EP3810338A1 - Procédé de production d'un revêtement optimisé et revêtement pouvant être obtenu au moyen de ce procédé - Google Patents

Procédé de production d'un revêtement optimisé et revêtement pouvant être obtenu au moyen de ce procédé

Info

Publication number
EP3810338A1
EP3810338A1 EP19731763.9A EP19731763A EP3810338A1 EP 3810338 A1 EP3810338 A1 EP 3810338A1 EP 19731763 A EP19731763 A EP 19731763A EP 3810338 A1 EP3810338 A1 EP 3810338A1
Authority
EP
European Patent Office
Prior art keywords
coating composition
coating
component
pigment
atomization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19731763.9A
Other languages
German (de)
English (en)
Inventor
Dirk EIERHOFF
Daniel Briesenick
Georg Wigger
Christian Bornemann
Siegfried RIEDIGER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP3810338A1 publication Critical patent/EP3810338A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B12/00—Arrangements for controlling delivery; Arrangements for controlling the spray area
    • B05B12/08—Arrangements for controlling delivery; Arrangements for controlling the spray area responsive to condition of liquid or other fluent material to be discharged, of ambient medium or of target ; responsive to condition of spray devices or of supply means, e.g. pipes, pumps or their drive means
    • B05B12/082—Arrangements for controlling delivery; Arrangements for controlling the spray area responsive to condition of liquid or other fluent material to be discharged, of ambient medium or of target ; responsive to condition of spray devices or of supply means, e.g. pipes, pumps or their drive means responsive to a condition of the discharged jet or spray, e.g. to jet shape, spray pattern or droplet size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/025—Discharge apparatus, e.g. electrostatic spray guns
    • B05B5/04—Discharge apparatus, e.g. electrostatic spray guns characterised by having rotary outlet or deflecting elements, i.e. spraying being also effected by centrifugal forces
    • B05B5/0403—Discharge apparatus, e.g. electrostatic spray guns characterised by having rotary outlet or deflecting elements, i.e. spraying being also effected by centrifugal forces characterised by the rotating member
    • B05B5/0407—Discharge apparatus, e.g. electrostatic spray guns characterised by having rotary outlet or deflecting elements, i.e. spraying being also effected by centrifugal forces characterised by the rotating member with a spraying edge, e.g. like a cup or a bell
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
    • G01N15/02—Investigating particle size or size distribution
    • G01N15/0205—Investigating particle size or size distribution by optical means, e.g. by light scattering, diffraction, holography or imaging
    • G01N15/0227—Investigating particle size or size distribution by optical means, e.g. by light scattering, diffraction, holography or imaging using imaging, e.g. a projected image of suspension; using holography
    • G01N15/1433—
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
    • G01N15/10—Investigating individual particles
    • G01N15/14—Electro-optical investigation, e.g. flow cytometers
    • G01N15/1468—Electro-optical investigation, e.g. flow cytometers with spatial resolution of the texture or inner structure of the particle
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/025—Discharge apparatus, e.g. electrostatic spray guns
    • B05B5/043—Discharge apparatus, e.g. electrostatic spray guns using induction-charging
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
    • G01N2015/0023—Investigating dispersion of liquids
    • G01N2015/0026—Investigating dispersion of liquids in gas, e.g. fog
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
    • G01N15/10—Investigating individual particles
    • G01N15/14—Electro-optical investigation, e.g. flow cytometers
    • G01N2015/1493—Particle size

Definitions

  • 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 (BZ1) (1), determining the average filament length of a rotary atomization the filament (2) formed according to step (1) provided filament (2), reduction of this determined mean filament length (3), application of at least the coating composition (BZ1) obtained according to step (3) with reduced median filament length to a substrate with formation at least a film (F1) (4) and physical curing, chemical curing and / or radiation curing at least the at least one film (F1) formed on the substrate in accordance with step (4) for forming the coating (B1) on the substrate (5) and one on a substrate coating (B1), which by means of this Procedure is available.
  • a coating composition (BZ1) (1) determining the average filament length of a rotary atomization the filament (2) formed according to step (1) provided filament (2), reduction of this determined mean filament length (3), application of at least the coating composition (BZ1) obtained according to step (3) with reduced median filament length
  • a number of coating compositions such as, for example, basecoats, are applied to the substrate to be coated using rotary atomization.
  • Such atomizers have a rapidly rotating application body, for example a bell plate, which atomizes the coating composition to be applied, in particular in the form of droplets, in the form of droplets due to the centrifugal force which forms filaments.
  • the coating composition is applied electrostatically in order to achieve the highest possible application efficiency and the best possible application to ensure low overspray.
  • the lacquer atomized by centrifugal forces in particular is usually charged by directly applying a high voltage to the coating composition to be applied (direct charging).
  • shear viscosity is a measure of the resistance of a material to flowing in a stretch flow.
  • expansion flows usually occur in all relevant technical processes in addition to the shear flows, such as in the case of capillary inlet and capillary outlet flows.
  • Trouton ratio the classically determined shear viscosity
  • 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 adequately taken into account.
  • the coating compositions used to produce these coatings should have the widest possible application window.
  • 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
  • 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 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.
  • 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.
  • the coating compositions (BZ1) used in the process according to the invention are basecoats, such as aqueous basecoats, by means of which basecoat layers can be produced, in particular as part of a multi-coat paint system.
  • the process according to the invention enables a more economical and ecological process to be carried out compared to conventional processes, since coatings have no or at least less optical defects and / or surface defects can be obtained, but this is possible without having to go through the usually required entire painting and baking process for the production of such coatings and the optimization of their aforementioned advantageous properties and in particular without the coatings obtained in this way with regard to their desired properties have to be examined in a comparatively complex manner 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.
  • Formation or occurrence of optical defects and / or surface defects can be realized technically by performing step (3) of the method according to the invention, ie by reducing the average filament length of the filaments formed in a rotary atomization of the coating composition (BZ1) provided according to step (1) , these filament lengths being determined within step (2).
  • step (3) of the method according to the invention ie by reducing the average filament length of the filaments formed in a rotary atomization of the coating composition (BZ1) provided according to step (1) , these filament lengths being determined within step (2).
  • the mean filament lengths of the filaments occurring during the atomization correlate with the occurrence of the aforementioned optical defects and / or surface defects or their avoidance / reduction.
  • the lower the middle Filament length the fewer defects occur. This makes it possible to be able to control the resulting properties, such as optical properties and / or surface properties of the coating to be produced, as a function of the medium filament lengths occurring during atomization, and in particular to avoid or at least reduce the occurrence of optical defects and / or surface defects.
  • the method according to the invention on the basis of the investigation of the atomization behavior of a coating composition (BZ1), determination of the medium filament lengths of the filaments formed and reduction of these medium filament lengths, the properties of the final coating, in particular with regard to an optimization with regard to the occurrence of pinholes, the cloudiness, the course or the appearance can be improved.
  • the mean filament length determined correlates better with these properties than other methods known from the prior art, such as CaBER measurements.
  • step (2) of the method according to the invention the influence of the expansion viscosity which occurs during a rotary atomization of coating composition which can be replaced for the production of coatings, such as the coating composition (BZ1), is taken into account to a sufficient extent.
  • 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 ' ⁇ and thus higher expansion rates than with conventional CaBER measurements for determining the expansion viscosity, in which, especially in the case of basecoats, only expansion rates of up to can be achieved to 1,000 s "1 , and the average filament lengths are therefore determined at the aforementioned comparatively high elongation rates.
  • the method according to the invention in contrast to conventional CaBER methods, achieves and takes into account a higher expansion viscosity and higher expansion rates
  • the method also allows for the consideration of cross flows that occur during rotary atomization - in addition to shear and elongation rates. Such cross flows are not taken into account in any of the usual known methods for examining shear or strain rheology.
  • aqueous basecoats provided as coating composition (BZ1) in step (1) pigments contained therein, in particular effect pigments such as aluminum effect pigments, with an increasing proportion, based on the total weight of the basecoat, to a shortening of the Length of the filaments (that is to say shorter mean filament lengths) lead at least to those filaments which occur during atomization and which are located on the bell edge of the bell plate. Shorter average filament lengths result in a shorter lifespan for these filaments at the edge of the bell cup. Such shorter average filament lengths in turn 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. This technical effect, i.e.
  • 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 multi-layer coating on the substrate.
  • the substrate used is preferably a precoated substrate.
  • 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.
  • 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.
  • one or more further coating agent compositions can be applied to the substrate within the process according to the invention, each of which is preferably different from the composition (BZ1) and from one another.
  • composition (BZ1) is a preferably aqueous basecoat
  • at least one further coating composition for example a Clear lacquer, in particular a solvent-based clear lacquer.
  • the clear lacquer can be a commercially available clear lacquer, which in turn is applied by customary methods, the layer thicknesses in turn being in the common ranges, for example 5 to 100 micrometers.
  • the method according to the invention preferably 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, before carrying out step (5), at least one further coating composition (BZ2) different from the coating composition (BZ1) to be applied to the film (F1) obtained according to step (4) to form a film (F2) and the to subject films (F1) and (F2) thus obtained together to step (5).
  • the coating composition (BZ2) is preferably a clear lacquer, particularly preferably a solvent-based clear lacquer.
  • the clear lacquer After the clear lacquer has been applied, it can be flashed off at room temperature (23 ° C.) for, for example, 1 to 80 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 color-giving 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, especially 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.
  • the coating (B1) obtained is preferably a basecoat film.
  • the substrate can in this case contain at least one of the abovementioned 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 means of cathodic deposition of an electrocoat.
  • Step (1) of the method according to the invention provides for the provision of a coating composition (BZ1).
  • step (2) of the method according to the invention the mean filament length of the filaments formed in a rotary atomization of the coating composition (BZ1) prepared according to step (1) is determined.
  • 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.
  • the Rotary atomization by means of atomizers initially produces so-called filaments 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 pieces (also referred to as “thread length”) and their diameter (also referred to as “thread diameter”).
  • the expansion viscosity that occurs is taken into account to a sufficient extent.
  • the skilled worker is familiar with the concept of the expansion viscosity he ⁇ displaystyle ⁇ eta _ ⁇ mathrm ⁇ e ⁇ with the unit Pascal second (Pa-s) as a measure of the resistance of a material to 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 what is known as a capillary breakup extensive rheometer (CaBER), which is sold, for example, by Thermo Scientific.
  • CaBER capillary breakup extensive rheometer
  • comparatively high values of the stretch viscosity mean a comparatively high stability of the filaments that arise during atomization.
  • the higher the stability of the filaments the longer the average lifespan of the filaments occurring during atomization (also referred to as thread lifespan) before they continue to disintegrate into drops, which then form the spray mist.
  • Such a comparatively high average lifespan of the filaments is usually accompanied by a higher average filament length of these filaments.
  • a method for determining the thread life, i.e. the life of a filament, in a stretch experiment using a CaBER measurement is given below in the method description
  • step (2) the mean filament length of those filaments which are located on the edge of the bell plate of a bell plate which stiffens the application body of a rotary atomizer which is used in the rotary atomization is preferably determined.
  • the mean filament length mentioned in step (2) is preferably determined by carrying out at least the following process steps (2a), (2b) and (2c), namely by means of
  • Coating agent composition (BZ1) by means of a rotary atomizer, which, as an application body, is a bell plate capable of rotation,
  • step (2b) optical detection of the filaments formed on the edge of the bell plate during the atomization according to step (2a) by means of at least one camera, and
  • the atomized coating composition (BZ1) can be electrostatically charged at the edge of the bell cup by applying a voltage.
  • the speed of rotation (speed of rotation) of the bell cup is adjustable.
  • the rotational speed is preferably at least 10,000 revolutions / min (rpm) and at most 70,000
  • 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.
  • 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 one for this (High-speed) rotary atomizers used are commercially available, examples being products from the Dürr Ecobell® series.
  • Such atomizers are suitable for preferably 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 (BZ1) within the process according to the invention.
  • the coating composition (BZ1) can be atomized electrostatically, but need not.
  • the coating agent composition atomized by centrifugal forces is electrostatically charged at the edge of the bell plate by preferably directly applying a voltage, such as high voltage, to the coating agent composition to be applied (direct charging).
  • the outflow rate of the coating composition to be atomized (BZ1) during the execution of step (2a) is adjustable.
  • the outflow rate of the coating composition to be atomized (BZ1) during 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 »150 to 600 ml / min, in particular in a range from 200 to 550 ml / min.
  • the outflow rate of the coating composition to be atomized (BZ1) during the implementation of step (2a) is in a range from 100 to 1,000 ml / min or from 200 to 550 ml / min and / or the rotational speed of the bell cup is in a range from 15,000 to 70,000
  • a basecoat particularly preferably an aqueous basecoat, is used as the coating composition (BZ1), in particular an aqueous basecoat which contains at least one effect pigment.
  • the atomization according to step (2a) is preferably carried out at a flow rate of the coating composition (BZ1) provided and to be atomized according to step (1) in a range from 100 to 1,000 ml / min and / or at a speed of rotation of the bell cup in a range of 15,000 up to 70,000 revolutions / min.
  • step (2b) of the method according to the invention the filaments formed on the edge of the bell plate during the atomization according to step (2a) are carried out by means of at least one camera.
  • step (2b) of the method according to the invention the atomization process according to step (2a) is optically recorded on the edge of the bell plate of the bell plate of the bell, in particular photographed and / or a corresponding video recording is made. In this way, information can be obtained about the disintegration of filaments formed during atomization directly on the edge of the bell plate.
  • the camera used to carry out step (2b) is preferably a high-speed camera.
  • Examples of such cameras are models from the Fastcam® series from the Photron Tokyo company in Japan, such as the Fastcam® SA-Z model.
  • the optical detection in step (2b) is preferably carried out by using 30,000 to 250,000 images per second, particularly preferably 40,000 to 220,000 images per second, more preferably 50,000 to 200,000 images per second, very particularly preferably 60,000 to 180,000 images, using the at least one camera, more preferably 70,000 to 160,000 frames per second, and in particular 80,000 to 120,000 frames per second, of the bell plate and in particular the bell plate edge are recorded.
  • the resolution of the images can be set variably. For example, resolutions of 512 x 256 pixels per image are possible.
  • Step (2c) of the method according to the invention provides for a digital evaluation of the optical data obtained by the optical detection according to step (2b).
  • the aim of this digital evaluation is to determine the mean length of the filaments of those filaments that form during atomization directly at the edge of the bell plate, namely at the edge of the bell plate.
  • step (2c) can be carried out by means of image analysis and / or video analysis of the optical data obtained according to step (2b), such as the images and / or videos recorded by the camera in step (2v).
  • Step (2c) is preferably carried out by means of software such as MATLAB® software based on a MATLAB® code.
  • the digital evaluation according to step (2c) preferably comprises several stages of image and / or video processing of the optical data obtained according to step (2b).
  • the determination of the average filament length according to step (2c) preferably includes the standard deviations of the average filament lengths.
  • the standard deviation can possibly occur inhomogeneity and / or
  • Step (2c) is again preferably carried out in several stages.
  • step (2c) The digital evaluation according to step (2c) is preferably carried out in at least six stages (a) to (f), namely
  • step (d) removing drops, fragmented filaments and filaments not on the bell edge from the images obtained according to step (c) to obtain images in which all the remaining objects are filaments,
  • step (e) removing those filaments from the images obtained in step (d) which are not entirely within the images
  • the removal according to stage (d) is preferably carried out by (i) determining the length of all hypotenuses of all objects located on the images, (ii) marking objects as drops and / or fragmented filaments on the images if the determined values of the hypotenuses of these objects falling below a certain value h and eliminating these objects and (iii) checking the remaining objects, namely the filaments, based on their position on the images to determine whether they were on the edge of the bell plate and eliminating those filaments which are not.
  • the value h corresponds to 15 pixels ⁇ or 300 miti).
  • a first stage the bell plate is preferably removed within the respective images taken and on which the digital evaluation is based.
  • each image is smoothed so strongly by means of a Gaussian filter that the entire bell plate, in particular the entire bell, can no longer be recognized.
  • the images thus smoothed are preferably binarized and inverted.
  • a third stage (c) the original images, i.e. the images used in stage (a), binarized and added together with the inverted images from stage (b).
  • the result is a binarized series of images without a bell edge, which in turn is preferably inverted for further evaluation.
  • the binarization takes place in each case in particular in order to better distinguish the filaments to be measured from the background of the images.
  • a fourth stage (d) conditions are preferably defined by means of which filaments can be distinguished from other objects such as drops.
  • the hypotenuse of the filaments are determined including all objects in the respective receptacles, preferably, which are calculated by x min, x m ax, Ymin and Y max of the objects.
  • the values are obtained by means of a MATLAB function which determines these extreme values, ie the corresponding x value in the x direction for each object, namely x min and x ⁇ x. and for each object specifies the corresponding y value in the y direction, namely y min and y max .
  • the hypotenuses of the objects must be greater than a certain value h in order for the object to be regarded as a filament.
  • the value h corresponds to 15 pixels (or 300 pm). All smaller objects, such as drops, are therefore no longer considered for further evaluation.
  • each object must have a y value that is in the immediate vicinity of the bell edge (already removed in the pictures).
  • the y value corresponds to a value that is on a defined path in the y direction, on which each object must be in order to be considered as a filament located on the edge of the bell.
  • the term “close proximity” is understood to mean y values that auto-iron at most 5 pixels from the edge of the bell or at most 5 pixels lie below the edge of the bell. This excludes all, in particular all longer fragments, which are not connected to the bell plate edge, for the extension of the determination of the filament length and only takes into account those filaments which are located on the bell plate edge.
  • a fifth stage (e) all objects remaining within the respective images after stage (d) have been carried out are preferably checked to see whether their minimum x value is greater than 0 and their maximum x value is less than 256. Only objects that meet this condition will be considered in the further course. This means that only filaments that are completely in the picture frame are evaluated. All remaining objects in a recording are preferably numbered.
  • a sixth stage (f) all objects remaining after stage (e) are preferably called up individually and preferably tapered using the skeleton method (skeleton method).
  • skeleton method This method is known to the person skilled in the art. As a result, only one pixel of each object is connected to a maximum of another pixel. The number of pixels per object or filament is then added up. Since the pixel size is known, the real length of the filaments can be calculated. This image evaluation evaluates around 15,000 filaments per shot. This ensures high statistics when determining the filament lengths. The mean filament length of these filaments then results from the totality of all filament lengths of the filaments examined in this way. In this way, the median length of the filaments formed during the atomization is obtained, which are located at the bell cup aunt of the bell cup.
  • step (3) of the method according to the invention the mean filament length determined in step (2) of the filaments formed during the rotary atomization of the coating composition (BZ1) is reduced.
  • the medium filament length is preferably reduced in accordance with step (3) 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 subsequent parameters
  • Coating agent composition (BZ1) as organic solvent contained as component (c) by at least one organic solvent different therefrom,
  • the spray viscosity of the coating composition (BZ1) can be increased or decreased using parameter (v).
  • 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).
  • binding agent is explained in more detail below.
  • Crosslinkers crosslinking agents are also to be subsumed under this.
  • 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 ( «) 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),
  • 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) containing organic solvents as component (c),
  • 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 (BZt),
  • Pigments by at least one different pigment in particular at least partial exchange 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 contained.
  • 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 at most ⁇ 5% by weight, deviates from the pigment content of the coating composition (BZ1) before carrying out this parameter adjustment (iii).
  • Coating composition (BZ1) contained as component (b) Pigments according to parameter adaptation (iv) in such a way that the at least one pigment contained in (BZ1) before the parameter adaptation (iv) is at least partially exchanged for at least one pigment which is essentially identical to it.
  • 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 as that or the effect pigments present in the coating composition (BZ1).
  • 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 .
  • a further additional condition for “essentially identical pigments” in the context of the present invention in connection with effect pigments is that the effect pigments in their mean particle size do not exceed ⁇ 20%, preferably ⁇ 15%, particularly preferably ⁇ 10% differentiate from each other.
  • 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.
  • the term “essentially identical pigment” is understood to mean that the color pigment (s) capable of at least partial exchange are, as a first condition, at least + 20%, preferably around, in their sparkle Differentiate at most ⁇ 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 a, ⁇ chromaticity CIE 1976 (CIELAB chromaticity): [ ⁇ a *) 2 + ⁇ b * ⁇ 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 average 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 (dN, 50% value), which is determined according to ISO 13320 (date: 2009) by means of laser diffraction.
  • dN the measured mean particle diameter
  • 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 average filament length to a substrate to form at least one film (F1).
  • step (4) in particular when (BZ1) is a basecoat, can do 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.
  • step (4) Application is preferably carried out in accordance with step (4) by means of atomization, such as pneumatic atomization or rotary atomization, in particular by means of rotary atomization of the coating composition (BZ1) obtained in step (3).
  • atomization such as pneumatic atomization or rotary atomization
  • step (3) coating composition obtained in step (3).
  • step (2a) to which reference is hereby made, apply equally to step (4) in the present case if step (4) is carried out by means of rotary atomization.
  • the term “pneumatic atomization” and pneumatic atomizers used for this purpose are also known to the person skilled in the art
  • 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 step (5) is carried out
  • Coating composition (BZ1) to apply various coating composition (BZ2) to 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 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).
  • Coating composition (BZ2) a clear coat, particularly preferably a solvent-based clear coat.
  • the clear lacquer 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. Then the kiarlack is preferably cured together with the applied coating composition (BZ1) within step (5).
  • step (5) of the method according to the invention a physical hardening, chemical hardening and / or radiation hardening is carried out at least by applying the
  • 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.
  • (1-component) basecoat materials which are preferred, can be flashed off at room temperature (23 ° C.) for 1 to 60 minutes and then preferably at slightly elevated temperatures of 30 to 90 ° C can be hardened.
  • 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 cured or no fully crosslinked paint film has yet been formed.
  • the curing that is to say the stoving, is preferably carried out thermally at temperatures from 30 to 200 ° C., such as 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 ° C.
  • 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.
  • 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 enables 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 .
  • several radiation sources can also be used for curing, for example two to four. These can also radiate in different wavelength ranges.
  • Coating agent composition used according to the invention 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 enables radiation curing without a photo
  • 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) is at least one polymer which can be replaced as a binder as component (a),
  • component (d) 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 which 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 refinishing can be used.
  • Coating agent compositions which 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.
  • 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 still have to be pretreated (e.g. by grinding), 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.
  • 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 optionally one or more of the further optional components mentioned below, add up to 100% by weight on the total weight of the coating composition.
  • the solids content of the coating Mitel composition used in the invention is in a range of 10 to 45 wt .-%, particularly preferably from 11 to 42.5 weight .-%, most preferably from 12 to 40 wt .-% "in particular 13-37 , 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.
  • binder preferably refers to the non-volatile fractions of a composition such as the coating composition used in accordance with the invention, with the exception of those used in film formation 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.
  • a basecoat such as an aqueous basecoat which contains at least one polymer which can be replaced as a binder as component (a), for example an SCS polymer described below, a crosslinking agent such as a melamine resin and / or a polymeric additive.
  • component (a) for example an SCS polymer described below
  • a crosslinking agent such as a melamine resin and / or a polymeric additive.
  • a so-called seed-core-shell polymer is particularly preferably used as component (a).
  • SCS polymer seed-core-shell polymer
  • Such polymers or aqueous dispersions containing such polymers are known, for example, from WO 2016/116299 L1.
  • the polymer is preferably a (meth) acrylic copolymer.
  • the polymer is preferably used in the form of an aqueous dispersion.
  • component (a) it is very particularly preferred to use a polymer having an average particle size in the range from 100 to 500 nm, which can be prepared by successive radical emulsion polymerization of three preferably different monomer mixtures (A), (B) and (C) of olefinically unsaturated monomers in water, the mixture (A) containing 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), 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
  • a polymer which is produced from the mixture (G) has a glass transition temperature of -50 to 15 ° C,
  • 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.
  • a free-radical emulsion polymerization that is to say a stage or also a polymerization stage
  • the stages can take place one after the other. It is also possible for the corresponding reaction solution to be stored for a certain period of time and / or transferred to another reaction vessel after completion of a stage and only then to carry out the next stage.
  • 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.
  • 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, vinylaromatic monomers.
  • the term (meth) acrylic or (meth) acrylate encompasses both methacrylates and acrylates. In any case, but not necessarily, (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.
  • the monomer mixture (A) preferably contains only mono-olefinically unsaturated monomers.
  • the monomer mixture (A) contains at least one monounsaturated ester 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.
  • the 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. That in stage i.
  • Polymer produced by the emulsion polymerization of the monomer mixture (A) 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.
  • the monomer mixture (B) preferably also contains the following monomers: firstly at least one monounsaturated ester of (meth) acrylic acid with an alkyl radical and secondly at least one vinyl olefinically unsaturated monomer containing 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 be determined using the method described below.
  • the olefinically unsaturated monomers of the mixture (C) are preferably selected so that the resulting polymer, comprising seed, core and shell, has an acid number of 10 to 25.
  • the mixture (C) preferably contains at least one alpha-beta unsaturated carboxylic acid, particularly preferably (meth) acrylic acid.
  • the olefinically unsaturated monomers of the mixture (C) are additionally or alternatively preferably selected so that the resulting polymer, comprising the seed, core and shell, has an OH number of 0 to 30, preferably 10 to 25. All the acid numbers and OH numbers mentioned above are values calculated on the basis of the total monomer mixture 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 seeds and seeds 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) After its preparation, the polymer (b) has an average particle size of 100 to 500 nm, preferably 125 to 400 nm, very particularly preferably 130 to 300 nm (measured by means of dynamic light scattering as described below; cf. determination methods.)
  • the coating composition used according to the invention preferably contains a proportion of component (a) such as at least one SGS 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 composition.
  • component (a) such as at least one SGS 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 composition.
  • 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).
  • the coating composition used according to the invention can contain at least one of the
  • Preferred polyurethanes are described, for example, in German patent application DE 199 48 004 L1, 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
  • Preferred polyurethane-polymer urea copolymers are polyurethane
  • Polyurea particles preferably those with an average particle size of 40 to 2000 nm, the polyurethane-polyurea particles, each in a converted form Form containing at least one isocyanate group-containing polyurethane prepolymer containing anionic and / or convertible groups and at least one polyamine containing two primary amino groups and one or more 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 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.
  • compositions used according to the invention particularly preferably comprise at least one hydroxy-functional one
  • Polyurethane-poly (meth) acrylate MS polymer again preferably at least one hydroxy-functional polyurethane-poly (meth) acrylic copolymer and at least one hydroxy-functional polyester and optionally a preferably hydroxy-functional polyurethane-poly urea polymer
  • 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
  • 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 are particularly 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, is 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.
  • filler is known to the person skilled in the art, for example from DIN 55943 (date: October 2001).
  • a “filler” 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 waterborne basecoat, which is used in particular to increase the volume.
  • “fillers” preferably differ from “pigments” by their refractive index, which is ⁇ 1.7 for fillers. Any customary filler known to those skilled in the art can be used as component (b).
  • 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.
  • 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
  • organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or polymer powder.
  • pigment is also known to the person skilled in the art, for example from DIN 55943 (date: October 2001).
  • 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 essentially, 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 for pigments is 1.7.
  • Pigments Colored pigments and effect pigments are preferably subsumed under the term “pigments”.
  • color pigments A person skilled in the art is familiar with the term color pigments.
  • color 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, colored 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.
  • color pigments are chromium oxide, chromium oxide hydratillion, cobalt green, ultramarine green, cobalt blue, ultramarine blue, manganese blue, ultramarine violet, cobalt and manganese violet, red iron oxide, cadmium, molybdenum red and ultramarine, iron oxide brown, 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 blsmutvanadate.
  • effect pigments are preferably those pigments which are optically effect-imparting or color and optically effect-imparting, in particular optically effect-giving.
  • optically effect and color pigment are therefore preferably interchangeable.
  • Preferred effect pigments are, for example, platelet-shaped metallic 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 oxychloride and / or metal oxide-mica-like pigments / bleach pigments / mica pigments or other effects or mica pigments / mica pigments such as mica or effect pigments (mica pigments) Iron oxide, multi-layer effect pigments from PVD films and / or liquid crystal polymer pigments. Flaky 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.
  • component (b), such as at least one effect pigment, to component (a), such as at least one SCS polymer in the coating composition is preferably 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) is preferably 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.
  • the coating composition used according to the invention is preferably aqueous. It is preferably a system which, as solvent (that is, 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.
  • solvent that is, as component (c)
  • 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 wt .-%, each based 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.
  • organic solvents examples include heterocyclic, aliphatic or aromatic hydrocarbons, mono- or polyhydric alcohols, in particular 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, Diethylene glycol dimethyl ether, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, acetone, fsophorone or mixtures thereof.
  • the coating composition used according to the invention can optionally also contain at least one thickener (also referred to as a thickener) as component (d).
  • 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.
  • 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.
  • Vendickungsmitte! based on Po [y (meth) acrylic acid and (meth) acrylic acid (meth) acrylate copolymer thickeners are optionally crosslinked and / or neutralized with a suitable base. Examples of such thickeners are. lkali Swellable Emulsions ”(ASE), and hydrophobically modified variants thereof, the“ Hydrophically modified Alkali Swellable Emulsions ”(HASE).
  • thickeners are preferably anionic.
  • Corresponding products such as Rheovis® AS 1 130 are commercially available.
  • Thickeners based on polyurethanes e.g. polyurethane associative thickeners
  • Corresponding products such as Rheovis® PU 1250 are commercially available.
  • suitable polymeric waxes are 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).
  • the coating composition can include 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, flow control agents, film-forming aids, sag control agents (SCAs), flame retardants with flame retardants. Contain corrosion inhibitors, siccatives, biocides and matting agents. They can be used in the known and customary proportions.
  • the coating composition used according to the invention can be obtained using the customary and known mixing processes and mixing units.
  • 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.
  • the coating (B1) preferably has a smaller number of surface defects and / or optical defects than a coating which can be obtained by the process according to the invention but without carrying out step (3).
  • 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).
  • 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 (rock layer thickness), the ranges from 0 to 20 pm and from> 20 to 40 pm can be counted separately, normalization of the results to an area of 200 cm 2 and addition to a total number.
  • a single pin prick is 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 examination and assessment of the appearance takes place in accordance with the determination method described below by assessing the course when the coating is wedge-coated 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.
  • 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 runners 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.
  • 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 according to DIN EN ISO 2808 (date: May 2007), method 12A, preferably using the MiniTest® 3100- 4100 measuring device from ElektroPhysik. In all cases, it is the rock layer thickness.
  • 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 back. 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).
  • M n 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 calibration substance to determine 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.
  • the OH number and the acid number are each determined by calculation.
  • the mean particle size is determined by means of dynamic light scattering (photon correlation spectroscopy) (PCS) based on DIN ISO 13321 ⁇ date: October 2004).
  • PCS dynamic light scattering
  • a “Malvem Nano S90” (from Malvern Instruments) at 25 ⁇ 1 ° C is used for the measurement.
  • 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 dispersion 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. 7.1 1 (Fa.
  • the mean particle size is understood to mean the arithmetic mean number of the measured mean particle diameter (Z average mean; number mean; d N, so % value). The standard deviation of a 5-fold determination is ⁇ 4%.
  • the mean particle size is understood to mean the arithmetic volume mean from the mean particle size of the individual preparations (V-average mean; volume mean; dv , 50% value (volume-related median value)). The maximum deviation of the volume mean from five individual measurements is ⁇ 15%. The check is carried out using polystyrene standards with certified particle sizes between 50 and 3000 nm.
  • the layer thicknesses are determined in accordance with DIN EN ISO 2808 (date: time 2007), method 12A using the MlniTest® 3100-4100 measuring device from ElektroPhysfk.
  • wedge-shaped multi-layer coatings are manufactured according to the following general rule:
  • a steel sheet with the dimensions 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 a ling 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.
  • the structure After a flash-off time of 4-5 minutes at room temperature (18 to 23 ° C) the structure is dried in a forced air oven for 10 minutes at 60 ° C. After removing the adhesive strip, a commercially available two-component clear coat (ProGloss® from BASF Coatings GmbH) with a target layer thickness (layer thickness of the dried material) of 40-45 pm is manually applied to the dried water-based lacquer layer using a flow cup gun. 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 ° G for a further 20 minutes.
  • a commercially available two-component clear coat ProGloss® from BASF Coatings GmbH
  • the occurrence of pinholes is assessed visually according to the following general rule: The dry layer thickness of the waterborne basecoat is checked and the areas from 0 to 20 pm and from 20 pm to the end of the wedge are marked on the steel sheet for the basecoat layer thickness wedge. 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 water-based 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 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-Gardner GmbH within the previously determined basecoat layer thickness ranges.
  • a laser beam is directed at an angle of 60 to 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 a so-called long wave range (1, 2 to 12 mm) with the help of
  • the Measuring device determines the characteristic "distinctness of imgage" (DOI) (the higher the value, the better the appearance).
  • multi-layer coatings are produced according to the following general procedure:
  • 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 it is also applied electrostatically 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 (PnoGloss from BASF Coatings GmbH) with a target layer thickness of 40-45 mm is applied to the dried water-based lacquer layer.
  • 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 cloudiness is then assessed using the cloud-runner measuring device from BYK-Gardner GmbH.
  • the device the three parameters "MottlinglS”, “Mottling45” and “Motling60”, which can be viewed as a measure of the cloudiness, measured at angles of 15 °, 45 ° and 60 ° relative to the angle of reflection of the light source used for the measurement. The larger the value, the more pronounced the cloudy picture.
  • the Haake CaBER 1 (Thermo Scientific) is used to investigate the elongation behavior of the samples used.
  • the sample is located between two parallel plates, the have a diameter of 8 mm and a distance of 2 mm to each other.
  • the upper plate is then moved upwards within 40 ms so that the new distance between the two plates is 10 mm.
  • the thread diameter i.e. the filament diameter
  • the thread diameter is recorded using a high-speed camera at a frame rate of 1000 frames per second and a resolution of 1024 x 1024 pixels.
  • the rheological properties of the material are determined from the course of the thread diameter. Such materials have a higher resistance to stretching currents (i.e. a higher stretching viscosity), which show a longer thread life (filament life).
  • the disintegration of the filaments on the edge of the bell is recorded using the high-speed camera Fastcam SA-Z (company Photron Tokyo, Japan) at a frame rate of 100,000 frames per second and a resolution of 512 x 256 pixels. 2000 pictures are used per picture for the picture evaluation.
  • the individual images are processed in several steps in order to be able to evaluate the length of the filaments.
  • the bell edge is removed from the respective images. To do this, each image is smoothed so much using a Gaussian filter that only the edge of the bell can be seen.
  • These images are then binarized and inverted (a). Then the original images are binarized (b) and added together with the inverted images (a).
  • the result is a binarized series of images without a bell edge, which is inverted for further evaluation (c).
  • conditions are defined so that filaments can be distinguished from other objects.
  • the hypotenuses of all objects are determined, which are determined using Xm in , Xmax. ymin and y ma * of the objects are calculated.
  • the hypotenuses of the objects must be greater than a certain value h in order for the object to be regarded as a filament. All smaller objects, such as drops, are no longer considered for further evaluation.
  • each object must have a y value that is in the immediate vicinity of the bell edge. This will make longer fragments that are not with the bell edge are excluded for the evaluation of the filament length.
  • the remaining objects must meet the requirement that their minimum x value is greater than 0 and their maximum x value is less than 250. This means that only filaments that are completely in the picture frame are evaluated. All objects that can meet the four conditions are retrieved individually and rejuvenated using the skeleton method. As a result, only one pixel of each object is connected to a maximum of another pixel. The number of pixels per filament is then added up. Since the pixel size is known, the real length of the filaments can be calculated. This image evaluation evaluates around 15,000 filaments per shot. This ensures high statistics when determining the filament lengths.
  • the solubility of the monomers in water is determined via an equilibrium with the gas space above the aqueous phase ⁇ analogous to the literature X.- S. Chai, GX Hou, FJ Schork, Journal of Applied Polymer Science Vol. 99, 1296-1301 (2006) ).
  • 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.
  • an emulsifier (10 ppm, based on the total mass of the sample mixture) is added.
  • 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 slope (S2) as soon as the excess monomer is removed from the mixture.
  • S1 almost constant value
  • S2 significantly negative slope
  • 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 glass transition temperatures of polymers, each consisting of
  • the glass transition temperature T g is determined experimentally in accordance with DIN 51005 (date: August 2005) "thermal analysis (TA) - terms” and DIN 53765 “thermal analysis - dynamic differential calorimetry (DDK)” (date: March 1994).
  • a sample is determined of 15 mg 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.
  • N2 inert gas purging
  • 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.
  • 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 heat flow against 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.
  • 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 aid for the person skilled in the synthesis, so that a desired glass transition temperature can be set via a few targeted experiments ,
  • the wetness level of a film formed after application of a coating composition such as a waterborne basecoat to a substrate is assessed.
  • 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 pm to 40 pm, by means of rotary atomization.
  • 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 electrocoat (KTL ) (CathoGuard® 800 der
  • 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
  • clear coats :
  • KTL cathodic electrocoat
  • the run inclination is determined in accordance with DIN EN ISO 28199-3, point 4.
  • the layer thickness is determined from which a first inclination to run on a hole can be visually observed.
  • the opacity is determined in accordance with DIN EN ISO 28199-3 (January 2010; point 7). Examples and comparative examples
  • Table 1.2 Key figures of the aqueous dispersion AD1 and the polymer it contains
  • 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 isobutyiketone at 110-140 ° G.
  • 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 on the basis of the residual absorption at 3310 cm-1.
  • the solids content of the isocyanate group-containing polymer solution was determined to be 45.3%.
  • microgel dispersion (PD1) thus obtained had the following key figures:
  • Solids content (130 ° C, 60 min, 1 g): 40.2% by weight
  • the yellow paste P1 is made from 17.3 parts by weight of Sicotrans yellow L 1918, available from BASF SE, 18.3 parts by weight of a polyester, 43.6 parts by weight, prepared according to Example D, column 16, lines 37-59 of DE 40 09 858 A1 a binder dispersion prepared in accordance with international patent application WO 92/15405, page 15, lines 23-28, 16.5 parts by weight of deionized water and 4.3 parts by weight of butyl glycol.
  • 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, 4, 7, 9-tetramethyl-5-decind io 1.52% in BG (available from BASF SE), 4, 1 part by weight of butyl glycol, 0.4 part by weight of 10% dimethylethanolamine in water and 0.3 part by weight of Acrysol RM-8 (available from The Dow Chemical Company).
  • the black paste P3 is made from 57 parts by weight of a polyurethane dispersion prepared in accordance with 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 , produced 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 (P! ur! ol® P900, available from BASF SE), 7 parts by weight of butyl diglycol and 12 parts by weight of deionized water.
  • a polyurethane dispersion prepared in accordance with 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 , produced according to Example D, column 16, lines 37-59 of DE 40 09 858 A1, 6.5 parts by
  • the barium sulfate paste P4 is made from 39 parts by weight of a polyurethane dispersion prepared in accordance with EP 0228003 B2, page 8, lines 6 to 18, 54 parts by weight of barium sulfate (Blanc fixe micra 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.
  • the steatite paste P5 is made from 49.7 parts by weight of an aqueous binder dispersion prepared according to WO 91/15528, p. 23, line 26 to p. 24, line 24, 28.9 parts by weight of steatite (Microta! C 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.
  • aqueous phase The components listed in Table 5.1 under “aqueous phase” are stirred together in the order given to form an aqueous mixture.
  • 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 1 , measured using a rotary viscometer (Rheolab QC device with temperature control system C-LTD80 / GC by Anton Paar) at 23 ° C.
  • Aqueous polyurethane to polyurea Aqueous polyurethane to polyurea
  • Butylglycol (Rheovis® PU 1250 available from 0.33 0.27 0.20
  • aqueous phase The components listed in Table 5.2 under “aqueous phase” are mixed together in the order given to form an aqueous mixture.
  • a pre-mix is made from the components listed under "Aluminum pigment pre-mix” or “Micapigment pre-mix”. These premixes are added separately to the aqueous mixture. After adding a premix, the mixture is stirred for 10 minutes in each case.
  • Aqueous phase Aqueous phase:
  • Polyurethane dispersion produced according to WO 92/15405, p. 13, line.
  • Polyester produced according to page 28, lines 13 to 33 (example
  • Polyester prepared according to Example D, column 16, lines 37-59 of DE
  • Pluriol® P900 available from BASF SE 0.6
  • Ratio pigment / binder 0.3 0.3
  • aqueous phase The components listed in table 5.3 under “aqueous phase” are mixed together in the order given to form an aqueous mixture.
  • a premix is made from the components listed under “Aluminum pigment premix ü . 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 1 , measured using a rotary viscometer (Rheolab QC device with temperature control system C-LTD80 / QC from Anton Paar) at 23 ° C.
  • Aqueous phase Aqueous phase:
  • Daotan® VTW 6464 available from Allnex 1.59 1.59 1.59 1.59 polyurethane modified polyacrylate; manufactured
  • 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
  • Polyester prepared according to Example D, column nn
  • aqueous phase The components listed in Table 5.4 under “aqueous phase” are stirred together in the order given to form an aqueous mixture.
  • 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 ”1 , measured with a rotary viscometer (Rheolab QC device with temperature control system C-LTD80 / QC from Anton Paar) at 23 ° C.
  • Aqueous phase Aqueous phase:
  • Aqueous binder dispersion AD1 26.33 26.33 26.33 26.33 26.33
  • Butylglycol (Rheovis® PU 1250 available from BASF SE) Aluminum plmafit premix:
  • Ratio pigment / binder 0.25 0.09 0.25 0.09
  • aqueous phase The components listed in Table 5.5 under “aqueous phase” are mixed together in the order given to form an aqueous mixture.
  • 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 was stirred for 10 minutes. Subsequently, with the aid of deionized water and dimethylethanolamine, 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.
  • Aqueous phase Aqueous phase:
  • Tinuvin® 123 available from
  • Example D column 16, lines 37-3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00 3.00
  • aqueous phase The components listed in table 5.6 under “aqueous phase” are mixed together in the order given to form an aqueous mixture.
  • 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 dimethyiethanolamine, 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 5.6; Production of waterborne basecoats WBL25 to WBL30
  • Aqueous binder dispersion AD1 26.33 26.33 26.33 26.33 26.33 26.33 26.33 26.33
  • 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 0.22 0.22 0.22 10% dimethyiethanolamine in water 0.51 0.51 0.51 0.51 0.51 0, 51 2,4,7, 9-tetramethy! -5-decindiol, 52% in BG
  • Pigment / binder ratio 0.25 0.09 0.25 0.09 0.25 0.09 0.25 0.09 0.09 0.09 0.09
  • aqueous phase The components listed in Table 5.7 under “aqueous phase” are stirred together in the order given to form an aqueous mixture.
  • 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 dimethyiethanolamine and a spray viscosity of 130 ⁇ 5 mPa-s (WBL31) or 80 ⁇ 5 mPa-s (WBL31a) at a shear stress of 1000 s ⁇ measured with a rotary viscometer (Rheolab QC device with temperature control system C-LTD80 / QC from the company Anton Paar) at 23 ° C. In the case of WBL31a, a higher amount of deionized water is used for this.
  • Aqueous phase Aqueous phase:
  • Polyurethane dispersion manufactured according to WO 92/15405, p. 13, line.
  • 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
  • Polyester prepared according to Example D, column 16, lines 37-59 of DE “ 7Q
  • Ratio pigment / binder 0.23 0.23 5.8 Production of water-based paints WBL32 and WBL33
  • aqueous phase The components listed in Table 5.8 under “aqueous phase” are stirred together in the order given to form an aqueous mixture.
  • 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 load 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.
  • Polyurethane dispersion produced according to WO 92/15405, p. 13, line.
  • Tinuvin® 123 available from BASF SE 0.75 0.75
  • Tinuvin® 384-2 available from BASF SE 0.47 0.47
  • Polyester produced according to Example D, column 16, lines 37-59 of DE
  • Aqueous phase Aqueous phase:
  • Daotan® VTW 6464 available from Allnex 1.75 1.75 1, 75 1, 75 polyurethane modified polyacrylate; manufactured
  • Butylglycol (Rheovis® PU1250 available from 0.26 0.26 0.26 0.26 0.26
  • Tinuvin® 123 available from BASF SE 0.71 0.71 0.71 0.71 0.71
  • Tinuvin® 384-2 available from BASF SE 0.44 0.44 0.44 0.44 0.44
  • the determination of the mean filament length at the bell edge shows that with increasing concentration of the aluminum pigments within the respective basecoats (the concentration increases from WBL1 to WBL3 or from WBL4 to WBL6), smaller filaments with shorter filament lengths are formed, which is due to the visually assessed degree of wetness correlated.
  • concentration of the aluminum pigments increases, the atomization becomes finer overall as smaller filaments are formed, and the result is a lower degree of wetness, which is contrary to what a person skilled in the art would appreciate due to the CaBER measurements and the increasing thread lifetimes within the WBL1 to series WBL3 or WBL4 to WBL6 would have expected.
  • WBL8 proved to be significantly more critical with regard to the occurrence of needlesticks, especially at a relatively low speed of 23,000 rpm. This behavior correlates with a longer filament length, which was determined experimentally in the case of WBL8 in comparison to WBL7 and which in turn is a measure for a coarser atomization or an increased degree of wetness.
  • Table 6.2 Results of the investigations regarding the occurrence of needlesticks
  • WBL11 and WBL15 or WBL12 and WBL16 each containing the same pigment and the same amount of pigment, show that the basecoats WBL13 to WBL16 each have a smaller flow rate of 300 ml / min and a speed of 43,000 rpm Specify the filament length as the corresponding reference sample WBL9 to WBL12 and thus atomize more finely. This is reflected in significantly better needlestick robustness and also less cloudiness.
  • WBL12 0.820 10.40 74.35 15.10 71.44 18.70 68.37 4 WBL9 and WBL11 each have a pigment / binder ratio of 0.35, whereas WBL10 and WBL12 each have a pigment / binder ratio of 0.13.
  • the experimental results show a correlation between the filament lengths or the resulting atomization properties and the appearance / course, here depending on the layer thickness:
  • a longer filament length i.e. a coarser and therefore wetter atomization leads to poorer flow values, which is illustrated by the short wave and DOI values obtained.
  • Morpho grain size .. ..
  • the tests on the water-based paints WBL32 and WBL33 as well as 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 co-binder (polyester), but especially a solvent, can be used to influence the atomization and the resulting degree of wetness, which is responsible for properties such as cloudy, needlestick robustness, etc.
  • the tests on the samples WBL32 and WBL33 were carried out at a speed of the ESTA bell of 63,000 rpm, that of the samples WBL34 and WBL35 or WBL34a and WBL35a at 43,000 rpm and 63,000 rpm. In all cases the outflow rate was 300 ml / min. Tables 6.13 and 6.14 summarize the results.
  • the examples demonstrate that the method according to the invention can be used to produce coatings which, by reducing the average filament lengths in accordance with step (3) of the method, improve the qualitative properties, in particular with regard to the number of needlesticks, degree of wetness, cloudiness and / or course or appearance and have opacity.
  • the method according to the invention is thus a simple and efficient method for producing coatings that are optimized in this regard.
  • Sample KL1 is a commercially available two-component clear coat (ProGloss from BASF Coatings GmbH), containing pyrogenic silica as a rheology aid (Aerosil® grades from Evonik), the base coat with ethyl 3-ethoxypropionate to a viscosity of 100 mPa-s was set at 1000 / s.
  • Sample KL1a corresponds to KL1 with the difference that the base varnish was adjusted to a viscosity of 50 mPa-s at 1000 / s with ethyl 3-ethoxypnopionate.
  • Sample KL1 b 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.
  • KL1b 1 4 36 42 In the case of KL1b, mean filament lengths were determined that were longer than in the case of KL1. The same applies to KL1a: here too, medium filament lengths were determined that were longer than in the case of KL1.
  • receptive measures such as reducing the spray viscosity (KL1a) or eliminating the rheological aids based on pyrogenic silica (KL1b) deteriorate the atomization compared to the reference KL1 (longer filaments on the bell edge during the atomization process), which is results in a deterioration in rotor stability,
  • the examples demonstrate 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.

Abstract

La présente invention concerne un procédé de production d'au moins un revêtement (B1) sur un substrat, qui comprend au moins les étapes (1) à (5), à savoir (1) la préparation d'une composition de produit de revêtement (BZ1), (2) la détermination de la longueur moyenne des filaments formés lors d'une pulvérisation par rotation de composition de produit de revêtement (BZ1) préparée à l'étape (1), (3) la réduction de cette longueur moyenne des filaments déterminée, (4) l'application d'au moins la composition de produit de revêtement (BZ1), obtenue après l'étape (3), avec une longueur moyenne des filaments réduite sur un substrat en formant au moins un film (F1), et (5) le durcissement physique, le durcissement chimique et/ou le durcissement par rayonnement d'au moins ledit au moins un film (F1) formé à l'étape (4) sur le substrat aux fins de formation du revêtement (B1) sur le substrat, ainsi qu'un revêtement (B1) appliqué sur un substrat, pouvant être obtenu au moyen de ce procédé.
EP19731763.9A 2018-06-25 2019-06-24 Procédé de production d'un revêtement optimisé et revêtement pouvant être obtenu au moyen de ce procédé Withdrawn EP3810338A1 (fr)

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WO2020002256A1 (fr) 2020-01-02
US20210162452A1 (en) 2021-06-03
JP2021529657A (ja) 2021-11-04
MX2020014209A (es) 2021-03-09

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