CA1216693A - Coating composition, process for the preparation of coatings, and coated substrate - Google Patents
Coating composition, process for the preparation of coatings, and coated substrateInfo
- Publication number
- CA1216693A CA1216693A CA000463230A CA463230A CA1216693A CA 1216693 A CA1216693 A CA 1216693A CA 000463230 A CA000463230 A CA 000463230A CA 463230 A CA463230 A CA 463230A CA 1216693 A CA1216693 A CA 1216693A
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- CA
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- Prior art keywords
- mol
- coating composition
- weight
- formaldehyde
- urea
- 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.)
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/53—Base coat plus clear coat type
- B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
- B05D5/067—Metallic effect
- B05D5/068—Metallic effect achieved by multilayers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
Abstract
Abstract of the Disclosure:
Coating composition, process for the preparation of coatings, and coated substrate The invention relates to a coating composition for the preparation of the base coat of a multilayer enamel consisting of at least one base and one transparent protective coat, the said coating composition containing binders based on organic resins, metallic pigments, org-anic solvents and, if appropriate, other pigments as well as customary additives and auxiliaries. The coating com-position contains, as binders, A) polyurethane elastomers and/or polyurea elastomers, B) polyesters and C) poly-condensates partially etherified with monoalcohols and consisting of melamine, benzoguanamine and/or urea with formaldehyde. The invention further relates to a process for the preparation of coatings using the coating com-position, and to a substrate coated with a multilayer enamel.
Coating composition, process for the preparation of coatings, and coated substrate The invention relates to a coating composition for the preparation of the base coat of a multilayer enamel consisting of at least one base and one transparent protective coat, the said coating composition containing binders based on organic resins, metallic pigments, org-anic solvents and, if appropriate, other pigments as well as customary additives and auxiliaries. The coating com-position contains, as binders, A) polyurethane elastomers and/or polyurea elastomers, B) polyesters and C) poly-condensates partially etherified with monoalcohols and consisting of melamine, benzoguanamine and/or urea with formaldehyde. The invention further relates to a process for the preparation of coatings using the coating com-position, and to a substrate coated with a multilayer enamel.
Description
lZ:16~;9~
05.0901983 9ASF Farben + Fasern Aktiengesellschaft, Hamburg Coating composition, process for the preparation of coatings, and coated substrate The ;nvention relates to a coating composition for the preparation of the base coat of a multilayer enamel consi~ting of at least one base and one transparent protective coat, the said coating composition containing binders based on organic resins, metallic pigments~ org-anic solvents and, if appropriate, other pigments as well as customary additives and au~;liaries.
U.S. Patent Spec;fication 3,639,147 describes a so-called two-layer metallic enamel of the abovementioned type. In th;s and other known metallic enamels~ the coat-ing composition used to prepare the base coat contains cellulose esters, espec;aLly cellulose acetobutyrate, in order to improve the metallic effect of the resulting enamel.
The addition of cellulose acetobutyrate has some associated disadvantages; thus, problems of incompatibil-ity with other enamel constituents frequently arise, the resulting coatings have a limited resilience and a poor interlayer adhesion~ and the coatings which have not yet been stoved are etched in the so-called wet-;n-wet pro-cess by the coating sompos;t;on applied for the prepar-ation of the transparent protective coat.
The object of the present invent;on ;s to avoid these d;sadvantages of the state of the art and to ~Z~693 produce a coating composition for the preparation of the base coat of multilayer metallic enamels, the use of which is associated with a good compatibility, a good adhesion and a lo~ degree of re-etching, and which leads to coatings having a good metallic effect without the use of cellulose acetobutyrate.
This object is achieved according to the inven-tion by a coating composition of the type mentioned at the outset, wherein the binders consist of the following components:
A) 20 to 60 X by weight of one or more polyurethane and/or urea elastomers prepared from a1) linear compounds with terminal hydroxyl and/or pr;mary and/or secondary amino groups and a2) aliphatic and/or cycloaliphatic diisocyan-ates, the molar ratio of a1 to a2 being 0.8 : 1 to 1.5 : 1, B) 10 to 50 % by weight of one or more polyesters prepared from b13 aromat;c and al;phat;c and/or cycloaliphatic polycarboxylic acids, 40 to 70 mol ~ of the polycarboxylic acids being aromatic and 60 to 30 mol X of the poly-carboxylic acids being aliphatic and/or cycloaliphatic, and 0 to 50 mol % of the total polycarboxylic acids being tricarboxylic acids, and b2) polyols, - 20 to 60 mol % of the polyols having 2 or 3 carbon atoms and 40 to 80 mol % having 4 or more carbon atoms, ~216693 - at least 40 mol X of the diols used having aliphatic side-chains, - 0 to 50 mol X of the polyols being triols and - the ratio of the components b1 and b2 corres-ponding to the following formula K = n1 ~ n2 (F - 2) n~
in which n1 denotes the number of mol of poly-ols~ nz denotes the number of mol of poly-carboxylic acids, F denotes the average molar value of the functionality of the polycarboxylic acids and K has a value of 1.05 to 1.5, and C) 5 to 25 X by weight of polycondensates partially etherified with monoalcohols and consisting of melamine, benzoguanamine and/or urea with formaldehyde, the molar ratio of melamine to formaldehyde in the case of melam;net formaldehyde resins being 1 : 4.5 to 1 . 6 and the molar ratio of benzoguanamine or urea to formaldehyde in the case of benzoguanamine/formaldehyde or urea/formaldehyde resins being 1 : 2.5 to 1 : 4, and the sum of the com-ponents A, B and C being 100 %.
Suitable st~rtino compounds a1 for th~ prapar-ation of component A) are linear compounds with terminal hydroxyl groups. Thus, glycols such as, for example, ethylene glycol, propylene glycol, diethylene glycol or dipropylene glycol can be used here. I_inear polyether glycols or polyester glycols ~ith terminal hydroxyl groups can also be used.
The higher-molecular polyhydroxy compounds should be free of aromat;c urethane groups (for examplepre-polymers from dihydroxy compounds and sub-stoichiometric quantities of aromatic d;isocyanates should not be used) so that the light fastness of the process products is still ensured. Although polyacetaLs and polyethers can be used in principle, they are less suitable on account of the;r susceptibility to oxidative degradation. It is preferred to use polyesters, in particular those from adipic acid and diols or mixtures of diols, for example ethylene glycol and propylene glycol, butane-1,4-diol,
05.0901983 9ASF Farben + Fasern Aktiengesellschaft, Hamburg Coating composition, process for the preparation of coatings, and coated substrate The ;nvention relates to a coating composition for the preparation of the base coat of a multilayer enamel consi~ting of at least one base and one transparent protective coat, the said coating composition containing binders based on organic resins, metallic pigments~ org-anic solvents and, if appropriate, other pigments as well as customary additives and au~;liaries.
U.S. Patent Spec;fication 3,639,147 describes a so-called two-layer metallic enamel of the abovementioned type. In th;s and other known metallic enamels~ the coat-ing composition used to prepare the base coat contains cellulose esters, espec;aLly cellulose acetobutyrate, in order to improve the metallic effect of the resulting enamel.
The addition of cellulose acetobutyrate has some associated disadvantages; thus, problems of incompatibil-ity with other enamel constituents frequently arise, the resulting coatings have a limited resilience and a poor interlayer adhesion~ and the coatings which have not yet been stoved are etched in the so-called wet-;n-wet pro-cess by the coating sompos;t;on applied for the prepar-ation of the transparent protective coat.
The object of the present invent;on ;s to avoid these d;sadvantages of the state of the art and to ~Z~693 produce a coating composition for the preparation of the base coat of multilayer metallic enamels, the use of which is associated with a good compatibility, a good adhesion and a lo~ degree of re-etching, and which leads to coatings having a good metallic effect without the use of cellulose acetobutyrate.
This object is achieved according to the inven-tion by a coating composition of the type mentioned at the outset, wherein the binders consist of the following components:
A) 20 to 60 X by weight of one or more polyurethane and/or urea elastomers prepared from a1) linear compounds with terminal hydroxyl and/or pr;mary and/or secondary amino groups and a2) aliphatic and/or cycloaliphatic diisocyan-ates, the molar ratio of a1 to a2 being 0.8 : 1 to 1.5 : 1, B) 10 to 50 % by weight of one or more polyesters prepared from b13 aromat;c and al;phat;c and/or cycloaliphatic polycarboxylic acids, 40 to 70 mol ~ of the polycarboxylic acids being aromatic and 60 to 30 mol X of the poly-carboxylic acids being aliphatic and/or cycloaliphatic, and 0 to 50 mol % of the total polycarboxylic acids being tricarboxylic acids, and b2) polyols, - 20 to 60 mol % of the polyols having 2 or 3 carbon atoms and 40 to 80 mol % having 4 or more carbon atoms, ~216693 - at least 40 mol X of the diols used having aliphatic side-chains, - 0 to 50 mol X of the polyols being triols and - the ratio of the components b1 and b2 corres-ponding to the following formula K = n1 ~ n2 (F - 2) n~
in which n1 denotes the number of mol of poly-ols~ nz denotes the number of mol of poly-carboxylic acids, F denotes the average molar value of the functionality of the polycarboxylic acids and K has a value of 1.05 to 1.5, and C) 5 to 25 X by weight of polycondensates partially etherified with monoalcohols and consisting of melamine, benzoguanamine and/or urea with formaldehyde, the molar ratio of melamine to formaldehyde in the case of melam;net formaldehyde resins being 1 : 4.5 to 1 . 6 and the molar ratio of benzoguanamine or urea to formaldehyde in the case of benzoguanamine/formaldehyde or urea/formaldehyde resins being 1 : 2.5 to 1 : 4, and the sum of the com-ponents A, B and C being 100 %.
Suitable st~rtino compounds a1 for th~ prapar-ation of component A) are linear compounds with terminal hydroxyl groups. Thus, glycols such as, for example, ethylene glycol, propylene glycol, diethylene glycol or dipropylene glycol can be used here. I_inear polyether glycols or polyester glycols ~ith terminal hydroxyl groups can also be used.
The higher-molecular polyhydroxy compounds should be free of aromat;c urethane groups (for examplepre-polymers from dihydroxy compounds and sub-stoichiometric quantities of aromatic d;isocyanates should not be used) so that the light fastness of the process products is still ensured. Although polyacetaLs and polyethers can be used in principle, they are less suitable on account of the;r susceptibility to oxidative degradation. It is preferred to use polyesters, in particular those from adipic acid and diols or mixtures of diols, for example ethylene glycol and propylene glycol, butane-1,4-diol,
2,2 dimethylpropane-1,3-diol, hexane-1,3-diol, hexane-1,6-diol or bishydroxymethylcyclohexane. Diols having more than four C atoms are preferred. Polyesters ~ith a narro~ molecular weight distribution, which can be obtained by the condensation of caprolactone and diols, are also very su;table~ ~uite outstanding resistance to hydrolysis, which is far superior to the usual properties of polyesters, can be ach;eved with hexanediol poly-carbonates or m;xed hexandiol/ad;p;c ac;d polycarbonates.
In addition to the said higher-molecular di-hydroxy compounds, small quant;t;es tabout 0.05 to 2 mol/
kg of elastomer) of lower-molecular diols having mole-cular weights of about 6Z to 400, for example ethylene glycol, butane-1,4-diol, butane-2,3-diol, 2,2-dimethyl-propane-1,3-diol or N-stearyL-N',N'-bis-hydroxyethYlurea, can also be used, if appropriate, in the formation of the prepolymer. Part;cular preference is given to dio~s having tertiary amino groups, for example N,N-bis-1~16~93 5 --(~-hydroxyethyl)methylamine, N~N-bis(l~-hydroxyethyl)iso-propylam;ne, N,N-b;s(l~-hydroxypropyl)tert.-amylam;ne or bis(3-aminopropyl)piperazine, because they further im-prove the stabil;ty of the polyurethanes to loss of strength on exposure to light.
The starting compounds a1 can also be linear diamines with primary and/or secondary am;no groups.
Examples of these are ethyLenediamine, 1,2- or 1,3-pro-pylened;amine, 1,6-hexanediamine, 2-methyl-1,6-hexane~
diamine, 1-methyl-2,4-d;aminocyclohexane, 1-amino-3-ammoniomethyl-3,5,5~-trimethylcyclohexane, 1,3- or 1,4-bis-aminomethylcyclohexane, 4,4 -diaminodicyclohexyl-methane or s;milar d;am;nes known per se. Other suitable chain lengtheners are hydrazine, methylhydrazine or adip;c acid dihydrazide, semicarbazidopropionic acid hydrazide and the like.
Component a1 is reacted with aliphatic and/or cycloaliphatic diisocyanates to give polyurethane elasto-mers or urea elastomers. Examples of suitable diisocyan-ates are hexamethylene 1,6-diisocyanate, 2,2~4-trimethyl-hexane d;;socyanate, 4,8-dioxa-6,6-dimethYlundecane 1,11-diisocyanate, lys;ne C1-C6-ester d;isocyanates, d;-cyclohexylmethane 4,4 -diisocyanate, 3,3 -dimethyldi-cyclohexylmethane 4,4 -diisocyanate (preferably in the form of m;xtures enriched in the cis/cis or cis/trans stereoisomers), cyclohexane 1,4-di~socyanate and very part;cularly 1-isocyanato-3-;socyanatomethyl 3,5,5-tr;-methylcyclohexane since this last compound gives poly-urethanes which have the least tendency to gel in solution ~Z16~93 and have the best solub;lity in soft solvent mixtures.
The reaction can be carried out ;n the melt and/or in inert solvents, for example ~oluene or xylene. It is usually carried out at temperatures of between 60 and 150C, preferably 80 to 120C, it being poss;ble for the reaction time to be between about 10 minutes and several hours.
Thus; possible components A) are either pure polyurethane elastomers or pure polyurea elastomers, as well as mixtures of these elastomers or mixed polyurethane/
polyurea elastomers contain;ng urethane and urea groups in one molecuLe.
The polyesters used as component ~) are prepared from polycarboxylic acids and polyols. Examples of suit-able polycarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthal;c acid, adipic acid, azelaic acid, sebacic acid or trimellitic acid. The glycols already mentioned as components a1 can be used as polyols. In addition to these, glycerol, trimethylol-ethane, trimethylolpropane or similar compounds are used as trioLs.
Amino resins, which are polycondensates of mel-amine, benzoguanamine and/or urea with formaldehyde, are used as component C). These are partially ether~fied with monoalcohols. Examples of possible monoalcohols here are methanol, ethanol, propanol or butanol.
The coating compositions according to the inven-tion have a good compatibility of all constituents, a good resil;ence and a good adhesion of the resulting ~2~66~13 coatings, as well as a low degree of re-etching in the wet-in-wet process. In particular, even when one-component and two-component clear lacquers having a high solids content are used for the transparent protective coat, the coating compositions are very ~u;table ~or overlacquering. Furthermore, the resulting multilayer enamels have a good metall;c effect, even if the coating compos;tions~according to the invention with a high solids content are applied. It has been found, moreover, that the coating compositions lead to an improved resistance to stone chips.
As an additional component D) for improving the metallic effect, the coating Gomposition advantageously contains a copolymer which has been prepared from 85 tc 9S % by weight of ethylene and 15 to 5 X by weight of vinyl acetate, in a proport;on of 5 to 15 X by weight, based on the sum of components A) to D).
The resin A) is advantageously based on polyester diols and diamines in a molar ratio of 0.8 : 1.2 to 1.2 : 0.8 as component a1.
The metallic effect can advantageously be further ;mproved if the coating composition contains as component E), in addition to components A~, B), C) and if appropri-ate D), polymeric microparticles hav;ng a size or size d;stribution in the range from 0.01 to 2 ~m, in a propor-t;on of 5 to lS X by weight, based on the sum of compon--ents A) to E), the said microparticles having been pre-pared by emulsion polymerization of a mixture of unsatur-ated monomers, some of which preferably contain carboxyl 121~;693 or hydroxyl ~roups and some of which are free of carbo~yL
and hydroxyl groups, and a polyfunctional crosslinking agent, the emulsion polymerization having been carried out in the aqueous phase and the water having been removed during or after the polymerization.
Polymeric microparticles of this type and the pre-paration of so-called microgels are described, for ex-ample, in European Patent Application A2-0,029~637.
The microparticles are preferably used in place of the ethylene/vinyl acetate copolymer. However, it is also possibLe to use the copolymer and the m;croparticles in conjunction w;th one another in order to improve the me~allic effect.
Examples of possible unsaturated monomers for the preparation of the micropart;cles are~ on the one hand, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropylmethacrylate, and, on the other hand, alkyl esters of acrylic acid and methacrylic acid preferably having 1 to 4 carbon atoms ;n the alkyl radical, as well as styrene and ~-methylstyrene.
Suitable polyfunctional crosslinking agents are compounds with two ethylenically unsaturated double bonds, which lead to crossl;nked m;cropart;cles insoluble ln the coating composition. Examples of these are: ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, methylene-bis-acrylamide, methylene-b;s-methacrylamide, divinylbenzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, divinylacetylene, trivinylbenzene, ~Z1669.~
_ 9 _ glycerol trimethacrylate, pentaerythritol tetramethacryl-ate, tr;allyl cyanurate, divinylethane and similar com-pounds such as those described in European Patent Application A2~0,029,637.
The invention also relates to a process for the preparation of coatings, in which a coating composition containing metallic pigments for the formation of a base coat is applied to a substrate, this being followed, after a period of exposure to the air, by the application according to the wet-in-wet process, of a second coating composition forming a transparent protective coat. In . the process according to the invention, the binders con-sist of the following components:
A) 20 to 60 X by weight of one or more polyurethane and/or urea elastomers prepared from a1~ linear compounds ~ith terminal hydroxyl and/or primary and/or secondary amino groups and a2) aliphatic and/or cycloaliphatic diisocyan-ates, the molar ratio of a1 to a2 being 0~8 : 1 to 1.5 : 1, B) 10 to 50 X.by weight of one or more polyesters prepared from b1) aromatic and al;phat;c and/or cycloallphatic polycarboxylic acids, 40 to 70 mol % of the polycarboxylic acids be;ng aromat;c and 60 to 30 mol X of the poly-carboxylic acids being aliphatic and/or cycloaliphatic, and 0 to 50 mol X of the total polycarboxylic acids being tricarboxylic acids, and b2) polyols, 12~669;~
20 to 60 mol % of the polyols having 2 or 3 carbon atoms and 40 to 80 mol % having 4 or more carbon atoms, at least 40 mol X of the diols used having aLiphatic side-chains, 0 to 50 mol % of the polyols being triols and the ratio of the components b1 and b2 corres-pond;ng to the follo~;ng formula K n1 ~2 (F Z) n2 ;n which n1 denotes the number of mol of poly-ols, n2 denotes the r,umber of mol of poly-carboxylic ac;ds, F denotes the average molar value of the functionality of the polycarboxylic ac;ds and K has a value of 1.05 to 1.5, and C) 5 to 25 X by weight of polycondensates part;ally ether;fied with monoalcohols and cons;sting of melamine, benzoguanam;ne and/or urea w;th formaldehyde, the molar rat;o of melam;ne to formaldehyde in the case of melam;ne/
formaldehyde resins being 1 : 4.5 to 1 : 6 and the molar ratio of benzoguanamine or urea to formaldehyde in the case of benzoguanamine/formaldehyde or urea/formaldehyde resins being 1 : 2.5 to 1 : 4, and the sum of the com-ponents A, ~ and C be;ng 1ûOX.
Advantageous embodiments of the process accord;ng to the ;nvention can be found in the sub-claims.
The ;nvent;on also relates to a substrate coated w;th a mult;layer enamel cons;st;ng of at least one base ~Z~6693 coat containing metallic pigments and at least one trans-parent protect;ve coat. The base coat has been prepared using the coating composition according to the ;nvention.
The invention is illustrated in greater detail below ~ith the aid of pract;cal examples.
Example_A 1 741 9 of a polyester of adipic ac;d and neopentyl glycol~ w;th~an OH number of 113, and 26.5 9 of diethylene glycol are weighed out into a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and are heated to 100C. A vacuum is then applied for half an hour in order to remove all moisture present. 1850 9 of butyl acetate, 393 9 of dicyclohexylmethane 4,4'-di-isocyanate and 0.3 9 of dibutyltin dilaurate are then addéd at 5-minute intervals and the temperature is kept a~ 100C for 1.5 hours. The NCO content is now deter-mined. It is 1.36 %.
A mixture of 18~0 g of butyl acetate, 1230 g of n-butanol and 70 g of hexamethylenediamine is introduced into a dilution vessel. The precursor conta;ning NCO
groups is added over a period of 15-20 minutes, with stirring~ This gives an almost colorless, viscous solu-tion with a solids content of 20 %.
Example A 2 As in Example A 1, the water is removed in vacuo from 1300 g of a caprolactone polyester with an OH number of 112, together with 73 9 of neopentylglycol. After the addit;on of 1850 g of butyl acetate, 688 g of 3-iso-cyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate are ~L2~L~6~3 init;ally introduced. After about 5 minutes, 0.3 9 of dibutyltin dilaurate is added. After a reaction time of 2 hours at 100C, the NCO content of the solution is 2.27 Z.
A mixture of 1490 9 of butyl acetate, 1671 9 of n-butanol and 88 9 of 1,3-diaminopropar,e is introduced into a dilution vessel. The precursor containing NCO
groups is-introduced over a period of 15 - 20 minutes, with stirring. This gives an almost colorless, viscous solution with a solids content of 30 %~
ExarpLe A 3 As in Example A 1, the water is removed in vacuo from 1500 9 of a polyester of hexane-1,6-diol, neopentyl g-lycol and adipic acid, with an OH number of 75. After ~he addition of 2200 9 of butyl acetate, 393 g of di-cyclohexylmethane 4,4'-diisocyanate are initially intro-duced and 0.3 9 of dibutyltin dilaurate is added after about 5 minutes. After a reaction time of 2 hours at 100C, the NCO content of the solution is 0.98 %.
A mixture of 2280 g of butyl acetate, 1490 9 of butanol and 98 9 of 1-amino-3-aminomethylcyclohexane is introduced into a dilution vessel. The precursor contain-in~ NCO groups is introduced over a peri~d of 15-20 m;n-utes with stirring. rhis gives a pale yellowish, v;scous solution with 3 solids content of 25 X.
Example B 1 -111.3 9 of propane--1,3-diol, 3Z9.9 9 of 2,2-di-methylpropane-1,3-diol, 1$3~5 9 of 1,1,1-trimethylol-propane, 216.7 9 of phthalic anhydride, 243.0 9 of iso-lZ~669~
phthalic acid~ 245oO g of adip;c acid, 30.0 9 of xylene and 2 9 of dibutyltin oxide are weighed out into a 2 liter four-necked flask fitted with a stirrer, an electrical re~
sistance heater, a thermometer and a packed column filled with Pall rings and equipped ~ith an overhead thermometer, a distillation br;dge, a condenser and a receiver. The reaction mixture ;s heated rapidly to 160C, with stirring.
From 160C, the temperature is increased over a period of 5 hours to 220C in such a way that the column over-head temperature does not exceed 103C. The temperature is kept at 220C and the esterification is continued until an acid number (according to DIN) of 15 is reached The reaction mixture is then cooled to 140C and the polyester is partially dissolved in 800 9 of a 1 : 1 mix-ture of xylene and ethylglycol acetate, with continued cooling. This results in a 60 % solution of a polyester with a molecular weight of 930 and an OH number (DIN) of 160, based on the solid polyester.
Example B 2 Using the apparatus described in Example B 1, 60.4 9 of ethane-1,2-diol, 74.0 9 of propane-1,2-diol, 227.9 g of 2,Z-dimethylpropane-1,3-diol, 229.9 9 of hexane-1,6-diol, 485.1 9 of isophthalic acid, 40.0 9 of a m;xture of aromat;cs with a boiling ran~e of 180 to 205C and 3.0 9 of dibutyltin oxide are weighed out.
The mixture is heated as in Example 1 and esterified up to an acid number of 20. It ;s then cooled to 160C, 213.3 9 of adipic acid and 93.5 g of trimellitic anhydride are added and the mixture is heated again to 200Co 1~6693 The temperature is kept at 200C and ester;f;cat;on ;s continued up ~o an ac;d number of Z5. The m;xture is cooled and d;ssolved as ;n Example 1. This results ;n a 60 % solut;on of a polyester with a molecular we;ght of 960 and an OH number of 115, based on the solid polyester.
Example B 3 -Using the apparatus and procedure descr;bed in Example ~ 1, the following are we;ghed out and ester;fied at a max;mum of 220C: 113.4 9 of ethane-1,2-diol, 142~6 9 of 2,Z-dimethylpropane-1,3-diol, 279.8 9 of neo-pentylgLycol hydroxypivalate, 91~9 9 of 1,1,1-trimethylol-propane. 303.5 9 of isophthalic acid, 203.5 9 of hexa-hydrophthalic anhydride, 200.2 9 of adipic acid, 30 9 of xylene and Z g of dibutyltin oxide.
Ester;fication ;s continued at 220C up to an ac;d number of 5. Th;s results in a 60 X solution of a polyester with a molecular weight of 1520 and an OH
number of 100, based on the solid polyester.
Example 3 4 Using the apparatus and procedure descr;bed in Example B 1, the follo~ing are weighed out and esterified at a maximum of 220C: 102.2 9 of propane-1,2-diol, 102.2 9 of propane-1,3-diol, 372.8 9 of 2,2-d;methyl-propane-1,3-diol, 60.0 9 of 1~1~1-trimethylolpropane~
331.6 9 of phthalic anhydr;de, 172.0 g of trimellitic anhydride, 196.3 9 of adipic acid and 40 9 of a mixture of aromatics with a boiling range of 180-205C. Heating is carried out as in Example 1, particular attent;on ~2~66~3 being paid to the overhead temperature, and ester;fication is continued at 200C up to an acid number of 1~. The mixture is cooled and partially dissolved as in Example 19 This results in 3 60 % solution of a polyester with a molecular weight of 780 and an OH number of 198, based on the solid polyester.
Example C M-elamine resin , The following are we;ghed out ;nto a 2 liter four-necked flask fitted w;th an electrical resistance heater, a stirrer~ a thermometer and a distillation apparatus for the recycling operaticn with a water separator: 560 9 of isobutanol, 250 9 of 37 % aqueous formaldehyde solution, 30 9 of toluene and O.OS g of 85 ~ phosphoric acid. The reaction mixture is heated to 40C and 95.3 9 of melam-ine are added. The mixture is heated to 85C and the temperature slowly raised to 100C so that the reaction mixture distils rapidly, water being separated out. The temperature is kept at 100C unt;l a compatib;lity of 1/5 with a petroleum ether of boiling range 135-180C
;s reached. The r~flux of the distillation unit is then closed and 300 9 of solvent are distilled off, during which time the temperature rises to 115C. The reaction m;xture ;s then cooled to 80C and d;luted w;th 65 9 of ;sobutanol. This results in a solution of a melamine resin with a solids content ~60 minutes, 100C~ of 55 %
and a viscosity of 250 seconds (DIN 53 211).
Example ~ Copolymer dispersion The following are weighed out into a heatable mixer fitted with a high-speed stirrer: 200 9 of xylene 12~l~6~3 and 100 9 of an ethylene/vinyl acetate copolymer with a vinyl acetate content of 12 ~; the mixture is heated to 100C and stirred until a homogeneous solution is obtained~ The solution is then cooled to 80C and pre-cipitated with 700 y of a mixture of xylene and butyl acetate, the temperature falling to 50C during this process. This results in a 10 X dispersion of the co- -polymer.
Example E 1 Preparation of a microgel concentrate 2510 9 of demineralized ~ater together with 34 9 of sodium lauryl-sulfate solution (35 %) are heated to 80C in a polymerization vessel fitted with a stirrer, a reflux condenser and two feed vessels.
A pre-emulsion consisting of 1267 9 of demineral-ized water, 65 9 of sodium lauryl-sulfate solution (35 %), 490 9 of butanediol diacrylate, 478 9 of methyl methacryl-ate and 14Q g of hydroxypropyl methacrylate is prepared, with stirring, in a separate stirrer vessel.
The in;tiator solution, consisting of 14 9 of ammonium persulfate and 660 9 of demineralized water, is introduced into a feed vessel. The pre-emulsion and the initiator solution are then metered in simultaneously so that the introduction of the pre-emulsion takes 2 hours and that of the initiator solution 3 hours. The tempera-ture is kept at 80C by cooling. After the introduct;on has ended, the temperature is kept at 80C for a further 1 hour.
This gives a 20 ~ dispersion of crosslinked par~
ticles wh;ch are not soluble in any organic solvent.
~Z16693 2000 g of this aqueous dispersion, together with b20 9 of n-butanol, are shaken vigorously for 10 minutes in a separating funnel. After an interval of 30 minutes, 2 phases are obtained. The lower, aqueous phase is dis-carded.
The butanol phase containing the microgel is transferred to a distillation flask equipped ~ith a water separator and a stirrer. 333 9 of the polyester described in Example ~ ~ and 500 g of ethylglycol acetate are intro-duced. The remaining water is then distilled off a?eo-tropically in vacuo at a maximum of 60C. This gives a microgel concentrate with a solids content of 32 X.
Example E 2 2000 9 of the aqueous dispersion described in Example E 1, together with 800 9 of butyl acetate, are shaken vigorously for 15 minutes in a separating funnel.
After an interval of 1.5 hours, 2 phases are obtained.
The aqueous phase is discarded. The organic phase is transferred to a distillation flask equipped with a water separator and a stirrer. 400 9 of a polyester of ad;pic acid and neopentylglycol, with an OH number of 123, are introduced. All water still present is then completely distilled off azeotropically in vacuo at a maximum of 60C. Th;s g;ves a m;crogel concentrate with a solids content of 60 Y.. 1500 g of this concentrate are treated with 280 9 of dicyclohexylmethane 4,4'-diisocyanate and 0.3 g of dibutyltin dilaurate, as in Example A 1. After a reaction t;me of 2 hours, the NCO content ;s 2.66 X.
A m;xture of 1090 g of butyl acetate, 218 g of ~12~6693 n-butanol and 95 g of 1-amino-3-aminomethylcyclohexane is introduced into a dilution vessel. The precursor contain-ing microgel and NC0 groups is ir,troduced over a period of 15 - 20 minutes, with stirring. This gives a turbid, pasty composition wi~h a bluish tinge, having a solids content of 40 %.
xamples 1 to 10 of base lacquers In a~stirrer vessel, the polyurethane/polyurea elastomer solutions described ;n Examples A 1 to A 3 are mixed, with stirring, ~ith the polyester solutions des-cribed in Examples ~ 1 to 3 4, the melamine/formaldehyde resin described in Example C and, if appropriate, the copolymer dispersion described in Example ~ and/or the microgel dispersion described in Examples E 1 and E Z, in such a way that a homogeneous mixture is formed, the composit;on of which, based on 100 parts by weight of the solid, corresponds to the data in Table 1. The quantity indicated in this table of a non-leafing aluminum bronze is then carefully made into a 65 % paste in aliphatic hydrocarbons with the 1.5-fold quantity of butyl acetate, based on the solid aluminum bronze, and added, with stir-ring, to the corresponding mixtures, described above, of polyurethane/polyurea elastomer solution, polyester, melamine/formaldehyde res;n solut;ons and, lf appropriate, copolymer dispersion and/or microgel, and dispersed.
The resulting mixtures are brought to a solids content of 25 X by weight with a mixture of 50 parts by weight of butyl acetate, 25 parts by weight of butylglycol acetate and 25 parts by weight of butanol.
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~Z~G693 Example K 1, clear lacquer based on acrylate 941 9 of a mixture of aromatics with a boiling range of 156 - 170C are weighed out into a 3 liter reaction vessel fitted with a thermometer, a stirrer, an electrical resistance heater, a reflux condenser and a feed vessel, and are heated to 140C, with stirring. A mix-ture of 223 9 of styrene, 223 9 of methyl methacrylate, 208 9 of butane-1,4-diol monoacrylate, 30 9 of acryl;c acid, 803 9 of n-butyl acrylate and 18 9 of di-tert.-butyl peroxide is metered uniformly from the feed vessel into the reaction vessel over a period of 3 hours and the temperature ;s kept at 140C. The reaction mixture is kept at 140C for a further 30 minutes and a solution of 4 9 of di-tert.-butyL peroxide in 50 9 of a mixture of aromatics with a boiling range of between 156 and 172C
is then added. After a further 2 hours at 140C, an acrylate resin solution with a solids content of 60 %
results. The acrylate resin has an acid number of 14, an OH number of 109 and a viscosity of 250 mPa.s tmeasured as a S0 X solut;on in xylene with an ICI viscometer).
Example K 2, clear lacguer 300 9 of the solution of melamine/formaldehyde resin described in Example C, 150 9 of xylene and 50 9 of butylglycol acetate are added, with stirring, to 550 9 of the 60 % acrylate resin solution described in Example K 1, and the whole is carefully mixed. This results in a clear lacquer with a solids content of 46.5 X.
Preparation of the coatings To prepare the coatings, sections of body sheet ~2~6~93 used in motorcar production enameling, which have been passivated by an iron phosphate treatment and have received a coat by means of cathodic electrophoretic enameling and a stoving filler, are coated with the base lacquers described in Examples t to 10 and the clear lacquer described in Example K 2.
For th;s purpose, the base lacquers described in Examples 1 t~ 1~ are adjusted with a solvent mixture of xylene and butyl acetate (70 : 30) to a viscosity of 16 seconds according to DIN 53 211, and the clear lacquer described in Example K 2 is adjusted with this solvent mixture to a viscosity of 78 seconds according to DIN
53 211.
The adjusted base lacquers are sprayed onto the described, pretreated body sheet sections with a cup gun having a nozzl~ width of 1.2 mm and operating under an air spraying pressure of 4 bar, in such a way that the resulting dry film thickness of the base lacquer is 12 to 17 ~um. After 5 minutes, the sprayed-on base lacquer is sprayed with the adjusted clear lacquer, under the said spraying conditions, in such a ~ay that the resulting dry film thickness of the clear lacquer is 35 to 40 ~m.
After exposure to the air for 15 minutes at room tempera-t~r~ the sheet sectlons are stoved in a circulating airoven for 30 minutes at 130C.
The coatings prepared in this way have an out-standing metallic effect, ~hich can be assessed by those skilled in the art, and meet the requirements of the tests listed in the technical terms of delivery of motor-car production enamel.
In addition to the said higher-molecular di-hydroxy compounds, small quant;t;es tabout 0.05 to 2 mol/
kg of elastomer) of lower-molecular diols having mole-cular weights of about 6Z to 400, for example ethylene glycol, butane-1,4-diol, butane-2,3-diol, 2,2-dimethyl-propane-1,3-diol or N-stearyL-N',N'-bis-hydroxyethYlurea, can also be used, if appropriate, in the formation of the prepolymer. Part;cular preference is given to dio~s having tertiary amino groups, for example N,N-bis-1~16~93 5 --(~-hydroxyethyl)methylamine, N~N-bis(l~-hydroxyethyl)iso-propylam;ne, N,N-b;s(l~-hydroxypropyl)tert.-amylam;ne or bis(3-aminopropyl)piperazine, because they further im-prove the stabil;ty of the polyurethanes to loss of strength on exposure to light.
The starting compounds a1 can also be linear diamines with primary and/or secondary am;no groups.
Examples of these are ethyLenediamine, 1,2- or 1,3-pro-pylened;amine, 1,6-hexanediamine, 2-methyl-1,6-hexane~
diamine, 1-methyl-2,4-d;aminocyclohexane, 1-amino-3-ammoniomethyl-3,5,5~-trimethylcyclohexane, 1,3- or 1,4-bis-aminomethylcyclohexane, 4,4 -diaminodicyclohexyl-methane or s;milar d;am;nes known per se. Other suitable chain lengtheners are hydrazine, methylhydrazine or adip;c acid dihydrazide, semicarbazidopropionic acid hydrazide and the like.
Component a1 is reacted with aliphatic and/or cycloaliphatic diisocyanates to give polyurethane elasto-mers or urea elastomers. Examples of suitable diisocyan-ates are hexamethylene 1,6-diisocyanate, 2,2~4-trimethyl-hexane d;;socyanate, 4,8-dioxa-6,6-dimethYlundecane 1,11-diisocyanate, lys;ne C1-C6-ester d;isocyanates, d;-cyclohexylmethane 4,4 -diisocyanate, 3,3 -dimethyldi-cyclohexylmethane 4,4 -diisocyanate (preferably in the form of m;xtures enriched in the cis/cis or cis/trans stereoisomers), cyclohexane 1,4-di~socyanate and very part;cularly 1-isocyanato-3-;socyanatomethyl 3,5,5-tr;-methylcyclohexane since this last compound gives poly-urethanes which have the least tendency to gel in solution ~Z16~93 and have the best solub;lity in soft solvent mixtures.
The reaction can be carried out ;n the melt and/or in inert solvents, for example ~oluene or xylene. It is usually carried out at temperatures of between 60 and 150C, preferably 80 to 120C, it being poss;ble for the reaction time to be between about 10 minutes and several hours.
Thus; possible components A) are either pure polyurethane elastomers or pure polyurea elastomers, as well as mixtures of these elastomers or mixed polyurethane/
polyurea elastomers contain;ng urethane and urea groups in one molecuLe.
The polyesters used as component ~) are prepared from polycarboxylic acids and polyols. Examples of suit-able polycarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthal;c acid, adipic acid, azelaic acid, sebacic acid or trimellitic acid. The glycols already mentioned as components a1 can be used as polyols. In addition to these, glycerol, trimethylol-ethane, trimethylolpropane or similar compounds are used as trioLs.
Amino resins, which are polycondensates of mel-amine, benzoguanamine and/or urea with formaldehyde, are used as component C). These are partially ether~fied with monoalcohols. Examples of possible monoalcohols here are methanol, ethanol, propanol or butanol.
The coating compositions according to the inven-tion have a good compatibility of all constituents, a good resil;ence and a good adhesion of the resulting ~2~66~13 coatings, as well as a low degree of re-etching in the wet-in-wet process. In particular, even when one-component and two-component clear lacquers having a high solids content are used for the transparent protective coat, the coating compositions are very ~u;table ~or overlacquering. Furthermore, the resulting multilayer enamels have a good metall;c effect, even if the coating compos;tions~according to the invention with a high solids content are applied. It has been found, moreover, that the coating compositions lead to an improved resistance to stone chips.
As an additional component D) for improving the metallic effect, the coating Gomposition advantageously contains a copolymer which has been prepared from 85 tc 9S % by weight of ethylene and 15 to 5 X by weight of vinyl acetate, in a proport;on of 5 to 15 X by weight, based on the sum of components A) to D).
The resin A) is advantageously based on polyester diols and diamines in a molar ratio of 0.8 : 1.2 to 1.2 : 0.8 as component a1.
The metallic effect can advantageously be further ;mproved if the coating composition contains as component E), in addition to components A~, B), C) and if appropri-ate D), polymeric microparticles hav;ng a size or size d;stribution in the range from 0.01 to 2 ~m, in a propor-t;on of 5 to lS X by weight, based on the sum of compon--ents A) to E), the said microparticles having been pre-pared by emulsion polymerization of a mixture of unsatur-ated monomers, some of which preferably contain carboxyl 121~;693 or hydroxyl ~roups and some of which are free of carbo~yL
and hydroxyl groups, and a polyfunctional crosslinking agent, the emulsion polymerization having been carried out in the aqueous phase and the water having been removed during or after the polymerization.
Polymeric microparticles of this type and the pre-paration of so-called microgels are described, for ex-ample, in European Patent Application A2-0,029~637.
The microparticles are preferably used in place of the ethylene/vinyl acetate copolymer. However, it is also possibLe to use the copolymer and the m;croparticles in conjunction w;th one another in order to improve the me~allic effect.
Examples of possible unsaturated monomers for the preparation of the micropart;cles are~ on the one hand, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropylmethacrylate, and, on the other hand, alkyl esters of acrylic acid and methacrylic acid preferably having 1 to 4 carbon atoms ;n the alkyl radical, as well as styrene and ~-methylstyrene.
Suitable polyfunctional crosslinking agents are compounds with two ethylenically unsaturated double bonds, which lead to crossl;nked m;cropart;cles insoluble ln the coating composition. Examples of these are: ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, methylene-bis-acrylamide, methylene-b;s-methacrylamide, divinylbenzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, divinylacetylene, trivinylbenzene, ~Z1669.~
_ 9 _ glycerol trimethacrylate, pentaerythritol tetramethacryl-ate, tr;allyl cyanurate, divinylethane and similar com-pounds such as those described in European Patent Application A2~0,029,637.
The invention also relates to a process for the preparation of coatings, in which a coating composition containing metallic pigments for the formation of a base coat is applied to a substrate, this being followed, after a period of exposure to the air, by the application according to the wet-in-wet process, of a second coating composition forming a transparent protective coat. In . the process according to the invention, the binders con-sist of the following components:
A) 20 to 60 X by weight of one or more polyurethane and/or urea elastomers prepared from a1~ linear compounds ~ith terminal hydroxyl and/or primary and/or secondary amino groups and a2) aliphatic and/or cycloaliphatic diisocyan-ates, the molar ratio of a1 to a2 being 0~8 : 1 to 1.5 : 1, B) 10 to 50 X.by weight of one or more polyesters prepared from b1) aromatic and al;phat;c and/or cycloallphatic polycarboxylic acids, 40 to 70 mol % of the polycarboxylic acids be;ng aromat;c and 60 to 30 mol X of the poly-carboxylic acids being aliphatic and/or cycloaliphatic, and 0 to 50 mol X of the total polycarboxylic acids being tricarboxylic acids, and b2) polyols, 12~669;~
20 to 60 mol % of the polyols having 2 or 3 carbon atoms and 40 to 80 mol % having 4 or more carbon atoms, at least 40 mol X of the diols used having aLiphatic side-chains, 0 to 50 mol % of the polyols being triols and the ratio of the components b1 and b2 corres-pond;ng to the follo~;ng formula K n1 ~2 (F Z) n2 ;n which n1 denotes the number of mol of poly-ols, n2 denotes the r,umber of mol of poly-carboxylic ac;ds, F denotes the average molar value of the functionality of the polycarboxylic ac;ds and K has a value of 1.05 to 1.5, and C) 5 to 25 X by weight of polycondensates part;ally ether;fied with monoalcohols and cons;sting of melamine, benzoguanam;ne and/or urea w;th formaldehyde, the molar rat;o of melam;ne to formaldehyde in the case of melam;ne/
formaldehyde resins being 1 : 4.5 to 1 : 6 and the molar ratio of benzoguanamine or urea to formaldehyde in the case of benzoguanamine/formaldehyde or urea/formaldehyde resins being 1 : 2.5 to 1 : 4, and the sum of the com-ponents A, ~ and C be;ng 1ûOX.
Advantageous embodiments of the process accord;ng to the ;nvention can be found in the sub-claims.
The ;nvent;on also relates to a substrate coated w;th a mult;layer enamel cons;st;ng of at least one base ~Z~6693 coat containing metallic pigments and at least one trans-parent protect;ve coat. The base coat has been prepared using the coating composition according to the ;nvention.
The invention is illustrated in greater detail below ~ith the aid of pract;cal examples.
Example_A 1 741 9 of a polyester of adipic ac;d and neopentyl glycol~ w;th~an OH number of 113, and 26.5 9 of diethylene glycol are weighed out into a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, and are heated to 100C. A vacuum is then applied for half an hour in order to remove all moisture present. 1850 9 of butyl acetate, 393 9 of dicyclohexylmethane 4,4'-di-isocyanate and 0.3 9 of dibutyltin dilaurate are then addéd at 5-minute intervals and the temperature is kept a~ 100C for 1.5 hours. The NCO content is now deter-mined. It is 1.36 %.
A mixture of 18~0 g of butyl acetate, 1230 g of n-butanol and 70 g of hexamethylenediamine is introduced into a dilution vessel. The precursor conta;ning NCO
groups is added over a period of 15-20 minutes, with stirring~ This gives an almost colorless, viscous solu-tion with a solids content of 20 %.
Example A 2 As in Example A 1, the water is removed in vacuo from 1300 g of a caprolactone polyester with an OH number of 112, together with 73 9 of neopentylglycol. After the addit;on of 1850 g of butyl acetate, 688 g of 3-iso-cyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate are ~L2~L~6~3 init;ally introduced. After about 5 minutes, 0.3 9 of dibutyltin dilaurate is added. After a reaction time of 2 hours at 100C, the NCO content of the solution is 2.27 Z.
A mixture of 1490 9 of butyl acetate, 1671 9 of n-butanol and 88 9 of 1,3-diaminopropar,e is introduced into a dilution vessel. The precursor containing NCO
groups is-introduced over a period of 15 - 20 minutes, with stirring. This gives an almost colorless, viscous solution with a solids content of 30 %~
ExarpLe A 3 As in Example A 1, the water is removed in vacuo from 1500 9 of a polyester of hexane-1,6-diol, neopentyl g-lycol and adipic acid, with an OH number of 75. After ~he addition of 2200 9 of butyl acetate, 393 g of di-cyclohexylmethane 4,4'-diisocyanate are initially intro-duced and 0.3 9 of dibutyltin dilaurate is added after about 5 minutes. After a reaction time of 2 hours at 100C, the NCO content of the solution is 0.98 %.
A mixture of 2280 g of butyl acetate, 1490 9 of butanol and 98 9 of 1-amino-3-aminomethylcyclohexane is introduced into a dilution vessel. The precursor contain-in~ NCO groups is introduced over a peri~d of 15-20 m;n-utes with stirring. rhis gives a pale yellowish, v;scous solution with 3 solids content of 25 X.
Example B 1 -111.3 9 of propane--1,3-diol, 3Z9.9 9 of 2,2-di-methylpropane-1,3-diol, 1$3~5 9 of 1,1,1-trimethylol-propane, 216.7 9 of phthalic anhydride, 243.0 9 of iso-lZ~669~
phthalic acid~ 245oO g of adip;c acid, 30.0 9 of xylene and 2 9 of dibutyltin oxide are weighed out into a 2 liter four-necked flask fitted with a stirrer, an electrical re~
sistance heater, a thermometer and a packed column filled with Pall rings and equipped ~ith an overhead thermometer, a distillation br;dge, a condenser and a receiver. The reaction mixture ;s heated rapidly to 160C, with stirring.
From 160C, the temperature is increased over a period of 5 hours to 220C in such a way that the column over-head temperature does not exceed 103C. The temperature is kept at 220C and the esterification is continued until an acid number (according to DIN) of 15 is reached The reaction mixture is then cooled to 140C and the polyester is partially dissolved in 800 9 of a 1 : 1 mix-ture of xylene and ethylglycol acetate, with continued cooling. This results in a 60 % solution of a polyester with a molecular weight of 930 and an OH number (DIN) of 160, based on the solid polyester.
Example B 2 Using the apparatus described in Example B 1, 60.4 9 of ethane-1,2-diol, 74.0 9 of propane-1,2-diol, 227.9 g of 2,Z-dimethylpropane-1,3-diol, 229.9 9 of hexane-1,6-diol, 485.1 9 of isophthalic acid, 40.0 9 of a m;xture of aromat;cs with a boiling ran~e of 180 to 205C and 3.0 9 of dibutyltin oxide are weighed out.
The mixture is heated as in Example 1 and esterified up to an acid number of 20. It ;s then cooled to 160C, 213.3 9 of adipic acid and 93.5 g of trimellitic anhydride are added and the mixture is heated again to 200Co 1~6693 The temperature is kept at 200C and ester;f;cat;on ;s continued up ~o an ac;d number of Z5. The m;xture is cooled and d;ssolved as ;n Example 1. This results ;n a 60 % solut;on of a polyester with a molecular we;ght of 960 and an OH number of 115, based on the solid polyester.
Example B 3 -Using the apparatus and procedure descr;bed in Example ~ 1, the following are we;ghed out and ester;fied at a max;mum of 220C: 113.4 9 of ethane-1,2-diol, 142~6 9 of 2,Z-dimethylpropane-1,3-diol, 279.8 9 of neo-pentylgLycol hydroxypivalate, 91~9 9 of 1,1,1-trimethylol-propane. 303.5 9 of isophthalic acid, 203.5 9 of hexa-hydrophthalic anhydride, 200.2 9 of adipic acid, 30 9 of xylene and Z g of dibutyltin oxide.
Ester;fication ;s continued at 220C up to an ac;d number of 5. Th;s results in a 60 X solution of a polyester with a molecular weight of 1520 and an OH
number of 100, based on the solid polyester.
Example 3 4 Using the apparatus and procedure descr;bed in Example B 1, the follo~ing are weighed out and esterified at a maximum of 220C: 102.2 9 of propane-1,2-diol, 102.2 9 of propane-1,3-diol, 372.8 9 of 2,2-d;methyl-propane-1,3-diol, 60.0 9 of 1~1~1-trimethylolpropane~
331.6 9 of phthalic anhydr;de, 172.0 g of trimellitic anhydride, 196.3 9 of adipic acid and 40 9 of a mixture of aromatics with a boiling range of 180-205C. Heating is carried out as in Example 1, particular attent;on ~2~66~3 being paid to the overhead temperature, and ester;fication is continued at 200C up to an acid number of 1~. The mixture is cooled and partially dissolved as in Example 19 This results in 3 60 % solution of a polyester with a molecular weight of 780 and an OH number of 198, based on the solid polyester.
Example C M-elamine resin , The following are we;ghed out ;nto a 2 liter four-necked flask fitted w;th an electrical resistance heater, a stirrer~ a thermometer and a distillation apparatus for the recycling operaticn with a water separator: 560 9 of isobutanol, 250 9 of 37 % aqueous formaldehyde solution, 30 9 of toluene and O.OS g of 85 ~ phosphoric acid. The reaction mixture is heated to 40C and 95.3 9 of melam-ine are added. The mixture is heated to 85C and the temperature slowly raised to 100C so that the reaction mixture distils rapidly, water being separated out. The temperature is kept at 100C unt;l a compatib;lity of 1/5 with a petroleum ether of boiling range 135-180C
;s reached. The r~flux of the distillation unit is then closed and 300 9 of solvent are distilled off, during which time the temperature rises to 115C. The reaction m;xture ;s then cooled to 80C and d;luted w;th 65 9 of ;sobutanol. This results in a solution of a melamine resin with a solids content ~60 minutes, 100C~ of 55 %
and a viscosity of 250 seconds (DIN 53 211).
Example ~ Copolymer dispersion The following are weighed out into a heatable mixer fitted with a high-speed stirrer: 200 9 of xylene 12~l~6~3 and 100 9 of an ethylene/vinyl acetate copolymer with a vinyl acetate content of 12 ~; the mixture is heated to 100C and stirred until a homogeneous solution is obtained~ The solution is then cooled to 80C and pre-cipitated with 700 y of a mixture of xylene and butyl acetate, the temperature falling to 50C during this process. This results in a 10 X dispersion of the co- -polymer.
Example E 1 Preparation of a microgel concentrate 2510 9 of demineralized ~ater together with 34 9 of sodium lauryl-sulfate solution (35 %) are heated to 80C in a polymerization vessel fitted with a stirrer, a reflux condenser and two feed vessels.
A pre-emulsion consisting of 1267 9 of demineral-ized water, 65 9 of sodium lauryl-sulfate solution (35 %), 490 9 of butanediol diacrylate, 478 9 of methyl methacryl-ate and 14Q g of hydroxypropyl methacrylate is prepared, with stirring, in a separate stirrer vessel.
The in;tiator solution, consisting of 14 9 of ammonium persulfate and 660 9 of demineralized water, is introduced into a feed vessel. The pre-emulsion and the initiator solution are then metered in simultaneously so that the introduction of the pre-emulsion takes 2 hours and that of the initiator solution 3 hours. The tempera-ture is kept at 80C by cooling. After the introduct;on has ended, the temperature is kept at 80C for a further 1 hour.
This gives a 20 ~ dispersion of crosslinked par~
ticles wh;ch are not soluble in any organic solvent.
~Z16693 2000 g of this aqueous dispersion, together with b20 9 of n-butanol, are shaken vigorously for 10 minutes in a separating funnel. After an interval of 30 minutes, 2 phases are obtained. The lower, aqueous phase is dis-carded.
The butanol phase containing the microgel is transferred to a distillation flask equipped ~ith a water separator and a stirrer. 333 9 of the polyester described in Example ~ ~ and 500 g of ethylglycol acetate are intro-duced. The remaining water is then distilled off a?eo-tropically in vacuo at a maximum of 60C. This gives a microgel concentrate with a solids content of 32 X.
Example E 2 2000 9 of the aqueous dispersion described in Example E 1, together with 800 9 of butyl acetate, are shaken vigorously for 15 minutes in a separating funnel.
After an interval of 1.5 hours, 2 phases are obtained.
The aqueous phase is discarded. The organic phase is transferred to a distillation flask equipped with a water separator and a stirrer. 400 9 of a polyester of ad;pic acid and neopentylglycol, with an OH number of 123, are introduced. All water still present is then completely distilled off azeotropically in vacuo at a maximum of 60C. Th;s g;ves a m;crogel concentrate with a solids content of 60 Y.. 1500 g of this concentrate are treated with 280 9 of dicyclohexylmethane 4,4'-diisocyanate and 0.3 g of dibutyltin dilaurate, as in Example A 1. After a reaction t;me of 2 hours, the NCO content ;s 2.66 X.
A m;xture of 1090 g of butyl acetate, 218 g of ~12~6693 n-butanol and 95 g of 1-amino-3-aminomethylcyclohexane is introduced into a dilution vessel. The precursor contain-ing microgel and NC0 groups is ir,troduced over a period of 15 - 20 minutes, with stirring. This gives a turbid, pasty composition wi~h a bluish tinge, having a solids content of 40 %.
xamples 1 to 10 of base lacquers In a~stirrer vessel, the polyurethane/polyurea elastomer solutions described ;n Examples A 1 to A 3 are mixed, with stirring, ~ith the polyester solutions des-cribed in Examples ~ 1 to 3 4, the melamine/formaldehyde resin described in Example C and, if appropriate, the copolymer dispersion described in Example ~ and/or the microgel dispersion described in Examples E 1 and E Z, in such a way that a homogeneous mixture is formed, the composit;on of which, based on 100 parts by weight of the solid, corresponds to the data in Table 1. The quantity indicated in this table of a non-leafing aluminum bronze is then carefully made into a 65 % paste in aliphatic hydrocarbons with the 1.5-fold quantity of butyl acetate, based on the solid aluminum bronze, and added, with stir-ring, to the corresponding mixtures, described above, of polyurethane/polyurea elastomer solution, polyester, melamine/formaldehyde res;n solut;ons and, lf appropriate, copolymer dispersion and/or microgel, and dispersed.
The resulting mixtures are brought to a solids content of 25 X by weight with a mixture of 50 parts by weight of butyl acetate, 25 parts by weight of butylglycol acetate and 25 parts by weight of butanol.
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~Z~G693 Example K 1, clear lacquer based on acrylate 941 9 of a mixture of aromatics with a boiling range of 156 - 170C are weighed out into a 3 liter reaction vessel fitted with a thermometer, a stirrer, an electrical resistance heater, a reflux condenser and a feed vessel, and are heated to 140C, with stirring. A mix-ture of 223 9 of styrene, 223 9 of methyl methacrylate, 208 9 of butane-1,4-diol monoacrylate, 30 9 of acryl;c acid, 803 9 of n-butyl acrylate and 18 9 of di-tert.-butyl peroxide is metered uniformly from the feed vessel into the reaction vessel over a period of 3 hours and the temperature ;s kept at 140C. The reaction mixture is kept at 140C for a further 30 minutes and a solution of 4 9 of di-tert.-butyL peroxide in 50 9 of a mixture of aromatics with a boiling range of between 156 and 172C
is then added. After a further 2 hours at 140C, an acrylate resin solution with a solids content of 60 %
results. The acrylate resin has an acid number of 14, an OH number of 109 and a viscosity of 250 mPa.s tmeasured as a S0 X solut;on in xylene with an ICI viscometer).
Example K 2, clear lacguer 300 9 of the solution of melamine/formaldehyde resin described in Example C, 150 9 of xylene and 50 9 of butylglycol acetate are added, with stirring, to 550 9 of the 60 % acrylate resin solution described in Example K 1, and the whole is carefully mixed. This results in a clear lacquer with a solids content of 46.5 X.
Preparation of the coatings To prepare the coatings, sections of body sheet ~2~6~93 used in motorcar production enameling, which have been passivated by an iron phosphate treatment and have received a coat by means of cathodic electrophoretic enameling and a stoving filler, are coated with the base lacquers described in Examples t to 10 and the clear lacquer described in Example K 2.
For th;s purpose, the base lacquers described in Examples 1 t~ 1~ are adjusted with a solvent mixture of xylene and butyl acetate (70 : 30) to a viscosity of 16 seconds according to DIN 53 211, and the clear lacquer described in Example K 2 is adjusted with this solvent mixture to a viscosity of 78 seconds according to DIN
53 211.
The adjusted base lacquers are sprayed onto the described, pretreated body sheet sections with a cup gun having a nozzl~ width of 1.2 mm and operating under an air spraying pressure of 4 bar, in such a way that the resulting dry film thickness of the base lacquer is 12 to 17 ~um. After 5 minutes, the sprayed-on base lacquer is sprayed with the adjusted clear lacquer, under the said spraying conditions, in such a ~ay that the resulting dry film thickness of the clear lacquer is 35 to 40 ~m.
After exposure to the air for 15 minutes at room tempera-t~r~ the sheet sectlons are stoved in a circulating airoven for 30 minutes at 130C.
The coatings prepared in this way have an out-standing metallic effect, ~hich can be assessed by those skilled in the art, and meet the requirements of the tests listed in the technical terms of delivery of motor-car production enamel.
Claims (9)
1. A coating composition for the preparation of the base coat of a multilayer enamel consisting of at least one base and one transparent protective coat, the said coating composition containing binders based on organic resins, metallic pigments, organic solvents and, if appropriate, other pigments as well as customary addit-ives and auxiliaries, wherein the binders consist of the following components:
A) 20 to 60 % by weight of one or more polyurethane and/or urea elastomers prepared from a1) linear compounds with terminal hydroxyl and/or primary and/or secondary amino groups and a2) aliphatic and/or cycloaliphatic diisocyan-ates, the molar ratio of a1 to a2 being 0.8 : 1 to 1.5 : 1, B) 10 to 50 % by weight of one or more polyesters prepared from b1) aromatic and aliphatic and/or cycloaliphatic polycarboxylic acids, 40 to 70 mol % of the polycarboxylic acids being aromatic and 60 to 30 mol % of the poly-carboxylic acids being aliphatic and/or cycloaliphatic, and 0 to 50 mol % of the total polycarboxylic acids being tricarboxylic acids, and b2) polyols, - 20 to 60 mol % of the polyols having 2 or 3 carbon atoms and 40 to 80 mol % having 4 or more carbon atoms, - at least 40 mol % of the diols used having aliphatic side-chains, - 0 to 50 mol % of the polyols being triols and - the ratio of the components b1 and b2 corres-ponding to the following formula in which n1 denotes the number of mol of poly-ols, n2 denotes the number of mol of poly-carboxylic acids, F denotes the average molar value of the functionality of the polycarboxylic acids and K has a value of 1.05 to 1.5, and C) 5 to 25 % by weight of polycondensates partially etherified with monoalcohols and consisting of melamine, benzoguanamine and/or urea with formaldehyde, the molar ratio of melamine to formaldehyde in the case of melamine/
formaldehyde resins being 1 : 4.5 to 1 : 6 and the molar ratio of benzoguanamine or urea to formaldehyde in the case of benzoguanamine/formaldehyde or urea/formaldehyde resins being 1 : 2.5 to 1 : 4, and the sum of the com-ponents A, B and C being 100 %.
A) 20 to 60 % by weight of one or more polyurethane and/or urea elastomers prepared from a1) linear compounds with terminal hydroxyl and/or primary and/or secondary amino groups and a2) aliphatic and/or cycloaliphatic diisocyan-ates, the molar ratio of a1 to a2 being 0.8 : 1 to 1.5 : 1, B) 10 to 50 % by weight of one or more polyesters prepared from b1) aromatic and aliphatic and/or cycloaliphatic polycarboxylic acids, 40 to 70 mol % of the polycarboxylic acids being aromatic and 60 to 30 mol % of the poly-carboxylic acids being aliphatic and/or cycloaliphatic, and 0 to 50 mol % of the total polycarboxylic acids being tricarboxylic acids, and b2) polyols, - 20 to 60 mol % of the polyols having 2 or 3 carbon atoms and 40 to 80 mol % having 4 or more carbon atoms, - at least 40 mol % of the diols used having aliphatic side-chains, - 0 to 50 mol % of the polyols being triols and - the ratio of the components b1 and b2 corres-ponding to the following formula in which n1 denotes the number of mol of poly-ols, n2 denotes the number of mol of poly-carboxylic acids, F denotes the average molar value of the functionality of the polycarboxylic acids and K has a value of 1.05 to 1.5, and C) 5 to 25 % by weight of polycondensates partially etherified with monoalcohols and consisting of melamine, benzoguanamine and/or urea with formaldehyde, the molar ratio of melamine to formaldehyde in the case of melamine/
formaldehyde resins being 1 : 4.5 to 1 : 6 and the molar ratio of benzoguanamine or urea to formaldehyde in the case of benzoguanamine/formaldehyde or urea/formaldehyde resins being 1 : 2.5 to 1 : 4, and the sum of the com-ponents A, B and C being 100 %.
2. The coating composition as claimed in claim 1, which additionally contains, as component D), a copolymer prepared from 85 to 95 % by weight of ethylene and 15 to 5 % by weight of vinyl acetate, in a proportion of 5 to 15 % by weight, based on the sum of components A) to D).
3. The coating composition as claimed in claim 1 wherein polyester diols and diamines in a molar ratio of 0.8 : 1 to 1.2 : 1 have been used as component a1) to prepare the resin A).
4. The coating composition as claimed in one of claims 1 to 3, which, in addition to components A), B), C) and if appropriate D), contains, as component E), poly-meric microparticles having a size or size distribution in the range from 0.01 to 2 µm, in a proportion of 5 to 15 % by weight, based on the sum of components A) to E), the said microparticles having been prepared by emulsion polymerization of a mixture of unsaturated monomers, some of which preferably contain carboxyl or hydroxyl groups and some of which are free of carboxyl and hydroxyl groups, and a polyfunctional crosslinking agent, the emulsion polymerization having been carried out in the aqueous phase and the water having been removed during or after the polymerization.
5. A process for the preparation of coatings, in which a coating composition containing metallic pigments for the formation of a base coat is applied to a substrate, this being followed, after a period of exposure to the air, by the application according to the wet-in-wet pro-cess of a second coating composition forming a transpar-ent protective coat, wherein the binders of the coating composition for the base coat consist of the following components:
A) 20 to 60 % by weight of one or more polyurethane and/or urea elastomers prepared from a1) linear compounds with terminal hydroxyl and/or primary and/or secondary amino groups and a2) aliphatic and/or cycloaliphatic diisocyan-ates, the molar ratio of a1 to a2 being 0.8 : 1 to 1.5 : 1, B) 10 to 50 % by weight of one or more polyesters prepared from b1) aromatic and aliphatic and/or cycloaliphatic polycarboxylic acids, 40 to 70 mol % of the polycarboxylic acids being aromatic and 60 to 30 mol % of the poly-carboxylic acids being aliphatic and/or cycloaliphatic, and 0 to 50 mol % of the total polycarboxylic acids being tricarboxylic acids, and b2) polyols, - 20 to 60 mol % of the polyols having 2 or 3 carbon atoms and 40 to 80 mol % having 4 or more carbon atoms, - at least 40 mol % of the diols used having aliphatic side-chains, - 0 to 50 mol % of the polyols being triols and - the ratio of the components b1 and b2 corres-ponding to the following formula in which n1 denotes the number of mol of poly-ols, n2 denotes the number of mol of poly-carboxylic acids, F denotes the average molar value of the functionality of the polycarboxylic acids and K has a value of 1.05 to 1.5, and C) 5 to 25 % by weight of polycondensates partially etherified with monoalcohols and consisting of melamine, benzoguanamine and/or urea with formaldehyde, the molar ratio of melamine to formaldehyde in the case of melamine/
formaldehyde resins being 1 : 4.5 to 1 : 6 and the molar ratio of benzoguanamine or urea to formaldehyde in the case of benzoguanamine/formaldehyde or urea/formaldehyde resins being 1 : 2.5 to 1 : 4, and the sum of the com-ponents A, B and C being 100 %.
A) 20 to 60 % by weight of one or more polyurethane and/or urea elastomers prepared from a1) linear compounds with terminal hydroxyl and/or primary and/or secondary amino groups and a2) aliphatic and/or cycloaliphatic diisocyan-ates, the molar ratio of a1 to a2 being 0.8 : 1 to 1.5 : 1, B) 10 to 50 % by weight of one or more polyesters prepared from b1) aromatic and aliphatic and/or cycloaliphatic polycarboxylic acids, 40 to 70 mol % of the polycarboxylic acids being aromatic and 60 to 30 mol % of the poly-carboxylic acids being aliphatic and/or cycloaliphatic, and 0 to 50 mol % of the total polycarboxylic acids being tricarboxylic acids, and b2) polyols, - 20 to 60 mol % of the polyols having 2 or 3 carbon atoms and 40 to 80 mol % having 4 or more carbon atoms, - at least 40 mol % of the diols used having aliphatic side-chains, - 0 to 50 mol % of the polyols being triols and - the ratio of the components b1 and b2 corres-ponding to the following formula in which n1 denotes the number of mol of poly-ols, n2 denotes the number of mol of poly-carboxylic acids, F denotes the average molar value of the functionality of the polycarboxylic acids and K has a value of 1.05 to 1.5, and C) 5 to 25 % by weight of polycondensates partially etherified with monoalcohols and consisting of melamine, benzoguanamine and/or urea with formaldehyde, the molar ratio of melamine to formaldehyde in the case of melamine/
formaldehyde resins being 1 : 4.5 to 1 : 6 and the molar ratio of benzoguanamine or urea to formaldehyde in the case of benzoguanamine/formaldehyde or urea/formaldehyde resins being 1 : 2.5 to 1 : 4, and the sum of the com-ponents A, B and C being 100 %.
6. The process as claimed in claim 5, wherein the coating composition for the base coat contains, as a further binder component D), a copolymer prepared from 85 to 95 % by weight of ethylene and 15 to 5 % by weight of vinyl acetate, in a proportion of 5 to 15 % by weight, based on the sum of components A) to D).
7. The process as claimed in claim 5, wherein polyester diols and diamines in a molar ratio of 0.8 : 1 to 1.2 : 1 have been used as component a1) to prepare the resin A).
8. The process as claimed in one of claims 5 to 7, wherein, in addition to components A), B), C) and if appropriate D), the coating composition contains, as component E), polymeric microparticles having a size or size distribution in the range from 0.01 to 2 µm, in a proportion of 5 to 15 % by weight, based on the sum of components A) to E), the said microparticles having been prepared by emulsion polymerization of a mixture of unsaturated monomers, some of which preferably contain carboxyl or hydroxyl groups and some of which are free of carboxyl and hydroxyl groups, and a polyfunctional crosslinking agent, the emulsion polymerization having been carried out in the aqueous phase and the water having been removed during or after the polymerization.
9. A substrate coated with a multilayer enamel con-sisting of at least one coat containing metallic pigments and at least one transparent protective coat, wherein a coating composition as claimed in one of claims 1 to 3 has been used to prepare the base coat.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833333072 DE3333072A1 (en) | 1983-09-14 | 1983-09-14 | COATING SIZE, METHOD FOR PRODUCING COATINGS AND COATED SUBSTRATE |
| DEP3333072.7 | 1983-09-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1216693A true CA1216693A (en) | 1987-01-13 |
Family
ID=6208989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000463230A Expired CA1216693A (en) | 1983-09-14 | 1984-09-14 | Coating composition, process for the preparation of coatings, and coated substrate |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4576868A (en) |
| EP (1) | EP0137256B2 (en) |
| JP (1) | JPH0635560B2 (en) |
| AT (1) | ATE25099T1 (en) |
| AU (1) | AU562121B2 (en) |
| BR (1) | BR8404585A (en) |
| CA (1) | CA1216693A (en) |
| DE (2) | DE3333072A1 (en) |
| ES (1) | ES8505712A1 (en) |
| ZA (1) | ZA847265B (en) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2548906B2 (en) * | 1984-04-28 | 1996-10-30 | 大日本インキ化学工業株式会社 | High solid content coating composition |
| US4710408A (en) * | 1986-07-11 | 1987-12-01 | Hercules Incorporated | Primer coating for cycloolefin polymer articles |
| DE3626424A1 (en) * | 1986-08-05 | 1988-02-11 | Bayer Ag | METHOD FOR THE ELECTROPHORETIC CONSTRUCTION OF AL-FREE SELF-CLEANING ENAMEL LAYERS ON STEEL SHEET PARTS |
| DE3628124A1 (en) * | 1986-08-19 | 1988-03-03 | Herberts Gmbh | AQUEOUS COATING AGENT, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF |
| US4791168A (en) * | 1987-04-15 | 1988-12-13 | Basf Corporation, Inmont Division | Polyurethane resins in water-dilutable basecoats having low flash and quick-drying characteristics |
| USRE34730E (en) * | 1987-04-15 | 1994-09-13 | Basf Corporation, Inmont Division | Polyurethane resins in water-dilutable basecoats having low flash and quick-drying characteristics |
| DE3834738A1 (en) | 1988-10-12 | 1990-04-19 | Basf Lacke & Farben | METHOD FOR PRODUCING A MULTI-LAYER COATING, AQUEOUS COATING COMPOSITION, WATER-DISCOVERABLE POLYACRYLATE RESINS AND METHOD FOR PRODUCING WATER-DISCOVERABLE POLYACRYLATE RESINS |
| DE69009514T2 (en) * | 1989-02-09 | 1994-09-22 | Nippon Oils & Fats Co Ltd | Coating agent with a high solids content, objects coated with it and coating processes therefor. |
| JPH02214787A (en) * | 1989-02-14 | 1990-08-27 | Nippon Paint Co Ltd | Cold drying coating composition |
| JPH06104789B2 (en) * | 1989-03-31 | 1994-12-21 | 日本ペイント株式会社 | Metal pigment composition and aqueous coating composition containing the same |
| US5166254A (en) * | 1990-12-03 | 1992-11-24 | E. I. Du Pont De Nemours And Company | Waterbased coating composition of methylol (meth)acrylamide acrylic polymer, acrylic hydrosol and melamine crosslinking agent |
| DE4100204A1 (en) * | 1991-01-05 | 1992-07-09 | Bayer Ag | COATING AGENTS AND ITS USE FOR THE PRODUCTION OF COATINGS |
| US6200683B1 (en) * | 1994-12-16 | 2001-03-13 | Ppg Industries Ohio, Inc. | Coil coating compositions with low temperature flexibility and improved stain resistance |
| WO1998027134A1 (en) * | 1996-12-18 | 1998-06-25 | Basf Coatings Ag | Coating agent and method for producing same |
| DE19709465C2 (en) | 1997-03-07 | 2001-07-12 | Basf Coatings Ag | Coating agents, process for the production of multi-layer coatings and use of the coating agents therefor |
| CN1061670C (en) * | 1997-05-21 | 2001-02-07 | 褚炎明 | Namometre automotive metal finish |
| US5962574A (en) * | 1997-07-25 | 1999-10-05 | Bee Chemical Company | Wet-on-wet primer with low film build U.V. light protection |
| EP1137728A1 (en) | 1998-10-31 | 2001-10-04 | BASF Coatings AG | Coating agent with a macromer unit for the production of multi-layered coatings |
| DE50006821D1 (en) | 1999-02-25 | 2004-07-22 | Basf Coatings Ag | THE USE OF TRICYCLODECANDIMETHANOL FOR THE PRODUCTION OF MULTILAYER PAINTINGS |
| DE19908001A1 (en) | 1999-02-25 | 2000-08-31 | Basf Coatings Ag | Highly scratch-resistant multi-layer coating, process for their production and their use |
| DE19909894A1 (en) | 1999-03-06 | 2000-09-07 | Basf Coatings Ag | Sol-gel coating for single-layer or multi-layer coatings |
| DE19914896A1 (en) | 1999-04-01 | 2000-10-05 | Basf Coatings Ag | Aqueous coating material, e.g. for painting cars or industrial substrates, contains a polyurethane binder based on bis-4-isocyanato-cyclohexyl-methane with a low trans-trans content, plus a crosslinker |
| DE19914898C2 (en) | 1999-04-01 | 2002-10-24 | Basf Coatings Ag | Crosslinking agents for pyrimidine based thermally curable compositions and their use |
| DE19938759A1 (en) | 1999-08-16 | 2001-02-22 | Basf Coatings Ag | Coating material and its use for the production of highly scratch-resistant multi-layer clear coats |
| DE19940857A1 (en) | 1999-08-27 | 2001-03-01 | Basf Coatings Ag | Sol-gel coating for single-layer or multi-layer coatings |
| DE19940858A1 (en) | 1999-08-27 | 2001-03-01 | Basf Coatings Ag | Sol-gel coating for single-layer or multi-layer coatings |
| US6613389B2 (en) | 2001-12-26 | 2003-09-02 | Dow Global Technologies, Inc. | Coating process and composition for same |
| US20060172074A1 (en) * | 2005-02-03 | 2006-08-03 | Diloreto Salvatore | Polyurea coating systems and related methods |
| DE102006002154A1 (en) * | 2006-01-17 | 2007-07-19 | Bayer Materialscience Ag | Polyurethane polyurea coatings |
| WO2009152044A1 (en) * | 2008-06-10 | 2009-12-17 | Dow Global Technologies Inc. | 1,3- or 1,4-bis(aminomethyl)cyclohexane-initiated polyols and rigid polyurethane foam made therefrom |
| EP3815898A1 (en) | 2019-10-28 | 2021-05-05 | Covestro Deutschland AG | Laminate of polycarbonate and polycarbonate blend for improved pavement |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1284755A (en) * | 1968-09-30 | 1972-08-09 | Celanese Coatings Co | Process for coating surfaces and compositions for use therein |
| AT305467B (en) * | 1970-02-25 | 1973-02-26 | Bayer Ag | Production of paint films by electrostatic powder coating |
| US3962369A (en) * | 1973-05-16 | 1976-06-08 | Ppg Industries, Inc. | Sealer-primer for elastomeric coatings |
| DE2806497C2 (en) * | 1978-02-16 | 1982-02-18 | Basf Farben + Fasern Ag, 2000 Hamburg | Multi-layer painting with a clear coat as the final layer |
| JPS6023792B2 (en) * | 1979-04-05 | 1985-06-10 | 関西ペイント株式会社 | Method of forming metallic coating film |
| DE3010719A1 (en) * | 1980-03-20 | 1981-09-24 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING METAL EFFECT PAINTINGS AND WEATHER-RESISTANT METAL EFFECT MULTI-LAYER PAINT PAINTINGS |
| DE3041648C2 (en) * | 1980-11-05 | 1982-10-07 | Basf Farben + Fasern Ag, 2000 Hamburg | Two-layer metallic paint, process for its manufacture and use |
| DE3108861A1 (en) * | 1981-03-09 | 1982-09-23 | Plate Bonn Gmbh, 5300 Bonn | Curable coating, use thereof for producing stone chip resistant coatings on motor vehicles, and production of coats |
| JPS5876469A (en) * | 1981-11-02 | 1983-05-09 | Nippon Paint Co Ltd | Metallic coating procedure and coating composition |
| US4391858A (en) * | 1981-11-20 | 1983-07-05 | Glasurit America, Inc. | Coating process |
| US4477536A (en) * | 1982-03-18 | 1984-10-16 | Glasurit America, Inc. | Process for preparing a multilayer coating |
| DE3210051A1 (en) * | 1982-03-19 | 1983-09-29 | Basf Farben + Fasern Ag, 2000 Hamburg | WATER-DISCOVERABLE COATING AGENT FOR PRODUCING THE BASE LAYER OF A MULTI-LAYER COATING |
| US4533703A (en) * | 1983-10-13 | 1985-08-06 | Ford Motor Company | Flexible basecoat/two component clearcoat coating composition |
-
1983
- 1983-09-14 DE DE19833333072 patent/DE3333072A1/en not_active Withdrawn
-
1984
- 1984-08-23 EP EP19840110027 patent/EP0137256B2/en not_active Expired - Lifetime
- 1984-08-23 AT AT84110027T patent/ATE25099T1/en not_active IP Right Cessation
- 1984-08-23 DE DE8484110027T patent/DE3462148D1/en not_active Expired
- 1984-09-13 BR BR8404585A patent/BR8404585A/en not_active IP Right Cessation
- 1984-09-13 AU AU33013/84A patent/AU562121B2/en not_active Ceased
- 1984-09-14 ES ES535962A patent/ES8505712A1/en not_active Expired
- 1984-09-14 JP JP19190784A patent/JPH0635560B2/en not_active Expired - Lifetime
- 1984-09-14 ZA ZA847265A patent/ZA847265B/en unknown
- 1984-09-14 CA CA000463230A patent/CA1216693A/en not_active Expired
- 1984-09-14 US US06/651,274 patent/US4576868A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ES535962A0 (en) | 1985-06-01 |
| JPH0635560B2 (en) | 1994-05-11 |
| DE3462148D1 (en) | 1987-02-26 |
| ZA847265B (en) | 1985-05-29 |
| AU562121B2 (en) | 1987-05-28 |
| DE3333072A1 (en) | 1985-03-21 |
| ES8505712A1 (en) | 1985-06-01 |
| US4576868A (en) | 1986-03-18 |
| EP0137256A3 (en) | 1985-05-15 |
| EP0137256B1 (en) | 1987-01-21 |
| AU3301384A (en) | 1985-03-21 |
| EP0137256A2 (en) | 1985-04-17 |
| JPS6086172A (en) | 1985-05-15 |
| BR8404585A (en) | 1985-08-06 |
| ATE25099T1 (en) | 1987-02-15 |
| EP0137256B2 (en) | 1992-11-04 |
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