EP0964896A1 - Method for producing scratch resistant coatings, especially for producing multi-layer enamels - Google Patents

Method for producing scratch resistant coatings, especially for producing multi-layer enamels

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Publication number
EP0964896A1
EP0964896A1 EP98913655A EP98913655A EP0964896A1 EP 0964896 A1 EP0964896 A1 EP 0964896A1 EP 98913655 A EP98913655 A EP 98913655A EP 98913655 A EP98913655 A EP 98913655A EP 0964896 A1 EP0964896 A1 EP 0964896A1
Authority
EP
European Patent Office
Prior art keywords
preferably
coating
ƒ
da
characterized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98913655A
Other languages
German (de)
French (fr)
Inventor
Fritz Bartol
Hubert Baumgart
Peter Betz
Ulrike RÖCKRATH
Georg Wigger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
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
Priority to DE1997109465 priority Critical patent/DE19709465C2/en
Priority to DE19709465 priority
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Priority to PCT/EP1998/001265 priority patent/WO1998040442A1/en
Publication of EP0964896A1 publication Critical patent/EP0964896A1/en
Application status is Withdrawn legal-status Critical

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes

Abstract

The invention relates to a method for producing scratch resistant coatings, especially scratch resistant multi-layer enamels, characterized in that the coating agents used contain; 1) a storage module E' in the rubber elastic range of at least 107.5 Pa and a dissipation loss factor tanδ of at least 0.05 at 200C after hardening, the storage module E' and the dissipation loss factor having been measured by dynamic mechanical thermo-analysis on free films with a layer thickness of 40 ± 10νm; 2) one or several polyacrylate resins with a hydroxyl value from 100 to 240, an acid value from 0 to 35 and a number average molecular weight of 1,500 to 10,000 as bonding agents; and 3) as a cross-linking agent one or more free or blocked isocyanates and/or triazine based constituents cross-linking hydroxyl groups of the binding agent to form ether and/or ester. The invention also relates to coating agents which are suited to this method.

Description

A process for producing scratch-resistant coatings, particularly for the production of gene Mehrschichtlackierun-

The present invention is a process for producing scratch-resistant coatings, particularly of scratch-resistant multicoat paint systems.

The present invention also relates to coating compositions suitable for this process.

In recent years, acid in the development and etchbeständiger clear coats for automotive paint series made great progress. More recently, now an increasing desire in the automotive industry for scratch-resistant clearcoats which retain the same in the other properties the existing level of properties.

Currently, there is but for the quantitative evaluation of the scratch resistance of a coating, various test methods, however, such as the examination using the BASF brush test, ilherstellern by means of the washing-brush equipment AMTEC or different test methods for automobile is among others disadvantageous in that the individual test results are often not correlatable , that is, the test results for the same coating can be very different depending on the chosen test method and the existence of a scratch resistance test allowed may not necessarily indicative of the behavior in another scratch test.

There is therefore a need for a method for the quantitative evaluation of the scratch resistance, are possible when using only an examination of the sample reliable statements about the scratch resistance of the coating. In particular, the results of this study should allow reliable conclusions on the scratch resistance of the coating in the various above tests the scratch resistance.

some studies of the physical processes in the generation of scratches and derived from relationships between the scratch resistance and other physical ISIN large coating are now described in the literature. A recent review of various literature on scratch-resistant coatings can be found for example in JL Courter, 23rd Annual International Waterborne, High-Solids and Powder Coatings Symposium, New Orleas 1996th

In addition, "Relationship Between Viscoelastic Property and Scratch Resistance of top coat clear film" Toso Kagaku 1994, for example, in the article by S. Sano et al, 2_9 (12), pages 475 -. 480, the scratch resistance of various thermally curing Mela determined in / acrylate or isocyanate / acrylate systems with the aid of a washing brush test and set the scratch resistance found in relation to the viscoelastic properties of the coating.

For the reasons described there test results the authors conclude that the coatings would then show a good scratch resistance when either the so-called "inter-crosslinking molecular weight" was below 500, or if the glass transition temperature of 15 ° C or is lower, which is in the case of clear coat films automotive is necessary, however, that in order to achieve sufficient hardness of the coatings, the glass transition temperature lies above 15 ° C. Also in the article by M. Rösler, E. G. pawl and Kunz in Farbe + Lack, Volume 10, 1994, pages 837-843, the scratch resistance of various coatings is examined by means of different test methods. DA in was found that hard coatings at the same load greater damage and thus a lower scratch resistance as soft coatings.

Furthermore, even in the conference report by BV Grego- rovich and PJ Mc Gonical, Proceedings of the Advanced Coatings Technology Conference, Illinois, USA, 3 to 5 November 1992, pages 121-125, found that by increasing the plastic nature (toughness) of the scratch resistance of coatings because of the improved plastic flow (annealing of the scraper) is improved, but the increase of the thermoplastic character boundaries are set by the other properties of the coating.

Further Progress are from P. Betz and A. Bartelt, in

Organic Coatings, 22 (1993), pages 27 - 37, various methods for determining the scratch resistance of coatings are known. This article also pointed out that the scratch resistance of loading layers except through the glass transition temperature, for example, still affected by the homogeneity of the network.

In this article it is proposed to increase the scratch resistance of the clear lacquer coatings by the incorporation of siloxane macromonomers, as these siloxane lead macromonomers in an increased homogeneity of the clear coat surface and above 60 ° C to an improved plastic flow. Furthermore, for example, Loren W. Hill, Journal of Coatings Technology, Vol. 64, No. 808, May 1992, pages 29 to 41, the relationship between the storage modulus and crosslinking density known. Notes or arrival gave as scratch-resistant coatings can be obtained, but are not included in this article.

Further, a method for coating surfaces is known from DE-C-39 18 968., be used in the clear lacquers based on hydroxyl-containing resins and poly isocyanates, whose composition is set such that the clear coat layer after curing has a molecular weight of the chain between crosslinks of up to 200 (measured by the method Xylolquell-) has. However, these clearcoats in scratch resistance of the resulting coatings are still in need of improvement.

Finally, from DE-A-43 10 414 and DE-A-42 04 518 non-aqueous clearcoat materials based on hydroxyl-containing acrylate resins and isocyanates for the production of multilayer lacquer coatings, in which the resultant coatings good by an improved scratch resistance and distinguish other characteristics. However, there is also in these clear coats, the desire for a further improved scratch resistance.

The present invention is therefore the object to-reasons, to provide a method for producing coatings with improved scratch resistance available. The coating compositions employed in this method should also paint as a clear coat and / or topcoat for producing a multi-, particularly in the motor vehicle sector, be suitable. Furthermore, the coating should tung medium have a high gloss and good chemical and weather resistance.

In addition, the objective evaluation of the scratch resistance of the cured coating should be independent of the selected test procedure on the basis of physical characteristics possible. Here, this process should be practically used to determine the physical parameters and with reasonable accuracy, a visual evaluation allow adequate characterization of possible scratch resistance.

This object is surprisingly achieved by a process for producing scratch-resistant coatings, which is characterized in that the coating compositions are used which

1 after curing has a storage modulus E 'in the rubber-elastic range of at least 10 7' ^ Pa and a loss factor tans at 20 ° C of at least 0.05, said the storage modulus E 'and the loss factor tans with the dynamic mechanical thermal analysis have been measured on homogeneous free films with a layer thickness of 40 ± 10 microns,

2. as a binder one or more polyacrylate resins having a hydroxyl number from 100 to 240, preferably more than 160 to 220, and particularly preferably 170 to 200, an acid number of 0 to 35, preferably from 0 to 25, and a number average molecular weight of 1,500 to 10,000, preferably 2,500 to 5,000, and

3. one or more free or blocking te isocyanates and / or with the hydroxyl groups of the binder under ether and / or ester formation include as a crosslinking agent crosslinking triazine-based components.

The present application is also a process for preparing a scratch-resistant multi-layer coating as well as suitable for this process coating agent.

It is surprising and was not foreseeable that only by measuring the viscoelastic properties by means of the dynamic mechanical thermal analysis (hereinafter also briefly DMTA called) on free films a universal, representative selection criterion for the provision of coating compositions, to scratch resistant, coatings, is available. The results of the DMTA measurements with the results of different test methods in the scratch resistance can be correlated so that only based on the results of the DMTA measurements statements about the results in other scratch resistance tests, such as the BASF brush test or the AMTEC test, or various test methods of automobile manufacturers, are possible.

In the following, the coating compositions used in the invention of invention process for producing scratch-resistant coatings are first explained in detail.

It is essential to the invention that the coating agent is selected so that the cured coating compositions in the rubber-elastic range, a storage modulus E 'of at least 10 7' 5 Pa, preferably of at least 10 7 'Pa, more preferably of at least 10 7' 7 Pa, and having a loss factor at 20 ° C of at least 0.05, preferably at least 0.07, the storage modulus e 'and the loss factor tans with the dynamic mechanical thermoanalysis on homogeneous free films with a layer thickness of 40 _ + 10 microns have been measured. The loss tangent tan is defined here as the quotient of the dul Verlustmo- E "and the storage modulus E '.

Dynamic mechanical thermal analysis is a widely known measurement method for determining the viscoelastic properties of coatings and examples play as described in Murayama, T., Dynamic Me- chanical Analysis of Polymeric Material, Esevier, New York, 1978 and Loren W. Hill , Journal of Coatings Technology, Vol. 64, No. 808, May, 1992, pages 31 to 33rd

The measurements can be carried out, for example, with the devices MK II, III MK or MK IV from Rheometrics Scientific.

The storage modulus E 'and the loss factor tans are measured on homogeneous free films. The free films are produced in known manner in that the coating composition is applied to substrates and cured, where the coating agent does not adhere. Examples of suitable substrates include glass, Teflon and polypropylene may be mentioned in particular.

Polypropylene has the advantage of ready availability and is therefore normally used as support material.

The layer thickness of the free films used for the measurement is generally 40 + _ 10 microns.

The specific selection of the coating compositions of the value of storage modulus in the rubber-elastic range and the loss factor at 20 ° C of the cured coating composition allows it easily to provide coating agents with the desired good scratch resistance, as both parameters are determined by simple DMTA measurements.

It is surprising that even coatings that have only a moderate or even low plastic component, but have a high to very high storage modulus, provide coatings having a high scratch resistance. With increasing tan delta value and the overall cient high storage modulus E ', however, increases the scratch resistance of the resulting coatings in general. At the same time other performance properties of the coatings can degrade, so that then, due to the other properties of the tan delta value should not exceed 0.1 in this case, a maximum of 0.2, preferably.

The inventive coating used in the process for producing scratch-resistant coatings include tung medium as a binder one or more polyacrylate resins having a hydroxyl number from 100 to 240, preferably more than 160 to 220, and particularly preferably 170 to 200, an acid number of 0 to 35, preferably 0 to 25, and a number average molecular weight from 1,500 to 10,000, preferably 2,500 to

5000. In principle, all polyacrylate resins are suitable with the indicated ratios (OH number, acid number and molecular weight), as long as they lead to crosslinking in coatings with the specified viscoelastic characteristics.

As is well known, but also the respectively selected monomer composition for example, has, inter alia, effect on these characteristics of the viscoelastic Removing the cured coating. For example, increases the storage modulus E 'in general with increasing styrene content of the acrylate from. Therefore, acrylic resins are preferably used as a binder, containing a maximum of 15 wt .-%, based on the total weight of all monomers of the acrylate resin, vinyl aromatic hydrocarbons, particularly styrene, in copolymerized form.

Further, as a binder in the novel coating compositions preferably acrylate with possible liehst many primary hydroxyl groups (particularly preferably at least 50% to 100% of the OH groups are primary OH groups) used, as by a more complete compared to secondary OH groups, the reaction of primary OH groups is also possible to increase the storage modulus e 'of the cured coatings.

Further, particularly preferably used having a glass transition temperature of -40 to +30 ° C, as a binder preferably acrylate resins having a glass transition temperature of at most 70 ° C.

The glass transition temperature can be by a specialist with the help of the formula

1 / Tg = Σ Wn / Tgn

T Q = glass transition temperature of the polymer W n = proportion by weight of the nth monomer TQ Π = glass transition temperature of the homopolymer of the nth monomer

be approximately calculated.

are preferred as a binding agent, finally,

Acrylate resins used which are obtainable by (a) from 25 to 62, preferably 41 wt .-% to 57 4-Hydroxy-n-butyl acrylate or 4-hydroxy-n-butyl methacrylate or a mixture of 4-hydroxy-n-butyl acrylate and 4-hydroxy-n-butyl methacrylate,

(B) 0 to 36 wt., Preferably 0 to 20 wt .-% of a different from (a) hydroxyl-containing ester of acrylic acid or a hydroxyl-containing ester of methacrylic acid or a mixture of such monomers,

(C) 28-75 wt., Preferably 34-54 wt .-% of one of (a) and (b) aliphatic or cycloaliphatic ester of methacrylic acid having at least 4 carbon atoms in the alcohol residue or a mixture of such monomers,

(D) 0 to 3, preferably 0 to 2 wt .-% of an ethylenically unsaturated carboxylic acid or a mixture of ethylenically unsaturated carboxylic acids and

(E) 0 to 20, preferably 5 to 15 wt .-% of one of (a), (b), (c) and (d) various ethylenically unsaturated monomers or a mixture of such monomers

are polymerized to polyacrylate resin, wherein the sum of the weight fractions of components (a), (b), (c), (d) and (e) always being 100 wt .-% results and the composition of the component (c) so is selected, that polymerization of component (c) is a poly methacrylate resin having a glass transition temperature of 0 to +80, preferably is 0 to + 60 ° C, was obtained.

The polyacrylate resins employed according to the invention preferably may be prepared by well known polymerization loading. Polymerization process for the preparation of polyacrylate resins are generally known and widely described (see eg. Houben-Weyl, Methoden der organischen Chemie, 4th edition, Volume 14/1, page 24 to 255 (1961)).

The polyacrylate resins employed according to the invention preferably are in particular produced by means of the Lösungspoly- merisationsverfahrens. Here, it is customary cherweise presented an organic solvent or solvent mixture and heated to boiling. then the monomer mixture to be polymerized, and one or more polymerization initiators are continuously give regis- tered in this organic solvent or solvent mixture. The polymerization takes place at temperatures between 100 and 160 ° C, preferably between 130 and 150 ° C. As polymerization free radical-forming initiators are preferably used. And quantity of initiator are usually chosen so that at the polymerization temperature during the inflow phase as constant as possible of free radicals.

As examples of initiators are: dialkyl peroxides such as di-tert-butyl peroxide., Dicumylperoxide; Hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide. Peresters such as tert. -Butylper- benzoate, tert.-Butyl perpivalate, tert.-Butyl per-3, 5, 5-trimethylhexanoate, tert. -Butylper-2-ethylhexanoate; Bisazo as azobisisobutyro .itril. The polymerization conditions (reaction temperature, feed time of the monomer mixture, amount and type of organic solvents and polymerization initiators, possible use of molecular weight regulators such as mercaptans, thioglycolic and chlorine hydrogens) are selected such that the polyacrylate resins preferably used have a number average molecular weight of from 1500 to 10,000, preferably (determined by Gelper eationschromatographie using a polystyrene standard) comprise 2500 to 5000.

The acid number of the polyacrylate resins employed in this invention may be of the skilled worker by using appropriate amounts of component (d) can be set. The same applies to the adjustment of the hydroxyl. They can be controlled to inserted the amount of component (a) and (b).

As component (a) is 4-hydroxy-n-butyl acrylate, 4-hydroxy-n-butyl methacrylate or a mixture of 4-hydroxy-n-butyl acrylate and used 4-hydroxy-n-butyl methacrylate. As component (a) is preferably used 4-hydroxy-n-butyl acrylate.

As polyacrylate component (a) are also described in European Patent Application EP 0767185 as well as US Patent 5,480,943, hydroxy-functional compounds mentioned 5,475,073 and 5,534,598.

In principle, each of (a) - Component (b) may - under the condition that polymerization of component (b) a poly acrylate resin having a glass transition temperature of 0 to +80, preferably 0 obtained to + 60 ° C hydroxyl-containing esters of acrylic acid or methacrylic acid or a mixture of such monomers. As examples are mentioned: hydroxyalkyl esters of acrylic acid such as hydroxyethyl acrylate and hydroxyalkyl esters of methacrylic acid and Hydroxypropylacry- lat, such as hydroxyethyl methacrylate and hydroxypropyl methacrylate, as well as the esterification products of hydroxyalkyl (meth) - acrylates with one or more molecules of ε-caprolactone.

As component (c) may each, and (a) (b) different aliphatic or cycloaliphatic ester of methacrylic acid with at least 4 C atoms in the alcohol residue or a mixture of such monomers to be set one in principle. Examples are: aliphatic specific esters of methacrylic acid having 4 to 20 carbon atoms in the alcohol radical, such as n-butyl, iso-butyl, tert-butyl tyl, 2-ethylhexyl, stearyl and lauryl methacrylate, and cycloaliphatic esters of methacrylic acid such. B. cyclohexyl. The composition of component (c) is selected such that polymerization of component (c) a polymethacrylate resin having a glass transition temperature of 0 to +80 ° C, preferably 0 to + 60 ° C forth is obtained.

As component (d) in principle be any ethylenically unsaturated carboxylic acid or a mixture of ethylenically unsaturated carboxylic acids may be used. As component (d) are preferably acrylic acid and / or methacrylic acid.

As component (e), in principle each of (a), (b), (c) and (d) various ethylenically unsaturated mono mer, or a mixture of such monomers. Examples of monomers useful as component (e) may be used, be mentioned vinylaromatic hydrocarbons such as styrene, α-alkylstyrene and vinyltoluene, amides of acrylic acid and methacrylic acid such as methacrylamide and acrylamide; Nitriles of methacrylic acid and acrylic acid; Vinyl ethers and vinyl esters. As component (e) are vinylaromatic hydrocarbons preferably used in particular styrene.

The composition of component (e) is preferably selected such that polymerization of component (e) a polymer having a glass transition temperature of from +70 to +120, preferably +80 is obtained to + 100 ° C. The coating compositions used in the process for producing scratch-resistant coatings contain a crosslinking agent as or more free or blocked isocyanates and / or with the hydroxyl groups of the internal demittels under ether and / or ester formation crosslinking triazine-based components. Blocked isocyanates are included so it is in the novel coating compositions are one-component (1K) clearcoats. Are free isocyanates contained, it is in the novel coating compositions are two-component (2K) clearcoat materials.

As a crosslinking agent in principle any usable in the coatings field polyisocyanate or a blend of sol-chen polyisocyanates can be used, provided that the cured coatings have the abovementioned viscoelastic properties. However, it is preferred to use polyisocyanates whose Isocyanatgrup- groups to aliphatic or cycloaliphatic radicals bound to have. Examples of such polyisocyanates

Hexamethylene diisocyanate, isophorone diisocyanate, trimethyl thylhexamethylendiisocyanat, cyanate Dicyclohexylmethandiiso- and 1, 3-bis- (2-Isocyanatopro-pyl-2) benzene

(TMXDI), 1,3- and 1, 4-bis (isocyanatomethyl) cyclohexane and adducts of these polyisocyanates with polyols, in particular low molecular weight polyols such as trimethylolpropane and derived isocyanurate groups of these polyisocyanates and / or biuret groups. Suitable polyisocyanates are especially preferred hexamethylene diisocyanate and isophorone, derived from these diisocyanates containing isocyanurate and / - or biuret groups which preferably contain more than 2 isocyanate groups in the molecule, as well as reaction products of hexamethylene diisocyanate and isophorone diisocyanate or a mixture of hexamethylene diisocyanate and isophorone diisocyanate with 0, 3 to 0.5 equivalents of a low molecular weight polyol having a molecular weight of 62 to 500, preferably from 104 to 204, in particular of a triol such as trimethylolpropane, are used.

For blocking the polyisocyanates in principle any usable for blocking polyisocyanates blocking agents can be used with a sufficiently low blocking temperature disassembly. Such blocking agents are well known in the art and need not be explained in more detail here. preferably blocked polyisocyanates are used, both with a blocking agent (I) as well as with a blocking agent (II) blocked Isocyanatgrup- pen contained, wherein

the blocking agent (I) is a dialkyl malonate or a mixture of dialkyl malonates

the blocking agent (II) of (I) Misc CH-acidic blocking agent, an oxime or a mixture of these blocking agents, and

the equivalent ratio of blocked with (I) and the isocyanate (II) containing blocked isocyanate groups zwichen 1.0: 1.0 and 9.0: 1.0, preferably between 8.0: 2.0 and 6.0: 4 0, more preferably between 7.5: 2.5 and 6.5: 3.5 is located.

The blocked polyisocyanates are preferably used and their preparation are described for example in DE-A-43 10 414, page 4, line 56 to page 5, line 50 will be described. As a blocking agent (I) dialkylmalonates, or a mixture of dialkyl malonates are used. As examples of usable dialkyl malonates dialkylmalonates each having 1 to 6 carbon atoms which diethyl malonate is preferably used to be called in the alkyl groups, such as dimethyl malonate and diethyl malonate.

As a blocking agent (II) different active methylene group-containing blocking agent and oximes and mixtures of these are used by .Blockierungsmitteln (I). Examples of blocking agent (II) are: Acetessigsäuremethyl-, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or dodecyl-ester, acetone oxime, methyl - ethylketoxim, acetylacetone, formaldoxime, acetaldoxime, Benzophenoxim, acetoxim and diisobutyl. As a blocking agent (II) is preferably a realkylestern Acetes- sigsäurealkylester having 1 to 6 carbon atoms in the alkyl radical or a mixture of such Acetessigsäu- or a ketoxime or a mixture of ketoximes employed. Acetaldehyde are particularly preferred alkyl acetate or methyl ethyl ketoxime as the blocking agent (II).

As a further blocking agents still dimethylpyrazole and / or triazoles are contemplated.

In the case of reacting as under etherification with the hydroxyl groups of the binder crosslinking agents are amino resins. Amino resins are well known in the art and are available for purchase products from many companies as a comparison. These are condensation products of aldehydes, especially formaldehyde, for example, urea, Mela, guanamine and benzoguanamine. The amino resins contain alcohol groups, preferably methylol se usually teilwei- or preferably completely etherified with alcohols. There are used especially with lower alcohols, especially with methanol or butanol etherified melamine-formaldehyde resins. Very particular preference with lower alcohols, especially with methanol and / or ethanol and / or butanol-etherified melamine-formaldehyde resins which contain 0.1 to 0.25 bonded to nitrogen atoms are hydrogen atoms in average per triazine ring, are used as crosslinking agents.

In the reacting form ester groups with the hydroxyl groups of the binder crosslinkers tria- zin-base is transesterification, as is preferred, tris (alkoxycarbonylamino) triazine or the like, as described for example in EP-A-604 922nd

The coating compositions usually comprise binder and crosslinking agent in amounts such that the binder or binders in an amount of 40 to 90, preferably 50 to 75 wt .-%, and the crosslinking agent or agents in an amount of 10 to 60, preferably 25 to 50 is provided wt .-%, wherein the weight percentages being based on binder + cross-linker = 100 wt .-%.

The coating compositions of the invention are water-based or, preferably, on a conventional basis, that is formulated on the basis of organic solvents. For the preparation of conventional clear coats are suitable solvent such as the solvents used for the manufacturing position of the acrylate.

The transparent coating compositions employed in this invention contain no or only transparent pigments. The coating compositions may also have other common additives include such as light stabilizers, leveling agents, etc.. but it can also be produced pigmented coating compositions which are not transparent. To achieve this, in principle, all for the production of pigmented lacquers geigneten organic or inorganic pigments or mixtures of such

Pigments are used. As examples of usable pigments are: azo pigments (for example, Pigment Red 57: 1, Pigment Yellow 1, Pigment Yellow 13 and Pigment Red 7), phthalocyanine pigments (e.g., Pigment Blue 15:. 3 and Phtalocyaningrün), carbonyl (eg. . pigment Red 88, pigment Red 177, pigment Yellow 123, pigment Violet 19, pigment Yellow 24, and pigment Orange 51 and 52), dioxazine pigments (for example, pigment Violet 23), titanium dioxide, carbon black, black iron oxide (magnetite, triiron tetroxide), iron oxide ( hematite, diiron trioxide), yellow iron oxide (iron oxide), iron oxide brown (mixed pigment of iron oxide red, yellow iron oxide and black iron oxide), chromium (dichromium trioxide), nickel titanium yellow, chrome titanium yellow and cobalt blue. Furthermore, effect pigments such as metal flake pigments, especially aluminum flake pigments and pearlescent pigments can be used.

In the production of pigmented lacquers that are not transparent, binders, crosslinking agents and the pigment or the mixture of pigments are generally used in such quantities that the, or 45 to 75 percent by the binder in an amount from 39 to 90, preferably .-% of the crosslinking agent or agents in an amount of 9 to 60, preferably 20 to 50 wt .-%, and the

Pigment or mixture of pigments in an amount of 1 to 40, preferably 5 to 15 wt.% Is present, said weight percentages being based on binder + crosslinking agent + pigment or mixture of pigments = 100 wt .-%. Even with the pigmented coating compositions that are not transparent, paint systems, especially single coatings are produced with excellent properties can.

The coating compositions of the invention can be applied to glass and a wide variety of metal substrates such as aluminum, steel, various iron alloys, among others. they are preferred as the clearcoat or topcoat in the field of automotive coating - used (automotive OEM finishing and -When using free isocyanates paint in the field of Automobilreparatur-). Of course, the coating compositions can also be applied to other substrates such as wood, paper, plastics, mineral substrates above in addition to their application to a wide variety of metals. Furthermore, they are also in the coating of packaging containers, as well as in the coating of films for the furniture industry, etc. can be used.

Coating compositions of the invention are preferably but topcoat employed in processes for producing a multilayer coating, in particular in the field of automotive OEM finishing. The present invention therefore also provides a process for the production of multilayer lacquer coatings, in which

(1) a pigmented basecoat is applied to the substrate surface,

(2) from the basecoat, a polymer film is formed,

(3) is applied to the resulting basecoat layer a more transparent topcoat and then (4) the basecoat film and the topcoat film are cured together,

characterized in that an inventive coating composition is used as a topcoat.

In step (1) of the present process in principle, all suitable for the production of two-coat finishes pigmented base paints may be set einge-. Such basecoats are well known in the art. It can be used both waterborne basecoats and basecoats based on organic solvents. Suitable base coats are described for example in US-A-3,639,147, DE-A-33 33 072, DE-A-38 14 853, GB-A-2012191, US-A-3,953,644, EP-A-260 447, DE-A 39 03 804, EP-A-320 552, DE-A-36 28 124, US-A-4,719,132, EP-A-297 576, EP-A-69 936, EP-A-89 497, EP-A-195 931, EP-A-228 003, EP-A-38 127 and DE-A-28 18 100. these patent documents also more information on that at issue base- coat / clear-coat method are to find.

In step (2) of the inventive method applied basecoat film is dried, in stage (1) that is, the basecoat film is removed from a part of the organic solvent or of the water at least in an evaporation phase. The basecoat film is dried overall generally at temperatures from room temperature to 80 ° C.

Thereafter, the topcoat of the invention is applied and the basecoat and topcoat are cured together, usually min by heating to temperatures of 120 to 155 ° C during a time of 20 to 40 wt. By suitable choice of cross-linker also lower inputs are firing temperatures as is customary in the field of repair and painting of plastics, of less than 100 ° C, preferably below 80 ° C, is possible.

The coatings produced using the coating compositions of the invention are characterized by an over conventional coatings significantly improved scratch resistance.

The scratch resistance of the cured coatings can, for example, by means of the on page 28 of the article by P. Betz and A. Bartelt, Progress in Organic Coatings, 22 in Fig 2 (1993), pp. 27 - 37, described BASF brush test, the however, with respect to the weight used was modified (2000g instead of 280 g specified therein) may be evaluated as follows.

In this method, the film surface is damaged with a screen mesh, which is loaded with a mass. The mesh fabric and the paint surface is wetted generously with a detergent solution. The test panel is proposed by means of a motor drive in reciprocal movements under the mesh and pushed back.

For the preparation of the test panels is first an ETL with a thickness of 18-22 microns, then a filler with a layer thickness of 35-40 .mu.m, then a black basecoat with a layer thickness of 20-25 microns, and finally the tested coating compositions having a film thickness applied 45 microns and cured in each case - of the 40th The panels are stored after application of the coatings of at least 2 weeks at room temperature before the test is carried out. The test piece is an eraser (Nos. 11, 31 micron mesh size, Tg 50 ° C) covered with eraser (4.5 x 2.0 cm, broad side perpendicular to the direction of scratching). The applied weight is 2000 g.

Before each test the mesh fabric will be renewed, with the running direction of the fabric mesh is parallel to the direction of scratching. With a pipette approximately 1 ml of a freshly stirred 0.25% Persil solution before the eraser is applied. The number of revolutions of the motor is adjusted so that 80 double strokes are performed in a time of 80 s. After the test, the remaining washing liquid is rinsed with cold tap water and the test panels with compressed air sen trockengebla-.

the gloss in accordance with DIN 67530 is measured before and after damage (measurement direction perpendicular to the direction of scratching).

Claims

Patentansprüche: 1st A process for producing scratch-resistant coatings, characterized in that daß be used medium coating, the1. Aushärtung by a storage modulus E 'in the rubber-elastic range of at least 107'5 Pa and a loss factor at 20 tanδ °C of at least 0.05, said the storage modulus E' and the loss factor with the tanδ dynamic mechanical thermoanalysis on homogeneous free films were measured with a layer thickness of 40 + 10 μm; 2. as a binder, one or more polyacrylate resins having a hydroxyl number from 100 to 240, a Säurezahl from 0 to 35 and a number average molecular weight from 1,500 to 10,000 sowie3. as a crosslinking agent one or more free or blok- kierte isocyanates and / or with the hydroxyl groups of the binder under ether and / or Esterbildung based components which crosslink tri- azinbasis enthalten.2. Coating agent, characterized in that they daß
1. Aushärtung by a storage modulus E 'in the rubber-elastic range of at least 10 7' 5 Pa and a loss factor at 20 tanδ °C of at least 0.05, said the storage modulus E 'and the loss factor with tanδ the dynamic-
Thermo-mechanical analysis have been measured ╬╝m on homogeneous free films with a layer thickness of 40 + _ 10
2. as a binder one or more Polyacrylathar- ze having a hydroxyl number from 100 to 240, a
Säurezahl from 0 to 35 and a number average molecular weight from 1,500 to 10,000 and
3. as a crosslinking agent one or more free or blok- kierte isocyanates and / or with the hydroxyl groups of the binder under ether and / or Esterbildung crosslinking components include tri- azinbasis.
3. The method according to claim 1 or coating according to claim 2, characterized in that the coating composition according to daß Aushärtung a storage modulus E 'in the rubber-elastic range of at least 10 7' Pa, preferably of at least 10 7 '7 Pa, and / or tanδ have a loss factor at 20 °C of at least 0.07.
4. Process or coating composition according to any one of Ansprüche 1 to 3, characterized in that daß the coating compositions as a binder one or more polyacrylate resins having a hydroxyl value of more than 160 to 220, preferably 170 to 200, and / or a S corresponds hold äurezahl from 0 to 25 and / or a number average molecular weight of from 2,500 to 5,000.
5. Process or coating composition according to any one of Ansprüche 1 to 4, characterized in that daß the coating compositions as a binder contain one or several re polyacrylate resins which are: - erhältlich using a maximum of 15 wt .-%, based on the total weight of the monomers used to prepare the polyacrylate, vinyl aromatic hydrocarbons and / - or
-a Glas├╝bergangstemperatur maximum of +70 ┬░C, preferably from -40 to +30 Glas├╝bergangstemperatur ┬░C comprise and / or
- in which at least 50% of the OH groups are primäre OH groups.
6. Process or coating composition according to any one of Ansprüche 1 to 5, characterized in that daß the coating compositions as a binder one or several re contain polyacrylate resins that are erhältlich by
(A) 21-62, preferably 41 to 57 wt .-%, 4-hydroxy-n-butyl acrylate or 4-hydroxy-n-butylmet- hacrylat or a mixture of 4-hydroxy-n-butyl acrylate and 4-hydroxy n-butyl methacrylate,
(B) 0 to 36 wt .-%, preferably 0 to 20 wt .-%, of a non- (a) containing ester of Acrylsäure or a hydroxyl-containing ester of Methacrylsäure or a mixture of such monomers,
(C) from 28 to 75 wt .-%, preferably 34-54 wt .-%, is one of (a) and (b) different rule aliphatic or cycloaliphatic ester of Methacryls├ñure having at least 4 carbon atoms in the alcohol radical or of a mixture of such monomers, (d) from 0 to 3, preferably 0 to 2 wt .-% of an ethylenically unges├ñttigten Carbons├ñure or a mixture of ethylenically unges├ñttigten Carbons├ñuren ​​and
(E) 0 to 20, preferably 5 to 15 wt .-%, of one of (a), (b), (c) and (d) various ethylenically ungesättigten monomer or a mixture of such monomers
are polymerized to polyacrylate resin, wherein the sum of the weight fractions of components (a), (b), (c), (d) and (e) always being 100 wt .-% results and the composition of component (c) so gew├ is ñhlt, da├ƒ in polymerization of component (c) a polymethacrylate resin having a Glas├╝bergangstemperatur from 0 to +80, preferably is 0 to + 60┬░C obtained.
7. A process or coating composition according to claim 6, characterized in that daß the coating compositions as binders include one or more polyacrylate resins erhältlich using a component (e) which is ausgewählt so daß at al Leiniger polymerization of component (e) a polymer having a Glasübergangstemperatur of from +70 to + 120°C is obtained.
8. A process or coating medium according to any of Ansprüche 1 to 7, characterized in that daß the coating compositions as a crosslinking agent containing isocyanates, blocked both with a blocking agent (I) as well as with a blocking agent (II) include isocyanates, wherein the blocking agent (I) is a dialkyl malonate or a mixture of dialkyl malonates, the blocking agent (II) is different from (I) CH-acidic blocking agent, an oxime or a mixture of these blocking agents, and the Äquivalentverhältnis between the with ( I) blocked isocyanate groups and blocked with (II) isocyanate groups is between 1.0: 1.0 and 9.0: 1.0, preferably between 8.0: 2.0 and 6.0:
4.0, more preferably between 7.5: 2.5 and 6.5: 3.5 is located.
9. A process or coating medium according to any of Ansprüche 1 to 7, characterized daß that
Coating agents contain as crosslinking isocyanates with free isocyanate groups.
10. A process or coating medium according to any of Ansprüche 1 to 9, characterized daß that
Coating agents in addition to isocyanates as further crosslinkers tris (alkoxycarbonylamino) triazine.
11. A process for preparing Mehrschichtlackierun- gen, in which
(L) a pigmented basecoat is applied to the Substratoberfläche,
(2) drying the basecoat film or crosslinked,
(3) to the resulting basecoat a transparent topcoat is applied and anschließend (4) is gehärtet the topcoat,
characterized in daß as a topcoat a coating-medium according to one of Ansprüche 2 to 10 is used.
12. The method according to claim 11, characterized in that it daß for the production of multilayer lacquer coatings in the automotive sector is used.
EP98913655A 1997-03-07 1998-03-06 Method for producing scratch resistant coatings, especially for producing multi-layer enamels Withdrawn EP0964896A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE1997109465 DE19709465C2 (en) 1997-03-07 1997-03-07 Coating compositions, methods for the production of multi-layer coatings and use of the coating agent therefor
DE19709465 1997-03-07
PCT/EP1998/001265 WO1998040442A1 (en) 1997-03-07 1998-03-06 Method for producing scratch resistant coatings, especially for producing multi-layer enamels

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EP (1) EP0964896A1 (en)
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WO (1) WO1998040442A1 (en)

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WO1998040442A1 (en) 1998-09-17
US6410646B1 (en) 2002-06-25
JP2001514692A (en) 2001-09-11
BR9808204A (en) 2000-05-16
DE19709465A1 (en) 1998-09-17
US20020095012A1 (en) 2002-07-18
DE19709465C2 (en) 2001-07-12
US6620884B2 (en) 2003-09-16

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