WO2007057200A1

WO2007057200A1 - Physically, thermally and physically and thermally curable aqueous mixtures containing metallic pigments, method for the production thereof and their use

Info

Publication number: WO2007057200A1
Application number: PCT/EP2006/011052
Authority: WO
Inventors: Egon Wegner; Stephan Schwarte; Peter Sonntag; Harry Libutzki; Norbert LÖW
Original assignee: Basf Coatings Ag
Priority date: 2005-11-17
Filing date: 2006-11-17
Publication date: 2007-05-24
Also published as: DE102005054867A1

Abstract

The invention relates to physically, thermally and physically and thermally curable aqueous mixtures containing metallic pigments, comprising: A) at least one polyurethane selected from the group consisting of physically curable, thermally self-crosslinking and/or thermally co-crosslinking saturated, unsaturated and/or olefinically unsaturated compounds of graft ionically and/or non-ionically stabilized polyurethanes as binders, and; B) at least one plate-like metallic pigment. The invention also relates to a method for producing these mixtures and to the use thereof.

Description

Physically, thermally and physically and thermally curable, metallic effect-containing, aqueous mixtures, process for their preparation and their use

The present invention relates to novel, physically, thermally and physically and thermally curable, metallic effect-containing, aqueous mixtures. In addition, the present invention relates to a novel process for the preparation of physically, thermally and physically and thermally curable, metallic effect-containing, aqueous mixtures. Last but not least, the present invention relates to the use of new, physically, thermally and physically and thermally curable, metallic effect-containing, aqueous mixtures as well as produced by the new process physically, thermally and physically and thermally curable, metal effect pigments containing aqueous mixtures, especially as coating materials , Adhesives and sealants for the production of coatings, adhesives and seals.

Physically, thermally and physically and thermally curable, metallic effect pigments, in particular aluminum effect pigments containing, aqueous mixtures which serve as water-based paints for producing effect and color and effect basecoats of multicoat paint systems by the wet-on-wet process are, for example, from the German patent applications DE 199 48 004 A1, DE 100 43 405 C1, in particular column 1, paragraph [0002], or DE 102 40 972 A1.

The known aqueous basecoats are easy to prepare, stable on storage and transportable. After long shearing, as can take place in particular in ring lines of paint shops, they show no deposition of metallic effect pigments. They show a very good application behavior and a very good course.

The corresponding known effect-imparting and color and effect basecoats have an isotropic pigment distribution and a very good overall appearance (Appearance) and are free of paint defects, such as light-dark shades (clouds) and specks.

However, the constantly growing technical and aesthetic demands of the market, in particular the demands of automobile manufacturers and their customers, require a continuous development of the technical and aesthetic achievements that have been achieved so far Levels. In particular, new aqueous basecoats must be made available, which make it possible to produce basecoats which have a particularly pronounced light-dark behavior (metallic flop). However, the advantages achieved by the known waterborne basecoats and the basecoats produced therefrom should not be lost but at least maintained in the same, preferably stronger, form.

Aqueous coating materials based on polyacrylates and polyesters as binders and aminoplast resins as crosslinking agents which contain a platelet-shaped aluminum effect pigment prepared by PVD processes (eg, Metalure® from Eckart) are known (cf., for example, "Preparatory formulation stoving enamel with metalure W 2001; REZ.-NR: 50-09026; DATE: 09.03.99 / cs ", Eckart-Werke, Güntersthal plant, D-91235 Velden), however, they still can not meet the requirements.

It is an object of the present invention to provide novel, physically, thermally and physically and thermally curable mixtures containing metallic effect pigments which are easy to prepare, stable in storage and transportable. After prolonged shearing, they should show no deposition of metallic effect pigments and other constituents.

You should u. a. excellent as coating materials, adhesives and sealants for the production of coatings, adhesive layers and seals.

The coating materials are said to be outstandingly suitable as aqueous basecoats for the production of effecting and color and effect basecoats of multicoat paint systems, in particular by the wet-on-wet method. They should show an excellent application behavior and an excellent course.

The effect-imparting and dye-producing and effecting basecoats should also have comparatively thin layers and comparatively low metallic effect pigment concentrations, a high hiding power, an excellent intercoat adhesion, a particularly high resistance to condensation, an isotropic pigment distribution, a very pronounced light-dark behavior (metallic flop), show a very high metallic brilliance and a very high gloss. They should be free of paint defects, such as light-dark Shades (clouds) and specks, his. Overall, they should even have a chrome-like mirror effect and, if they are also color, have a particularly elegant, effective color effect with low sparkle effect (glitter effect).

Accordingly, the novel, physically, thermally and physically and thermally curable, metallic effect-containing, aqueous mixtures containing

A) at least one polyurethane selected from the group consisting of physically curable, thermally self-crosslinking and / or thermally externally crosslinking, saturated, unsaturated and / or grafted with olefinically unsaturated compounds, ionically and / or nonionically stabilized polyurethanes, as a binder and

B) at least one platelet-shaped metallic effect pigment produced by PVD processes,

found, which are hereinafter referred to as "mixtures according to the invention".

In addition, the novel process for the preparation of physically, thermally and physically and thermally curable, metallic effect-containing, aqueous mixtures was found in which at least one polyurethane (A) and at least one platelet metallic effect pigment (B) dispersed in an aqueous medium and the resulting mixture homogenized and which is hereinafter referred to as "inventive method".

Last but not least, the novel use of the mixtures according to the invention and of the mixtures according to the invention produced by the process according to the invention was found, in particular, as coating materials, adhesives and sealants for the production of coatings, adhesive layers and seals, which is referred to below as "use according to the invention".

Other subjects of the invention will become apparent from the description.

With regard to the prior art, it was surprising and unforeseeable for the skilled person that the object on which the present invention was based, could be solved with the aid of the mixtures according to the invention, the method according to the invention and the use according to the invention.

In particular, it was surprising that the mixtures according to the invention were easy to prepare, in particular by the process according to the invention. In addition, it was surprising that they were stable in storage and transportable even with strongly changing temperatures. There was also no gas evolution. Even after long shearing, they showed no deposition of metallic effect pigments and other ingredients.

They have been excellently suited for numerous applications in various fields of technology. In particular, they were outstandingly suitable as coating materials, adhesives and sealants for the production of coatings, adhesive layers and seals with outstanding performance properties.

The coating materials were outstandingly suitable as water-based paints for the production of effecting and color and effect basecoats of multicoat paint systems, in particular by the wet-on-wet method. They showed an excellent application behavior and an excellent course.

The effect-imparting and color and effect basecoats also showed comparatively thin layers and comparatively low metallic effect pigment concentrations, a high hiding power, an excellent intercoat adhesion, a particularly high resistance to condensation, an isotropic pigment distribution, a very pronounced light-dark behavior (metallic flop), a very high metallic brilliance and a very high gloss. They were free of paint defects, such as light-dark shades (clouds) and specks. Overall, they even showed a chrome-like mirror effect and had, if they were also color giving, a particularly elegant, effective color effect with little sparkle effect (glitter effect).

The mixtures according to the invention comprise at least one, in particular one, polyurethane (A) as binder.

The polyurethane (A) is selected from the group consisting of physically curable, thermally self-crosslinking and / or thermally foreign-crosslinking, saturated, unsaturated and / or grafted with olefinic unsaturated compounds, ionically and / or nonionically stabilized polyurethanes selected.

On the properties of "physically curable", "thermally self-crosslinking" and thermally Fremdvernetzend "and the material conditions that underlie these properties is based on the German patent application DE 100 10 416 A1, page 3, lines 1 1 to 30, and page 5, lines 33 to 41, and page 5, line 47, to page 8, line 6, referenced. The explanations given there in connection with (meth) acrylate (co) polymers apply mutatis mutandis.

Preferably, the polyurethane (A) is thermally externally crosslinking. The thermal crosslinking or curing can still be supported by the physical curing of the polyurethane (A).

Preferably, the polyurethane (A) is grafted with olefinically unsaturated compounds.

An unsaturated, preferably olefinically unsaturated, polyurethane (A) is particularly preferably used as the graft base. Most preferably, the olefinically unsaturated polyurethane (A) contains terminal and lateral, in particular lateral, olefinically unsaturated groups.

Most preferably, the polyurethane (A) is ionic, in particular anionic, stabilized. Above all, carboxylate groups are used for this purpose.

Examples of suitable polyurethanes (A) are known from the German patent applications

DE 40 09 858 A1, column 6, line 18, to column 10, line 23,

DE 44 37 535 A1, page 2, line 27, to page 6, line 22,

DE 199 14 896 A1, column 4, line 26, to column 11, line 5,

DE 100 43 405 C1, column 5, paragraph [0030],

- DE 199 48 004 A1, page 3, line 14, to page 13, line 48,

DE 100 53 890 A1, column 3, paragraph [0016], to column 18, paragraph [0123], or DE 102 23 652 A1, column 3, paragraph [0019], to column 16, paragraph [0101]

known.

Preferably, the anionically stabilized, grafted with olefinic unsaturated compounds, olefinic unsaturated polyurethanes (A) of DE 199 48 004 A1 are used.

The content of the novel mixtures of the polyurethanes (A) can vary very widely and depends on the requirements of the individual case. Preferably, the content is adjusted so that a pigment / binder ratio of 0.05 to 1 and in particular 0.05 to 0.5 results in the mixtures according to the invention.

The mixtures according to the invention contain at least one, in particular a platelet-shaped metallic effect pigment (B) produced by PVD processes.

In particular, the leaflet-shaped metallic effect pigment (B) is an aluminum effect pigment.

The PVD processes (β-physical deposition) are vacuum coating processes for producing thin layers, in which the metal, in particular aluminum, is converted into the gas phase by purely physical methods in order to be deposited on the substrate (see Römpp Online, Georg Thieme Verlag, 2004, "PVD Procedure").

Preferably, the metal is evaporated in a high vacuum on a temporary substrate, whereby a metal layer (B ¹ ) results. Preferably, the temporary substrate is a plastic film. Particularly preferably, the temporary substrate comprises an anti-adhesion layer or release layer on which the metal layer (B ") is deposited.

Subsequently, the metal layer (B ') is removed from the temporary substrate by stripping, preferably with a non-polar organic solvent, after which the resulting metal flakes (B ") are sheared, preferably by stirring the dispersion containing them, whereby the platelet-shaped metallic effect pigment (B ) results. Preferably, the platelet-shaped metallic effect pigment (B) has a thickness of 20 to 80 and in particular 30 to 50 nm.

Preferably, the platelet-shaped metallic effect pigment (B) has a maximum particle size of 20 to 50 and in particular 25 to 45 microns.

The flake-form metallic effect pigment (B) particularly preferably has a customary and known passivation layer, such as, for example, a silicon dioxide layer provided with functional anchor groups or an organophosphorus layer.

The leaflet-shaped metallic effect pigments (B), in particular the aluminum effect pigments (B), are products known per se and are marketed, for example, by Eckart under the trademarks Metalure® or Hydroshine®.

The content of the inventive mixtures of the platelet-shaped metallic effect pigments (B) can vary very widely and depends on the requirements of the individual case. Preferably, the content is adjusted so that a pigment / binder ratio of 0.05 to 1 and in particular 0.05 to 0.5 results in the mixtures according to the invention.

The mixtures according to the invention are aqueous, d. that is, they contain water in which the above-described components (A) and (B) are dispersed or emulsified. The water content and thus the solids content of the mixtures according to the invention can likewise vary very widely and also depend on the requirements of the individual case and in particular on the dispersibility of the above-described constituent (A) and on whether further additives (C) are present. Preferably, the solids content is from 5 to 50, preferably 5 to 40 and in particular 5 to 30 wt .-%, each based on a mixture according to the invention.

The mixtures according to the invention may also contain at least one further additive (C). In the case of using crosslinking polyurethanes (A), the additive (C) is a crosslinking agent. Examples of suitable crosslinking agents (C) are known from German patent application DE 199 48 004 A1, page 14, line 32, to page 16, line 14. Preferably, they are used in the amounts indicated there.

In addition, the mixtures according to the invention may additionally contain at least one pigment, in particular coloring pigment (C), which differs from the platelet-shaped metallic effect pigments (B). Examples of suitable pigments (C), in particular coloring pigments (C), are known from the German patent applications

- DE 199 48 004 A1, page 14, lines 8 to 18, or

DE 102 40 972 A1, page 4, paragraphs [0022] to [0025],

known.

The content of the inventive mixtures of the coloring pigments (C) can vary very widely and depends on the requirements of the individual case.

Preferably, the content is adjusted so that the weight ratio (B): (C) = 1

: 0.01 to 1: 3, preferably 1: 0.1 to 1: 2.5 and especially 1: 0.5 to 1: 2. Aesthetically appealing, elegant, effective color effects with low

Sparkle effect (glitter effect) is achieved when the weight ratio (B): (C) = 1

: 0.8 to 1: 1, 2, in particular 1: 1.

Last but not least, the mixtures according to the invention may contain at least one customary and known coating additive in effective amounts as additive (C). Examples of suitable paint additives (C) are known from German patent application DE 199 48 004 A1, page 16, line 15, to page 17, line 5.

The preparation of the mixtures according to the invention is preferably carried out by means of the method according to the invention. The above-described

Components (A) and (B) and optionally (C) in an aqueous medium, in particular in water, dispersed, after which the resulting mixture is homogenized. From a methodological point of view, the method according to the invention has no methodical particularities, but can be determined by means of the customary and known mixing methods and mixing units, such as stirred kettles, dissolvers, stirred mills,

Kneaders, static mixers or extruders. In the process of the invention, the platelet-shaped metallic effect pigment (B) is preferably used in the form of pigment pastes. In particular, they are used in the form of the pigment pastes described in German Patent Application DE 102 40 972 A1, page 3, paragraph [0019], to page 5, paragraph [0031], which contains at least one platelet-shaped metallic effect pigment (B) instead of there described effect pigments or in addition to these.

Because of the numerous particular advantages of the mixtures according to the invention and the mixtures prepared by means of the process according to the invention, in particular of the mixtures according to the invention prepared by the process according to the invention, these numerous uses can be supplied.

They are preferably used as coating materials, adhesives and sealants for the production of coatings, adhesive layers, seals for the coating, bonding and sealing of substrates of all kinds. Examples of suitable substrates are known from German patent application DE 199 48 004 A1, page 17, lines 12 to 36.

They are particularly preferably used as coating materials for the production of single-layered and multi-layered, in particular multi-layer, effect-imparting coatings. With very particular preference they are used as waterborne basecoats for the production of effecting and color and effect basecoats of multicoat paint systems, preferably multi-layer finishes for motor vehicles, in particular high-grade passenger cars.

With very particular preference the multicoat paint systems are prepared by wet-on-wet processes in which

(1) applying at least one aqueous basecoat to a primed or unprimed substrate, thereby resulting in at least one aqueous basecoat film (1),

(2) applying at least one clearcoat to the aqueous basecoat film (1) resulting in at least one clearcoat film (2), and (3) at least the aqueous basecoat films (1) and the clearcoat film (s) (2) co-cure, resulting in the basecoat (1) and the clearcoat (2).

Examples of such wet-on-wet processes are known from German patent application DE 199 48 004 A1, page 17, line 37, to page 19, line 22.

Preferably, the resulting effect and color and effect coatings according to the invention, in particular the multicoat systems _{according to} the invention, have a flop index FLχ- _Rite > 15, preferably> 17 and in particular> 19, calculated in each case according to the formula of the company X-Rite:

FL _X-Rite = 2.69 (L * ₁₅ ^° -L * ₁₁₀ ^o) ¹ ^'11 / (LV) ^0186th

Preferably, in the case of the color and effect coatings according to the invention, in particular the multicoat paint systems according to the invention, the measured value L * _{15 of the} formula X-Rite is> 100, preferably> 110 and in particular> 120. Surprisingly, the relevant dyeing and effecting agents according to the invention Coatings, in particular the multicoat paint systems according to the invention, no more light-dark shades (clouds).

Overall, the effect-imparting and color-producing and effect-imparting coatings according to the invention, in particular the multicoat paint systems according to the invention, have an outstanding performance property profile, which is excellently balanced in terms of mechanics, optics, corrosion resistance, intercoat adhesion and substrate adhesion. Of particular note here is the outstanding overall visual appearance (appearance) and the particularly pronounced viewing-angle-dependent light-dark behavior (metallic flop), which can be attributed to the inventive basecoat free from paint defects. The metallic flop can be so pronounced that a chrome-like mirror effect is achieved. In addition, the color and effect coatings according to the invention, in particular the multi-layer coatings according to the invention, exhibit aesthetically pleasing, elegant, effective color effects with a low sparkle effect (glitter effect).

Examples and Comparative Experiments example 1

The preparation of the water-based paint 1

A stirred vessel was charged with 24 parts by weight of a thickening agent (paste of a sodium magnesium phyllosilicate, Laponite® RD, 3% in water). 19 parts by weight of the polyurethane dispersion according to the German patent application DE 40 09 858 A1, column 16, lines 10 to 35, "C. Preparation of an aqueous polyurethane resin dispersion ", added with stirring. Subsequently, a mixture of 3.2 parts by weight of a commercially available water-dilutable melamine-formaldehyde resin (Cymel® 327) and 1.0 part by weight of an aqueous polyester resin dispersion according to German Patent Application DE 40 09 858 A1, column 16, lines 37 to 59, "D. Preparation of an aqueous polyester resin dispersion, 2.0 parts by weight of butylglycol and 0.2 parts by weight of dimethylethanolamine (10 percent in deionized water) are added with stirring. The resulting mixture was blended with 3.0 parts by weight of the polyurethane-modified polyacrylate resin according to German patent application DE 44 37 535 A1, page 7, line 55, to page 8, line 23, "D. Preparation of the polyurethane-modified polyacrylate according to the invention ", offset. 1.35 parts by weight of the commercial wetting agent Surfynol® 100 (50% in butylglycol), 1.0 part by weight of polypropylene glycol (number average molecular weight: 900 daltons), 1.2 parts by weight of a 50 percent solution of the commercial polyurethane thickener Nopco were added to the resulting mixture ® DSX 1550 in butylglycol and 0.5 part by weight of the commercial, non-associative thickener Viscalex® HV30 (methacrylate copolymer based on (C 1 -C 6) -alkyl (meth) acrylate and (meth) acrylic acid according to German patent DE 100 43 405 C1, column 11, paragraph [0075]) and, in portions, 20 parts by weight of water. The resulting mixture was coated with a paste of 8.0 parts by weight of a flake-form aluminum effect pigment (B) prepared by a PVD process (Alu-Hydroshine® WS3001 from Eckart) and 8.0 parts by weight of a mixture according to German patent application DE 102 40 972 A1, page 7, paragraph [0053], from Viscalex® HV30, an organic amine, Surfynol® 100, the nonionic surfactant (nonionic surfactant) Hydropalat® 3037 from Cognis and water. The resulting mixture was homogenized to give the waterborne basecoat 1 having the following physical-technical characteristics:

Solids content (2 hours / 120 ^° C.): 14 to 16% by weight, - solvent content: 14 to 16% by weight,

Flash point:> 70 ^° C., binder content: 13% by weight Pigment content: 0.8% by weight and pigment / binder ratio: 0.06

For the application, the aqueous basecoat ^{1 was} adjusted to a pH of 7.8 to 8.2 with a ten percent aqueous dimethylethanolamine solution and deionized water and an application viscosity of 60 mPas at 23 ° C. and a shear of 1000 s ^-1 .

To simulate the loop stability of the waterborne basecoat material 1, 750 ml of it were poured into a commercially available 1 liter lacquer box and stirred for 20 days at room temperature with a helical stirrer. The peripheral speed was 0.1 m / s. Even after 20 days, there were no deposits of particles on the bottom of the can. The waterborne basecoat 1 was therefore outstandingly suitable for the production of non-speckle effect multicoat paint systems.

Comparative experiment V 1

The preparation of the water-base varnish V 1

In a stirred vessel 23.2 parts by weight Laponite® RD were submitted. For this purpose, 20.5 parts by weight of the polyurethane dispersion according to German Patent Application DE 40 09 858 A1, column 16, lines 10 to 35, "C. Preparation of an aqueous Polyurethanharzdispersion «added with stirring. Subsequently, a mixture of 3.7 parts by weight of Cymel® 327 and 1.0 part by weight of an aqueous polyester resin dispersion according to German patent application DE 40 09 858 A1, column 16, lines 37 to 59, "D. Preparation of an aqueous polyester resin dispersion, 2.0 parts by weight of butylglycol and 0.2 parts by weight of dimethylethanolamine (10 percent in deionized water) are added with stirring. The resulting mixture was mixed with 3.7 parts by weight of the polyurethane-modified polyacrylate resin according to German Patent Application DE 44 37 535 A1, page 7, line 55, to page 8, line 23, "D. Preparation of the polyurethane-modified polyacrylate according to the invention ", offset. To the resulting mixture was added, while stirring, 1.0 part by weight of polypropylene glycol (number average molecular weight: 900 daltons), 2.3 parts by weight of isobutanol, 3.0 parts by weight of 2-ethylhexanol, 2.1 parts by weight of n-propoxypropanol, 1.6 parts by weight of butoxypropanol, 1 , 0 parts by weight of a modified polydimethylsiloxane, 0.66 parts by weight of the 50 percent solution of the commercial polyurethane thickener Nopco® DSX1550 in butyl glycol and 0.65 parts by weight of the commercial thickener Viscalex® HV 30 and added portionwise 20 parts by weight of water. The resulting mixture was treated with an aluminum effect pigment paste of 3.6 parts by weight of Alu-Hydrolux® 612 from Eckart, 0.5 parts by weight of Alu-Hydrolux® 2154 from Eckart, 3.4 parts by weight of the polyester resin dispersion according to German patent application DE 40 09 858 A1, Column 16, lines 37 to 59, "D. Preparation of an aqueous polyester resin dispersion, 4.0 parts by weight of butylglycol and 0.5 part by weight of dimethylethanolamine (10% in deionized water) are added with stirring.

The mixture was homogenized, resulting in water-based varnish V 1. The was adjusted to a pH of 7.8 to 8.2 with a ten percent aqueous dimethylethanolamine solution and deionized water and an application viscosity of 90 mPas at 23 ° C and a shear of 1000 s " ¹ .

To simulate the ring line stability of the applicable water-based lacquer V 1, 750 ml of this were filled into a commercially available 1 liter lacquer box and during

Stirred for 20 days at room temperature with a helical stirrer. The

Peripheral speed was 0.1 m / s. Even after 20 days showed no

Deposits of particles at the bottom of the can. The water-based lacquer V 1 was therefore outstandingly suitable for the production of non-speckle effect multicoat paint systems.

Example 2 and Comparative Experiment V 2

The Preparation of the Multicoat Paint Systems 1 (Example 2) and V 1 (Comparative Experiment V 2) For the preparation of the multicoat system 1 of Example 2, the waterborne basecoat 1 of Example 1 was used.

For the preparation of the multi-layer coating V 1 of Comparative Experiment V 2 of the water-based paint V 1 of Comparative Experiment V 1 was used.

Example 2:

On body panels of dimension 30 times 70 cm, which had been coated with a customary and known, cathodically deposited and baked electrodeposition coating, was a commercial water filler from BASF

Coatings AG applied, after which the resulting filler layers during 5 minutes at 20 ⁰ C and a relative humidity of 65% and flashed in a

Convection oven were dried at 80 ⁰ C for 20 minutes. After cooling the

Body panels to 20 ⁰ C, the waterborne basecoat 1 was applied in two spray coats. The first application was carried out pneumatically (distance: 0.5 m;

Paint: 300 Nl / min; Atomizing air quantity: 320 Nl / min; Atomizing air pressure: 4.8 bar;

Horn air quantity: 380 Nl / min; Horn air pressure: 5.2 bar), corresponding to one

Dry film thickness of 2 to 3 μm. It was then flashed for 2 minutes at 20 ⁰ C and a relative humidity of 65%. The second application was also pneumatic under the conditions mentioned above, corresponding to a dry film thickness of 2 to 3 microns. Subsequently, the

Water-based lacquer layers for 10 minutes at 80 ⁰ C dried. After this

Cooling of the body panels to 2O ⁰ C, the aqueous basecoat films were overcoated with a commercially available two-component clearcoat from BASF Coatings AG, corresponding to a dry film thickness of 40 microns. After that, the

Surfacer layers, aqueous basecoat films and the clearcoat films during 30

Minutes at 140 ⁰ C baked together. After sanding the

Clearcoats were a commercially available scratch-resistant two-component clearcoat of

Company PPG applied and baked for 30 minutes at 140 ° C, whereby the multi-layer coating 1 resulted.

Comparative experiment V 2:

On body panels of dimension 30 times 70 cm, which had been coated with a customary and known, cathodically deposited and baked electrodeposition coating, a commercial filler from BASF Coatings AG was applied, after which the resulting filler layers for 5 minutes at 20 ° C and a relative Humidity of 65% aired and in a convection oven baked at 140 ⁰ C for 30 minutes. After cooling the body panels to 2O ⁰ C, the water-based paint V 1 was applied in two spray coats. The first application was carried out by means ESTA (bell speed: 45,000 ^{min -1;} shaping air ESTA: 120 Nl / min; voltage: 65 kV; pitch: 0.25 m; outflow quantity of paint: 170 ml / min), corresponding to a dry layer thickness of 8-10 microns. The second application was carried out pneumatically (distance: 0.32 m, discharge amount of paint: 540 Nl / min, atomizing air quantity: 300 Nl / min, atomizing air pressure: 4.8 bar, horn air quantity: 395 Nl / min, horn air pressure: 5.2 bar), corresponding to a dry film thickness of 4 to 6 microns. The aqueous basecoat films were flashed off after each of the first and second application for 2 minutes each. They were then dried at 80 ^° C. for 10 minutes. After cooling the body panels to 2O ⁰ C, the aqueous basecoat films were overcoated with a commercially available two-component clearcoat from BASF Coatings AG, corresponding to a dry film thickness of 40 microns. Subsequently, the aqueous basecoat films and clearcoat films were baked together at 13O ⁰ C for 30 minutes, resulting in the multi-layer coating V 1 resulted.

Comparison of Multicoat Paint Systems 1 and V 1:

The multicoat paint systems 1 and V 1 were measured using a spectrophotometer from X-Rite (eg MA48 Multi-Angle Spectrophotometer). From the brightness values for the viewing angles 15 °, 45 ° and 110 ° determined on the basis of the two multicoat paint systems, the so-called X-Rite flop index can be calculated according to the formula

FL _x . _Rite = 2.69 (L * ₁₅ -L * ₁₁ o.) ^1l11 / (L * 45-) ° ' ^ββ

be calculated. In the multicoat paint system 1, a FL _x resulted. _Ri ( _e = 20 to 21) whereas in the multicoat _{paint system} V 1 only one FLχ- _Ri t _e = 11 to 12 resulted.

Thus, in the case of the multicoat system 1 of Example 2, the metallic flop was much more pronounced than in the multicoat system V 1 of Comparative Experiment V 2 - even though the layer thickness of the basecoat in the multicoat system 1 was very much less than the layer thickness of the multicoat system 1 Basecoat in multicoat paint V 1 with a maximum of 16 μm.

Furthermore, the multicoat paint systems 1 and V 1 were observed under diffuse light from a distance of 2 to 3 m in plan view (80 °) and oblique view (40 °) with respect to the light-dark shades (clouds) are visually assessed and graded (grade 1: no clouds visible, to grade 5: clouds very clearly visible). For both multicoat paint systems, the rating was 3 in both supervision and oblique view. This meant that there were no significant clouds.

Examples 3 to 9

The preparation of the aqueous basecoat series 2 to 8

Example 3 (water-based paint series 2):

For the preparation of the aqueous basecoat series 2 with the waterborne basecoats 2.1 to 2.4 (Examples 3.1 to 3.4), the aqueous basecoat 1 of Example 1 was a pigment paste based on the aqueous, acrylated polyurethane dispersion according to German Patent Application DE 40 10 176 A1, page 8, lines 37 to 43, i. V. m. Page 7, lines 46 to 65, containing, based on the pigment paste, 30 wt .-% of transparent titanium dioxide (PW6), added in varying amounts, so that the following weight ratios of aluminum effect pigment (B): titanium dioxide (C) resulted:

Example water-based paint (B): (C)

3.1 2.1 1: 0, 125

3.2 2.2 1: 0, 25

3.3 2.3 1: 0, 5

3.4 2.4 1: 1

Example 4 (water-based paint series 3):

For the preparation of the aqueous basecoat series 3 with the yellow water-based paints 3.1 to 3.4 (Examples 4.1 to 4.4), the water-based paint 1 of Example 1 was a pigment paste based on the aqueous, acrylated polyurethane dispersion according to German Patent Application DE 40 10 176 A1, page 8, lines 37 to 43, i. V. m. Page 7, lines 46 to 65, containing, based on the pigment paste, 37 wt .-% opacifying iron oxide yellow (PY42), added in different amounts, so that the following weight ratios of aluminum effect pigment (B): iron oxide Yellow (C) resulted:

Example water-based paint (B): (C) 4.1 3.1 1: 0.125 4.2 3.2 1: 0.25

4.3 3.3 1: 0.5

4.4 3.4 1: 1

Example 5 (water-based paint series 4):

For the preparation of the water-based paint series 4 with the yellow waterborne basecoats 4.1 to 4.4 (Examples 5.1 to 5.4), the waterborne basecoat 1 of Example 1 was a pigment paste based on the aqueous, acrylated polyurethane dispersion according to the German patent application DE 40 10 176 A1, page 8, lines 37 to 43, i. V. m. Page 7, lines 46 to 65, containing, based on the pigment paste, 34 wt .-% isoindolinone yellow (PY110), added in different amounts, so that the following weight ratios of aluminum effect pigment (B): isoindolinone yellow (C) resulted:

Example water-based paint (B): (C)

5.1 4.1 1: 0.125

5.2 4.2 1: 0.25

5.3 4.3 1: 0.5

5.4 4.4 1: 1

Example 6 (water-based paint series 5):

For the preparation of the water-based paint series 5 with the red waterborne basecoats 5.1 to 5.6 (Examples 6.1 to 6.6), the waterborne basecoat 1 of Example 1 was a pigment paste based on the aqueous polyurethane dispersion according to German Patent Application DE 40 09 858 A1, column 16, lines 10 to 35, containing, based on the pigment paste, 24 wt .-% quinacridone red (PR122), added in varying amounts, so that the following weight ratios of aluminum effect pigment (B): quinacridone red (C) resulted:

Example water-based paint (B): (C)

6.1 5.1 1: 0.01

6.2 5.2 1: 0.1

6.3 5.3 1: 0.125

6.4 5.4 1: 0.25

6.5 5.5 1: 0.5

6.6 5.6 1: 1 Example 7 (water-based paint series 6):

For the preparation of the water-based paint series 6 with the blue water-based paints 6.1 to 6.4 (Examples 7.1 to 7.4), the water-based paint 1 of Example 1 was a pigment paste based on the aqueous polyurethane dispersion according to German Patent Application DE 40 09 858 A1, column 16, lines 10 to 35, containing, based on the pigment paste, 13.5 wt .-% indanthrone blue (PB60), added in varying amounts, so that the following weight ratios of aluminum effect pigment (B): indanthrone blue (C) resulted:

Example water-based paint (B): (C)

7.1 6.1 1: 0, 125

7.2 6.2 1: 0, 25

7.3 6.3 1: 0, 5

7.4 6.4 1: 1

Example 8 (water-based paint series 7):

For the preparation of the water-based paint series 7 with the green water-based paints 7.1 to 7.4 (Examples 8.1 to 8.4), the water-based paint 1 of Example 1 was a pigment paste based on the aqueous polyurethane dispersion according to German Patent Application DE 40 09 858 A1, column 16, lines 10 to 35, containing, based on the pigment paste, 22.4 wt .-% chlorinated copper phthalocyanine green (PG7), added in varying amounts, so that the following weight ratios of aluminum effect pigment (B): chlorinated copper phthalocyanine green (C) resulted:

Example water-based paint (B): (C)

8.1 7.1 1: 0, 125

8.2 7.2 1: 0, 25

8.3 7.3 1: 0, 5 8.4 7.4 1: 1

Example 9 (water-based paint series 8):

For the preparation of the water-based paint series 8 with the black water-based paints 8.1 to 8.4 (Examples 9.1 to 9.4), the water-based paint 1 of Example 1 was a pigment paste based on the aqueous polyurethane dispersion according to German Patent Application DE 40 09 858 A1, column 16, lines 10 to 35, containing, based on the pigment paste, 10 wt .-% color cast (PB7), in different Amounts added so that the following weight ratios of aluminum effect pigment (B): color cast (C) resulted:

Example water-based paint (B): (C) 9.1 8.1 1: 0.125

9.2 8.2 1: 0.25

9.3 8.3 1: 0.5

9.4 8.4 1: 1

To simulate the loop stability of the waterborne basecoats of series 2 to 8, 750 ml of a water-based lacquer were each introduced into a commercially available 1 liter lacquer box and stirred for 20 days at room temperature with a helical stirrer. The peripheral speed was 0.1 m / s. Even after 20 days, no deposits of particles appeared at the bottom of the cans. The aqueous basecoats were therefore outstandingly suitable for the production of non-speckle effect multicoat paint systems.

Examples 10 to 16

The production of the multicoat paint systems of the series 2 to 8

For the preparation of the white metallic colored multicoat paint systems 2.1 to 2.4 (Examples 10.1 to 10.4), the aqueous basecoat materials 2.1 to 2.4 of Examples 3.1 to 3.4 were used.

For the preparation of the yellow metallic colored multicoat paint systems 3.1 to 3.4 (Examples 1 1.1 to 11.4), the aqueous basecoat materials 3.1 to 3.4 of Examples 4.1 to 4.4 were used.

For the preparation of the yellow metallic colored multicoat paint systems 4.1 to 4.4 (Examples 12.1 to 12.4), the waterborne basecoats 4.1 to 4.4 of Examples 5.1 to 5.4 were used.

For the preparation of the red-metallic-colored multicoat paint systems 5.1 to 5.6 (Examples 13.1 to 13.6), the aqueous basecoat materials 5.1 to 5.6 of Examples 6.1 to 6.6 were used. For the preparation of the blue-metallic-colored multicoat paint systems 6.1 to 6.4 (Examples 14.1 to 14.4), the aqueous basecoat materials 6.1 to 6.4 of Examples 7.1 to 7.4 were used.

For the preparation of the green-metallic-colored multicoat paint systems 7.1 to 7.4 (Examples 15.1 to 15.4), the aqueous basecoat materials 7.1 to 7.4 of Examples 8.1 to 8.4 were used.

For the preparation of the black metallic colored multicoat paint systems 8.1 to 8.4 (Examples 16.1 to 16.4), the aqueous basecoat materials 8.1 to 8.4 of Examples 9.1 to 9.4 were used.

The waterborne basecoats of series 2 to 8 were prepared analogously to the instructions of Example 2.

The spectrophotometric investigations were carried out as described in Example 2. Table 1 gives an overview of the obtained values of the X-Rite flop index and of the brightness value L * _{15 ° which is} essential for the formation of light-dark shades (clouds). In addition, gloss and haze (20 °) according to DIN 67530, the course with the measuring device: Byk / Gardner - Wave scan plus (Long wave = LW, short wave = SW) and caused by the Schwitzwasserkonstantklima test (SKK) hue deviation mdE ¹ determined. The results are also shown in Table 1.

Table 1: Essential performance properties of the multicoat paint systems of series 2 to 8

Series No .: FL _X-Rite L * ₁₅ . Gloss Haze course mdE ¹

Color (example) LW SW

Series 2:

White 2.1 (10.1) 19, 3 147, 1 103 589 2.5 22.4 0, 63

2. 2 (10.2) 19, 2 146, 9 104 602 2.6 24 0, 9

2.3 (10.3) 17, 1 143, 2 101 537 3.4 23.1 0, 69 2.5 (10.4) 15 138.9 100 499 4.8 23.2 0.53

Series 3:

Yellow 3.1 (11.1) 19.5 146.4 103 589 4.4 22.1 0.74

3.2 (11.2) 18.8 145.4 102 571 208 24 0.97

3.3 (11.3) 17.1 141.7 101 537 2.6 23.4 0.69

3.4 (11.4) 15 136.7 99 487 3.4 26.1 0.71

Series 4:

yellow

4.1 (12.1) 19.9 147.6 103 588 3.8 38.9 1.79

4.2 (12.2) 19.4 146 102 563 2.6 25.3 0.94

4.3 (12.3) 19.1 144.2 102 564 2.2 23 1.16 4.4 (12.4) 18 140.4 101 528 1.9 14.6 1.02

Series 5:

red

5.1 (13.1) 20.9 139.4 100 523 2.6 22 0.63 5.2 (13.2) 21.1 121.4 96 379 5.8 23 0.77

5.3 (13.3) 20.4 145.6 99 508 1.8 15 1.69

5.4 (13.4) 20.3 142.8 101 539 1.8 14.5 0.98

5.5 (13.5) 19.9 136.7 102 571 2.6 13.8 0.81

5.6 (13.6) 19.3 129.1 97 4.52 1.3 13 0.88

Series 6:

blue

6.1 (14.1) 22.1 145.6 101 552 4.6 20.5 0.9

6.2 (14.2) 22.4 142 100 523 2.6 22 0.63 6.3 (14.3) 22.7 135.5 98 452 3 26 0.75

6.4 (14.4) 22.7 125.7 96 379 5.8 23 0.77

Series 7:

Green 7.1 (15.1) 21.5 147.3 104 618 1.7 16.7 0.78

7.2 (15.2) 21.6 146.3 103 601 2.3 18.5 1.09

7.3 (15.3) 21.5 143.4 102 573 2.9 22.4 0.82 7.4 (14.4) 21, 4 139 100 524 3 20.4 1, 07

Series 8:

Black 8.1 (16.1) 22.4 139, 6 102 562 2.5 20, 5 0, 75

8..2 (16.2) 23.3 131, 8 100 522 2 15 0, 97

8.3 (16.3) 23.7 120, 1 98 439 2.5 20, 5 0, 78

8.4 (16.4) 24.2 103, 6 94 322 3.5 20 0, 45

The results compiled in Table 1 support the fact that the

Multicoat paint systems had an excellent flop effect, which was accompanied - if at all - by a very low sparkle effect. This resulted

Color metallic effects of a very elegant, pastel-colored optical impression. There were almost no clouds observed (grades 1 to 3). Gloss and Haze and the course were also excellent. The load of the multi-layer coatings in the Schwitzwasserkonstantklima test had only a very small color shift to

Result, which underpinned the particular condensation resistance of the multi-layer coatings. Overall, the multi-layer coatings had an excellent overall appearance. They were therefore excellent for painting

Automobiles of the upper class suitable. Their contours were replaced by the

Waterborne paints series 2 to 8, in particular the

Water-based paints 2.4, 3.4, 4.4, 5.6, 6.4, 7.4 and 8.4, traced pastelike in an aesthetically particularly impressive way.

Claims

claims

1. Physically, thermally and physically and thermally curable,

Containing effect pigments, aqueous mixtures containing

A) at least one polyurethane selected from the group consisting of physically curable, thermally self-crosslinking and / or thermally externally crosslinking, saturated, unsaturated and / or ionically and / or nonionically stabilized polyurethanes grafted with olefinically unsaturated compounds, as binders,

B) at least one platelet-shaped metallic effect pigment produced by PVD processes.

2. Mixtures according to claim 1, characterized in that the leaflet-shaped metallic effect pigment (B) is an aluminum effect pigment.

3. Mixtures according to claim 1 or 2, characterized in that the leaflet-shaped metallic effect pigment (B) has a thickness of 20 to 80 nm.

4. Mixtures according to one of claims 1 to 3, characterized in that the platelet-shaped metallic effect pigment (B) has a maximum particle size of 20 to 50 microns.

5. Mixtures according to one of claims 1 to 4, characterized in that the platelet-shaped metallic effect pigment (B) was prepared by vapor deposition of the metal in a high vacuum on a temporary substrate and removing the resulting metal layer (B ') from the temporary substrate.

6. Mixtures according to claim 5, characterized in that the temporary substrate is a plastic film.

7. Mixtures according to claim 5 or 6, characterized in that the temporary substrate comprises an anti-adhesive layer or release layer.

8. Mixtures according to one of claims 5 to 7, characterized in that the metal layer (B ') has been removed by stripping from the temporary substrate, after which the resulting metal sheets (B ") were sheared, resulting in the leaflet-shaped metallic effect pigment (B).

9. Mixtures according to one of claims 1 to 8, characterized in that the metallic effect pigment (B) has at least one passivation layer.

10. Mixtures according to one of claims 1 to 9, characterized in that the mixtures still contain at least one of the metallic effect pigment (B) different pigment (C).

11. Mixtures according to claim 10, characterized in that the pigment (C) is coloring.

12. Mixtures according to claim 10 or 11, characterized in that the weight ratio (B): (C) = 1: 0.01 to 1: 3.

13. Mixtures according to claim 12, characterized in that the weight ratio (B): (C) = 1: 0.1 to 1: 2.5.

14. Mixtures according to claim 13, characterized in that the weight ratio (B): (C) = 1: 0.5 to 1: 2.

15. A process for the preparation of physically, thermally and physically curable, metallic effect pigments containing aqueous mixtures according to one of claims 1 to 14, characterized in that at least one polyurethane (A) and at least one platelet-shaped metallic effect pigment (B) in an aqueous Medium dispersed and homogenized the resulting mixture.

16. Use of the physically, thermally and physically and thermally curable, metallic effect pigments containing aqueous mixtures according to any one of claims 1 to 14 and the method according to claim 15 produced physically, thermally and physically and thermally curable, metallic effect pigments containing aqueous mixtures as coating materials , Adhesives and sealants for the production of

Coatings, adhesive layers and seals.

17. Use according to claim 16, characterized in that the coating materials are used for the production of single-layered and multi-layered effect-giving as well as color and effect-imparting coatings.

18. Use according to claim 17, characterized in that the coating materials are water-based paints, which serve to produce effect as well as color and effect basecoats of multicoat paint systems.

19. Use according to claim 18, characterized in that the multicoat paint systems are prepared by wet-on-wet processes in which

(1) applying at least one water-based paint to a primed or unprimed substrate, whereby at least one

Waterborne basecoat layer (1) results,

(2) applying at least one clearcoat to the aqueous basecoat film (1) resulting in at least one clearcoat film (2), and

(3) at least the aqueous basecoat films (1) and the clearcoat film (s) (2) co-cure, resulting in the basecoat (1) and the clearcoat (2).

20. Use according to one of claims 17 to 19, characterized in that the effect and the color and effect coatings have a flop index FL _{x RKe} > 15, calculated according to the formula of the company X-Rite:

FL _x . _Rite = 2.69 (L * ₁₅ -L * iio0 ¹ " ¹¹ / (L * 45θ ° ^l86 -

21. Use according to claim 20, characterized in that FLχ. _Rite > 17.

22. Use according to claim 21, characterized in that FLχ. _Rite > 19.

23. Use according to one of claims 17 to 22, characterized in that in the color and effect coatings of the measured value L * i ₅ - the formula of the company X-Rite> 100.

24. Use according to claim 23, characterized in that the measured value L ^* ₁₅ -> 110.