone (MIBK) (MIBK), first Benzene, dimethylbenzene and diluent naphtha, ester, such as acetic acid methoxyl group propyl ester, n-butyl acetate and 2-ethoxyethyl acetate；, eight first Base trisiloxanes and its mixture.

In one embodiment, solvent is selected from aliphatic hydrocarbon, clicyclic hydrocarbon and aromatic hydrocarbon, such as petroleum solvent, hexamethylene, first Benzene, dimethylbenzene and diluent naphtha, ester, such as acetic acid methoxyl group propyl ester, n-butyl acetate and 2-ethoxyethyl acetate, prestox Trisiloxanes and its mixture, preferably boiling point are 110 DEG C or those higher solvents.

Solvent usually accounts for the 2-50% (volume) of coating composition, such as the 3-40% or 4-30% of coating composition, or 5-25% (volume).

The example of additive are as follows:

(i) non-reacted fluid, such as organopolysiloxane, such as dimethyl silicone polymer, methyl phenyl silicone, stone Oil, and combinations thereof；

(ii) surfactant, such as propylene oxide or the derivative of ethylene oxide, such as alkylphenol-ethylene oxide condensate (alkylphenol ethoxylate), the Etoxylated monoethanolamide of unsaturated fatty acid, such as linoleic ethoxylation monoethanol Amide, lauryl sodium sulfate；And soybean lecithin；

(iii) wetting agent and dispersing agent, such as M.Ash and I.Ash, " Handbook of Paint and Coating Raw Materials, Vol.1 ", 1996, Gower Publ.Ltd. are retouched in Great Britain, 821-823 and 849-851 pages Those of state.

(iv) thickener and antisettling agent (such as thixotropic agent), such as colloidal silicon dioxide, aluminium hydrosilicate (bentonite), three Aluminum stearate, aluminum monostearate, xanthan gum, chrysotile, gas-phase silica, rilanit special, organo-clay, polyamide wax And polyethylene wax；

(v) dyestuff, such as bis- (butylamino) anthraquinones of Isosorbide-5-Nitrae-and other anthraquinone derivatives, toluidine dyes etc.；With

(vi) antioxidant, such as bis- (tert-butyl) quinhydrones, bis- (tert-butyl) phenol of 2,6-, resorcinol, 4- tert-butyl Tea phenol, three (2,4- di-tert-butyl-phenyl) phosphite esters, (3- (3,5- di-tert-butyl-hydroxy phenyl) propionic acid of pentaerythrite four Ester), bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate etc..

Additive usually accounts for the 0-30% dry weight of coating composition, such as 0-15%.

Preferably, coating composition includes one or more thickeners and/or antisettling agent (such as thixotropic agent), and amount is excellent It is selected as the 0.2-10% of coating composition, such as 0.5-5%, such as 0.6-4% dry weight.

In addition, the coating composition for being used to form coating may include pigment and filler.

In the context of the present invention, pigment and filler are combined as the component that can be added in coating composition, Influence to bond properties is limited." pigment " is usually characterized by that they keep final lacquer coat opaque and not translucent, And " filler " is usually characterized by that they will not make coating not translucent, therefore will not be hidden in appointing below coating significantly What material.

The example of pigment is titanium dioxide, iron oxide red, zinc oxide, carbon black, graphite, iron oxide yellow, molybdate red, molybdic acid Huang, zinc sulphide, antimony oxide, sodium silicoaluminate, quinacridone, phthalocyanine blue, phthalocyanine green, Black Rouge, indanthrone blue, cobalt oxide aluminium, Carbazole dioxazines, chromium oxide, iso-indoles orange, bis-acetoacet-o-tolidiole, benzimidazolone, quinophthalone Huang, different Yin Diindyl quinoline ketone Huang, tetrachloroisoindolinone, quinophthalone are yellow.

The example of filler be calcium carbonate, such as calcite, dolomite, talcum, mica, feldspar, barium sulfate, kaolin, Nephelin, silica, perlite, magnesia and silica flour etc..Filler (and pigment) can also be with nanotube or fiber Form is added, and therefore, other than the example of above-mentioned filler, coating composition also may include fiber, such as WO 00/ Those of usually specifically described in 77102, the document is incorporated herein by reference.

Any pigment and/or filler usually account for the 0-60% of coating composition, such as 0-50%, preferably 5-45%, such as 5-40% or 5-35% or 0.5-25% or 1-20% dry weight.In view of the density of any pigment and/or filler, these groups Divide the 0.2-20% for usually accounting for coating composition, such as 0.5-15% solid volume.

In order to which coating composition is easy to coat (such as by spraying, brushing or roller coating technology), the viscosity of coating composition Usually 25-25000mPas, such as 150-15000mPas, especially 200-4000mPas.

Specific embodiment

In an interested embodiment, the present invention provides a kind of solvent type antifouling paint compositions, and it includes 18- The erodible non-silicone base sizing system of 40% dry weight, one or more metalliferous biologies of 20-55% dry weight kill The one or more non-reacted polyoxyalkylene-modified silicone oil for agent and the 0.2-5% dry weight of going out.

In another interested embodiment, the present invention provides a kind of solvent type antifouling paint compositions, it includes The erodible non-silicone base sizing system of 18-40% dry weight, one or more metalliferous biologies of 20-55% dry weight One or more non-reacted polyoxyalkylene-modified silicone oil of agent for killing and 0.2-5% dry weight, wherein polyoxyalkylene chain is poly- (ethylene oxide -co- oxypropylene) chain, wherein ethylene oxide (PEG) and the weight ratio of oxypropylene (PPG) are greater than 25:75, such as 95: In the range of 5-25:75, such as 90:10-30:70, preferably 75:25-35:65, more preferable 60:40-40:60.

It is abietyl sizing system, silyl acrylate with the preferred sizing system that the embodiment above is applied in combination Sizing system, nonaqueous dispersion base sizing system and metal acrylate alkali sizing system.

Nonpolluting coating

Another aspect of the invention is a kind of nonpolluting coating (sometimes referred to as " lacquer coat " or " coating "), it includes vulnerable to invading Non-silicone base sizing, one or more metalliferous biocides and the one or more non-reacted polyoxyalkylenes of erosion change The silicone oil of property.Each component is as above to the further definition of coating composition, and when allowing dry, any description, preferably It is also applied for simply representing the coating of coating composition with variant.

Preferably, nonpolluting coating includes 1-40, such as 2-30, especially 3-20g/m²One or more non-reactions Property polyoxyalkylene-modified silicone oil and 10-500, such as 15-350, such as 20-250, such as 30-200, especially 50-150g/ m²One or more metalliferous biocides.

The preparation of coating composition

Corresponding nonpolluting coating is prepared using antifouling paint compositions.

Coating composition can be prepared by any appropriate technology common in coating material production field.Therefore, it is possible to use mixed Conjunction machine, high speed disperser, ball mill, ball mill, grinder, three-roll grinder etc. mix various composition.Coating group It closes object and prepares and transport usually as one pack system or bicomponent system, the system should be just sufficiently mixed using preceding group of merging. Following filter can be used to filter for paint according to the present invention: bag filter, patron filter, line gap filter, wedge shape Line filter, metal edge filter, EGLM turnoclean filter (for example, Cuno), DELTA bacterial strain filter (such as Cuno) and Jenag Strainer filter (such as Jenag), or pass through vibration filtering.It is suitable to describe in embodiment The example of preparation method.

First optional aspect-coating system of the invention

The invention further relates to a kind of nonpolluting coating system, it includes at least first coating and second coating,

A) first coating includes erodible non-silicone base sizing system, and the first coating also includes one kind Or a variety of non-reacted polyoxyalkylene-modified silicone oil；

B) second coating includes erodible non-silicone base sizing system, and the second coating also includes one kind Or a variety of metalliferous biocides.

In the optinal plan of the main aspect of the present invention, nonpolluting coating includes 1-40, such as 2-30, especially 3-20g/ m²The one or more non-reacted polyoxyalkylene-modified silicone oil and 10-500, such as 15-350, such as 20-250, example Such as 30-200, especially 50-150g/m²One or more metalliferous biocides.

It should be appreciated that first coating and second coating are prepared on substrate as follows: being prepared on first coating Second coating.Furthermore, it is to be understood that first coating can be in already existing coating (for example, corrosion-inhibiting coating or aging is antifouling Or decontamination coating etc.) on prepare, or directly on natural substrates prepare (see below " application of coating composition " part).This Outside, although second coating is preferably outermost layer, second coating in principle can be with the other coating of outer cladding (such as finishing coat).

It is without being bound to any particular theory, it is believed that outermost coating (i.e. second coating) includes metalliferous biocidal Agent, and first coating (lower layer) contains polyoxyalkylene-modified silicone oil, then moves to outermost layer and provides and be directed to this hair The similar effect of effect described in bright main aspect.

Therefore, nonpolluting coating system includes at least first coating and second coating.Firstly, first coating and second coating (in addition to sizing system is not necessarily identical) is (appropriate in " sizing system " above, " non-reacted polyoxyalkylene-modified silicone oil " When), " solvent, additive, pigment and filler ", the part such as " biocide containing metal " (as appropriate) be described.Then, first The specific features of coating are described in following " first coating ... " part, and the specific features of second coating are following " second coating ... " partially further describes.

It will be appreciated that though first coating and second coating usually have the same or similar type relative to sizing system (or even identical), but first coating and second coating are different.Particularly, first coating and second coating at least with At least one of lower aspect is different: the i) content and/or type and ii of metalliferous biocide) it is polyoxyalkylene-modified Silicone oil content and/or type.

How to prepare the further embodiment of first coating and second coating in following " application of coating system " and It summarizes " Ship Structure " part.

The first coating of coating system

Substantially such as above-mentioned " the solvent type antifouling paint combination of coating composition for establishing the first coating of coating system Object " is partially to the description of antifouling paint, the difference is that first coating does not have (as mandatory ingredient) to include metalliferous Biocide.Otherwise, first coating is as described above, be subject to necessary modification.

In one embodiment, first coating includes:

The erodible non-silicone base sizing system of 18-40% dry weight,

One or more non-reacted polyoxyalkylene-modified siloxanes of 0.2-5% dry weight,

One or more additives, and

One or more pigment and filler.

In an above-mentioned variant, first coating further include one or more metalliferous biocides or its Allogene agent for killing, the biology of the type and amount that especially above-mentioned " metalliferous biocide " part further illustrates Agent for killing.

The second coating of coating system

Substantially such as above-mentioned " the solvent type antifouling paint combination of coating composition for establishing the second coating of coating system Object " is partially to the description of antifouling paint, the difference is that second coating does not have (as mandatory ingredient) to include polyoxyalkylene Modified silicone oil.Otherwise, second coating is as described above, be subject to necessary modification.

In one embodiment, second coating includes:

The erodible non-silicone base sizing system of 18-40% dry weight,

One or more metalliferous biocides of 20-55% dry weight,

One or more additives, and

One or more pigment and filler.

In an above-mentioned variant, second coating further includes one or more non-reacted polyoxyalkylene-modified Silicone oil, the silicon of the type and amount that especially above-mentioned " non-reacted polyoxyalkylene-modified silicone oil " part further illustrates Oil.

The application of coating composition

Coating composition of the invention is usually applied at least part substrate surface.

Term " application " is used with its common meaning in coatings industry.Therefore, " application " is by any conventional hand Duan Jinhang's, for example, passing through brushing, roller, spraying, impregnating.The commercially side of most interested " application " coating composition Formula is spraying.Therefore, coating composition is preferably sprayable.Spraying is set using Typical spray well known by persons skilled in the art It is standby to carry out.Coating is usually applied with 50-600 μm of thickness of dry film, such as 50-500 μm, such as 75-400 μm or 20-150 μm, or 30-100μm。

Moreover, (referring to ASTM D 4400-99, that is, be applied to vertically about it with appropriate film thickness for sag resistance Ability of the surface without sagging), coating composition is preferably at least 70 μm of wet-film thickness, and for example, at least 200 μm, such as extremely Few 300 μm of wet-film thickness, especially at least 600 μm, has sag resistance by preferably at least 400 μm.

Term " at least part substrate surface " refers to that coating composition can be applied to any part on surface.For being permitted For applying, coating composition is applied at least in a part of substrate (such as ship) more, and wherein surface (such as hull) can It can be contacted with water, such as seawater.

Term " substrate " refers to the solid material for applying coating composition thereon.Substrate generally comprises metal, such as steel, The polyester of iron, aluminium or glass fiber reinforcement.In most interested embodiment, substrate is metal base, especially steel substrate. In another embodiment, substrate is the polyester base material of glass fiber reinforcement.In some embodiments, substrate is ship knot At least part of the outmost surface of structure.

Term " surface " refers to the outer boundary of object with the use of its ordinary meaning.The specific example on such surface is ship The surface of oceangoing ship structure, such as ship (including but not limited to ship, yacht, motorboat, motor boat, ocean-going ship, towboat, oil tanker, container Ship and other freighters, submarine and all types of naval ships), pipeline, land and coastal waters be mechanical, various types of buildings and Object, as bridge pier, pile, bridge substructure, flotation gear, hydraulic set and structure, underwater oil well structures, fishing net and other Aquatic breeding facility, cooling equipment and buoy etc., especially suitable for hull and ship and pipeline.

The surface of substrate can be " natural " surface (such as steel surface).However, substrate is general coated with such as anticorrosive paint And/or inter coat, so that the surface of substrate is made of this coating.When it is present, (anti-corrosion and/or centre) coating usually with 100-600 μm of total thickness of dry film applies, such as 150-450 μm, such as 200-400 μm.Alternatively, substrate can have lacquer coat, Such as the antifouling paint coat or the like of abrasion.

In an important embodiment, substrate is the metal base (such as steel substrate) coated with anticorrosive paint, institute Stating anticorrosive paint is the epoxy resin-based coating of such as corrosion-proof ring, such as cured epoxy group coating or shop primer, for example, being rich in The shop primer of zinc.In another relevant embodiment, substrate is the glass fiber reinforcement coated with epoxy primer coating Polyester base material.

The coating of the main aspect of the present invention is typically used as outermost coating (i.e. surface covering), that is, is exposed to environment (for example, water Raw environment) coating.It will be appreciated, however, that the coating of the main aspect of the present invention is alternatively as layered system application, wherein Coating described in the main aspect of the present invention is coated with one or more layers one or more other coating composition, to improve to painting The control of the leaching rate of component can be leached in material.

Before coating composition is applied to Ship Structure, Ship Structure can be initially coated with paint base system, the priming paint System may include several layers, and can be any conventional primer being used in combination with the coating composition for being applied to Ship Structure System.Therefore, paint base system may include anti-corrosion primer, and being optionally followed by is one layer of adhesion promotion priming paint.

Therefore, it the invention further relates to the method for establishing nonpolluting coating system on substrate surface, comprises the following sequential steps:

A) one or more layers paint base composition is applied to the surface of the substrate, so that the substrate primed is formed,

B) one or more layers solvent type antifouling paint compositions is applied to the surface of the substrate primed, and make institute A layer dried/cured is stated, to form the nonpolluting coating as described in (main aspect) above.

In some variations of the above method, nonpolluting coating can be further coated with finishing coat.

In this way, the invention further relates to establish the method for nonpolluting coating system on substrate surface (according to the first optional side Face), it comprises the following sequential steps:

A) one or more layers solvent type antifouling paint compositions is applied to the surface of the substrate, for example, according to specific Situation can be natural substrates or the substrate already provided with one or more layers coating, and make the layer dried/cured, thus shape At as above for first coating defined in the first optional aspect, and

B) one or more layers solvent type antifouling paint compositions is applied to the surface of the first coating, and make the layer Dried/cured, to be formed as above for second coating defined in the first optional aspect.

The invention further relates to the methods (according to the first optional aspect) for establishing nonpolluting coating system on substrate surface, including Following sequential steps:

A) one or more layers paint base composition is applied to the surface of the substrate, and make the layer dried/cured, thus The substrate primed is formed,

B) one or more layers solvent type antifouling paint compositions is applied to the surface of the substrate primed, and make institute A layer dried/cured is stated, thus formed as above for first coating defined in the first optional aspect, and

C) one or more layers solvent type antifouling paint compositions is applied to the surface of the first coating, and make the layer Dried/cured, to be formed as above for second coating defined in the first optional aspect.

The invention further relates to the methods that nonpolluting coating system is established on the surface of the nonpolluting coating system of aging, including with Lower sequential steps:

A) one or more layers seal coat/midcoat layer compositions is applied to the surface of the substrate, make the layer it is dry/ Solidification, so that the substrate for applying seal coat is formed,

B) one or more layers solvent type antifouling paint compositions is applied to the surface of the substrate for applying seal coat, and Make the layer dried/cured, thus formed as above for first coating defined in the first optional aspect, and

The invention further relates to the method that nonpolluting coating system is established on the surface of the nonpolluting coating system of aging, packets Include following sequential steps:

A) one or more layers solvent type antifouling paint compositions is applied to the surface of the nonpolluting coating system of the aging, And make the layer dried/cured, thus formed as above for first coating defined in the first optional aspect, and

Ship Structure

The present invention further provides a kind of Ship Structures, " the antifouling painting comprising more than at least part of its outer surface Outermost nonpolluting coating defined in layer " part.Particularly, a part at least as the outer surface with outermost coating is described The submergence part of structure.

The present invention also provides a kind of Ship Structures, comprising above " of the invention at least part of its outer surface Outermost nonpolluting coating system defined in first optional aspect " part.Particularly, at least as the outer surface for having outermost coating A part be the structure submergence part.

The characteristic of the coating composition, the method for establishing coating on substrate surface and the coating according to Instruction described above.

In one embodiment, the nonpolluting coating system of Ship Structure can be by erosion resistant coating and antifouling painting as described herein Coating systems composition.

In an optional embodiment, the antifouling paint compositions are applied to used nonpolluting coating system surface On, for example, on used nonpolluting coating surface.

In a specific embodiment of above-mentioned Ship Structure, total thickness of dry film of erosion resistant coating is 100-600 μm, such as 150-450 μm, such as 200-400 μm；And total thickness of dry film of nonpolluting coating is 20-500 μm, such as 20-400 μm, such as 50- 300μm。

Another embodiment of Ship Structure is that the outmost surface of at least part structure is coated with nonpolluting coating System, the nonpolluting coating system includes:

The erosion resistant coating of epoxy group coating, by applying 1-4 layers, if layer 2-4 is established, total thickness of dry film is 150-400 μm； With

Nonpolluting coating (according to main aspect), by applying 1-2 layers of foundation, total thickness of dry film is 20-400 μm.

Another embodiment of Ship Structure is the outmost surface of wherein at least a part of structure coated with antifouling Coating system (the first optional aspect), it includes:

The erosion resistant coating of epoxy group coating, by applying 1-4 layers, if layer 2-4 is established, total thickness of dry film is 150-400 μm；

The first coating (referring to the first optional aspect) of nonpolluting coating, by applying 1-2 layers of foundation, total thickness of dry film is 20-400μm；With

The second coating (referring to the first optional aspect) of nonpolluting coating, by applying 1-2 layers of foundation, total thickness of dry film is 20-400μm。

Purposes

Another aspect of the present invention relates to one or more non-reacted polyoxyalkylene-modified silicone oil and one or more The combined purposes of metalliferous biocide, for improving the coating comprising erodible non-silicone base sizing system The anti-pollution of composition.

The performance of each component " sizing system ", " non-reacted polyoxyalkylene-modified silicone oil ", " solvent, addition above The part such as agent, pigment and filler ", " metalliferous biocide " describes.

General remark

Although description of the invention and claims are sometimes referred to a kind of sizing, a kind of biocide etc., but it should Understand, coating composition defined in the present invention may include one, two, or more of individual component.In such embodiment party In case, the total amount of each component should correspond to the amount defined above for each component.

The expressions such as " (s) ": compound (s), siloxanes (s), reagent (s) in expression formula there may be it is a kind of, two kinds or More kinds of individual components.

On the other hand, when using " one " is expressed, there is only a kind of (1) respective components.

It should be understood that it is compo composition when referring to coating composition.In addition, unless otherwise stated, The amount of all % solid volumes for being expressed as the coating is interpreted as the % of the compo composition (or final coating) Solid volume.

It should be appreciated that statement " % dry weight " refers to the respectively group of the dry weight based on coating or coating composition (depending on the circumstances) The percentage divided.For most of practical applications (therefore, unless otherwise indicated), when being related to final coating, " % is dry Weight " is identical as " the % dry weight " of coating composition.

Embodiment

Material

Sizing:

Chinese gum rosin comes from Arawaka Chemical Industries (China), gum rosin

Hypale CH comes from Arakawa Chemical Industries (China) Foral AX-E, comes from Eastman Chemicals (Holland), hydrogenated rosin

Acronal 9020, comes from BASF (Germany), the xylene solution of 60wt%, and acrylate is total to sizing

Synocryl 7013-SD50 comes from Archema (Spain), butanol/petroleum (1:2) solution of 50wt%, third Olefin(e) acid is total to sizing

NSP-100 comes from Nitto Kasei (Japan), solution dimethylbenzene/ethylbenzene (1:1) of 50wt%, silanization propylene Acid copolymer sizing solution

Plasticizer；The xylene solution of 45wt%,

Polyoxyethylene-modified silicone oil:

Oil 1, non-reacted polyether-modified silicone oil, HLB 10.5, PEG/PPG ratio 50/50

Oil 2, non-reacted polyether-modified silicone oil, HLB 17.0, PEG/PPG ratio 50/50

Oil 3, non-reacted polyether-modified silicone oil, HLB 13.0, PEG/PPG ratio 60/40

Oil 4, non-reacted polyether-modified silicone oil, HLB 18.6, PEG/PPG ratio 30/70

Oil 5, non-reacted polyether-modified silicone oil, HLB 15.1, PEG/PPG ratio 80/20

Oil 6, non-reacted polyether-modified silicone oil, HLB 15.4, PEG/PPG ratio 30/70

Reference oil 1:Wacker AK 1000 comes from Wacker Chemie (Germany), non-reactive silicone oil, and HLB is (uncomfortable With), PEG/PPG ratio (not applicable)

Reference oil 2:Pluronic L-35, comes from Sigma-Aldrich (), and polyoxyethylene-block-polyoxypropylene-is embedding Section-polyoxyethylene copolymer, non-reacted polyether oil, HLB (not applicable), PEG/PPG rate 50/50

Reference oil 3:Pluronic L-64 comes from BASF (Germany), polyoxyethylene-block-polyoxypropylene-block-polyoxy Ethylene copolymer, non-reacted polyether oil, HLB (not applicable), PEG/PPG rate 40/60

Reference oil 4:BlueSil FLD 550 comes from Bluestar Silicones (Spain), non-reactive silicone oil, HLB (not applicable), PEG/PPG ratio (not applicable)

Reference oil 5:BlueSil 510V100 comes from Bluestar Silicones (Spain), non-reactive silicone oil, HLB (not applicable), PEG/PPG ratio (not applicable)

Reference oil 6:OFX-5211 (is chemically equal to DC Q2-5211), comes from Xiameter (U.S.), non-reacted Polyether-modified silicone oil, HLB 12.9, PEG/PPG ratio 100/0

Reference oil 7:KF-945 comes from Shin-Etsu (Japan), non-reacted polyether-modified silicone oil, HLB 3.9, PEG/PPG ratio 100/0

Biocide:

Nordox cuprous oxide paints grade, comes from Nordox (Norway), cuprous oxide

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

Zineb Nautec comes from United Phosphorous (India), zinc ethylene bisdithiocarbamate (generation Gloomy zinc)

Solvent:

Dimethylbenzene

MIBK；Methyl iso-butyl ketone (MIBK)

Additive:

Thickener:

Bentone 38 comes from Elementis Specialties (Britain)

Wetting agent:

Nuosperse 657RD comes from Elementis Specialties (Holland)

Disperbyk 164 comes from BYK Chemie (Germany)

Antigelling agent:

DTBHQ comes from HangZhou Thomas (China), 2,5- di-tert-butyl hydroquinones

Thixotropic agent:

Aditix M 60 comes from Supercolori (Italy), modified polyethylene wax

Dehydrating agent:

Pigment and filler:

Zinc oxide Red Seal comes from Umicore (Holland)

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

Iron oxide pigment；Micronox R01 comes from Promindsa (Spain)

Casiflux F75 comes from Ankerpoort (Holland), In Natural Silicate calcium

From Lapinus Fibers BV (Holland), artificial glass Glass fiber

Method

Polishing speed test

Lab rotor test

Using with Kiil et al. (Kiil, S, Weinell, C E, Yebra, D M, Dam-Johansen, K, " Marine biofouling protection:design of controlled release antifouling paints.”In:Ng, K M,Gani,R,Dam-Johansen,K(eds.)Chemical Product Design；Towards a Perspective Through Case Studies, 23IDBN-13:978-0-444-52217-7.Part II (7), Elsevier (2006)) in Similar the rotating device measurement polishing performance and leaching performance.Described device is made of rotary rig, the rotary rig There are two coaxial cylinders for tool, and wherein (rotor, diameter 0.3m can highly rotate for 0.17m) inner cylinder.Cylinder contains immersion In the slot of about 400-500L artificial sea water (being shown in Table 1).

The slot is equipped with baffle plate to interrupt liquid flowing, thus enhances turbulent flow and can quickly mix and releases from paint vehicle The substance put, and enhance the heat transmitting from humidity control system.Purpose using two cylinders is generated close to Couette The approximation of flowing (flowing between two parallel walls, one of wall are mobile with constant speed).Rotor 25 DEG C (unless It is otherwise noted) with the operating of 20 nautical miles/hour, and pH is adjusted to 8.2 using 1M sodium hydroxide or 1M hydrochloric acid often.

Sample is prepared using projection film (3M PP2410), wherein by utilizing Doctor Blade applicator with 200 μm Spacing coating double compositions paint (Hempadur 4518, come from Hempel ' s Marine Paints A/S) prime to film Layer.Coating sample is applied with the spacing for being separated by 250 μm using Doctor Blade applicator.It, will be coated after 1 day dry Film be cut into the band of 2cm, thus taken in length (21cm) item and generate 8 1.5x2cm²Sample.By the long strip It is mounted on the rotor, and standing and drying 1 week.

After one week, start to test, and during the test, take out sample after 35,65 and 140 days, is thrown with checking Light and leaching depth.Sample is dried three days at ambient conditions, two halves is cut to later and is embedded into paraffin.Plane falls Then the inner front side of sample determines film overall thickness using optical microscopy (coatings cross-section observation) and leaches thickness degree.

Marine rotor test

Stainless steel test board (13.5x 7cm) (its curvature is that the curvature of drum-shaped roller of 1m is corresponding with diameter) is first First coat the epoxy primer (Hempadur 15553 comes from Hempel A/S) of 40-50 μm (DFT).After 24 hours, by the plate The commercial epoxy inter coat (HEMPADUR 47182 comes from Hempel A/S) of 80 μm (DFT) is coated by aerial spraying.

After drying minimum 24 hours in the lab at room temperature, applied by aerial spraying with about 150-200 μm of DFT Test coating.Before test, plate is at least 1 week dry in the lab at room temperature.Use coating layer thickness tester The original depth of (Isoscope, Fischer) measurement coating system.

Test board is fixed on the convex surface for the drum-shaped roller that diameter is 1 meter, and is rotated in the seawater, seawater be positioned at North latitude 41.13 and east longitude 1.43, the salinity at Spain, the test site Vilanovai la Geltr ú, northeast is 37-38 ‰, average The seawater that temperature is 17-18 DEG C.

Anti-pollution test

It will promote acrylic acid test board (15 × 20cm of clagging in side sandblasting²) applied first by aerial spraying Cover 80 μm (DFT) of commercial ethylene bottom oil priming paint (Hempanyl 16280 comes from Hempel ' s Marine Paints A/S). After drying minimum 24 hours in the lab at room temperature, applies test coating using scraper type spreader, be condensed applicating implement Having film width is four gap sizes of 80mm.Apply one layer of coating with 90-100 μm of DFT.After at least 72 hours dry, Test board is fixed on the top of the shelf and is immersed in seawater.

It is tested in Spain northeast Vilanova i la Geltr ú

In the test site, it is 37-38 ‰ that plate, which is immersed salinity, and mean temperature is in 17-18 DEG C of seawater.Every 1-12 Week plate is checked, and the grade according to shown in table 2 assesses anti-pollution.For being always stained for algae and type of animal Provide a score.

It is tested in Singapore

In the test site, it is 29-31 ‰ that plate, which is immersed salinity, and temperature is in 29-31 DEG C of seawater.Every 1-12 weeks, Plate is checked, and the grade according to shown in table 2 assesses anti-pollution.Algae and being always stained for type of animal are provided One score.

The measurement of HLB value

HLB (hydrophile-lipophile balance) value of polyoxyalkylene-modified silicone oil is measured according to Griffin method:

HLB value=20*M_h/M

Wherein M_hFor the weight of (polyoxyalkylene) hydrophilic in molecule group, and wherein M is the weight of entire molecule.

The preparation of coating composition for test example

Coating composition is prepared according to standardization program.In organic solvent by sizing initial dispersion, then be added part or Whole additives such as thixotropic agent etc., is eventually adding part or all of pigment such as zinc oxide, fiber etc., in the Diaf that the impeller disk is housed It is mixed on dissolvers.Then, it is added remaining pigment such as cuprous oxide, zinc ethylene bisdithiocarbamate (zineb), And start the temperature-activated that may need its any component (such as thixotropic agent).Finally by coating composition and remaining addition Agent and sizing mixing, and its rheological characteristic is adjusted by finally adding remaining organic solvent.

In general, mixing and grinding the solid component of coating composition.Alternatively, can add in initial or later additive Add and polyoxyalkylene-modified silicone oil is added in step.

Coating composition can be used as one pack system paint preparation, or be prepared by mixing two or more components, such as Two kinds of premixs, a kind of premix comprising one or more resins and a kind of premix comprising one or more curing agent Close object.

It should be appreciated that statement " % dry weight " refers to the respectively group of the dry weight based on coating or coating composition (depending on the circumstances) The percentage divided.For most of practical applications (therefore, unless otherwise indicated), when being related to solidify coating, " % is dry Weight " is identical as " the % dry weight " of coating composition.

Test example

The effect of oil is added under the biocide of different level:

Embodiment 1-9 shows the effect that polyoxyalkylene-modified silicone oil is added under the biocide of different level. Embodiment 1-3, embodiment 4-6 and embodiment 7-9 respectively show and the coating composition phase without polyoxyalkylene-modified silicone oil Than adding polyoxyalkylene-modified silicone oil and providing better performance to coating composition.

The effect of polyoxyalkylene-modified silicone oil is added in various sizings:

Embodiment 10-16 shows the polyoxy that a small amount of (0.5-2.5wt.%) is added into the sizing of rosin and acrylate Change the effect of the modified silicone oil of alkene.Than not polyoxyalkylene-modified silicone oil adding polyoxyalkylene-modified silicone oil on a small quantity Composition provide better performance.Embodiment 14 lacks the biocide of 2 weight %, but shows and reference implementation example 13 identical performances.

Embodiment 17-18, which is shown, adds a small amount of (2.5wt%) into the sizing of rosin and silylation acrylate The effect of polyoxyalkylene-modified silicone oil.It is more polyoxyalkylene-modified than not adding polyoxyalkylene-modified silicone oil on a small quantity The composition of silicone oil provides better performance.

Embodiment 19-20, which is shown, adds a small amount of (1-2.5wt%) into the sizing of rosin and silylation acrylate Polyoxyalkylene-modified silicone oil effect.It is more polyoxyalkylene-modified than not adding polyoxyalkylene-modified silicone oil on a small quantity The composition of silicone oil provide better performance.

Embodiment 22-30 shows the polyoxyalkylene-modified silicone oil that 5wt% is added into following various sizing systems Effect: abietyl sizing system, nano acrylic ester base sizing system and silyl acrylate base sizing system.Addition is poly- The modified silicone oil of oxyalkylene provides better performance than the composition of not polyoxyalkylene-modified silicone oil.

Embodiment 31-37 shows the effect of polyoxyalkylene-modified silicone oil under different oil levels.In Spain and newly Add slope, oil has positive influence under different level.

For showing the reference model paint of the effect of different polyoxyalkylene silicone oil:

The oil listed in the test example 40-53 for adding 1wt% or 0.5wt% into these models paint.

Embodiment 40-52 shows polyoxyalkylene-modified silicone oil (oily 1-6) than unmodified silicone oil (reference oil 1,4 and 5) The polyoxyalkylene oily (reference oil 2 and 3) of siloxanes does not perform better than.Reference oil 6 and 7 is the polyoxy with 100%PEG chain Change the modified silicone oil of alkene.

Prove that polyoxyalkylene-modified silicone oil is painted in the model of the effect in the double-deck system: mould used in embodiment 38 Type paint is used as basis paint in embodiment 53-55, adds or do not add polyoxyalkylene-modified silicone oil.

Claims

1. a kind of solvent type antifouling paint compositions, it includes:

A. erodible non-silicone base sizing system,

B. one or more metalliferous biocides, and

C. one or more non-reacted polyoxyalkylene-modified silicone oil,

Wherein, it is based on the coating composition, the total amount of one or more non-reacted polyoxyalkylene-modified silicone oil is 0.05-10% dry weight.

2. coating composition according to claim 1, wherein the polyoxyalkylene-modified silicone oil, which has, is selected from polyoxy second The polyoxyalkylene chain of alkene chain, polyoxypropylene chains and poly- (ethylene oxide -co- oxypropylene) chain.

3. coating composition according to claim 2, wherein the polyoxyalkylene chain is selected from polyoxyethylene chain and poly- (oxygen second Alkene -co- oxypropylene) chain, wherein ethylene oxide (PEG) and the weight ratio of oxypropylene (PPG) they are 90:10-30:70, preferably 75:25- 35:65, more preferable 60:40-40:60.

4. coating composition according to any one of the preceding claims, wherein one or more non-reacted polyoxies Change the HLB value that the modified silicone oil of alkene respectively has 9-18 and preferred 11-17.

5. coating composition according to any one of the preceding claims, wherein the non-silicone base sizing system includes Selected from abietyl sizing system, silyl acrylate sizing system, nonaqueous dispersion base sizing system and metal acrylate The component of alkali sizing system；It is preferably selected from abietyl sizing system, silyl acrylate sizing system and metal propylene The component of hydrochlorate base sizing system；It is more preferably selected from the component of abietyl sizing system, silyl acrylate sizing system.

6. coating composition according to any one of the preceding claims, wherein it is based on the coating composition, described one Kind or the total amount of a variety of metalliferous biocides are 3-65% dry weight, such as 5-60% dry weight.

7. coating composition according to any one of the preceding claims, wherein one or more metalliferous biologies Agent for killing is selected from metal-dithiocar-bamate, bis- (1- hydroxyl -2 (1H)-pyridine thiosulfuric acid-O, S)-copper (pyrithiones Copper), acrylic acid copper, bis- (1- hydroxyl -2 (1H)-pyridine thiosulfuric acid-O, S)-zinc (zinc pyrithione), copper oxide (I), oxidation Cuprous, metallic copper, copper metal alloy, metal salt and N- cyclohexyl diazonium two dislike pairing copper.

8. coating composition according to claim 7, wherein one or more metalliferous biocides are selected from Cuprous oxide, copper pyrithione and zinc pyrithione.

9. coating composition according to claim 8, wherein one or more metalliferous biocides include Cuprous oxide and at least one of copper pyrithione and zinc pyrithione.

10. coating composition according to claim 9, wherein cuprous oxide and copper pyrithione and/or zinc pyrithione Total amount weight ratio be 25:1-1:1.

11. a kind of nonpolluting coating, it includes:

A. erodible non-silicone base sizing,

B. one or more metalliferous biocides, and

C. one or more non-reacted polyoxyalkylene-modified silicone oil,

12. a kind of nonpolluting coating system, including at least first coating and second coating,

A. the first coating includes erodible non-silicone base sizing system, and the first coating also includes a kind of or more The non-reacted polyoxyalkylene-modified silicone oil of kind；With

B. the second coating includes erodible non-silicone base sizing system, and the second coating also includes a kind of or more The metalliferous biocide of kind.

13. nonpolluting coating according to claim 11 or nonpolluting coating system according to claim 12, wherein institute Stating coating system includes 2-30g/m²The one or more non-reacted polyoxyalkylene-modified silicone oil and 20-250g/m²'s One or more metalliferous biocides.

It is described in any item outermost comprising claim 11 and 13 at least part of outer surface 14. a kind of Ship Structure Layer nonpolluting coating or the described in any item coating systems of claim 12-13.

15. the group of one or more non-reacted polyoxyalkylene-modified silicone oil and one or more metalliferous biocides It shares in the purposes for the anti-pollution for improving coating composition, the coating composition is viscous comprising erodible non-silicone base Material system, wherein be based on the coating composition, the total amount of one or more non-reacted polyoxyalkylene-modified silicone oil For 0.05-10% dry weight.