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CN101111571B - Anti-corrosion coatings containing thioamide groups - Google Patents

Anti-corrosion coatings containing thioamide groups Download PDF

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CN101111571B
CN101111571B CN200680003468XA CN200680003468A CN101111571B CN 101111571 B CN101111571 B CN 101111571B CN 200680003468X A CN200680003468X A CN 200680003468XA CN 200680003468 A CN200680003468 A CN 200680003468A CN 101111571 B CN101111571 B CN 101111571B
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coating
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CN101111571A (en
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H·博格曼
M·费尔南德斯冈萨雷斯
K·罗施曼
G·菲舍尔
M·施罗德
G·梵德米伦
A·格特里齐
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BASF SE
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BASF SE
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Priority claimed from DE102005061320A external-priority patent/DE102005061320A1/en
Priority claimed from DE200510061317 external-priority patent/DE102005061317A1/en
Priority claimed from DE200510061319 external-priority patent/DE102005061319A1/en
Priority claimed from DE200510061318 external-priority patent/DE102005061318A1/en
Application filed by BASF SE filed Critical BASF SE
Priority claimed from PCT/EP2006/050462 external-priority patent/WO2006079643A1/en
Publication of CN101111571A publication Critical patent/CN101111571A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • C09D5/082Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/086Organic or non-macromolecular compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50Multilayers
    • B05D7/52Two layers

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
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Abstract

The present invention relates to an application of coatings containing at least one compound (D) which contains at least one thioamide group of formula -C(S)-NR<1>R<2>, wherein corrosion protection is realized by means of drying and solidifying the coatings under atmospheric conditions.

Description

The protective system that contains the sulfo-amide group
The present invention relates to be used for the coating material of atomospheric corrosion control.
DE-A 29 43 833 discloses thiocarbamide and the thiourea derivative purposes as additive in comprising the moisture convertible coating composition of free sulfuric acid, hydrogen peroxide and silicon-dioxide.The main phosphorus compound that uses is handled; In this specification sheets, thioacetamide is included in wherein as ancillary component.
To know disclosed be that base material to be applied is immersed in 20-35 ℃ the bath, hot water rinsing in 60-70 ℃ scope then, dry under the temperature more than 70 ℃ subsequently.
EP-A 878 519 discloses the preferred aqueous composition that does not contain chromium that is used to produce corrosion control coating, and it comprises 0.2-50g/l thiocarbonyl group compound, 0.1-5g/l phosphoric acid salt and water soluble binders or base-material dispersion.Can choose wantonly and have 10-500g/l SiO 2The thiocarbonyl group compound for example can be thiocarbamide, thioamides, sulfo-aldehyde or thiocarboxylic acid.
Wherein said corrosion control coating requires heating and drying coated material in thermal environment, has perhaps applied the base material of heating in advance.This requires temperature is 50-250 ℃.The coat-thickness of 0.1-20 μ m is only disclosed; It is invalid or uneconomical that the coat-thickness that exceeds this scope is described to.
JP-A 2002-64856, JP-A 2002-241957, JP-A 297384 and JP-A 2003-73856 disclose the various aqueous compositions that are used for production corrosion control coating, it comprises different aqueous polymer dispersions, other components and thiocarbonyl group compound, as thiocarbamide or thioacetamide.The thioamides that openly will not contain a more than thioamides group is used for atomospheric corrosion control.
Can clearly be seen that from described prior art thioamides mainly is disclosed in the coil coating up to now, this class coating is meant that coiling (being called coiled material) is with the coating on the coiling metal strip that stores and transport after producing.These metal strips constitute the starting material of most of sheet metal workpiece, and example is a trolley part, vehicle body manufacture component, tool housing, exterior building facing, top ceiling or window sectional material.For these purposes, suitable metal sheet is by suitable technique such as punching press, boring, folding, section barization and/or deep-draw and moulding.Suitable words are assembled big assembly such as body of a motor car by many single parts are welded together.
The coiled material coating is to use the coating continuously coating metal strip that is generally liquid.To be 0.2-2mm and width carry by coiled material coating production line and coating in the method with the speed of 200m/min at the most for the metal strip of 2m at the most thickness.For this reason, for example can use cold coiling bar, electro-galvanizing thin plate, galvanizing steel bar or the aluminium and/or the aluminum alloy bar of mild steel or architectural grade steel.Typical production line comprises feed operation platform, bar storage area, cleaning and pretreating zone, has the first coat operations platform of roaster and cooling zone, downstream, the second coat operations platform that has stove, laminating operation platform, cooling operation platform and bar store and up-coiler.
The feature of coiled material coating is that the coating of coating is thin, and wherein dry coating thickness is usually less than 80 μ m, usually less than 60 μ m, and less than 50 μ m, even less than 40 μ m.In addition, metal sheet is processed with high productivity, and this requires short residence time(SRT); In other words, this requires after applied coatings dry at elevated temperatures, so that coating can fast setting.
This class coating method certainly only carries out on the production line of this purpose being used in particular for, and the therefore for example existing body of constructing can not apply with these class methods.
The objective of the invention is to develop permission to can not be in especially to the unit of those purposes exploitations the process for corrosion control that applies of coating and drying and/or solidified assembly.
This purpose by in atomospheric corrosion control, use comprise at least a contain at least one thioamides group ((C=S)-NR 1R 2) the coating of compound (D) realize.
Compare with corrosion control via coiled material coating, atomospheric corrosion control is in atomospheric corrosion control with the difference in the requirement of coating and coating, the thickness that coating has is significantly higher than coiled material coating and dry at ambient temperature and curing, thereby the dry and remarkable longer time cycle of solidifying requirements.In this time cycle process, uncured coating is easy to be subjected to the influence of water smoke or weather conditions, thereby the requirement of coating significantly is different from requirement to coil coating.
Additionally found a kind ofly by corrosion control coating being applied to the method on the metallic surface with the preparaton process metal surfaces that comprises base-material, pigment and/or filler and anticorrosive agent at least, wherein said anticorrosive agent is at least a compound (D).
Preferred compound (D) is:
(D1) general formula (II) R 4 n-R 3-(C=S) NR 1R 2Thioamides and
(D2) contain the thioamides of at least two thioamides groups,
Wherein n is the natural number of 1-5, and radicals R 1, R 2, R 3And R 4Have following definition:
R 1And R 2Independently of one another for H or have the linearity of 1-20 carbon atom or alkyl branching, optional replacement, have the cycloalkyl of 3-12 carbon atom or have the aryl of 6-12 carbon atom, wherein radicals R 1And R 2Can also form 5-12 person's ring with nitrogen-atoms,
R 3For (n+1) valency alkyl with 1-30 carbon atom and
R 4Be functional group.
The inventive method can be used for especially providing anticorrosion to the metallic surface that in use contacts with atmosphere, but described surface can also be those that in use contact with water, soil or other corrosive mediums.
Treat that by the inventive method rot-resistant metallic surface can be any required surface in principle.Yet preferably they construct the surface of body and/or its required component for metal structure or metal.Metal is constructed body and is connected by architectural grade steel such as girder steel, steel pipe or steel plate by riveting, weld or being spirally connected usually with structure, forms and constructs body accordingly.In one embodiment of the invention, the goods of coating can be fixing metal structure such as buildings, bridge, electric pole, jar, container, buildings, pipeline, power plant, chemical plant, boats and ships, crane, pillar, bulkhead, valve, pipe, jar, accessory, flange, tube stub, hall, roof and architectural grade steel.Under the situation of this embodiment, corrosion control coating is used by scene coating or spraying usually.This corrosion control can be control for the first time or upgrade.In other words the drying of such corrosion control coating and being solidificated under the atmospheric condition carries out at ambient temperature and in the presence of air and typical atmospheric water.Atmospheric moisture can have any desirable value relatively, but is preferably more preferably 30-70% of 10-80%.Depend on required degree of protection, by the surface anticorrosion of corrosion control coating be also referred to as slightly, moderate and severe corrosion control.
With regard to the character of metal, can comprise any required metal in principle.Yet, included metal or alloy especially usually as the metal building material and require rot-resistant those.
Described surface especially is the surface of iron, steel, zinc, zinc alloy, aluminum or aluminum alloy.Steel can comprise the known conventional alloying component of those of skill in the art.Described surface can be the surface of the structure be made up of described metal or alloy fully.Perhaps they can be the surface of the structure that scribbles Zn, Zn alloy, Al or Al alloy, and wherein said structure itself can be made up of as other metals, alloy, polymkeric substance or matrix material other materials.In a preferred embodiment of the invention, described surface is the surface of steel or zinc-plated and/or Aluminium Coated Steel of being untreated.
Zinc alloy or aluminium alloy are known to those of skill in the art.The typical composition of zinc alloy especially comprises Al, Pb, Si, Mg, Sn, Cu or Cd.The typical composition of aluminium alloy especially comprises Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti.Term " zinc alloy " also is intended to comprise the Al/Zn alloy that the approximate equivalent of Al and Zn wherein exists.Those of skill in the art select the type and the amount of alloying constituent according to required end-use.For example can Zn coating or aluminum coating be applied on the steel by hot dipping method such as galvanizing or by sherardizing galvanizing.When assembly is fixed or its geometrical shape when not allowing, can also use corresponding coating by thermal spray (spray zinc-plated, spraying aluminize).
The preparation that is used for corrosion control coating is applied to the metallic surface according to the present invention comprises at least a base-material.This base-material can also be chosen wantonly and contain crosslinkable groups.The base-material that is used for corrosion control lacquer and coating is known to those of skill in the art.
The preparation that is used for applied coatings according to the present invention comprises at least a base-material (A) and crosslinkable component (B).Crosslinkable component can be at least a linking agent that also uses except base-material, and perhaps can be the crosslinkable groups that is connected with base-material this moment.Base-material can also have crosslinkable groups certainly and can additionally use linking agent.
Here there is multiple possible combination.For example, can use base-material and linking agent independently of each other.This moment, base-material comprised the reactive functional group that can react with the complementary interaction functional group in the linking agent.Perhaps base-material can also be the self-crosslinking base-material, and it comprises and can carry out crosslinking reaction (" id reaction ") with the group of self kind or carry out the reactive functional group of crosslinking reaction with complementary interaction functional group on the same polymer.Can also linking agent be reacted to each other.
Base-material (A) can be typical base-material.The example of suitable base-material comprises (methyl) acrylate (being total to) polymkeric substance, the polyvinylesters of partial hydrolysis, polyester, Synolac, polylactone, polycarbonate, polyethers, Resins, epoxy-amine adduct, polyureas, polymeric amide, polyimide or urethane.Certainly can also use different mixture of polymers, condition is not mix to cause any undesired effect.
The character that depends on used binder systems for use, curing can be undertaken by various mechanism.For example related curing can be pure physical solidification, and this takes place by the evaporation solvent for use.It can also be the oxidative cure of reacting by binder systems for use and airborne oxygen.At last, can also be chemically crosslinked (reactive crosslinked).Reactive binder systems for use comprises crosslinkable component.Crosslinkable component can have lower molecular weight, be oligomeric or polymeric.Described system can be preferably single-component system (1K) or bicomponent system (2K).Reactive cross-linking system also comprises the moisture-curing binder systems for use, and wherein atmospheric water plays curing component.Be understood that binder systems for use can also solidify by the combination of different curings.Under the situation of 2K system, before using preparaton, base ingredient and curing component are mixed in known mode in principle.
The present invention can use water-soluble or organic dissolubility binder systems for use to carry out.Preferred water base binder systems for use.
Be used for corrosion control coating, the binder systems for use of especially water base corrosion control system is known to those of skill in the art in principle.They for example can be Resins, epoxy, polyacrylic ester, cinnamic acrylic ester polymkeric substance, polyester, Synolac, urethane or styrene butadiene polymkeric substance.
The amount of base-material (A) in preparaton is 15-70 weight % based on the amount of all components (comprising solvent) of this preparaton.Those of skill in the art set this amount according to the desired properties of coating.This amount is preferably 20-60 weight %, more preferably 25-50 weight %.
The polymkeric substance of preferred especially base-material (A) is selected from:
-(A1) polyacrylic ester,
-(A2) urethane and
-(A3) styrene butadiene polymkeric substance.
Extra possible is (A4) Synolac.
Polyacrylic ester (A1) is made up of following monomer usually:
A1a) 40-100 weight %, preferred 60-100 weight %, the more preferably at least a main monomer that contains the group of free redical polymerization of 80-100 weight %,
A1b) 0-40 weight %, preferred 0-25 weight %, more preferably 0-15 weight %A1a) in addition the group that contains free redical polymerization other copolymerisable monomers and
A1c) 0-4 weight %, preferred 0.01-2 weight %, more preferably at least a linking agent of 0.05-1 weight % at least.
Main monomer A1a) comprises the group of free redical polymerization and be selected from (methyl) vinylformic acid C 1-C 20Alkyl ester, have the carboxylic acid of 20 carbon atoms at the most vinyl ester, have vinyl aromatic compounds, olefinically unsaturated nitriles, vinyl halide, the vinyl ether that comprises the alcohol of 1-10 carbon atom, aliphatic hydrocrbon or these monomeric mixtures of 20 carbon atoms at the most with 2-8 carbon atom.
Example comprises having C 1-C 10(methyl) alkyl acrylate of alkyl is as methyl methacrylate, methyl acrylate, n-butylacrylate, ethyl propenoate and 2-ethylhexyl acrylate.
Also especially suitable is the mixture of (methyl) alkyl acrylate.
Vinyl ester with carboxylic acid of 1-20 carbon atom for example is vinyl laurate, stearic acid vinyl ester, propionate, branched paraffin carboxylic acid's vinyl ester and vinyl-acetic ester.
Suitable vinyl aromatic compounds comprises Vinyl toluene, alpha-methyl styrene, p-methylstyrene, α-butylstyrene, 4-n-butylbenzene ethene, the positive decyl vinylbenzene of 4-and optimization styrene.The example of nitrile is vinyl cyanide and methacrylonitrile.
Vinyl halide is the alefinically unsaturated compounds that chlorine, fluorine or bromine replace, preferred vinylchlorid and vinylidene chloride.
Vinyl ether for example comprises vinyl methyl ether or vinyl isobutyl ether.Preferred vinyl ether is those of alcohol that comprise 1-4 carbon atom.
Preferred (methyl) alkyl acrylate of suitable monomers (A1a), preferred vinylformic acid (C 2-C 10Alkyl) ester and methacrylic acid (C 2-C 10Alkyl) ester, vinyl aromatic compounds, the mixture of these compounds in addition.
Very particularly preferably methyl methacrylate, n-butylacrylate, vinylformic acid n-hexyl ester, vinylformic acid octyl group ester, 2-ethylhexyl acrylate and vinylbenzene and these monomeric mixtures are as monomer (A1a).
Especially preferable methyl methyl acrylate, n-butylacrylate, 2-ethylhexyl acrylate and vinylbenzene and these monomeric mixtures are as monomer (A1a).
Other copolymerisable monomers A1b) be to be different from down described those monomer with free redical polymerization group at (A1a), preferably except the two keys of free redical polymerization, also comprise at least 1, preferred 1-3, more preferably 1-2, very preferably monomer, especially (methyl) vinylformic acid C of 1 other functional group such as hydroxyl, carboxylacyl amine group or carboxyl 1-C 10Hydroxyalkyl acrylate, (methyl) acrylamide, ethylenic unsaturated acid or acid anhydrides, especially carboxylic acid, as (methyl) vinylformic acid, Ba Dousuan, or dicarboxylic acid, as methylene-succinic acid, toxilic acid or fumaric acid.
(methyl) vinylformic acid is represent methylidene vinylformic acid and vinylformic acid in this manual.
Linking agent A1c) for having at least 2, preferred 2-6, more preferably 2-4, very preferably 2-3 is individual, especially that class of 2 two keys of free redical polymerization.
Linking agent A1c) the two keys of at least two free redical polymerizations can be selected from (methyl) acrylic acid groups, vinyl ether group, vinyl ester group, allyl ethers group and allyl ester group.
Linking agent A1c) these free redical polymerization groups in can be identical or different.
Compd A 1c with identical free redical polymerization group) example is 1,2-ethylene glycol bisthioglycolate (methyl) acrylate, 1, ammediol two (methyl) acrylate, 1,2-propylene glycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, trishydroxymethyl glycerol two (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, 1,4-butyleneglycol divinyl ether, 1,6-hexylene glycol divinyl ether, 1,4-cyclohexanediol divinyl ether and Vinylstyrene.Preferred Vinylstyrene, 1,4 butanediol diacrylate and 1,6 hexanediol diacrylate.
Compd A 1c with different free redical polymerization groups) example is the vinylformic acid allyl ester, allyl methacrylate, vinylformic acid methylallyl ester, methyl methacrylate is for allyl ester, (methyl) vinylformic acid fourth-3-alkene-2-base ester, (methyl) vinylformic acid but-2-ene-1-base ester, (methyl) acrylate 3-methyl but-2-ene-1-base ester, (methyl) vinylformic acid and Geraniol, geraniol, the ester of styryl carbinol, allylin or diallyl ether, TriMethylolPropane(TMP) mono allyl ether or diallyl ether, ethylene glycol monoallyl ether, diglycol monotertiary allyl ethers, propylene glycol mono allyl ether, the dipropylene glycol mono allyl ether, 1, ammediol mono allyl ether, 1,4-butyleneglycol mono allyl ether also has methylene-succinic acid diallyl ester in addition.Special preferable methyl vinylformic acid allyl ester.
Polyacrylic ester (A1) can use typical emulsification and dispersing auxiliary and polymerization starter to be prepared by monomer according to the emulsion polymerisation process that belongs to general knowledge in a usual manner.
The dispersion agent that is fit to the enforcement free radical water emulsion polymerization is normally used emulsifying agent, and its amount is 0.1-5 weight %, especially 0.2-3 weight % based on monomer, protective colloid, and its amount is 5-40 weight %, especially 5-25 weight % based on monomer.
Emulsifying agent commonly used for example is high fatty alcohol ammonium sulfate or an alkali metal salt, as dodecyl sodium sulfate, and Fatty Alcohol(C12-C14 and C12-C18) ammonium phosphate salt or an alkali metal salt, degree of ethoxylation is the ethoxylation C of 3-30 8-C 10Alkylphenol and degree of ethoxylation are the ethoxylation C of 5-50 8-C 25Fatty Alcohol(C12-C14 and C12-C18).Can also use the mixture of nonionic and ionic emulsifier.Also suitable is phosphate radical-or sulfate radical is functional, ethoxylation and/or propoxylation alkylphenol and/or Fatty Alcohol(C12-C14 and C12-C18).Other suitable emulsifying agents are listed in Houben-Weyl, Methoden der organischen Chemie, XIV volume, Makromolekulare Stoffe[macromolecular cpd], Georg Thieme Verlag, Stuttgart, 1961, the 192-209 pages or leaves.
Suitable protective colloid is the high molecular crude substance, as starch, methylcellulose gum, pectin and gelatin, and synthetic such as polyvinyl alcohol and polyvinylpyrrolidone.Other protective colloids are described in detail in Houben-Weyl, and are the same, in the 411-420 page or leaf.
For example suitable is the multipolymer of urethane and olefinic monomer and (methyl) vinylformic acid and/or toxilic acid.
Suitable polymerization starter comprises that all can cause free-radical emulsion polymerization those in water-bearing media.They usually based on monomer with 0.1-10 weight %, the amount of preferred 0.2-4 weight % is used.Exemplary compounds is an inorganic peroxide, as Sodium persulfate and ammonium, and hydrogen peroxide, organo-peroxide as dibenzoyl peroxide or t-butyl hydroperoxide, also has azo-compound such as azo isobutyronitrile.These initiators are suitable for 50-100 ℃ temperature of reaction, and this temperature is that free-radical emulsion polymerization is common.If need about 40-60 ℃ than low reaction temperatures, then preferably redox system such as peralcohol and reductibility aided initiating-hydroxyl methane-sulfinic acid, the sodium salt of xitix or the combination of iron (II) salt.
Dispersion comprises primary dispersion body and secondary dispersion used according to the present invention.Under the situation of primary dispersion body, directly at aqueous phase with for example emulsion or microemulsion form polymerization base monomer, wherein monomer is dispersed in aqueous phase with the droplet dia of 0.1-0.2 μ m, and under the situation of secondary dispersion, in another processing step with the ready-formed polymer dispersed, polymerization in organic solvent usually, then with polymer dispersed in water, suitable then words are removed from dispersion and are desolvated, and preferably remove by distillation.
Preparing aqueous polymer dispersion itself by the free-radical emulsion polymerization method is known (referring to Houben-Weyl, Methoden der organischen Chemie, XIV volume, Makromolekulare Stoffe, the same, the 133rd page and each page subsequently).
Have been found that specially suitable method is following feed process, wherein starting point is by a part, the common monomer of 20 weight % at the most, water, first the expecting of emulsifying agent and initiator composition.To add the residual monomer that is the emulsification form and suitable words conditioning agent adaptably and to also have the further polymerization starter aqueous solution with rate of polymerization.
At least a portion acidic group that after (being total to) polymerization, can neutralize and exist in (being total to) polymkeric substance.This for example uses oxide compound, oxyhydroxide, carbonate or the supercarbonate of basic metal or alkaline-earth metal, and preferred oxyhydroxide carries out, and they can two or more combine with any required counter ion or its, and example is Li +, Na +, K +, Cs +, Mg 2+, Ca 2+Or Ba 2+Also being suitable for neutral is ammonia or amine, especially tertiary amine, as methylamine, and dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, Tributylamine, diisopropyl ethyl amine, benzyl dimethyl amine, monoethanolamine, diethanolamine, trolamine, hydroxyethyl dimethyl amine, hydroxyethyl diethylamide, single Propanolamine, dipropanolamine, tripropanol amine, piperidines, piperazine, N, N '-lupetazin, morpholine or pyridine.
Preferably ammonia is used for neutralization.In preferred and 50-100mol%, more preferably 75-100mol%, the very preferably acidic group in 90-100mol%, especially 100mol% (being total to) polymkeric substance.
The solids content that the aqueous polymer dispersion of polyacrylic ester (A1) preferably has is 35-65%, more preferably 45-55 weight %.
The glass transition temperature Tg of this multipolymer is preferably 0-60 ℃, more preferably 5-40 ℃ (according to DIN EN ISO11357 by dsc measurement).
In the 3rd preferred embodiment of the present invention, binder systems for use is the water dispersion of urethane (A2) or is mainly aqueous dispersion.
Urethane (A2) water dispersion that is used to produce corrosion control coating is known for those of skill in the art in principle.The details that is used for the urethane of coating and preparation thereof for example be disclosed in " Paints andCoatings, 2.9 polyurethane coatings " [Ullmann ' s Encyclopedia of TechnicalChemistry, 2000 the 6th edition, electronic edition] in.The water dispersion of urethane (A2) can be primary dispersion body or secondary dispersion.
The urethane that is used for water dispersion can known in principle mode be synthesized by conventional vulcabond and glycol.Consider effective film forming and good elasticity, the glycol that is particularly suitable for this purpose is number-average molecular weight M nBe about 500-5000g/mol, preferably those of about 1000-3000g/mol.Can use polyether glycol and polyester glycol for this reason.The amount of such diol of higher molecular weight is generally 10-100mol% with respect to the summation of all glycol.The required consistency and elasticity of film can be controlled for the low molecular weight diols of about 60-500g/mol by use number-average molecular weight Mn except already mentioned glycol.
For the synthetic urethane that is used for water dispersion, use in addition to comprise at least one isocyanate groups or the monomer that isocyanate groups is reactive group and additionally has at least one hydrophilic radical.These groups can be non-ionic groups, as polyoxyethylene group, and acidic-group, as COOH, sulfonate radical or phosphonate groups, or basic group, as amino.Preferably they are acidic-group.For as the base-material of this preparaton, preferably can with in the suitable alkali with all or part acidic group.Preferred for this reason ammonia or amine.Other details of relevant this class polyurethane dispersions and preparation thereof are described in detail in WO2005/005565 page 4 the 13rd and walk to the 14th page of the 14th row.Other examples of suitable polyurethane are disclosed in US 5,707,941 or WO 2004/101638, especially page 2 the 31st walk to the 14th page of the 11st row.
Urethane can also be modified.For example described compound can be an oxidative cure based polyurethane Synolac.For this preparation, for example can make the triglyceride level of unsaturated fatty acids carry out partial hydrolysis.Gained OH group can react in the polyurethane preparation process with isocyanate groups.
In order to implement the present invention, preferably can additionally use mean particle size to be no more than 1000nm, preferably less than 500nm, be more preferably less than 200nm, especially the urethane of 20-200nm (A2).
Styrene butadiene polymkeric substance (A3) can be that the aqueous emulsion polymerization that causes of the free radical in the presence of the emulsifying agent of 0.1-5 weight part is synthetic at water with based on the monomer total amount by following monomer:
A3a) 19.9-80 weight part any conjugated aliphatic hydrocarbon [monomer A 3a]],
A3b) 19.9-80 parts by weight of ethylene base aromatic substance [monomer A 3b]],
A3c) 0-10 weight part ethylenically unsaturated carboxylic acids and/or dicarboxylic acid and/or corresponding carboxylic acid amides [monomer A 3c]],
A3d) 0-20 weight part olefinically unsaturated nitriles [monomer A 3d]] and
A3e) 0-20 weight parts monomers A3b) but-A3d) in addition copolymerization [monomer A 3e]],
Ethylenically unsaturated monomer A3a wherein)-A3e) total amount is 100 weight parts.
Aqueous copolymer dispersion uses following monomer preparation usually:
25-70 weight parts monomers A3a),
25-70 weight parts monomers A3b),
0-8 weight parts monomers A3c),
0-15 weight parts monomers A3d) and
0-15 weight parts monomers A3e),
Often use following monomer preparation:
25-60 weight parts monomers A3a),
25-70 weight parts monomers A3b),
0.5-5 weight parts monomers A3c),
0-10 weight parts monomers A3d) and
0-10 weight parts monomers A3e).
Suitable any conjugated aliphatic hydrocarbon [monomer A 3a]] preferably include divinyl, isoprene, 1,3-pentadiene, dimethylbutadiene and/or cyclopentadiene, preferred divinyl.
Vinyl aromatic compounds [monomer A 3b]] especially comprise vinylbenzene, alpha-methyl styrene and/or Vinyl toluene, optimization styrene.
Preferred ethylenically unsaturated carboxylic acids and/or the dicarboxylic acid [monomer A 3c] that uses] be α with 3-6 carbon atom, β-monoethylenically unsaturated monocarboxylic and dicarboxylic acid, as vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid, preferably (methyl) vinylformic acid and methylene-succinic acid, more preferably vinylformic acid.Used carboxylic acid amides is the acid amides of above-mentioned ethylenically unsaturated carboxylic acids, preferred (methyl) acrylamide.
Preferred olefinically unsaturated nitriles class is vinyl cyanide and/or methacrylonitrile [monomer A 3d]] but and preferred copolymerization of ethylene based compound [monomer A 3e]] be that wherein alkyl comprises 22 or the still less vinylformic acid of a carbon atom and/or the ester of methacrylic acid, example is (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid isopropyl esters, (methyl) butyl acrylate cores, (methyl) 2-ethylhexyl acrylate, the allyl ester that also has the saturated mono carboxylic acid, vinyl ester, vinyl ether, vinyl ketone, the dialkyl of unsaturated dicarboxylic acid, vinyl-acetic ester and/or vinyl pyridine, vinylchlorid, vinylidene chloride.
The consumption of emulsifying agent is preferably 0.2-4.5 weight part/above-mentioned monomer A 3a of 100 weight parts)-A3e).Suitable emulsifying agent especially comprises the Fatty Alcohol(C12-C14 and C12-C18) of ethoxylation and the sulfuric acid monoester of ethoxylized fatty alcohol, they comprise linearity or the branched-alkyl with 8-18 carbon atom in each case, that this alkyl is connected in via ether is poly--or oligomeric-inferior ethoxyl sequence on.Suitable poly--or oligomeric-inferior ethoxyl sequence comprise that the polymerization degree is a 2-30 ethylene oxide unit, the preferred ethylene oxide oligopolymer of 2-7 ethylene oxide unit.
Particularly preferred fatty alcohol-ether and fatty alcohol ether sulfate are to comprise C 8-C 18Alkyl alcohol is as those of Fatty Alcohol(C12-C14 and C12-C18), for example octyl group, decyl, lauryl, myristyl, oil base or anti-oil base alcohol.Preferred especially oligomeric inferior ethoxyl lauryl sulfate, oligomeric inferior ethoxyl sulfuric acid palmityl ester, oligomeric inferior ethoxyl sulfuric acid stearyl and oligomeric inferior ethoxyl sulfuric acid oil base ester, wherein oligomeric inferior ethoxyl sequence especially preferably is made up of 2-7 ethylene oxide unit.
The mixture of the homology isomery alkyl that can use pure initial compounds as Fatty Alcohol(C12-C14 and C12-C18) this moment or obtain usually under the situation of using synthetic fatty alcohol, example is C 12And C 13The mixture of Fatty Alcohol(C12-C14 and C12-C18).Degree of ethoxylation is only represented the mean value of distribution usually.
The free acidic group of sulfate group usually as ammonium salt or an alkali metal salt with in and form exist, but neutralization also can be undertaken by used alkali in the metered charge process.
Additionally can use the ester or the monoesters of polyoxyethylene sulfosuccinic acid alkyl ester as emulsifying agent.In these compounds, sulfo-succinic acid is had 2-30 ethylene oxide unit, preferred 2-7 ethylene oxide unit, especially 2-5 ethylene oxide unit is poly--or low polyoxyethylene single or secondary esterification, the end group of described ester and monoesters is made up of the alkyl with 8-18 carbon atom, and this alkyl is linearity or branching.C 8-C 18The carbon containing alkyl especially comprises following: octyl group, decyl, lauryl, myristyl, stearyl and anti-oil base alcohol.
Free radical water emulsion polymerization causes by water-soluble radical initiator in the mode that those of skill in the art know.This specific class initiator comprises organic and/or inorganic peroxide, as basic metal peroxydisulfate and/or azo-compound, or the combined system of forming by at least a reductive agent and at least a superoxide and/or hydroperoxide, sodium salt as t-butyl hydroperoxide and hydroxyl methane-sulfinic acid, or hydrogen peroxide and xitix, or additionally comprise and dissolve in the polymerisation medium on a small quantity and the combined system of the metallic compound that its metal component can exist with multiple valence state, example is xitix/ferrous sulfate (II)/hydrogen peroxide, and wherein xitix usually can be by the sodium salt of hydroxyl methane-sulfinic acid, S-WAT, sodium bisulfite and/or Sodium Pyrosulfite replacement and hydrogen peroxide are by t-butyl hydroperoxide or alkali metal peroxide vitriol and/or ammonium peroxydisulfate replacement.Replace water-soluble ferrous (II) salt, use the combination of water-soluble Fe/V salt usually.Initiator system can add with its wear rate in the free radical water emulsion polymerization process continuously or in batches.In every kind of specific situation, this depend in a manner known way the chemical property of initiator system and polymerization temperature the two.Superoxide very particularly preferably, example is the basic metal peroxydisulfate, as Sodium persulfate or ammonium.Usually will be generally in the radical initiator adding polymerization reactor of the aqueous solution via the charging that separates.
The desired quantity of water soluble starter can easily be determined by suitable tentative experiment.Water soluble starter is usually based on the total mass for the treatment of polymerization single polymerization monomer to be the amount adding of 0.1-2.0 weight %.
For letex polymerization, additionally can add known molecular weight regulator, as sulfhydryl compound, as uncle's lauryl mercaptan, or two poly alpha methylstyrenes.Can also add other auxiliary agents in letex polymerization, as be used for the coordination agent of destructive metal ion, example is an ethylenediamine tetraacetic acid (EDTA) Na salt (EDTA-Na); Inhibitor, example are hydroquinone monomethyl ethers; Or froth suppressor.Molecular weight regulator and auxiliary agent are known and for example are described in Houben-Weyl, Methoden der organischenChemie, and the XIV/1 volume, the 297th page reaches each page subsequently, 1961, Stuttgart.
In a particular embodiment of the letex polymerization for preparing aqueous copolymer dispersion, maybe advantageously before just beginning, polymerization in reaction mixture, adds the 15 weight % at the most in the used emulsifying agent total amount, reaching the rest part that adds whole used emulsifying agents in time of 40% at the most of starting ingredient total conversion rate then, i.e. 85 weight % at the most.
But what also the desired properties of aqueous copolymer dispersion is played a decisive role is to be used for polymeric co-poly carboxylic acid and/or dicarboxylic acid [monomer A 3c]] answer 1-50% to be neutralized.The hydroxy-acid group that preferred 5-45% is derived from them is neutralized by alkali.
Specially suitable alkali is the aqueous solution of alkalimetal oxide or oxyhydroxide, very preferably the aqueous solution of ammonium hydroxide, sodium hydroxide or potassium hydroxide.
Verified advantageously in polymerization process via conventional feeder sleeve with component A3a)-A3e) infeed in the polymerization reactor.In an embodiment of this method, by mixing device with component A3a)-A3e) and at least a portion water in its feeder process, sneak in the emulsion.
Specially suitable mixing tank is a dynamic mixer, and its hybrid element comprises moving-member, and static mixer, does not promptly have the hybrid element of moving-member in inside, and it is especially according to online operate.
Suitable mixer instance is as being described in A.Echte, Handbuch der technischenPolymerchemie, VCH Verlagsgesellschaft Weinheim, the 104th page and subsequently in each page (1993).
The example of suitable dynamic on-line mixing device is ZFL-Zeitschrift f ü r Lebensmittel-technologie und-Verfahrenstechnik (1982) 33 (3), the 139th page reaches the Kratz interchanger described in each page subsequently, pulverizer with the rotor-stator operate, as gear dispersion machine, colloidal mill and corundum disc type grinding machine, and high pressure and ultrasonic homogenizer.
Other suitable dynamic on-line mixing devices are continuous tube mixers.
Suitable static on-line mixing device for example is ZFL-Zeitschrift f ü r Lebensmittel-technologie und-Verfahrenstechnik (1982), 33 (3), the 139th page reaches those described in each page subsequently, as the Ross-ISG mixing tank, wherein fluid streams is carried by being divided into the porous internals of son stream, then son is flowed transversal displacement and merge once more with different order, or comprise the static mixer of the fixedly hybrid element of two or more same types, one of described hybrid element is installed in pipe or the conduit after one and stagger separately 90 ° (for example Kenics, Sulzer SMV and Sulzer SMX mixing tank).
Other suitable static on-line mixing devices are shearing slit mixing tanks, the jet spread machine described in EP-B-101 007.
Other suitable mixing tanks also comprise online emulsive equipment, as film, jet mixer, mixing nozzle, and the crooked tubular type equipment with basic annular or elliptic cross-section.
Synolac (A4) is the condensation resin that is formed by polyvalent alcohol, polycarboxylic acid and fatty oil or free natural acid and/or synthetic fatty acid; At least a polyvalent alcohol must have 3 or bigger functionality.
The example of suitable dicarboxylic acid comprises aliphatic dicarboxylic acid such as hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, aliphatic series cycloaliphatic dicarboxylic acid such as dimer (fatty acid) yl, it is unsaturated fatty acids reaction product each other, the cycloaliphatic dicarboxylic acid is as 1,4-or 1,3-cyclohexane cyclohexanedimethanodibasic, tristane dioctyl phthalate, and aromatic dicarboxylic acid such as m-phthalic acid, terephthalic acid or phthalic acid.Certainly can also use the derivative of dicarboxylic acid.Specially suitable is acid anhydrides such as Tetra hydro Phthalic anhydride, hexahydrophthalic anhydride or four dehydrogenation Tetra hydro Phthalic anhydrides.
Suitable glycol example comprises fatty alcohol, as ethylene glycol, glycol ether, triglycol, propylene glycol, 1,3-butyleneglycol, 1, ammediol, 1,4-butyleneglycol, neopentyl glycol, 1-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl glycol, pentanediol, hexylene glycol, ethohexadiol, dodecanediol, neopentyl glycol hydroxy new pentane acid ester, alicyclic alcohol, as 1,4-or 1,3-cyclohexanedimethanol, 3 (or 4), 8 (or 9)-two (hydroxymethyl), three ring [5.2.1.0 2,6] decane isomer mixture and two (4-hydroxy-cyclohexyl) methane or-propane, and dimer diol (hydrogenation dimer (fatty acid) yl).Certainly can also use the derivative of alcohol in a known way, as ester, especially Dui Ying methyl or ethyl ester.
Except linear base-material, can also use the branching base-material.The monomer that is suitable for producing branching comprises tribasic carboxylic acid or its acid anhydrides such as trimellitic acid 1,2-anhydride or 1,3,5-benzenetricarboxylic acid and trivalent alcohol such as trimethylol-alkanes, and the example comprises trimethylolethane or TriMethylolPropane(TMP).
Preferred polyhydric alcohols is glycerine, tetramethylolmethane, trimethylolethane, TriMethylolPropane(TMP), various glycol such as ethylene glycol, propylene glycol, glycol ether, neopentyl glycol.
Preferred polycarboxylic acid be phthalic acid (acid anhydride) (PAn), m-phthalic acid, terephthalic acid, trimellitic acid 1,2-anhydride, hexanodioic acid, nonane diacid, sebacic acid.
The suitable oil ingredient or the example of lipid acid comprise siccative oil, as Toenol 1140, oiticica oil or tung oil, semi-drying oil, as soybean oil, sunflower oil, Thistle oil, ricinine oil or oil slick, non-drying oil, as Viscotrol C, Oleum Cocois or peanut oil, or the free fatty acids of above-mentioned oil, or synthetic monocarboxylic acid.
The molar mass of typical case's Synolac is 1500-20000g/mol, preferred 3500-6000g/mol.Acid number is preferably 2-30mg KOH/g, or is 35-65mg KOH/g under water-dilutable resin situation.The OH value is 300mg KOH/g at the most usually, preferably 100mg KOH/g at the most.
As polymkeric substance (A), what it will also be appreciated that above-mentioned polymkeric substance certainly mixes body or mixture.
Preferred wherein according to DIN EN ISO 11357 those following polymeric dispersions of the present invention of second-order transition temperature by the polymkeric substance (A) of DSC method measurement:
-be 0-60 ℃ under the situation of polyacrylic ester (A1),
-under the situation of urethane (A2), be at most 75 ℃, or
-be 0-60 ℃ under the situation of styrene butadiene polymkeric substance (A3),
-be 0-60 ℃ under the situation of Synolac (A4).
Especially preferred those following polymeric dispersions of the present invention of the second-order transition temperature of polymkeric substance (A) wherein:
-be 5-40 ℃ under the situation of polyacrylic ester (A1),
-be 0-60 ℃ under the situation of urethane (A2), or
-be 5-40 ℃ under the situation of styrene butadiene polymkeric substance (A3),
-be 5-40 ℃ under the situation of Synolac (A4).
Preferred those following polymeric dispersions of the DIN53495 water-intake rate of polymkeric substance (A) (" mensuration of polymkeric substance test-water-intake rate ", method 3 is at 23 ℃ in following 24 hours) wherein in addition:
-under the situation of polyacrylic ester (A1), be no more than 25 weight %, preferably be no more than 10 weight %, more preferably no more than 5 weight %,
-under the situation of urethane (A2), be 100 weight % at the most, preferred 50 weight % at the most, more preferably 30 weight % at the most, or
-under the situation of styrene butadiene polymkeric substance (A3), be no more than 15 weight %, preferably be no more than 8 weight %, more preferably no more than 3 weight %,
-under the situation of Synolac (A4), be no more than 25 weight %, preferably be no more than 10 weight %, more preferably no more than 5 weight %.
Preferably use in addition
Figure S06803468X20070801D000151
Those following polymeric dispersions of granularity of the polymkeric substance (A) that Autosizer2C measures:
-under the situation of polyacrylic ester (A1) 50-400nm, more preferably 80-250nm,
-under the situation of urethane (A2)<1000nm, more preferably<500nm, very preferably<200nm,
Especially 20nm is to being lower than 200nm, or
-under the situation of styrene butadiene polymkeric substance (A3) 50-400nm, more preferably 80-250nm,
-under the situation of Synolac (A4) 50-400nm, more preferably 80-250nm.
Linked (B) can contain the heat cross-linking group.
The example of suitable thermal cross-linking agent is based on the linking agent of epoxide, and wherein two or more epoxide groups interconnect via linking group.Example comprises the low-molecular weight compound with two epoxide groups, as hexanediol diglycidyl ether, phthalic acid diglycidylether or cycloaliphatic compounds as 3 ', 4 '-epoxy cyclohexane formic acid 3,4-epoxy cyclohexane methyl ester.Other examples of suitable crosslinking agents comprise the linking agent based on aminoresin, and example is melamine-formaldehyde resin, urea-formaldehyde resins or three (carbalkoxy) triazine.
Especially preferably end capped polyisocyanates is used as linking agent.When end-blocking, isocyanate groups and end-capping reagent are reversibly reacted.When being heated to comparatively high temps, end-capping reagent is eliminated once more.The example of suitable end-capping reagent is disclosed in DE-A 199 14 896, and the 12nd hurdle the 13rd walks in the 13rd hurdle the 2nd row.
End-capping reagent is described in D.A.Wicks, Z.W.Wicks, and Progress in OrganicCoatings, 36,148-172 (1999), 41,1-83 (2001) and 43 is among the 131-140 (2001).
The suitable class examples for compounds is phenols, imidazoles, triazole species, pyrazoles, oximes, N-hydroxyl acid imide, hydroxybenzoate, secondary amine, lactan, the acid cyclic ketone of CH-, malonic ester or Acetacetic acid alkyl ester.Preferred acetoxime, Diacetylmonoxime, ∈-hexanolactam, 3, diethyl malonate, phenol and tertiary butyl benzyl amine.
If separately use linking agent, then use 0.5-10 weight % usually, preferred 1-8 weight %, more preferably 2-6 weight %.Be understood that the mixture that can also use different linking agents, condition is that this can not have a negative impact to coating performance.
The present composition can further comprise at least a component (C) that is selected from filler in small, broken bits, pigment and dyestuff.
Filler in small, broken bits is generally mineral filler.Filler and/or pigment certainly comprise extra organic coating with for example hydrophobization or hydrophilization.
The mean particle size of filler should not surpass 10 μ m.Mean particle size is preferably 10nm-8 μ m, more preferably 100nm-5 μ m, for example 2-4 μ m.Under rounded grain or approximate circle particulate situation, this value refers to diameter; Have under erose particle such as the needle-shaped particles situation, it refers to the longest axle.Granularity is meant primary particle size.Those of skill in the art know that certainly subdivided solids usually agglomeration takes place and forms larger particle, and this must powerfully disperse in use.Granularity is selected according to the desired properties of coating by those of skill in the art.
Pigment especially can be anti-corrosion paint.These can comprise active and passivation anti-corrosion paint.
The example of active anti-corrosion paint especially comprises phosphoric acid salt, the phosphoric acid salt of phosphorous acid group or the phosphoric acid salt of modification are as the pigment based on following material: zinc phosphate, ortho-phosphoric acid zinc-aluminium, the zinc orthophosphate molybdenum, ortho-phosphoric acid zinc-aluminium molybdenum, secondary calcium phosphate, ortho-phosphoric acid zinc silicate calcium strontium, the polyphosphoric acid zinc-aluminium, polyphosphoric acid strontium aluminium, ortho-phosphoric acid polyphosphoric acid zinc silicate calcium aluminium strontium, polyphosphoric acid Calucium Silicate powder aluminium.Other examples comprise inorganic phosphate and the combination with electrochemical activity organic inhibitor of low solubility, as the Zn salt of usefulness 5-nitroisophthalic acid or the zinc phosphate of Ca salt modification.In addition, can also use iron phosphide, the hydroxyl zinc phosphide, borosilicate pigment such as barium metaborate or boron zinc phosphate, molybdate such as zinc molybdate, Sodium orthomolybdate zinc or calcium molybdate, the pigment with ion-exchange performance is as the unformed SiO with calcium ion modification 2Or the silicate of modification correspondingly, metal oxide such as ZnO, or metal-powder are as zinc powder.Be understood that and use typical organic anti-corrosive pigment, as the Zn salt or the Ca salt of 5-nitroisophthalic acid.
The passivation anti-corrosion paint prolongs the evolving path of corrosive component and therefore increases corrosion resistance.Example especially comprises sheet or layer shape pigment such as mica, rhombohedral iron ore, layered silicate, linear polysilicate such as wollastonite, talcum or tinsel such as aluminium flake or iron plate.
Other details of relevant anti-corrosion paint for example are disclosed in " Pigments, 4.2 anti-corrosion paints ", Ullmann ' s Encyclopedia of Technical Chemistry, 2000 the 6th edition, in the electronic edition.
Pigment can also be typical coloured pigment and/or pigment changeable colors along with angle.
Pigment changeable colors along with angle is meant and presents sheet structure and give top coat all pigment with the special decoration color effects.Pigment changeable colors along with angle is known to those of skill in the art.Example comprises pure metal pigment, and as aluminium, iron or copper pigment, the mica of the mica of coated interference pigment such as titanium dioxide coating, the mica of ferric oxide coating, mixed oxide coating (is for example used titanium dioxide and Fe 2O 3Coating), the aluminium of metal oxide coated, or liquid crystal pigment.
The typical organic or inorganic that coloured pigment especially can be used for paint industry absorbs pigment.The example of organic absorption pigment is an azo pigment, phthalocyanine pigment, quinacridone pigment and pyrrolopyrrole pigment.The example of inorganic absorption pigment is an iron oxide pigment, titanium dioxide and carbon black.
The example of dyestuff is azoic dyestuff, azines, anthraquinone dye, acridine dye, cyanine dyes, oxazine dye, polymethin dyes, thiazine dyes and triarylmethane dye.These dyestuffs can be used as alkalescence or cationic dyestuff, mordant dye, substantive dyestuff, dispersed dye, ingrain dye(stuff), vat pigment, metal complex dye, reactive dyestuffs, matching stain, thioxine dyes, para-dye or substantive dyestuff.
Can use filler to influence the performance of coating, as the orientation of hardness, rheological or pigment changeable colors along with angle.Filler is inertia usually on color; In other words, their intrinsic absorption is low and specific refractory power is similar to coating media.The example of filler comprises talcum, lime carbonate, and kaolin, barium sulfate, Magnesium Silicate q-agent, pure aluminium silicate, crystallinity silicon-dioxide, amorphous silica, microballon or the hollow beads of 0.1-10 μ m are for example made and be of a size of to aluminum oxide by glass, pottery or polymkeric substance.Can additionally use any required solid, inert organic granular as filler, as urea-formaldehyde condensation products, micronization polyolefin-wax or micronization amide waxe.Inert filler can also use by mixture separately.Yet, preferably only use a kind of filler in each case.
The preferred 15-40 volume of pigment and/or the filler ratio in polymeric dispersions %, more preferably 20-40 volume %, very preferably 20-35 volume %.Accurately amount is set according to the desired properties of coating by those of skill in the art.When using conducting pigment, consumption is the amount when using non-conducting filler usually.
Opposite with other values is, pigment and/or proportion of filler here provide with volume %, as the tolerance with respect to the pigment volume concentration (PVC) (PVC) of the volume of the tap density of pigment and/or filler and polymeric dispersions.
Pigment volume concentration (PVC) is normally defined the ratio that is formed divided by the cumulative volume of the polymer beads of solid inorganic composition (pigment and filler) and base material polymer water dispersion by the cumulative volume of solid inorganic composition (pigment and filler); Referring to Ullmanns
Figure S06803468X20070801D000181
Der technischen Chemie, the 4th edition, the 15th volume, the 668th page.
Be understood that the mixture that can also use different pigment.Amount of pigment is generally 20-70 weight %.Accurately amount is set according to the desired properties of coating by those of skill in the art.When using conducting pigment, consumption is the amount when using non-conducting filler usually.The preferred amounts of conducting pigment and filler is 40-70 weight %; The preferred amounts of non-conductive pigment is 20-50 weight %.
Compound (D) is for comprising at least one, preferred 1-6, more preferably 1-4, very preferably 1-3, particularly 1-2, especially 2 thioamides groups ((C=S)-NR 1R 2) those.
Further preferred compound (D) for contain at least one thioamides group ((C=S)-NR 1R 2) and at least one thioamides group ((C=S)-NR 1R 2) in addition the compound (D1) of other functional groups (seeing below).
Other preferred compounds (D) have 1-20 carbon atom, and this does not comprise radicals R 1And R 2The middle any carbon atom that exists preferably has 2-20, and more preferably 3-20, very preferably 4-20, particularly 5-20 is individual, especially 6-20 carbon atom.
In compound (D), be those of 100g/l at least preferably in the solubleness in glycol monomethyl n-butyl ether (butyl glycol) under 23 ℃.
Following those combinations of preferred especially thioamides (D) and base-material (B), wherein the HLB value of thioamides (D) or its solubleness and base-material (B) makes after selecting and thioamides and base-material highly compatible promptly presents effective consistency.
Containing at least one thioamides group (I)-(C=S) NR 1R 2Compound (D) in, R 1And R 2Be H or have 1-20 carbon atom independently of one another, preferred 1-10 carbon atom, the alkyl more preferably linearity of 1-6 carbon atom or branching, that choose replacement wantonly.R 1And R 2Can also be cycloalkyl or the aryl with 6-12 carbon atom, wherein radicals R with 3-12 carbon atom 1And R 2Can also form 5-12 person's ring with nitrogen-atoms.Extra substituting group especially can be to contain oxygen or nitrogenous substituting group, and example is OH group or NH 2Group.In addition, in containing the group of at least 3 carbon atoms, non-adjacent and non-terminal carbon can be replaced by O and/or N atom.Preferred group R 1And R 2Example comprise methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl and n-hexyl.Preferred group R 1And R 2In at least one is H, more preferably two groups are H.
The used thioamides of the present invention is preferably general formula (II) R 4 n-R 3-(C=S) NR 1R 2Compound (D1), it contains thioamides group and one or more functional group, and/or for containing the compound (D2) of at least two thioamides groups.
In compound (D1), the thioamides group is via (n+1) valency alkyl R 3With n functional group R 4Connect, wherein n is the natural number of 1-5.Preferred n is 1-3, more preferably 1 or 2.
R 3Be preferably and have 1-30 carbon atom, preferred 1-20 carbon atom, more preferably (n+1) valency aliphatic series of 1-10 carbon atom, alicyclic, aromatics or araliphatic alkyl.This alkyl can also be chosen wantonly by heteroatoms at interval, but is preferably simple alkyl.Self-evident to those of skill in the art is that possible in principle n value is also determined by carbonatoms.Common alkyl R 3Each carbon atom have and on average be no more than a functional group.
With radicals R 3The one side that links to each other is the thioamides group, also has n functional group R 4These functional groups can maybe can be different types of functional group for identical type.
Functional group R 4For example can for ether, imino-, ketone group, aldehyde radical ,-OH ,-NH 2,-NHR 5,-NR 5R 5' ,-COOH ,-COOR 5,-CONH 2,-CONHR 5,-CONR 5R 5 ',-NHCOR 5,-NR 5 'COR 5,-NHCONHR 5,-SH ,-CN ,-Si (OH) 3,-SO 3H ,-PO (OH) 2,-Si (OR 5) 3,-PO (OR 5) 2Or-PS (OR 5) 2, R wherein 5And R 5 'Independently of one another for having 1-6 carbon atom, the alkyl of preferred 1-4 carbon atom, preferably linearity or branched-alkyl are very particularly preferably respectively done for oneself-CH 3It will also be appreciated that quaternary ammonium group or season ammonium.
In this article, at least some acidic-groups can exist by negatively charged ion, and at least some basic groups exist with protonated form.
In a preferred embodiment of the invention, functional group R 4For only containing N and/or O atom as heteroatomic that class group.Such examples of groups comprise ether, imino-,-OH ,-NH 2,-NHR 5,-NR 5R 5 ',-COOH ,-COOR 5,-CONH 2,-CONHR 5,-CONR 5R 5 ',-NHCOR 5,-NR 5 'COR 5,-NHCONHR 5
Functional group preferably include ether ,-OH and/or-NH 2
Preferred especially ether.
In a preferred embodiment of the invention, radicals R 3Be divalent aliphatic, alicyclic or aromatic hydrocarbyl.This alkyl can also be chosen wantonly by heteroatoms at interval, but is preferably simple alkyl.Especially can mention general formula-(CH this moment 2) k-linearity 1, ω-alkylidene group, wherein k is 1-30, preferred 1-20, the more preferably natural number of 1-10.Described group can also for divalent aromatic radical as 1,4-phenylene, or general formula-(CH 2) k,-(C 6H 4)-or-(CH 2) k,-(C 6H 4)-(CH 2) k"-the replacement aromatic group, wherein k ' and k " be 1-10 independently of one another, the natural number of preferred 1-3.
The example of particularly preferred thioamides (D1) comprises general formula HO-(CH 2) k-(C=S) NR 1R 2The 'omega '-hydroxy carboxylic acid thioamides, wherein group and index are as defined above.K in these compounds is preferably 3-8.Such examples for compounds comprises 2-hydroxyl thioacetamide, 3-hydroxyl thiopropionamide, 4-hydroxyl sulfo-butyramide, 5-hydroxyl sulfo-valeramide, 6-hydroxyl sulfo-hexanamide, 7-hydroxyl sulfo-heptamide, 8-hydroxyl sulfo-decoylamide, 9-hydroxyl sulfo-pelargonamide and 10-hydroxyl sulfo-decyl amide.
Preferred thioamides (D1) further comprises general formula R 11-O-(CH 2) k-(C=S) NR 1R 2ω-alkoxyl group carboxylic acid thioamides, wherein group and index are as defined above.K in these compounds is preferably 1-8.
R 11Here can be for having 1-20 carbon atom, preferred 1-10 carbon atom, more preferably the linearity of 1-8 carbon atom or branching, the optional alkyl that replaces.The example is methyl, ethyl, sec.-propyl, n-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-hexyl, n-heptyl, n-octyl, positive decyl, dodecyl, n-tetradecane base, n-hexadecyl, Octadecane base, NSC 62789 base and 2-ethylhexyl.
The example of such thioamides is methyl, ethyl, sec.-propyl, normal-butyl, the tertiary butyl and the 2-ethylhexyl ether of 2-hydroxyl thioacetamide, 3-hydroxyl thiopropionamide, 4-hydroxyl sulfo-butyramide, 5-hydroxyl sulfo-valeramide, 6-hydroxyl sulfo-hexanamide, 7-hydroxyl sulfo-heptamide, 8-hydroxyl sulfo-decoylamide, 9-hydroxyl sulfo-pelargonamide and 10-hydroxyl sulfo-decyl amide.
Preferred thioamides (D1) further comprises general formula H-[X i] j-O-(CH 2) k-(C=S) NR 1R 2ω-oxyalkylated hydroxycarboxylic acid thioamides, wherein group and index are as defined above.K in these compounds is preferably 1-8.
Each X iCan be selected from independently of each other-CH for i=1-j 2-CH 2-O-,-CH 2-CH (CH 3)-O-,-CH (CH 3)-CH 2-O-,-CH 2-C (CH 3) 2-O-,-C (CH 3) 2-CH 2-O-,-CH 2-CHVin-O-,-CHVin-CH 2-O-,-CH 2-CHPh-O-and-CHPh-CH 2-O-is preferably selected from-CH 2-CH 2-O-,-CH 2-CH (CH 3)-O-and-CH (CH 3)-CH 2-O-, more preferably-CH 2-CH 2-O-, wherein Vin is a vinyl, Ph is that phenyl and j can be the number of 1-250.
Preferred 50mol% at least, preferred 70mol%, more preferably the group of 100mo1% is the ethylene oxide group.
The compound (D2) that contains at least two thioamides groups can be rubeanic acid R under the simplest situation 1R 2N (S=C)-(C=S) NR 1R 2
In addition to these, described compound is a general formula R 6The NR of (-(C=S) 1R 2) mCompound, wherein m thioamides group is by linking group R 6Interconnect, and n is at least 2, the natural number of preferred 2-20.These compounds can be low-molecular weight compound, oligomeric compound or polymerizable compound.
Linking group R 6Comprise linearity or branched aliphatic, alicyclic, aromatics and/or araliphatic alkyl, wherein non-adjacent carbon atom can also be by heteroatoms, especially O and/or N atom, or functional group is at interval or replace, and can additionally contain functional group.Extra functional group especially can be radicals R as defined above 4
In a preferred embodiment of the invention, D2 is a low-molecular weight compound.This moment R 6Have 1-30 carbon atom, preferred 2-20 carbon atom, more preferably 2-10 carbon atom, and the m value in these compounds is 2-6, preferred 2-4, more preferably 2.
In an especially preferred embodiment, (D2) be general formula (III) R 1R 2N (S=C)-R 7-(C=S) NR 1R 2Thioamides.This moment R 7For comprising the divalent linker of 1-30 carbon atom.
R 7Especially comprise general formula-(CH 2) k-linearity 1, ω-alkylidene group, wherein k is 1-30, preferred 2-20, the more preferably natural number of 2-8.Described group can be a divalent aromatic radical, as 1, and 4-phenylene, or general formula-(CH 2) k,-(C 6H 4)-or-(CH 2) K '-(C 6H 4)-(CH 2) K "-the replacement aromatic group, wherein k ' and k " be 1-10 independently of one another, the natural number of preferred 1-3.
The example of this compounds D2 comprises dithio Malonamide, dithio adipamide, 1,4-dithio benzenedicarboxamide or 1,2-dithio benzenedicarboxamide.
R 7Further preferably can comprise general formula-(CH 2) K '-R 8-(CH 2) K "-group, R wherein 8Be the divalence functional group, especially contain the functional group of P.Such examples of groups comprises-OP (O) (OR 9) O-,-P (O) (OR 9)-,-P (S) (OR 9)-,-P (S) (SR 9), R wherein 9Be H, monovalent metallic ion or alkyl, preferably have the linearity or the branched-alkyl of 1-6 carbon atom.
The preparation that contains the compound of thioamides group is known to those of skill in the art.For example they can by corresponding nitrile by with H 2S reacts and prepares.
In another preferred embodiment of the present invention, (D2) hang the polymkeric substance of thioamides group for comprising at least two ends and/or side.Term " polymer " " comprise oligopolymer and comprise the high-molecular weight compounds that obtains by polymerization by one or more monomers in a usual manner.Described polymkeric substance can be the polymkeric substance or the branched polymer of substantially linear.The average molar mass M that contains the polymkeric substance of thioamides group nBe generally 300-10000000g/mol, preferred 500-1000000g/mol, more preferably 1000-100000g/mol.
Thioamides group in the polymkeric substance can be that end group maybe can be a side group.The thioamides group that side is hung can be located immediately on the main polymer chain, perhaps can be connected on the main polymer chain via spacer.
Polymkeric substance can contain the polymkeric substance of itrile group and make itrile group and H2S reacts in known mode in principle and obtains the thioamides group and prepare after polymerization by preparation at first.This illustrates (scheme (I)) to the polymkeric substance that contains acrylonitrile unit below.
Figure S06803468X20070801D000231
As the raw material of reaction, can use the homopolymer that contains itrile group or the multipolymer of all kinds in principle.Unique restriction to selection is at H 2In the reaction of S and polymkeric substance, should there be the disadvantageous effect that causes by undesirable secondary reaction.Be suitable for the synthetic monomer example that contains the polymkeric substance of itrile group and comprise α, ω-vinyl nitrile is as vinyl cyanide, allyl cyanide, crotononitrile, pentenenitrile or hexene nitrile, general formula H 2C=C (CH 3) CONH-R 10(methyl) acrylamide of-CN or general formula H 2C=C (CH 3) COO-R 10(methyl) acrylate of-CN, wherein R 10Be bivalent hydrocarbon radical in each case.Preferred vinyl cyanide.The example of suitable comonomer comprises alkene, and preferred vinyl aromatic substance such as vinylbenzene, alpha-methyl styrene or substituted phenylethylene and (methyl) vinylformic acid or (methyl) acrylate are as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate or 2-ethylhexyl acrylate.Implement the multipolymer that preferred feedstock of the present invention for example comprises vinylbenzene and vinyl cyanide.
With H 2The reaction of S can advantageously be carried out in the presence of alkali.For example can use pressure exerting device and methyl alcohol is carried out this reaction as solvent.Transforming degree for example can by 13C NMR spectrography is by comparing CN-and CSNH 2The intensity of signal and determine and should be 20-100%, preferred 40-100% usually.
According to the present invention, can use the purification form or contain the compound (D) of the reaction mixture form of reactant, wherein reactant content can be at most 90%, and preferably at the most 75% or lower.
Another kind may be can be used for polymerization with the monomer of the reactive group of the suitable combination thing reaction that contains the thioamides group with additionally containing.Can mention as an example contain the maleic anhydride group and can be for example with ω-hydroxyl thioamides or omega-amino-thioamides respectively as following scheme (II) and the polymkeric substance that (III) reacts the example.
Figure S06803468X20070801D000232
Figure S06803468X20070801D000241
The polymkeric substance of prove out for example comprise maleic anhydride and as modification with the comonomer of raw material multipolymer as (methyl) vinylformic acid, (methyl) acrylate, vinyl ether and/or alkene.For example described multipolymer can be a styrene-maleic anhydride copolymer.
In order to produce coating, can use single thioamides or thioamides D1 and/or D2 that two or more are different.Those of skill in the art are according to specifically selecting in the possible in principle thioamides of the desired properties of coating.Self-evident to those of skill in the art is the thioamides D1 of not all kind and/or binder systems for use, solvent system or the surface that D2 is fit to all kinds equally.By selecting specific functional group or linking group, can regulate thioamides to specific system optimization.For example, can prepare the application-specific in aqueous coating system or organic coating system respectively and tend to more hydrophilic or more hydrophobic Compound D 1 and/or D2.
Certainly thioamides D1 and/or the D2 that the present invention is used mixes use with other thioamides that depart from above-mentioned definition, and with other thiocarbonyl group compound uses or mix use with other anticorrosive agents usually, condition is negative performance not occur.Usually, the ratio of the used thioamides of the present invention should be at least 50 weight % with respect to the total amount of all used organic anti-corrosive erosion agent, preferably at least 75 weight %.Especially preferably only use thioamides D1 and/or D2.
The thioamides that the present invention uses is usually with 0.25-10 weight %, preferred 0.5-8 weight %, and more preferably the amount of 1-6 weight % is used.
As component (E), preparation of the present invention comprises suitable solvent usually, and each component is solution and/or dispersion in described solvent, to allow evenly to be applied to the surface.Yet, can also not contain solvent in principle or not solvent-laden substantially form is mixed with powder coating with said preparation.The preferred solvent that uses.
Suitable solvent be can dissolve, dispersion, suspension or emulsification The compounds of this invention those.These can be organic solvents, and concentration is 5-25%, preferred 5-20%, the more preferably ammonia soln of 5-15%, or water.Certainly can also use the mixture of different organic solvents or the mixture of organic solvent and water.Those of skill in the art are according to suitably selecting in the possible in principle solvent of the classification of required end-use and used The compounds of this invention.
The example of organic solvent comprises hydro carbons such as toluene, dimethylbenzene or the mixture that in crude oil refining, obtains, as determining the hydrocarbon-fraction of boiling range, ethers such as THF or polyethers such as polyoxyethylene glycol, ether alcohol such as glycol monomethyl n-butyl ether (butyl glycol), dihydroxypropane single-ether, one contract propylene glycol monomethyl ether or propylene glycol monomethyl ether, ether ethyl glycol acetate such as butyl glycol acetate or propylene glycol methyl ether acetate, ketone such as acetone, alcohols such as methyl alcohol, ethanol or propyl alcohol, or lactan, as N-Methyl pyrrolidone, the N-ethyl pyrrolidone, N-(normal-butyl) pyrrolidone or N-cyclohexyl pyrrolidone.
Can also use aromatics or aliphatic hydrocrbon or its mixture.The example of such hydrocarbon is toluene or dimethylbenzene.Preferred aromatic hydrocarbon mixture is possible mainly comprise aromatics C 7-C 14Hydrocarbon and boiling range are those of 110-300 ℃, preferred especially toluene, o-Xylol, m-xylene, p-Xylol, Three methyl Benzene isomer, tetramethyl-benzene isomer, ethylbenzene, cumene, naphthane, and the mixture that comprises these.
The example is from ExxonMobil Chemical
Figure S06803468X20070801D00025185037QIETU
Product, especially
Figure 200680003468X100002S06803468X20070801D00025185037QIETU
100 (CAS No.64742-95-6 is mainly C 9And C 10Aromatic substance, the about 154-178 of boiling range ℃), 150 (the about 182-207 of boiling range ℃) and 200 (CAS No.64742-94-5), and from Shell's
Figure 200680003468X100002S06803468X20070801D00025185037QIETU
Product.The hydrocarbon mixture that comprises paraffinic hydrocarbons, naphthenic hydrocarbon and aromatic substance also can title Kristalloel (Kristalloel30 for example, the about 158-198 of boiling range ℃, or Kristalloel60:CAS No.64742-82-1), petroleum solvent (equally for example CAS No.64742-82-1) or solvent naphtha (lightweight: the about 155-180 of boiling range ℃; Heavy: the about 225-300 of boiling range ℃) commercial.The aromatic content of this class hydrocarbon mixture greater than 90 weight %, is preferably greater than 95% usually, more preferably greater than 98%, very preferably greater than 99 weight %.Maybe advantageously use the hydrocarbon mixture of naphthalene content with special reduction.
Can use the preparation that comprises water or main aqueous solvent mixture in addition.This is meant and comprises at least 50 weight %, preferably at least 65 weight %, more preferably those mixtures of at least 80 weight % water.Other components are water miscibility solvents.Example comprises monohydroxy-alcohol such as methyl alcohol, ethanol or propyl alcohol, higher alcohols such as ethylene glycol or polyether glycol, and ether alcohol such as butyl glycol or methoxypropanol.
The amount of solvent is selected according to the desired properties and the required application process of preparation by those of skill in the art.Usually, the weight ratio of coating composition and solvent is 10:1-1:10, preferably about 2:1, but the present invention and be not intended to be limited to this ratio.Certainly can also at first prepare enriched material and only at the scene it is diluted to desired concn.
Said preparation prepares by each component and the solvent powerful mixing with said preparation.Suitable mixing or dispersion assembly are known to those of skill in the art.
Except component (A)-(D) and optional (E), said preparation can further comprise one or more auxiliary agents and/or additive (F).This analog assistant and/or additive are used to finely tune coating performance.20 weight % of the summation of all components preferably were no more than 10% beyond their amount was no more than usually and desolventizes.
The proper auxiliary agent example is coloured pigment and/or pigment changeable colors along with angle, thermofixation reactive diluent, auxiliary rheological agents, the UV absorption agent, photostabilizer, free-radical scavengers, free radical adds polygalacturonase inhibitor, heat cross-linking catalyzer, slip additive, polymerization retarder, defoamer, emulsifying agent, the devolatilization agent, wetting agent, dispersion agent, tackifier, flow control agent, film coalescence aid, rheology control additive (thickening material), fire retardant, siccative, anti, other inhibiter, wax and matting agent, for example by textbook " Lackadditive " [paint additive], Johan Bieleman edits for they, Wiley-VCH, Weinheim, New York, 1998 or German patent application DE19914896A1 the 13rd hurdle the 56th walk in 15 hurdles the 54th row known.
Preferred additives is the dibutyl tin dilaurate as the heat cross-linking catalyzer.
System component is as follows usually:
(A) 30-70 weight %, more preferably 35-65 weight %, more preferably 40-55 weight %,
(B) 10-50 weight %, more preferably 20-40 weight %, more preferably 20-30 weight %,
(C) 15-45 volume %, more preferably 20-45 volume %, 20-40 volume % very preferably,
(D) 0.05-10 weight %, more preferably 0.1-8 weight %, 0.2-6 weight % very preferably,
(E) 0-45 weight %, more preferably 0-35 weight %, 0-25 weight % very preferably,
Condition is that the summation of all the components is 100 weight %.
The present invention further provides a kind of mixture of forming by following component:
-at least a dispersive base-material (A),
-at least a comprise at least one thioamides group ((C=S)-NR 1R 2) compound (D) and
-water.
These mixtures of the present invention are preparation corrosion control valuable initial product with coating.
Additionally provide a kind of production to be used for the method for the coating of corrosion control, having comprised:
-at first with base-material (A) with the dispersion in water and at least a comprise at least one thioamides group ((C=S)-NR 1R 2) compound (D) mix and
-only after finishing component (A) and mixing (D) in the gained mixture at least a pigment of adding and/or filler.
This preparation method's advantage is that inhibition compound (D) can be because of not absorbing inactivation on pigment and/or filler, thereby gained coating has higher corrosion control effect.
In order to implement the inventive method, use the said preparation process metal surfaces.
In slight, moderate or severe corrosion control, this can use and finish by for example spray application or coating, and the coating of wherein using is solidified under atmospheric condition subsequently.Certainly can also use the identical or different coating of two-layer or more multi-layered composition successively.The total thickness of this class corrosion control lacquer is determined according to the desired properties of corrosion control coating by those of skill in the art.Be generally at least 40 μ m, preferred at least 50 μ m, more preferably at least 60 μ m, very preferably at least 80 μ m, particularly at least 100 μ m, especially at least 125 μ m usually are at least 150 μ m, even are at least 175 μ m or at least 200 μ m.Total coating thickness, promptly the corrosion control coating of being used to some extent thickness together on be limited to 2mm, preferably less than 1.5mm, be more preferably less than 1mm, very preferably less than 800 μ m, especially less than 500 μ m.
Coating of the present invention can any required mode be used, for example by coating or spray application.
Curing is by the decision of the character of linking agent and carry out under atmospheric condition usually.
Solidify temperature required especially by used linking agent decision.Solidify under can be at the linking agent more relatively poor low temperature of height reactant cross-linker than reactivity.
Term " atomospheric corrosion control " is meant that in the context of the invention the coating that comprises at least a thioamides (D) is at least 40 μ m at dried coat-thickness, preferred at least 50 μ m, more preferably at least 60 μ m, at least 80 μ m very preferably, and coat-thickness is at most 2mm, preferably less than 1.5mm, be more preferably less than 1mm, very preferably less than 800 μ m, especially less than 500 μ m, wherein coating composition on being applied to the surface after in typical envrionment conditions, promptly for example in curing in the presence of air and typical atmospheric water under envrionment temperature or the room temperature, and do not use extra equipment or device.Typical solidification value depends on that surrounding environment is greater than 0 ℃ to 40 ℃ in the presence of air and typical atmospheric water, preferred 5-35 ℃, and more preferably 10-30 ℃, very preferably 15-25 ℃.Relative humidity can be any required relative humidity and be preferably 10-80%, more preferably 30-70%.The clear completely crued time of given binder systems for use of those of skill in the art may be according to reality envrionment conditions in vogue and difference.
Especially preferably dispersion of the present invention and preparation are used for preferably corroding classification C3 or higher at corrosion classification C2 (according to DIN ENISO12944) or higher, more preferably corrode in the corrosion control composition of classification C4 or more senior middle school's use.
For non-steel alloy and zinc, press following the definition based on these corrosion classifications of mass loss that exposes storage per unit area after 1 year or thickness minimizing according to DIN EN ISO12944:
C2 (low-corrosiveness): non-steel alloy: mass loss〉10-200g/m 2
Thickness reduces〉1.3-25 μ m
Zinc: mass loss〉0.7-5g/m 2
Thickness reduces〉0.1-0.7 μ m
C3 (moderate corrosion): non-steel alloy: mass loss〉200-400g/m 2
Thickness reduces〉25-50 μ m
Zinc: mass loss〉5-15g/m 2
Thickness reduces〉0.7-2.1 μ m
C4 (highly corrosive): non-steel alloy: mass loss〉400-650g/m 2
Thickness reduces〉50-80 μ m
Zinc: mass loss〉15-30g/m 2
Thickness reduces〉2.1-4.2 μ m
C5-I/M (very high): non-steel alloy: mass loss〉650-1500g/m 2
Thickness reduces〉80-200 μ m
Zinc: mass loss〉30-60g/m 2
Thickness reduces〉4.2-8.4 μ m
Embodiment
Synthesizing of 7-(2 '-ethylhexyl) sulfo-heptamide
In the high-pressure mini still, add 26.0g (0.108mol) 7-(2-ethyl hexyl oxy) heptonitrile and the diethylamine of 15.9g (0.217mol) in 130ml ethanol.
Injection 7.4g (o.217mol) hydrogen sulfide also stirs this mixture 4 hours down at 60 ℃.On rotatory evaporator, remove then and desolvate and by column chromatography purification crude product.Obtain 23.1g yellow liquid (mixture of 25% product and 75% raw material).
The dispensing information of corrosion control undercoat
The performance test of atomospheric corrosion control use based on commercially available paint with the cinnamic acrylic ester water dispersion (
Figure S06803468X20070801D000281
Optive410, BASF Corp.) corrosion control preparaton carries out.Used dispersion has following performance:
Solids content 49-51%
pH 7.5-8.5
Brookfield viscosity 500-1000cps
Density 1.06g/cm 3
Minimum film-forming temperature (MFFT (according to ASTM D2354)) About 12 ℃
Granularity About 110nm
Prepare test formulations according to following universal description:
With 393.4g cinnamic acrylic ester dispersion and 2.2g commercial coating defoamer (polysiloxane and the hydrophobic solid mixture in polyoxyethylene glycol;
Figure S06803468X20070801D000291
022, Byk) mix, add by the 0.6g anionic dispersing agents (acid phosphoric acid ester of fatty alcohol alkoxy compound by Dispermate afterwards;
Figure S06803468X20070801D000292
A-EP, BASF AG), the mixture formed of 11.0g strong aqua and 58.6g water.Under agitation additionally mix the mixture of 7.2g phenoxypropanol (film coalescence aid) and 7.2g gasoline 180-210 ℃ (film coalescence aid).
Add 85.0g rhombohedral iron ore pigment then
Figure S06803468X20070801D000293
130M, Lanxess), 82.1g is based on the anti-corrosion paint of zinc phosphate molybdenum
Figure S06803468X20070801D000294
ZMP, alkaline zinc orthophosphate molybdenum hydrate, Heubach), 36.0g Magnesium Silicate q-agent (filler; Talcum 20M2 is Luzenac) with the filler (30 weight %ZnS) of 127.8g based on barium sulfate and zinc sulphide The use granulated glass sphere (
Figure S06803468X20070801D00029185409QIETU
3mm) whole mixture was disperseed 30 minutes at least.
Under further stirring, add other 166.4g cinnamic acrylic ester dispersion, 1.9g then 022 and 3.7g water and commercially available inhibiter (inhibiter L1,
Figure S06803468X20070801D00029185422QIETU
) the 1:1 mixture and remove granulated glass sphere by screening.
Be 25% commercial polyurethane base thickening material at last with this batch of material and 3.7g concentration PU85, BASF AG) mixture of solution and 13.2g butyl glycol (solvent) mixes and suitable words use strong aqua that pH regulator is about 9.5.This obtain the 1000g solids content be 61% and pigment/volumetric concentration (PVC) be 23% corrosion control priming paint.
The coating that 100g is obtained and 2.5g concentration are that the butyl glycol solution (embodiment 1) of 33% 7-(2 '-ethylhexyl) sulfo-heptamide mixes.
In order to contrast, another coating sample does not add thioamides (Comparative Examples 1).
Use preparaton by steel plate, the preparation of salt-fog test
To test with priming paint and be diluted to required viscosity (300-1000mPas (ICIRotothinner ball)) with complete remollescent water and use the Ungalvanized Steel Plate (200 * 80 * 0.9mm) on of box blade blade coating in cleaning; The slit sizes of selecting blade is so that dry coating thickness is 60-85 μ m.
At room temperature dry 6 days and 50 ℃ of following thermal conditionings after 1 day, with the dorsal part of metallic test plate with the solvent-based coating coating preventing corrosion, and the edge is used Film is pasted.
Use scriber delineation metallic test plate to base material in a side that scribbles the test undercoat at last.Salt-fog test/evaluation
The use test plate carries out salt-fog test (duration of test runs: 240 hours) according to DIN EN ISO7253.As Fig. 1 to metal sheet take pictures (Comparative Examples 1 is in the left side, and embodiment 1 is in the centre, and the repetition of embodiment 1 is at right-hand side).
The corrosion that it is evident that the metal sheet of embodiment 1 is compared much less with Comparative Examples 1.

Claims (15)

1. comprise at least a at least one thioamides group-(the C=S)-NR that contains 1R 2The purposes of coating in atomospheric corrosion control of compound (D), the coating that wherein comprises at least a thioamides (D) is at least 40 μ m and 2mm at the most at dried coat-thickness, and solidification value is for from greater than 0 ℃ to 40 ℃ and carry out under the relative atmospheric moisture of 10-80%
R wherein 1And R 2Independently of one another for H or have the linearity of 1-20 carbon atom or alkyl branching, optional replacement, have the cycloalkyl of 3-12 carbon atom or have the aryl of 6-12 carbon atom, wherein radicals R 1And R 2Can also form 5-12 unit ring with nitrogen-atoms.
2. according to the purposes of claim 1, wherein said compound (D) is selected from as follows:
(D1) general formula (II), R 4 n-R 3-(C=S) NR 1R 2Thioamides and
(D2) contain the thioamides of at least two thioamides groups,
Wherein n is natural number and the radicals R of 1-5 1, R 2, R 3And R 4Have following definition:
R 1And R 2Independently of one another for H or have the linearity of 1-20 carbon atom or alkyl branching, optional replacement, have the cycloalkyl of 3-12 carbon atom or have the aryl of 6-12 carbon atom, wherein radicals R 1And R 2Can also form 5-12 unit ring with nitrogen-atoms,
R 3For (n+1) valency alkyl with 1-30 carbon atom and
R 4Be functional group, this functional group be selected from ether, imino-, ketone group, aldehyde radical ,-OH ,-NH 2,-NHR 5,-NR 5R 5' ,-COOH ,-COOR 5,-CONH 2,-CONHR 5,-CONR 5R 5' ,-NHCOR 5,-NR 5' COR 5,-NHCONHR 5,-SH ,-CN ,-Si (OH) 3,-SO 3H ,-PO (OH) 2,-Si (OR 5) 3,-PO (OR 5) 2,-PS (OR 5) 2And quaternary ammonium group, wherein R 5And R 5' independently of one another for having the alkyl of 1-6 carbon atom.
3. according to the purposes of claim 1, wherein said coating comprises at least a following base-material (A) that is selected from: polyvinylesters, polyester, polyethers, Resins, epoxy-amine adduct, polyureas, polymeric amide, polyimide and the urethane of (methyl) acrylic ester polymer, partial hydrolysis.
4. according to the purposes of claim 2, wherein said coating comprises at least a following base-material (A) that is selected from: polyvinylesters, polyester, polyethers, Resins, epoxy-amine adduct, polyureas, polymeric amide, polyimide and the urethane of (methyl) acrylic ester polymer, partial hydrolysis.
5. according to the purposes of claim 3 or 4, wherein said (methyl) acrylic ester polymer is (methyl) acrylate copolymer.
6. according to the purposes of claim 3 or 4, wherein said polyester is Synolac, polylactone or polycarbonate.
7. according to each purposes among the claim 1-4, wherein said coating comprises at least a following base-material (A) that is selected from:
-(A1) polyacrylic ester,
-(A2) urethane,
-(A3) the styrene butadiene polymkeric substance and
-(A4) Synolac.
8. according to the purposes of claim 7, DIN 53495 water-intake rates of base-material (A)-" mensuration of polymkeric substance test-water-intake rate " wherein, method 3, under 23 ℃ in 24 hours-as follows:
-under the situation of polyacrylic ester (A1), be no more than 25 weight %,
-under the situation of urethane (A2), be 100 weight % at the most, or
-under the situation of styrene butadiene polymkeric substance (A3), be no more than 15 weight %,
-under the situation of Synolac (A4), be no more than 25 weight %.
9. according to the purposes of claim 7, wherein said base-material (A) uses with polymeric dispersions, wherein uses The granularity that Autosizer 2C measures:
-under the situation of polyacrylic ester (A1) 50-400nm,
-under the situation of urethane (A2)<1000nm,
-under the situation of styrene butadiene polymkeric substance (A3) 50-400nm,
-under the situation of Synolac (A4) 50-400nm.
10. purposes according to Claim 8, wherein said base-material (A) uses with polymeric dispersions, wherein uses
Figure FSB00000319908900022
The granularity that Autosizer 2C measures:
-under the situation of polyacrylic ester (A1) 50-400nm,
-under the situation of urethane (A2)<1000nm,
-under the situation of styrene butadiene polymkeric substance (A3) 50-400nm,
-under the situation of Synolac (A4) 50-400nm.
11. according to each purposes among the claim 1-4, wherein said coating comprises at least a pigment and/or filler (C).
12. according to each purposes among the claim 1-4, wherein compound (D) has 6-20 carbon atom, this does not comprise and is present in radicals R 1And R 2In any carbon atom.
13. according to each purposes among the claim 1-4, wherein compound (D) is 100g/l at least in the solubleness in the glycol monomethyl n-butyl ether under 23 ℃.
14., be used for the atomospheric corrosion control of buildings, bridge, electric pole, container, power plant, chemical plant, boats and ships, crane, pillar, bulkhead, pipe, accessory and architectural grade steel according to each purposes among the claim 1-4.
15. a method of producing corrosion control with coating comprises:
-at first with base-material (A) with dispersion in water and at least a at least two thioamides groups-(the C=S)-NR that comprises 1R 2Compound (D2) mix R wherein 1And R 2Independently of one another for H or have the linearity of 1-20 carbon atom or alkyl branching, optional replacement, have the cycloalkyl of 3-12 carbon atom or have the aryl of 6-12 carbon atom, wherein radicals R 1And R 2Can also with nitrogen-atoms form 5-12 unit ring and
-only after finishing component (A) and mixing (D2) in the gained mixture at least a pigment of adding and/or filler.
CN200680003468XA 2005-01-28 2006-01-26 Anti-corrosion coatings containing thioamide groups Expired - Fee Related CN101111571B (en)

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
DE102005004292.9 2005-01-28
DE200510004292 DE102005004292A1 (en) 2005-01-28 2005-01-28 Method for applying corrosion protection layer on metallic surfaces comprises treating the surface with a formulation having binding agent, pigment and/or filler and corrosion protecting agent, which is a thioamide group containing compound
DE102005061320A DE102005061320A1 (en) 2005-12-20 2005-12-20 New copolymer, formed from monoethylenic unsaturated dicarboxylic acid derivative and two different monoethylenic unsaturated monomers, useful as corrosion inhibitors and additives to aqueous systems
DE200510061317 DE102005061317A1 (en) 2005-12-20 2005-12-20 Method for applying integrated pre-treatment layers, comprises applying cross linkable preparation containing e.g. corrosion protection agent, on metallic surface and thermally- and/or photochemically cross linking the layer
DE200510061319 DE102005061319A1 (en) 2005-12-20 2005-12-20 Use of coating substances comprising a compound that comprises thioamide group in atmospheric corrosion protection of e.g. building, bridges, current masts, tank, container, pipelines, power stations, chemical plants, ships and cranes
DE102005061320.9 2005-12-20
DE200510061318 DE102005061318A1 (en) 2005-12-20 2005-12-20 Preparation, useful for obtaining corrosion protection layers to metallic surfaces, comprises a binding agent system, corrosion preventing polymer agent, solvent and a component of fine-particle filler, pigment or dye
DE102005061318.7 2005-12-20
DE102005061317.9 2005-12-20
DE102005061319.5 2005-12-20
PCT/EP2006/050462 WO2006079643A1 (en) 2005-01-28 2006-01-26 Anti-corrosion coatings containing thioamide groups

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CNA2006800035273A Pending CN101111572A (en) 2005-01-28 2006-01-24 Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces
CN2006800035593A Expired - Fee Related CN101111574B (en) 2005-01-28 2006-01-24 Preparation and method for applying corrosion protection layers
CN2006800035470A Expired - Fee Related CN101111573B (en) 2005-01-28 2006-01-24 Method for applying corrosion protection layers comprising thioamides to metallic surfaces
CN200680003468XA Expired - Fee Related CN101111571B (en) 2005-01-28 2006-01-26 Anti-corrosion coatings containing thioamide groups

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CNA2006800035273A Pending CN101111572A (en) 2005-01-28 2006-01-24 Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces
CN2006800035593A Expired - Fee Related CN101111574B (en) 2005-01-28 2006-01-24 Preparation and method for applying corrosion protection layers
CN2006800035470A Expired - Fee Related CN101111573B (en) 2005-01-28 2006-01-24 Method for applying corrosion protection layers comprising thioamides to metallic surfaces

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CN101111571A (en) 2008-01-23
CN101111572A (en) 2008-01-23
CN101111573A (en) 2008-01-23
CN101155882A (en) 2008-04-02
CN101111573B (en) 2012-03-28
CN101111574B (en) 2010-06-16
CN101111574A (en) 2008-01-23

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