CA2101876A1 - Water-thinnable two-component coating composition - Google Patents
Water-thinnable two-component coating compositionInfo
- Publication number
- CA2101876A1 CA2101876A1 CA002101876A CA2101876A CA2101876A1 CA 2101876 A1 CA2101876 A1 CA 2101876A1 CA 002101876 A CA002101876 A CA 002101876A CA 2101876 A CA2101876 A CA 2101876A CA 2101876 A1 CA2101876 A1 CA 2101876A1
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- CA
- Canada
- Prior art keywords
- acid
- groups
- mol
- water
- thinnable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
Abstract Water-thinnable two-component coating composition A water-thinnable two-component coating composition, comprising 1) a polyisocyanate component and 2) a polyester resin which is composed of the starting components (a), (b), (c), (d) and (e) or their ester-forming derivatives, the ratio of the sum of the hydroxyl equivalents to the sum of the carboxyl equivalents in the reactants being between 1:0.5 and 1:2.0, where (a) is at least one dicarboxylic acid which is not a sulfo monomer, (b) is 0 to 15 mol% of at least one difunctional sulfo or phosphono monomer, whose functional groups are carboxyl and/or hydroxyl groups, with at least one sulfonate or phosphonate group, (c) is at least one glycol, (d) is 0 to 40 mol% of a higher-functional compound (functionality >2), whose functional groups are hydroxyl and/or carboxyl groups, and (e) is 0 to 20 mol% of a monofunctional carboxylic acid, the amounts of free hydroxyl groups being between 30 and 350 milliequivalents of OH/100 g and the content of free neutralized and/or neutralizable acid groups being between 5 and 350 meq/100 g.
These coating compositions are suitable in particular for the preparation of primers, fillers, topcoats and one-coat finishes.
These coating compositions are suitable in particular for the preparation of primers, fillers, topcoats and one-coat finishes.
Description
2 ~ 7 ~
9~/K 052 Water-thinna~le two-component coating c~mposition The invention relates to a water-thinnable two-component coating composition based on polyester resins, to a process for its preparation and to its use as a coating.
The switch from conventional coatings to water-thinnable systems is proceeding at full pace. In one-component systems, in particular, the replacement of conventional binders by aqueous binders has already reached an advanced stage.
What is proving difficult is the use of conventional binders in high-quality two-component systems. Especially in the case of chemically crosslinking polyurethane coatings, which due to their outstanding properties are of great importance in the coatings sector, it has so far not been possible to dispense with organic solvents. The use of aqueous binders appeared problematic in that the polyisocyanate compounds employed as curing agents react with water with the formation of N-substituted polyurea compounds and the elimination o~ carbon dioxlde.
It is known from EP 0 358 979 that specific polyhydroxy polyacrylates are capable of emulsifying polyisocyanate curing agen-ts in water and curing to give crosslinking films.
EP 0 469 38~ describes a two-component coating composi-tion comprising an a~ueous dispersion of a polyurethane and a water-dispersible polyisocyanate, which cures at room temperature.
Surprisingly, it has now been found that selected water-thinnable polyester resins described in greater detail :
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below are particularly favorable for combining unblocked polyisocyanate curing agents, having an excellent emulsifier effect for them.
The invention therefore provides a water-thinnable two-component coating composition comprising 1) a polyisocyanate component composed of one or more organic polyisocyanates, and 2) a polyester resin which is composed of the starting components (a), (b), (c), (d) and (e) or their ester-forming derivatives, the sum of the r~actants being 100 mol% and the ratio of the sum of the hydroxyl equivalents to the sum of the carboxyl equivalents in the reactants being between 1~0.5 and 1.2Ø
The polyester resin is composed of (a) at least one dicarboxylic acid that is not a sulfo monomer, (b) 0 to 15 mol~, preferably l to 6 mol%, of at least one difunctional sulfo or phosphono monomer, whose functional groups are carboxyl and/or hydroxyl groups, with at least one sulfonate or phosphonate group, (c) at least one glycol, (d) 0 to 40 mol%, preferably 8 to 20 mol~, of a higher-functional compound (functionality ~2), whose ~unctiona:L groups are hydroxyl and/or carboxyl group~, and (e) 0 to 20 mol% of a mono-functional aarboxylic acid.
In this polyester resin the quantity of free hydroxyl groups is between 30 and 350 millie~uival~nts of OH/100 g, preferably between 100 and 253 meq of OH/100 g, ~ and the content of free neutralized and/or neutralizable : acid groups, in particular sulfonic, phosphonic and carboxylic acid groups, is between 5 and 350 meq/100 g~
preferably between 10 and 120 m~q/100 g.
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The in~ention further relates to a process ~or the preparation of this coating composition and to its use as a coating.
The polyisocyanate component 1) is any desired organic polyisocyanate, preferably a diisocyanate having aliphat-ically, cycloaliphatically, araliphatically and/or aromatically attached free isocyanate groups which is liquid at room temperatureO The polyisocyanate component 1~ generally has a viscos.ity of 50 to 20,000 mPa.s at 23C. It is particularly preferably a polyisocyanate or polyisocyanate mixture containing only a].ipha-tically and/or cycloaliphatically attached isocyanate group~ and having an (average) NCO functionality of between 2~0 and $Ø
The polyisocyanate~ may if required be used as a mixture with small amounts o~ inert solvents, in order to reduce the viscosity tQ a value within the stated ranges.
~owever, the amount of such solvents is preferably calculated so that, in the coatings according to the invention which are ultimately obtained, not more than 30~ by weight of solvent is present, the calculation including the solvent which may still be present in the : polyester resin dispersions or solutions. Examples vf suitable solvents for the polyisocyanates are aromatic hydrocarbons, such as solvent naphtha or other solvents, such as butylglycol, N methylpyrrolidone, methoxy-: propanol, isopropanol, butanol and acetone.
The polyisocyanates, preferably diisocyanates, arecompounds known in the polyurethane or coatings sector, such as aliphatic, cycloaliphatic or aromatic diiso-cyanates. They are preferably of the ~ormula Q(NCO~2, where Q is a hydrocarbon radical having 4 to 40 carbon atoms, in particular 4 to 20 carbon atoms, and is prefer-ably an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical having ` 6 to 15 carbon atoms, an aromatic hydrocarbon radical - . . . . - . . .
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having 6 to 15 carbon atoms or an araliphatic hydrocarbonradical having 7 to 15 carbon atoms. Examples of such diisocyanates to be employed with preference are tetra-methylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclo-hexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4,4'-diisocyanato-dicyclohexylmethane, 4,4'-diisocyanato-2,2-dicyclo-hexylpropane, 1,4-diisocyanatobenzene, 2,4- or 2,6-diiso-cyanatotoluene or mixtures of these isomers, 4,4'- or 2,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanato-2,2-diphenylpropane, p-xylylene diisocyanate and a,a,a',a'-tetramethyl-m- or -p-xylylene diisocyanate, or mixtures composed of these compounds.
In addition to these simple polyisocyanates those con-taining heteroatoms in the radical linking the isocyanate groups are also suitable. Examples of these polyiso-cyanates are those containing carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups, acylated urea yroups or biuret groups. With regard to further suitable polyisocyanates, reference is made by ; way of example to German Offenlegungsschrift 29 28 552.
Highly suitable examples are coating-grade polyiso-cyanates based on hexamethylene diisocyanate or on 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate - (IPDI) and/or bis(isocyanatocyclohexyl)methane, in particular those based exclusively on hexamethylene diisocyanate. Coating-grade polyisocyanates based on these diisocyanates are to be understood as meaning the derivatives of these diisocyanates which have biuret, urethane, uretdione and/or isocyanurate groups and are known per se, which after their preparation have, if required, been freed in a known manner, preferably by distillation, from excess starting diisocyanate down to a residual content of less than 0.5% by weight. The preferred aliphatic polyisocyanates to be used in accordance wlth the invention include the polyisocyanates .
_ 5 ~ 7S
which are based on hexamethylene diisocyanate, fulfill the abovementioned criteria and contain biuret groups, as can be obtained by, for example, the processes of US Patents 3,124,605, 3,358,010, 3,903,126, 3,903,127 or 3,976,622 and which comprise mixtures of N,N,N--tris(6-isocyanatohexyl~biuret w.ith minor amounts of its high~r homologs, and the cyclic trimers o~
hexamethylene diisocyanate which fulfill the above criteria, as can be obtained in accordance with US-A-4,324,879, which essentially consist of N,N,N-tris-(6-isocyanatohexyl) isocyanurate in a mixture with minor amounts o-f its higher homologs. Of particular preference are mixtures of poly.isocyanates based on hexamethylene diisocyanate which contain uretdione and/or isocyanurate groups and which fulfill the above criteria, as are formed by the catalytic oligomerization of hexamethylene diisocyanate using trialkyl phosphanes. The last-mentioned mixtures particularly preferably have a viscosity of 50 to 20,000 mPa.s at 23C and an NCO
functionality of between 2.0 and 5Ø
Also suitable are hydrophilic polyisocyanates which are stabilized in the aqueous phase by a sufficient number of anionic groups and/or by te.rminal or lateral polyether : chains, as are described in EP 0 469 389, EP 0 061 628 and EP 0 206 059.
The aromatic polyisocyanates which are also suitable in accordance with the invention but are less preferrecl are in particular coating-grade polyisocyanatss based on 2,4-diisocyanatoto}uene or technical-grade mixtures thereof with ~,6-diisocyanatotoluene or based on 4,4'-diisocyanatodiphenylmethane or its mixtures with its isomers and/or higher homologs. Examples of aromatic : coating polyisocyanates of this type are the isocyanates containin~ urethane groups, as are obtained by reaction o~ excess amounts of 2,4~diisocyanatotoluene with polyhydric alcohols such as trimethylolpropane and the possible subsequent distillative removal of the unreacted ..
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diisocyanate excess. Examples of further aromatic coating polyisocyanates are the trimers of the monomeric diiso-cyanates mentioned by way of example, i.e. the corresponding isocyanato-isocyanu.rates which, following their preparation, may have been freed from excess monomeric diisocyanates, pre~erably by distillation.
It is o~ course also possible in principle to use unmodi-fied polyisocyanates of the type men-tioned by way of example, provided they conform to the statement~ made regarding viscosity.
The polyisocyanate component 11 can also comprise any desired mixtures of the polyisocyanates mentioned.
The polyester resin (2) is, as described above, composed of the starting components (a), (b), (c), (d) and (e) or their ester-forming derivatives.
The terms higher-functional, multifunctional or poly-~unctional as used herein refer to compounds having more than two re~ctive hydroxyl and/or carboxyl group~; the term glycol refers to a compound having two and the term :20 polyol to a compound having more than two hydroxyl substituents.
.
The dicarboxylic acid aomponent (a) of the polyester comprises axomatic, cycloaliphatic or aliphatic saturated or unsaturated dicarboxylic acids and dimeric fatty acids or mixtures of two or more of these dicarboxylic acidsO
:Examples of these dicarboxylic acids are oxalic, malonic, glutaricl adipic, pimelic, azelaic, sebacic, fumaric, maleic and intaconic acid, 1,3-cyclopentanedicarboxylic acid, l,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane-:30 dicarboxylic acid, 1~4-cyclohexanedicarboxylic acid, phthalic, terephthalic and isophthalic acid, 2,5-norbornanedicarboxylic acid, 1,4-naphthalenedi-carboxylic acid, biphenyldicarboxylic acid, 4,4'-sulfonyldibenzoic acid and 2,5-naphthalene-.
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dicarboxylic acid, and their esters and anhydrides~
Preferred dicarboxylic acid components (a) are phthalic, isophthalic and terephthalic acid, phthalic anhydride, adipic acid, succinic acid and its anhydride, dimeric fatty acids, sebacic and azelaic acid, 1,3 cyclohexanedi-carboxylic acid and glutaric acid and esters thereof~
Component (b) of the polyPster is a difunctional aroma-tic, cycloaliphati~ or aliphatic compound having reactive carboxyl and/or hydroxyl groups which also has a group -S03x- or -P(O)(OX)2-, where X is hydrogen or a metal ion such as Na+, Li+, X+, Mg~+, Ca2+, Cu2+ or a nitrogen-containing cation of aliphatic, cycloaliphatic or aromatic compounds`, such as ammonia, triethylamine, dimethylethanolamine, diethanolamine, triethanolamine and pyridine.
The groups -S03X- or -P(O)(OX)2- can be attached to an aromatic nucleus such as phenyl, naphthyl, biphenylyl nucleus, methylenediphenyl or anthracenyl. Hydroxy- and carboxyarylsulfonic acids are preferredO
Examples of component (b) are sulfoisophthalic acid, sul~oterephthalic acid, sulfophthalic acid, sulfo-salicylic acid, sulfosuccinic acid and esters thereof.
Particular pre~erence is given to the Na salts of sul~oisophthalic acid, sul~oisophthalic acid dimethyl ester, sulfosalicylic acid and sulfosuccinic acid.
The proportion of component (b) i9 0 to 15 mol%, particu-larly preferably up to 6 mol%.
The glycol component (c) may comprise low molecular weight aliphatic, cycloaliphatic or aromatic glycols, polyhydroxy polyethers or polycarbonate-polyols. Examples of low moleculax weight glycols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2~2-dimethyl-1,3-propanediol, 1,3-buthnediol, 1,4-butanediol, , .
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1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclo-hexanedimethanol, 1,4-cyclohexanedimethanol, perhydro-bisphenol A and p-xylylenediol, and 2-ethyl-2-butyl-propanediol.
Suitable polyhydroxy polyethers are compounds of the formula H- [ ~O~ ( CHR ) n~ 3 mOH
in which 0 R is hydrogen or a low alkyl radical which may have various substituents~
n is a number from 2 to 6 and m i5 a number from 6 to 120.
Examples are poly(oxytetxamethylene) glycols, poly~oxy-ethylene) glycols and poly(oxypropylene) glycols. The preferred polyhydroxy polyet,hers are poly(oxypropylene) glycols having a molecular weight in the range from 400 to 5000.
The polycarbonate-polyols or polycarbonate-diols are compounds of the formula o ~O-R-(O-C-O-R-)n-OH
in which R is an alkylene radical. These O~-~unctional polycarbonates can be prepared by reacting polyols ~uch ~ as propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, ; diethylene glycol, triethyIene glycol, 1,4-bishydroxy-methylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, neopentylglycol, trimethylolpropane and pentaerythritol with dicarbonates such as dimethyl, diethyl or diphenyl carbonate or pho~gene. Mixture~ of these polyols can also ; be employed.
~he proportion of component ~c) should be calculated so .
.
, , , , ' ' , 2 ~ 7 i) as to eonform to the ratio o-f hydroxyl equivalents to carboxyl equivalents which was indicated initially.
The higher-functional component (d) which preferably contains 3 to 6 hydroxyl and/or carboxyl groups preEer-ably comprises trimethylolpropane, trimethylolethane,glycerol, ditrimethylolpropane, pentaerythritol, dipenta-erythritol, bishydroxyalkanecarboxylic acids, such as dimethylolpropionic acid, trimellitic anhydride and polyanhydrides as deseribed in DE 28 11 913 or mixtures of two or more of these compounds, the propor-tion of the higher-functional component (d) being preferably 5 to 30 mol%, in particular 8 to 20 mol%.
The monofunctional carboxylic acids (e) are primarily fatty aeids such as eapric aeid, lauric acid, stearic aeid and palmitie acid, but it is also possible to employ branched carboxylie aeids, sueh as isovalerie aeid and isooetanoie aeid.
The number-average molecular weight of the polyester resin, determined experimentally using gel permeation chromatography, may lie between 500 and 4000, and is preferably from 1000 to 3500.
The glass transition temperature of the polyesters is preferably between -60C and 100C.
In order, if desired, to achieve as far as possible a quantitative cocondensation of the sulfo or phosphono monomer, it may be neeessary to carry out the synthesis of the deseribed polyesters in a multistage proeess. For this purpose all of the hydroxy funetional eomponents are initially reacted in the presence of catalysts with the sulfo or phosphono monomers and, i~ appropriate, with carboxylic acid-containing eomponents in sueh a way that, in the eondensation, 95% of the quantity of distillate ealeulated for quantitative eonversion i5 obtained. The aliphatie earboxylie aeid eomponents, if appropriate, are '. ,~
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then reacted, the condensation being continued up to the desired content of carboxylic acid equivalentsO
When using a bishydroxyalkanecarboxylic acid, an OH-func-tional polyester is Eirst prepared which is then sub jected to a condensation reaction with the bishydroxy-alkanecarboxylic acid and a further dicarboxylic acid to give the desired polyester.
If polycarboxylic anhydrides are used to introduce the anionic groups, then an O~-functional polyester is reacted with the anhydride to give the half-ester, and condensation is then continued up to the desired acid number.
The reaction takes place at temperatures between 140C
and 240C, preferakly between 160C and 220C. To avoid losses of glycol, the condensate is distilled using a distillation column. Suitable catalysts are preferably organometallic compounds, in particular compounds con-taining zinc, tin or titanium, for example zinc acetate, dibutyltin oxide or tetrabutyl titanate. The amount of catalyst is preferably 0.1 to 1.5% by weight of the totll batch amount.
The acid groups can be introduced via the individual components into the polyester already in neutralized form; where free acid groups ars present in the poly-ester, they can if desired be neutralized with aqueoussolutions of alkali metal hydroxides or with amines, for example with trimethylamine, triethylamine, dimethyl-aniline, diethylaniline, triphenylamine, dimethylethanol-amine, aminomethylpropanol, dimethylisopropanolamine or ; 30 with ammonia.
The polyester can be isolated in bulk, but it is pre~er-able to prepare a 50 to 95% solution in a water-miscible organic solventO Suitable solvents in this respect are preferably oxygenated solvents such as alcohols, ketones, : .
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esters and ethers, for example ethanol, n-propanol, isopropanol, isobutanol, butyl acetate and butylglycol, or nitrogen-containing solvents such as N-methylpyrrol-idone. The viscosity of these solutions is preferably between 0.5 and 40 Pa.s at 60C.
This solution is then used to prepare the polyester dispersion, so that amounts of 15 to 65% by weight of polyester, O to 30% by weight of organic solvents and 35 to 85~ by weight of water are present in the disper-sions. The resulting pH is 2 to 8.5, preferably 4.0 to 8Ø
The content of polyester res.in in the aqueous coating composition is .in general 5 to 40% by weight, preferably 15 to 30% by weight, based on the overall aqueous coating composition.
In addition to the polyester resin, the aqueous coating composition can also contain, as binders, up to 60% by weight, preferably up to 30% by weight, based on the polyester resin, of other oligomeric or polymeric materials, such as cro slinkin~, water-soluble or water-dispersible phenolic resins, polyurethane resins, epoxy ~ resins or acrylic resins, etc., as described for example in European Offenlegungsschrift 89 497.
To prepare the ready~to-use coatings the polyisocyanate component 1) is emulsified in the aqueous dispersion/solution o-E the polyester resin 2), the dissolved or dispersed polyester resin adopt.ing the function of an emulsifier for the added polyisocyanate.
This is krue in particular for the preferred case in which polyisocyanates are used which are not hydrophilic-ally modified. It is also possible to use as polyiso-cyanate component 1) hydrophilic-modified polyisocyanates which, due to the incorporated ionic or nonionic hydrophilic centres, are autodispersible.
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Mixing can be carried out by simply stirring the com ponents together at room temperature. The amount of polyisocyanate component is preferably calculated so as to result in an NCO/OH equivalen-t ratio, based on the isocyanate groups of component 1) and the alcoholic hydroxyl groups of component 2), of 0.5:1 to 5:1, in particular 0.8:1 to 3:1.
Prior to the addition of the polyisocyanate component, the auxiliaries and additives customary in coatings technology can be incorporated into the polyester resin 2), i.e. the dispersion or solution of the polymers. These include for example antifoams, leveling assistants, pigments and pigment dispersants.
The resulting coatings according to the invention are suitable ~or practically all areas of application which currently employ solvent-corltaining, solvent-free or other types of aqu00us paint and coating sy~tems having an enhanced range of properties.
They are preferably used for topcoats and one-coat finishes, in which case the substrates to be coated may be, for example, metal, mineral construction materials such as limestone, cement or gypsum, fiber-ceme~t construction materials, concrete, wood or timber materials, paper, asphalt, bitumen, plastics of various kinds, textiles or leather. The metallic substrates are preferably in all cases automobiles.
Another pre~erred use is as a primer or sur~acer, in which case the substrates to be coated may be, ~or example, metal, mineral construction materials such as limestone, cement or gypsum, fiber-cement construction materials, concrete, wood or timber materials, paper, asphalt, bitumen, textiles or leather~ The metallic substrates are again preferably automobiles.
2 ~ 7 ~
~xamples:
The polyester synthesis is carried out in a 4 l four-neck flask ~itted with a packed column (column tube: 30 mm diameter, 2000 mm length; packing: glass rings of 6 mm diameter and 6 mm length) and a descending bridge-shaped distillation head, with temperature sensing of the reacting material under a protective gas atmosphere (protective gas feed, nitrogen). I~ low-boiling alcohols, especially methanol, are distilled off a~ condensate, the receiver should be cooled using an ice bath The abbreviations used below are explained on page 17.
Polyester 1 Initial amounts as in Table 1 Melt neopentylglycol and trimethylolpropane, add IPA and 1.5 g of dibutyltin oxide, heat so that the overhead temperature does not exceed 100C, subject the mixture to condensation at 190C to 200C until the content of acid groups is 10 meq of COOH/100 g.
Cool to 140C, add ADPA and DMPA, heat so that the overhead -temperature does not exceed 100~C, subiect the mixture to condensation at temperatures of up to 200C
until a value of 64 meq of COOH/100 g is reached. ~hen cool to 80C, add 62.2 g of dimethylethanolamine and ~:~ 290 g of N-methylpyrrolidone and di~perse in 2818 g of wat~r.
Polyester 2 Initial amounts as in Tabl.e 1 Melt the hydroxyl group-containing reactants, add 5-SIP-~a, TPA and 1~5 g of dibutyltin oxide, heat so that the overhead temperature does not exceed 100C, subject the mixture to condensation at 185C to 195C until 135 g of distillate are obtainedO
Cool to 120C, add IPA and 1.0 g of dibutyltin oxide, heat so that the overhead temperature does not exceed 100C, subject the mixture to condensation at temper-.
'' 2~0~l87~
atures of up to 190C until the content of free carboxyl groups is 55 meq of COOH/100 g, then continue condensation a-t 180C to 200C and 100 mbar until a value of 7 meq of COOH/100 g is reached.
720 g of N-methylpyrrolidone are added at 140C and the batch is then dispersed with 4680 g of water.
Polye~ter 3 Initial amounts as in Table 1 Melt neopentylglycol and trimethylolpropane, add TPA, IPA
and 1 5 g o~ dibutyltin oxide, heat 50 that the overhead tempexature does not exceed 100C, subject the mixture to condensation at 190C~to 200C until the content of acid ~roups is 10 meq of COOH/100 g.
Cool to 140C, add TMA~ and stir at this temperature 15 until a value of 71 meq of COOH/100 g is reached. ~hen cool to 80C, add 175 g of N-methylpyrrolidone and 80 g of dimethylethanolamine, and disperse in 1800 g of water.
Polyester 4 Initial amounts as in Table 1 Melt neopentylglycol and trimethylolpropane, add TPA, IPA, LA and 2.5 g of dibutyltin oxide, heat so that the overhead temperature does not exceed 100C, subject the mixture to condensation at 190C to 200C until the content of acid groups i9 10 meq of COO~/100 g.
Cool to 140C/ add ADPA and DMPA, heat so that the overhead temperature does no~ exceed 100C, subject the mixture to condensation at temperatures o up to 200C
until a value of 56 me~ of COO~/100 g is reached. Than cool to 80C, add 300 g of ~-methylpyrrolidone and 70 g of dime-thylethanolamine, and disperse in 2430 g of water.
Table 1 (* see over) ,~
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Rey. IPA = isophthalic acid TPA = terephthalic acid ADPA = adipic acid 5-SIP-Na = 5-sulfoisophthalic acid Na salt NPG = neopentylglycol TMP = trimethylol]propane DMPA = dimethylolp.ropionic acid EG = ethylene glycol LA = lauric acid TMAA = trimellitic anhydride PEG = polyethylene ~lycol 2-Component primer The dispersion batch is prepared by mixing 65.8 part~ by weight of the polyester (1), (2), (3) or (4) having a solids content of 38~ by wei~ht with 0.2 part by weight of a commercially available silicone~free antifoam (Additol VXW 4973 from Hoechst AG), 0.3 part by weight oE
a commercially available wetting and dispersing auxiliary (Additol XL 250 from Hoechst AG) and 0.4 part by weight of a commercially available leveling agent (Additol ; XW 390 from Hoechst AG~o After simply stirring, 14.0 parts by weight of titanium dioxide (Kronos 2310 from Kronos~Titan GmbH), 11.0 partR by weight of a barium sulfate (Blanc fixe micro from Sachtleben GmbH), 3.7 parts by weight o-f a talc (Naintsch E 7 from Naintsch Mineralwerke Gmb~) and 0.1 part by weight of a carbon black (Flammru~ 101 from Degussa AG) are added to the batch, which is dispersed for about 30 m:inutes in a dissolver at a speed of 6000 rpm.
A variety of polyisocyanates can be employed as the curing component, for example (I) ~asonat FDS 342~ ~rom :BA5F AG, (II) Desmodur VPhS 2550, lIII) Desmodur N 3300 and (IV) Desmodur N 100 from Bayer AG.
The dispersion batch was then mixed with 12.5 parts by weight o~ a suitable polyisocyanate which has, if ~:~
:, ' . . ~ . ' 2 ~ 7 ~
appropriate, been previously diluted with methoxypropyl acetate; the composition of the batch in accordance with the invention is as follows:
. . .
Example A Example B Example C ~xample D
_ Binder 1 2 3 4 25.00 25.00 .~5.00 25.0~
Pigments 28.80 28.80 28.80 28.80 Auxiliaries0.~0 0.90 0.90 0.90 Total solids54.7054~70 54.70 54.70 Deionized waker 42.05 40.05 42.05 42.05 Organic solvent 3.25 5.25 3.25 3.25 Total 100~00 100.00 100.00 100.00 _ _ __ _ Polyisocyanate (III) 12.50 ~I) 12.50 (II) 12.50 (III) 12.50 Methoxypropyl ': acetate6.25 0.00 0.00 12.50 ~ _ The ready-to-process batches have a con-tent of organic solvents of only 2.89 to 12.60~ by weight. The coatings are applied to the substrate at a wek-~ilm thickness of 150 300 ~m ~corresponding to a dry-film thickness of 25 ko 50 ym) and dried for 30 minutes ak 80C in a circulating-air oven.
The cured coating ~ilms of Examples A to D can be charac-terized as fo1lows:
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Solvent resistance Example A Example B Example C Example D
_ ____ Isopropanol good-moderate very good m~derate ~sderate Isopropanol/water (1:1) gcod very good moderate ~Lderate Ethanol very good- ve~y good- moderate moderate good good Ethanol/water (1:1) good very good mLderate moderate Pre~iumrgrade gasolLne good moderate moderate n~derate Example A ~ le B Exa~ple C ~xample D
_ Pendulum hardness 75"-100" 100"-110" 25"-40" 15"-25 acc. to DIM 53157 60 ~los~ 50% 43~ 88% 73 acc. to DIN 67530 Hot-wet test acc. to good-moderate good-~oderate good moderate Sal~ spra~ test good very good- ~ery good- very good-acc. to ASTM~B117-6~ good good good Topcoat appeaLance good good very good good Sto~e chip:
topcoat adhesion good good go,od-mcderate very good penetrations good ~x~derate good very good _ 2-Component topcoat The dispersion batch is prepared by mixing 71.1 parts by weight of polyester (1) or ~4) having a solids content of 38% by ~eight with 0O2 part by weight of a commercially available silicone-free antifoam (Additol VXW 4973 from Hoechst AG), 0.3 part by weight of a commercially available wetting and dispersing auxiliary ~Additol XL 250 from ~oechst AG) and 0.4 part ~y weight of a commeFcially available leveling agent ~Additol XW 390 .
.
,: ' ', .
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.
from Hoechs-t AG). After the simple stirring o the additives together with one another, 24.6 parts by weight o~ titanium dioxide (Kronos 2310 from Kronos-Titan GmbH) are added to the batch, which is dispersed for about 30 minutes in a dissolver at a speed of 6000 rpm.
A variety of polyisocyanates can be employed as the curing component, for example lI) Basonat FDS 3425 from BASF AG, (II~ Desmodur VPLS 2550, (III~ Desmodur N 3300 and (IV) Desmodur N 100 from Bayer AG.
The dispersion batch was then mixed with 13.4 parts ~y weight of a suitable polyisocyanate which is, if appro-priate, previously ~i;luted with methoxypropyl acetate;
the composition of the batch in accordance with the invention i~ as ~ollows:
_ Example A Example B Example C Example D
Binder 1 2 3 4 25.00 25.00 25.00 25~00 Pigments 28.80 28.80 28.80 28.80 Auxiliari~s 0.90 0.90 0.90 0.90 Total solids54.70 54.70 54.70 54.70 Deionized water42.05 40.05 42.05 42.05 Organic solvent3.25 5.25 3.25 3.25 __ .
Total 100.00 100.00 100.00 100.00 _ .
Polyisocyanate (III) 12.50 ~I) 12.50 ~II) 12.50 (III) 12.50 Methoxypropyl :
acetate 6.25 0.~0 n.oo 12.50 .
' ,, , : . - ., .
.
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~ 2~ -The ready-to-procPss batches have a content of organic solvents of only 8.5 to 13.3% by weight. The coatings are applied to the substrate at a wet-film thicknes~ of 200-400 ~m (corresponding to a dry-film thickness of 30 to 60 ~m) and dried for 30 minutes at 80C in a circulating-air oven.
The cured coating films of Examples E and F can be characterized as follows:
Solvent resistance Example E Example F
.
Isopropanol very good very good-good Isopropanol/water ~1:1) very good very good-good Ethanol very good-good good Ethanol/water (1:1) very good good Premium-grade gasoline very good-good good-mod~rate Example E Example F .
.
Pendulum hardness about 115" about 145"
acc. to DIN 53157 .
60 Gloss about 87% about 87%
acc. to DIN 67530 Topcoat appearance good good Stone chip:
topcoat adhesion good good penetrations good very good-goQd _22_2~8,~
The cured films from all the examples are tested in accordance with the following test proc~dures:
Pendulum hardness: in accordance with DIN 53 157 Degree of gloss: in accordance with DIN 67 530, measured at an angle of Ç0 Hot-wet test: in accordance with DIN 50 017 SK.
After 240 hours with atmospheric humidity of 100% and at a temperature o~ 40C, bli~tering, gloss and the quality of the coating surface were subjectively assessed according to a rating scale (1 = ver~ good, 5 = very poor) Salt spray test. in accordance with ASTM-B 117-69.
After 240 hours in a salt spray atmosphere, blistering and corrosive penetration at the predetermined corrosion points were subjectively assessed according to a rating scale (1 = very good, 5 = very poor) Topcoat appearance: the gloss and surface of the topcoat were subjectively asses~ed according to a rating scale (1 = very good, 5 = very poor) 25 Stone chip: The stone-chip resistance was te~ted using a stone chip testing device in accordance with the VDA [German Motor Industry Association]
(model 508 from Erichsen). For these tests, in each case 1 kg of scrap steel (angular, ~-5 mm) was projected under compressed-air acceleration (2 bar) on to the test panels. Vsing sample panels, an assessm~nt was made of the topcoat adhesion (very good = no abrasion, very poor = complete del~mination) and of the penetrations down to the :, .
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metal (very good = no penetrations, very poor = a large number of penetrations~.
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9~/K 052 Water-thinna~le two-component coating c~mposition The invention relates to a water-thinnable two-component coating composition based on polyester resins, to a process for its preparation and to its use as a coating.
The switch from conventional coatings to water-thinnable systems is proceeding at full pace. In one-component systems, in particular, the replacement of conventional binders by aqueous binders has already reached an advanced stage.
What is proving difficult is the use of conventional binders in high-quality two-component systems. Especially in the case of chemically crosslinking polyurethane coatings, which due to their outstanding properties are of great importance in the coatings sector, it has so far not been possible to dispense with organic solvents. The use of aqueous binders appeared problematic in that the polyisocyanate compounds employed as curing agents react with water with the formation of N-substituted polyurea compounds and the elimination o~ carbon dioxlde.
It is known from EP 0 358 979 that specific polyhydroxy polyacrylates are capable of emulsifying polyisocyanate curing agen-ts in water and curing to give crosslinking films.
EP 0 469 38~ describes a two-component coating composi-tion comprising an a~ueous dispersion of a polyurethane and a water-dispersible polyisocyanate, which cures at room temperature.
Surprisingly, it has now been found that selected water-thinnable polyester resins described in greater detail :
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below are particularly favorable for combining unblocked polyisocyanate curing agents, having an excellent emulsifier effect for them.
The invention therefore provides a water-thinnable two-component coating composition comprising 1) a polyisocyanate component composed of one or more organic polyisocyanates, and 2) a polyester resin which is composed of the starting components (a), (b), (c), (d) and (e) or their ester-forming derivatives, the sum of the r~actants being 100 mol% and the ratio of the sum of the hydroxyl equivalents to the sum of the carboxyl equivalents in the reactants being between 1~0.5 and 1.2Ø
The polyester resin is composed of (a) at least one dicarboxylic acid that is not a sulfo monomer, (b) 0 to 15 mol~, preferably l to 6 mol%, of at least one difunctional sulfo or phosphono monomer, whose functional groups are carboxyl and/or hydroxyl groups, with at least one sulfonate or phosphonate group, (c) at least one glycol, (d) 0 to 40 mol%, preferably 8 to 20 mol~, of a higher-functional compound (functionality ~2), whose ~unctiona:L groups are hydroxyl and/or carboxyl group~, and (e) 0 to 20 mol% of a mono-functional aarboxylic acid.
In this polyester resin the quantity of free hydroxyl groups is between 30 and 350 millie~uival~nts of OH/100 g, preferably between 100 and 253 meq of OH/100 g, ~ and the content of free neutralized and/or neutralizable : acid groups, in particular sulfonic, phosphonic and carboxylic acid groups, is between 5 and 350 meq/100 g~
preferably between 10 and 120 m~q/100 g.
' ' ~ , _ 3 _ 2 ~ 7 ~
The in~ention further relates to a process ~or the preparation of this coating composition and to its use as a coating.
The polyisocyanate component 1) is any desired organic polyisocyanate, preferably a diisocyanate having aliphat-ically, cycloaliphatically, araliphatically and/or aromatically attached free isocyanate groups which is liquid at room temperatureO The polyisocyanate component 1~ generally has a viscos.ity of 50 to 20,000 mPa.s at 23C. It is particularly preferably a polyisocyanate or polyisocyanate mixture containing only a].ipha-tically and/or cycloaliphatically attached isocyanate group~ and having an (average) NCO functionality of between 2~0 and $Ø
The polyisocyanate~ may if required be used as a mixture with small amounts o~ inert solvents, in order to reduce the viscosity tQ a value within the stated ranges.
~owever, the amount of such solvents is preferably calculated so that, in the coatings according to the invention which are ultimately obtained, not more than 30~ by weight of solvent is present, the calculation including the solvent which may still be present in the : polyester resin dispersions or solutions. Examples vf suitable solvents for the polyisocyanates are aromatic hydrocarbons, such as solvent naphtha or other solvents, such as butylglycol, N methylpyrrolidone, methoxy-: propanol, isopropanol, butanol and acetone.
The polyisocyanates, preferably diisocyanates, arecompounds known in the polyurethane or coatings sector, such as aliphatic, cycloaliphatic or aromatic diiso-cyanates. They are preferably of the ~ormula Q(NCO~2, where Q is a hydrocarbon radical having 4 to 40 carbon atoms, in particular 4 to 20 carbon atoms, and is prefer-ably an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic hydrocarbon radical having ` 6 to 15 carbon atoms, an aromatic hydrocarbon radical - . . . . - . . .
': , : , , , , : , : ': : ':'' ' , ' ' ' - -. .
_ 4 _ 2~ 7i~
having 6 to 15 carbon atoms or an araliphatic hydrocarbonradical having 7 to 15 carbon atoms. Examples of such diisocyanates to be employed with preference are tetra-methylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclo-hexane, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4,4'-diisocyanato-dicyclohexylmethane, 4,4'-diisocyanato-2,2-dicyclo-hexylpropane, 1,4-diisocyanatobenzene, 2,4- or 2,6-diiso-cyanatotoluene or mixtures of these isomers, 4,4'- or 2,4'-diisocyanatodiphenylmethane, 4,4'-diisocyanato-2,2-diphenylpropane, p-xylylene diisocyanate and a,a,a',a'-tetramethyl-m- or -p-xylylene diisocyanate, or mixtures composed of these compounds.
In addition to these simple polyisocyanates those con-taining heteroatoms in the radical linking the isocyanate groups are also suitable. Examples of these polyiso-cyanates are those containing carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups, acylated urea yroups or biuret groups. With regard to further suitable polyisocyanates, reference is made by ; way of example to German Offenlegungsschrift 29 28 552.
Highly suitable examples are coating-grade polyiso-cyanates based on hexamethylene diisocyanate or on 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate - (IPDI) and/or bis(isocyanatocyclohexyl)methane, in particular those based exclusively on hexamethylene diisocyanate. Coating-grade polyisocyanates based on these diisocyanates are to be understood as meaning the derivatives of these diisocyanates which have biuret, urethane, uretdione and/or isocyanurate groups and are known per se, which after their preparation have, if required, been freed in a known manner, preferably by distillation, from excess starting diisocyanate down to a residual content of less than 0.5% by weight. The preferred aliphatic polyisocyanates to be used in accordance wlth the invention include the polyisocyanates .
_ 5 ~ 7S
which are based on hexamethylene diisocyanate, fulfill the abovementioned criteria and contain biuret groups, as can be obtained by, for example, the processes of US Patents 3,124,605, 3,358,010, 3,903,126, 3,903,127 or 3,976,622 and which comprise mixtures of N,N,N--tris(6-isocyanatohexyl~biuret w.ith minor amounts of its high~r homologs, and the cyclic trimers o~
hexamethylene diisocyanate which fulfill the above criteria, as can be obtained in accordance with US-A-4,324,879, which essentially consist of N,N,N-tris-(6-isocyanatohexyl) isocyanurate in a mixture with minor amounts o-f its higher homologs. Of particular preference are mixtures of poly.isocyanates based on hexamethylene diisocyanate which contain uretdione and/or isocyanurate groups and which fulfill the above criteria, as are formed by the catalytic oligomerization of hexamethylene diisocyanate using trialkyl phosphanes. The last-mentioned mixtures particularly preferably have a viscosity of 50 to 20,000 mPa.s at 23C and an NCO
functionality of between 2.0 and 5Ø
Also suitable are hydrophilic polyisocyanates which are stabilized in the aqueous phase by a sufficient number of anionic groups and/or by te.rminal or lateral polyether : chains, as are described in EP 0 469 389, EP 0 061 628 and EP 0 206 059.
The aromatic polyisocyanates which are also suitable in accordance with the invention but are less preferrecl are in particular coating-grade polyisocyanatss based on 2,4-diisocyanatoto}uene or technical-grade mixtures thereof with ~,6-diisocyanatotoluene or based on 4,4'-diisocyanatodiphenylmethane or its mixtures with its isomers and/or higher homologs. Examples of aromatic : coating polyisocyanates of this type are the isocyanates containin~ urethane groups, as are obtained by reaction o~ excess amounts of 2,4~diisocyanatotoluene with polyhydric alcohols such as trimethylolpropane and the possible subsequent distillative removal of the unreacted ..
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diisocyanate excess. Examples of further aromatic coating polyisocyanates are the trimers of the monomeric diiso-cyanates mentioned by way of example, i.e. the corresponding isocyanato-isocyanu.rates which, following their preparation, may have been freed from excess monomeric diisocyanates, pre~erably by distillation.
It is o~ course also possible in principle to use unmodi-fied polyisocyanates of the type men-tioned by way of example, provided they conform to the statement~ made regarding viscosity.
The polyisocyanate component 11 can also comprise any desired mixtures of the polyisocyanates mentioned.
The polyester resin (2) is, as described above, composed of the starting components (a), (b), (c), (d) and (e) or their ester-forming derivatives.
The terms higher-functional, multifunctional or poly-~unctional as used herein refer to compounds having more than two re~ctive hydroxyl and/or carboxyl group~; the term glycol refers to a compound having two and the term :20 polyol to a compound having more than two hydroxyl substituents.
.
The dicarboxylic acid aomponent (a) of the polyester comprises axomatic, cycloaliphatic or aliphatic saturated or unsaturated dicarboxylic acids and dimeric fatty acids or mixtures of two or more of these dicarboxylic acidsO
:Examples of these dicarboxylic acids are oxalic, malonic, glutaricl adipic, pimelic, azelaic, sebacic, fumaric, maleic and intaconic acid, 1,3-cyclopentanedicarboxylic acid, l,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane-:30 dicarboxylic acid, 1~4-cyclohexanedicarboxylic acid, phthalic, terephthalic and isophthalic acid, 2,5-norbornanedicarboxylic acid, 1,4-naphthalenedi-carboxylic acid, biphenyldicarboxylic acid, 4,4'-sulfonyldibenzoic acid and 2,5-naphthalene-.
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dicarboxylic acid, and their esters and anhydrides~
Preferred dicarboxylic acid components (a) are phthalic, isophthalic and terephthalic acid, phthalic anhydride, adipic acid, succinic acid and its anhydride, dimeric fatty acids, sebacic and azelaic acid, 1,3 cyclohexanedi-carboxylic acid and glutaric acid and esters thereof~
Component (b) of the polyPster is a difunctional aroma-tic, cycloaliphati~ or aliphatic compound having reactive carboxyl and/or hydroxyl groups which also has a group -S03x- or -P(O)(OX)2-, where X is hydrogen or a metal ion such as Na+, Li+, X+, Mg~+, Ca2+, Cu2+ or a nitrogen-containing cation of aliphatic, cycloaliphatic or aromatic compounds`, such as ammonia, triethylamine, dimethylethanolamine, diethanolamine, triethanolamine and pyridine.
The groups -S03X- or -P(O)(OX)2- can be attached to an aromatic nucleus such as phenyl, naphthyl, biphenylyl nucleus, methylenediphenyl or anthracenyl. Hydroxy- and carboxyarylsulfonic acids are preferredO
Examples of component (b) are sulfoisophthalic acid, sul~oterephthalic acid, sulfophthalic acid, sulfo-salicylic acid, sulfosuccinic acid and esters thereof.
Particular pre~erence is given to the Na salts of sul~oisophthalic acid, sul~oisophthalic acid dimethyl ester, sulfosalicylic acid and sulfosuccinic acid.
The proportion of component (b) i9 0 to 15 mol%, particu-larly preferably up to 6 mol%.
The glycol component (c) may comprise low molecular weight aliphatic, cycloaliphatic or aromatic glycols, polyhydroxy polyethers or polycarbonate-polyols. Examples of low moleculax weight glycols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2~2-dimethyl-1,3-propanediol, 1,3-buthnediol, 1,4-butanediol, , .
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1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclo-hexanedimethanol, 1,4-cyclohexanedimethanol, perhydro-bisphenol A and p-xylylenediol, and 2-ethyl-2-butyl-propanediol.
Suitable polyhydroxy polyethers are compounds of the formula H- [ ~O~ ( CHR ) n~ 3 mOH
in which 0 R is hydrogen or a low alkyl radical which may have various substituents~
n is a number from 2 to 6 and m i5 a number from 6 to 120.
Examples are poly(oxytetxamethylene) glycols, poly~oxy-ethylene) glycols and poly(oxypropylene) glycols. The preferred polyhydroxy polyet,hers are poly(oxypropylene) glycols having a molecular weight in the range from 400 to 5000.
The polycarbonate-polyols or polycarbonate-diols are compounds of the formula o ~O-R-(O-C-O-R-)n-OH
in which R is an alkylene radical. These O~-~unctional polycarbonates can be prepared by reacting polyols ~uch ~ as propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, ; diethylene glycol, triethyIene glycol, 1,4-bishydroxy-methylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane, neopentylglycol, trimethylolpropane and pentaerythritol with dicarbonates such as dimethyl, diethyl or diphenyl carbonate or pho~gene. Mixture~ of these polyols can also ; be employed.
~he proportion of component ~c) should be calculated so .
.
, , , , ' ' , 2 ~ 7 i) as to eonform to the ratio o-f hydroxyl equivalents to carboxyl equivalents which was indicated initially.
The higher-functional component (d) which preferably contains 3 to 6 hydroxyl and/or carboxyl groups preEer-ably comprises trimethylolpropane, trimethylolethane,glycerol, ditrimethylolpropane, pentaerythritol, dipenta-erythritol, bishydroxyalkanecarboxylic acids, such as dimethylolpropionic acid, trimellitic anhydride and polyanhydrides as deseribed in DE 28 11 913 or mixtures of two or more of these compounds, the propor-tion of the higher-functional component (d) being preferably 5 to 30 mol%, in particular 8 to 20 mol%.
The monofunctional carboxylic acids (e) are primarily fatty aeids such as eapric aeid, lauric acid, stearic aeid and palmitie acid, but it is also possible to employ branched carboxylie aeids, sueh as isovalerie aeid and isooetanoie aeid.
The number-average molecular weight of the polyester resin, determined experimentally using gel permeation chromatography, may lie between 500 and 4000, and is preferably from 1000 to 3500.
The glass transition temperature of the polyesters is preferably between -60C and 100C.
In order, if desired, to achieve as far as possible a quantitative cocondensation of the sulfo or phosphono monomer, it may be neeessary to carry out the synthesis of the deseribed polyesters in a multistage proeess. For this purpose all of the hydroxy funetional eomponents are initially reacted in the presence of catalysts with the sulfo or phosphono monomers and, i~ appropriate, with carboxylic acid-containing eomponents in sueh a way that, in the eondensation, 95% of the quantity of distillate ealeulated for quantitative eonversion i5 obtained. The aliphatie earboxylie aeid eomponents, if appropriate, are '. ,~
'.
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then reacted, the condensation being continued up to the desired content of carboxylic acid equivalentsO
When using a bishydroxyalkanecarboxylic acid, an OH-func-tional polyester is Eirst prepared which is then sub jected to a condensation reaction with the bishydroxy-alkanecarboxylic acid and a further dicarboxylic acid to give the desired polyester.
If polycarboxylic anhydrides are used to introduce the anionic groups, then an O~-functional polyester is reacted with the anhydride to give the half-ester, and condensation is then continued up to the desired acid number.
The reaction takes place at temperatures between 140C
and 240C, preferakly between 160C and 220C. To avoid losses of glycol, the condensate is distilled using a distillation column. Suitable catalysts are preferably organometallic compounds, in particular compounds con-taining zinc, tin or titanium, for example zinc acetate, dibutyltin oxide or tetrabutyl titanate. The amount of catalyst is preferably 0.1 to 1.5% by weight of the totll batch amount.
The acid groups can be introduced via the individual components into the polyester already in neutralized form; where free acid groups ars present in the poly-ester, they can if desired be neutralized with aqueoussolutions of alkali metal hydroxides or with amines, for example with trimethylamine, triethylamine, dimethyl-aniline, diethylaniline, triphenylamine, dimethylethanol-amine, aminomethylpropanol, dimethylisopropanolamine or ; 30 with ammonia.
The polyester can be isolated in bulk, but it is pre~er-able to prepare a 50 to 95% solution in a water-miscible organic solventO Suitable solvents in this respect are preferably oxygenated solvents such as alcohols, ketones, : .
, .
2 1 ~
esters and ethers, for example ethanol, n-propanol, isopropanol, isobutanol, butyl acetate and butylglycol, or nitrogen-containing solvents such as N-methylpyrrol-idone. The viscosity of these solutions is preferably between 0.5 and 40 Pa.s at 60C.
This solution is then used to prepare the polyester dispersion, so that amounts of 15 to 65% by weight of polyester, O to 30% by weight of organic solvents and 35 to 85~ by weight of water are present in the disper-sions. The resulting pH is 2 to 8.5, preferably 4.0 to 8Ø
The content of polyester res.in in the aqueous coating composition is .in general 5 to 40% by weight, preferably 15 to 30% by weight, based on the overall aqueous coating composition.
In addition to the polyester resin, the aqueous coating composition can also contain, as binders, up to 60% by weight, preferably up to 30% by weight, based on the polyester resin, of other oligomeric or polymeric materials, such as cro slinkin~, water-soluble or water-dispersible phenolic resins, polyurethane resins, epoxy ~ resins or acrylic resins, etc., as described for example in European Offenlegungsschrift 89 497.
To prepare the ready~to-use coatings the polyisocyanate component 1) is emulsified in the aqueous dispersion/solution o-E the polyester resin 2), the dissolved or dispersed polyester resin adopt.ing the function of an emulsifier for the added polyisocyanate.
This is krue in particular for the preferred case in which polyisocyanates are used which are not hydrophilic-ally modified. It is also possible to use as polyiso-cyanate component 1) hydrophilic-modified polyisocyanates which, due to the incorporated ionic or nonionic hydrophilic centres, are autodispersible.
. . . .
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Mixing can be carried out by simply stirring the com ponents together at room temperature. The amount of polyisocyanate component is preferably calculated so as to result in an NCO/OH equivalen-t ratio, based on the isocyanate groups of component 1) and the alcoholic hydroxyl groups of component 2), of 0.5:1 to 5:1, in particular 0.8:1 to 3:1.
Prior to the addition of the polyisocyanate component, the auxiliaries and additives customary in coatings technology can be incorporated into the polyester resin 2), i.e. the dispersion or solution of the polymers. These include for example antifoams, leveling assistants, pigments and pigment dispersants.
The resulting coatings according to the invention are suitable ~or practically all areas of application which currently employ solvent-corltaining, solvent-free or other types of aqu00us paint and coating sy~tems having an enhanced range of properties.
They are preferably used for topcoats and one-coat finishes, in which case the substrates to be coated may be, for example, metal, mineral construction materials such as limestone, cement or gypsum, fiber-ceme~t construction materials, concrete, wood or timber materials, paper, asphalt, bitumen, plastics of various kinds, textiles or leather. The metallic substrates are preferably in all cases automobiles.
Another pre~erred use is as a primer or sur~acer, in which case the substrates to be coated may be, ~or example, metal, mineral construction materials such as limestone, cement or gypsum, fiber-cement construction materials, concrete, wood or timber materials, paper, asphalt, bitumen, textiles or leather~ The metallic substrates are again preferably automobiles.
2 ~ 7 ~
~xamples:
The polyester synthesis is carried out in a 4 l four-neck flask ~itted with a packed column (column tube: 30 mm diameter, 2000 mm length; packing: glass rings of 6 mm diameter and 6 mm length) and a descending bridge-shaped distillation head, with temperature sensing of the reacting material under a protective gas atmosphere (protective gas feed, nitrogen). I~ low-boiling alcohols, especially methanol, are distilled off a~ condensate, the receiver should be cooled using an ice bath The abbreviations used below are explained on page 17.
Polyester 1 Initial amounts as in Table 1 Melt neopentylglycol and trimethylolpropane, add IPA and 1.5 g of dibutyltin oxide, heat so that the overhead temperature does not exceed 100C, subject the mixture to condensation at 190C to 200C until the content of acid groups is 10 meq of COOH/100 g.
Cool to 140C, add ADPA and DMPA, heat so that the overhead -temperature does not exceed 100~C, subiect the mixture to condensation at temperatures of up to 200C
until a value of 64 meq of COOH/100 g is reached. ~hen cool to 80C, add 62.2 g of dimethylethanolamine and ~:~ 290 g of N-methylpyrrolidone and di~perse in 2818 g of wat~r.
Polyester 2 Initial amounts as in Tabl.e 1 Melt the hydroxyl group-containing reactants, add 5-SIP-~a, TPA and 1~5 g of dibutyltin oxide, heat so that the overhead temperature does not exceed 100C, subject the mixture to condensation at 185C to 195C until 135 g of distillate are obtainedO
Cool to 120C, add IPA and 1.0 g of dibutyltin oxide, heat so that the overhead temperature does not exceed 100C, subject the mixture to condensation at temper-.
'' 2~0~l87~
atures of up to 190C until the content of free carboxyl groups is 55 meq of COOH/100 g, then continue condensation a-t 180C to 200C and 100 mbar until a value of 7 meq of COOH/100 g is reached.
720 g of N-methylpyrrolidone are added at 140C and the batch is then dispersed with 4680 g of water.
Polye~ter 3 Initial amounts as in Table 1 Melt neopentylglycol and trimethylolpropane, add TPA, IPA
and 1 5 g o~ dibutyltin oxide, heat 50 that the overhead tempexature does not exceed 100C, subject the mixture to condensation at 190C~to 200C until the content of acid ~roups is 10 meq of COOH/100 g.
Cool to 140C, add TMA~ and stir at this temperature 15 until a value of 71 meq of COOH/100 g is reached. ~hen cool to 80C, add 175 g of N-methylpyrrolidone and 80 g of dimethylethanolamine, and disperse in 1800 g of water.
Polyester 4 Initial amounts as in Table 1 Melt neopentylglycol and trimethylolpropane, add TPA, IPA, LA and 2.5 g of dibutyltin oxide, heat so that the overhead temperature does not exceed 100C, subject the mixture to condensation at 190C to 200C until the content of acid groups i9 10 meq of COO~/100 g.
Cool to 140C/ add ADPA and DMPA, heat so that the overhead temperature does no~ exceed 100C, subject the mixture to condensation at temperatures o up to 200C
until a value of 56 me~ of COO~/100 g is reached. Than cool to 80C, add 300 g of ~-methylpyrrolidone and 70 g of dime-thylethanolamine, and disperse in 2430 g of water.
Table 1 (* see over) ,~
. ~
' ~ :
.
o ~ o M~
U~ ~~ '' ~ ~ ~ ~
O t u) ~ , O ~I ~ In ~ ~
O ~ C~ D
~
o ~1 ~
r~ n ~ ~, o ~Q
r C~ ~ rr ;
n Y) U ~ O In O ~9 ~D
O
.~
, ' `'` ' ' ' ', ~ ' , "
- 2 1 ~ 6 -- lÇ --C:~
o o ~ o o 1 w i ,i 3 ~
;~ ~ $
,~ :
...... ~, ~ r . ~ :
,.. , ., . , : . , . ~ -.
: . . , , : . , .. : .'~ ~
: ..
- : . . :
2 1 ~ 1 8 !) ~
Rey. IPA = isophthalic acid TPA = terephthalic acid ADPA = adipic acid 5-SIP-Na = 5-sulfoisophthalic acid Na salt NPG = neopentylglycol TMP = trimethylol]propane DMPA = dimethylolp.ropionic acid EG = ethylene glycol LA = lauric acid TMAA = trimellitic anhydride PEG = polyethylene ~lycol 2-Component primer The dispersion batch is prepared by mixing 65.8 part~ by weight of the polyester (1), (2), (3) or (4) having a solids content of 38~ by wei~ht with 0.2 part by weight of a commercially available silicone~free antifoam (Additol VXW 4973 from Hoechst AG), 0.3 part by weight oE
a commercially available wetting and dispersing auxiliary (Additol XL 250 from Hoechst AG) and 0.4 part by weight of a commercially available leveling agent (Additol ; XW 390 from Hoechst AG~o After simply stirring, 14.0 parts by weight of titanium dioxide (Kronos 2310 from Kronos~Titan GmbH), 11.0 partR by weight of a barium sulfate (Blanc fixe micro from Sachtleben GmbH), 3.7 parts by weight o-f a talc (Naintsch E 7 from Naintsch Mineralwerke Gmb~) and 0.1 part by weight of a carbon black (Flammru~ 101 from Degussa AG) are added to the batch, which is dispersed for about 30 m:inutes in a dissolver at a speed of 6000 rpm.
A variety of polyisocyanates can be employed as the curing component, for example (I) ~asonat FDS 342~ ~rom :BA5F AG, (II) Desmodur VPhS 2550, lIII) Desmodur N 3300 and (IV) Desmodur N 100 from Bayer AG.
The dispersion batch was then mixed with 12.5 parts by weight o~ a suitable polyisocyanate which has, if ~:~
:, ' . . ~ . ' 2 ~ 7 ~
appropriate, been previously diluted with methoxypropyl acetate; the composition of the batch in accordance with the invention is as follows:
. . .
Example A Example B Example C ~xample D
_ Binder 1 2 3 4 25.00 25.00 .~5.00 25.0~
Pigments 28.80 28.80 28.80 28.80 Auxiliaries0.~0 0.90 0.90 0.90 Total solids54.7054~70 54.70 54.70 Deionized waker 42.05 40.05 42.05 42.05 Organic solvent 3.25 5.25 3.25 3.25 Total 100~00 100.00 100.00 100.00 _ _ __ _ Polyisocyanate (III) 12.50 ~I) 12.50 (II) 12.50 (III) 12.50 Methoxypropyl ': acetate6.25 0.00 0.00 12.50 ~ _ The ready-to-process batches have a con-tent of organic solvents of only 2.89 to 12.60~ by weight. The coatings are applied to the substrate at a wek-~ilm thickness of 150 300 ~m ~corresponding to a dry-film thickness of 25 ko 50 ym) and dried for 30 minutes ak 80C in a circulating-air oven.
The cured coating ~ilms of Examples A to D can be charac-terized as fo1lows:
~, :
, -: . . , ., .. ; . . . ~
: , . . ~ . . : .. , .. , ~ : :
- , . ... .
.. : . . : . ~ ... :
' - : .. ' ' : . ' ' .
8 ~ ~;
Solvent resistance Example A Example B Example C Example D
_ ____ Isopropanol good-moderate very good m~derate ~sderate Isopropanol/water (1:1) gcod very good moderate ~Lderate Ethanol very good- ve~y good- moderate moderate good good Ethanol/water (1:1) good very good mLderate moderate Pre~iumrgrade gasolLne good moderate moderate n~derate Example A ~ le B Exa~ple C ~xample D
_ Pendulum hardness 75"-100" 100"-110" 25"-40" 15"-25 acc. to DIM 53157 60 ~los~ 50% 43~ 88% 73 acc. to DIN 67530 Hot-wet test acc. to good-moderate good-~oderate good moderate Sal~ spra~ test good very good- ~ery good- very good-acc. to ASTM~B117-6~ good good good Topcoat appeaLance good good very good good Sto~e chip:
topcoat adhesion good good go,od-mcderate very good penetrations good ~x~derate good very good _ 2-Component topcoat The dispersion batch is prepared by mixing 71.1 parts by weight of polyester (1) or ~4) having a solids content of 38% by ~eight with 0O2 part by weight of a commercially available silicone-free antifoam (Additol VXW 4973 from Hoechst AG), 0.3 part by weight of a commercially available wetting and dispersing auxiliary ~Additol XL 250 from ~oechst AG) and 0.4 part ~y weight of a commeFcially available leveling agent ~Additol XW 390 .
.
,: ' ', .
. '. : , . ~ . :
.
from Hoechs-t AG). After the simple stirring o the additives together with one another, 24.6 parts by weight o~ titanium dioxide (Kronos 2310 from Kronos-Titan GmbH) are added to the batch, which is dispersed for about 30 minutes in a dissolver at a speed of 6000 rpm.
A variety of polyisocyanates can be employed as the curing component, for example lI) Basonat FDS 3425 from BASF AG, (II~ Desmodur VPLS 2550, (III~ Desmodur N 3300 and (IV) Desmodur N 100 from Bayer AG.
The dispersion batch was then mixed with 13.4 parts ~y weight of a suitable polyisocyanate which is, if appro-priate, previously ~i;luted with methoxypropyl acetate;
the composition of the batch in accordance with the invention i~ as ~ollows:
_ Example A Example B Example C Example D
Binder 1 2 3 4 25.00 25.00 25.00 25~00 Pigments 28.80 28.80 28.80 28.80 Auxiliari~s 0.90 0.90 0.90 0.90 Total solids54.70 54.70 54.70 54.70 Deionized water42.05 40.05 42.05 42.05 Organic solvent3.25 5.25 3.25 3.25 __ .
Total 100.00 100.00 100.00 100.00 _ .
Polyisocyanate (III) 12.50 ~I) 12.50 ~II) 12.50 (III) 12.50 Methoxypropyl :
acetate 6.25 0.~0 n.oo 12.50 .
' ,, , : . - ., .
.
, 2 ~ 7 ~ `
~ 2~ -The ready-to-procPss batches have a content of organic solvents of only 8.5 to 13.3% by weight. The coatings are applied to the substrate at a wet-film thicknes~ of 200-400 ~m (corresponding to a dry-film thickness of 30 to 60 ~m) and dried for 30 minutes at 80C in a circulating-air oven.
The cured coating films of Examples E and F can be characterized as follows:
Solvent resistance Example E Example F
.
Isopropanol very good very good-good Isopropanol/water ~1:1) very good very good-good Ethanol very good-good good Ethanol/water (1:1) very good good Premium-grade gasoline very good-good good-mod~rate Example E Example F .
.
Pendulum hardness about 115" about 145"
acc. to DIN 53157 .
60 Gloss about 87% about 87%
acc. to DIN 67530 Topcoat appearance good good Stone chip:
topcoat adhesion good good penetrations good very good-goQd _22_2~8,~
The cured films from all the examples are tested in accordance with the following test proc~dures:
Pendulum hardness: in accordance with DIN 53 157 Degree of gloss: in accordance with DIN 67 530, measured at an angle of Ç0 Hot-wet test: in accordance with DIN 50 017 SK.
After 240 hours with atmospheric humidity of 100% and at a temperature o~ 40C, bli~tering, gloss and the quality of the coating surface were subjectively assessed according to a rating scale (1 = ver~ good, 5 = very poor) Salt spray test. in accordance with ASTM-B 117-69.
After 240 hours in a salt spray atmosphere, blistering and corrosive penetration at the predetermined corrosion points were subjectively assessed according to a rating scale (1 = very good, 5 = very poor) Topcoat appearance: the gloss and surface of the topcoat were subjectively asses~ed according to a rating scale (1 = very good, 5 = very poor) 25 Stone chip: The stone-chip resistance was te~ted using a stone chip testing device in accordance with the VDA [German Motor Industry Association]
(model 508 from Erichsen). For these tests, in each case 1 kg of scrap steel (angular, ~-5 mm) was projected under compressed-air acceleration (2 bar) on to the test panels. Vsing sample panels, an assessm~nt was made of the topcoat adhesion (very good = no abrasion, very poor = complete del~mination) and of the penetrations down to the :, .
- , - ~ - .
.'' ' . : : : . : .
.
: . ' ' ' ' ' ' ' ~:
: . ' ' ., . :
2 ~ 7 ~
metal (very good = no penetrations, very poor = a large number of penetrations~.
: :
,.
' , ' ~ ~ ' :
~: ' , .` ~ .:
Claims (6)
1. A water-thinnable two-component coating composition, comprising 1) a polyisocyanate component composed of one or more organic polyisocyanates, and
2) a polyester resin which is composed of the starting components (a), (b), (c), (d) and (e) or their ester-forming derivatives, the sum of the reactants being 100 mol% and the ratio of the sum of the hydroxyl equivalents to the sum of the carboxyl equivalents in the reactants being between 1:0.5 and 1:2.0, where (a) is at least one dicarboxylic acid which is not a sulfo monomer, (b) is 0 to 15 mol% of at least one difunctional sulfo or phosphono monomer, whose functional groups are carboxyl and/or hydroxyl groups, with at least one sulfonate or phosphonate group, (c) is at least one glycol, (d) is 0 to 40 mol% of a higher-functional compound (functionality >2), whose functional groups are hydroxyl and/or carboxyl groups, and (e) is 0 to 20 mol% of a monofunctional carboxylic acid, the amounts of free hydroxyl groups being between 30 and 350 milliequivalents of OH/100 g, preferably between 100 and 250 meq of OH/100 g, and the content of free neutralized and/or neutralizable acid groups, in particular sulfonic, phosphonic and carboxylic acid groups, being between 5 and 350 meq/100 g, preferably between 9 and 120 meq/100 g.
2. A water-thinnable two-component coating composition as claimed in claim 1, comprising a polyester resin prepared from (a) aliphatic, aromatic or cycloaliphatic dicarb-oxylic acids, (b) hydroxy- and carboxyarylsulfonic acids or salts thereof, (c) aliphatic, aromatic or cycloaliphatic glycols, and (d) compounds containing 3 to 6 hydroxyl groups and/or carboxyl groups.
2. A water-thinnable two-component coating composition as claimed in claim 1, comprising a polyester resin prepared from (a) aliphatic, aromatic or cycloaliphatic dicarb-oxylic acids, (b) hydroxy- and carboxyarylsulfonic acids or salts thereof, (c) aliphatic, aromatic or cycloaliphatic glycols, and (d) compounds containing 3 to 6 hydroxyl groups and/or carboxyl groups.
3. A water-thinnable two-component coating composition as claimed in claim 1, comprising a polyester resin prepared from (a) phthalic, isophthalic and terephthalic acid, phthalic anhydride, adipic acid, sebacic and azelaic acid, 1,3-cyclohexanedicarboxylic acid or glutaric acid and esters thereof, (b) sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid, sulfosalicylic acid and esters or salts thereof, (c) ethylene glycol, 1,2-propanediol, 1,3-butane-diol, 1,6-hexanediol or perhydrobisphenol A, (d) trimethylolpropane, trimethylolethane, glycerol, ditrimethylolpropane, pentaerythritol, dipenta-exythritol, dimethylolpropionic acid or tri-mellitic anhydride.
4. A water-thinnable two-component coating composition as claimed in claim 1, comprising a polyester resin composed of 1 to 6 mol% of component (b) and 8 to 20 mol% of component (d).
5. The use of a water-thinnable two-component coating composition as claimed in claims 1 to 4 for the preparation of topcoats and one-coat finishes.
6. The use of a water-thinnable two-component coating composition as claimed in claims 1 to 4 for the preparation of primers or fillers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4227355A DE4227355A1 (en) | 1992-08-19 | 1992-08-19 | Water-dilutable two-component coating compound |
| DEP4227355.2 | 1992-08-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2101876A1 true CA2101876A1 (en) | 1994-02-20 |
Family
ID=6465823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002101876A Abandoned CA2101876A1 (en) | 1992-08-19 | 1993-08-04 | Water-thinnable two-component coating composition |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0583728B2 (en) |
| JP (1) | JPH06172703A (en) |
| KR (1) | KR940004030A (en) |
| AT (1) | ATE160796T1 (en) |
| AU (1) | AU663398B2 (en) |
| BR (1) | BR9303417A (en) |
| CA (1) | CA2101876A1 (en) |
| CZ (1) | CZ169893A3 (en) |
| DE (2) | DE4227355A1 (en) |
| DK (1) | DK0583728T3 (en) |
| ES (1) | ES2111098T3 (en) |
| GR (1) | GR3025875T3 (en) |
| MX (1) | MX9304998A (en) |
| NO (1) | NO932933L (en) |
| ZA (1) | ZA936040B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723518A (en) * | 1994-06-03 | 1998-03-03 | Bayer Aktiengesellschaft | Aqueous two-component polyurethane coating compositions and a method for their preparation |
| US6803112B1 (en) | 2000-03-29 | 2004-10-12 | Sun Chemical Corporation | Radiation curable aqueous compositions for low extractable film packaging |
| US7007711B1 (en) | 1999-07-16 | 2006-03-07 | Bayer Aktiengesellschaft | Dispersion nozzle with variable throughput |
| US7037953B2 (en) | 2000-03-29 | 2006-05-02 | Sun Chemical Corporation | Radiation curable aqueous compositions |
| US7148307B2 (en) | 2002-08-14 | 2006-12-12 | Bayer Aktiengesellschaft | Water-dilutable polyesters with cyclic imide and isocyanurate structure |
| US7183352B2 (en) | 2002-08-14 | 2007-02-27 | Bayer Materialscience Ag | Water-dilutable polyesters with cyclic imide structure |
| US10544327B2 (en) | 2015-09-09 | 2020-01-28 | Covestro Deutschland Ag | Scratch-resistant aqueous 2K PU coatings |
| US10774239B2 (en) | 2015-09-09 | 2020-09-15 | Covestro Deutschland Ag | Scratch-resistant two-component polyurethane coatings |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4226242A1 (en) * | 1992-08-08 | 1994-02-10 | Herberts Gmbh | Water-thinnable coating agent based on polyol and polyisocyanate, process for its preparation and its use |
| DE19504947C2 (en) * | 1994-06-20 | 2003-07-03 | Bollig & Kemper Gmbh & Co Kg | Multi-layer coating |
| US5872182A (en) * | 1994-09-09 | 1999-02-16 | H. B. Fuller Licensing & Financing, Inc. | Water-based polyurethanes for footwear |
| WO1996040811A1 (en) * | 1995-06-07 | 1996-12-19 | H.B. Fuller Licensing & Financing, Inc. | Aqueous non-gelling, anionic polyurethane dispersions and processfor their manufacture |
| DE19538061C2 (en) * | 1995-10-13 | 2001-01-04 | Basf Coatings Ag | Water-dilutable polyester |
| DE19644044A1 (en) * | 1996-10-31 | 1998-05-07 | Huels Chemische Werke Ag | Aqueous two-component polyurethane coating compositions, process for their preparation and their use |
| SE9902501D0 (en) * | 1999-07-01 | 1999-07-01 | Perstorp Ab | Composition for polyurethanes |
| AU6386301A (en) | 2000-04-20 | 2001-11-07 | Akzo Nobel Nv | Branched hydroxyl-functional polyester resin and its use in aqueous cross-linkable binder compositions |
| KR100728463B1 (en) * | 2000-04-20 | 2007-06-13 | 아크조 노벨 엔.브이. | Branched hydroxyl-functional polyester resin and its use in aqueous cross-linkable binder compositions |
| DE10145344A1 (en) * | 2001-09-14 | 2003-04-24 | Audi Ag | Process for producing a multi-layer coating of a vehicle body and coating material |
| WO2004076515A1 (en) | 2003-02-28 | 2004-09-10 | Bayer Materialscience Ag | Method and device for producing a two-component lacquer mixture |
| US20050277732A1 (en) * | 2004-06-14 | 2005-12-15 | Yu Poli C | Two-component coating composition |
| EP2236531A1 (en) | 2009-03-31 | 2010-10-06 | Bayer MaterialScience AG | New aqueous 2K PUR coating system for improved corrosion protection |
| JP5991822B2 (en) * | 2012-02-10 | 2016-09-14 | Ｂａｓｆジャパン株式会社 | One-component clear coating composition and method for forming a multilayer coating film using the same |
| EP3822297A1 (en) | 2019-11-15 | 2021-05-19 | Covestro Deutschland AG | Polysiloxane functionalized polyurethanes for enhancing hydrophobisation of surfaces |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4150946A (en) * | 1975-11-04 | 1979-04-24 | Rhone-Poulenc Industries | Water-soluble polyurethanes and compositions and application thereof to substrates |
| US4152485A (en) * | 1977-08-05 | 1979-05-01 | Toyo Boseki Kabushiki Kaisha | Magnetic recording medium |
| US4307219A (en) * | 1980-04-30 | 1981-12-22 | Minnesota Mining And Manufacturing Company | Aqueous solvent dispersible linear polyurethane resins |
| JPS61135547A (en) * | 1984-12-07 | 1986-06-23 | Minoru Oshio | Production of fried rice cracker containing shrimps |
| GB8913644D0 (en) * | 1989-06-14 | 1989-08-02 | Ici America Inc | Aqueous dispersions |
| US5102977A (en) * | 1990-01-18 | 1992-04-07 | Ruco Polymer Corporation | Internally catalyzed sulfonate bearing hydroxyl terminated powder coating polyesters |
| DE4111392A1 (en) † | 1991-01-19 | 1992-10-15 | Bayer Ag | USE OF BINDER COMBINATIONS AND A METHOD FOR PRODUCING COATINGS |
| DE4134064A1 (en) * | 1991-10-15 | 1993-04-22 | Bayer Ag | BINDER COMBINATION, A METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DE4135571A1 (en) † | 1991-10-29 | 1993-05-06 | Bayer Ag, 5090 Leverkusen, De | COATING AGENTS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF COATINGS |
-
1992
- 1992-08-19 DE DE4227355A patent/DE4227355A1/en not_active Withdrawn
-
1993
- 1993-08-04 CA CA002101876A patent/CA2101876A1/en not_active Abandoned
- 1993-08-11 DE DE59307764T patent/DE59307764D1/en not_active Expired - Lifetime
- 1993-08-11 EP EP93112873A patent/EP0583728B2/en not_active Expired - Lifetime
- 1993-08-11 ES ES93112873T patent/ES2111098T3/en not_active Expired - Lifetime
- 1993-08-11 AT AT93112873T patent/ATE160796T1/en not_active IP Right Cessation
- 1993-08-11 DK DK93112873.0T patent/DK0583728T3/en active
- 1993-08-17 KR KR1019930015872A patent/KR940004030A/en not_active Application Discontinuation
- 1993-08-17 MX MX9304998A patent/MX9304998A/en not_active IP Right Cessation
- 1993-08-18 BR BR9303417A patent/BR9303417A/en not_active Application Discontinuation
- 1993-08-18 ZA ZA936040A patent/ZA936040B/en unknown
- 1993-08-18 NO NO932933A patent/NO932933L/en unknown
- 1993-08-18 CZ CZ931698A patent/CZ169893A3/en unknown
- 1993-08-18 AU AU44679/93A patent/AU663398B2/en not_active Ceased
- 1993-08-18 JP JP5204153A patent/JPH06172703A/en not_active Withdrawn
-
1998
- 1998-01-14 GR GR980400048T patent/GR3025875T3/en unknown
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5723518A (en) * | 1994-06-03 | 1998-03-03 | Bayer Aktiengesellschaft | Aqueous two-component polyurethane coating compositions and a method for their preparation |
| US7007711B1 (en) | 1999-07-16 | 2006-03-07 | Bayer Aktiengesellschaft | Dispersion nozzle with variable throughput |
| US6803112B1 (en) | 2000-03-29 | 2004-10-12 | Sun Chemical Corporation | Radiation curable aqueous compositions for low extractable film packaging |
| US7037953B2 (en) | 2000-03-29 | 2006-05-02 | Sun Chemical Corporation | Radiation curable aqueous compositions |
| US7148307B2 (en) | 2002-08-14 | 2006-12-12 | Bayer Aktiengesellschaft | Water-dilutable polyesters with cyclic imide and isocyanurate structure |
| US7183352B2 (en) | 2002-08-14 | 2007-02-27 | Bayer Materialscience Ag | Water-dilutable polyesters with cyclic imide structure |
| US10544327B2 (en) | 2015-09-09 | 2020-01-28 | Covestro Deutschland Ag | Scratch-resistant aqueous 2K PU coatings |
| US10774239B2 (en) | 2015-09-09 | 2020-09-15 | Covestro Deutschland Ag | Scratch-resistant two-component polyurethane coatings |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE160796T1 (en) | 1997-12-15 |
| GR3025875T3 (en) | 1998-04-30 |
| CZ169893A3 (en) | 1994-03-16 |
| AU663398B2 (en) | 1995-10-05 |
| ES2111098T3 (en) | 1998-03-01 |
| EP0583728A1 (en) | 1994-02-23 |
| NO932933D0 (en) | 1993-08-18 |
| JPH06172703A (en) | 1994-06-21 |
| DK0583728T3 (en) | 1998-01-26 |
| BR9303417A (en) | 1994-03-15 |
| ZA936040B (en) | 1994-04-10 |
| EP0583728B1 (en) | 1997-12-03 |
| AU4467993A (en) | 1994-02-24 |
| NO932933L (en) | 1994-02-21 |
| KR940004030A (en) | 1994-03-14 |
| DE4227355A1 (en) | 1994-02-24 |
| EP0583728B2 (en) | 2002-08-28 |
| DE59307764D1 (en) | 1998-01-15 |
| MX9304998A (en) | 1994-05-31 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |