WO1995005425A1 - Agent de revêtement contenant au moins un polyester renfermant des groupes hydroxyle, son procede de fabrication et son utilisation comme vernis de base dans un procede de fabrication d'un revetement multicouche pour la protection et/ou la decoration - Google Patents

Agent de revêtement contenant au moins un polyester renfermant des groupes hydroxyle, son procede de fabrication et son utilisation comme vernis de base dans un procede de fabrication d'un revetement multicouche pour la protection et/ou la decoration Download PDF

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Publication number
WO1995005425A1
WO1995005425A1 PCT/EP1994/002570 EP9402570W WO9505425A1 WO 1995005425 A1 WO1995005425 A1 WO 1995005425A1 EP 9402570 W EP9402570 W EP 9402570W WO 9505425 A1 WO9505425 A1 WO 9505425A1
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WO
WIPO (PCT)
Prior art keywords
weight
polyester
coating
coating agent
hydroxyl
Prior art date
Application number
PCT/EP1994/002570
Other languages
German (de)
English (en)
Inventor
Peter Hoffmann
Michael Brünnemann
Original Assignee
Basf Lacke + Farben Ag
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Lacke + Farben Ag filed Critical Basf Lacke + Farben Ag
Priority to SK164-96A priority Critical patent/SK16496A3/sk
Priority to EP94924838A priority patent/EP0739394A1/fr
Priority to PL94312967A priority patent/PL312967A1/xx
Priority to JP7506709A priority patent/JPH09501708A/ja
Priority to BR9407255A priority patent/BR9407255A/pt
Publication of WO1995005425A1 publication Critical patent/WO1995005425A1/fr
Priority to BG100351A priority patent/BG100351A/xx

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/532—Base coat plus clear coat type the two layers being cured or baked together, i.e. wet on wet
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers

Definitions

  • Coating agent containing at least one hydroxyl-containing polyester process for its production and its use as a basecoat and in processes for producing a multilayer, protective and / or decorative coating
  • the present invention relates to a coating composition, in particular basecoat, containing at least one hydroxyl-containing polyester.
  • the present invention also relates to a method for producing the coating compositions and a method for producing a multilayer, protective and / or decorative coating on a substrate surface.
  • the invention also relates to the use of the coating compositions as a basecoat and the use of the coating compositions in the refinishing, in particular of automobile bodies.
  • Metallic pigments are often used in the base layer, which lead to the so-called metallic coatings.
  • the basecoat film shows only very little or no solubility when the clearcoat film is applied to the predried but not yet hardened basecoat film.
  • a certain detachment of the basecoat layer when applying the clearcoat layer is quite desirable for reasons of adhesion between the basecoat and clearcoat layers.
  • DE-PS-28 18 093 are multilayered
  • the object of the present invention is therefore to provide coating compositions, in particular basecoats, which have improved properties compared to the known coating compositions.
  • the coating compositions when used as basecoats, should ensure both a good metallic effect of the multi-layer coating and good adhesion to the clearcoat arranged on the basecoat film.
  • the coating agents should cure at room temperature or at a slightly elevated temperature so that they can be used in automotive refinishing. Furthermore, they should meet the requirements that are normally placed on a basecoat.
  • the coating compositions should therefore, for example, be quick-drying, stable in storage and overpaintable, and have good flop formation (good metallic effect) and good adhesion to the clearcoat.
  • a coating agent in particular a basecoat, containing at least one hydroxyl-containing polyester, which is characterized in that
  • the hydroxyl-containing polyester has a weight-average molecular weight Mw of 40,000-200,000 and a non-uniformity Mw / Mn> 8 and 2. at least 50 to produce the polyester
  • % By weight of aromatic dicarboxylic acids or their derivatives capable of esterification have been used, but the phthalic anhydride content is at most 80% by weight and the% by weight information in each case relates to the total weight of the acid used to prepare the polyester components are related.
  • the present invention also relates to a process for the preparation of these coating compositions. Furthermore, the present invention also relates to a method for producing a multilayer, protective and / or decorative coating on a substrate surface, in which
  • the present invention also relates to the use of the coating compositions as a basecoat and to the use of the coating compositions for the repair coating, in particular for the refinishing of automobile bodies. It is surprising and was not foreseeable that the polyester used according to the invention gives coating agents which ensure both a good metallic effect of the multi-layer coating and good adhesion to the clear lacquer arranged on the base lacquer layer. In addition, the coating compositions have the advantage that they cure at room temperature or slightly elevated temperature and can therefore be used in automotive refinishing.
  • the coating compositions according to the invention meet the requirements that are normally placed on a basecoat.
  • the coating compositions are quick-drying, stable in storage and can be overpainted and have good flop formation and good adhesion to the clearcoat. Furthermore, they have a good color match even when mixed with basecoats based on other polyesters which have different molecular weights and degrees of branching.
  • the coating agents as binders are a hydroxyl-containing polyester with a weight-average molecular weight of 40,000-200,000, preferably from 50,000 to 120,000, and with a non-uniformity (the non-uniformity is defined as the quotient of the weight-average molecular weight Mw and the number-average molecular weight) weight Mn) of> 8, preferably> 8 to 200 and particularly preferably 10 to 100.
  • the weight-average and number-average molecular weights are determined by gel permeation chromatography against polystyrene standard.
  • the hydroxyl-containing polyesters preferably have OH numbers of 20-150 mg KOH / g, preferably 60-110 mg KOH / g. These polyesters preferably also have acid numbers of 5-20 mg KOH / g, particularly preferably 10-15 mg KOH / g, and / or amine numbers 0-40 mg KOH / g.
  • aromatic dicarboxylic acids are used to produce these hydroxyl-containing polyesters, but the phthalic anhydride content is at most 80% by weight.
  • cycloaliphatic dicarboxylic acids are preferably used. The percentages by weight are based in each case on the total weight of the acid components used to produce the polyesters. It is only this combination of a high weight-average molecular weight with a broad molecular weight distribution and the use of a minimum proportion of aromatic dicarboxylic acids as the structural component that ensures that the coating agents have the required good properties, in particular good adhesion with a good metallic effect at the same time.
  • polyesters used according to the invention are obtainable by reacting
  • aromatic dicarboxylic acids or their esterifiable derivatives are used as the acid component (a) for the preparation of the polyesters.
  • phthalic anhydride is used to produce the polyesters, a maximum of 80% by weight of the acid component may consist of phthalic anhydride.
  • Up to 50% by weight of aliphatic and / or cycloaliphatic polycarboxylic acids can be used together with the aromatic dicarboxylic acids. In this case, preferably less than 20% by weight and particularly preferably no cycloaliphatic di- or polycarbonate acids are used.
  • Suitable aliphatic dicarboxylic acids for the preparation of the hydroxyl group-containing polyesters according to the invention are adipic acid, glutaric acid, acetic acid, sebacic acid, fumaric acid, maleic acid, succinic acid, muconic acid, itaconic acid and the like. a ..
  • esterifiable derivatives of the abovementioned polycarbonaurs such as, for example, their mono- or polyvalent esters with aliphatic alcohols with 1 to 4 carbon atoms or hydroxyl alcohols with 1 to 4 carbon atoms.
  • the anhydrides of the above acids can also be used if they exist.
  • Monocarboxylic acids can also be used together with the polycarboxylic acids, such as, for example, benzoic acid, tert-butylbenzoic acid, lauric acid, isononanoic acid and fatty acids of naturally occurring oils. Isononanoic acid is preferably used as the monocarboxylic acid.
  • the proportion of monocarboxylic acids is preferably less than 20% by weight, based on the total weight of the carboxylic acids used to prepare the polyesters.
  • component (a) less than 20% by weight and particularly preferably no cycloaliphatic dicarboxylic acids, e.g. Tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane dicarboxylic acids, 4-methylhexahydrophthalic acid, endomethylene tetrahydrophthalic acid, tricyclodecane dicarboxylic acid, endomethylene hexahydrophthalic acid, camphoric acid, cyclohexane tetracarbonate acid, cyclobutantetra acid and cyclobutantetracarboxylic acid are used.
  • cycloaliphatic dicarboxylic acids e.g. Tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexane dicarboxylic acids, 4-methylhexahydrophthalic acid, endomethylene tetrahydrophthalic acid, tricyclodecane dicarboxylic acid, endomethylene hex
  • Suitable alcohol components (b) for the preparation of the polyester are polyhydric alcohols, such as ethylene glycol, propanediols, butanediols, hexanediols, neopentylglycol, diethylene glycol, cyclohexanediol, cyclohexanedimethanol, trimethylpentanediol, ethylbutylpropanediol, ditrimethylolpropane, trimethylolpropane diol, trimethylolpropane diol Pentaerythritol, dipentaerythritol, trishydroxyethyl isocyanate, polyethylene glycol, polypropylene glycol, optionally together with monohydric alcohols, such as butanol, octanol, lauryl alcohol, ethoxylated or propyoxylated phenol.
  • polyhydric alcohols such as ethylene glycol, propane
  • component (c) Particularly suitable as component (c) for the production of the polyesters are compounds which are reactive towards the functional groups of the polyester Have group, except for the compounds mentioned as component (d).
  • Suitable polyisocyanates are, for example, tolylene diisocyanates, hexamethylene diisocyanates and isophorone diisocyanate. Diepoxide compounds are understood to mean epoxy resins with an average of about 2 epoxy groups per molecule.
  • Suitable monoepoxide compounds are, for example, olefin oxides, such as octylene oxide, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, styrene oxide, glycidyl methacrylate, glycidylhexane vinyl monoxide, dipentene monoxide, and carboxylic acid pentoxide monoxides, glyceryl pentoxides and glyceryl pentoxides and carboxides,
  • olefin oxides such as octylene oxide, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-butylphenol glycidyl ether, cresy
  • Compounds which are suitable as component (d) for the preparation of the polyesters are, for example, compounds which, in addition to a group which is reactive toward the functional groups of the polyester, also have a tertiary amino group.
  • Mono isocyanates having at least one tertiary amino group are preferably used as components (d) which are reactive with the reaction product of (a), (b) and, if appropriate, (c).
  • These can be prepared, for example, by reacting suitable diisocyanates, such as isophorone diisocyanate, with amino alcohols with a tertiary amino group, such as, for example, hydroxyethyl pyridine or dimethylaminoethanol, or with polyamines with at least one tertiary and at least one secondary or primary amino group.
  • suitable diisocyanates such as isophorone diisocyanate
  • amino alcohols with a tertiary amino group such as, for example, hydroxyethyl pyridine or dimethylaminoethanol
  • polyamines with at least one tertiary and at least one secondary or primary amino group.
  • the monoisocyanates are reacted with free hydroxyl groups
  • Polyester to form urethane formation on the Binder system bound Polyamines having at least one tertiary and at least one primary or secondary amino group can also be used as component (d).
  • An example of this is dimethylaminopropylamine.
  • the tertiary amino groups can also be introduced into the polyester by using polyols and / or polycarboxylic acids containing amino groups.
  • aminocarboxylic acids having at least one tertiary amino group can be used together with the polycarboxylic acids.
  • examples include pyridine-2-carboxylic acid, pyridine-3-carboxylic acid, pyridine-4-carboxylic acid and pyridine-2,6-dicarboxylic acid.
  • the reaction product of an amino alcohol with at least one tertiary amino group and a polycarboxylic anhydride and the reaction product of a polyamine with at least one tertiary and at least one primary or secondary amino group and a polycarboxylic acid anhydride can be used.
  • Amino alcohols with at least one tertiary amino group can be used as the alcohol component (b).
  • Examples include 2-hydroxyethyl pyridine, dimethylaminopropanol, methyl diethanolamine, methyl dipropanolamine and dihydroxyethylaniline.
  • Reaction products of epoxy resins with carboxylic acids and / or amines can also be used as alcohol component (b).
  • the alcohol product (b) can thus be the reaction product of low molecular weight
  • Epoxy resins with polycarboxylic acids and / or polycarbonate Acid anhydrides and aminocarboxylic acids with at least one tertiary amino group can be used, with esterification then optionally also being carried out with the acid and alcohol components and, if appropriate, modification with polyisocyanates.
  • Low molecular weight epoxy resins are understood to mean epoxy resins with a molecular weight of approximately less than 2,000. When using epoxy resins, low-chlorine types should be used, since otherwise the products may be strongly discolored.
  • polyesters can be carried out according to the known and customary methods, as described, for example, in various standard works, such as
  • the molecular weight and the degree of branching of the polyester can be regulate in a simple manner familiar to the person skilled in the art via the use ratio of the alcohol components (diol and polyol) and the di- or polycarboxylic acids.
  • the weight-average molecular weight Mw and the non-uniformity Mw / Mn of the polyester are the higher the closer the Ratio OH / acid groups goes towards 1 and the degree of branching is increased. This is achieved by using only a small excess of polyols and driving the condensation to a high conversion of> 98%.
  • the degree of branching is controlled by the proportion of highly functional compounds. Degree of branching, degree of condensation and the molar ratios of the polyols must be carefully coordinated with one another in order to avoid gelling of the condensation resin.
  • the degree of branching is preferably 0.6 to 1.2 branches per 1000 g of polyester resin (solid).
  • esterification conditions are chosen so that the reaction is as complete as possible. That the reaction is continued until the desired acid numbers have been reached.
  • the reaction is usually carried out at temperatures between 180 and 280 ° C., if appropriate in the presence of a suitable esterification catalyst, such as, for example, lithium octoate, dibutyltin oxide, dibutyltin dilaurate, p-toluenesulfonic acid and the like.
  • a suitable esterification catalyst such as, for example, lithium octoate, dibutyltin oxide, dibutyltin dilaurate, p-toluenesulfonic acid and the like.
  • the polyesters are usually prepared in the presence of small amounts of a suitable solvent as entrainer.
  • Aromatic hydrocarbons such as in particular xylene, and cycloaliphatic hydrocarbons, for example cyclohexane, are used as entraining agents.
  • reaction is carried out in the presence of an esterification catalyst, it is usually used in an amount of 0.01 to 0.5% by weight, based on the solids of the polyester resin solution and based on the solids of the catalyst solution .
  • the coating compositions according to the invention generally contain up to 20% by weight, preferably 6 to 9% by weight, based in each case on the total weight of the coating composition and on the solids content of the polyester resin solution, of the hydroxyl-containing polyester .
  • the coating compositions according to the invention preferably contain at least one cellulose ester, preferably in amounts of 10-40% by weight, particularly preferably from 15 to 30% by weight, in each case based on the solids of the film-forming solids and based on the solids content of the cellulose ester solution.
  • suitable cellulose esters are cellulose nitrate, cellulose propionate, cellulose butyrate, cellulose acetobutyrate, cellulose acetopropionate, mixtures thereof and the like.
  • Cellulose aceto-butyrate is preferably used.
  • a cellulose ester with an acetyl group content of 12-16% by weight and a buturyl group content is preferred from 35 to 43% by weight and a hydroxyl group content from 1 to 2.5% by weight and a weight-average molecular weight of 100,000 to 250,000 (number-average molecular weight 35,000 to 65,000).
  • This cellulose acetobutyrate is called CAB1 for short.
  • CAB2 another cellulose acetobutyrate, hereinafter referred to as CAB2 for short, can be used to produce metallic basecoats.
  • This CAB2 has an acetyl group content of 1-5% by weight, a buturyl group content of 48-52% by weight, a hydroxyl group content of 1-2.5% by weight and a weight average molecular weight of 100,000 to 250,000 on.
  • Mixtures of CAB1 and CAB2 can be used to produce the metallic basecoats, in which the content of CAB1 is preferably at least 60% by weight, based on the total content of CAB.
  • the CABl type or a mixture of the CAB1 and CAB2 is also preferably used as the cellulose ester to produce pigmented uni base coats.
  • the sole use of CAB2 is also possible.
  • the coating compositions according to the invention also usually contain 60-90% by weight, preferably 70-85% by weight, in each case based on the total weight of the coating composition, of at least one solvent.
  • Suitable solvents are the solvents already mentioned in the production of the polyester and ketones, such as Acetone, methyl isobutyl ketone and the like.
  • Preferred solvents are esters, e.g. Butyl acetate, 1-methoxy propyl acetate, ethylene glycol diacetate, 2-ethoxy ethyl acetate, butyl glycol acetate, ethyl diglycol acetate and the like are used.
  • Highly substituted aromatics such as e.g. Solvent
  • NaphthaS heavy benzene various Solvess ⁇ B types
  • Shell Sol and Deasol® as well as higher-boiling aliphatic and cycloaliphatic hydrocarbons, such as various white spirits, mineral turpentine, tetralin, decalin, depanol and the like.
  • the criteria for the selection of the solvent are, among other desirable properties, that it does not react with the film-forming material and that it can be easily removed in the application and curing process.
  • the amount of solvent is controlled in such a way that the coating agent is enabled to close the coating to a smooth surface or to let it melt, so that an acceptable application is ensured.
  • the consistency of the coatings is controlled by the addition of a sufficient amount of solvent in such a way that the mass can be handled and applied with the formation of a suitable coating without the defects, the occurrence of which is known from the spraying method.
  • the coating agents may also contain a crosslinking agent which is reactive towards the hydroxyl groups of the polyester. But it is also the formulation of physically drying coating agents, i.e. cross-linking agent-free coating agent possible. If the coating compositions contain a crosslinking agent, it is usually used in amounts of 5 to 20% by weight, based on the total weight of the coating composition.
  • polyisocyanates can be used as crosslinking agents, such as aromatic isocyanates, such as 2,4-, 2,6-tolylene diisocyanate and mixtures thereof, 4,4'-diphenylmethane diisocyanate, m-phenylene, p-phenylene -, 4,4-Diphenyl-, 1,5-naphthalene, 1,4-naphthalene, 4, 4-toluidine, xylylene diisocyanate and substituted aromatic systems such as Dianisidine diisocyanates, 4,4 diphenyl ether diisocyanates or chlorodiphenylene diisocyanates and higher functional aromatic isocyanates, such as 1, 3, 5-tri-isocyanatobenzene, 4,4 ', 4 "- triisocyanate triphenyl methane, 2,4,6-triisocyanatotoluene and 4, 4'-diphenyldimethylmethane-2,2 ', 5,5'-tet
  • polyisocyanates can also be linked to form prepolymers with a higher molecular weight.
  • prepolymers with a higher molecular weight.
  • These include adducts of tolylene diisocyanate and trimethylolpropane, a biuret formed from 3 molecules of hexamethylene diisocyanate and the trimers of hexamethylene diisocyanate and 3,5,5-trimethyl-l-isocyanato-3-isocyanatomethylcyclohexane.
  • capping means such as Phenols, alcohols, acetoacetic esters, ketoxime and caprolactam, converted isocyanates. These combinations are stable at room temperature and generally harden only at temperatures above 100 ° C. In special cases, e.g. when using acetic acid esters for capping, crosslinking can also occur at below 100 °.
  • the amount of the crosslinking agent used is generally chosen so that the ratio of the isocyanate groups of the crosslinking agent to the hydroxyl groups of the polyester is in the range from 1: 3 to 3: 1. Combinations with polyisocyanates and / or resins carrying isocyanate groups crosslink rapidly, even at room temperature.
  • Aminoplastic resins can also be used as crosslinking agents, e.g. Melamine-formaldehyde condensation products, benzoguanamine-formaldehyde condensation products, urea resins and the like.
  • suitable aminoplast resins are, for example, the commercially available melamine resins, Maprenal MF 600, MF650, MF 800 from Hoechst AG.
  • the amount of these optionally used aminoplast resins is usually between 3 and 8% by weight, based on the weight of the coating composition.
  • the coating compositions according to the invention can, if appropriate, also other resins, such as Polyurethane resins included.
  • Suitable polyurethane resins usually have number average molecular weights of 3000 to 7000.
  • polyurethane resins described in EP-A-355 433, DE-OS 35 45 618 and DE-OS 38 13 866 can be used.
  • the use of other polyurethane resins usually used in basecoats is also possible.
  • the amount of these optionally added polyurethane resins is usually between 15 and 40% by weight, based on the weight of the coating composition and based on solid polyurethane resin.
  • the coating compositions according to the invention may also contain epoxy ester resins, such as, for example, reaction products of epoxy resins and carboxylic acids, epoxy-modified acrylics and epoxy-modified polyesters.
  • epoxy ester resins such as, for example, reaction products of epoxy resins and carboxylic acids, epoxy-modified acrylics and epoxy-modified polyesters.
  • the commercially available, epoxy-modified decorated fatty acid polyester Uralac AB733X-90 from DSM Kunststoffharze GmbH can be used.
  • the amount of these epoxy-modified resins which may be added is usually between 0 and 4% by weight, based on the weight of the coating composition.
  • the coating compositions according to the invention are used as base lacquers, they also contain, as a further constituent, pigments which are customary in coating technology.
  • pigments can have particle sizes in the range from 1-50 ⁇ m and have an inorganic nature, for example titanium dioxide, iron oxide, chromium oxide, lead chromate or carbon black, or an organic nature, such as e.g. Phthalocyanine blue, phthalocyanine green, carbazole violet, anthrapyrimidine yellow, vlavanthrone yellow, isoindoline yellow, indanthrone blue, quinine grindone violet and pherylene red.
  • metal pigments which consist of flat flakes of aluminum, copper, tin, nickel or stainless steel, because they can be used to achieve so-called metal effects, by means of which a different light reflection depending on from the viewing angle.
  • the amount of these pigments used is usually between 1 and 40% by weight, based on the total weight of the coating composition.
  • the coating agents can also contain customary fillers, such as, for example, silica, talc, kaolin, metallic oxides, silicates, sulfides and the like. These fillers are usually used in an amount between 0 and 10% by weight, based on the weight of the coating composition.
  • the coating compositions according to the invention can also contain customary auxiliaries and additives in customary amounts, preferably 0.01-10% by weight, based on the total weight of the coating composition. Examples of suitable auxiliaries and additives are leveling agents, such as silicone oils, plasticizers, such as phosphoric acid esters and phthalic acid esters, viscosity-controlling additives, matting agents, UV absorbers, light stabilizers and the like.
  • the coating compositions preferably also contain a crosslinking catalyst, usually in an amount of up to 10% by weight, based on the weight of the coating composition.
  • crosslinking catalyst can generally be dispensed with if the polyester already contains tertiary amino groups.
  • crosslinking catalysts are, for example, phosphoric acid, p-toluenesulfonic acid, tin dibutyl dilaurate, tin dioctyl dilaurate, amines, for example aliphatic diamines such as ethylenediamine,
  • Hexanediamine aliphatic polyamines, such as diethylene triamine, triethylene tetraamine, tetraethylene pentamine, alicyclic amines, such as piperidine, piperazine, aromatic amines, ethanolamine, triethylamine, diazabicyclooctane, amidines such as diazabicyclonones, diazabicycloundecene, and low molecular weight.
  • 1 to 10 parts by weight of the catalyst (solid) are used for 100 parts by weight of the polyester.
  • the coating compositions are prepared in a known manner by mixing and, if appropriate, dispersing the individual components.
  • the coating compositions according to the invention can be applied by spraying, flooding, dipping, rolling, knife coating or brushing onto a substrate in the form of a film applied, the film then being cured to a firmly adhering coating.
  • These coating compositions are usually cured at room temperature or at a slightly elevated temperature, advantageously at temperatures below 100 ° C., preferably at temperatures below 80 ° C.
  • the coating compositions can also be cured under baking conditions, ie at temperatures of at least 100 ° C.
  • Metals and wood, plastic, glass and the like are particularly suitable as substrates. Because of the short curing time and low curing temperatures, the Uber according to the invention Traction agents are preferably used for automotive refinishing, but - depending on the crosslinker used - they can also be used for automotive serial painting.
  • compositions according to the invention are also suitable as the base color of a mixing system, in particular one
  • the coating compositions according to the invention are particularly preferably used in a mixing system for the production of conventional coating compositions.
  • Mixing systems of this type are described, for example, in the as yet unpublished German application P 42 32 721.0. These mixing systems described there are characterized in that they
  • the coating compositions according to the invention based on hydroxyl-containing polyesters and cellulose acetobutyrate are used for the production of component B.
  • the good color matching of the resulting coating compositions is particularly advantageous, in particular if hydroxyl-containing polyesters according to the invention with a degree of branching of 0.6 to 1.2 branches are used per 1000 g of polyester resin (solid).
  • crosslinking agents (C) z. B. used the crosslinking agents already mentioned. However, physically drying coating compositions can also be produced with the aid of this mixing system, in which case component (C) can be dispensed with.
  • the coating compositions according to the invention are preferably used as a basecoat for a multi-layer coating of the basecoat / clearcoat type.
  • This mixing system has the particular advantage, particularly from an economic point of view, that the base paints A containing water-dilutable or water-dispersible binders create the possibility of adding only one base paste series for both aqueous and organically dissolved systems use.
  • the use of essentially water-free, preferably completely water-free base colors according to the invention also offers the advantage that containers can be used for the storage of these base colors which are not protected against corrosion by water (for example by means of a suitable interior coating) have to be.
  • water-sensitive pigments can also be used for the formulation of the base colors under certain conditions, as a result of which the selection of pigments available is increased considerably.
  • Component A of the mixing system can contain all paint-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 paints) 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 the most universal possible range of use 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 color-imparting pigments and components A containing only effect pigments.
  • 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 customary metal plates and metal flake pigments.
  • non-metallic effect pigments such as pearlescent or interference pigments
  • 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, irzazine orange, Sicotrans yellow, heliogen green and others
  • Suitable binders for use in component A are all water-thinnable 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. in the base color.
  • water-thinnable 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. Suitable examples in the literature for the inputs ⁇ set in water-based paints polyurethane resins described, provided these polyurethane resins - in a modification of the production described in the respective literature - can be represented in the form of organic solutions.
  • Suitable polyurethane resins are the resins described in the following documents:
  • suitable polyacrylate resins are, for example, the resins described in DE-OS 38 32 826.
  • Water-thinnable or water-dispersible polyester resins and aminoplast resins which can be prepared in the form of organic solutions are also suitable as binders for component A.
  • the present invention therefore also relates to a method for producing a multilayer, protective and / or decorative coating on a substrate surface, in which
  • a transparent top coating composition is applied directly after the application of the base coating composition, preferably after a short flash-off time without a baking step.
  • the base layer is then baked together with the cover layer (“wet-on-wet method”).
  • This hardening of the base layer and the top layer usually takes place at a temperature below 100 ° C., preferably below 80 ° C., in the case of auto repair painting. Otherwise, curing usually takes place at a temperature between 100 and 150 ° C. and a time between 15 and 30 minutes.
  • the dry film layer thicknesses of the resulting base layer are generally between 8 and 20 ⁇ m, that of the top coat layer usually between 20 and 60 ⁇ m .
  • Suitable clear coats for this process are, for example, the clear coats described in EP-A-379 598 based on hydroxyl-containing components, cellulose esters and isocyanates. Also suitable as clearcoat are the clearcoats described in DE-A-39 42 803 based on polymers containing silyl groups and the clearcoats described in DE-A-40 24 204 based on polycondensation and polyaddition products containing hydroxyl groups.
  • the temperature is raised to 135 ° C., at which the start of distillation can be observed. While maintaining a column top temperature of below 100 ° C., the temperature is slowly increased to a maximum product temperature of 210 ° C. The water formed is continuously distilled off azeotropically. After reaching an acid number of 12 to 14 mg KOH / g and a viscosity of 18 to 19 dPa.s (60% in xylene, plate and cone viscometer at 23 ° C), the mixture is cooled and the solids content is 80% with butyl acetate solved.
  • the polyester resin 1 thus obtained has a viscosity (measured with a plate-cone viscometer at 23 ° C., 60% in xylene) of 14.2 dPa.s and a number-average molecular weight of 3000 and a weight-average molecular weight of 105,000 (determined by gel permeation chromatography against polystyrene as standard).
  • the inconsistency Mw / Mn is 35 and the OH number is 96.5 mg KOH / g.
  • Example 2 corresponds to a resin of the composition from Example 1, with the exception that 0.05% dibutyltin oxide is used as the catalyst (based on solid starting materials).
  • the manufacturing process is identical. After an acid number of 12 to 14 mg KOH / g and a viscosity of 13 to 15 dPa.s (60% in xylene, plate and cone viscometer at 23 ° C) is reached, the mixture is cooled, dissolved in 6% xylene and after reaching a temperature of less than 120 ° C with butyl acetate to a solids content of 65%.
  • the polyester resin 2 thus obtained has a viscosity (measured with a plate-cone viscometer at 23 ° C., 60% in butyl acetate) of 13.5 dPa.s and a number-average molecular weight of 3100 and a weight-average molecular weight of 155,000 (determined by gel permeation chromatography against polystyrene as standard).
  • the inconsistency Mw / Mn is 52 and the OH number is 96 mg KOH / g.
  • the polyester resin solution has a viscosity of 9.8 dPa.s (ICI plate cone viscometer at 23 ° C.) and an acid number of 11.6 mg KOH / g (based on solids) .
  • the polyester thus obtained has a number-average molecular weight of 4500 g / mol, a weight-average molecular weight of 65500 g / mol (measured by GPC against polystyrene as the standard) and an OH number of 57 mg KOH / g and a disagreement uniformity Mw / Mn from 15. 1.4 Preparation of a hydroxyl-containing polyester VI
  • the temperature is raised to 135 ° C., at which the start of distillation can be observed. While maintaining a column head temperature of below 100 "C, the temperature is slowly increased to a maximum product temperature of 210" C. The water formed is continuously distilled off azeotropically. After reaching an acid number of 12 to 14 mg KOH / g and a viscosity of 6.1 dPa.s (60% in 1-methoxypropyl acetate, cone-plate viscometer at 23 ° C.). is cooled and dissolved in butyl acetate to a solids content of 60%.
  • the polyester resin VI obtained in this way has a viscosity (measured with the plate-cone viscometer at 23 ° C.) of 2.6 dPa.s and a number-average molecular weight of 2050 and a weight-average molecular weight of 9100 (determined by gel-mereation chromatography against polystyrene as standard)-.
  • the inconsistency Mw / Mn is 5, the OH number 146 mg KOH / g. 1.5
  • the components are mixed and slowly melted under inert gas. Distillation commences at 140 ° C. Then the mixture is further heated within 5 to 7 hours while maintaining a column top temperature of a maximum of 100 ° C. to 220 ° C.
  • the Visko® is condensed to an acid number of below 15 mg KOH / g The density is then 8.5 dPa.s (measured 55% in butyl acetate, plate-cone viscometer at 23 ° C.) After the acid number has been reached, the resin is discharged as a melt. Processable solutions of the resin can be melted and dissolved in the desired
  • the viscosity in xylene with a solids content of 55% is 9.1 dPa.s (plate-cone viscometer at 23 ° C).
  • the polyester V2 thus obtained has a number average molecular weight of 2250 and a weight average molecular weight of
  • the components are mixed and melted slowly. Distillation begins at 135 ° C.
  • the mixture is then heated further to 220 ° within 5 to 7 hours while maintaining a column top temperature of a maximum of 100 ° C. It is condensed up to an acid number of 16 mg KOH / g, the viscosity is then 8.5 dPa.s (measured 60% in xylene, plate-cone viscometer at 23 ° C). After the target values have been reached, the mixture is cooled, diluted with xylene to a solids content of 90% and further with butyl acetate to a solids content of 65%. The viscosity of the resin solution is 17.8 dPa.s (plate-cone viscometer at
  • the acid number is 15.5 mg KOH / g.
  • the polyester V3 thus obtained has a number average molecular weight of 3294 and a weight average molecular weight of 260,000 (measured by gel permeation chromatography against polystyrene as a standard) ⁇
  • the Inconsistency Mw / Mn is 79, the OH number 75 mg KOH / g. 1.7
  • the components are mixed and slowly melted under inert gas. Distillation begins at 140 ° C. The mixture is then heated further from 5-100 hours to a maximum of 220 ° C while maintaining a column top temperature. It is condensed to an acid number of less than 10 mg KOH / g, the viscosity is then about 14.5 dPa.s (measured 60% in xylene). After the acid number has been reached, the resin is adjusted to a theoretical solids content of 90% with xylene and to a solids content of theoretical with butyl acetate. 65% solved.
  • the polyester resin solution has a viscosity of 8.8 dPa.s (ICI plate cone viscometer at 23 ° C) and an acid number of 8.0 mg KOH / g (based on solid).
  • the polyester thus obtained has a number average molecular weight of 3250 g / mol and a weight average molecular weight of 61000 g / mol. (measured by GPC against polystyrene as standard), a non-uniformity MW / Mn of 19 and an OH number of 46 mg KOH / g. 2.1 Cellulose Acetobutyrate Solution 1
  • a cellulose acetobutyrate solution containing 15% CAB and 85% butyl acetate was used.
  • the cellulose acetobutyrate used has an acetyl group content of 13 to 16%, a butyl group content of 36 to 42%, a hydroxyl group content of 1 to 2% and a weight-average molecular weight of approximately 40,000.
  • the cellulose acetobutyrate solution 2 used has a cellulose acetobutyrate content of 15% and a butyl acetate content of 85%.
  • the cellulose acetobutyrate has a content of 2.5 to 4% acetyl groups, a butyryl group content of 36 to 42% and a hydroxyl group content of 1 to 2%.
  • the weight average molecular weight of the cellulose acetobutyrate is approximately 40,000.
  • the coating compositions according to the invention are produced by the customary methods, by first stirring the wax precipitation until the wax precipitation is free of specks. The cellulose acetobutyrate solution is then added with rapid stirring. Then the remaining ingredients are added except for the aluminum pigment and the solvent. The aluminum pigment is first pasted with 5 parts of butyl acetate and this pasting is added to the other constituents with stirring. Then the remaining quantities Solvent added.
  • the composition of the basecoats 1 to 4 and VI to V5 is given in Table 1. The basecoats are applied to 40 x 60 cm metal sheets.
  • a commercially available, conventional filler (commercial product Glasurit basic filler EP AC 01-1492 from Glasurit GmbH, Weg, with an epoxy-functional binder and an amino-functional hardener) served as the substrate.
  • the filler was applied by spraying and then dried at 80 ° C. for 20 minutes after a flash-off time of 10 minutes.
  • the dry film thickness of the filler is 50 to 80 ⁇ m.
  • the respective basecoat was then applied by spray application, by first applying 1 spray coat and, after a flash-off time of 5 min, a second spray coat. After a flash-off time of 20 min, also at room temperature, the clear coat was applied.
  • the commercially available clear coat Glasurit AF 23-0185 from Glasurit GmbH based on a polyacrylate was mixed as a clear coat in a ratio of 2: 1 with hardener SC 29-0173 from Glasurit GmbH Isocyanate base (mixture of a trimerized isocyanate containing isocyanate groups based on hexamethylene diisocyanate and isophorone diisocyanate) overcoated.
  • the clear lacquer application was carried out by spraying, in that one spraying step and, after a flash-off time of 2 minutes, a second spraying step is carried out. After a flash-off time of 10 minutes at ambient temperature, drying is then carried out for 30 minutes at 60 ° C.
  • the layer thickness of the base layer is 20-25 ⁇ m, that of the clear coat layer 60-80 ⁇ m.
  • Table 1 Composition of coating agents 1 to 3 and VI to V5
  • CAB 2 2 > 1 6, - - 6, "6,” 6, - 6, "33, - 6, -1 6, -
  • Wax 1 3) 127, - 27, - 27, - 27, - 27, - 27, - 27, - 27, -
  • the wax precipitation was prepared by introducing 44 parts of xylene and heating to 80-100 ° C. Then 6 parts of a commercially available ethyl vinyl acetate copolymer (commercial product EVA 1-wax BASI® from BASF AG, Ludwigshafen;
  • DABCO diazabicyclooctane
  • the adhesion test is carried out with a high-pressure cleaner at 80 bar pressure and a flow rate of 800 l / h and cold temperature. The distance from the nozzle to the test panel was 5 cm.
  • the coated steel sheets (see above) were stored at room temperature for 7 days and thus dried. Then a triangle with a side length of 10 cm is cut through the lacquer layers with a knife. The cut must be made up to the substrate. The sides of the triangle are then loaded with the high-pressure cleaner jet for 10 seconds each.
  • a square-cut metal grid with a 1/2 "mesh size and a total of 6" edge length is placed over the triangle (144 squares). Every square in which there is a loss of adhesion between the clear coat and basecoat is counted.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention a pour objet un agent de revêtement, en particulier un vernis de base, renfermant au moins un polyester à groupes hydroxyle, caractérisé en ce que (1) le polyester à groupe hydroxyle présente un poids moléculaire moyen, Mw, de 40.000 à 200.000 et une hétérogénéité Mw/Mn ⊃ 8, (2) et en ce qu'on utilise pour la fabrication du polyester au moins 50% en poids d'acides dicarboxyliques aromatiques ou de leurs dérivés estérifiables, la proportion en anhydride phtalique s'élevant au maximum à 80% en poids, les pourcentages en poids respectifs se rapportant au poids total des acides carboxyliques utilisés pour la fabrication du polyester. L'invention a également pour objet un procédé de fabrication de l'agent de revêtement, ainsi que son utilisation comme vernis de base dans un procédé de fabrication d'un revêtement multicouche protecteur et/ou ornemental.
PCT/EP1994/002570 1993-08-14 1994-08-03 Agent de revêtement contenant au moins un polyester renfermant des groupes hydroxyle, son procede de fabrication et son utilisation comme vernis de base dans un procede de fabrication d'un revetement multicouche pour la protection et/ou la decoration WO1995005425A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
SK164-96A SK16496A3 (en) 1993-08-14 1994-08-03 Coating containing at least one hydroxyl group-containing polyester, process for preparing the same and its use
EP94924838A EP0739394A1 (fr) 1993-08-14 1994-08-03 Agent de rev tement contenant au moins un polyester renfermant des groupes hydroxyle, son procede de fabrication et son utilisation comme vernis de base dans un procede de fabrication d'un revetement multicouche pour la protection et/ou la decoration
PL94312967A PL312967A1 (en) 1993-08-14 1994-08-03 Coating medium containing at least one polyester incorporating hydroxylic groups, method of obtaining such coating medium and application thereof as a base coating as well as in the processes of pplying multilayered protective and/or decorative coatings
JP7506709A JPH09501708A (ja) 1993-08-14 1994-08-03 ヒドロキシル基を有するポリエステル少なくとも１つを含有する被覆剤、該被覆剤の製法ならびに該被覆剤の下塗ラッカーとしての使用及び多層の保護被覆及び／又は装飾被覆を得る方法への使用
BR9407255A BR9407255A (pt) 1993-08-14 1994-08-03 Composição de revestimento compreendendo pelo menos um poliéster que contém grupos hidroxila processo para sua preparação e seu uso como revestimento-base e em processos para a produção de um revestimento múltiplo protetor e/ou decorativo
BG100351A BG100351A (en) 1993-08-14 1996-02-12 Coating containing at least one hydroxyl group-containoing polyester, process for preparing the same and its use as base lacquer and in a process for producing a multilayered protective and/or decorative coating

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4327416.1 1993-08-14
DE4327416A DE4327416A1 (de) 1993-08-14 1993-08-14 Überzugsmittel enthaltend mindestens einen hydroxylgruppenhaltigen Polyester, Verfahren zu seiner Herstellung sowie dessen Verwendung als Basislack und in Verfahren zur Herstellung eines mehrschichtigen, schützenden und/oder dekorativen Überzuges

Publications (1)

Publication Number Publication Date
WO1995005425A1 true WO1995005425A1 (fr) 1995-02-23

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PCT/EP1994/002570 WO1995005425A1 (fr) 1993-08-14 1994-08-03 Agent de revêtement contenant au moins un polyester renfermant des groupes hydroxyle, son procede de fabrication et son utilisation comme vernis de base dans un procede de fabrication d'un revetement multicouche pour la protection et/ou la decoration

Country Status (12)

Country Link
EP (1) EP0739394A1 (fr)
JP (1) JPH09501708A (fr)
BG (1) BG100351A (fr)
BR (1) BR9407255A (fr)
CA (1) CA2168451A1 (fr)
CZ (1) CZ29896A3 (fr)
DE (1) DE4327416A1 (fr)
HU (1) HU214788B (fr)
PL (1) PL312967A1 (fr)
SK (1) SK16496A3 (fr)
WO (1) WO1995005425A1 (fr)
ZA (1) ZA945583B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MD4029B2 (ro) * 2007-11-05 2010-04-30 Виталие КОТЕЛЯ Procedeu de obţinere a compoziţiei pentru acoperirea decorativă a elementelor de construcţie şi procedeu de aplicare a acoperirii
EP3009248A1 (fr) 2014-10-13 2016-04-20 RECTICEL Automobilsysteme GmbH Procédé de production d'une peau élastomère ayant une surface grainée

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004026904A1 (de) 2004-06-01 2005-12-22 Basf Ag Hochfunktionelle, hoch- oder hyperverzweigte Polyester sowie deren Herstellung und Verwendung
JP5991822B2 (ja) * 2012-02-10 2016-09-14 Ｂａｓｆジャパン株式会社 １液型クリヤー塗料組成物及びそれを用いた複層塗膜形成方法
EP3058039A1 (fr) * 2013-10-16 2016-08-24 BASF Coatings GmbH Composition de revêtement aqueuse et réalisation de couches de laque de finition en utilisant la composition de revêtement

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3826693A1 (de) * 1987-08-07 1989-02-16 Kansai Paint Co Ltd Beschichtungszusammensetzung fuer eine deckschicht

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3826693A1 (de) * 1987-08-07 1989-02-16 Kansai Paint Co Ltd Beschichtungszusammensetzung fuer eine deckschicht

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MD4029B2 (ro) * 2007-11-05 2010-04-30 Виталие КОТЕЛЯ Procedeu de obţinere a compoziţiei pentru acoperirea decorativă a elementelor de construcţie şi procedeu de aplicare a acoperirii
EP3009248A1 (fr) 2014-10-13 2016-04-20 RECTICEL Automobilsysteme GmbH Procédé de production d'une peau élastomère ayant une surface grainée
WO2016058983A1 (fr) 2014-10-13 2016-04-21 Recticel Automobilsysteme Gmbh Procédé de production d'une peau élastomère présentant une surface grenue

Also Published As

Publication number Publication date
CZ29896A3 (en) 1996-10-16
HU9600324D0 (en) 1996-04-29
SK16496A3 (en) 1997-06-04
BR9407255A (pt) 1996-09-24
CA2168451A1 (fr) 1995-02-23
HUT75505A (en) 1997-05-28
HU214788B (hu) 1998-05-28
PL312967A1 (en) 1996-05-27
JPH09501708A (ja) 1997-02-18
DE4327416A1 (de) 1995-02-16
ZA945583B (en) 1995-03-07
BG100351A (en) 1997-01-31
EP0739394A1 (fr) 1996-10-30

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