CA2174663A1 - Two-component paint system - Google Patents
Two-component paint systemInfo
- Publication number
- CA2174663A1 CA2174663A1 CA002174663A CA2174663A CA2174663A1 CA 2174663 A1 CA2174663 A1 CA 2174663A1 CA 002174663 A CA002174663 A CA 002174663A CA 2174663 A CA2174663 A CA 2174663A CA 2174663 A1 CA2174663 A1 CA 2174663A1
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- CA
- Canada
- Prior art keywords
- weight
- water
- component
- paint
- paint system
- 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
Links
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
-
- 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
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Paints Or Removers (AREA)
- Road Signs Or Road Markings (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Particle Formation And Scattering Control In Inkjet Printers (AREA)
- Ink Jet (AREA)
- Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
- Prostheses (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a paint system composed of two components (I) and (II), which is characterized in that component (I) comprises (A) from 5 to 50% by weight of at least one binder, (B) from 0 to 20% by weight of at least one cross-linking agent, (C) from 0.5 to 60% by weight of at least one pigment, (D) from 5 to 80% by weight of water, (E) from 0 to 40% by weight of at least one organic solvent, (F) from 0 to 5% by weight of at least one rheology-controlling additive, and (G) from 0 to 10% by weight of at least one further conventional paint auxiliary, the sum of the percentages by weight indicated for components (A), (B), (C), (D), (E), (F) and (G) always being 100% by weight, and component (II) comprises (H) from 70 to 99% by weight of water, (J) from 0 to 10% by weight of at least one organic solvent, (K) from 0.1 to 10% by weight of at least one rheology-controlling additive, and (L) from 0 to 10% by weight of at least one further conventional paint auxiliary, the sum of the percentages by weight indicated for com-ponents (H), (J), (R) and (L) always being 100% by weight.
Description
~ 1 7 ~ 6 6 3 ' j r r PAT 93 443 19.11.1993 BASF Lacke und Farben A~, MUnster ~ omponent paint system The invention relates to a paint system composed of two components and to the use of this paint system for the production of automotive refinishes.
DE-A-41 10 520 describes a mixer system for the production of aqueous automotive refinishes, which system involves automotive refinishes being proAl~ce~ by mixing a pigment-contA;~;ng base color, which contains less than 5% by weight of water, with a pigment-free aqueous component.
In the two-component paint system described in DE-A-41 10 520 the pigment-contA;n;~g base colors have unfavorable flow characteristics, which have an adverse effect both on meterability and on miscibility with the pigment-free aqueous component. One of the consequences of this is that the precise match;ng of predetermined colors is rendered more difficult.
The object of the present invention is to provide a paint system composed of two components which does not have the disadvantages described above.
-This object i8 achieved by the provision of a paint ~ystem composed of two components (I) and (II), which i8 characterized in that component (I) comprises (A) from 5 to 50%, preferably from 10 to 30%, by weight of at least one binder (B) from 0 to 20% , prefersbly from 0 to 5%, by weight of at least one cro~81 ;n~;ng agent, (C) from 0.5 to 60~, preferably from 0.5 to 40%, by weight of at least one pigment (D) from 5 to 80%, preferably from 10 to 70%, by weight of water (E) from 0 to 40%, preferably from 5 to 20%, by weight of at lea~t one orgsnic solvent, (F) from 0 to 5%, preferably from 0 to 2%, by weight of at lea~t one rheology-controlling additive, snd (G) from 0 to 10%, preferably from 2 to 5%, by weight of at lea~t one further oo.lvel~tional psint auxiliary, the ~um of the percentage~ by weight indicated for component~ (A), (B), (C), (D), (E), (F) and (G) alway~
being 100% by weight, and component (II) comprises (H) from 70 to 99%, preferably from 80 to 99%, by weight of water (J) from 0 to 10%, preferably from 0 to 2%, by weight of at least one organic solvent, (K) from 0.1 to 10%, preferably from 1 to 3%, by weight of at least one rheology-controlling additive, and (L) from 0 to 10%, preferably from 0.5 to 3%, by weight of at least one further ~ol.ve..tional paint auxiliary, the sum of the percentages by weight ; n~ c~ted for com-ponent~ (H), (J), (~) and (L) always being 100% by weight.
The advantages of the two-component paint ~y~tem provided in accordance with the invention are in particular that the components are readily meterable and miscible, making the production of paints having predetermined colors very ea~y. In many ca~es it i~ no longer neces~ary to formulate the paints pro~n~ u~ing the paint system according to the invention to proce~ing vificosity in an additional operation. A
further advantage lies in the high freeze-thaw stability of component (I).
As constituent (A) in component (I) it iB possible to employ all water-soluble or water-dispersible h;nAPr~
which are suitable for paints. In particular it is possible to employ water-soluble or water-dispersible polyurethane resins, polyester resins, polyacrylate resins, polyacrylate resins prepared in the ~L~ ~ence of polyurethane and/or polyester resins, or mixtures of these resins as constituent (A) in component (I).
15 Bxamples of suitable polyurethane resins are described in the following documents: EP-A-355 433, DE-A-35 45 618, DE-A-38 13 866. t8ic] DE-A-32 10 051, DE-A-26 24 442, DE-A-37 39 332, US-A-4,719,132, BP-A-89 497, US-A-4,558,090, US-A-4,489,135,, tsic~ DE-A-36 28 124, EP-A-158 099, D8-A-29 26 584, ~P-A-195 931, DE-A-33 21 180 and DE-A-40 05 961.
A~ constituent (A) in component (I) it i~ preferred to employ polyurethane res~ns which have a number-average molecular weight (determined by gel permeation chromatography usinq polystyrene as stAnAArd) of from 1000 to 30,000, preferably from 1500 to 20000, and an acid number of from 5 to 70 mg of KOH/g, preferably from 10 to 30 mg of KOH/g, and which can be prepared by reacting prepolymers which contain isocyanate groups with compound~ which are reactive toward isocyanate groups .
The preparation of prepolymers contA ~ n ~ nq i~ocyanate groups can be effected by reacting polyols having a hydroxyl number of from 10 to 1800 mg, preferably from 50 to 1200 mg of ROH/g, with excess polyisocyanates at temperatures of up to 150C, preferably from 50 to 130C, in organic solvents which are incapable of reacting with isocyanates. The ratio of equivalents of NCO to OH groups i8 between 2.0:1.0 and > 1.0:1.0, preferably between 1.4:1 and 1.1:1.
The polyols employed for the preparation of the prepolymer may be of low and/or high molecular weight and may contain groups which are slow to react and are anionic or are capable of forming anions. It iB also possible to make partial use of low molecular weight polyols having a molecular weight of from 60 to 400 in order to prepare the prepolymers which contain isocyanate yLGu~ , in which case quantities of up to 30% by weight of the overall polyol oonstituents, preferably from about 2 to 20% by weight, are employed.
To obtain an NCO prepolymer of high fleY; h; 1 ~ ty a high proportion should be added of a predominantly linear polyol having a preferred 0~ number of from 30 to 150 mg of KOH/g. Up to 97% by weight of the overall polyol may consist of ~aturated and unsaturated polyesterfi and/or polyethers having a molecular mass Mn of from 400 to 5000. The polyether diols chosen should not introduce excessive quantities of ether groups, since otherwise the polymers formed swell in water.
Polye~ter diols are prepared by esterification of organic dicarboxylic acid~ or their anhydride~ with organic diols, or are derived from a hydroxycarboxylic acid or from a lactone. In order to prepare branched polyester polyols, a minor proportion of polyols or polycarboxylic acids having a higher functionality can be employed.
Typical multifunctional isocyanates which are employed are aliphatic, cycloAl;phAtic and/or aromatic polyisocyanates having at least two isocyanate groups per molecule. Preference is given to the isomers or isomer mixtures of organic diisocyanates. Because of their good resistance to ultraviolet light, (cyclo)~l;phAtic d~isocyanates give products having a low tendency to yellowing. The polyisocyanate component u~ed to form the prepolymer may also contain a proportion of polyisocyanates of higher functionality, provided that this does not bring about any gelling.
Products which have proven suitable as triisocyanates are those obt~;~e~ by trimerization or oligomerization of diisocyanate~ or by reaction of diisocyanates with polyfunctional compounds which contain OH or N~ groups.
If desired, the average functionality can be lowered by addition of monoisocyanates.
Example6 of polyisocyanates which can be employed are phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, bisphenylene diisocyanate, naphthylene diisocyante, ~;ph~nylmethane diisocyanate, i~ophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, dicyclohexylmethane ~ ocyanate, trimethylene diisocyanate, tetramethylene diisoayanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate and trimethylhexane diisocyanate.
Polyurethanes are generally incompatible with water unless during their synthesis specific constituents are incorporated and/or particular preparation steps are carried out. Thus, in order to prepare the polyurethane resins, it iB possible to use compo~n~ which contsin two H-active groups which are reactive with isocyanate group~, and at least one group which ensure~
dispersibility in water. Suitable groups of this kind are nonionic ylou~s (e.g. polyethers), anionic yLO
mixtures of these two yLOup~ ~ or cationic y ou~_.
_ 2174663 To introduce anionic groups into polyurethane resin molecules, compounds are used which contain at least one group which i~ reactive toward isocyanate groups and at least one group which is cApAhle of forming anions. Suitable group6 which are reactive toward i~ocyanate groups are in particular hydroxyl group~, and also primary and/or secondary amino groups. Groups capable of forming An;on~ are carboxyl, sulfonic acid and/or phosphonic acid groups. Preference is given to employing Alk~noic acids having two substituent~ on the carbon atom. The substituent may be a hydroxyl group, an alkyl group or an alkylol group. These polyols have at least one, generally from 1 to 3, carboxyl y~Gu~- in the molecule. They have from two to about 25, preferably from 3 to 10 carbon atoms. The carboxyl-contA;n;ng polyol may make up from 3 to 100% by weight, preferably from 5 to 50% by weight, of the overall polyol constituent in the NC0 prepolymer.
The isocyanate y~GU~B of the prepolymer which contains isocyanate groups are reacted with a modifying agent.
In this context the modifying sgent is preferably added in a quantity 80 aB to re~ult in chain exten~ions and therefore in increa~e~ in molecular weight. The modifying agents preferably employed are organic compound~ which contain hydroxyl and/or ~econdary and/or primary amino yLG~, especially di-, tri-and/or polyols of higher functionality. Exsmple [sic]
g of polyols which can be employed are trimethylol-propane, 1,3,4 butanetriol [ BiC ], glycerol, erythritol, mesoerythritol, arabitol, adonitol, etc.
Trimethylolpropane is preferably employed.
As constituent (A) in component (I) it is possible in principle to employ all water-soluble or water-dispersible polyacrylate resins which are suitable for aqueous paints. A very large number of such resins has been described, and a very wide selection of them is available commercially. Particularly suitable polyacrylate resins are described in DE-A-38 32 826 and in DE-A-38 41 540.
As constituent (A) in component (I) it is also possible to employ water-soluble or water-dispersible polyester resins.
A~ constituent (B) in component (I) it is possible, for example, to employ blocked polyisocyanates and/or water-soluble or water-dispersible am; no resins. It i~
preferred - if desired in the presence of cosolvents -to employ water-soluble or water-dispersible melamine resins. These are in general etherified melamine/formaldehyde co~Ae~Ation products. The solubility or dispersibility in water of the amino resins depends, apart from the de~ ee of condensation, which should be as low as possible, on the etherifying - 217~663 component, with only the lowest members of the alcohol or of the ethylene glycol monoether series giving condensation products which are soluble in water. The melamine resins which are etherified with methanol have S the greatest significance. If solubilizers are used, it is also possible to disperse butanol-etherified melamine resins in the aqueous phase. The possibility also exists of incorporating carboxyl groups into the conden~ation product. Transetherification products of highly etherified co~pnsAtion products of formaldehyde with hydroxycarboxylic acids, via their carboxyl groups, are soluble in water after neutralization.
As constituent (C), components (I) may contain all conventional paint pigments which do not react with water or dissolve in water. The pigments may comprise inorganic or organic compounds and may be effect pigments and/or color pigments. In order to ensure a degree of appl; ~Ah; lity which is as close as possible to universal, and in order to maximize the possible colors, it is preferred to incorporate, in one component (I), either only color pigments or only effect pigments, but not mixtures of color and effect pigments.
Effect pigments which can be employed are metal flake pigments such as commercial aluminum bronzes, aluminum bronzes chromated in accordance with DE-A-36 36 183, -and commercial stainless-steel bronzeg, and also nonmetallic effect pigments such a~, for example, pearle~cent or interference pigments. Example~ of ~uitable inorganic color pigments are titanium dioxide, iron oxides, Sicotrans yellow and carbon black.
Examples of ~uitable organic color pigments are indanthrene blue, Cromophthal red, Irgazin orange and Heliogen green.
As constituent (E), component (I) may contain at least one organic solvent. ~xamples of f uitable solvents are in particular water-miscible ~olvents such as, for example, alcohols, esters, ketones, keto ester~, glycol ether esters and the like. Alcohols and glycol ethers are preferably employed, and butyl glycol and butanols are particularly preferred.
As constituent (F) component (I) may contain at least one rheology-controlling additive. Examples of rheology-controlling additives are crossl; nke~ polymer microparticle~ as dif~closed, for example, in EP-A-38 127, inorganic phyllosilicates, for example aluminum-magnesium silicates, sodium-magnesium phyllosilicates and f~odium-magnesium-fluorine-lithium phyllosilicates of the montmorillonite type, and al~o ~ynthetic polymer~ cont~n~ng ionic y Gupf and/or groups which have an a~sociated action, ~uch as polyvinyl alcohol~ poly(meth)acrylAm~de, poly(meth)acrylic acid, polyvinylpyrrolidone, styrene/maleic anhydride or ethylene/maleic anhydride copolymers and derivatives thereof, or else hydrophobically modified, ethoxylated urethanes or polyacrylates. As rheology-controlling additives it is preferred to employ inorganic phyllosilicates.
Particular preference i8 given to employing, as rheology-controlling additive, a combination of a polyacrylate resin which contains carboxyl yLUUp~
having an acid number of from 60 to 780 mg, preferably from 200 to 500 mg of ROH/g, with a sodium-magne~ium phyllosilicate.
~ he sodium-magnesium phyllosilicate is ~Ype~; ently incorporated into the paint component in the form of an aqueous paste. The paste preferably contain~ 3% by weight of phyllosilicate and 3% by weight of polypropylene glycol or 2% by weight of phyllosilicate and 0.6% by weight of poly~Lo~lene glycol or 2% by weight of phyllosilicate and 2% by weight of other commercial, surface-active substances, all percentages being based on the overall weight of the paste.
Component (I) of the paint ~ystem according to the invention should preferably not contain any rheology-controlling additive, especially not any inorganicphyllosilicate as rheology-controlling additive. The rheology-controlling additives which are nece~sary for the paints which can be prepared using the paint ~ystem 217466~
according to the invention should preferably be contained exclusively in component (II). It is particularly preferred that, in the cases in which an inorganic phyllosilicate i8 employed as rheology-controlling additive, the inorganic phyllosilicate isexclusively contained in paint component (II).
As well as constituent (F), component (I) may also contain, as constituent (G), at least one further conventional paint additive. Examples of such additives are antifoams, dispersion auxiliaries, emulsifiers and leveling ass~stants.
Component (I) is prepared by methods known to the person skilled in the art by mixing and, if desired, dispersing the individual constituents. Thus, for example, color pigments are conventionally incorporated by dispersion of the respective pigments in one or more binders. The dispersion of the pigments is carried out using conventional devices such as, for example, bead mills and sand mills.
The effect pigments are conventionally incorporated by homogeneous mixing of the effect pigments with one or more solvents. This mixture i6 then, using a stirrer or di~solver, stirred into a mixture of one or more of the above-described binders, if desired with the addition of further organic solvent~.
~174663 Constituent~ (J), (K) and (L) of paint component (II) corre~pond to constituents (E), (F) and (G) of paint component (I).
The paint sy~tem according to the invention is ~uitable for the production of aqueous paints which are intended to have a color determined precisely beforehand. By mixing correspondingly pigmented paint components (I) in proportions which are necessary to achieve the corresponding colors, and adding paint component (II), it is possible to obtain aqueous paints which are accurate in color and can be processed immediately. The paint system according to the invention is particularly suitable for mixer systems for production of automotive refinishes (cf. e.g. Glasurit-Handbuch, 11th Edition, Kurt R., [BiC~ Vincentz-Verlag, Hanover 1984, pages 544 to 547). Using the paint system according to the invention it is of course also possible to produce paints for other areas of application, for example the painting of plastic~ or the production-line fini~hing of motor vehicle bodies.
The invention iB illustrated in more detail below with reference to exemplary embodiments. In these embodiment~ all ~ n~ tions as to parts and percentages are by weight, unless expressly noted otherwise.
~17466~
1. PreParation of an organic Polyurethane resin solution 686.3 g of a polyester having a number-average molecular weight of 1400 based on a commercial un~aturated dimeric fatty acid (having an iodine number of 10 mg of I2/g, a monomer content of not more than 0.1%, a trimer content of not more than 2%, an acid number of from 195 to 200 mg of KOH/g and a hydrolysis number of from 197 to 202 mg of KOH/g), isophthAl;c acid and heY~ne~;ol are placed under protective gas in an appropriate reaction vessel with stirrer, reflux condenser and feed vessel, and 10.8 g of hexanediol, 55.9 g of dimethylolpropionic acid, 344.9 g of methyl ethyl ketone and 303.6 g of 4,4'-di-(isocyanato-cyclohexyl) methane are added in succession. This mixture is maintA;~e~ under reflux until the isocyanate content has fallen to 1.0%. Subsequently 26.7 g of trimethylolpropane are added to the mixture, which is maintained under reflux to a viscosity of 12 dPas (for a solution of one part of resin solution in one part of N-methylpyrrol~Q~e). 1378.7 g of butylglycol are then added. After a vacuum distillation in which the methyl ethyl ketone is removed, the resin solution is neutralized with 32.7 g of dimethylethanol~m;ne. The ~olids content of the resulting resin solution is 44%.
Under intensive stirring, it is diluted to a solids content of 41% by weight by A~; ng butylglycol.
217~6G3 2. Preparation of an aqueous polyurethane resin dispersion 686.3 g of a polyester having a number-average molecular weight of 1400 based on a commercial unsaturated dimeric fatty acid (having an iodine number of 10 mg of I2/g, a monomer content of not more than 0.1%, a trimer content of not more than 2~, an acid number of from 195 to 200 mg of KO~/g and a hydrolysis number of from 197 to 202 mg of ROH/g), isophth~l;c acid and hexanediol are placed under protective gas in an appropriate reaction vessel with stirrer, reflux conden~er and feed vessel, and 10.8 g of hexanediol, 55.9 g of dimethylolpropionic acid, 344.9 g of methyl ethyl ketone and 303.6 tlacuna] of 4,4'-di-(isocyanatocyclohexyl) methane are added in succession.
This mixture i8 maintained under reflux until the i~ocyanate content has fallen to 1.0%. Subsequently 26.7 g of trimethylolpropane are added to the mixture, which i8 maint~;ne~ under reflux to a viscosity of 12 dPas (for a solution of one part of resin solution in one part of N-methylpyrrolidone). Any excess isocyanate present is destroyed by ~ n~ 47 . 7 g of butylglycol. Subsequently 32.7 g of dimethylethanol-amine, 2688.3 g of deionized water and 193.0 g of butylglycol are added to the reaction mixture with vigorou~ stirring. After the removal of the methyl ethyl ketone by vacuum distillation, an aqueous 217~663 dispersion is obtained which has a solids content of - about 27%.
DE-A-41 10 520 describes a mixer system for the production of aqueous automotive refinishes, which system involves automotive refinishes being proAl~ce~ by mixing a pigment-contA;~;ng base color, which contains less than 5% by weight of water, with a pigment-free aqueous component.
In the two-component paint system described in DE-A-41 10 520 the pigment-contA;n;~g base colors have unfavorable flow characteristics, which have an adverse effect both on meterability and on miscibility with the pigment-free aqueous component. One of the consequences of this is that the precise match;ng of predetermined colors is rendered more difficult.
The object of the present invention is to provide a paint system composed of two components which does not have the disadvantages described above.
-This object i8 achieved by the provision of a paint ~ystem composed of two components (I) and (II), which i8 characterized in that component (I) comprises (A) from 5 to 50%, preferably from 10 to 30%, by weight of at least one binder (B) from 0 to 20% , prefersbly from 0 to 5%, by weight of at least one cro~81 ;n~;ng agent, (C) from 0.5 to 60~, preferably from 0.5 to 40%, by weight of at least one pigment (D) from 5 to 80%, preferably from 10 to 70%, by weight of water (E) from 0 to 40%, preferably from 5 to 20%, by weight of at lea~t one orgsnic solvent, (F) from 0 to 5%, preferably from 0 to 2%, by weight of at lea~t one rheology-controlling additive, snd (G) from 0 to 10%, preferably from 2 to 5%, by weight of at lea~t one further oo.lvel~tional psint auxiliary, the ~um of the percentage~ by weight indicated for component~ (A), (B), (C), (D), (E), (F) and (G) alway~
being 100% by weight, and component (II) comprises (H) from 70 to 99%, preferably from 80 to 99%, by weight of water (J) from 0 to 10%, preferably from 0 to 2%, by weight of at least one organic solvent, (K) from 0.1 to 10%, preferably from 1 to 3%, by weight of at least one rheology-controlling additive, and (L) from 0 to 10%, preferably from 0.5 to 3%, by weight of at least one further ~ol.ve..tional paint auxiliary, the sum of the percentages by weight ; n~ c~ted for com-ponent~ (H), (J), (~) and (L) always being 100% by weight.
The advantages of the two-component paint ~y~tem provided in accordance with the invention are in particular that the components are readily meterable and miscible, making the production of paints having predetermined colors very ea~y. In many ca~es it i~ no longer neces~ary to formulate the paints pro~n~ u~ing the paint system according to the invention to proce~ing vificosity in an additional operation. A
further advantage lies in the high freeze-thaw stability of component (I).
As constituent (A) in component (I) it iB possible to employ all water-soluble or water-dispersible h;nAPr~
which are suitable for paints. In particular it is possible to employ water-soluble or water-dispersible polyurethane resins, polyester resins, polyacrylate resins, polyacrylate resins prepared in the ~L~ ~ence of polyurethane and/or polyester resins, or mixtures of these resins as constituent (A) in component (I).
15 Bxamples of suitable polyurethane resins are described in the following documents: EP-A-355 433, DE-A-35 45 618, DE-A-38 13 866. t8ic] DE-A-32 10 051, DE-A-26 24 442, DE-A-37 39 332, US-A-4,719,132, BP-A-89 497, US-A-4,558,090, US-A-4,489,135,, tsic~ DE-A-36 28 124, EP-A-158 099, D8-A-29 26 584, ~P-A-195 931, DE-A-33 21 180 and DE-A-40 05 961.
A~ constituent (A) in component (I) it i~ preferred to employ polyurethane res~ns which have a number-average molecular weight (determined by gel permeation chromatography usinq polystyrene as stAnAArd) of from 1000 to 30,000, preferably from 1500 to 20000, and an acid number of from 5 to 70 mg of KOH/g, preferably from 10 to 30 mg of KOH/g, and which can be prepared by reacting prepolymers which contain isocyanate groups with compound~ which are reactive toward isocyanate groups .
The preparation of prepolymers contA ~ n ~ nq i~ocyanate groups can be effected by reacting polyols having a hydroxyl number of from 10 to 1800 mg, preferably from 50 to 1200 mg of ROH/g, with excess polyisocyanates at temperatures of up to 150C, preferably from 50 to 130C, in organic solvents which are incapable of reacting with isocyanates. The ratio of equivalents of NCO to OH groups i8 between 2.0:1.0 and > 1.0:1.0, preferably between 1.4:1 and 1.1:1.
The polyols employed for the preparation of the prepolymer may be of low and/or high molecular weight and may contain groups which are slow to react and are anionic or are capable of forming anions. It iB also possible to make partial use of low molecular weight polyols having a molecular weight of from 60 to 400 in order to prepare the prepolymers which contain isocyanate yLGu~ , in which case quantities of up to 30% by weight of the overall polyol oonstituents, preferably from about 2 to 20% by weight, are employed.
To obtain an NCO prepolymer of high fleY; h; 1 ~ ty a high proportion should be added of a predominantly linear polyol having a preferred 0~ number of from 30 to 150 mg of KOH/g. Up to 97% by weight of the overall polyol may consist of ~aturated and unsaturated polyesterfi and/or polyethers having a molecular mass Mn of from 400 to 5000. The polyether diols chosen should not introduce excessive quantities of ether groups, since otherwise the polymers formed swell in water.
Polye~ter diols are prepared by esterification of organic dicarboxylic acid~ or their anhydride~ with organic diols, or are derived from a hydroxycarboxylic acid or from a lactone. In order to prepare branched polyester polyols, a minor proportion of polyols or polycarboxylic acids having a higher functionality can be employed.
Typical multifunctional isocyanates which are employed are aliphatic, cycloAl;phAtic and/or aromatic polyisocyanates having at least two isocyanate groups per molecule. Preference is given to the isomers or isomer mixtures of organic diisocyanates. Because of their good resistance to ultraviolet light, (cyclo)~l;phAtic d~isocyanates give products having a low tendency to yellowing. The polyisocyanate component u~ed to form the prepolymer may also contain a proportion of polyisocyanates of higher functionality, provided that this does not bring about any gelling.
Products which have proven suitable as triisocyanates are those obt~;~e~ by trimerization or oligomerization of diisocyanate~ or by reaction of diisocyanates with polyfunctional compounds which contain OH or N~ groups.
If desired, the average functionality can be lowered by addition of monoisocyanates.
Example6 of polyisocyanates which can be employed are phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, bisphenylene diisocyanate, naphthylene diisocyante, ~;ph~nylmethane diisocyanate, i~ophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, dicyclohexylmethane ~ ocyanate, trimethylene diisocyanate, tetramethylene diisoayanate, pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate and trimethylhexane diisocyanate.
Polyurethanes are generally incompatible with water unless during their synthesis specific constituents are incorporated and/or particular preparation steps are carried out. Thus, in order to prepare the polyurethane resins, it iB possible to use compo~n~ which contsin two H-active groups which are reactive with isocyanate group~, and at least one group which ensure~
dispersibility in water. Suitable groups of this kind are nonionic ylou~s (e.g. polyethers), anionic yLO
mixtures of these two yLOup~ ~ or cationic y ou~_.
_ 2174663 To introduce anionic groups into polyurethane resin molecules, compounds are used which contain at least one group which i~ reactive toward isocyanate groups and at least one group which is cApAhle of forming anions. Suitable group6 which are reactive toward i~ocyanate groups are in particular hydroxyl group~, and also primary and/or secondary amino groups. Groups capable of forming An;on~ are carboxyl, sulfonic acid and/or phosphonic acid groups. Preference is given to employing Alk~noic acids having two substituent~ on the carbon atom. The substituent may be a hydroxyl group, an alkyl group or an alkylol group. These polyols have at least one, generally from 1 to 3, carboxyl y~Gu~- in the molecule. They have from two to about 25, preferably from 3 to 10 carbon atoms. The carboxyl-contA;n;ng polyol may make up from 3 to 100% by weight, preferably from 5 to 50% by weight, of the overall polyol constituent in the NC0 prepolymer.
The isocyanate y~GU~B of the prepolymer which contains isocyanate groups are reacted with a modifying agent.
In this context the modifying sgent is preferably added in a quantity 80 aB to re~ult in chain exten~ions and therefore in increa~e~ in molecular weight. The modifying agents preferably employed are organic compound~ which contain hydroxyl and/or ~econdary and/or primary amino yLG~, especially di-, tri-and/or polyols of higher functionality. Exsmple [sic]
g of polyols which can be employed are trimethylol-propane, 1,3,4 butanetriol [ BiC ], glycerol, erythritol, mesoerythritol, arabitol, adonitol, etc.
Trimethylolpropane is preferably employed.
As constituent (A) in component (I) it is possible in principle to employ all water-soluble or water-dispersible polyacrylate resins which are suitable for aqueous paints. A very large number of such resins has been described, and a very wide selection of them is available commercially. Particularly suitable polyacrylate resins are described in DE-A-38 32 826 and in DE-A-38 41 540.
As constituent (A) in component (I) it is also possible to employ water-soluble or water-dispersible polyester resins.
A~ constituent (B) in component (I) it is possible, for example, to employ blocked polyisocyanates and/or water-soluble or water-dispersible am; no resins. It i~
preferred - if desired in the presence of cosolvents -to employ water-soluble or water-dispersible melamine resins. These are in general etherified melamine/formaldehyde co~Ae~Ation products. The solubility or dispersibility in water of the amino resins depends, apart from the de~ ee of condensation, which should be as low as possible, on the etherifying - 217~663 component, with only the lowest members of the alcohol or of the ethylene glycol monoether series giving condensation products which are soluble in water. The melamine resins which are etherified with methanol have S the greatest significance. If solubilizers are used, it is also possible to disperse butanol-etherified melamine resins in the aqueous phase. The possibility also exists of incorporating carboxyl groups into the conden~ation product. Transetherification products of highly etherified co~pnsAtion products of formaldehyde with hydroxycarboxylic acids, via their carboxyl groups, are soluble in water after neutralization.
As constituent (C), components (I) may contain all conventional paint pigments which do not react with water or dissolve in water. The pigments may comprise inorganic or organic compounds and may be effect pigments and/or color pigments. In order to ensure a degree of appl; ~Ah; lity which is as close as possible to universal, and in order to maximize the possible colors, it is preferred to incorporate, in one component (I), either only color pigments or only effect pigments, but not mixtures of color and effect pigments.
Effect pigments which can be employed are metal flake pigments such as commercial aluminum bronzes, aluminum bronzes chromated in accordance with DE-A-36 36 183, -and commercial stainless-steel bronzeg, and also nonmetallic effect pigments such a~, for example, pearle~cent or interference pigments. Example~ of ~uitable inorganic color pigments are titanium dioxide, iron oxides, Sicotrans yellow and carbon black.
Examples of ~uitable organic color pigments are indanthrene blue, Cromophthal red, Irgazin orange and Heliogen green.
As constituent (E), component (I) may contain at least one organic solvent. ~xamples of f uitable solvents are in particular water-miscible ~olvents such as, for example, alcohols, esters, ketones, keto ester~, glycol ether esters and the like. Alcohols and glycol ethers are preferably employed, and butyl glycol and butanols are particularly preferred.
As constituent (F) component (I) may contain at least one rheology-controlling additive. Examples of rheology-controlling additives are crossl; nke~ polymer microparticle~ as dif~closed, for example, in EP-A-38 127, inorganic phyllosilicates, for example aluminum-magnesium silicates, sodium-magnesium phyllosilicates and f~odium-magnesium-fluorine-lithium phyllosilicates of the montmorillonite type, and al~o ~ynthetic polymer~ cont~n~ng ionic y Gupf and/or groups which have an a~sociated action, ~uch as polyvinyl alcohol~ poly(meth)acrylAm~de, poly(meth)acrylic acid, polyvinylpyrrolidone, styrene/maleic anhydride or ethylene/maleic anhydride copolymers and derivatives thereof, or else hydrophobically modified, ethoxylated urethanes or polyacrylates. As rheology-controlling additives it is preferred to employ inorganic phyllosilicates.
Particular preference i8 given to employing, as rheology-controlling additive, a combination of a polyacrylate resin which contains carboxyl yLUUp~
having an acid number of from 60 to 780 mg, preferably from 200 to 500 mg of ROH/g, with a sodium-magne~ium phyllosilicate.
~ he sodium-magnesium phyllosilicate is ~Ype~; ently incorporated into the paint component in the form of an aqueous paste. The paste preferably contain~ 3% by weight of phyllosilicate and 3% by weight of polypropylene glycol or 2% by weight of phyllosilicate and 0.6% by weight of poly~Lo~lene glycol or 2% by weight of phyllosilicate and 2% by weight of other commercial, surface-active substances, all percentages being based on the overall weight of the paste.
Component (I) of the paint ~ystem according to the invention should preferably not contain any rheology-controlling additive, especially not any inorganicphyllosilicate as rheology-controlling additive. The rheology-controlling additives which are nece~sary for the paints which can be prepared using the paint ~ystem 217466~
according to the invention should preferably be contained exclusively in component (II). It is particularly preferred that, in the cases in which an inorganic phyllosilicate i8 employed as rheology-controlling additive, the inorganic phyllosilicate isexclusively contained in paint component (II).
As well as constituent (F), component (I) may also contain, as constituent (G), at least one further conventional paint additive. Examples of such additives are antifoams, dispersion auxiliaries, emulsifiers and leveling ass~stants.
Component (I) is prepared by methods known to the person skilled in the art by mixing and, if desired, dispersing the individual constituents. Thus, for example, color pigments are conventionally incorporated by dispersion of the respective pigments in one or more binders. The dispersion of the pigments is carried out using conventional devices such as, for example, bead mills and sand mills.
The effect pigments are conventionally incorporated by homogeneous mixing of the effect pigments with one or more solvents. This mixture i6 then, using a stirrer or di~solver, stirred into a mixture of one or more of the above-described binders, if desired with the addition of further organic solvent~.
~174663 Constituent~ (J), (K) and (L) of paint component (II) corre~pond to constituents (E), (F) and (G) of paint component (I).
The paint sy~tem according to the invention is ~uitable for the production of aqueous paints which are intended to have a color determined precisely beforehand. By mixing correspondingly pigmented paint components (I) in proportions which are necessary to achieve the corresponding colors, and adding paint component (II), it is possible to obtain aqueous paints which are accurate in color and can be processed immediately. The paint system according to the invention is particularly suitable for mixer systems for production of automotive refinishes (cf. e.g. Glasurit-Handbuch, 11th Edition, Kurt R., [BiC~ Vincentz-Verlag, Hanover 1984, pages 544 to 547). Using the paint system according to the invention it is of course also possible to produce paints for other areas of application, for example the painting of plastic~ or the production-line fini~hing of motor vehicle bodies.
The invention iB illustrated in more detail below with reference to exemplary embodiments. In these embodiment~ all ~ n~ tions as to parts and percentages are by weight, unless expressly noted otherwise.
~17466~
1. PreParation of an organic Polyurethane resin solution 686.3 g of a polyester having a number-average molecular weight of 1400 based on a commercial un~aturated dimeric fatty acid (having an iodine number of 10 mg of I2/g, a monomer content of not more than 0.1%, a trimer content of not more than 2%, an acid number of from 195 to 200 mg of KOH/g and a hydrolysis number of from 197 to 202 mg of KOH/g), isophthAl;c acid and heY~ne~;ol are placed under protective gas in an appropriate reaction vessel with stirrer, reflux condenser and feed vessel, and 10.8 g of hexanediol, 55.9 g of dimethylolpropionic acid, 344.9 g of methyl ethyl ketone and 303.6 g of 4,4'-di-(isocyanato-cyclohexyl) methane are added in succession. This mixture is maintA;~e~ under reflux until the isocyanate content has fallen to 1.0%. Subsequently 26.7 g of trimethylolpropane are added to the mixture, which is maintained under reflux to a viscosity of 12 dPas (for a solution of one part of resin solution in one part of N-methylpyrrol~Q~e). 1378.7 g of butylglycol are then added. After a vacuum distillation in which the methyl ethyl ketone is removed, the resin solution is neutralized with 32.7 g of dimethylethanol~m;ne. The ~olids content of the resulting resin solution is 44%.
Under intensive stirring, it is diluted to a solids content of 41% by weight by A~; ng butylglycol.
217~6G3 2. Preparation of an aqueous polyurethane resin dispersion 686.3 g of a polyester having a number-average molecular weight of 1400 based on a commercial unsaturated dimeric fatty acid (having an iodine number of 10 mg of I2/g, a monomer content of not more than 0.1%, a trimer content of not more than 2~, an acid number of from 195 to 200 mg of KO~/g and a hydrolysis number of from 197 to 202 mg of ROH/g), isophth~l;c acid and hexanediol are placed under protective gas in an appropriate reaction vessel with stirrer, reflux conden~er and feed vessel, and 10.8 g of hexanediol, 55.9 g of dimethylolpropionic acid, 344.9 g of methyl ethyl ketone and 303.6 tlacuna] of 4,4'-di-(isocyanatocyclohexyl) methane are added in succession.
This mixture i8 maintained under reflux until the i~ocyanate content has fallen to 1.0%. Subsequently 26.7 g of trimethylolpropane are added to the mixture, which i8 maint~;ne~ under reflux to a viscosity of 12 dPas (for a solution of one part of resin solution in one part of N-methylpyrrolidone). Any excess isocyanate present is destroyed by ~ n~ 47 . 7 g of butylglycol. Subsequently 32.7 g of dimethylethanol-amine, 2688.3 g of deionized water and 193.0 g of butylglycol are added to the reaction mixture with vigorou~ stirring. After the removal of the methyl ethyl ketone by vacuum distillation, an aqueous 217~663 dispersion is obtained which has a solids content of - about 27%.
3. Preparat~on of plgment pa~te~
3.1 PreParation of a pigment Paste contA;~; nq aluminum pigment 15.5 part~ of an aluminum bronze chromated in accordance with DE-A-36 36 183 (aluminum content 65%, average particle diameter 15 ~m) are homogeneously dispersed in 14 parts of butylglycol by stirring for 15 minutes and then run with stirring into a mixture of 51 parts of the polyurethane resin solution prepared lS according to ~ection 1., 19.5 parts of a commercial, methanol-etherified melamine resin (75% in isobutanol) and 10 parts of butylglycol. This mixture is stirred for a further 30 minutes using a high-speed stirrer at 1000 rpm.
3.2 Preparation of a blue-pigmented ~iqment paste 7 parts of Paliogen blue, 57 parts of the polyurethane resin solution prepared according to section 1., 15 parts of butylglycol and 21 parts of a commercial, methanol-etherified melamine resin (75% in isobutanol) are mixed with stirring and dispersed in a sand mill.
3.1 PreParation of a pigment Paste contA;~; nq aluminum pigment 15.5 part~ of an aluminum bronze chromated in accordance with DE-A-36 36 183 (aluminum content 65%, average particle diameter 15 ~m) are homogeneously dispersed in 14 parts of butylglycol by stirring for 15 minutes and then run with stirring into a mixture of 51 parts of the polyurethane resin solution prepared lS according to ~ection 1., 19.5 parts of a commercial, methanol-etherified melamine resin (75% in isobutanol) and 10 parts of butylglycol. This mixture is stirred for a further 30 minutes using a high-speed stirrer at 1000 rpm.
3.2 Preparation of a blue-pigmented ~iqment paste 7 parts of Paliogen blue, 57 parts of the polyurethane resin solution prepared according to section 1., 15 parts of butylglycol and 21 parts of a commercial, methanol-etherified melamine resin (75% in isobutanol) are mixed with stirring and dispersed in a sand mill.
4. Preparatton of components (I) accord~ng to the invont~on 4.1 Preparation of comPonent (I)-1 30 parts of the pigment paste prepared according to section 3.1 are mixed thoroughly with 40 parts of the aqueous polyurethane resin dispersion prepared according to ~ection 2. and 30 part~ of deionized water. The component (I) obt~; nPA in thi~ way i8 readily meterable, can be mixed very well with component~ (I) pigmented with other colors, for example with component (I)-2 (see below), and has an eYcellent stability on storage.
4.2 Preparation of components ~I~-2 30 parts of the pigment paste prepared according to ~ection 3.2 are thoroughly mixed with 40 parts of the aqueous polyurethane resin disper~ion prepared according to section 2. and 30 parts of deionized water. A component (I) iB obtA; ne~ which is readily meterable, can be mixed readily with components (I) pigmented with other colors, such as with component (I)-1 (see above), and has a very good stability on ~torage.
217~663 5. Preparat~on of a component (II) according to the invention 35.5 parts of deionized water, 1.5 partff of butyl glycol, 0.5 part of a commercial antifoam and 5 parts of a 3.5% fftrength solution of a commercial polyacrylate thickener in water are added with stirring to 57.5 partff of a preswollen aqueous paste cont~;n;ng 3% by weight of an inorganic sodium-magnesium phyllosilicate thickener and 3% by weight of polypropylene glycol having a nu~mber-average molecular weight of 900, the percentages being based on the overall weight of the paste. The component (II) prepared in this way is very readily miscible with the components (I)-l and (I)-2 prepared according to section 4.1 and section 4.2, and has an excellent fftability on storage.
4.2 Preparation of components ~I~-2 30 parts of the pigment paste prepared according to ~ection 3.2 are thoroughly mixed with 40 parts of the aqueous polyurethane resin disper~ion prepared according to section 2. and 30 parts of deionized water. A component (I) iB obtA; ne~ which is readily meterable, can be mixed readily with components (I) pigmented with other colors, such as with component (I)-1 (see above), and has a very good stability on ~torage.
217~663 5. Preparat~on of a component (II) according to the invention 35.5 parts of deionized water, 1.5 partff of butyl glycol, 0.5 part of a commercial antifoam and 5 parts of a 3.5% fftrength solution of a commercial polyacrylate thickener in water are added with stirring to 57.5 partff of a preswollen aqueous paste cont~;n;ng 3% by weight of an inorganic sodium-magnesium phyllosilicate thickener and 3% by weight of polypropylene glycol having a nu~mber-average molecular weight of 900, the percentages being based on the overall weight of the paste. The component (II) prepared in this way is very readily miscible with the components (I)-l and (I)-2 prepared according to section 4.1 and section 4.2, and has an excellent fftability on storage.
Claims (6)
1. Paint system composed of two components (I) and (II), characterized in that component (I) comprises (A) from 5 to 50% by weight of at least one binder, (B) from 0 to 20% by weight of at least one crosslinking agent, (C) from 0.5 to 60% by weight of at least one pigment, (D) from 5 to 80% by weight of water, (E) from 0 to 40% by weight of at least one organic solvent (F) From 0 to 5% by weight of at least one rheology-controlling additive, and (G) from 0 to 10% by weight of at least one further conventional paint auxiliary, the sum of the percentages by weight indicated for components (A), (B), (C), (D), (E), (F), and (G) always being 100% by weight, and component (II) comprises (H) from 70 to 99% by weight of water, (J) from 0 to 10% by weight of at least one organic solvent, (R) from 0.1 to 10% by weight of at least one rheology-controlling additive, and (L) from 0 to 10% by weight of at least one further conventional paint auxiliary, the sum of the percentages by weight indicated for components (H), (J), (K), (J) and (L) always being 100% by weight.
2. Paint system according to claim 1, characterized in that constituent (A) consists of at least one water-dilutable polyurethane resin or of a mixture of at least one water-dilutable polyurethane resin and at least one water-dilutable polyester resin and/or at least one water-dilutable polyacrylate resin.
3. Paint system according to claim 1 or 2, characterized in that constituent (B) consists of at least one amino resin or of at least one blocked polyisocyanate or of a mixture of at least one amino resin and at least one blocked polyisocyanate.
4. Paint system according to one of claims 1 to 3, characterized in that constituent (R) is an inorganic phyllosilicate.
5. Use of a paint system according to one of claims 1 to 4 for the production of automotive refinishes.
6. Use of a paint system according to one of claims 1 to 4 for the production of paints for plastics substrates
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4339951.7 | 1993-11-24 | ||
| DE4339951A DE4339951A1 (en) | 1993-11-24 | 1993-11-24 | Paint system consisting of two components |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2174663A1 true CA2174663A1 (en) | 1995-06-01 |
Family
ID=6503267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002174663A Abandoned CA2174663A1 (en) | 1993-11-24 | 1994-11-19 | Two-component paint system |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0730626B2 (en) |
| JP (1) | JP4049807B2 (en) |
| AT (1) | ATE170904T1 (en) |
| BR (1) | BR9408134A (en) |
| CA (1) | CA2174663A1 (en) |
| DE (2) | DE4339951A1 (en) |
| DK (1) | DK0730626T3 (en) |
| ES (1) | ES2123943T5 (en) |
| WO (1) | WO1995014745A1 (en) |
| ZA (1) | ZA949248B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6451896B1 (en) | 2000-04-28 | 2002-09-17 | E. I. Du Pont De Nemours And Company | Coating system for the preparation of aqueous coating compositions |
| US7923113B2 (en) | 2005-12-15 | 2011-04-12 | Akzo Nobel Coating International B.V. | Multilayer coating system |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19528929C2 (en) * | 1995-08-07 | 1999-07-01 | Feron Aluminium | Process for the production of plastic films which are used for the production of film capacitors |
| DE19942515A1 (en) * | 1999-09-07 | 2001-03-08 | Basf Coatings Ag | Mixing system for the production of water-thinnable coating agents |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| DE3545618A1 (en) * | 1985-12-21 | 1987-06-25 | Basf Lacke & Farben | WATER-DISCOVERABLE COATING AGENT FOR PRODUCING THE BASE LAYER OF A MULTILAYER COATING |
| 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 |
| DE3739332A1 (en) * | 1987-11-20 | 1989-06-01 | Basf Lacke & Farben | Process for the production of a multilayer, protective and/or decorative coating, and water-thinnable coating compositions |
| DE3825278A1 (en) * | 1988-07-26 | 1990-02-01 | Basf Lacke & Farben | METHOD FOR PRODUCING MULTI-LAYER, PROTECTIVE AND / OR DECORATIVE COATINGS ON SUBSTRATE SURFACES |
| US5017673A (en) * | 1989-10-12 | 1991-05-21 | Basf Corporation | Nonionically stabilized polyester urethane resin for water-borne coating compositions |
| DE3940316A1 (en) * | 1989-12-06 | 1991-06-13 | Bollig & Kemper | AQUEOUS DISPERSIONS OF CROSS-LINKED POLYMER MICROPARTICLES |
| JP2694225B2 (en) * | 1990-05-21 | 1997-12-24 | 日本ペイント株式会社 | Aqueous paint composition |
| ES2112846T3 (en) † | 1990-07-13 | 1998-04-16 | Basf Corp | AQUEOUS METAL BASED LAYER COMPOSITION, BASED ON LATEX ACRYLIC RESINS, USING A WATER-DILUTABLE RESIN AND A HECTORITE CLAY FOR RHEOLOGICAL CONTROL AS A MEANS OF ALUMINUM. |
| US5114485A (en) † | 1990-09-21 | 1992-05-19 | Multicolor Specialties, Inc. | Water-in-water multicolor paint and method |
| US5104922A (en) † | 1990-10-22 | 1992-04-14 | E. I. Du Pont De Nemours And Company | Stable aqueous aluminum flake dispersion |
| DE4143688B4 (en) * | 1991-03-30 | 2007-03-29 | Basf Coatings Ag | Use of a mixing system and process for the preparation of water-based paints and water-dilutable coating compositions |
| DE4301991A1 (en) † | 1993-01-26 | 1994-07-28 | Herberts Gmbh | Modular system and its use in processes for the production of aqueous coating compositions |
-
1993
- 1993-11-24 DE DE4339951A patent/DE4339951A1/en not_active Withdrawn
-
1994
- 1994-11-19 ES ES95902776T patent/ES2123943T5/en not_active Expired - Lifetime
- 1994-11-19 WO PCT/EP1994/003832 patent/WO1995014745A1/en active IP Right Grant
- 1994-11-19 CA CA002174663A patent/CA2174663A1/en not_active Abandoned
- 1994-11-19 AT AT95902776T patent/ATE170904T1/en not_active IP Right Cessation
- 1994-11-19 DK DK95902776T patent/DK0730626T3/en active
- 1994-11-19 DE DE59406895T patent/DE59406895D1/en not_active Expired - Lifetime
- 1994-11-19 EP EP95902776A patent/EP0730626B2/en not_active Expired - Lifetime
- 1994-11-19 JP JP51482195A patent/JP4049807B2/en not_active Expired - Fee Related
- 1994-11-19 BR BR9408134A patent/BR9408134A/en not_active IP Right Cessation
- 1994-11-22 ZA ZA949248A patent/ZA949248B/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6451896B1 (en) | 2000-04-28 | 2002-09-17 | E. I. Du Pont De Nemours And Company | Coating system for the preparation of aqueous coating compositions |
| US7923113B2 (en) | 2005-12-15 | 2011-04-12 | Akzo Nobel Coating International B.V. | Multilayer coating system |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2123943T3 (en) | 1999-01-16 |
| ZA949248B (en) | 1995-08-01 |
| WO1995014745A1 (en) | 1995-06-01 |
| EP0730626B1 (en) | 1998-09-09 |
| ES2123943T5 (en) | 2003-06-16 |
| DE4339951A1 (en) | 1995-06-01 |
| EP0730626B2 (en) | 2002-11-13 |
| BR9408134A (en) | 1997-08-05 |
| DE59406895D1 (en) | 1998-10-15 |
| JPH09505617A (en) | 1997-06-03 |
| DK0730626T3 (en) | 1999-06-07 |
| JP4049807B2 (en) | 2008-02-20 |
| ATE170904T1 (en) | 1998-09-15 |
| EP0730626A1 (en) | 1996-09-11 |
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Legal Events
| Date | Code | Title | Description |
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| FZDE | Discontinued |