WO2001018129A1 - Systeme mixte pour produire des agents de revetement diluables dans l'eau - Google Patents

Systeme mixte pour produire des agents de revetement diluables dans l'eau Download PDF

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Publication number
WO2001018129A1
WO2001018129A1 PCT/EP2000/008211 EP0008211W WO0118129A1 WO 2001018129 A1 WO2001018129 A1 WO 2001018129A1 EP 0008211 W EP0008211 W EP 0008211W WO 0118129 A1 WO0118129 A1 WO 0118129A1
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Prior art keywords
water
mixing system
weight
binder
dilutable
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PCT/EP2000/008211
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German (de)
English (en)
Inventor
Bernhard Lettmann
Bernd Mayer
Michael Grabbe
Norbert WÜNNEMANN
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Basf Coatings Ag
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Publication of WO2001018129A1 publication Critical patent/WO2001018129A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/80—Processes for incorporating ingredients

Definitions

  • the present invention relates to a mixing system for producing water-dilutable coating compositions with a precisely defined tint from different basic colors.
  • the present invention also relates to a method for producing these coating compositions with a precisely defined tint, in which different basic colors are stored separately and are mixed into the coating composition in the desired shade only shortly before application.
  • the present invention further relates to the use of the mixing system for the production of waterborne basecoats for the coating of automobile bodies and / or plastic parts and for the production of aqueous coating compositions for refinishing.
  • Usual methods for repairing damaged areas on a possibly multi-layer coating include careful cleaning and sanding, if necessary filling and filling at the damaged area. After a further pretreatment, the damaged area usually becomes opaque and runs off into the adjacent areas with effect paints, e.g. Metallic basecoats, or sprayed with plain paints. After the coating thus produced has dried on, the coating and the adjacent parts are sprayed with a clear lacquer and, after a necessary flash-off time, the clear lacquer coating is preferably dried together with the previously applied layers at temperatures between 50 and 100 ° C.
  • Solid paints are usually used as effect lacquers and / or uni-lacquers applied in a two-layer process for repairing damaged areas Lacquers are used which, in addition to binders, contain coloring and / or effect pigments and a high proportion of organic solvent mixtures.
  • These paints are either supplied by the paint manufacturer in the desired shade, or the shade is made from a mixing system of several basic colors before application.
  • This production from a mixing system has the advantage that not every color has to be manufactured and stored individually and that production, distribution and warehousing costs can thus be reduced. In both cases, it is necessary that the paint supplied has sufficient storage stability (at least 12 months).
  • the color accuracy of the basic colors is also very important for a mixing system.
  • Coloring pigments can also be caused by prolonged exposure to water, e.g. B. in an alkaline medium.
  • water e.g. B. in an alkaline medium.
  • the application of the aqueous coating composition before the basecoat / clearcoat coating is intended to improve the metallic effect, in particular the brightness of the surface.
  • This process described in EP-A-320 552 is mainly suitable for the production of a first coat of paint, but the description also refers to the possibility of using this process in the field of refinish painting.
  • the aqueous coating composition used in the process of EP-A 320 552 is prepared by incorporating an aluminum pigment paste into aqueous mixed lacquers.
  • the aluminum paste used represents an increase of aluminum bronze in organic solvents and an emulsifier. However, this aluminum paste settles within a few hours and thus leads to sediment. However, this in turn regularly leads to color deviations.
  • This deposited paste can only be stirred to a limited extent using suitable stirring units. In addition, such agitation units are generally not available to painters. Such aluminum pastes are therefore not suitable for the construction of mixing systems for refinishing.
  • aqueous coating compositions obtained after incorporation of the aluminum paste into the aqueous mixed lacquers also show inadequate storage stability which does not meet the requirements of the lacquer finishers.
  • EP-A-195 931 and EP-A-297 576 disclose aqueous coating compositions for the production of a multi-layer coating in the field of serial painting.
  • the aqueous coating compositions are prepared by incorporating a pigment paste into the aqueous binder dispersion.
  • the pigment paste is produced by rubbing the corresponding pigments with the smallest possible amounts of a grinding resin and, if necessary, with organic solvents and, if appropriate, with water.
  • EP-B-38 127 also discloses aqueous coating compositions for the production of a multi-layer coating in the field of serial painting.
  • the aqueous coating compositions are in turn produced by incorporating a pigment paste into the aqueous binder dispersion.
  • the pigment paste is produced by rubbing the pigments with a Meiamin resin and organic solvents.
  • the structure of a mixing system for the field of refinishing and the measures required for this are again not described.
  • These pigmented aqueous coating compositions of EP-B-38 127 are also unsuitable for the field of refinishing because of their inadequate storage stability.
  • EP-A-368 499 describes water-thinnable coating compositions, in particular those containing metallic pigments, with improved storage stability.
  • the storage stability is achieved by firstly using an anhydrous binder solution composed of 25 to 95% by weight of a Polyether or polyester polyol, 2.5 to 50 wt .-% of an aminoplast resin and 0 to 50 wt .-% of an organic solvent into which the pigments are incorporated.
  • This binder solution is adjusted to the desired viscosity with water shortly before application.
  • EP-A-368 499 does not describe the use of the anhydrous binder solutions in a mixing system.
  • EP-A-0 468 293 and EP-A-0 471 972 describe aqueous lacquers based on various building blocks. However, it is necessary that the effect module is anhydrous.
  • DE-A-41 10 520 describes a mixing system which is said to be suitable for producing aqueous pigmented coating compositions with a precisely defined tint. In particular, water-based paints are to be produced with it.
  • the mixing system consists of various base colors (A), which contain less than 5% by weight of water, are preferably anhydrous and contain pigments, solvents and water-dilutable binders, and a pigment-free aqueous component (B), which in particular contains water-dilutable binders and / or rheological additives contains.
  • EP 0 608 773 discloses a process for the production of aqueous coating compositions, in particular for the production of aqueous one-component effect basecoats with a low solvent content, using a module system or mixing system or modular system which is stable in storage over a long period, the individual modules of the Systems are easy to mix with each other to achieve a desired effect.
  • a module system is used that contains an effect module with a high water content of at least 20%.
  • the present invention is therefore based on the object of providing a mixing system which makes it possible to produce water-dilutable coating compositions with a precisely defined tint from different basic colors.
  • this mixing system should enable the production of aqueous coating compositions which are suitable for refinishing, in particular damaged areas on automobile bodies.
  • a high level of color accuracy of the basic colors should be ensured in order to achieve the desired color tones without complex measures by the painter to be able to set as precisely and reproducibly as possible.
  • the base colors used for the construction of this mixing system must have very good storage stability (> 12 months).
  • the aqueous coating compositions produced using this mixing system should lead to coatings with good mechanical properties both in the case of effect lacquers and in the case of plain colors.
  • This mixing system should guarantee the formulation of coating agents which ensure this high quality level with a reduced proportion of organic solvents compared to the coating agents usually produced.
  • This is a mixing system for the production of water-dilutable coating agents with a precisely defined tint from different basic colors, the mixing system A) different basic colors A which contain water,
  • Pigments, Ab 10 to 80% by weight of at least one water-dilutable or water-dispersible binder which can be prepared in the form of organic solutions, and
  • component B contains at least one water-containing, pigment-free component B which contains at least one rheology-controlling additive and, if appropriate, at least one water-dilutable or water-dispersible binder and, if appropriate, further auxiliaries and additives.
  • This object is at least achieved in that the water content of component A is 5% by weight and less than 20% by weight.
  • the water content is preferably 6-19% by weight, most preferably 8-16% by weight.
  • the present invention also relates to a process for the production of water-dilutable coating compositions with a precisely defined tint, in which different basic colors of a mixing system are produced and stored separately and are only mixed shortly before the application of the coating composition, characterized in that the mixing system according to the invention is used.
  • the present invention also relates to the use of the mixing systems for the production of aqueous coating compositions for refinishing, in particular for the production of waterborne basecoats for refinishing, in particular for automobile bodies.
  • the mixing system according to the invention makes it possible to produce aqueous coating compositions which are distinguished by an exact and reproducible setting of the desired color without the need for expensive measures. This is guaranteed by a high degree of color accuracy and a correspondingly good storage stability of the base colors.
  • Another advantage can be seen in the fact that the base colors produced according to the invention are resistant to freezing / thawing.
  • the aqueous coating compositions thus produced have the advantage that they form coatings with good mechanical properties. The colors are more environmentally friendly than conventional water-free systems.
  • the mixing system according to the invention also provides coating agents in the field of refinish coating which meet the high requirements with regard to the quality of the refinish coating and which, as solvents, predominantly contain water and in which organic solvents are only present in small amounts .
  • this reduced solvent content leads to an improvement in occupational safety (fire protection) and to a reduction in the environmental impact when the paint films dry. This is particularly important in the field of refinishing car bodies, since the effect paints used in this area usually contain a very high proportion of solvent of up to 90% in order to ensure a good metallic effect.
  • Component A of the mixing system can contain all typical pigments, provided that they do not react with water within a short period of time (period between the mixing of components A and B and the application of the lacquers) and that they do not dissolve in water.
  • Component A can contain effect pigments and / or coloring pigments on an inorganic or organic basis. In order to ensure as universal a range of use as possible and to be able to implement as many shades as possible, it is preferred to construct a mixing system based on components A containing only coloring pigments and components A containing only effect pigments. To produce component A, all of the effect pigments customarily used in the formulation of aqueous coating compositions can be used.
  • suitable effect pigments are commercially available aluminum bronzes, the aluminum bronzes chromated according to DE-OS 3636183, commercially available stainless steel bronzes and other conventional metal flakes and metal flake pigments.
  • Non-metallic effect pigments such as pearlescent or interference pigments, are also suitable for the production of component A.
  • suitable coloring pigments on an inorganic basis are titanium dioxide, iron oxides, carbon black and others.
  • suitable coloring pigments on an organic basis are indanthrene blue, cromophthal red, irgazin orange, sicotrans yellow, heliogen green and others.
  • Suitable binders for use in component A are all water-dilutable or water-dispersible binders which are usually used in aqueous coating compositions and which can be prepared in the form of organic solutions.
  • the water dilutability or water dispersibility of the resins can also be adjusted by using appropriate solubilizers as cosolvents or solvents.
  • Decisive for the selection of the binders is on the one hand the good storage stability in organic solution, in particular also the ability to avoid settling of the pigments, and on the other hand the problem-free incorporation of the base color into component B or the problem-free incorporation of component B into the base color.
  • the incorporation of the base color into component B or the reverse incorporation can also be achieved by using dispersing additives such as Example ionic or nonionic surfactants can be controlled.
  • Such additives should, however, be used in the smallest possible amounts so as not to impair the water resistance of the resulting coatings.
  • water-dilutable or water-dispersible polyurethane resins are used as binders for component A.
  • polyacrylate resins polyacrylate resins
  • polyester resins polyacrylate resins
  • aminoplast resins and mixtures thereof are used as binders for component A.
  • polyurethane resins used as binders in the base colors are known in principle.
  • the polyurethane resins described in the literature for use in waterborne basecoats are suitable, provided that these polyurethane resins - in a modification of the preparation described in the respective literature - can be prepared in the form of organic solutions.
  • Suitable polyurethane resins are the resins described in the following documents:
  • the prepolymer containing isocyanate groups can be prepared by reacting polyols having a hydroxyl number of 10 to 1800, preferably 50 to 1200 mg KOH / g, with excess polyisocyanates at temperatures of up to 150 ° C., preferably 50 to 130 ° C., in organic solvents, that cannot react with isocyanates.
  • the equivalent ratio of NCO to OH groups is between 2.0: 1.0 and> 1.0: 1.0, preferably between 1.4: 1 and 1.1: 1.
  • the polyols used to prepare the prepolymer can be of low molecular weight and / or of high molecular weight and they can contain inert anionic groups.
  • Low molecular weight polyols can be used to increase the hardness of the polyurethane. They have a molecular weight of 60 to about 400 and can contain aliphatic, alicyclic or aromatic groups. Quantities of up to 30% by weight of the total polyol constituents, preferably about 2 to 20% by weight, are used.
  • a high proportion of a predominantly linear polyol with a preferred OH number of 30 to 150 mg KOH / g should be added.
  • Up to 97% by weight of the All polyols can consist of saturated and unsaturated polyesters and / or polyethers with a molecular weight Mn of 400 to 5000.
  • the selected polyether diols should not introduce excessive amounts of ether groups, otherwise the polymers formed will swell in water.
  • Polyester diols are produced by esterification of organic dicarboxylic acids or their anhydrides with organic diols or are derived from a hydroxy carboxylic acid or a lactone. To produce branched polyester polyols, polyols or polycarboxylic acids with a higher valency can be used to a small extent.
  • Aliphatic, cycloaliphatic and / or aromatic polyisocyanates with at least two isocyanate groups per molecule are used as typical multifunctional isocyanates.
  • the isomers or isomer mixtures of organic diisocyanates are preferred. Due to their good resistance to ultraviolet light, (cyclo) aliphatic diisocyanates produce products with a low tendency to yellowing.
  • the polyisocyanate component used to form the prepolymer can also contain a proportion of higher-quality polyisocyanates, provided that this does not cause gel formation.
  • Products which have been found to be suitable as triisocyanates are those which result from trimerization or oligomerization of diisocyanates or from the reaction of diisocyanates with compounds containing polyfunctional OH or NH groups.
  • the average functionality can optionally be reduced by adding monoisocyanates.
  • diisocyanates of the general formula (I) are used to prepare high-solids polyurethane resin solutions.
  • X is a divalent, aromatic hydrocarbon radical, preferably an optionally halogen, methyl or methoxy substituted naphthylene, biphenylene or 1, 2-, 1, 3- or 1, 4-phenylene radical, particularly preferably for one 1,3-phenylene radical and R 1 and R 2 represent an alkyl radical having 1 to 4 carbon atoms, particularly preferably a methyl radical.
  • Diisocyanates of the formula (I) are known (their preparation is described, for example, in EP-A-101 832, US Pat. No. 3,290,350, UP-PS 4,130,577 and US Pat. No. 4,439,616) and some are commercially available (1, 3-bis (2-isocyanatoprop-2-yl) benzoI is sold, for example, by the American Cyanamid Company under the trade name TMXDI (META) R ).
  • diisocyanates of the formula (I) In addition to the diisocyanates of the formula (I) or instead, other aliphatic and / or cycloalipatic and / or aromatic polyisocyanates can also be used. Examples of additional polyisocyanates that can be used are phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, bisphenylene diisocyanate,
  • Polyurethanes are generally not compatible with water unless special components are incorporated into their synthesis and / or special manufacturing steps are carried out.
  • compounds which contain two H-active groups which react with isocyanate groups and at least one group which ensures water dispersibility can be used to prepare the polyurethane resins.
  • Suitable carrier groups are non-ionic groups (e.g. polyethers), anionic groups, mixtures of these two groups or cationic groups.
  • an acid number can be built into the polyurethane resin that the neutralized product can be stably dispersed in water.
  • compounds which contain two H-active groups reacting with isocyanate groups and at least one group capable of forming anions.
  • Suitable groups that react with isocyanate groups are, in particular, hydroxyl groups and primary and / or secondary amino groups.
  • Groups capable of forming anions are carboxyl, sulfonic acid and / or phosphonic acid groups.
  • Carboxylic acid or carboxylate groups are preferably used. They should be so inert that the isocyanate groups of the diisocyanate preferably react with the other groups of the molecule that are reactive toward isocyanate groups.
  • alkanoic acids with two substituents on the ⁇ -carbon atom are used.
  • the substituent can be a hydroxyl group, an alkyl group or an alkylol group.
  • These polyols have at least one, generally 1 to 3 carboxyl groups in the molecule. They have two to about 25, preferably 3 to 10, carbon atoms.
  • the polyol containing carboxyl groups can make up 3 to 100% by weight, preferably 5 to 50% by weight, of the total polyol component in the NCO prepolymer.
  • the through the Carboxyl group neutralization in salt form available amount of ionizable carboxyl groups is generally at least 0.4 wt .-%, preferably at least 0.7 wt .-%, based on the solid.
  • the upper limit is about 6% by weight.
  • the amount of dihydroxyalkanoic acids in the unneutralized prepolymer gives an acid number of at least 5, preferably at least 10. At very low acid numbers, further measures are generally required to achieve water dispersibility.
  • the upper limit of the acid number is 70, preferably 40 mg KOH / g, based on the solid.
  • the NCO prepolymers used according to the invention can be prepared by simultaneously reacting the polyol or polyol mixture with an excess of diisocyanate. On the other hand, the implementation can also be carried out step by step in the prescribed order. Examples are described in DE OS 26 24442 and DE OS 32 10051. The reaction temperature is up to 150 ° C, with a temperature in the range of 50 to 130 ° C being preferred. The reaction continues until practically all of the hydroxyl functions have been converted.
  • the NCO prepolymer contains at least about 0.5% by weight of isocyanate groups, preferably at least 1% by weight of NCO, based on solids.
  • the upper limit is approximately 15% by weight, preferably 10% by weight, particularly preferably 5% by weight.
  • the reaction can optionally be carried out in the presence of a catalyst such as organotin compounds and / or tertiary amines.
  • a catalyst such as organotin compounds and / or tertiary amines.
  • organic solvents that do not require active hydrogen Zerewitinoff included, possible.
  • the amount of solvent can vary within wide limits and should be sufficient to form a prepolymer solution with a suitable viscosity. In general, 10 to 70% by weight of solvent, preferably 20 to 50% by weight of solvent, based on the solid.
  • the isocyanate groups still present in the prepolymer are reacted with a modifier. This reaction leads in particular to a further linkage and increase in the molecular weight.
  • the amount of this modifier is determined by its functionality and the NCO content of the prepolymer.
  • the equivalent ratio of the active hydrogen atoms in the modifier to the NCO groups in the prepolymer should generally be less than 3: 1 and preferably in the range between 1: 1 and 2: 1.
  • Preferred modifiers for the reaction with the prepolymer are di-, particularly preferably tri- and / or polyols.
  • Trimethylolpropane Trimethylolpropane, glycerin, erythritol, mesoerythritol, arabitol, adonite etc. Trimethylolpropane is preferably used.
  • Prepolymers with the tri- and / or polyols is preferably by the Stoichiometry of the compounds used is controlled so that chain extensions occur.
  • polyacrylate resins used as binders for component A are also known and are described, for example, in DE-OS 3832826. Suitable are generally water-dilutable or water-dispersible polyacrylate resins which can be prepared in the form of organic solutions.
  • binders for component A are water-dilutable or water-dispersible polyester resins which can be prepared in the form of organic solutions.
  • binders for component A are water-dilutable or water-dispersible polyester resins which can be prepared in the form of organic solutions.
  • corresponding commercially available water-dilutable or water-dispersible polyester resins are used, as are the polyester resins usually used in water-based paints.
  • Water-thinnable or water-dispersible aminoplast resins are also suitable as binders for component A.
  • Water-dilutable melamine resins are preferably used. These are generally etherified melamine-formaldehyde condensation products. Apart from the degree of condensation, which should be as low as possible, the water solubility of the aminoplast resins depends on the etherification component, only the lowest members of the alcohol or ethylene glycol monoether series giving water-soluble condensates. The most important are the melamine resins etherified with methanol. If solubilizers are used, butanol-etherified melamine resins can also be dispersed in the aqueous phase. It is also possible to insert carboxyl groups in the condensate. Transetherification products of highly etherified formaldehyde condensates Oxycarboxylic acids are water-soluble through their carboxyl groups after neutralization and can be contained in the base colors.
  • binders Mixtures of the named binders and, in addition or alone, other water-dilutable or water-dispersible binders can of course also be used as binders in the base colors A.
  • the base colors A preferably contain water-thinnable polyurethane resins or water-thinnable aminoplast resins or mixtures of water-thinnable polyurethane resins and aminoplast resins as binders.
  • the base color contains one or more organic solvents.
  • suitable solvents are in particular water-soluble or water-dilutable solvents, such as e.g. Alcohols, esters, ketones, keto esters, glycol ether esters etc. Alcohols and glycol ethers are preferably used, particularly preferably butyl glycol and butanols.
  • the polyurethane resin solution is prepared in a ketone, such as. B. methyl ethyl ketone or acetone.
  • a ketone such as. B. methyl ethyl ketone or acetone.
  • the solvent is then exchanged by removing the ketone (methyl ethyl ketone, acetone) by distillation.
  • Particularly preferred solvents for the production of the polyurethane resin are methoxypropyl acetate, ethoxyethyl acetate and N-methylpyrroline, which do not have to be exchanged (no active hydrogen) and can remain in component A.
  • These solvents can also be used in a mixture with ketones for the production of the polyurethane resins, but the ketones do not remain in the base color, but are exchanged after the production of the polyurethane resin.
  • Component A can also contain conventional auxiliaries and additives.
  • additives are defoamers, dispersing aids, emulsifiers, leveling agents, etc.
  • Component A is produced by methods known to those skilled in the art by mixing and, if appropriate, dispersing the individual components.
  • Color pigments are usually incorporated by rubbing (dispersing) the respective pigments with one or more of the binders described above, which are preferably used in the form of their solutions in organic solvents. Possibly. additional organic solvent can be added for rubbing. Rubbing this Pigments are made using conventional devices such as pearl mills and sand mills.
  • the effect pigments are usually incorporated by homogeneously mixing the effect pigments with one or more solvents. This mixture is then stirred into a mixture of one or more of the binders described above, if appropriate with the addition of further organic solvents, by means of a stirrer or dissolver.
  • the binders are preferably used in the form of their solutions in organic solvents.
  • component B Another component of the mixing system which is essential to the invention is the water-containing component B. It is conceivable to use a component B which only contains deionized water and thus only serves to adjust the processing viscosity or the processing solids of the base colors. However, component B preferably contains at least one rheology-controlling additive. Possibly. Component B can also contain other auxiliaries and additives, one or more water-dilutable or water-dispersible binders and organic solvents.
  • Crosslinked polymeric microparticles such as are disclosed, for example, in EP-A-38127 and / or other customary theological additives are used as the rheology-controlling additive.
  • inorganic sheet silicates such as, for example, act as thickeners
  • Inorganic phyllosilicates are preferably used as thickeners.
  • the sodium magnesium layered silicate is preferably used in the form of an aqueous paste.
  • Particularly preferred pastes contain either 3% by weight of layered silicate and 3% by weight of polypropylene glycol or
  • aqueous pastes of the thickener should only be added to component B and not to component A.
  • Suitable for use in component B are the water-dilutable or water-dispersible polyurethane, polyacrylate, polyester and aminoplast resins already mentioned in the description of component A, so that reference is only made to pages 12 to 20 of the present description.
  • these binders can not only be used as an organic solution but also preferably in a water-containing form.
  • This transfer of the resins into the aqueous phase takes place, for example, by neutralizing the carrier groups (groups capable of forming anions or cations, such as Example carboxyl groups) and subsequent dilution with water, if appropriate with prior partial removal of the organic solvent used in the preparation of the resin or by direct build-up of the resin in the presence of water.
  • the carrier groups groups capable of forming anions or cations, such as Example carboxyl groups
  • binders for component B are water-dilutable or water-dispersible polyurethane resins which cannot be prepared in the form of organic solutions. These are, in particular, polyurethane resins in which the prepolymer containing NCO groups has been reacted with a polyamine as modifier.
  • polyurethane resins are usually prepared in such a way that the NCO prepolymer described on pages 12 to 18 of the present application is first made water-dilutable or water-dispersible.
  • the anionic groups of the NCO prepolymer are at least partially neutralized with a tertiary amine.
  • the resulting increase in dispersibility in water is sufficient for infinite dilutability. It is also sufficient to consistently disperse the neutralized polyurethane.
  • the isocyanate groups still present are reacted with the modifier. This reaction leads to a further linkage and an increase in the molecular weight.
  • Water-soluble compounds are preferred as modifiers because they improve the dispersibility of the polymer Increase the final product in water.
  • Organic diamines are suitable because they usually build up the highest molecular weight without gelling the resin. The prerequisite for this, however, is that the prepolymer is dispersed in water before the chain extension or is in another sufficient dilution.
  • the amount of the modifier is determined by its functionality and the NCO content of the prepolymer.
  • the presence of excess active hydrogen, especially in the form of primary amino groups, can result in polymers with undesirably low molecular weights.
  • the chain can be extended at least partially with a polyamine which has at least three amino groups with a reactive hydrogen.
  • This type of polyamine can be used in such an amount that unreacted amine nitrogen atoms with 1 or 2 reactive hydrogen atoms are present after the polymer has been extended.
  • Such useful polyamines are di-ethylene triamine, triethylene tetramine, dipropylene triamine and dibutylene triamine.
  • Preferred polyamines are the alkyl or cycloalkyl triamines, such as diethylenetriamine.
  • small amounts of monoamines, such as ethylhexylamine can also be added.
  • water-dilutable or water-dispersible binders for component B are also suitable as water-dilutable emulsion polymers described in DE-OS3841540. These emulsion polymers can be obtained by
  • Stage used monomer or the mixture of ethylenically unsaturated monomers used in the second stage would lead to a polymer with a glass transition temperature 0732) of - 60 to + 20 ° C, and wherein the
  • Reaction conditions are chosen so that the resulting polymer has a number average molecular weight of 200,000 to 2,000,000 and wherein the ethylenically unsaturated monomer or monomer mixture used in the first stage and the ethylenically unsaturated monomer or in the second stage
  • Monomer mixture in type and amount can be selected so that the emulsion polymer obtained has a hydroxyl number of 2 to 100 mgKOH / g, preferably 10 to 50 mgKOH / g, and the difference
  • T G1 ' T G2 is 10 to 170 ° C > preferably 80 to 150 ° C.
  • Emulsion polymers are known by a two-stage emulsion polymerization in an aqueous medium
  • Equipment can be produced by the known methods.
  • the polymerization temperature is generally in the range from 20 to 100 ° C., preferably 40 to 90 ° C.
  • the quantitative ratio between the monomers and the water can be selected so that the resulting dispersion has a solids content of 30 to 60% by weight, preferably 35 to 50% by weight.
  • Carboxyl groups are that the monomers or monomer mixtures used, but also small amounts (e.g. as a result of
  • Impurities may contain hydroxyl and / or carboxyl groups.
  • the content of hydroxyl and carboxyl groups should preferably be at most so high that one from that used in the first stage
  • Polymer or monomer mixture produced polymer has an OH number of at most 5 mgKOH / g and an acid number of at most 3 mgKOH / g.
  • the emission polymer used according to the invention should have a number-average molar mass (determination: gel permeation chromatography with polystyrene as standard) from 200,000 to 2,000,000, preferably from 300,000 to 1,500,000, and usually acid numbers below 100 mg KOH / g and OH numbers from 2 to 100 mg KOH / g. If the emulsion polymer contains no or only very few acid groups (acid number approximately below 3 mg KOH / g), it is advantageous to add a carboxyl-containing resin, for example a carboxyl-containing polyurethane, polyester or polyacrylate resin, to the coating composition. The amounts of the carboxy group-containing resin are to be selected so that the acid number of the mixture of emulsion polymer and carboxyl group-containing resin is greater than or equal to 10 mg KOH / g.
  • Component B may also optionally contain one or more organic solvents and, if appropriate, other customary auxiliaries and additives.
  • suitable organic solvents are the solvents already mentioned in the description of component A.
  • the content of organic solvent is usually 0 to 3% by weight, based on the total weight of component B.
  • suitable auxiliaries and additives are also those in the description of the Component A called additives.
  • the amount of these additives used is usually 0 to 10% by weight, based on the total weight of the
  • component B contains binders, water-dilutable or water-dispersible are preferred as binders
  • Polyurethane resins and / or aminoplast resins or polyacrylate resins are used.
  • the mixing system according to the invention for the production of aqueous coating compositions with precisely defined tinting consists of different pigment-containing base colors (component A) and at least one water-containing component B. Depending on the desired color of the aqueous coating composition, one or more base colors of the mixing system with at least one are then used to produce the aqueous coating composition water-containing component B mixed immediately before application of the aqueous coating agent.
  • Typical mixing systems consist of 15 to 60, preferably 20 to 40, different basic colors and auslbis ⁇ , preferably 1 to 3, different components B.
  • the base colors can also contain 0 to 10% by weight, based on the total weight of component A, of conventional auxiliaries and additives.
  • the mixing system is particularly preferably built up from base colors which only contain effect pigments and base colors which only contain color pigments.
  • Contain particularly preferred base colors (component A) based on inorganic color pigments Aa) 1 to 70% by weight of at least one inorganic color pigment,
  • component A contains water as an additional constituent in an amount of at least 5% by weight and less than 20% by weight, preferably 6 to 19% by weight, most preferably 8 to 16% by weight.
  • base colors can also be used as component A, which contain a combination of at least one organic coloring and at least one inorganic coloring pigment.
  • Mixtures are preferably used as component B which contain Ba) 60 to 100% by weight, preferably 80 to 97% by weight, water,
  • Bb 0 to 10% by weight, preferably 2 to 5% by weight, of at least one rheology-controlling additive, this amount being based on the weight of the pure additive without solvent component and
  • the various base colors A are mixed in such a ratio that the desired color tone results.
  • the mixing ratio of component A with the various component (s) is determined by the requirement that the resulting coating agent has the desired viscosity, the desired solids content and the desired organic solvent content, etc., regardless of the color.
  • the solids content (amount of solid binder used plus amount of pigment used) and the content of organic Solvents, among others, vary with the intended use of the aqueous coating compositions.
  • the solids content for metallic coatings is preferably 7 to 25% by weight and for plain-colored coatings preferably 10 to 45% by weight, based in each case on the total weight of the aqueous coating compositions.
  • a preferred embodiment of the mixing system according to the invention is a mixing system in which all base colors contain the same or, in the case of a binder mixture, the same binders. All base colors of the mixing system particularly preferably have the same ratio of the amount of solid binder used (i.e. without solvent) to the amount of organic solvent used.
  • the mixing ratio of the various binders to one another in the individual base colors should preferably be constant in each case, so that after mixing with component B, constant mixing ratios with regard to the binders can be achieved regardless of the color tone. If a mixture of the binders which are also used in component A is used in component B, so in component B the mixing ratio of the various binders to one another should preferably be equal to the mixing ratio of these binders in component A.
  • the base colors A contain water-dilutable polyurethane resins and possibly aminoplast resin as a binder and component B contains polyurethane resins as a binder.
  • the aqueous coating compositions produced using the mixing system according to the invention can be applied to a wide variety of substrates, such as, for. B. metal, wood, plastic or paper.
  • the aqueous coating compositions produced by means of the mixing system according to the invention are particularly suitable for the refinishing of damaged areas, in particular for automotive refinishing.
  • the coating compositions are applied directly after their production by mixing components A and B to the correspondingly prepared damaged parts (for example by spatula and fillers) using customary methods, in particular spraying.
  • the aqueous coating compositions prepared using the mixing system according to the invention are preferably used to produce a base layer. After the base layer thus produced has dried on at room temperature or by forced drying (for example 10 minutes at 60 ° C., 80 ° C. or IR drying), a suitable transparent top coating composition is applied. Both organically dissolved and aqueous one- or two-component clear coats and powder clear coats are suitable as top coats. Two-component clear coats based on a hydroxyl-containing acrylate copolymer and a polyisocyanate are frequently used. Clear varnishes of this type are described, for example, in patent applications DE 34 12534, DE 3609 519, DE 37 31 652 and DE 38 23 005.
  • suitable 1-component clear lacquers for example based on a binder containing hydroxyl groups and an amino resin hardener, are also known and are described, for example, in Kittel, Textbook of Lacquers and Coatings, Volume IV; Publisher WA Colomb described in H. Heeremann GmbH, Berlin-Oberschwandorf 1976. Of course, all other clear coats not explicitly mentioned here are also suitable.
  • the base layer is then dried together with the cover layer.
  • drying generally takes place. at temperatures below 100 ° C, preferably below 80 ° C.
  • the dry film layer thicknesses of the base layer are generally a. between 5 and 25 ⁇ m, which the top layer generally between 30 and 70 ⁇ m.
  • the base layer is applied together with the top layer at elevated temperatures, e.g. approx. 120 ° C, dried.
  • the dry film layer thicknesses of the top layer are generally here. between 30 and 50 ⁇ m.

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

Abstract

L'invention concerne un système mixte permettant de produire des agents de revêtement diluables dans l'eau, dont la teinte est fixée de manière précise à partir de couleurs de base. Ce mélange mixte comprend : A) différentes couleurs de base A qui contiennent de l'eau, Aa) entre 0,5 et 70 % en poids d'au moins un pigment conférant la couleur et/ou un effet, Ab) entre 10 et 80 % en poids d'au moins un liant diluable dans l'eau ou dispersible dans l'eau, se présentant sous forme de solutions organiques, et Ac) un ou plusieurs solvants organiques, ainsi qu'éventuellement des auxiliaires et des additifs. La somme des proportions en pour-cent des constituants Aa) à Ac) s'élevant à 100 % en poids. Ce mélange mixte contient : au moins un constituant B exempt de pigment et contenant de l'eau, qui comprend au moins un additif rhéologique, ainsi qu'éventuellement au moins un liant diluable dans l'eau ou dispersible dans l'eau, à l'exception de réseaux acryliques, et éventuellement d'autres auxiliaires et additifs, la teneur en eau du constituant A étant comprise entre 5 à 20 % en poids, de préférence ente 8 et 16 % en poids. L'invention concerne en outre un procédé permettant de produire des agents de revêtement à l'aide de ce système mixte, ainsi que l'utilisation dudit système mixte pour produire des peintures à base d'eau pour recouvrir des carrosseries d'automobile et/ou des pièces en matière plastique, notamment pour la mise en peinture de réparation d'automobiles.
PCT/EP2000/008211 1999-09-07 2000-08-23 Systeme mixte pour produire des agents de revetement diluables dans l'eau WO2001018129A1 (fr)

Applications Claiming Priority (2)

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DE19942515A DE19942515A1 (de) 1999-09-07 1999-09-07 Mischsystem zur Herstellung wasserverdünnbarer Überzugsmittel
DE19942515.9 1999-09-07

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Cited By (3)

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US7985821B2 (en) 2006-01-27 2011-07-26 Momentive Performance Materials Inc. Low VOC epoxy silane oligomer and compositions containing same
EP2873703A1 (fr) 2013-11-18 2015-05-20 BASF Coatings GmbH Système de mélange pour la fabrication de compositions de peintures de finition ainsi que de compositions de revêtement appliquées à la spatule
WO2018015484A1 (fr) 2016-07-20 2018-01-25 Basf Coatings Gmbh Système de mélange pour la fabrication d'agents aqueux de revêtement de réparation, procédé pour leur préparation ainsi qu'agent aqueux de revêtement de réparation préparé par le système de mélange

Families Citing this family (3)

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US7288584B2 (en) 2002-01-29 2007-10-30 Ppg Industries Ohio, Inc. Mixing scheme and process for the preparation of a refinish coating composition
EP1331249A1 (fr) * 2002-01-29 2003-07-30 PPG Industries Ohio, Inc. Système de mélange et procédé pour préparer une composition de peinture de retouche
US10358520B2 (en) 2014-02-26 2019-07-23 Basf Coatings Gmbh Polymer in multicoat color and/or effect paint systems

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Publication number Priority date Publication date Assignee Title
DE4110520A1 (de) * 1991-03-30 1992-10-01 Basf Lacke & Farben Mischsystem zur herstellung wasserverduennbarer ueberzugsmittel
DE4301991A1 (de) * 1993-01-26 1994-07-28 Herberts Gmbh Modulsystem und dessen Verwendung bei Verfahren zur Herstellung von wäßrigen Überzugsmitteln
EP0614951A2 (fr) * 1993-03-10 1994-09-14 Herberts Gesellschaft mit beschränkter Haftung Procédé de préparation de compositions de revêtement aqueuses à couleur unique en utilisant des systèmes de modules
DE4339951A1 (de) * 1993-11-24 1995-06-01 Basf Lacke & Farben Aus zwei Komponenten bestehendes Lacksystem
EP0752455A1 (fr) * 1991-03-30 1997-01-08 BASF Lacke + Farben AG Système de mélange pour préparer des revêtements diluables à l'eau

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4110520A1 (de) * 1991-03-30 1992-10-01 Basf Lacke & Farben Mischsystem zur herstellung wasserverduennbarer ueberzugsmittel
EP0752455A1 (fr) * 1991-03-30 1997-01-08 BASF Lacke + Farben AG Système de mélange pour préparer des revêtements diluables à l'eau
DE4301991A1 (de) * 1993-01-26 1994-07-28 Herberts Gmbh Modulsystem und dessen Verwendung bei Verfahren zur Herstellung von wäßrigen Überzugsmitteln
EP0608773A1 (fr) * 1993-01-26 1994-08-03 Herberts Gesellschaft mit beschränkter Haftung Procédé pour la préparation de revêtements aqueux en utilisant des systèmes modulaires
EP0614951A2 (fr) * 1993-03-10 1994-09-14 Herberts Gesellschaft mit beschränkter Haftung Procédé de préparation de compositions de revêtement aqueuses à couleur unique en utilisant des systèmes de modules
DE4339951A1 (de) * 1993-11-24 1995-06-01 Basf Lacke & Farben Aus zwei Komponenten bestehendes Lacksystem

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7985821B2 (en) 2006-01-27 2011-07-26 Momentive Performance Materials Inc. Low VOC epoxy silane oligomer and compositions containing same
EP2873703A1 (fr) 2013-11-18 2015-05-20 BASF Coatings GmbH Système de mélange pour la fabrication de compositions de peintures de finition ainsi que de compositions de revêtement appliquées à la spatule
US10427187B2 (en) 2013-11-18 2019-10-01 Basf Coatings Gmbh Mixer system for producing topcoat compositions and coating compositions used as filler
WO2018015484A1 (fr) 2016-07-20 2018-01-25 Basf Coatings Gmbh Système de mélange pour la fabrication d'agents aqueux de revêtement de réparation, procédé pour leur préparation ainsi qu'agent aqueux de revêtement de réparation préparé par le système de mélange
US10907069B2 (en) 2016-07-20 2021-02-02 Basf Coatings Gmbh Mixing system for producing aqueous repair coating products, method for the production thereof, and aqueous repair coating products produced from the mixing system

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