EP3810337A1

EP3810337A1 - Method for producing an optimized coating, and coating which can be obtained using said method

Info

Publication number: EP3810337A1
Application number: EP19731762.1A
Authority: EP
Inventors: Dirk EIERHOFF; Daniel Briesenick; Georg Wigger; Christian Bornemann; Siegfried RIEDIGER
Original assignee: BASF Coatings GmbH
Current assignee: BASF Coatings GmbH
Priority date: 2018-06-25
Filing date: 2019-06-24
Publication date: 2021-04-28
Also published as: JP7112173B2; WO2020002252A1; MX2020014212A; CN112423900A; US20210260611A1; JP2021528246A

Abstract

The invention relates to a method for producing at least one coating (B1) on a substrate, having at least the steps (1) to (5), namely providing a coating agent composition (BZ1) (1), ascertaining at least one characteristic of the drop size distribution within a spray formed during the atomization process of the coating agent composition (BZ1) provided in step (1) and/or the homogeneity of said spray (2), reducing the at least one characteristic ascertained in step (2) and/or the homogeneity of the spray (3), applying at least the coating agent composition (BZ1) obtained in step (3) with a reduced characteristic of the drop size distribution and/or reduced homogeneity onto a substrate, thereby forming at least one film (F1) (4), and physically curing, chemically curing, and/or radiation-curing at least the at least one film (F1) which is formed on the substrate by applying the coating agent composition (BZ1) in step (4) in order to form the coating (B1) on the substrate. The invention also relates to a coating (B1) which can be found on a substrate and which can be obtained using said method.

Description

Process for producing an optimized coating and by means of this

Process available coating

The present invention relates to a method for producing at least one coating (B1) on a substrate, which comprises at least steps (1) to (5), namely providing a coating composition (BZ1J (1), determining at least one parameter of the droplet size distribution within a atomizing the spray composition (BZ1) provided according to step (1) and / or the homogeneity of this spray (2), reducing the at least one parameter and / or homogeneity of the spray (3) determined according to step (2), applying at least the coating composition (BZ1) obtained after step (3) with a reduced characteristic of the droplet size distribution and / or reduced homogeneity on a substrate to form at least one film (F1) (4) and physical curing, chemical curing and / or radiation curing at least that by applying (BZ1) according to step t (4) at least one film (F1) formed on the substrate for forming the coating (B1) on the substrate, as well as a coating (B1) located on a substrate, which coating can be obtained using this method.

State of the art

In the automotive industry in particular, a number of coating compositions, such as, for example, basecoats, are applied to the substrate to be coated by means of rotary atomization. Such atomizers have a rapidly rotating application body, such as a bell cup, which atomizes the coating composition to be applied, in particular in the form of droplets, into a spray mist, in particular due to the acting centrifugal force, with the formation of filaments. The coating composition is usually applied electrostatically in order to ensure the highest possible application efficiency and the lowest possible overspray. At the edge of the bell plate, the lacquer atomized by centrifugal forces in particular is usually charged by directly applying a high voltage to it Coating agent composition to be applied (direct charging) After the respective coating composition has been applied to the substrate, the resulting film is - optionally after additional application of one or more further coating compositions above it

Form of one or more films - hardened or baked to obtain the resulting desired coating.

An optimization of coatings obtained in this way in particular with regard to certain desired properties of the coating, such as avoiding or at least reducing the tendency to form or occur optical defects and / or surface defects such as, for example, pinpricks, cloudy conditions and / or their appearance, is comparatively complex and usually only empirically possible. This means that corresponding coating compositions or usually entire test series thereof, within which various parameters have been varied, must first be produced and then applied to a substrate and hardened or baked, as described in the preceding paragraph. The rows of coatings then obtained must then be examined for the desired properties in order to be able to assess a possible improvement in the properties examined. This procedure usually has to be repeated several times, with further parameter variation, until the desired improvement in the investigated property (s) of the coating has been achieved after curing or baking.

It is known in the prior art to investigate and characterize the coating composition used to produce such coatings based on their shear viscosity behavior (shear rheology) in order to better understand their respective application behavior. For example, capillary rheometers can be used here. However, a disadvantage of this approach, which focuses on the investigation of shear rheology, is that the quite significant influence of the expansion viscosity occurring during rotary atomization is not taken into account or is not taken into account to a sufficient extent (expansion rheology). The stretch viscosity is a measure of the resistance of a material to flowing in a stretch flow. Such expansion currents occur Usually in all relevant technical processes in addition to the shear flows, such as in the case of capillary inlet and capillary outlet flows. In the case of Newtonian flow behavior, the stretch viscosity can be calculated from its constant ratio to the classically determined shear viscosity (Trouton ratio). In the case of non-Newtonian flow behavior, which occurs much more frequently in practice in a large number of applications, it is usually necessary to experimentally determine the elongation viscosity as a parameter independent of the shear viscosity with the aid of an elongation rheometer, if the elongation rheology is used in the the above description and characterization should be taken into account to a sufficient extent. In particular when the aforementioned rotary atomization process is carried out, the expansion viscosity can have a very significant influence on the atomization process and the disintegration of the filaments, which then form the spray mist. Methods for determining the expansion viscosity are known in the prior art. The expansion viscosity is usually determined using a Capillary Breakup Extensional Rheometer (CaBER). So far, however, no method is available in which - without actually subjecting the material to be atomized to atomization - both tensile and shear forces are equally taken into account.

There is therefore a need for a method for producing coatings which makes it possible to obtain coatings with improved properties with regard to avoidance or at least a reduction in the tendency to form or occur optical defects and / or surface defects without the entire painting and stoving process required to produce such coatings has to be carried out, and in particular without the coatings obtained in this way having to be examined in a comparatively complex manner with regard to their desired properties in order to be able to assess a possible improvement in the properties examined. This is all the more true since this procedure usually has to be repeated several times until the desired improvement in the investigated property (s) of the coating has been achieved, which is disadvantageous both from an ecological and an economic point of view. task

It is therefore an object of the present invention to provide a process for producing coatings which is advantageous both from an economic and an ecological point of view and which makes it possible to obtain coatings with improved properties, in particular with a view to avoiding or at least reducing them the tendency to form or the appearance of optical defects and / or surface defects. In particular, it is an object of the present invention to produce coatings which have a lower and, in particular, significantly lower tendency to form disruptive areas such as pinholes and / or are characterized by improved appearance. The coating compositions used to produce these coatings should have the widest possible application window. In particular, it is an object of the present invention to provide such a method for the use of aqueous basecoats as coating compositions for the preparation of basecoat layers, in particular as part of a multi-layer coating.

solution

This object is achieved by the subjects claimed in the patent claims and the preferred embodiments of these subjects described in the following description.

A first subject of the present invention is therefore a method for producing at least one coating (B1) on a substrate, which comprises at least steps (1) to (5), namely

(1) providing a coating composition (BZ1),

(2) determining at least one parameter of the drop size distribution within a spray formed when the coating composition (BZ1) provided according to step (1) is atomized and / or the homogeneity of this spray, where the homogeneity of the spray corresponds to the ratio of two quotients Tn / T oi _aii and T ^ / T _To tai2 to each other as a measure of the local distribution of transparent and non-transparent drops at two different positions within the spray, where Tn is the number of transparent drops in the first position 1, T _T 2 the number of transparent drops in the second position 2, T _To taii the number of all drops in the spray and thus the sum of transparent drops and non-transparent drops in position 1 and the _cup Number of all drops of the spray and thus the sum of transparent drops and non-transparent drops at position 2, position 1 being closer to the center of the spray than position 2,

(3) Reduction of the at least one parameter of the drop size distribution and / or homogeneity of the spray formed during the atomization of the coating composition (BZ1) determined according to step (2),

(4) applying at least the one obtained after step (3)

Coating agent composition (BZ1) with a reduced characteristic of the drop size distribution and / or reduced homogeneity on a substrate to form at least one film (F1) and

(5) physical curing, chemical curing and / or radiation curing of at least the at least one film (F1) formed on the substrate by applying the coating composition (BZ1) according to step (4) to form the coating (B1) on the substrate.

Another object of the present invention is a coating (B1) located on a substrate, which is obtainable by the process according to the invention, i.e. the first subject of the present invention.

The determination of the drop size distribution of the drops formed by the atomization according to step (2) includes the determination of at least one parameter known to the person skilled in the art, such as a suitable mean diameter of the Drops such as in particular the Dio value (arithmetic diameter; "1.0" moment), D _3g value (volume-equivalent mean diameter; "3.0" moment), D32 value (Sauter diameter (SMD); "3 , 2 “- moment), d _{N, 5} o _% value (number-related

Median value) and / or dv _{, 5} o _% value (volume-related median value). The determination of the droplet size distribution includes the determination of at least one such parameter, in particular a determination of the DIQ value of the drops. The above-mentioned parameters are each the corresponding numerical mean of the droplet size distribution. The moments of the distributions are marked here with the capital letter "D", the index defines the corresponding moment. The parameters marked with the lower case letter “d” are the percentiles (10%, 50%, 90%) of the corresponding sum curve of the distribution, whereby the 50% percentile corresponds exactly to the median value. The index "N" refers to the number-based distribution, the index "V" to the volume-based distribution

Reducing at least one parameter of the drop size distribution of the drops formed by the atomization according to step (2) and / or of the homogeneity within step (3) is, according to the invention, a reduction in the respective determined value of the parameter, such as the dio value and / or the determined Value of homogeneity (i.e. the ratio of the quotients T-ri / _T Totaii and TT2 / TT _OIH I2 to each other).

It has surprisingly been found that the method according to the invention makes it possible to produce coatings with improved properties, in particular with a view to avoiding or at least reducing the tendency to form and / or the occurrence of optical defects and / or surface defects. In particular, it was found that the method according to the invention can be used to produce coatings which have a lower and, in particular, significantly lower tendency to form imperfections such as pinholes and / or are distinguished by improved appearance. This applies in particular if the coating compositions (BZ1) used in the process according to the invention are basecoats, such as aqueous basecoats, by means of which Basecoat layers, in particular as part of a multi-layer coating, can be produced.

It was also surprisingly found that the method according to the invention makes a mistaken comparison with conventional methods, making the process more economical and ecological, since coatings can be obtained without or at least with fewer optical defects and / or surface defects, but this is possible without the usual requirement The entire coating and baking process for the production of such coatings and the optimization of their advantageous properties must be carried out and in particular without the coatings obtained in this way having to be examined in a comparatively complex manner with regard to their desired properties in order to be able to assess a possible improvement in the properties examined. This is particularly advantageous from an economic and ecological point of view, since this procedure usually has to be repeated several times in the context of conventional processes until the desired improvement in the properties of the coating has been achieved. The method according to the invention is thus less complex in this regard and has (time) economic and economic advantages over corresponding conventional methods.

In particular, it was surprisingly found that the aforementioned advantages with regard to avoiding or at least reducing the tendency to form or the occurrence of optical defects and / or surface defects can be achieved technically by carrying out step (3) of the method according to the invention, ie by Reduction of the at least one characteristic of the drop size distribution and / or homogeneity of the spray formed in the atomization of the coating composition (BZ1) provided according to step (1) determined according to step (2), the determination of this core size (s) and / or the homogeneity within Step (2) takes place. By means of the method according to the invention, a surprising reduction in this parameter and / or the homogeneity and / or the homogeneity can be achieved on the basis of this determined parameter {n) and / or the determined homogeneity for a coating composition (BZ1) and thereby at least reducing the occurrence of optical defects and / or surface defects of the coating to be produced. A coating that is produced using the same method, but without performing step (3), serves as a comparison. It was surprisingly found that the parameter (s) of the drop size distribution and / or the homogeneity of the spray correlate with the occurrence of the aforementioned optical defects and / or surface defects or their avoidance / reduction. The smaller the respective characteristic of the drop size distribution and / or the homogeneity, the fewer defects occur. This makes it possible to control the resulting properties, such as optical properties and / or surface properties of the coating to be produced, and in particular to avoid the occurrence of optical defects and / or surface defects, depending on the characteristics of the drop size distribution and / or the homogeneity that occur during atomization at least to decrease. In other words, by means of the method according to the invention, based on the investigation of the atomization behavior of a coating composition (BZ1), determination of the parameter (s) mentioned in step (2) and / or the homogeneity and reduction of this parameter (s) and / or the homogeneity in step (3) the properties of the final coating are improved, in particular with regard to optimization with regard to the occurrence of pinholes, cloudiness, streakiness, the course or appearance. In particular, it was surprisingly found that these determined parameter (s) and / or the determined homogeneity correlate better with these properties than other methods known from the prior art, such as CaBER measurements.

It was also found that, in particular, by determining the parameter (s) and / or the homogeneity mentioned in step (2) and / or the homogeneity, the influence of the expansion viscosity which occurs when atomizing coating compositions which can be replaced to produce coatings, such as the coating composition (BZ1), is sufficient Dimensions is taken into account. This is particularly successful because comparatively high expansion speeds can be taken into account in this determination, namely expansion rates of up to 100,000 s ¹ , and thus higher expansion rates than with conventional CaBER measurements for determining the expansion viscosity at which especially in the case of basecoats, only stretching rates of up to 1,000 s ¹ can be achieved, and the parameter (s) and / or the homogeneity mentioned in step (2) and / or the homogeneity are therefore determined at the aforementioned comparatively high stretching rates. The fact that the method according to the invention with step (2) itself involves performing atomization makes it possible to take both shear rheology and expansion rheology sufficiently into account in a single procedure and not by means of methods that only use individual elements (shear rheology or expansion rheology) can capture.

As mentioned above, it was also surprisingly found that by means of the method according to the invention, in particular in the case of aqueous basecoats used as coating compositions (BZ1) for atomization, conclusions can be drawn from the particle size distributions of the drops, that is to say the determined drop size distribution, in particular based on determinations of the Dio values can be drawn as a parameter of the drops and / or the homogeneity of the spray on the appearance of the coating to be produced. Smaller drop sizes mean "finer" atomization of the coating composition used. Atomization as fine as possible is desirable since this is accompanied by a lower degree of wetness, that is to say a less wet appearance of the film formed after application of the coating composition used. It is known to the person skilled in the art that an excessively high degree of wetness can lead to an undesirable occurrence of stoves and / or pinpricks, to a poorer color tone and / or flop and / or to the appearance of cloudy conditions. Likewise, corresponding conclusions can be drawn based on the quotient Tt / Tt ^ i as a measure of the local distribution of transparent and non-transparent drops and thus as a measure of the homogeneity of the spray produced during atomization. T corresponds to the number of transparent drops and Tt _oί3 i the number of all drops and thus the sum of transparent drops and non-transparent drops. In a spray mist formed during an atomization such as a rotary atomization, the proportion of non-transparent drops, for example the proportion of (effect) pigment-containing drops, increases from the inside out due to the centrifugal force. That changes Ratio of the quotient T _Ti / T _Totaii to the quotient T Tio _t a _ß within the spray with increasing distance to the edge of the bell is comparatively strong (if a rotary atomizer is used in step (2)), this means that the composition of the spray from the inside changes significantly to the outside. On the basis of the determination of the ratio of the quotient Tp / T-ro _t aii to the quotient T-nfTi _tMi or on the basis of how strongly this changes from the inside out, it can thus be determined whether a material used with increasing values of this ratio is separated more strongly during application into areas with different concentrations of (effect) pigments and is therefore more inhomogeneous or more susceptible to the formation of surface defects such as stripes than another material.

Detailed description

Process for producing a coating (B1) on a substrate

The method according to the invention for producing at least one coating (B1) on a substrate comprises at least steps (1) to (5).

The coating (B1) is preferably part of a multi-layer coating on the substrate. The coating (B1) preferably represents a basecoat layer of a multilayer coating on the substrate. The substrate used is preferably a pre-coated substrate.

By means of the method according to the invention, at least the coating (B1) is at least partially applied to a substrate, preferably at least one surface of the substrate is preferably completely covered.

The method according to the invention contains at least steps (1) to (5), but can optionally include further steps. Steps (1) to 5) are preferably carried out in numerical order. Preferably, steps (2a) and (2b), which are described further below, are carried out simultaneously within step (2), ie the optical detection according to step (2b) is preferably carried out while step (2a) is being carried out. Optionally and preferably, one or more further coating compositions which, in each case, are preferably different from the composition (BZ1) and from one another can be applied to the substrate within the process according to the invention. In particular if the composition (BZ1) is a preferably aqueous basecoat, after step (4) - in the case of a wet-on-wet application - or after step (5) has been carried out, at least one further coating composition, for example a Clear varnish like a solvent-based clear varnish. The clearcoat can be a commercially available clearcoat, which in turn is applied by customary methods, the layer thicknesses in turn being in the usual ranges, for example 5 to 100 micrometers.

The method according to the invention preferably comprises at least one further one

Step (4a), which is carried out before step (5) but after step (4). Step (4a) provides for, before carrying out step (5), at least one further coating composition (BZ2) different from the coating composition (BZ1) on the film (F1) obtained in step (4) to form a film ( F2) and to subject the films (F1) and (F2) thus obtained together to step (5). The coating composition (BZ2) is preferably a Klariack, particularly preferably a solvent-based Klariack.

After the clear lacquer has been applied, it can be flashed off at room temperature (23 ° C.) for, for example, 1 to 60 minutes and optionally dried. The clear lacquer is then preferably cured together with the applied coating composition (BZ1) within step (5). Crosslinking reactions take place, for example, whereby an effect-giving and / or coloring and effect-giving multilayer coating is produced on a substrate.

Metallic substrates are preferably used in the process according to the invention. In principle, non-metallic ones are also possible Substrates, in particular plastic substrates, The substrates used can be coated. If a metal substrate is to be coated, it is preferably coated with an electro-dip coating before the application of a filler and / or primer filler and / or a basecoat. If a plastic substrate is coated, this is preferably pretreated before the application of a filler and / or primer filler and / or a basecoat. The most commonly used methods for this are flame treatment, plasma treatment and corona discharge. Flaming is preferably used. As mentioned above, the coating composition (BZ1) used is preferably a basecoat, in particular a waterborne basecoat. Accordingly, the coating (B1) obtained is preferably a basecoat film. If necessary, the substrate can in this case contain at least one of the above-mentioned coatings, that is to say a filler and / or primer filler and / or electrocoat layer, before the basecoat is applied. The substrate used preferably has an electrocoat layer (ETL), particularly preferably an electrocoat layer applied by cathodic deposition of an electrocoat.

Step 1)

Step (1) of the method according to the invention provides for a

Coating composition (BZ1) before.

Step 2)

In step (2) of the method according to the invention, at least one parameter of the droplet size distribution within a spray formed during atomization of the coating composition (BZ1) provided according to step (1) and / or the homogeneity of this spray is determined, the homogeneity of the spray being the ratio of two quotients Tn / Tr _ota n and T _T 2 / Ttoΐ3ΐ2 correspond to each other as a measure of the local distribution of transparent and non-transparent drops at two different positions within the spray, where Tu is the number of transparent drops at the first position 1, T _T 2 the number of transparent drops in the second position 2, Tr _ota n the number of all drops in the spray and thus the sum of transparent drops and non- transparent drops at position 1 and T _Totai 2 _{corresponds to} the number of all drops in the spray and thus the sum of transparent drops and non-transparent drops at position 2, position 1 being closer to the center of the spray than position 2.

The atomization is preferably carried out by means of a rotary atomizer or a pneumatic atomizer.

The term “rotary atomization” or “high-speed rotary atomization” or “high-speed rotary atomization” is known to the person skilled in the art. Such rotary atomizers have a rotating application body which atomizes the coating composition to be applied into a spray in the form of drops due to the acting centrifugal force. The application body is a preferably metallic bell cup.

In the case of rotary atomization using atomizers, so-called filaments first form on the edge of the bell plate, which then further decompose into the aforementioned drops in the course of the atomization process, which then form a spray mist. The filaments thus represent a preliminary stage of these drops. The filaments can be described and characterized by their filament length (also referred to as “thread length”) and their diameter (also referred to as “thread diameter”).

The term “pneumatic atomization” and pneumatic atomizers used for this purpose are also known to the person skilled in the art.

When step (2) is carried out, the expansion viscosity occurring during atomization is taken into account to a sufficient extent. The skilled worker is familiar with the term expansion viscosity with the unit of Pascal second (Pa-s) as a measure of the resistance of a material to the flow in an expansion flow. Methods for determining the expansion viscosity are also known to the person skilled in the art. The expansion viscosity is usually determined using a so-called Capillary Breakup Extensional Rheometer (CaBER), which is sold, for example, by Thermo Scientific. Preferably, the middle parameter mentioned in step (2) or the homogeneity is determined by carrying out at least the following process steps (2a), (2b) and (2c), namely by means of

(2a) atomizing the coating composition (BZ1) provided according to step (1) by means of an atomizer, a spray being formed by the atomization,

(2b) optical detection of the drops of the spray formed by atomization according to step (2a) by a traversing optical measurement through the entire spray and

(2c) determining at least one parameter of the drop size distribution within the spray and / or the homogeneity of the spray on the basis of optical data obtained by the optical detection according to step (2b).

Step (2a)

Step (2a) of the method according to the invention relates to atomization of the coating composition (BZ1) by means of an atomizer, a spray being formed by the atomization. As mentioned above, the atomizer is preferably a rotary atomizer or a pneumatic atomizer. If a rotary atomizer is used, it preferably has a bell cup capable of rotation as the application body. Optionally, the atomized coating composition (BZ1) can be electrostatically charged at the edge of the bell cup by applying a voltage.

If a rotary atomizer is used in step (2a), the rotation speed (rotation speed) of the bell-mouth plate can be adjusted. In the present case, the rotational speed is preferably at least 10,000 revolutions / min (rpm) and at most 70,000 revolutions / min. The rotational speed is preferably in a range from 15,000 to 70,000 rpm, particularly preferably in a range from 17,000 to 70,000 rpm, in particular from 18,000 to 65,000 rpm or from 18,000 to 60,000 rpm. From a rotational speed of 15,000 revolutions per minute, a corresponding rotary atomizer in the sense of this invention is preferably referred to as a high-speed rotary atomizer. Rotary atomization in general and high speed rotary atomization in particular are widely used in the automotive industry. The used for this

(High-speed) rotary atomizers are commercially available, examples include products from the Dürr Ecobe! I @ series. Such atomizers are preferably suitable for the electrostatic application of a large number of different coating compositions, such as paints, which are used in the automotive industry. Basecoats, in particular aqueous basecoats, are particularly preferably used as coating compositions within the process according to the invention. The coating composition can be applied electrostatically, but need not. In the case of an electrostatic application, the coating composition atomized by centrifugal forces is electrostatically charged at the edge of the bell head by preferably directly applying a voltage, such as high voltage, to the coating composition to be applied (direct charging).

The outflow rate of the coating composition to be atomized during the implementation of step (2a) is adjustable. The outflow rate of the coating composition to be atomized during the implementation of step (2a) is preferably in a range from 50 to 1,000 ml / min, particularly preferably in a range from 100 to 800 ml / min, very particularly preferably in a range from 150 to 600 mi / min, especially in a range from 200 to 550 ml / min.

Preferably, the outflow rate of the coating composition to be atomized during the execution of step (2a) is in a range from 100 to 1,000 ml / min or from 200 to 550 ml / min and the speed of the bell cup in the case of a rotary atomization is in a range of 15,000 up to 70,000 revolutions / min or from 15,000 to 60,000 rpm. In step (2a) of the process according to the invention, a basecoat, particularly preferably an aqueous basecoat, is preferably used as the coating composition, in particular an aqueous basecoat which contains at least one effect pigment.

Step (2b)

In step (2b) there is an optical detection of the drops of the spray formed by atomization according to step (2a) by a traversing optical measurement through the entire spray.

Carrying out this traversing measurement enables a holistic recording of the entire spray and thus of the entire spectrum of drops forming the spray. This makes it possible to record all the droplet sizes forming the spray. The entire spray can be measured holistically (and not just individual areas of the spray). The traversing measurement allows the drops to be measured optically, i.e. point-specific, in many places in the spray of atomization), whereby a more precise determination is made in the subsequent step (2c) than if the measurement is not traversing. The traversing measurement is preferably carried out by moving the atomizing head of the atomizer used while the step (2b) is being carried out. Alternatively, however, a relative movement of the measuring system is also possible.

The traversing optical measurement according to step (2b) can be carried out at different traversing speeds. This speed can be linear or non-linear. The area weighting can be simplified by selecting the traversing speed: an increase in traversing speed with increasing area segments fulfills this purpose, so that the product of area and dwell time is constant. The traversing speed is preferably selected so that at least 10,000 counts per area segment of the spray are obtained , In this context, the term “counts” denotes the number of drops detected during the measurement within the spray or different surface segments of the spray. The surface segments represent positions within the spray. The optical detection according to step (2b) of the method according to the invention is preferably carried out by an optical measurement which is based on scattered light tests on the drops contained in the spray and is carried out on them. This measurement is preferably carried out using at least one laser.

The optical detection according to step (2b) of the method according to the invention is preferably carried out by means of phase Doppler anemometry (PDA) and / or by means of the time shift measurement technique (TS). At least one characteristic of the drop size distribution can be determined in step (2c) from the optical data obtained using PDA when step (2b) is carried out. In step (2c), at least one parameter of the drop size distribution and the homogeneity of the spray can be determined from the optical data obtained by TS when step (2b) is carried out.

The optical measurement is preferably carried out on a measurement axis which is traversed repeatedly, as shown for example in FIG. 1. The repetition is preferably 1 to 5 times, particularly preferably it is carried out at least 5 times. The measurement is particularly preferably carried out with at least 10,000 counts per measurement and / or at least 10,000 counts per surface segment within the spray. A double measurement of the individual events is preferably prevented by an internal evaluation. 1, a rotary atomizer is used as an example.

Step (2b) can be carried out at different tilt angles of the atomizer relative to the measuring device, by means of which the measurement according to step (2b) takes place. A variation of the tilt angle from 0 to 90 ° is possible. In Fig. 1, this is exemplary at 45 °.

The optical detection according to step (2b) is preferably carried out with a detector. Use of PDA in step (2b)

The procedure for determining the droplet size distribution can be carried out using phase Doppler anemometry (PDA). This method is known to the person skilled in the art basically known, for example from F. Onofri et al., Part. Part. Sys. Charact. 1996, 13, pages 112-124 and A. Tratnig et al., J. Food. Engin. 2009, 95, pages 126-134. The PDA method is a measurement method which is based on the fact that an interference plane pattern is formed in the intersection volume of two coherent laser beams. The particles moving during a flow, such as the drops of the spray, i.e. sprays, which are examined according to the present invention, scatter light when crossing the cutting volume of the laser beams with the so-called Doppler frequency, which is directly proportional to the speed at the location of the measurement , The radius of curvature of the particle surface can be determined from the different phase of the scattered light signal on preferably at least two detectors used, which are located at different locations in space. In the case of spherical particles, the particle diameter follows from this; in the case of drops, the respective drop diameter. For high measurement accuracy, it is advantageous to design the measurement setup, especially with regard to the scattering angle, so that a single scattering mechanism (first-order reflection or refraction) dominates. The scattered light signal is usually converted by photomultipliers into electronic signals and evaluated with the aid of covariance processors or with the aid of an FFT analysis (Fast Fourier Transformation Analysis) with regard to the Doppler frequency and the difference in the phase positions. The use of a Bragg cell preferably permits the controlled manipulation of the wavelength of one of the two laser beams and thus the generation of a current interference plane pattern.

PDA systems usually measure the phase shifts (ie the difference in phase positions) in received light signals by using different reception apertures (masks).

In step (2b) of the method according to the invention, a mask is preferably used in the case of implementation by means of PDA, by means of which drops with a maximum possible drop diameter of 518.8 μm can be detected. Corresponding devices suitable for carrying out the PDA process are commercially available, for example the single PDA from DantecDynamics (P60, Lexel Argon laser, FibreFlow).

When performing step (2b), the PDA is preferably operated in forward scatter at an angle of 60-70 ° with a wavelength of 514.5 nm (orthogonally polarized) in reflection. The receiving optics preferably have a focal length of 500 mm, the transmitting optics preferably a focal length of 400 mm.

The optical measurement according to step (2b) using PDA is carried out traversing in the radial-axial direction in relation to the tilted atomizer used, preferably at a tilt angle of 45 °. Basically, however, as mentioned above, tilt angles in a range from 0 to 90 °, preferably> 0 to <90 ° such as from 10 to 80 ° are possible. The optical measurement is preferably carried out 25 mm vertically below the side of the atomizer inclined to the traversing axis. Measurements have shown a completed drop formation process at this position. Such a structure is shown as an example in FIG. 1. In this case, a defined traversing speed is preferably specified, so that the individual detected events are resolved in terms of location by means of the associated signals resolved over time. A comparison to grid-resolved measurements provides identical results for the weighted global distribution parameters, but still enables the examination of any interval ranges on the traversing axis. Furthermore, this method is many times faster than screening, which means that the material expenditure can be reduced with constant flow rates.

Use of TS in step (2b)

The determination of the droplet size distribution can be carried out alternatively or in addition to the PDA technology by means of the time shift measurement technique. The time shift method (TS) (also called time shift method (ZW)) is basically also known to the person skilled in the art, for example from an article by W. Schäfer et al., ICLASS 2015, 13th Triennial International Conference on Liquid Atomization and Spray Systems, Tainan, Taiwan, pages 1 to 7 and an article by M. Kuhnhenn et al., (LASS Eunope 2016, 27th Annual Conference on Liquid Atomization and Spray Systems, 4-7 September 2016, Brighton UK, pages 1 to 8 and from W. Schäfer et al., Particuology 2016, 29, pages 80-85,

The time shift method (TS) is a measurement method which is based on the backscattering of light (for example laser light) by particles, as in the case of the present invention, by means of the drops in the spray mist (spray) produced by the atomization. TS measurement technology is based on the light scattering of a single particle from a shaped light beam such as a laser beam. The scattered light of the individual particle is interpreted as the sum of all scattering orders available at the location of the detector used. When approaching geometric optics, this corresponds to examining the propagation of individual light rays through the particle with a varying number of internal reflections. The laser beam used to carry out the time-shift method is usually focused by lenses. The light that was scattered by the particles is divided into perpendicular and parallel polarized light and is preferably detected separately by at least two photodetectors. The signal coming from the detectors in turn provides the necessary information to determine a determination of the size of the droplets and / or homogeneity. The wavelength of the light of the illuminating beam used is of the same order of magnitude or is smaller than that of the particles to be measured. The laser beam should therefore be selected so that it does not exceed the size of the drops in order to obtain the time shift signal. If this value is exceeded, the signal is no longer suitable to serve as a basis for determining the above-mentioned variable. Otherwise there is the problem that the signal components of the different scatterings overlap and therefore cannot be recorded and differentiated individually. The time shift method can be used to determine characteristic properties of the particles, for example to determine the droplet size distribution. In addition, the time shift method (TS) can be used to distinguish between bubbles, ie transparent drops (T) and solid-containing particles, ie non-transparent drops (NT). Appropriate devices suitable for this purpose are commercially available, for example devices from the SpraySpyieF series from AOM Systems. Carrying out traversing measurements using devices from the SpraySpy® series is known in principle, but is known in the prior art only used to determine the width of the spray jet, but not to determine the homogeneity of the spray and / or parameters of the drop size distribution.

The optical measurement according to step (2b) using TS is carried out traversing in the radial-axial direction in relation to the tilted atomizer used, preferably at a tilt angle of 45 °. Basically, however, as mentioned above, tilt angles in a range from 0 to 90 °, preferably> 0 to <90 ° such as from 10 to 80 ° are possible. The optical measurement is preferably carried out 25 mm vertically below the flank of the atomizer inclined to the traversing axis. Measurements have shown a completed drop formation process at this position. Such a structure is shown as an example in FIG. 1. In this case, a defined traversing speed is preferably predefined, so that the individual detected events are resolved in terms of location via the associated temporally resolved signals. A comparison to grid-resolved measurements provides identical results for the weighted global distribution parameters, but still enables the examination of any interval ranges on the traversing axis. Furthermore, this method is many times faster than screening, which means that the material expenditure can be reduced with constant flow rates.

Step (2c)

Step (2c) of the method according to the invention is a determination of at least one parameter of the droplet size distribution within the spray and / or the homogeneity of the spray on the basis of optical data obtained by the optical detection according to step (2b).

As already mentioned above, the determination according to the invention of the droplet size distribution of the droplets formed by the atomization according to step (2a) preferably includes the determination of corresponding parameters known to the person skilled in the art, such as the D-io value (arithmetic diameter; "1.0" moment), D30 value (volume-equivalent mean diameter; "3.0" - moment), D ₃ 2-value (Sauter diameter (SMD); "3.2" - moment), dN _, so% value (number-related median value ) and / or dv, 50% value (volume-related median value), at least one of these parameters of the drop size distribution within Step (2c) is determined. In particular, the determination of the drop size distribution includes a determination of the dio value of the drops. This takes place in particular if step (2b) is carried out using a PDA and / or TS.

If step (2b) is carried out by means of a PDA, the optical data obtained after step (2b) has been carried out are preferably evaluated using an algorithm for any tolerances within step (2c). A tolerance of approx. 10% for the PDA system used limits the validation to spherical drops, an increase also includes slightly deformed drops. This enables an observation of the sphericity of the measured drops along the measurement axis.

If step (2b) is carried out by means of TS, the optical data obtained after step (2b) has been carried out are also preferably evaluated using an algorithm for any tolerances.

The homogeneity of the spray describes the ratio of the two quotients Tn / Tjotan and re / TiotaE to each other as a measure of the local distribution of transparent and non-transparent drops at two different positions within the spray, where T _{Ti is} the number of transparent drops at the first position 1, T _T2 the number of transparent drops at the second position 2, Tjotaii the number of all drops of the spray and thus the sum of transparent drops and non-transparent drops at position 1 and T _To tai2 the number of all drops of the spray and thus the sum of transparent drops and non-transparent drops at position 2, position 1 being closer to the center of the spray than position 2. The homogeneity can be determined in particular if TS is used when step (2b) is carried out.

Position 1, which is closer to the center of the spray than position 2, preferably represents an area segment within the spray which differs from position 2. Position 1 is - since it is closer to the center of the spray than position 2 - further inside the spray located as position 2, which is accordingly further outside in the spray, in any case further outside than position 1. If you imagine the spray in the form of a cone, there is Position 1 further inside the cone than position 2. Both positions 1 and 2 are preferably on a measuring axis that leads through the entire spray. This is shown as an example in FIG. 1. The distance between the two positions 1 and 2 within the spray is preferably at least 10%, preferably at least 15%, particularly based on the entire length of the part of the measuring axis which is located within the spray and which corresponds to a value of 100% preferably at least 20% and in particular at least 25% of this length of the measuring axis.

The data thus obtained by means of TS in accordance with step (2b) can thus be evaluated for the transparent spectrum (T) and the non-transparent spectrum (NT) of the drops. The ratio of the number of measured drops of both spectra serves as a measure for the local distribution of transparent and non-transparent drops. An integral view along the measurement axis is possible. In particular, the ratio of the transparent drops (T) to the total number of drops (Total) is preferably determined at a position of x = 5 mm or x = 25 mm along the measurement axis. These positions then correspond to the aforementioned positions 1 (x = 5 mm) and 2 (x = 25 mm). The corresponding values are in turn set in relation to describe the homogeneity of the spray (sprays), which changes from the inside out.

Step 3)

in step (3) of the method according to the invention, at least one parameter of the droplet size distribution and / or homogeneity of the spray formed during the atomization of the coating composition (BZ1) is reduced in accordance with step (2).

The reduction in step (3) is preferably carried out by adapting at least one parameter within the recipe for the coating composition (BZ1) provided in step (1). This adjustment of at least one parameter within the recipe for the coating composition (BZ1) preferably comprises at least one adjustment selected from the group of adjustments of the following parameters: (i) increase or decrease in the amount of at least one in the

Coating agent composition (BZ1) as binder component (a) containing polymers,

(ii) at least partial replacement of at least one polymer contained in the coating composition (BZ1) as binder component (a) by at least one different from it

Polymer,

(iii) increasing or decreasing the amount of at least one in the

Coating composition (BZ1) as component (b) containing pigment and / or filler,

(iv) at least partial exchange of at least one in the

Coating agent composition (BZ1) as component (b) containing filler with at least one different filler and / or at least partial replacement of at least one pigment contained in component (BZ1) as component (b) with at least one different pigment,

(v) increasing or decreasing the amount of at least one organic solvent and / or water contained in the coating composition (BZ1) as component (c),

(vi) at least partial replacement of at least one organic solvent contained as component (c) in the coating composition (BZ1) by at least one organic solvent different therefrom,

(vii) increasing or decreasing the amount of at least one additive contained as component (d) in the coating composition (BZ1),

(viii) at least partial exchange of at least one in the

Coating composition (BZ1) as additive containing component (d) by at least one additive different from this and / or adding at least one further additive different from this, (ix) change the order of addition of the to produce the

Coating agent composition (BZ1) components used, and / or

(x) Increase or decrease in the energy input of the mixing in the production of the coating composition (BZ1).

Using the parameter (v), the spray viscosity of the coating composition (BZ1) in particular can be increased or decreased. Parameters (vii) and / or (viii) include / include in particular the exchange and / or the addition of thickeners as additives or the change in their quantity in (BZ1). Such thickeners are described below in the context of component (d). Parameters (i) and / or (ii) include / include in particular the exchange and / or the addition of binders or the change in their amount in (BZ1). The term binding agent is explained in more detail below. Crosslinkers (crosslinking agents) are also to be subsumed under this. Accordingly, the parameters (i) and / or (ii) also include a change in the relative weight ratio of crosslinking agent and that binder component which enters into a crosslinking reaction with the crosslinking agent. Parameters (i) to (iv) include / comprise in particular the exchange and / or the addition of binders and / or pigments or the change in their amount in (BZ1). Accordingly, these parameters (i) to (iv) also implicitly include a change in the pigment / binder ratio within (BZ1).

The adjustment of at least one parameter within the recipe for the coating composition (BZ1) particularly preferably comprises at least one adjustment selected from the group of adjustments of the following parameters:

(iii) increasing or decreasing, in particular increasing, the amount of at least one pigment and / or filler, in particular effect pigments, present as component (b) in the coating composition (BZ1),

(iv) at least partial replacement of at least one contained in the coating composition (BZ1) as component (b) Filler by at least one different from this filler and / or at least partial replacement of at least one in the

Coating composition (BZ1) as component (b) containing pigment by at least one pigment different therefrom, in particular at least partially replacing at least one in the

Coating agent composition (BZ1) as component (b) containing pigment by at least one pigment different therefrom, the pigment in each case preferably being an effect pigment,

(v) increasing or decreasing the amount of at least one in the

Coating agent composition (BZ1) as component (c) organic solvents and / or water contained therein, preferably increasing the amount of water in the coating agent composition (BZ1) as component (c) therein and / or preferably reducing the amount of at least one in the Coating composition (BZ1) as organic solvent containing component (c),

(vil) increasing or decreasing the amount of at least one additive contained in the coating composition (BZ1) as component (d), and / or

(viii) at least partial replacement of at least one additive contained in the coating composition (BZ1) as component (d) by at least one additive different from this and / or addition of at least one further additive different from this.

The adjustment of at least one parameter within the recipe for the coating composition (BZ1) very particularly preferably comprises at least one adjustment selected from the group of adjustments of the following parameters:

(iii) increasing or decreasing, in particular increasing, the amount of at least one pigment and / or filler, in particular effect pigments, present as component (b) in the coating composition (BZ1), (iv) at least partial exchange of at least one in the

Coating agent composition (BZ1) as component (b) containing filler by at least one different filler and / or at least partial replacement of at least one in the

Coating agent composition (BZ1) as component (b) containing pigment by at least one pigment different therefrom, the pigment in each case preferably being an effect pigment, and / or

(v) increasing or decreasing the amount of at least one in the

Coating agent composition (BZ1) as component (c) organic solvent and / or water contained therein, preferably increasing the amount of water in the coating agent composition (BZ1) as component (c) and / or preferably reducing the amount of at least one in the Coating composition (BZ1) as component (c) organic solvent.

The amount of at least one pigment or pigment contained in the coating composition (BZ1) as component (b) according to (iii) is preferably increased or decreased in such a way that the pigment content resulting from the increase or decrease by a maximum of ± 10% by weight , particularly preferably a maximum of ± 5% by weight, deviates from the pigment content of the coating composition (BZ1) before carrying out this parameter adjustment (iii).

Preferably, the at least partial replacement of at least one pigment contained in the coating composition (BZ1) as component (b) takes place according to parameter adjustment (iv) in such a way that the at least one pigment contained in (BZ1) before the parameter adjustment (iv) is at least partially only replaced by at least one essentially identical pigment is exchanged. For the purposes of the present invention in connection with effect pigments, the term “essentially identical pigment” means that the effect pigment or pigments capable of at least partial exchange are at least 80% by weight, preferably at least 85% by weight, as the first condition. , particularly preferably at least 90% by weight, very particularly preferably at least 95% by weight, in particular at least 97.5% by weight, in each case based on their total weight, but preferably in each case less than 100% by weight , has / have an identical chemical composition to that or the effect pigments present in the coating composition (BZ1). For example, effect pigments are essentially identical to one another if they are each aluminum effect pigments, but which have a different coating, such as chromating in one case and a silicate layer in the other case, or coating in one case and not in the other case , Another additional condition for essentially identical pigments in the sense of the present invention in connection with effect pigments is that the effect pigments differ in their mean particle size by at most ± 20%, preferably by at most ± 15%, particularly preferably by at most ± 10% differ. The mean particle size is the arithmetic number average of the measured mean particle diameter (d _N, 50 _% value; number-related median value), which is determined by laser diffraction in accordance with ISO 13320 (date: 2009). The term effect pigment per se is explained in more detail below and further.

For the purposes of the present invention in connection with color pigments, the term “essentially identical pigment” is understood to mean that the color pigment or pigments capable of at least partial exchange are, as a first condition, at least ± 20%, preferably at most ±, in terms of their colourfulness Differentiate 15%, particularly preferably by at most ± 10%, in particular by at most ± 5%, of color pigment (s) present in the coating composition (BZ1) before the parameter adjustment (iv). The chromaticity denotes the ö, & - chromaticity CIE 1976 (CIELAB chromaticity): and is determined according to DIN EN ISO 11664-4 (date: June 2012). A further additional condition “essentially identical pigments” in the sense of the present invention in connection with color pigments is that the color pigments differ in their mean particle size by at most ± 20%, preferably by at most ± 15%, particularly preferably by at most ± 10% differ. The mean particle size is the arithmetic number average of the measured mean particle diameter (d _N, 50 _% value), which is determined by laser diffraction in accordance with ISO 13320 (date: 2009). The term color pigment per se is explained in more detail below and further.

Step (4)

Step (1) of the method according to the invention provides for the application of at least the coating composition (BZ1) obtained according to step (3) with a reduced characteristic of the drop size distribution and / or reduced homogeneity to a substrate with the formation of at least one film (F1).

The application in step (4), in particular if (BZ1) is a basecoat, can be the most in the layer thicknesses customary in the automotive industry in the range from, for example, 5 to 100 micrometers, preferably 5 to 60 micrometers, particularly preferably 5 to 30 micrometers preferably from 5 to 20 micrometers.

The application in step (4) is preferably carried out by means of atomization, such as pneumatic atomization or rotary atomization, in particular by means of rotary atomization of the coating composition (BZ1) obtained after step (3).

The embodiments described in connection with step (2a), to which reference is hereby made apply equally to step (4) if step (4) is carried out by means of rotary atomization. The concept of "pneumatic Atomization ”and pneumatic atomizers used for this purpose are also known to the person skilled in the art

As already mentioned above, the method according to the invention comprises at least one further step {4a) which is carried out before step (5) is carried out, but after step (4) is carried out. Step (4a) provides for at least one of the other to be carried out before performing step (5)

Coating composition (BZ1) to apply various coating compositions (BZ2) to the rim (F1) obtained according to step (4) to form a film (F2) and to subject the films (F1) and (F2) thus obtained together to step (5). Preferably the

Coating composition (BZ2) a clear coat, particularly preferably a solvent-based clear coat. After the clear lacquer has been applied, it can be flashed off at room temperature (23 ° C.) for, for example, 1 to 60 minutes and optionally dried. The clear lacquer is then preferably cured together with the applied coating composition (BZ1) within step (5).

Step (5)

In step (5) of the method according to the invention, a physical curing, chemical curing and / or radiation curing of at least the at least one film (F1) formed on the substrate by applying the coating composition (BZ1) according to step (4) is used to form the coating (B1) performed on the substrate.

The term physical curing preferably includes thermal curing, ie a baking of the at least one film (F1) applied in accordance with step (4). Before baking, drying is preferably carried out according to known methods. For example, (I-component) basecoat materials, which are preferred, can be flashed off at room temperature (23 ° C.) for 1 to 60 minutes and subsequently cured preferably at temperatures of 30 to 90 ° C. which may be slightly elevated. In the context of the present invention, ventilation and drying are understood to mean evaporation of organic solvents and / or water, as a result of which the paint is drier but not yet hardened or a completely crosslinked lacquer film is not yet formed. The curing, that is to say the stoving, is preferably carried out thermally at temperatures from 30 to 200 ° C. and from 60 to 150 ° C. The coating of plastic substrates is basically analogous to that of metal substrates. However, hardening is generally carried out at significantly lower temperatures of 30 to 90 ° G.

The chemical curing is preferably carried out by means of crosslinking reactions of suitable crosslinkable functional groups, which are preferably parts of the polymer used as binder (a). Any customary crosslinkable functional group known to the person skilled in the art can be considered. In particular, the crosslinkable functional groups are selected from the group consisting of hydroxyl groups, amino groups, carboxylic acid groups, isocyanates, polyisocyanates and epoxides. Chemical curing is preferably carried out in combination with chemical curing.

Suitable radiation sources for radiation curing are, for example, low-pressure mercury lamps, medium-pressure lamps, high-pressure lamps and fluorescent tubes, pulse lamps, metal halide lamps (halogen lamps), lasers, LEDs and, in addition, electron flash devices, which enable radiation curing without a photoinitiator, or excimer lamps. Radiation curing takes place by exposure to high-energy radiation, that is to say UV radiation or daylight, or by irradiation with high-energy electrons. The radiation dose usually sufficient for crosslinking in UV curing is in the range from 80 to 3,000 mJ / cm ² . Of course, several radiation sources can also be replaced for curing, for example two to four. These can also radiate in different wavelength ranges. Coating agent composition used according to the invention

The following embodiments relate both to the method according to the invention and to the coating (B1) according to the invention, which is further described below. The embodiments described below relate in particular to the coating composition (BZ1) used.

The coating composition used according to the invention preferably contains

At least one polymer which can be replaced as a binder as component (a),

• at least one pigment and / or at least one filler as a component

(Federation

• Water and / or at least one organic solvent as component (c).

The term “comprising” or “containing” in the sense of the present invention, in particular in connection with the coating composition used according to the invention, preferably has the meaning “consisting of”. With regard to the coating composition used according to the invention, for example, in addition to components (a), (b) and (c), one or more of the further optional components mentioned below, such as component (d), may be present therein. All components can each be present in their preferred embodiments mentioned below.

The coating composition used according to the invention is preferably a coating composition that can be replaced in the automotive industry. Both coating compositions that can be used in the context of OEM series painting as well as in the context of a refinish are replaceable. Coating agent compositions that can be replaced in the automotive industry are, for example, electrocoat materials, primers, fillers, basecoats, in particular waterborne basecoats (aqueous basecoats), topcoats including clearcoats, especially solvent-based clear coats. The use of water-based paints is particularly preferred.

The term basecoat is known to the person skilled in the art and is defined, for example, in the Römpp Lexicon, Lacquers and Printing Inks, Georg Thieme Verlag, 1998, 10th edition, page 57. Accordingly, a basecoat in particular includes a coloring and / or used in automotive painting and general industrial painting to understand coloring and an optical effect intermediate coating material. This is generally applied to a metal or plastic substrate pretreated with filler or primer, sometimes directly on the plastic substrate. Old paintwork, which may need to be pretreated (e.g. by sanding), can also serve as substrates. It is now quite common to apply more than one base coat. Accordingly, in such a case, a first basecoat layer forms the background for a second. To protect a basecoat layer, in particular against environmental influences, at least one additional clearcoat layer is applied to it. A waterborne basecoat is an aqueous basecoat in which the proportion of water is> the proportion of organic solvents, based on the total weight of water and organic solvents in% by weight within the waterborne basecoat.

The proportions in% by weight of all components contained in the coating composition used according to the invention, such as components (a), (b) and (c) and, if appropriate, one or more of the further optional components mentioned below add up to 100% by weight. %, based on the total weight of the coating composition.

The solids content of the coating composition used according to the invention is preferably in a range from 10 to 45% by weight, particularly preferably from 11 to 42.5% by weight, very particularly preferably from 12 to 40% by weight, in particular from 13 to 37 , 5 wt.%, Each based on the total weight of the coating composition. The solids content, i.e. the non-volatile content, is determined using the method described below. Component (a)

For the purposes of the present invention, the term “binding agent” preferably means, in accordance with DIN EN ISO 4618 (German version, date: March 2007), the non-volatile fractions of a composition such as the coating composition used according to the invention, with the exception of the coating composition used according to the invention contained pigments and / or fillers understood. The non-volatile content can be determined according to the method described below. A binder component is therefore any component that contributes to the binder content of a composition such as the coating composition used in accordance with the invention. An example is a basecoat such as an aqueous basecoat which comprises at least one polymer which can be replaced as a binder as component (a), for example an SCS polymer described below, and a crosslinking agent such as

Contains melamine resin and / or a polymeric additive.

A so-called seed-core-shell polymer (SCS polymer) is particularly preferably used as component (a). Such polymers or aqueous dispersions containing such polymers are, for example, from WO

2016/116299 A1 known. The polymer is preferably a (meth) acrylic copolymer. The polymer is preferably used in the form of an aqueous dispersion. A very particularly preferred component (a) is a polymer having an average particle size in the range from 100 to 500 nm, which can be prepared by successive radicals

Emulsion polymerization of three preferably different monomer mixtures (A), (B) and (C) of olefinically unsaturated monomers in water, the mixture (A) at least 50% by weight of monomers with a solubility in water of less than 0.5 g / l at 25 ° C and a polymer which is prepared from the mixture (A) has a glass transition temperature of 10 to 65 ° C, the mixture (B) contains at least one polyunsaturated monomer and a polymer which is prepared from the mixture (B) one

Glass transition temperature from -35 to 15X, and

a polymer which is produced from the mixture (C) has a glass transition temperature of -50 to 15 ° C,

and where

i. the mixture (A) is first polymerized,

ii. then the mixture (B) in the presence of the i. prepared polymer is polymerized, and

iil. then the mixture (C) in the presence of the under ii. prepared polymer is polymerized.

The preparation of the polymer comprises the successive radical emulsion polymerization of three mixtures (A), (B) and (C) of olefinically unsaturated monomers, each in water. It is therefore a multi-stage radical emulsion polymerization, i. the mixture (A) is polymerized first, then ii. in the presence of the i. prepared polymer, the mixture (B) is polymerized and further iii. in the presence of the under ii. prepared polymer, the mixture (C) is polymerized. All three monomer mixtures are thus polymerized via a free-radical emulsion polymerization (that is to say a stage or also a polymerization stage) which is carried out separately, these stages taking place in succession. In terms of time, the stages can take place one after the other. It is also possible that after the completion of a stage the corresponding reaction solution is stored for a certain period of time and / or transferred to another reaction vessel and only then is the next stage carried out. In addition to the polymerization of the monomer mixtures (A), (B) and (C), the preparation of the polymer preferably comprises no further polymerization steps.

Mixtures (A), (B) and (C) are mixtures of olefinically unsaturated monomers. Suitable olefinically unsaturated monomers can be mono- or poly-olefinically unsaturated. Examples of suitable mono-olefinically unsaturated monomers include, in particular, (meth) acrylate-based mono-olefinically unsaturated monomers, mono-olefinically unsaturated monomers containing allyl groups and other mono-olefinically unsaturated monomers containing vinyl groups, such as, for example, vinyl aromatic monomers. The term (meth) acrylic or (meth) acrylate in the context of the present invention encompasses both methacrylates and acrylates. In any case, but not exclusively, (meth) acrylate-based mono-olefinically unsaturated monomers are preferably used.

Mixture (A) contains at least 50% by weight, preferably at least 55% by weight, of olefinically unsaturated monomers with a water solubility of less than 0.5 g / l at 25 ° C. A corresponding preferred monomer is styrene. The solubility of the monomers in water is determined using the method described below. The monomer mixture (A) preferably contains no hydroxy-functional monomers. The monomer mixture (A) likewise preferably does not contain any acid-functional monomers. The monomer mixture (A) very particularly preferably does not contain any monomers with functional groups containing heteroatoms. This means that heteroatoms, if any, are only in the form of bridging groups. This is the case, for example, in the (methacrylate-based, simple olefinically unsaturated monomers described above which have an alkyl radical as the radical R. The monomer mixture (A) preferably contains only mono-olefinically unsaturated monomers. The monomer mixture (A) preferably contains at least one simple unsaturated esters of (meth) acrylic acid with an alkyl radical and at least one vinyl group-containing simple olefinically unsaturated monomer with a radical arranged on the vinyl group which is aromatic or which is mixed, saturated, aliphatic-aromatic, in which case the aliphatic portions of the radical are alkyl groups Monomers contained in the mixture (A) are selected so that a polymer produced therefrom has a glass transition temperature of 10 to 65 ° C., preferably 30 to 50 ° C. The glass transition temperature can be determined using the method described below i. by the E emulsion polymerization of the monomer mixture (A) produced polymer is also referred to as seed. The seed preferably has an average particle size of 20 to 125 nm (measured by means of dynamic light scattering as described below; cf. determination methods Mixture (B) contains at least one polyolefinically unsaturated monomer, preferably at least one polyolefinically unsaturated monomer. A corresponding preferred monomer is hexanediol diacrylate. The monomer mixture (B) preferably contains no hydroxy-functional monomers. The monomer mixture (B) likewise preferably does not contain any acid-functional monomers. The monomer mixture (B) very particularly preferably does not contain any monomers with functional groups containing heteroatoms. This means that heteroatoms, if any, are only in the form of bridging groups. This is the case, for example, in the (meth) acrylate-based, simple olefinically unsaturated monomers described above which have an alkyl radical as the radical R. In addition to the at least one polyolefinically unsaturated monomer, the monomer mixture (B) preferably also comprises the following monomers: firstly at least one monounsaturated ester of (meth) acrylic acid with an alkyl radical and secondly at least one monolefinically unsaturated monomer containing vinyl groups with one of the vinyl group which is aromatic or which is mixed saturated-aliphatic-aromatic, in which case the aliphatic portions of the radical are alkyl groups. The proportion of polyunsaturated monomers is preferably from 0.05 to 3 mol%, based on the total molar amount of monomers of the monomer mixture (B). The monomers contained in the mixture (B) are selected so that a polymer produced therefrom has a glass transition temperature of -35 to 15 ° C., preferably of -25 to + 7 ° C. The glass transition temperature can be determined using the method described below. That in stage ii. polymer produced by the emulsion polymerization of the monomer mixture (B) in the presence of the seeds is also referred to as the core. After stage ii. the result is a polymer which comprises the seed and the core. The polymer, which after stage ii. obtained, preferably has an average particle size of 80 to 280 nm, preferably 120 to 250 nm (measured by means of dynamic light scattering as described below; cf. determination methods).

The monomers contained in the mixture (C) are selected so that a polymer produced therefrom has a glass transition temperature of from -50 to 15 ° C., preferably from -20 to + 12 ° C. The glass transition temperature can using the method described below. The olefinically unsaturated monomers of the mixture (C) are preferably selected so that the resulting polymer, comprising the seed, core and shell, has an acid number of 10 to 25. Accordingly, the mixture (C) preferably contains at least one alpha-beta unsaturated carboxylic acid, particularly preferred (meth) acrylic acid. The olefinically unsaturated monomers of the mixture (C) are additionally or alternatively preferably selected such that the resulting polymer, comprising the seed, core and shell, has an OH number of 0 to 30, preferably 10 to 25 With all the acid numbers and OH mentioned above - Numbers are values calculated on the basis of the total monomer mixtures used. The monomer mixture (C) preferably contains at least one alpha-beta unsaturated carboxylic acid and at least one monounsaturated ester of (meth) acrylic acid with an alkyl radical substituted by a hydroxyl group. The monomer mixture (C) particularly preferably comprises at least one alpha-beta unsaturated carboxylic acid, at least one monounsaturated ester of (meth) acrylic acid with an alkyl radical substituted by a hydroxyl group and at least one monounsaturated ester of (meth) acrylic acid with an alkyl radical. If an alkyl radical without further specification is mentioned in the context of the present invention, this is always to be understood as a pure alkyl radical without functional groups and heteroatoms. That in stage iii. Polymer produced by the emulsion polymerization of the monomer mixture (C) in the presence of seed and core is also referred to as a shell. After stage iii. the result is a polymer which comprises the seed, core and shell, ie polymer (b). The polymer (b) has after its preparation an average particle size of 100 to 500 nm _"preferably 125 nm to 400, very particularly preferably from 130 to 300 nm (as described below measured by dynamic light scattering;.. Determination see methods)

The coating composition used according to the invention preferably contains a proportion of component (a) such as at least one SCS polymer in a range from 1.0 to 20% by weight, particularly preferably from 1.5 to 19% by weight, very particularly preferably from 2.0 to 18.0% by weight, in particular from 2.5 to 17.5% by weight, most preferably from 3.0 to 15.0% by weight, in each case based on the total weight of the coating ngsm composition. The The proportion of component (a) in the coating composition can be determined or determined by determining the solids content (also called non-volatile content, solids content or solids content) of an aqueous dispersion containing component (a).

Additionally or alternatively, preferably additionally, to the at least one previously described SCS polymer as component (a), the coating composition used according to the invention can contain at least one polymer different from the polymer as binder of component (a), in particular at least one polymer selected from the group consisting of from polyurethanes, polyureas, polyesters, poly (meth) acrylics and / or copolymers of the abovementioned polymers, in particular polyurethane poly (meth) acrylates and / or polyurethane polyureas.

Preferred polyurethanes are described, for example, in German patent application DE 199 48 004 A1, page 4, line 19 to page 11, line 29 (polyurethane prepolymer B1), in European patent application EP 0 228 003 A1, page 3, line 24 to page 5, Line 40, in European patent application EP 0 634 431 A1, page 3, line 38 to page 8, line 9, and international patent application WO 92/15405, page 2, line 35 to page 10, line 32.

Preferred polyesters are, for example, in DE 4009858 A1 in column 6, line 53 to column 7, line 61 and column 10, line 24 to column 13, line 3 or WO 2014/033135 A2, page 2, line 24 to page 7, line 10 and page 28, line 13 to page 29, line 13.

Preferred polyurethane-poly (meth) acrylate copolymers ((meth) acrylated

Polyurethanes) and their production are described, for example, in WO 91/15528 L1, page 3, line 21 to page 20, line 33 and in DE 4437535 A1, page 2, line 27 to page 6, line 22.

Preferred polyurethane-polyurea copolymers are polyurethane-polyurea particles, preferably those with an average particle size of 40 to 2000 nm, the polyurethane-polyurea particles, each in converted form Form, at least one isocyanate-containing polyurethane prepolymer containing anionic and / or convertible into anionic groups and at least one polyamine containing two primary amino groups and one or two secondary amino groups. Such copolymers are preferably used in the form of an aqueous dispersion. Such polymers can in principle be produced by known polyaddition of, for example, polyisocyanates with polyols and polyamines. The mean particle size of such polyurethane-polyurea particles is determined as described below (measured by means of dynamic light scattering as described below; cf. determination methods).

The proportion of such polymers different from the SCS polymer in the

The coating composition is preferably smaller than the proportion of the SCS polymer. The polymers described are preferably hydroxy-functional and particularly preferably have an OH number in the range from 15 to 200 mg KOH / g, particularly preferably from 20 to 150 mg KOH / g.

The coating compositions used according to the invention particularly preferably comprise at least one hydroxy-functional polyurethane-poly (meth) acrylate copolymer, again preferably at least one hydroxy-functional polyurethane-poly (meth) acrylate copolymer and at least one hydroxy-functional polyester and optionally a preferably hydroxy-functional polyurethane-polyurea copolymer.

The proportion of the other polymers as binders of component (a) - in addition to an SCS polymer - can vary widely and is preferably in the range from 1.0 to 25.0% by weight, preferably 3.0 to 20.0% by weight .-%, particularly preferably 5.0 to 15.0 wt .-%, each based on the total weight of the

Coating composition

In addition, the coating composition can contain at least one typical crosslinking agent known per se. If it contains a crosslinking agent, it is preferably at least one aminoplast resin and / or at least one blocked or free polyisocyanate, preferably an aminoplast resin. Among the aminoplast resins, melamine resins in particular are preferred. If the coating composition contains crosslinking agents, the proportion of these crosslinking agents, in particular aminoplast resins and / or blocked or free polyisocyanates, particularly preferably aminoplast resins, including preferably melamine resins, preferably in the range from 0.5 to 20.0% by weight. %, preferably 1.0 to 15.0% by weight, particularly preferably 1.5 to 10.0% by weight, in each case based on the total weight of the coating composition. The proportion of crosslinking agent is preferably smaller than the proportion of the SCS polymer in the coating composition.

Component (b)

A specialist is familiar with the terms “pigments” and “fillers”. The term “filler” is known to the person skilled in the art, for example from DIN 55943 {date: October 2001). For the purposes of the present invention, a “filler ^1” is preferably understood to mean a component which is essentially, preferably completely, insoluble in the coating composition used according to the invention, such as, for example, a water-based lacquer, which is used in particular to increase the volume. For the purposes of the present invention, “fillers” preferably differ from “pigments” by their refractive index, which is <1.7 for fillers. Any customary filler known to the person skilled in the art can be used as component (b). Examples of suitable fillers are kaolin, dolomite, calcite, chalk, calcium sulfate, barium sulfate, graphite, silicates such as magnesium silicates, in particular corresponding sheet silicates such as hectorite, bentonite, montmorillonite, talc and / or mica, silicas, in particular pyrogenic silicas, hydroxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or polymer powder.

The term “pigment” is also known to the person skilled in the art, for example from DIN 55943 (date: October 2001). In the context of the present invention, a “pigment” is preferably understood to mean powdery or platelet-shaped components which are used in the coating agent used according to the invention. Composition such as a waterborne basecoat are substantially, preferably completely, insoluble. These are preferably colorants and / or substances which, owing to their magnetic, electrical and / or electromagnetic properties, can be used as pigments. Pigments differ from "fillers" preferably by their refractive index, which is 2: 1.7 for pigments.

Color pigments and. Are preferred under the term "pigments"

Effect pigments subsumed.

A person skilled in the art is familiar with the term color pigments. The terms “coloring pigment” and “color pigment” are interchangeable in the sense of the present invention. A corresponding definition of the pigments and further specifications thereof is regulated in DIN 55943 (date: October 2001). Inorganic and / or organic pigments can be used as the color pigment. White pigments, colored pigments and / or black pigments are used as particularly preferred color pigments. Examples of white pigments are titanium dioxide, zinc white, zinc sulfide and lithopone. Examples of black pigments are carbon black, iron-manganese black and spinel black. Examples of color pigments are chromium oxide, chromium, cobalt green, ultramarine green, cobalt blue, ultramarine blue, manganese blue, ultramarine violet, cobalt and manganese violet, red iron oxide, cadmium, molybdenum red and Uftramarinrot, brown iron oxide, mixed brown, spinel and corundum and chrome orange, yellow iron oxide, nickel titanium yellow, chrome titanium yellow , Cadmium sulfide, cadmium zinc sulfide, chrome yellow and bismuth vanadate.

A person skilled in the art is familiar with the term effect pigments. A corresponding definition can be found, for example, in the Römpp Lexikon, Lacke und Druckfarben, Georg Thieme Verlag, 1998, 10th edition, pages 176 and 471. A definition of pigment genes in general and further specifications thereof can be found in DIN 55943 (date: October 2001) regulated. Effect pigments are preferably those pigments which are optically effect-imparting or color and optically effect-imparting, in particular optically effect-giving. The terms "optically effect and color pigment", "optically effect pigment" and "Effect pigment" are therefore preferably interchangeable. Preferred effect pigments are, for example, platelet-shaped metal effect pigments such as platelet-shaped aluminum pigments, gold bronzes, fire-colored bronzes and / or iron oxide-aluminum pigments, pearlescent pigments such as fish silver, basic lead carbonate, bismuth oxide chloride and / or metal oxide-mica pigments and / or graphite pigments or other, like effect pigments (mica) Iron oxide, multi-layer effect pigments from PVD films and / or liquid crystal polymer pigments. Flake-like effect pigments, in particular flake-like aluminum pigments and metal oxide mica pigments, are particularly preferred.

The coating composition used according to the invention, such as, for example, a waterborne basecoat, particularly preferably comprises at least one effect pigment as component (b).

The coating composition used according to the invention preferably contains a proportion of effect pigment as component (b) in a range from 1 to 20% by weight, particularly preferably from 1.5 to 18% by weight, very particularly preferably from 2 to 16% by weight. %, in particular from 2.5 to 15% by weight, most preferably from 3 to 12% by weight or from 3 to 10% by weight, in each case based on the total weight of the coating composition. The total proportion of all pigments and / or fillers in the coating composition is preferably in the range from 0.5 to 40.0% by weight, more preferably from 2.0 to 20.0% by weight, particularly preferably from 3.0 to 15.0% by weight, based in each case on the total weight of the coating composition.

The relative weight ratio of component (b) such as at least one effect pigment to component (a) such as at least one SCS polymer in the coating composition is in a range from 4: 1 to 1: 4, particularly preferably in a range from 2: 1 to 1: 4, very particularly preferably in a range from 2: 1 to 1: 3, in particular in a range from 1: 1 to 1: 3 or from 1: 1 to 1: 2.5. Component (c)

The coating composition used according to the invention is preferably aqueous. It is preferably a system which, as solvent (ie as component (c)), mainly water, preferably in an amount of at least 20% by weight, and organic solvents in smaller proportions, preferably in an amount of <20% by weight .-%, each based on the total weight of the coating composition. The coating composition used according to the invention preferably contains a proportion of water of at least 20% by weight, particularly preferably at least 25% by weight, very particularly preferably at least 30% by weight, in particular at least 35% by weight, in each case on the total weight of the coating composition.

The coating composition used according to the invention preferably contains a proportion of water which is in a range from 20 to 65% by weight, particularly preferably in a range from 25 to 60% by weight, very particularly preferably in a range from 30 to 55% by weight. -%, based in each case on the total weight of the coating composition.

The coating composition used according to the invention preferably contains a proportion of organic solvents which is in a range from <20% by weight, particularly preferably in a range from 0 to <20% by weight, very particularly preferably in a range from 0.5 to <20 wt .-% or up to 15 wt .-%, each based on the total weight of the

Coating composition.

Examples of such organic solvents are heterocyclic, aliphatic or aromatic hydrocarbons, mono- or polyhydric alcohols, especially methanol and / or ethanol, ethers, esters, ketones and amides, such as. B. N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, toluene, xylene, butanol, ethyl and butyl glycol and their acetates, butyl diglycol, Diethylengfykoldimethylether, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, acetone, isophorone or mixtures thereof called.

Other optional components

The coating composition used according to the invention may optionally also contain at least one thickener (also referred to as thickening agent!) As component (d). Examples of such thickeners are inorganic thickeners, for example metal silicates such as layered silicates, and organic thickeners, for example poly (meth) acrylic acid thickeners and / or (meth) acrylic acid (meth) acrylate copolymer thickeners, polyurethane thickeners and polymeric waxes. The metal silicate is preferably selected from the group of smectites. The smectites are particularly preferably selected from the group of montmorillonites and hectorites. In particular, the montmorillonites and hectorites are selected from the group consisting of aluminum-magnesium silicates and sodium-magnesium and sodium-magnesium-fluorine-lithium layered silicates. These inorganic layered silicates are sold, for example, under the Laponite® brand. Thickeners based on poly {meth) acrylic acid and (meth) acrylic acid re (meth) acrylate copolymer thickeners are optionally crosslinked and / or neutralized with a suitable base. Examples of such thickeners are “alkali swellable emulsions” (ASE), and hydrophobically modified variants thereof, the “hydrophically modified alkali swellable emulsions” (HASE). These thickening agents are preferably anionic. Corresponding products such as Rheovis® AS 1 130 are commercially available. Thickeners based on polyurethanes (e.g. polyurethane associative thickeners) are optionally crosslinked and / or neutralized with a suitable base. Corresponding products such as Rheovis® PU 1250 are commercially available. Suitable polymeric waxes are, for example, optionally modified polymeric waxes based on ethylene-vinyl acetate copolymers. A corresponding product is commercially available, for example, under the name Aquatix® 8421.

The coating composition used in accordance with the invention can, depending on the desired application, one or more commonly used additives included as further component (s) (d). For example, the coating composition can contain at least one additive selected from the group consisting of reactive thinners, light stabilizers, antioxidants, deaerating agents, emulsifiers, slip additives, polymerization inhibitors, initiators for radical polymerizations, adhesion promoters, leveling agents _» film-forming aids _» sag control agents (SCAs), flame retardants, SCAs, Corrosion Inhibitors _» Contain solvents, biocides and matting agents. They can be used in the known and customary proportions.

The coating composition used according to the invention can be produced using the customary and known mixing processes and mixing units.

Coating according to the invention

Another object of the present invention is at least one coating (B1) located on a substrate which can be obtained according to the method according to the invention.

All preferred embodiments described above in connection with the method according to the invention for producing the coating (B1) are also preferred embodiments with regard to the coating (B1) obtainable by means of this method.

Preferably, the coating (B1) to a coating process of the invention _", but without performing Schrit (3), is available on to surface defects and / or optical _defects" a smaller number. In particular, the coating (B1) has an improved appearance and / or an improved needlestick robustness compared to a coating which can be obtained by the process according to the invention but without carrying out step (3).

The surface defects and / or optical defects are preferably selected from the group of pinholes, stoves, runners, cloudy conditions and / or Appearance (visual appearance). As mentioned above, the coating (B1) is preferably a basecoat film, such as a waterborne basecoat film, which in turn can be part of a multi-layer paint system. The examination and assessment of the occurrence of pinholes is carried out in accordance with the determination method described below by counting the pinpricks when the coating is wedged onto a substrate in a layer thickness range from 0 to 40 pm (dry layer thickness), the ranges from 0 to 20 pm and from> 20 up to 40 pm are counted separately, normalization of the results to an area of 200 cm ² and addition to a total number. A single pin prick is preferably already a defect. The examination and assessment of the occurrence of cookers is carried out in accordance with the determination method described below by determining the cooker limit, i.e. the layer thickness of a coating such as a basecoat layer from which cookers appear, in accordance with DIN EN ISO 28199-3, point 5. (Date: January 2010 ). A single cooker is preferably already a defect. The investigation and assessment of the occurrence of cloudiness is carried out according to the determination method described below with the measuring device ctoud-runner from BYK-Gardner GmbH, whereby the three parameters "Mot! Ing15", "Mottling45" and "Mottling60" as a measure of the cloudiness , measured at angles of 15 °, 45 ° and 60 ° relative to the reflection angle of the light source used for the measurement, the cloudiness being more pronounced if the corresponding parameter (s) (a) higher (n) value ( e) has or have. The examination and assessment of the appearance is carried out in accordance with the determination method described below by means of the assessment of the course when the coating is applied to the wedge on a substrate in a layer thickness range from 0 to 40 pm (dry layer thickness), different ranges, for example from 10-15 pm, 15- 20 pm and 20-25 pm are marked and by means of the Wave scan measuring device from Byk-Gardner GmbH, the examination and assessment is carried out within these layer thickness ranges. A laser beam is directed at the surface to be examined at an angle of 60 ^s , and the fluctuations of the reflected light in the short wave range (0.3 to 1, 2 mm) and in the long wave are measured over a measuring distance of 10 cm Range {1, 2 to 12 mm) registered with the aid of the measuring device {long wave = LW; short wave = SW; the lower the values, the better the course). The Investigation and assessment of the occurrence of runners is carried out according to the determination method described below by determining the inclination of the run according to DIN EN ISO 28199-3, point 4, (date: January 2010). A defect preferably occurs when runners appear from a layer thickness which is below a layer thickness which is 125% of the target layer thickness. If the target layer thickness is, for example, 12 pm, a defect occurs if runners occur at a layer thickness of 12 pm + 25%, that is to say at 16 pm. The layer thicknesses are determined in accordance with DIN EN ISO 2808 (date: May 2007), method 12L, preferably using the MiniTest® 3100- 4100 measuring device from ElektroPhysik. In all cases, it is the rock layer thickness.

The terms “pinholes”, “stove”, “runner” and “gradient” are known to the person skilled in the art, for example from the Römpp Chemie lexicon, varnishes and printing inks,

1998, 10th edition. The term cloudiness is also known to the person skilled in the art.

According to DIN EN ISO 4618 (date: January 2015), the cloudiness of a paint job means the non-uniform appearance of a paint job, caused by irregular, arbitrarily distributed areas on the surface that differ in color and / or gloss. Such a stain-like inhomogeneity disturbs the uniform overall impression of the coating and is usually undesirable. A method for determining the cloudiness is given below.

Positioning methods

1. Determination of the non-volatile content

The non-volatile content (of the solid) is determined in accordance with DIN EN ISO 3251 (date: June 2008). 1 g of sample are weighed into a previously dried aluminum dish and dried in a drying cabinet for 60 minutes at 125 ° C., cooled in a desiccator, and then weighed out. The residue based on the total amount of the sample used corresponds to the non-volatile fraction. If necessary, the volume of the non-volatile component can be determined in accordance with DIN 53219 (date: August 2009).

2. Determination of the number average molecular weight

Unless otherwise stated, the number-average molecular weight (M _n ) is determined using a vapor pressure osmometer type 10.00 (Knauer) on series of concentrations in toluene at 50 ° C. with benzophenone as the calibration substance for determining the experimental calibration constant of the measuring device used according to E. Schröder, G. Müller, K.-F. Arndt, "Guide to Polymer Characterization", Akademie- Verlag, Berlin, pp. 47-54, 1982.

3. Determination of the OH number and the acid number

The OH number and the acid number are each determined by calculation.

4. Determination of the average particle size of SCS polymers and

Polyurethane-Folvhamstoff-Fartikeln

The mean particle size is determined by means of dynamic light scattering (photon correlation spectroscopy) (PCS) based on DIN ISO 13321 (date: October 2004). A “Malvern Nano S90” (from Malvem Instruments) is used for the measurement at 25 ± 1 ° C. The device covers a size range from 3 to 3000 nm and is equipped with a 4mW He-Ne laser at 633 nm. The respective samples are diluted with particle-free, deionized water as the dispersing medium and then measured in a 1 ml polystyrene cuvette with a suitable scattering intensity , The evaluation was carried out using a digital correlator with the aid of the evaluation software Zetasizer Vers. 7.11 (Fa. Malvem Instruments). It is measured five times and the measurements are repeated on a second, freshly prepared sample. With regard to the SCS polymer, the mean particle size is understood to mean the arithmetic number average of the measured mean particle diameter (Z-average mean; number average; 0N, 50% value). The standard deviation of a 5-fold determination is s 4%. With regard to the polyurethane-polyurea particles that can be used, the average particle size is understood to mean the arithmetic volume average from the average particle size of the individual preparations (V-average mean; volume average; dv, 50% value). The maximum deviation of the volume average from five individual measurements is ± 15%. The check is carried out using polystyrene standards with certified particle sizes between 50 and 3000 nm.

5. Determination of the layer thicknesses

The layer thicknesses are determined in accordance with DIN EN ISO 2808 (date: May 2007), method 12A, using the MiniTest® 3100-4100 measuring device from ElektroPhysik.

6. Assessment of the occurrence of needle pricks and the layer thickness-dependent course

To assess the occurrence of pinholes and the layer thickness-dependent course, wedge-shaped multi-layer coatings are produced according to the following general rule:

A steel sheet measuring 30 x 50 cm coated with a standard KTL (CathoGuard® 800 from BASF Coatings GmbH) is provided with an adhesive strip (Tesa tape, 19 mm) on one longitudinal edge in order to be able to determine differences in layer thickness after coating. A water-based bag is applied electrostatically as a wedge with a target layer thickness (layer thickness of the dried material) of 0-40 pm. The outflow rate is between 300 and 400 ml / min; the speed of the ESTA-G locke is varied between 23,000 and 43,000 rpm; the exact details of the application parameters selected in each case are given below within the experimental section. After a flash-off time of 4-5 minutes at room temperature (18 to 23 ° C), the assembly is dried in a forced air oven at 60 ° C for 10 minutes. To Removal of the adhesive strip is manually applied to the dried water-based lacquer layer using a flow cup gun using a commercially available two-component clear lacquer (ProGloss® from BASF Coatings GmbH) with a target layer thickness (layer thickness of the dried material) of 40-45 pm. The resulting clear lacquer layer is flashed off at room temperature (18 to 23 ° C.) for 10 minutes; Then the curing takes place in a convection oven at 140 ° C for a further 20 minutes.

The occurrence of pinholes is assessed visually according to the following general rule: The dry layer thickness of the waterborne basecoat is checked and for the basecoat layer thickness wedge the ranges from 0-20 pm and from 20 pm to the end of the wedge are marked on the steel sheet. The pinholes are evaluated visually in the two separate areas of the water-based lacquer wedge. The number of needle stitches is counted for each area. All results are normalized to an area of 200 cm ² and then added to a total number. In addition, a record is made of the dry layer thickness of the water-based lacquer wedge at which needle sticks no longer occur.

The course of the course, which is dependent on the layer thickness, is assessed according to the following general rule: the dry layer thickness of the waterborne basecoat is checked, and different areas, for example 10-15 pm, 15-20 pm and 20-25 pm, are marked on the steel sheet for the basecoat film thickness wedge. The determination or assessment of the course depending on the layer thickness is carried out with the aid of the Wave Scan measuring device from Byk-Gandner GmbH within the previously determined basecoat layer thickness ranges. For this purpose, a laser beam is directed at an angle of 60 ° onto the surface to be examined, and the fluctuations of the reflected light in the so-called short wave range (0.3 to 1.2 mm) and in the so-called long wave range (1, 2 to 12 mm) registered with the aid of the measuring device (long wave = LW; short wave = SW; the lower the values, the better the appearance). In addition, the measure "distinctness of imgage" (DOI) is determined as a measure of the sharpness of an image reflected in the surface of the multilayer structure (the higher the value, the better the appearance). 7. Determination of cloudiness

To determine the cloudiness, multi-layer coatings are produced according to the following general instructions:

A water-based lacquer is applied to a steel sheet with the dimensions 32 x 60 cm coated with a conventional filler paint by double application; the application in the first step is electrostatic with a

Target layer thickness of 8-9 pm, in the second step, after a 2-minute flash-off time at room temperature, application is also electrostatic with a target layer thickness of 4-5 pm. The resulting waterborne basecoat is then dried again after 5 minutes at room temperature (18 to 23 ° C) in a forced air oven for 5 minutes at 80 ° C. Both basecoats are applied at a speed of 43,000 rpm and a flow rate of 300 ml / min. A commercially available two-component clear lacquer (ProGloss from BASF Coatings GmbH) with a target layer thickness of 40-45 pm is applied to the dried water-based lacquer layer. The resulting layer of kiarlack is flashed off at room temperature (18 to 23 ° C.) for 10 minutes; Then the curing takes place in a convection oven at 140 ° C for a further 20 minutes.

The cloudiness is then assessed using the cloud-runner measuring device from BYK-Gardner GmbH in accordance with alternative b). Among other things, the device the three parameters "Mottling15", "Mottling45" and "Mottling60", which can be viewed as a measure of the cloudiness, measured at angles of 15 °, 45 ° and 60 ° relative to the reflection angle of the light source used for the measurement. The larger the value, the more pronounced the cloudy picture.

8. Assessment of streakiness

The streak is assessed using the method described in patent specification DE 10 2009 050 075 B4. The homogeneity indices mentioned and defined therein or the average homogeneity index can likewise detect the occurrence of streaks during application, even if these indices were used in the patent specification mentioned to assess the cloudiness are. The higher the corresponding values, the more pronounced stripes can be seen on the substrate.

3- Determination of the particle ear distribution including the Din value and the ratio of the parameters TTI / ΊGT «M and Tt ^ / Tt» «? as a measure of the homogeneity of the spray formed during atomization by means of the method according to the invention

The underlying particle size distributions are determined using a commercial single PDA from DantecDynamics (P60, Lexel Argon fiber, FibreFlow) and a commercial time shift measuring device from AOM Systems (SpraySpy®). Both devices are built and aligned according to the Hereteller specifications. The settings for the SpraySpy® time shift measuring device have been adjusted by the manufacturer for the pallet of materials to be used. The PDA is operated in forward scatter at an angle of 60-70 ° with a wavelength of 514.5 nm (orthogonally polarized) in refiection. The receiving optics have a focal length of 500 mm, the transmitting optics have a focal length of 400 mm. For both systems, the structure is oriented relative to the atomizer. The general structure is shown in FIG. 1. A rotary atomizer has been used as an example in FIG. 1. The measurement is carried out traversing in the radial-axial direction in relation to the tilted atomizer (tilt angle 45 °), 25 mm vertically below the atomizer flank inclined to the traversing axis. In this case, a defined traversing speed is specified so that the individual detected events are spatially resolved via the associated time-resolved signals. A comparison to grid-resolved measurements provides identical results for the weighted global distribution parameters, but still enables the investigation of any interval range on the cross axis. Furthermore, this method is many times faster than screening, which means that the material expenditure can be reduced with constant flow rates. Detectable drops are recorded with maximum validation tolerance. The raw data are then evaluated using an algorithm for any tolerances. A tolerance of approx. 10% for the PDA system used limits the validation to spherical particles; an increase also includes slightly deformed drops. This makes it possible to consider the sphericity of the measured Allows drops along the measurement axis. The SpraySpy® system is able to distinguish between transparent and non-transparent drops. The measurement axis (see figure according to FIG. 1) is traversed repeatedly and both measurement methods are used. The system-internal evaluation prevents a double measurement of the individual events. The data obtained in this way can thus be evaluated for the transparent spectrum (T) and the non-transparent spectrum (NT). The ratio of the number of measured drops of both spectra serves as a measure for the local distribution of transparent and non-transparent drops. An integral view along the measurement axis is possible. In particular, the ratio of the transparent particles (T) to the total number of particles (total) is determined at a position 1 of x = 5 mm and at a position 2 of x = 25 mm along the measurement axis; the corresponding values are in turn related to describe the homogeneity of the spray which changes from the inside to the outside. For both systems, Single-PDA and SpraySpy®, common distribution moments such as Di ₀ values can be determined based on the raw data.

10, determination of the solubility of the monomers of the mixture (A) in water, which can be used for the preparation of SCS polymers

The solubility of the monomers in water is determined by establishing an equilibrium with the gas space above the aqueous phase (analogously to the literature X.- S. Chat, QX Hou, FJ Sehork, Journal of Applied Polymer Science Vol. 99, 1296-1301 (2006) ). For this purpose, a mass of the respective monomer is added to a defined volume of water such as 2 ml in a 20 ml gas space sample tube that this mass cannot dissolve completely in the selected volume of water. In addition, an emulsifier (10 ppm, based on the total mass of the sample mixture) is added. In order to maintain the equilibrium concentration, the mixture is shaken constantly. The protruding gas phase is exchanged for inert gas, so that an equilibrium is restored. The proportion of the substance to be detected is measured in each case in the gas phase removed (for example by means of gas chromatography). The equilibrium concentration in water can be determined by graphically evaluating the proportion of the monomer in the gas phase. The slope of the curve changes from an almost constant value (S1) to a significantly negative value Slope (S2) as soon as the excess monomer was removed from the mixture. The equilibrium concentration is reached at the intersection of the straight line with the slope S1 and the straight line with the slope S2. The determination described is carried out at 25 ° C.

11. Determination of the glass transition temperatures of polymers which are each obtainable from monomers of the mixtures fAi (B) or IG)

The glass transition temperature T _g is experimentally based on DIN 51005

(Date: August 2005) "Thermal Analysis (TA) - Terms" and DIN 53765 "Thermal Analysis - Dynamic Differential Calorimetry (DDK)" (Date: March 1994). A sample of 15 mg is weighed into a sample pan and inserted into a DSC device. It is cooled to the starting temperature and then a first and a second measuring run are carried out with an inert gas purging (N2) of 50 ml / min with a heating rate of 10 K / min, with cooling to the starting temperature again between the measuring runs. The measurement takes place in the temperature range from about 50 ° C lower than the expected glass transition temperature to about 50 ° C higher than the expected glass transition temperature. According to DIN 53765, point 8.1, the glass transition temperature is the temperature in the second measuring run at which half the change in the specific heat capacity (0.5 delta cp) is reached. It is determined from the DDK diagram (plot of the heat flow against the temperature). It is the temperature that corresponds to the intersection of the center line between the extrapolated baselines before and after the glass transition with the measurement curve. The well-known Fox equation can be used for a targeted estimate of the glass transition temperature to be expected during the measurement. Since the Fox equation is a good approximation, which is based on the glass transition temperatures of the homopolymers and their parts by weight without including the molecular weight, it can be used as a useful tool for the person skilled in the synthesis, so that a desired glass transition temperature can be set in a few targeted experiments , 12. Determination of the wetness wheel

The degree of wetness of a film formed after application of a coating composition such as a waterborne basecoat to a substrate is evaluated. The coating composition is applied electrostatically as a constant layer in the desired target layer thickness (layer thickness of the dried material), such as a target layer thickness which is in a range from 15 μm to 40 μm, by means of rotary atomization. The outflow rate is between 300 and 400 ml / min and the rotational speed of the ESTA bell of the rotary atomizer is in a range of 23,000 and 63,000 rpm (the precise details of the application parameters chosen in each case are given at the relevant points below within the experimental part ) indicated. One minute after the job is completed, the film formed on the substrate is visually assessed for its degree of wetness. This is recorded on a scale from 1 to 5 (1 = very dry to 5 = very wet).

13- Determining the appearance of stoves

To determine the tendency to cook, a multi-layer coating is produced in accordance with DIN EN ISO 28199-1 (date: January 2010) and DIN EN ISO 28199-3 (date: January 2010) according to the following general rule: one with a hardened cathodic electrocoating layer (KTL ) (CathoGuand® 800 from BASF Coatings GmbH) coated perforated sheet with dimensions 57 cm x 20 cm made of steel (according to DIN EN ISO 28199-1, point 8.1, version A) is analogous to DIN EN ISO 28199-1, point 8.2 (version A) prepared. Then, in accordance with DIN EN ISO 28199-1, point 8.3, the application of an aqueous basecoat is carried out electrostatically in a single application as a wedge with a target layer thickness (layer thickness of the dried material; rock layer thickness) in the range from 0 pm to 30 pm. The resulting basecoat is dried in the forced air oven for 5 minutes at 80 ° C without prior flashing off. The determination of the cooker limit, i.e. the basecoat layer thickness from which the cooker appears, is carried out according to DIN EN ISO 28199-3, point 5. 14. Determination of the appearance of runners

To determine the inclination of the barrel, multi-layer coatings are produced in accordance with DIN EN ISO 28199-1 (date: January 2010) and DIN EN ISO 28199-3 (date: January 2010) according to the following general regulation: a) Waterborne basecoats

One with a hardened cathodic electrocoat (KTL) (CathoGuard®

800 from BASF Coatings GmbH) coated perforated sheet of 57 cm x 20 cm made of steel (according to DIN EN ISO 28199-1, point 8.1, version A) is analogous to DIN EN ISO 28199-1, point 8.2 (version A) prepared The following follows according to DIN EN ISO 28199-1, point 8.3

Application of an aqueous basecoat electrostatically in a single application as

Wedge with a target layer thickness (layer thickness of the dried material) in the range from 0 pm to 40 pm. The resulting basecoat film is dried in a forced air oven for 5 minutes at 80 ° C after a flash-off time of 18 minutes at 18-23 ° C. The sheets are ventilated standing upright and dried in between. b) clear coats:

One with a hardened cathodic electrocoat (KTL) (CathoGuard®

800 from BASF Coatings GmbH) and perforated sheet with dimensions of 57 cm x 20 cm made of steel (according to DIN EN ISO 28199-1, point 8.1, version A) coated with a commercially available water-based paint (ColorBrite from BASF Coatings GmbH) is made analogous to DIN EN ISO 28199-1, point 8.2 (version A) prepared. Then, in accordance with DIN EN ISO 28199-1, point 8.3, a clear coat is applied electrostatically in a single application as a wedge with a target layer thickness (layer thickness of the dried material) in the range from 0 pm to 60 pm. The resulting clear lacquer layer is cured after a flash-off time of 18 minutes at 18-23 ° C in a forced air oven for 20 minutes at 140 ° C. The sheets are flashed off and hardened standing upright.

The inclination of the rotor is determined in accordance with DIN EN ISO 28199-3, point 4. In addition to the layer thickness at which a runner is 10 mm from the lower edge of the hole, the layer thickness is determined from which the first inclination of a hole can be observed visually.

15. Determination of the opacity

The opacity is determined in accordance with DIN EN (SO 28199-3 (January

2010; Point 7).

Examples and comparative examples

The following examples and comparative examples serve to explain the invention, but are not to be interpreted as restrictive.

Unless stated otherwise, the parts are parts by weight and percentages are percentages by weight.

1. Preparation of an aqueous dispersion AD1

1.1 The components mentioned below and used to produce the aqueous dispersion AD1 have the following meanings:

DMEA diethyl ethanolamine

Deionized water

EF 800 Aerosol® EF-800, commercially available emulsifier from

Cytec company

APS ammonium peroxodisulfate

1,6-HDDA 1,6-hexanediol diacrylate

2-HEA 2-hydroxyethyl acrylate

MMA methyl methacrylate

1.2 Preparation of the aqueous dispersion AD1 containing a multi-stage SCS

polyacrylate

Monomer mixture (Al stage i.

80% by weight of items 1 and 2 according to Table 1.1 below are placed in a steel reactor (5 L volume) with a reflux condenser and heated to 80.degree. The remaining portions of the components listed under “Template” in Table 1.1 were premixed in a separate vessel. This mixture and separately the initiator solution (Table 1.1, positions 5 and 6) are simultaneously added dropwise to the reactor within 20 min, with a proportion of the monomers in the reaction solution, based on the total amount of stage i. used Monomers, of 6.0 wt .-% is not exceeded during the entire reaction period. The mixture is then stirred for 30 minutes.

Monomer mixture (Bl stage ii.

The components specified under “Mono” in Table 1.1 are premixed in a separate vessel. This mixture is added dropwise to the reactor within 2 hours, with a proportion of the monomers in the reaction solution, based on the total amount of in stage ii. monomers used, of 6.0 wt .-% is not exceeded during the entire reaction period. The mixture is then stirred for 1 hour.

Monomer mixture fCl stage iii.

The components specified in table 1.1 under "Mono 2" are premixed in a separate vessel. This mixture is added dropwise to the reactor over the course of 1 hour, with a proportion of the monomers in the reaction solution, based on the total amount in stage iii. monomers used, of 6.0 wt .-% is not exceeded during the entire reaction period. Then 2

Hours stirred.

Then the reaction mixture is cooled to 60 ° C and the

Neutralization mixture (table 1.1, positions 20, 21 and 22) premixed in a separate vessel. The neutralization mixture is added dropwise to the reactor within 40 min, the pH of the reaction solution being adjusted to a pH of 7.5 to 8.5. The reaction product is then stirred for a further 30 min, cooled to 25 ° C. and filtered.

The solids content of the aqueous dispersion AD1 thus obtained was determined for the reaction control. The result, together with the pH value and the determined particle size, is given in Table 1.2. Table n: Aqueous dispersion AD1 containing a multi-stage polyacrylate

Table 1.2: Key figures of the aqueous dispersion AD1 and the polymer it contains

2. Preparation of an aqueous polyurethane-polyurea dispersion PP1

Preparation of a partially neutralized prepolymer solution

559.7 parts by weight of a linear polyester polyol and 27.2 parts by weight of dimethylolpropionic acid (from GEO Specialty Chemicals) were dissolved in 344.5 parts by weight of methyl ethyl ketone under nitrogen in a reaction vessel equipped with a stirrer, internal thermometer, reflux condenser and electric heater. The linear polyester diol was previously prepared from dimerized fatty acid (Pripol® 1012, from Croda), isophthalic acid (from BP Chemicals) and hexane-1,6-diol (from BASF SE) (weight ratio of the starting materials: dimeric fatty acid to isophthalic acid too Hexane-1, 6-diol = 54.00: 30.02: 15.98) and had a hydroxyl number of 73 mg KOH / g solids, an acid number of 3.5 mg KOH I g solids and a calculated, number average molecular weight of 1379 g / mol and a number average molecular weight of 1350 g / mol determined by vapor pressure osmometry. 213.2 parts by weight of dicyclohexylmethane-4,4'-diisocyanate (Desmodur® W, Covestro AG) with an isocyanate content of 32.0% by weight and 3.8 parts by weight of dibutyltin dilaurate ( Merck) added. The mixture was then heated to 80 ° C. with stirring. The stirring was continued at this temperature until the isocyanate content of the solution was 1.49% by weight and was constant. Then 626.2 parts by weight of methyl ethyl ketone were added to the prepolymer and the reaction mixture was cooled to 40.degree. After 40 ° C. had been reached, 11.8 parts by weight of triethylamine (from BASF SE) were added dropwise in the course of two minutes and the mixture was stirred for a further 5 minutes.

Implementation of the prepolymer with diethylenetriamine diketimine

Then 30.2 parts by weight of a 71.9% by weight solution of diethylenetriaminediketimine in methyl isobutyl ketone (ratio of isocyanate groups of the prepolymer to diethylenetriaminediketimine (with a secondary amino group): 5: 1 mol / mol, corresponds to two NCO groups per blocked, primary amino group ) mixed in within one minute, the reaction temperature rising briefly by 1 ° C. after addition to the prepolymer solution. The dissolution of diethylenetriamine diketimine in methyl isobutyl ketone was previously by azeotropically circling water of reaction in the reaction of diethylenetriamine (from BASF SE) with methyl isobutyl ketone in methyl isobutyl ketone at 110 - 140 ° C. The mixture was adjusted to an amine equivalent mass (solution) of 124.0 g / eq by dilution with methyl isobutyl ketone. A blocking of the primary amino groups of 98.5% was determined by means of IR spectroscopy based on the residual absorption at 3310 cm-1. The solids content of the isocyanate group-containing polymer solution was determined to be 45.3%.

Dispersion and vacuum distillation

After stirring at 40 ° C for 30 minutes, the contents of the reactor were dispersed in 1206 parts by weight of deionized water (23 ° C) within 7 minutes. Methyl ethyl ketone was distilled off from the resulting dispersion at 45X under vacuum and any solvent and water losses were compensated for with deionized water, so that a solids content of 40% by weight resulted. A white, stable, high-solids, low-viscosity dispersion with crosslinked particles was obtained which did not show any settling even after 3 months. The microgel dispersion (PD1) thus obtained had the following key figures:

Solids content (130 ° C, 60 min, 1 g): 40.2% by weight

Methyl ethyl ketone content (GC): 0.2% by weight

Methyl isobutyl ketone (GC) content: 0.1% by weight

Viscosity (23 ° C, rotational viscometer, shear rate = 1000 / s): 15 mPa-s

Acid number: 17.1 mg KOH / g

Solids content

Degree of neutralization (calculated): 49%

pH (23 ° C): 7.4

Particle size (photon correlation spectroscopy,

Volume average): 167 nm

Gel fraction (freeze-dried): 85.1% by weight

Gel content (130 ° C): 87.3% by weight 3. Production of coloring and filler pastes

3.1 Production of a gum paste P1

The yellow paste P1 is made from 17.3 parts by weight of Sicotrans yellow L 1916, available from BASF SE, 18.3 parts by weight of a polyester stiffened according to Example D, column 16, lines 37-59 of DE 40 09 858 A1, 43.6 parts by weight one prepared according to international patent application WO 92/15405, page 15, lines 23-28

Binder dispersion, 16.5 parts by weight of deionized water and 4.3 parts by weight of butyl glycol.

3.2 Production of a white paste P2

The white paste P2 is made from 50 parts by weight of titanium rutile 2310, 6 parts by weight of a polyester produced according to Example D, column 16, lines 37-59 of DE 40 09 858 A1, 24.7 parts by weight of one according to the patent application EP 022 8003 B2, p. 8, lines 6 to 18 prepared binder dispersion, 10.5 parts by weight of deionized water, 4 parts by weight of 2, 7.9-tetramethyl-5-decindole, 52% in BG (available from BASF SE), 4.1 parts by weight Butylglycol, 0.4 parts by weight of 10% dimethylethanolamine in water and 0.3 parts by weight of Acrysol RM-8 (available from The Dow Chemical Company).

3.3 Production of a black paste P3

The black paste P3 is made from 57 parts by weight of a polyurethane dispersion prepared according to WO 92/15405, page 13, line 13 to page 15, line 13, 10 parts by weight of carbon black (carbon black Monarch® 1400 from Cabot Corporation), 5 parts by weight of a polyester , prepared according to Example D, column 16, lines 37-59 of DE 40 09 858 A1, 6.5 parts by weight of a 10% aqueous dimethylethanolamine solution, 2.5 parts by weight of a commercially available polyether (Pluriol® P900, available from BASF SE ), 7 parts by weight of butyl diglycol and 12 parts by weight of deionized water.

3.4 Production of a barium sulfate paste P4

The barium sulfate paste P4 is made from 39 parts by weight of a polyurethane dispersion prepared in accordance with EP 0228003 B2, p. 8, lines 6 to 18, 54 parts by weight of barium sulfate (Blanc fixe micro from Sachtleben Chemie GmbH), 3.7 parts by weight of butyl glycol and 0.3 parts by weight of Agitan 282 (available from Munzing Chemie GmbH) and 3 parts by weight of deionized water.

3.5 Production of a steatite paste PS

The steatite paste P5 is made from 49.7 parts by weight of an aqueous binder dispersion prepared according to WO 91/15528, page 23, line 26 to page 24, line 24, 28.9 parts by weight of steatite (Microtalc IT extra from Mondo Minerals BV) , 0.4 parts by weight of Agitan 282 (available from Munzing Chemie GmbH), 1.45 parts by weight of Disperbyk®- 184 (available from BYK-Chemie GmbH), 3.1 parts by weight of a commercially available polyether (Pluriol® P900, available from BASF SE) and 16.45 parts by weight of deionized water.

4. Production of further intermediates

4.1 Production of a mixed lacquer ML1

Based on the patent specification EP 1534792-B1, column 11, lines 1-13, 81.9 parts by weight of deionized water, 2.7 parts by weight of Rheovis® AS 1130 (available from BASF SE), 8.9 parts by weight of 2.4.7, 9-tetramethyl-5-decindiol, 52% in BG (available from BASF SE), 3.2 parts by weight of Dispex Ultra FA 4437 (available from BASF SE) and 3.3 parts by weight of 10% dimethylethanolamine mixed in water; the resulting mixture is then homogenized.

4.2 Production of a mixed lacquer ML2

47.38 parts by weight of the aqueous dispersion AD1, 42.29 parts by weight of deionized water, 6.05 parts by weight of 2,4.7, 9-tetramethyl-5-d ecindole, 52% in butyiglycol (available from BASF SE), 2 , 52 parts by weight of Dispex Ultra FA 4437 (available from BASF SE), 0.76 parts by weight of Rheovis® AS 1130 (available from BASF SE) and 1.0 part by weight of 10% dimethylethanolamine in water are mixed together and the resulting mixture is then homogenized.

ML1 and ML2 are used to produce effect pigment pastes. 5. Production of aqueous basecoats

5.1 Production of water-based paints WBL1 and WBL2

The components listed in Table 5.1 under "aqueous phase" are stirred together in the order given to form an aqueous mixture. In the next step, a premix is made from the components listed under "Aluminum pigment premix" or "Micapigment premix". These premixes are added separately to the aqueous mixture. After adding a premix, the mixture is stirred for 10 minutes in each case. Then using deionized water and dimethylethanolamine to a pH of 8 and a spray viscosity of 95 ± 10 mPa-s at a shear stress of 1000 s ¹ , measured with a rotary viscometer (Rheolab QC device with temperature control system C-LTD80 / QC from Anton Paar) at 23 ° C.

Table 5.1: Production of the water-based paints WBL1 and WBL2

WBL1 WBL2

Aqueous phase:

3% Na-Mg layered silicate solution 14.4 13.4 deionized water 11.5 11.4

1-propoxy-2-propano! 2.4

/ i-butoxy propanol 1.9 1.1

2-ethylhexanol 2.8

Aqueous binder dispersion AD1 22.6

Aqueous polyurethane-polyurea dispersion PD1 6.6

Polyurethane dispersion, manufactured; according to WO 92/15405, p. 13, line.

29.3 13 to p. 15, line 13

Polyester; produced according to page 28, lines 13 to 33 (example

3.8 1.5 BE1) WO 2014/033135 A2

Polyester; prepared according to Example D, column 16, lines 37-59 of DE

2.2

4009858 A1

Polyurethane modified polyacrylate; produced according to p. 7, line 55

2.2 to p.8, line 23 of DE 4437535 A1

Melamine formakie resin (Cymel® 203 from Allnex) 2.8

Melamine / brmaldehyde resin (Maprenal® 909 / 93IB from INEOS

3.3 Melamines GmbH)

10% dimethylethanolamine in water 0.7 1.0 Piuriol® P900, available from BASF SE 0.6

2,4,7,9-tetramethyl-5-decindiol, 52% in BG (available from BASF

0.2

SE)

Isobutanoi 3.1

Isopropanol 1.8

Butyfglykoi 1.1 2.6

Hydrosol A170, available from DHC Solvent Chemie GmbH 0.4

Methoxypropanol 2.0

Isopar® L, available from Exxon Mobile 1, 5

50% by weight solution of Rheovis® PU 1250 in butyiglycol

0.3 0.3

(Rheovis® PU1250 available from BASF SE)

BYK-347® from Altana / BYK-Chemie GmbH 0.4

Yellow paste P1 1.7 1.7

White paste P2 0.7 0.7

Black paste P3 3.4 3.4

Barium sulfate paste P4 0.7 0.7

Steatite paste P5 1.4 1.4 Aluminlumplgment-Vormlechung:

Mixing lacquer ML1 12.2 12.2

Mixture of two commercially available aluminum pigments, available

from Altana-Eckart (Stapa® Hydrolux 2153 & Hydrolux 600 in 4.0 4.0

Ratio 1: 1)

Mica pigment premix:

Mixed paint ML1 1.0 1.0

Commercially available micapigment Mearlin® Exterior Fine Russet 459V

0.3 0.3 from BASF SE)

Total: 100.0 100.0

Ratio pigment / blinding agent: 0.3 0.3

Solid (discontinued): 21.6% 21.7%

5.2 Production of waterborne basecoats WBL3 to WBL6

The components listed in Table 5.2 under "aqueous phase" are mixed together in the order given to form an aqueous mixture. In the next step, a premix is made from the components listed under Aluminum Pigment Premix. This premix is added to the aqueous mixture. After the addition, the mixture is stirred for 10 minutes. Then, using deionized water and dimethyiethanolamine, a pH of 8 and a spray viscosity of 85 ± 5 mPa s at a shear stress of 1000 s ¹ , measured with a rotary viscometer {Rheolab QC device with temperature control system C-LTD80 / QC from Anton Paar) at 23 ° C.

Within the WBL3 to WBL4 series, the proportion of aluminum pigment and thus the pigment / binder ratio have been reduced. The same applies to the WBL5 to WBLi series. Table 5.2: Production of water-based paints WBL3 to WBL6

Aqueous® phase;

3% Na-Mg layered silicate solution 17.87 17.87 17.87 17.87 deionized water 12.23 16.74 12.07 16.68

2-ethylhexanol 1.99 1.99 1.99 1.99

Polyurethane dispersion, manufactured according to WO

25.41 25.41 25.41

92/15405, p. 13, lines 13 to S, 15, line 13

Daotan® VTW 6464, available from Allnex 1, 59 1.59 1, 59 1.59

Polyurethane modified polyacrylate; manufactured

according to page 7, line 55 to page 8, line 23 of DE 4437535 2.78 2.78 2.78 2.78 A1

3% by weight aqueous Rheovis® AS 1 130

Solution, Rheovis® AS 1130 available from BASF 5.08 5.08 5.08 5.08

SE

Melamine formaldehyde resin (Cymel® 1133 der

3.57 3.57 3.57 3.57 company Allnex)

10% dimethylethanolamine in water 0.95 0.95 0.95 0.95 Pluriol® P900, available from BASF SE 0.40 0.40 0.40 0.40

2,4,7,9-T etramethyl-5-decindiol, 52% in BG

1.35 1, 35 1, 35 1, 35 (available from BASF SE)

Triisobutyl phosphate 1.19 1, 19 1, 19 1, 19

Isopropanol 1.95 1.95 1.95 1.95

Butyl glycol 2.54 2.54 2.54 2.54

50% by weight solution of Rheovis® PU1250 in

Butylglycol (Rheovis® PU1250 available from 0.24 0.24 0.24 0.24 BASF SE)

Tinuvin® 123, available from BASF SE 0.64 0.64 0.64 0.64 Tinuvin® 384-2, available from BASF SE 0.40 0.40 0.40 0.40

Aluminum pigment Vormlschung:

Aluminum pigment Stapa® Hydrolux 600, _ „„

2.71

available from Altana-Eckart

Aluminum pigment Stapa® Hydrolux 200,

7.38 2.77 available from Altana-Eckart

Butyl glycol 9.60 9.60 9.60 9.60

Polyester; prepared according to Example D, column

3.00 3.00 3.00

16, lines 37-59 of DE 40 09 858 A1

Total; 100.00 100.00 100.00 100.00

Pigment / binder ratio: 0.35 0.13 0.35 0.13 5.3 Production of waterborne basecoats WBL7 to WBL10

The components listed in Table 5.3 under “aqueous phase” are stirred together in the order given to form an aqueous mixture. In the next step, a premix is prepared from the components listed under aluminum pigment premix. This premix is added to the aqueous mixture The addition is stirred for 10 minutes and then with the aid of deionized water and dimethylethanolamine to a pH of 8 and a spray viscosity of 85 ± 5 mPa-s at a shear stress of 1000 s ¹ , measured with a rotary viscometer (Rheolab device QC with temperature control system C-LTD80 / QC from Anton Paar) set at 23 ° C.

Within the WBL7 to WBL8 series, the proportion of aluminum pigment and thus the pigment / binder ratio have been reduced. The same applies to the WBL9 to WBL10 series.

Table 5.3: Production of water-based paints WBL7 to WBL10

Aqueous phase;

3% Na-Mg layered silicate ng 14.45 14.45 14.45 14.45 deionized water 8.99 13.50 8.83 13.44

2-Ethylhexane 1.91 1.91 1.91 1.91

Aqueous binder dispersion AD1 26.33 26.33 26.33 26.33

Aqueous polyurethane-polyurea dispersion PD1 6.09 6.09 6.09 6.09

Polyester; produced according to page 28, lines 13 to 33

3.01 3.01 3.01 3.01 (example BE1) WO 2014/033135 A2

Melamine formaldehyde resin (Cymel® 203 from the company

6.67 6.67 6.67 6.67 Allnex)

deionized water 1, 69 1, 69 1, 69 1.69

Rheovis® AS 1130, available from BASF SE 0.22 0.22 0.22 0.22 10% diethyl ethanolamine in water 0.51 0.51 0.51 0.51

2,4,7,9-tetramethyl-5-decindiol, 52% in BG (available

0.29 0.29 0.29 0.29 from BASF SE)

Butyl glycol 3.89 3.89 3.89 3.89

50% by weight solution of Rheovis® PU 1250 in

0.07 0.07 0.07 0.07 butyl glycol (Rheovis® PU 1250 available from BASF SE)

Aluminum pigment premix:

Mixing varnish ML2 18.66 18.66 18.66 18.66

Aluminum pigment Stapa® Hydrolux 600, available from

2.71

Altana-Eckart company

Aluminum pigment Stapa® Hydrolux 200, available from

7.38 2.77 from Altana-Eckart

Total: 100.00 100.00 100.00 100.00

Ratio pigment / binder: 0.25 0.09 0.25 0.09 5.4 Production of water-based paints WBL17 to WBL24, WBL17a and WBL21a

The components listed in Table 5.4 under "aqueous phase" are stirred together in the order given to form an aqueous mixture. In the next step, a premix is made from the components listed under "Aluminum pigment premix". This premix is added to the aqueous mixture. After the addition, the mixture is stirred for 10 minutes. Then, using deionized water and dimethylethanolamine, a pH of 8 and a spray viscosity of 85 ± 5 mPa-s at a shear stress of 1000 s ⁴ , measured with a rotary viscometer (Rheolab QC device with temperature control system C-LTD80 / QC from Anton Paar) at 23 ° C.

In addition, the samples WBL17 and WBL21 were tested for a spray viscosity of 120 ± 5 mPa-s at a shear stress of 1000 s ⁴ , using a rotary viscometer (Rheolab QC device with temperature control system C-LTD80 / QC from Anton Paar) at 23 ° C, set (resulting in WBL17a or WBL21a).

Table 5.4: Production of waterborne basecoats WBL17 to WBL24

Aqueous phase:

3% Na-Mg

17.87 17.87 17.87 17.87 17.87 17.87 17.87 17.87 Schichisiläkat solution

deionized water 11.45 12.07 16.45 16.68 11.61 12.07 16.51 16.68 2-ethylhexanol 1, 99 1, 99 1.99 1, 99 1.99 1, 99 1.99 1.99

Poly nethand ispersiors,

manufactured according to WO

25.41 25.41 25.41 25.41 25.41 25.41 25.41 25.41

92/15405, p. 13, Z, 13 to p.

15, line 13

Daotan® VTW 6464,

1, 59 1.59 1, 59 1, 59 1.59 1, 59 1.59 1.59 available from Allnex

polyurethane Modified

polyacrylate; manufactured

2.78 2.78 2.78 2.78 2.78 2.78 2.78 2.78 according to page 7, line 55 to page 8, line.

23 of DE 4437535 A1

3% by weight aqueous

Rheovis® AS 1130 solution,

5.08 5.08 5.08 5.08 5.08 5.08 5.08 5.08 Rheovis® AS 1130 available

from BASF SE

Melaminförmaldehydharz

{Cymel® 1133 from 3.57 3.57 3.57 3.57 3.57 3.57 3.57 3.57 Allnex)

10%

Dimethylethanolamine in 0.95 0.95 0.95 0.95 0.95 0.95 0.95 0.95

water

Pluriol® P900, available from

0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40

BASF SE

2,4,7,9-tetramethyl-5-decindiol, 52% in BG 1.35 1, 35 1, 35 1, 35 1.35 1.35 1.35 1.35 (available from BASF SE)

Triisobutyl phosphate 1, 19 1.19 1.19 1, 19 1.19 1, 19 1, 19 1.19 isopropanol 1, 95 1.95 1.95 1, 95 1, 95 1, 95 1, 95 1.95

Butyl glycol 2.54 2.54 2.54 2.54 2.54 2.54 2.54 2.54

50% by weight solution of

Rheovis® PU 1250 in

Butylglycol (Rheovis® 0.24 0.24 0.24 0.24 0.24 0.24 0.24 0.24

PU 1250 available from BASF

SE)

Tinuvin® 123 available from

0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64

BASF SE

Tinuvin® 384-2, available from

0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40

BASF SE

Aluminum pigment Stapa® IL

HYDROLAN 9157, available 8.00 3.00

from company Altena-Eckart

Aluminum pigment Stapa® IL

HYDROLAN 214 N0.55,

7.38 2.77 available from Altana-Eckart

Aluminum pigment Stapa® IL

HYDROLAN 2197, available 7.84 2.94 from Altana-Eckart

Aluminum pigment Stapa® IL

HYDROLAN 2153, available 7.38 2.77 from Altana-Eckart

Butyl glycol 9.60 9.60 9.60 9.60 9.60 9.60 9.60 9.60

Polyester; manufactured according to

Example D, column 16, lines 37-3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00

59 of DE 40 09 858 A1

Total: 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

relationship

0.35 0.13 0.35 0.13 0.35 0.13 0.35 0.13

Pigment / binder;

5.5 Production of waterborne basecoats WBL25 to WBL30

The components listed in Table 5.5 under "aqueous phase" are mixed together in the order given to form an aqueous mixture. In the next step, a premix is made from the components listed under "Aluminum pigment premix". These premixes are added separately to the aqueous mixture. After adding a premix, the mixture is stirred for 10 minutes in each case. Then using deionized water and dimethylethanolamine to a pH of 8 and a spray viscosity of 85 ± 10 mPa-s at a shear stress of 1000 s ¹ , measured with a rotary viscometer (Rheolab QC device with temperature control system C-LTD80 / QC from Anton Paar) at 23 ° C. Table 5.5: Production of water-based paints WBL25 to WBL30

3% Na-Mg layered silicate solution 14.45 14.45 14.45 14.45 14.45 14.45 deionized water 8.21 8.83 13.21 13.44 8.21 13.21 2-ethylhexanol 1 , 91 1.91 1.91 1.91 1.91 1.91

Aqueous aqueous dispersion AD1 26.33 26.33 26.33 26.33 26.33 26.33

Aqueous polyyrethane-polyurea dispersion

6.09 6.09 6.09 6.09 6.09 6.09 PD1

Polyester: manufactured according to page 28, lines

3.01 3.01 3.01 3.01 3.01 3.01 13 to 33 (example BE1) WO 2014/033135 A2

Melamine formaldehyde resin (Cymel® 203 der

6.67 6.67 6.67 6.67 6.67 6.67 from Allnex)

deionized water 1.69 1.69 1.69 1.69 1.69 1.69

Rheovis® AS 1130, available from BASF SE 0.22 0.22 0.22 0.22 0.22 0.22 1Q% dimethyiethanolamine in water 0.51 0.51 0.51 0.51 0.51 0, 51 2,4,7,9-tetramethyl-5-decindiol, 52% in BG

0.29 0.29 0.29 0.29 0.29 0.29 (available from BASF SE)

Butyl glycol 3.89 3.89 3.89 3.89 3.89 3.89

50% by weight solution of Rheovis® PU1250

in butyl glycol (Rheovis® PU1250 available from 0.07 0.07 0.07 0.07 0.07 0.07 BASF SE)

Aluminlumplgment-Vonrnischung

Mixing varnish ML2 18.66 18.66 18.66 18.66 18.66 18.66

Aluminum pigment Stapa® IL HYDROLAN

8.00 3.00

9157, available from Altana-Eckart

Aluminum pigment Stapa® IL HYDROLAN 214

7.38 2.77

0.55, available from Altana-Eckart

Aluminum pigment Stapa® HYDROLUX 2197,

8.00 3.00 available from Altana-Eckart

Total: 100.00 100.00 100.00 100.00 100.00 100.00

Pigment / binder ratio: 0.25 0.09 0.25 0.09 0.25 0.09

5.6 Production of waterborne basecoats WBL31 and WBL31a

The components listed in table 5.6 under "aqueous phase" are mixed together in the order given to form an aqueous mixture. In the next step, a premix is made from the components listed under "Aluminum pigment premix". This premix is added to the aqueous mixture. After the addition, the mixture is stirred for 10 minutes. The pH is then adjusted to 8 using deionized water and dimethylethanolamine and a spray viscosity of 130 ± 5 mPa-s (WBL31) or 80 ± 5 mPa-s (WBL31a) at a shear stress of 1000 s ^{' 1} , measured with a rotary viscometer (Rheolab QC device with temperature control system C-LTD80 / QC from Anton Paar) at 23 ° C. In the case of WBL31a, a higher amount of deionized water is used for this.

Table 5.6: Production of water-based paints WBL31 and WBL31a

Aqueous phase:

3% Na-Mg layered silicate solution 17.00 17.00 deionized water 10.89 10.89

2-ethylhexanol 1.89 1.89

Polyurethane dispersion, produced according to WO 92/15405, p. 13, line.

24.17 24.17

13 to p. 15, line 13

Daotan® VTW 6464, available from Allnex 1, 51 1, 51

Polyurethane modified polyacrylate; produced according to p. 7, line 55

2.64 2.64 to p.8, line 23 of DE 4437535 A1

3% by weight aqueous Rheovis® AS 1130 solution, Rheovis® AS

4.83 4.83

1130 available from BASF SE

Melamine formaldehyde resin (Cymel © 1133 from Allnex) 3.40 3.40

10% dimethyl ethanol in water 0.90 0,

Pluriol® P900, available from BASF SE 0.38 0,

, 4,7,9-T etramethyl-5-decindk) l, 52% in BG (available from BASF

1, 28 £ 1.2 E8

SE)

Triisobutyl phosphate 1, 13 1, 13

Isopropanol 1, 85 1, 85

Butyl glycol 2.42 2.42

50% by weight solution of Rheovis® PU1250 in butyl glycol

0.23 0.23

(Rheovis® PU 1250 available from BASF SE)

Tinuvin® 123, available from BASF SE 0.61 0.61

Tinuvin® 384-2, available from BASF SE 0.38 0.38 deionized water 7.91 12.10

Alumlnlumpigment-Vormlschung:

Aluminum pigment Stapa® HYDROLUX VP56450, available from

3.26 3.26

Altana-Eckart company

Aluminum pigment Stapa® HYDROLUX 1071, available from the company

1, 30 1, 30

Altana Eckart

Butyl glycol 9.21 9.21

Polyester; prepared according to Example D, column 16, 1. 37-59 of DE

2.79 2.79

40 09 858 A1

Total: 100.00 104.19

Ratio pigment / binder: 0.23 0.23 5.7 Production of water-based paints WBL32 and WBL33

The components listed in Table 5.7 under "aqueous phase" are stirred together in the order given to form an aqueous mixture. In the next step, a premix is made from the components listed under "Butylglycol / polyester blend (3: 1)". This premix is added to the aqueous mixture. After the addition, the mixture is stirred for 10 minutes. Then, using deionized water and dimethylethanolamine, a pH of 8 and a spray viscosity of 135 ± 5 mPa-s at a shear stress of 1000 s ^“1 , measured with a rotary viscometer (Rheolab QC device with temperature control system C-LTD80 / QC from Anton Paar) at 23 ° C.

Table 5.7: Production of the water-based paints WBL32 and WBL33

Aqueous phase:

3% Na-Mg layered silicate solution 20.82 20.82 deionized water 13.34 13.34

2-ethylhexanol 2.32 2.32

Polyurethane dispersion, produced according to WO 92/15405, p. 13, line.

29.60 29.60

13 to p. 15, line 13

Daotan® VTW 6464, available from Allnex 1.85 1.85

Polyurethane modified polyacrylate; produced according to p. 7, line 55

3.24 3.24 to p.8, line 23 of DE 4437535 A1

3% by weight aqueous Rheovis® AS 1130 solution, Rheovis® AS

5.92 5.92

1130 available from BASF SE

Melamine formaldehyde resin (Cymel® 1133 from Allnex) 4.16 4.16

10% dimethylethanolamine in water 1.11 1.11

Pluriol® P900, available from BASF SE 0.47 0.47

2,4,7,9-tetramethyl-5-deciindol, 52% in BG (available from BASF

1.57 1.57

SE)

Triisobutyl phosphate 1, 39 1, 39

Isopropanol 2.27 2.27

Butyl glycol 2.96 2.96

50% by weight solution of Rheovis® PU1250 in butyl glycol

0.28 0.28

(Rheovis® PU 1250 available from BASF SE)

Tinuvin® 123, available from BASF SE 0.75 0.75

Tinuvin® 384-2, available from BASF SE 0.47 0.47

Butyl glycol 5.63 9.38

Polyester; prepared according to Example D, column 16, lines 37-59 of DE

1.88 3.13

40 09 858 A1

Total: 100.00 105.00 5.8 Production of the water-based paints WBL34, WBL35, WBL34a and WBL35a The components listed in table 5.8 under "aqueous phase" are mixed together in the order given to form an aqueous mixture. After stirring for 10 minutes, the pH is then adjusted to 8 with the aid of deionized water and dimethylethanolamine and the spray viscosity is 120 ± 5 mPa-s (WBL34 and WBL35) or 80 ± 5 mPa-s (WBL34a and WBL35a) at a shear stress of 1000 s ^' \ measured with a rotary viscometer (Rheolab QC device with temperature control system C-LTD80 / QC from Anton Paar) at 23 ° C.

Table 5.8: Production of the water-based paints WBL34, WBL34a, WBL35 and WBL35a

Aqueous phase:

3% Na-Mg layered silicate solution 19.69 19.69 19.69 19.69 deionized water 12.62 12.62 12.62 12.62 2-ethylhexanol 2.19 2.19 2.19 2.19

Polyurethane dispersion, manufactured according to WO

28.00 28.00 28.00 28.00 92/15405, p. 13, line 13 to p. 15, line 13

Daotart® VTW 6464, available from Allnex 1, 75 1, 75 1, 75 1, 75

Polyurethane modified polyacrylate; manufactured

according to page 7, line 55 to page 8, line 23 of DE 4437535 3.06 3.06 3.06 3.06

A1

3% by weight aqueous Rheovis® AS 1130

Solution, Rheovis® AS 1130 available from BASF 5.60 5.60 5.60 5.60

SE

3.93 3.93 3.93 3.93 from Allnex)

10% dimethytethanolamine in water 1, 05 1, 05 1, 05 1.05 Piuriol® P900, available from BASF SE 0.44 0.44 0.44 0.44 2,4,7,9-tetramethyi-5 decindioi, 52% in BG

1, 49 1.49 1.49 1.49 (available from BASF SE)

Triisobutyl phosphate 1, 31 1, 31 1.31 1, 31

Isopropanol 2.15 2.15 2.15 2.15

Butyiglycol 2.80 2.80 2.80 2.80

50% by weight solution of Rheovis® PU1250 in

Butyiglycol (Rheovis® PU1250 available from 0.26 0.26 0.26 0.26

BASF SE)

Tinuvin® 123, available from BASF SE 0.71 0.71 0.71 0.71 Tinuvin® 384-2, available from BASF SE 0.44 0.44 0.44 0.44 butyiglycol 12.50 - 12.50 deionized water 3.00 3.00

Total: 87.50 100.00 90.50 103.00 6. Investigations and comparison of the properties of the aqueous basecoats and the coatings obtained therefrom

6.1 Comparison between the waterborne basecoats WBL5 and WBL9 with regard to the occurrence of rigidity or the homogeneity of the spray created during atomization

The tests on the water-based paints WBL5 and WBL9 (these paints each contain identical amounts of the identical aluminum pigment) with regard to streakiness or the homogeneity of the spray are carried out according to the methods described above. Table 6.1 summarizes the results.

Table 6.1: Comparison of streakiness using the homogeneity index Hl (according to patent specification DE 10 2009 050 075 B4) and the key figures Tti / T-rotan, T _T2 / T _Totai2 or the ratio thereof

The numbers 15 to 110 in connection with the homogeneity index Hl relate to the respective selected angle in ° when the measurement is carried out, in which the data to be determined are determined a certain number in ° away from the gloss angle. For example, HI15 means that this Homogeneity index refers to data recorded 15 ° away from the glancing angle

WBL5 and WBL9 have identical pigmentation, but differ in their basic composition.

The values in Table 6.1 show that the different tendency towards streaking, which is determined by means of the homogeneity indices according to patent DE 10 2009 050 075 B4, with the ratio of the key figures T _Ti / T _T o _t aii at x = 5 mm ( inside) and Tt2 / Tt _0ΐ3ΐ 2 x = 25 mm (outside) correlated:

The higher the value of the quotient of Tn / Ti _otaii and T 2 / T _Totai 2, the more non-transparent (NT), i.e. (effect) pigment-containing particles in a spray formed during atomization take from the inside out to. This means that a material is stronger when applied in areas with different

Concentrations of (effect) pigments is separated and is therefore more inhomogeneous or more susceptible to the formation of streaks.

In contrast to methods known from the prior art, such as a time-shift method which measures either only transparent or only non-transparent particles, the method according to the invention for characterizing the atomization includes a differentiation between transparent and non-transparent particles and combines both Information with each other. As shown in the example above, this differentiation and combination is necessary to understand the processes involved in the atomization of pigment-containing paints.

6.2 Comparison between the waterborne basecoats WBL1 and WBL2 with regard to the

Occurrence of pinpricks

The tests on the water-based paints WBL1 and WBL2 with regard to the occurrence of pinholes are carried out according to the method described above. Table 6.2 summarizes the results. Table 6.2 Results of the investigations regarding the occurrence of needlesticks

Outflow rate: 300 ml / min; Speed: 23000 rpm

WBL D10 Ipm] pinpricks

WBL1 32.0 0

WBL2 44.3> 100 WBL2 turned out to be significantly more critical in relation to the occurrence of needle pricks compared to WBL1. This behavior correlates with a larger value of D-io, which was determined experimentally in the case of WBL2 compared to WBL1 and which in turn is a measure of a coarser atomization or an increased degree of wetness.

6.3 Comparison between the waterborne basecoats WBL3, WBLA, WBL6 to WBL8 and WBL10 with regard to the assessment of cloudiness, the occurrence of pinpricks and the layer thickness-dependent course. The tests on waterborne basecoats WBL3, WBL4, WBL6 to WBL8 and WBL10 with regard to the assessment of cloudiness, pinpricks and the course depending on the layer thickness are carried out according to the methods described above. Tables 6.3 and 6.4 summarize the results.

Table 6.3: Results of the investigations with regard to needlesticks and cloudiness (measured with the cloud runner from Byk-Gardner)

Outflow rate: 300 ml / min: speed: 43000 rpm

WBL Dis [pm] needlesticks MottlingiS Motllng45 MottlingGO WBL3 23.5> 100 3.8 4.2 4.1

WBL4 26.8> 100 2.9 4.4 3.5

WBL6 31.5> 100 4.8 4.4 6.3

WBL7 19.1 0 3.3 3.9 3.9

WBL8 15.9 0 2.7 3.8 3.4

WBL10 15.6 0 4.1 4.4 6.1

A direct comparison of the sample pairs WBL3 and WBL7, WBL4 and WBL8 or WBL6 and WBL10, which each contain the same pigment and the same amount of pigment, shows that the basecoats WBL7, WBL8 and WBL10 at an outflow rate of 300 ml / min and a speed of 43,000 rpm each have a smaller D-io value than the corresponding reference sample WBL3, WBL4 and WBL6 and thus atomize more finely. This is reflected in significantly better needlestick robustness and also less cloudiness.

Table 6.4: Results of the investigations with regard to the course depending on the layer thickness

Outflow rate: 300 ml / min; Speed: 43000 rpm

10-15 pm 15-20 pm 20-25 pm

WBL The [pm] SW DOI SW DOI SW DOI

WBL3 23.5 11.5 77.3 16.1 72.2 17.2 71.6

WBL5 30.1 14.7 64.6 19.9 63.8 24.0 60.8

WBL4 26.8 8.60 85.05 11.90 83.82 14.30 82.73

WBL6 31.5 10.40 74.35 15.10 71.44 18.70 68.37 WBL3 and WBL5 each have a pigment / binder ratio of 0.35, whereas WBL4 and WBL6 each have a pigment / binder ratio of 0.13 exhibit.

The experimental results show a correlation between the D ₁₀ values or the resulting atomization properties and the appearance / course, here depending on the layer thickness: When comparing the

Samples with an identical pigment / binder ratio of 0.35 (WBL3 and WBL5) or 0.13 (WBL4 and WBL6) show that a larger di o value, i.e. a coarser and therefore wetter atomization leads to poorer flow values, which is illustrated by the short wave and DOI values obtained.

6.4 Comparison between the waterborne basecoats WBL3 to WBL10 to WBL17 to WBL20 and WBL25 to WBL28 with regard to opacity, cloud tendency, needle sticks and flow (influence of pigment)

The tests on the water-based paints WBL3 to WBL10, WBL17 to WBL20 and WBL25 to WBL28 with regard to opacity, cloudiness, needle sticks and flow were carried out according to the methods described above. In particular, it clarifies how the atomization and the resulting coating properties can be influenced by replacing the aluminum pigment used, in particular with regard to its grain size. The outflow rate in all experiments was 300 ml / min; the speed of the ESTA-G locke was 43,000 rpm. Tables 6.5 to 6.9 summarize the results. Table 6.5: Results of the investigations with regard to opacity, cloudiness (visual evaluation) and pinpricks

Aluminum pigment

Dio DeckverNadel¬

WBL morphology pW clouds

Ipm] like [pm] stitches

WBL17 Comfiake 19 fine 24.8 9 2-3 90

WBL18 Comfiake 34 coarse 33.2 11 3-4 130

WBL19 Comfiake 19 fine 0.13 29.0 14 3 120

O O

WBL20 Comfiake 34 coarse 0.13 33.3 16 34 160

¹¹ bacterial counts according to the technical Datenbla ^ss tt Eckart

) p / b = pigment-binder ratio

Table 6.6: Results of the investigations regarding opacity, cloudiness (visual evaluation)

Aluminum pigment

D «Deckver¬

WBL morphology pfb ² »clouds

[pm] like [pm]

WBL25 Comfiake 19 fine 0.25 19.3 10 2-3

WBL26 Comfiake 34 coarse 0.25 17.6 12 3-4

WBL27 Comfiake 19 fine 0.09 16.3 14 3

WBL28 Comfiake 34 coarse 0.09 15.9 16 34

¹¹ bacterial counts according to the technical data sheet from Eckart

²⁾ p / b = pigment-binder ratio

Table 6.7: Results of the investigations with regard to the layer thickness-dependent course

Aluminum pigment 10-15 pm SD 15-20 pm SD 20-25 pm SD

Morpho grain size D «

WBL SW DOI SW DOI SW DOI logie d50 ¹ > [pm] [pm]

WBL3 Comfiake 16 fine 0.35 23.5 11.5 77.3 16.1 72.2 17.2 71.6

WBL5 Comfiake 34 coarse 0.35 30.1 14.7 64.6 19.9 63.8 24.0 60.8

WBL4 Comfiake 16 fine 0.13 26.8 8.6 85.1 11.9 83.8 14.3 82.7

WBL6 Comfiake 34 coarse 0.13 31.5 10.4 74.3 15.1 71.4 18.7 68.4

¹¹ bacterial counts according to the technical data sheet from Eckart

2 ¹ p / b = pigment-binder ratio Table 6.8: Results of the investigations with regard to the course depending on the layer thickness

Aluminum pigment 15-20 pm SD 20-25 pm SD 25-31 pm SD

Mor ho- grain size D

Table 6.9: Results of the investigations regarding cloudiness

Aluminum pigment

g60

In all cases examined (with different pigment contents in each case), an exchange of the effect pigment used, in particular with regard to its smaller grain size (based on the d50 value of the pigment) leads to smaller D10 values. This resulting finer atomization has a positive effect on the opacity, the tendency to clouds as well as pinpricks and the course (SW and DOI). 6.5 Comparison between the water-based paints WBL17 to WBL24 with regard to pinholes (influence of the pigment content)

The investigations on the water-based paints WBL17 to WBL24 as well as WBL29 and WBL30 with regard to pinholes were carried out according to the method described above. In particular, it clarifies how the atomization and the resulting coating properties can be influenced based on the amount of aluminum pigments used. The outflow rate in all experiments was 300 ml / min; the speed of the ESTA bell was 43,000 rpm. Table 6.10 summarizes the results.

Table 6.10: Results of the investigations regarding needle sticks

Aluminum pigment

Grain size ²⁾ D «

WBL morphology p / b needlesticks

döO ¹ »[pm] [pm]

WBL17 Comflake 19 fine 0.35 24.8 90

WBL19 Comflake 19 fine 0.13 29.0 120

WBL18 Comflake 34 coarse 0.35 33.2 130

WBL20 Comflake 34 coarse 0.13 33.3 160

WBL21 silver dollar 12 fine 0.35 24.0 90

WBL22 silver dollar 12 fine 0.13 28.6 140

WBL23 Silver Dollar 24 Coarse 0.35 29.3 80

WBL24 silver dollar 24 rough 0.13 32.4 100

1 ^} Number of bacteria according to the technical data sheet from Eckart

²¹ p / b = pigment-binder ratio

A comparison of the respective sample pairs, which differ only with regard to the pigment-binder ratio, i.e. with regard to the amount of pigment, showed that an increase in the amount of aluminum pigment used led to better atomization (smaller dio values) and thus had a positive effect on needlesticks were. 6.6 Comparison between the waterborne basecoats WBL17 and WBL17a as well as WBL21 and WBL21a with regard to needlesticks, degree of wetness and cloudiness (influence of spray viscosity or amount of water) Pinpricks, degree of wetness and cloudiness were carried out according to the methods described above. In particular, it clarifies how the spraying viscosity (i.e. the amount of water added) can be used to influence the atomization and the resulting coating properties. The outflow rate in all experiments was 300 ml / min; the speed of the ESTA-G locke was 43,000 rpm. Tables 6.1 1 and 6.12 summarize the results.

Table 6.11: Results of the investigations with regard to needlesticks

Spritzvis ositit D «

WBL needle sticks

[mPa · «] ¹ * [pm]

WBL17 80 24.8 90

WBL17a 120 29.0 120

WBL21 80 33.2 130

WBL21a 120 33.3 160

Table 6.12: Results of the investigations regarding cloudiness and degree of wetness

spray viscosity

WBL M wetness clouds

[mPa s] ¹ >

WBL31 130 36.2 4 4

WBL31a 80 24.0 2 2-3

The examples show that a lower spray viscosity during the atomization of the material produces finer droplets (smaller dio values), which have a positive effect on the sensitivity of the needlestick, as well as the wetness and cloudiness of the coating. 6.7 Comparison between the waterborne basecoats WBL34 and WBL35 or WBL34a and WBL35a with regard to the degree of wetness

The tests on the water-based paints WBL34 and WBL35 or WBL34a and WBL35a with regard to the degree of wetness were carried out according to the method described above. In particular, it clarifies how an additional amount of a solvent can be used to influence the atomization and the resulting degree of nit, which is responsible for properties such as cloudiness, needlestick robustness, etc. The tests on the samples were carried out at an ESTA bell speed of 43,000 rpm and 63,000 rpm. In all cases, the outflow rate was 300 ml / min. Table 6.13 summarizes the results.

Table 6.13: Results of the studies regarding the degree of nit

Speed spray viscosity D «

WBL degree of wetness

[Ulmin] [mPa-s] ¹ > Qim]

WBL34 63000 120 30.3 2

WBL35 63000 120 47.3 5

WBL34a 63000 80 31.3 2

WBLSSa 63000 80 47.1 4

WBL34 43000 120 31.4 2

WBL35 43000 120 49.7 5

WBL34a 43000 80 32.8 2

WBL35a 43000 80 38.2 4

For both outflow rates (63,000 rpm and 43,000 rpm), it was possible to show for the respective sample pairs that were set to the same spray viscosity (120 mPa-s or 80 mPa-s) that the addition of butylglycol resulted in the D ₁₀ value and thus also the degree of wetness, which is the cause of, for example, sensitivity to clouds or needlestick, is influenced; the solvent causes a significant increase in the Di ₀ value as a measure of the particle size during the atomization and thus a much wetter deposited film. 6.8 The examples demonstrate that the method according to the invention can be used to produce coatings which, by reducing at least one parameter of the droplet size distribution within the spray and / or the homogeneity of the spray according to step (3) of the method, improve the qualitative properties, in particular with regard to the number of Show pinpricks, degree of wetness, cloudiness and / or course or appearance and opacity. The method according to the invention is thus a simple and efficient method for producing coatings that are optimized in this regard.

7. Investigations on clear lacquers or the films and coatings obtained therefrom

Comparison between the clear coats KL1, KL1a and KL1b regarding

runners limits

The tests on the clear coats KL1 and KLla and KL1b with regard to their run behavior were carried out according to the method described above. In particular, it clarifies how the runner behavior can be influenced on the basis of the spray viscosity adapted by the addition of a solvent and on the omission of additives known to the person skilled in the art, such as rheology control agents. The following materials are used:

Clear lacquer KL1

Sample KL1 is a commercially available two-component clearcoat (ProGloss from BASF Coatings GmbH), containing pyrogenic silica as a rheological aid (Aerosil® types from Evonik), the base coat with ethyl 3-ethoxypropionate to a viscosity of 100 mPa-s was set at 1000 / s.

Clear lacquer KL1a

Sample KL1a corresponds to KL1 with the difference that the base paint was adjusted to a viscosity of 50 mPa-s at 1000 / s with ethyl 3-ethoxypropionate. Clear lacquer KL1b

Sample KL1b corresponds to KL1 with the difference that it contains no pyrogenic silica as a rheological aid. The base varnish was also adjusted to a viscosity of 100 mPa-s at 1000 / s with ethyl 3-ethoxypropionate as in the case of KL.

The tests were carried out on the samples at an ESTA bell speed of 55,000 rpm. The outflow rate was 550 ml / min. Table 7.1 summarizes the results.

Table 7.1: Results of the investigations regarding the runner behavior

You runner start (> 0 mm) runner limit {> 10 mm)

Clear coat [pm] Ipm] [m ^h »1

KL1 41.28 48 58

KL1a 41.95 38 44

KL1b 42.96 36 42

The results show that receptive measures influencing the viscosity behavior, such as reducing the spray viscosity (KL1a) or eliminating the rheology aids based on pyrogenic silica (KL1b), worsen the atomization in comparison to the reference KL1 (larger dio values), which is reflected in a deterioration in rotor stability. The examples show that the process according to the invention can be used to produce coatings which, by reducing the medium filament lengths in step (3) of the process, have improved qualitative properties, in particular with regard to the runner behavior. The method according to the invention is thus a simple and efficient method for producing coatings that are optimized in this regard.

Claims

Expectations;

1. A method for producing at least one coating (B1) on a

Substrate which comprises at least steps (1) to (5), namely

(1) providing a coating composition (BZ1),

(2) Determination of at least one parameter of the droplet size distribution within a spray formed during atomization of the coating composition (BZ1) provided in step (1) and / or the homogeneity of this spray, the homogeneity of the spray being the ratio of two quotients Tn / Ti _o 'and T _T2 / T _To tai2 to each other as a measure of the local distribution of transparent and non-transparent drops at two different positions within the spray, where T _Ti the number of transparent drops at the first position 1, Tj2 the number of transparent drops at the second position 2, T _To tan the number of all drops of the spray and thus the sum of transparent drops and non-transparent drops at position 1 and T _To tai2 the number of all drops of the spray and thus the sum of transparent drops and non- corresponds to transparent drops at position 2, position 1 closer to the center of the spray is as position 2,

(4) Application of at least the coating composition (BZ1) obtained after step (3) with a reduced characteristic of the drop size distribution and / or reduced Homogeneity on a substrate to form at least one film

(F1) and

2. The method according to claim 1, characterized in that the coating (B1) is part of a multi-layer coating on the substrate.

3. The method according to claim 1 or 2, characterized in that the coating (B1) is a basecoat layer of a multi-layer coating on the substrate.

4. The method according to any one of the preceding claims, characterized in that the coating composition (BZ1) provided in step (1) at least one polymer which can be replaced as a binder as component (a), at least one pigment and / or at least one filler as component (b ) and water and / or at least one organic solvent as component (c).

5. The method according to any one of the preceding claims, characterized in that before carrying out step (5) at least one further coating composition (BZ2) different from the coating composition (BZ1) on the film (F1) obtained according to step (4), forming a Films (F2) is applied and the films thus obtained <F1) and (F2) are subjected to step (5) together.

6. The method according to any one of the preceding claims, characterized in that the determination of the at least one parameter of the pot size distribution in steps (2) and the reduction of the at least a characteristic of the drop size distribution in step (23) includes the determination or reduction of the Di ₀ value of the drops as a characteristic.

7. The method according to any one of the preceding claims, characterized in that the determination according to step (2) is carried out by carrying out at least the following method steps (2a), (2b) and (2c), namely mitete

8. The method according to claim 7, characterized in that the optical detection according to step (2b) is carried out by means of phase Doppler anemometry (PDA) and / or by means of the time-shrft measurement technique (TS).

9. The method according to claim 7 or 8, characterized in that the optical measurement according to step (2b) traversing in the radial-axial direction with respect to the tilted atomizer used at a tilt angle of 0 ^® to 90 °.

10. The method according to any one of claims 7 to 9, characterized in that the determination of the at least one parameter of the droplet size distribution according to step (2c) is carried out on the basis of optical data obtained by the optical detection according to step (2b) using phases -Doppler anemometry (PDA) and / or by means of the time shift- Measurement technology (TS) have been obtained, and that the determination of the homogeneity according to step (2c) is based on optical data obtained by the optical detection according to step (2b), which were obtained by means of time-shift measurement technology (TS).

1 1. The method according to any one of the preceding claims, characterized in that the reduction of at least one characteristic of the drop size distribution and / or the determined homogeneity of the spray determined according to step (2) by adapting at least one parameter within the recipe of the step (1 ) provided coating composition (BZ1).

12. The method according to claim 11, characterized in that the adjustment of at least one parameter within the recipe of the coating composition (BZ1) comprises at least one adjustment selected from the group of adjustments of the following parameters:

(i) increasing or decreasing the amount of at least one in the

Coating agent composition (BZ1) as binder component (a) containing polymers,

(ii) at least partial exchange of at least one of the

Coating agent composition (BZ1) as binder component (a) containing polymers by at least one polymer different from this,

(iii) increasing or decreasing the amount of at least one pigment and / or filler contained as component (b) in the coating composition (BZ1),

(iv) at least partial exchange of at least one in the

Coating agent composition (BZ1) as component (b) containing filler with at least one different filler and / or at least partial replacement of at least one pigment contained in coating agent composition (BZ1) as component (b) with at least one different pigment, (v) increasing or decreasing the amount of at least one organic solvent and / or water contained in the coating composition (BZ1) as component (c),

(vi) at least partial replacement of at least one organic solvent contained in the coating composition (BZ1) as component (c) by at least one organic solvent different therefrom,

(viii) at least partial exchange of at least one in the

Coating agent composition (BZ1) as component (d) containing additive by at least one additive different from this and / or adding at least one other additive different from this, (ix) changing the order of addition of those used to prepare the

Coating agent composition (BZ1) components used, and / or

(x) Increase or decrease in the energy input of the mixing during the production of the coating composition (BZ1).

13. The method according to claim 11 or 12, characterized in that the adaptation of at least one parameter within the recipe of the

Coating composition (BZ1) comprises at least one adjustment selected from the group of adjustments of the following parameters:

(iv) at least partial replacement of at least one filler contained in the coating composition (BZ1) as component (b) by at least one filler different from this and / or at least partial replacement of at least one in the Coating composition (BZ1) as component (b) containing pigment by at least one different pigment,

(v) increasing or decreasing the amount of at least one in the

Coating agent composition (BZ1) as component (c) organic solvent and / or water contained therein,

(vii) Increase or decrease the amount of at least one contained in the coating composition (BZ1) as component (d)

Additive, and / or

(viii) at least partial replacement of at least one component (d) contained in the coating composition (BZ1)

Additive by at least one additive different from this and / or addition of at least one other additive different from this.

14. The method according to any one of claims 11 to 13, characterized in that the adjustment of at least one parameter within the recipe of the coating composition (BZ1) comprises at least one adjustment selected from the group of adjustments of the following parameters: (iii) increase or decrease, in particular Increase, the amount of at least one pigment and / or filler contained in the coating composition (BZ1) as component (b), in particular

Effect pigment,

(iv) at least partial replacement of at least one contained in the coating composition (BZ1} as component (b)

Filler by at least one different filler and / or at least partial replacement of at least one pigment contained in the coating composition (BZ1) as component (b) by at least one different pigment, and / or (v) increasing or decreasing the amount of at least one in the

Coating composition (BZ1) as component (c) organic solvent and / or water contained therein.

15. The method according to any one of the preceding claims, characterized in that the application according to step (4) is carried out by atomizing the coating composition (BZ1) obtained after step (3).

16. A coating (B1) located on a substrate, which is obtainable by the method according to one of the preceding claims.

17. The coating (B1) according to claim 16, characterized in that it has a smaller number of surface defects and / or optical defects than a coating which can be obtained by the method according to one of the preceding claims, but without carrying out step (3) Has defects.