WO2011051313A1 - Formulations aqueuses - Google Patents

Formulations aqueuses Download PDF

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Publication number
WO2011051313A1
WO2011051313A1 PCT/EP2010/066219 EP2010066219W WO2011051313A1 WO 2011051313 A1 WO2011051313 A1 WO 2011051313A1 EP 2010066219 W EP2010066219 W EP 2010066219W WO 2011051313 A1 WO2011051313 A1 WO 2011051313A1
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Prior art keywords
cosolvent
group
glycol
ether
aqueous formulations
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PCT/EP2010/066219
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German (de)
English (en)
Inventor
Hans Georg Grablowitz
Maria Almato Guiteras
Juan Miguel Garcia Martinez
Rolf Gertzmann
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Bayer Materialscience Ag
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Publication of WO2011051313A1 publication Critical patent/WO2011051313A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents

Definitions

  • the invention relates to the preparation of aqueous, cosolvent-containing formulations which exhibit rapid physical drying and their use as coating agents on substrates.
  • Water-based systems are increasingly playing a major role in lower commercially available coating materials due to increased ecological and occupational hygiene aspects.
  • the actual binder is often used in the form of a solvent-free aqueous dispersion.
  • physically drying one-component polymers are a particularly important product class because they require no further curing component and can film through the evaporation of water at room temperature alone. It depends strongly on the physical properties of the polymer, whether the filming process leads to a closed film with corresponding favorable coating properties.
  • polymers can only film at room temperature if the molecular chains can penetrate one another.
  • the molecular weight of the polymer must not be too high and further, the polymer must have at least one phase whose glass and / or melting temperature is below room temperature, since the segment mobility of the polymer chains for mutual penetration is otherwise not high enough.
  • the minimum film-forming temperature MFT
  • the MFT is often close to the glass transition temperature of the polymer or a corresponding phase.
  • the object of the invention is achieved by the objects of the present invention.
  • An object of the present invention are therefore containing aqueous formulations
  • Another object of the present invention are therefore containing aqueous formulations
  • cosolvents B which have a solubility parameter ⁇ ⁇ in the range from 12.00 to 14.00 (cal / cm 3 ) 1/2 .
  • the arithmetic mean ⁇ is in the range of 10.05 to 13.50, most preferably in the range of 10, 10 to 13.00.
  • the aqueous composition according to the invention preferably contains from 10 to 90% by weight of component A.
  • the percentages by weight relate to the total weight of the aqueous formulation. With particular preference the proportion by weight is from 30 to 70% by weight and very particularly preferably from 35 to 65% by weight.
  • the water-based binder component A) may consist of one or more binders.
  • binder A selected from the group consisting of poly (meth) acrylates, polystyrene (meth) acrylates, polyvinyl esters, polyesters, polyesterurethanes, styrene-butadiene copolymers, alkyd resins, polyethers, epoxy resin amine. Adducts, polyureas, epoxy-functional polymers, polychloroprenes, polyvinyl ethers, polyvinyl chlorides, acrylonitrile-butadiene polymers, ethylene-vinyl acetate polymers, polyolefins and polyurethanes.
  • binder A selected from the group consisting of (AI) poly (meth) acrylates, polystyrene (meth) acrylates and
  • Ale 0 to 4% by weight, preferably 0.01 to 2, particularly preferably at least 0.05 to 1% by weight of at least one crosslinking agent.
  • Main monomers AI a) contain a radically polymerizable group and are selected from the group consisting of C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitrites, vinyl halides, vinyl ethers of alcohols containing 1 to 10 carbon atoms and aliphatic hydrocarbons having 2 to 8 carbon atoms.
  • Exemplary principal monomers Ala) are (meth) acrylic acid alkyl esters having a C 1 -C 20 -alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for example, vinyl laurate, stearate, vinyl propionate and vinyl acetate.
  • Suitable vinylaromatic compounds are vinyltoluene a- and p-methylstyrene, a-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds, preferably vinyl chloride and vinylidene chloride.
  • Vinyl ethers include, for example, vinyl methyl ether or vinyl isobutyl ether.
  • Suitable monomers Ala) are preferably the alkyl (meth) acrylates, preferably (C 2 -C 10 -alkyl) acrylates and methacrylates, and the vinylaromatics, as well as mixtures of these compounds. Very particular preference is given to methyl methacrylate, n-butyl acrylate, n-hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate and styrene and mixtures of these monomers as monomers (Ala).
  • methyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate and styrene and mixtures of these monomers as monomers Ala) are preferred.
  • copolymerizable monomers Alb) are other monomers having a free-radically polymerizable group than those mentioned under Ala), preferably those which, besides the free-radically polymerizable double bond, have at least one, preferably 1 to 3, more preferably 1 to 2 and most preferably one further functional group, such as, for example, hydroxyl groups, epoxy groups, carbonyl groups, carboxamide groups or carboxy groups, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates, (meth) acrylamide, ethylenically unsaturated acids or acid anhydrides, in particular carboxylic acids, such as (meth) acrylic acid Cystonic acid or dicarboxylic acids, eg itaconic acid, maleic acid or fumaric acid.
  • Vernetzer Ale are those which preferably have at least two free-radically polymerizable double bonds, more preferably 2 to 6, most preferably 2 to 4, even more preferably 2.
  • the at least two free-radically polymerizable double bonds of the crosslinking agents a1) may be selected from the group consisting of (meth) acrylic, vinyl ether, vinyl ester, allyl ether and allyl ester groups.
  • These radically polymerizable groups in the crosslinkers a1) may be the same or different.
  • Examples of compounds a1) having the same radically polymerizable groups are 1,2-ethanediol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,2-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate , 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioldi (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, and divinylbenzene.
  • Example of compounds a1) having various radically polymerizable groups are allyl acrylate, allyl methacrylate, methallyl acrylate, methallyl methacrylate, (meth) acrylic acid but-3-en-2-yl ester, (meth) acrylic acid but-2-en-1-yl ester, ( Meth) acrylic acid 3-methylbut-2-en-1-yl ester, esters of (meth) acrylic acid with geraniol, citronellol, cinnamyl alcohol, glycerol mono- or diallyl ether, trimethylolpropane mono- or diallyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, propylene glycol monoallyl ether, Dipropylenglykolmonoallylether, 1,3-Propandiolmonoallylether, 1, 4-butanediol monoallyl ether and also Itaconkladiallylester.
  • 5-oxa-hept-6-en-1-yl (meth) acrylate (meth) acrylic acid 3,4-dihydro-2H-pyran-2-ylmethylester and 2-hydroxy-but-3-ene l -yl (meth) acrylate.
  • the polyacrylates (AI) can be prepared in a manner known per se according to the generally known methods of emulsion polymerization from the monomers using the customary emulsifying and dispersing auxiliaries and polymerization initiators. Such auxiliaries, amounts used and typical conditions are known in the art (see Houben-Weyl, Methods of Organic Chemistry, Volume XIV, Macromolecular substances, loc cit, pages 133 ff).
  • both primary and secondary dispersions can be used according to the invention.
  • the polymerization of the base monomers takes place directly in the aqueous phase
  • prefabricated polymers are present in a wide range of amounts.
  • ren process step usually by polymerization in an organic solvent, then dispersing the polymer in water, optionally followed by a preferably distillative separation of the solvent from the dispersion.
  • the free-radical polymerizations can be prepared in batch, semi-batch or continuous processes; preference is given to the semi-batch process, in which case the monomers are usually metered in uniformly over a defined period of time for the polymerization. It is also possible to generate different polymer phases by the temporal change of the streams.
  • the acid groups contained in the (co) polymer can still be at least partially neutralized. This can be done, for example, with oxides, hydroxides, carbonates or bicarbonates of alkali metals or alkaline earth metals, preferably with hydroxides to which any one or more counterions may be associated, eg Li + , Na + , K + , Cs + , Mg 2+ , Ca 2 + or Ba 2+ .
  • ammonia or amines in particular tertiary amines, for example methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, tributylamine, diisopropylethylamine, benzyldimethylamine, monoethanolamine, diethanolamine, triethanolamine, hydroxyethyldimethylamine, hydroxyethyldiethylamine, monopropanolamine , Dipropanolamine, tripropanolamine, piperidine, piperazine, ⁇ , ⁇ '-dimethylpiperazine, morpholine or pyridine.
  • tertiary amines for example methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, tributylamine, diisopropylethylamine, benzyldimethylamine, monoethanolamine, diethanolamine, triethanolamine, hydroxyeth
  • 50 to 100 mol% of the acid groups are neutralized in the (co) polymer, particularly preferably 75 to 100 mol%, very particularly preferably 90 to 100 and in particular 100 mol%.
  • the glass transition temperature Tg of the copolymers or at least one phase of the copolymers is preferably in the range from 20 to 110 ° C., more preferably in the range from 25 to 105 ° C. (measured by the DSC method according to DIN EN ISO 11357).
  • Polyurethanes (A2) can be obtained by reacting
  • A2a at least one polyfunctional isocyanate having 4 to 30 C atoms
  • A2b diols of which A2bl) 10 to 100 mol%, based on the total amount of
  • Diols (A2b) have a molecular weight of 500 to 5000, and A2b2) 0 to 90 mol%), based on the total amount of the diols (A2b), have a molecular weight of 60 to 500 g / mol, • A2c) optionally further polyhydric compounds other than the diols (A2b) with reactive groups which are alcoholic hydroxyl groups or primary or secondary amino groups, and
  • Suitable monomers in A2a) are the polyisocyanates customarily used in polyurethane chemistry, for example aliphatic, aromatic and cycloaliphatic di- and polyisocyanates, the aliphatic hydrocarbon radicals having, for example, 4 to 12 carbon atoms, and the cycloaliphatic or aromatic hydrocarbon radicals, for example 6 to 15 carbon atoms or the araliphatic hydrocarbon radicals have, for example, 7 to 15 carbon atoms, with an NCO functionality of at least 1.8, preferably 1.8 to 5 and particularly preferably 2 to 4 in question, and in particular their isocyanurates, biurets, allophanates and uretdiones.
  • the diisocyanates are preferably isocyanates having 4 to 20 C atoms. Preference is given to diisocyanates selected from the group consisting of tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, esters of lysine diisocyanate, tetramethylxylylene diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, 1,4-, 1 , 3- or 1, 2-diisocyanatocyclohexane, trans / trans, the cis / cis and the cis / trans isomers of 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane,
  • Particularly preferred aliphatic and cycloaliphatic diisocyanates are selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, meta- Tetramethylxylylene diisocyanate (m-TMXDI) and 1,1-methylenebis [4-isocyanato] cyclohexane (H 12 MDI).
  • aromatic diisocyanates are selected from the group consisting of 2,4- o of 2,6-tolylene diisocyanate and their isomer mixtures, m- o de r p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane and their isomer mixtures , 1,3- or 1,4-phenylene diisocyanate, 1-chloro-2,4-phenylenediisocyanate, 1,5-naphthylene diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanato-3,3 ' dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-d ii so cyano, tetramethyl xylyl di diisocyanate, 1,4-diisocyanatobenzene or diphenyl ether-4,4'-diisocyanate,
  • Suitable polyisocyanates are polyisocyanates having isocyanurate groups, uretdione diisocyanates, polyisocyanates containing biuret groups, polyisocyanates containing urethane or allophanate groups, polyisocyanates containing oxadiazinetrione groups or iminooxadiazinedione groups, uretonimine-modified polyisocyanates of straight-chain or branched C 4 -C 20 -alkylene diisocyanates, cycloaliphatic diisocyanates having a total of from 6 to 20 C, Atoms or aromatic diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof.
  • Particularly suitable diols A2b) are relatively high molecular weight diols A2bl) which have a molecular weight of about 500 to 5000, preferably about 1000 to 3000 g / mol.
  • the diols A2bl) are, in particular, polyesterpolyols which are known, for example, from Ullmann's Encyklopadie der ischen Chemie, 4th Edition, Volume 19, pages 62 to 65. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms, and / or unsaturated. Examples include: suberic acid, azelaic acid, phthalic acid, hydrochloric, phthalic, tetrahydrophthalic, hexahydrophthalic, maleic, maleic, fumaric, dimer fatty acids.
  • dicarboxylic acids of the general formula HOOC- (CH 2 ) y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, for example succinic acid, adipic acid, dodecanedicarboxylic acid and sebacic acid.
  • Suitable polyhydric alcohols are, for example, ethylene glycol, propan-1, 2-diol, propane-1,3-diol, butane-1,3-diol, butane-1,4-diol, butyne-1,4-diol ol, pentane-1, 5-diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methylpropane-1,3-diol, furthermore diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, Dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycols into consideration.
  • x is a number from 1 to 20, preferably an even number from 2 to 20.
  • examples of these are ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-l, 8-diol and dodecane-l, 12-diol.
  • polycarbonate diols e.g. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.
  • lactone-based polyesterdiols which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules.
  • Preferred lactones are those derived from hydroxycarboxylic acids of the general formula HO- (CH 2 ) z -COOH, where z is a number from 1 to 20, preferably an odd number from 3 to 19, eg ⁇ -Caprolactone, ß-propiolactone, ⁇ -butyrolactone and / or methyl- ⁇ -caprolactone and mixtures thereof.
  • suitable starter components are the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols.
  • the corresponding polymers of ⁇ -caprolactone are particularly preferred.
  • Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
  • the polymers of lactones it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.
  • suitable monomers (A2bl) are polyether diols.
  • ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, for example in the presence of BF 3 or by addition of these Compounds optionally in admixture or in succession, on starting components with reactive hydrogen atoms, such as alcohols or amines, for example water, ethylene glycol, propane-1,2-diol, propane-1,3-diol, 2,2-bis (4-hydroxydiphenyl) propane or aniline available.
  • reactive hydrogen atoms such as alcohols or amines
  • Particularly preferred is polytetrahydrofuran having a molecular weight of 500 to 5000 g / mol, and especially 1000 to 4500 g / mol.
  • Suitable monomers (A2bl) are polycarbonate polyols.
  • polyester diols and polyether diols can also be used as mixtures in a ratio of 0.1: 1 to 1: 9.
  • diols A2b in addition to the diols A2bl), it is also possible to use low molecular weight diols A2b2) having a molecular weight of from about 50 to 500, preferably from 60 to 200, g / mol.
  • the monomers A2b2) used are in particular the synthesis components of the short-chain alkanediols mentioned for the preparation of polyester polyols, preference being given to the unbranched diols having 2 to 12 carbon atoms and an even number of carbon atoms and pentanediol-1,5 and neopentyl glycol.
  • the proportion of the diols (A2bl), based on the total amount of the diols A2b) is 10 to 100 mol% and the proportion of the diols A2b2), based on the total amount of the diols A2b) 0 to 90 mol%.
  • the ratio of the diols A2bl) to the diols A2b2) is particularly preferably 0.2: 1 to 5: 1, particularly preferably 0.5: 1 to 2: 1.
  • the monomers A2c which are different from the diols A2b), generally serve for crosslinking or chain extension. They are generally more than divalent non-aromatic alcohols, amines having 2 or more primary and / or secondary amino groups, and compounds which carry one or more primary and / or secondary amino groups in addition to one or more alcoholic hydroxyl groups.
  • Alcohols of higher valency than 2 which can serve to set a certain degree of branching or crosslinking, are e.g. Trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, sugar alcohols, such as e.g. Sorbitol, mannitol, diglycerol, erythritol, or sugar.
  • monoalcohols which, in addition to the hydroxyl group, carry a further isocyanate-reactive group, such as monoalcohols having one or more primary and / or secondary amino groups, for example monoethanolamine.
  • monoalcohols having one or more primary and / or secondary amino groups for example monoethanolamine.
  • Polyamines having 2 or more primary and / or secondary amino groups can be used in the prepolymer mixing process above all when the chain extension or crosslinking is to take place in the presence of water, since amines generally react faster than alcohols or water with isocyanates , This is often required when aqueous dispersions of high molecular weight crosslinked polyurethanes or polyurethanes are desired.
  • the procedure is to prepare prepolymers with isocyanate groups, to rapidly disperse them in water and then to chain extend or crosslink them by adding compounds containing several isocyanate-reactive amino groups.
  • Amines suitable for this purpose are generally polyfunctional amines of the molecular weight range from 32 to 500 g / mol, preferably from 60 to 300 g / mol, which contain at least two primary, two secondary or one primary and one secondary amino group.
  • diamines such as diaminoethane, diaminopropanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine, IPDA), 4,4'-diaminodicyclohexylmethane, 1 , 4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as diethylenetriamine or 1,8-diamino-4-aminomethyloctane or higher amines such as triethylenetetramine, tetraethylenepentamine or polymeric amines such as polyethyleneamines, hydrogenated polyacrylonitriles or at least partially hydrolyzed poly-N-vinylformamides each with a molecular weight up to 2000, preferably up to 1000 g
  • the amines may also be in blocked form, e.g. in the form of the corresponding ketimines, ketazines or amine salts.
  • Oxazolidines also represent blocked polyamines, which can be used for the preparation of the polyurethanes for chain extension of the prepolymers. When using such capped polyamines they are generally mixed with the prepolymers in the absence of water and this mixture is then mixed with the dispersion water or a portion of the dispersion water, so that the corresponding polyamines are released hydrolytically.
  • the proportion of polyamines may be up to 10, preferably up to 8 mol% and particularly preferably up to 5 mol%, based on the total amount of components A2b) and A2c).
  • monoalcohols can be used for chain termination in minor amounts, ie preferably in amounts of less than 10 mol%, based on the components A2b) and A2c). They serve mainly to limit the molecular weight of the polyurethane.
  • Examples are methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-Butano l, Ethyl englyko lmonomethylether, ethylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, n-hexanol, n-heptanol, n-octanol , n-decanol, n-dodecanol (lauryl alcohol) and 2-ethylhexanol.
  • the polyurethanes in addition to the components A2a), A2b) and A2c) from A2a), A2b) and A2c) different monomers A2d), the at least one isocyanate group or at least one to isocyanate groups reactive group and, moreover, at least one hydrophilic group or a group which can be converted into hydrophilic groups bear.
  • hydrophilic groups or potentially hydrophilic groups is abbreviated to "(potentially) hydrophilic groups”. The (potentially) hydrophilic groups react much more slowly with isocyanates than the functional groups of the monomers which serve to build up the polymer main chain.
  • the (potentially) hydrophilic groups may be nonionic or, preferably, ionic, ie cationic or anionic, hydrophilic groups, or potentially ionic hydrophilic groups, and more preferably anionic hydrophilic groups, or potentially anionic hydrophilic groups.
  • the proportion of components with (potentially) hydrophilic groups in the total amount of components A2a), A2b), A2c) and A2d) is generally such that the molar amount of the (potentially) hydrophilic groups, based on the weight amount of all monomers A2a) to A2b), 30 to 1000, preferably 50 to 500 and particularly preferably 80 to 300 mmol / kg.
  • Suitable nonionic hydrophilic groups are, for example, mixed or pure polyethylene glycol ethers of preferably from 5 to 100, preferably from 10 to 80, ethylene oxide repeat units.
  • the polyethylene glycol ethers may also contain propylene oxide units. If this is the case, the content of propylene oxide units should not exceed 50% by weight, preferably 30% by weight, based on the mixed polyethylene glycol ether.
  • the content of polyethylene oxide units is generally 0 to 10, preferably 0 to 6 wt .-%, based on the amount by weight of all monomers A2a) to A2d).
  • Preferred monomers with nonionic hydrophilic groups are the polyethylene glycol and diisocyanates which carry a terminally etherified polyethylene glycol radical.
  • Ionic hydrophilic groups are especially anionic groups such as the sulfonate, the carboxylate and the phosphate group in the form of their alkali metal or ammonium salts, as well as cationic groups such as ammonium groups, in particular protonated tertiary amino groups or quaternary ammonium groups.
  • Suitable monomers with potentially anionic groups are usually aliphatic, cycloaliphatic, araliphatic or aromatic mono- and dihydroxycarboxylic acids which carry at least one alcoholic hydroxyl group or one primary or secondary amino group.
  • Such compounds are represented, for example, by the general formula RG-R U -DG wherein RG is at least one isocyanate-reactive group, DG is at least one dispersive group and R 11 is an aliphatic, cycloaliphatic or aromatic radical containing from 1 to 20 carbon atoms.
  • RG are -OH, -SH, -NH 2 or -NHR 12 , wherein R 12 is methyl, ethyl, iso -propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, cyclopentyl or cyclohexyl can.
  • such components are e.g. mercaptoacetic acid, mercaptopropionic acid, thiolactic acid, mercaptosuccinic acid, glycine, iminodiacetic acid, alanine, ⁇ -alanine, leucine, isoleucine, aminobutyric acid, hydroxyacetic acid, hydroxypivalic acid, lactic acid, hydroxysuccinic acid, hydroxydecanoic acid, dimethylolpropionic acid, dimethylolbutyric acid, ethylenediaminetriacetic acid, hydroxydodecanoic acid, hydroxyhexadecanoic acid , 12-hydroxystearic acid, aminonaphthalenecarboxylic acid, hydroxethanesulfonic acid, hydroxypropanesulfonic acid, mercaptoethanesulfonic acid, mercaptopropanesulfonic acid, aminomethanesulfonic acid, taurine, ammopropanesulfonic acid,
  • Potentially ionic hydrophilic groups are, in particular, those which undergo simple neutralization, hydrolysis or quaternization reactions in the abovementioned ionic groups can be converted hydrophilic groups, ie, for example, acid groups, anhydride groups or tertiary amino groups.
  • Ionic monomers A2d) or potentially ionic monomers A2d) are e.g. in Ullmanns Enzyklopadie der ischen Chemie, 4th Edition, Volume 19, pp. 311-313.
  • monomers with tertiary amino groups are of particular practical importance as potentially cationic monomers A2d), for example: tris (hydroxyalkyl) -amines, ⁇ , ⁇ '-bis (hydroxyalkyl) -alkylamines, N-hydroxyalkyldialkylamines, tris (aminoalkyl) - amines, ⁇ , ⁇ '- bis (aminoalkyl) alkylamines, N-aminoalkyl-dialkylamines, wherein the alkyl radicals and alkanediyl moieties of these tertiary amines independently of one another consist of 2 to 6 carbon atoms.
  • polyethers having tertiary nitrogen atoms preferably having two terminal hydroxyl groups e.g. by the alkoxylation of two amine-containing hydrogen atoms, e.g. Methylamine, aniline, or ⁇ , ⁇ '-dimethylhydrazine, in a conventional manner are accessible, into consideration.
  • Such polyethers generally have a molecular weight between 500 and 6000 g / mol.
  • tertiary amines are prepared either with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid or hydrohalic acids, strong organic acids such as formic, acetic or lactic acid, or by reaction with suitable quaternizing agents such as C 1 -C 6 alkyl halides, e.g. Bromides or chlorides, or di-Ci-C6-alkyl sulfates or di-Ci-C6-alkyl carbonates in the ammonium salts. If monomers having potentially ionic groups are used, their conversion into the ionic form may take place before, during, but preferably after the isocyanate polyaddition, since the ionic monomers are often difficult to dissolve in the reaction mixture.
  • acids preferably strong mineral acids such as phosphoric acid, sulfuric acid or hydrohalic acids, strong organic acids such as formic, acetic or lactic acid
  • suitable quaternizing agents such as C 1 -C 6 alkyl halides, e.g. Brom
  • the anionic hydrophilic groups are particularly preferably in the form of their salts with an alkali ion or an ammonium ion as the counterion.
  • the polyurethanes may contain both nonionic hydrophilic and ionic hydrophilic groups, preferably simultaneously nonionic hydrophilic and anionic hydrophilic groups.
  • the molecular weight of the polyurethanes can be adjusted by selecting the proportions of the mutually reactive monomers and the arithmetic mean of the number of reactive functional groups per molecule. Normally, the components A2a), A2b), A2c) and A2d) and their respective molar amounts are chosen so that the ratio
  • : 1 to 2 1, preferably 0.8: 1 to 1.5, more preferably 0.9: 1 to 1.2: 1. Most preferably, the molar ratio is as close as possible to 1: 1.
  • components A2a), A2b), A2c) and A2d) are monomers having only one reactive group generally in amounts of up to 15 mol%, preferably up to 8 mol%, based on the total amount of components A2a), A2b ), A2c) and A2d) are used.
  • the polyaddition of the components A2a) to A2d) is generally carried out at reaction temperatures of 20 to 180 ° C, preferably 50 to 150 ° C under atmospheric pressure.
  • reaction times can range from a few minutes to a few hours. It is known in the field of polyurethane chemistry how the reaction time is affected by a variety of parameters such as temperature, concentration of monomers, reactivity of the monomers.
  • the usual catalysts can be used.
  • all catalysts customarily used in polyurethane chemistry which are known to the person skilled in the art, are suitable for this purpose.
  • Rhackkessel come into consideration as polymerization, especially when provided by the concomitant use of solvents for a low viscosity and good heat dissipation.
  • extruders in particular self-cleaning multi-screw extruders, are particularly suitable because of the usually high viscosities and the usually short reaction times.
  • a prepolymer which carries isocyanate groups.
  • the components A2a) to A2d) are in this case selected such that the ratio of NCO groups to NCO-reactive groups as defined is greater than 1.0 to 3, preferably 1.05 to 1.5.
  • the prepolymer is first dispersed in water and simultaneously and / or subsequently by reaction of the isocyanate groups with alkali metal.
  • metal hydroxides or amines carrying more than 2 isocyanate-reactive amino groups, crosslinked or with amines carry the 2 isocyanate-reactive amino groups, chain-extended. Chain extension also occurs when no amine is added.
  • isocyanate groups are hydrolyzed to amine groups which react with remaining isocyanate groups of the prepolymers with chain extension.
  • Cosolvents B all the aliphatic and aromatic organic solvents known to those skilled in the art, which have a relatively high polarity due to their structure. These include organic solvents which in addition to carbon and hydrogen contain at least one other electronegative heteroatom, such as oxygen, nitrogen and sulfur.
  • the cosolvent B) consists exclusively of carbon, oxygen and hydrogen atoms.
  • the cosolvent B) is particularly preferably selected from the group consisting of alkylene glycol monoethers and cyclic alkylene carbonates.
  • the cosolvent B) is selected from the group consisting of propylene carbonate (PC) and propylene glycol monomethyl ether (PM).
  • the cosolvent B) consists exclusively of carbon, oxygen and hydrogen atoms.
  • the cosolvent C) is particularly preferably selected from the group consisting of alkylene glycol monoether, ethylene glycol monoether, dialkylene glycol monoether, trialkylene glycol monoether, alkylene glycol diether, dialkylene glycol diether, alkylene glycol ether acetate, dialkylene glycol ether acetate and cyclic alkylene carbonates.
  • Preferred alkylene glycol monoethers as cosolvent C) are selected from the group consisting of propylene glycol monomethyl ether (PM), propylene glycol monoethyl ether (PE), propylene glycol mono-n-propyl ether (PNP), propylene glycol mono-tert-butyl ether (PTB), propylene glycol mono-n-butyl ether ( PNB) and propylene glycol monohexyl ether.
  • Preferred ethylene glycol monoethers as cosolvent C) are selected from the group consisting of ethylene glycol hexyl ether, ethylene glycol octyl ether and ethylene glycol phenylene ether.
  • Preferred dialkylene glycol monoethers as cosolvent C) are selected from the group consisting of dipropylene glycol monomethyl ether (DPM), dipropylene glycol mono-n-propyl ether (DPNP), dipropylene glycol mono-tert-butyl ether (DPTB), dipropylene glycol mono-n-butyl ether (DPNB), dipropylene glycol monohexyl ether, diethylene glycol n butyl ether (BDG), diethylene glycol hexyl ether and diethylene glycol octyl ether.
  • DPM dipropylene glycol monomethyl ether
  • DPNP dipropylene glycol mono-n-propyl ether
  • DPTB dipropylene glycol mono-tert-butyl ether
  • DPNB dipropylene glycol mono-n-butyl ether
  • BDG diethylene glycol hexyl ether
  • diethylene glycol octyl ether
  • Preferred trialkylene glycol monoethers as cosolvent C) are selected from the group consisting of tripropylene glycol monomethyl ether (TPM) and tripropylene glycol mono-n-butyl ether (TPNB).
  • Preferred alkylene glycol diethers as cosolvent C) are selected from the group consisting of propylene glycol dimethyl ether, propylene glycol benzyl methyl ether, propylene glycol butyl methyl ether, propylene glycol dibutyl ether, ethylene glycol diethyl ether and ethylene glycol dibutyl ether.
  • Preferred dialkylene glycol diethers as cosolvent C) are selected from the group consisting of dipropylene glycol dimethyl ether, dipropylene glycol butyl methyl ether and dipropylene glycol dibutyl ether.
  • Preferred alkylene glycol ether acetates as cosolvent C) are selected from the group consisting of propylene glycol methyl ether acetate (PM acetate), propylene glycol ethyl ether acetate (PE acetate), propylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate and ethylene glycol butyl ether acetate.
  • Preferred dialkylene glycol ether acetates as cosolvent C) are selected from the group consisting of dipropylene glycol methyl ether acetate (DPM acetate) and diethylene glycol butyl thoroacetate.
  • alkylene glycol monoethers as cosolvent C are selected from the group consisting of propylene glycol monoethyl ether (PE), propylene glycol mono-n-propyl ether (PNP), propylene glycol mono-tert-butyl ether (PTB), propylene glycol mono-n-butyl ether (PNB) and propylene glycol monohexyl ether.
  • Particularly preferred ethylene glycol monoethers as cosolvent C) are selected from the group consisting of ethylene glycol hexyl ether, ethylene glycol octyl ether and ethylene glycol phenyl ether.
  • dialkylene glycol monoethers as cosolvent C are selected from the group consisting of dipropylene glycol monomethyl ether (DPM), dipropylene glycol mono- n-propyl ether (DPNP), dipropylene glycol mono-tert-butyl ether (DPTB), dipropylene glycol mono- n-butyl ether (DPNB), dipropylene glycol monohexyl ether, diethylene glycol n-butyl ether (BDG), diethylene glycol hexyl ether and diethylene glycol octyl ether.
  • DPM dipropylene glycol monomethyl ether
  • DPNP dipropylene glycol mono- n-propyl ether
  • DPTB dipropylene glycol mono-tert-butyl ether
  • DPNB dipropylene glycol mono- n-butyl ether
  • BDG diethylene glycol hexyl ether
  • Particularly preferred trialkylene glycol monoethers as cosolvent C) are selected from the group consisting of tripropylene glycol monomethyl ether (TPM) and tripropylene glycol mono-n-butyl ether (TPNB).
  • TPM tripropylene glycol monomethyl ether
  • TPNB tripropylene glycol mono-n-butyl ether
  • alkylene glycol diethers as cosolvent C) are selected from the group consisting of propylene glycol dimethyl ether, propylene glycol, ethylene glycol, propylene glycol butyl methyl ether, propylene glycol dibutyl ether, ethylene glycol diethyl ether and ethylene glycol dibutyl ether.
  • dialkylene glycol diethers as cosolvent C are selected from the group consisting of dipropylene glycol dimethyl ether, dipropylene glycol butyl methyl ether and dipropylene glycol dibutyl ether.
  • alkylene glycol ether acetates as cosolvents C) are selected from the group consisting of propylene glycol methyl ether acetate (PM acetate), propylene glycol ethyl ether acetate (PE acetate), propylene glycol butyl ether acetate, ethylene glycol ethyl ether acetate and ethylene glycol butyl ether acetate.
  • dialkylene glycol ether acetates as cosolvent C are selected from the group consisting of dipropylene glycol methyl ether acetate (DPM acetate) and diethylene glycol butyl ether acetate.
  • the cosolvent C) is selected from the group consisting of alkylene glycol monoethers with the exception of propylene glycol monomethyl ether, dialkylene glycol monoethers, alkylene glycol ether acetates and dialkylene glycol ether acetates.
  • Formulation components are preferably selected from the group consisting of defoaming agents, thickeners, pigments, dispersing agents, catalysts, Anti-skinning agents, wetting agents, leveling agents, anti-settling agents and emulsifiers.
  • Another object of the present invention are coating compositions containing the aqueous formulations of the invention.
  • Conventional additives and other auxiliaries such as pigments, plasticizers, fillers, stabilizers, surfactants, rheology additives, biocides, metal oxides such as zinc oxide or magnesium oxide, crosslinkers such as melamine resins, polyisocyanates, carbodiimides and metal salt complexes, leveling agents, defoamers, dispersing aids and catalysts can be added to the coating compositions.
  • novel aqueous formulations are preferably suitable for painting and sealing wood and wooden materials, coating metallic surfaces (metal coating), coating and painting asphalt or bituminous coatings, coating and painting of mineral substrates and for painting and sealing of substrates selected from the Group consisting of plastic, glass, glass fibers, carbon fibers, woven and non-woven textiles, nonwovens, leather, paper, hard fibers and straw.
  • aqueous formulations according to the invention for coating metallic surfaces and plastics and for lacquering and sealing wood is preferred.
  • Bayhydrol AH XP 2741 aqueous polystyrene acrylate dispersion having a minimum film formation temperature of 60 ° C., Bayer MaterialScience AG, DE Alberdingk AC 2514, aqueous self-crosslinking polyacrylate dispersion having a minimum film forming temperature of 43 ° C., Alberdingk, DE
  • Byk 341 additive based on a polydimethylsiloxane to reduce surface tension
  • Byk Chemie DE Dehydran 1620: Defoamer based on a polysiloxane, Cognis, DE Acrysol RM 8-W: Non-ionic associative polyurethane-based thickener, Rohm & Haas, US
  • the corresponding dispersion is initially charged with stirring. Thereafter, the previously mixed cosolvents are added slowly and for 10 min. mixed at 2.0-2.2 m / s.
  • the Byk additives are successively added to the mixture and 10 min. stirred at 1.8 - 2.0 m / s and then the defoamer Dehydran 1620 is added and another 5 min. at 1.8 - 2.0 m / s stirred. Finally, the thickener is added with 5 min. at 0.5 - 1.0 m / s is stirred.
  • T4 The drying time T4 is measured on the basis of DIN 53150.
  • Table 3 Overview of the formulations with the mixing ratio of the co-sols 1: 1 * formulations according to the invention
  • Table 4 Overview of the formulations with the mixing ratio of the co-solvents 4: 6 * formulations according to the invention

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne la production de formulations aqueuses contenant un co-solvant qui présentent un séchage physique rapide, ainsi que leur utilisation comme agents de revêtement sur des substrats.
PCT/EP2010/066219 2009-10-30 2010-10-27 Formulations aqueuses WO2011051313A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP09013666 2009-10-30
EP09013666.4 2009-10-30

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WO2011051313A1 true WO2011051313A1 (fr) 2011-05-05

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN103436140A (zh) * 2013-08-23 2013-12-11 苏州长盛机电有限公司 一种铜材用防腐蚀涂料

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WO1998053796A1 (fr) * 1997-05-29 1998-12-03 The Dow Chemical Company Compositions feuillogenes contenant plusieurs solvants
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WO2001034394A1 (fr) * 1999-11-07 2001-05-17 Aprion Digital Ltd Fluide de preparation de plaques d'impression et son procede d'utilisation
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DE4128572A1 (de) * 1990-08-29 1992-03-05 Atochem North America Nichtchromatierte massen und verfahren zur aufbringung von schutzfilmen auf die oberflaeche von metallen
WO1998053796A1 (fr) * 1997-05-29 1998-12-03 The Dow Chemical Company Compositions feuillogenes contenant plusieurs solvants
WO1999006478A1 (fr) * 1997-07-31 1999-02-11 The Dow Chemical Company Composition contenant une resine amphi-ionique et un complexe metallique polyvalent
WO2001034394A1 (fr) * 1999-11-07 2001-05-17 Aprion Digital Ltd Fluide de preparation de plaques d'impression et son procede d'utilisation
US20030232955A1 (en) * 2002-02-18 2003-12-18 Martin Melchiors Aqueous coating compositions based on epoxybutene polyethers
EP1864823A1 (fr) * 2005-03-31 2007-12-12 Seiko Epson Corporation Liquide de traitement, liquide d amorce d impression et composition d encre pour support d impression a jet d encre, procede d impression a jet d encre utilisant ceux-ci et texte imprime
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103436140A (zh) * 2013-08-23 2013-12-11 苏州长盛机电有限公司 一种铜材用防腐蚀涂料
CN103436140B (zh) * 2013-08-23 2016-06-01 苏州长盛机电有限公司 一种铜材用防腐蚀涂料

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