Patent Application
20210262911
The present invention relates to a method for determining the drop size distribution within a spray and/or the homogeneity of this spray, the spray being formed on atomization of a coating material composition, which comprises at least the steps (1) to (3), specifically atomization of the coating material composition by means of an atomizer, the atomization producing a spray, optical capture of the drops of the spray formed, by a traversing optical measurement (2), and determination of at least one characteristic variable of the drop size distribution within the spray and/or of the homogeneity of the spray, on the basis of optical data obtained as per step (2), and also to methods for compiling an electronic database and for screening coating material compositions when developing paint formulations, carried out on the basis of the aforesaid method.
Nowadays in the automobile industry in particular there are a range of coating material compositions, such as basecoat materials, that are often applied by means of rotational atomization to the particular substrate that is to be coated. Such atomizers feature a fast-rotating application element such as a bell cup, for example, which atomizes the coating material composition to be applied, atomization taking place in particular by virtue of the acting centrifugal force, forming filaments, to produce a spray mist in the form of drops. The coating material composition is typically applied electrostatically, in order to maximize application efficiency and minimize overspray. At the edge of the bell cup, the coating material, atomized by means of centrifugal forces in particular, is charged by direct application of a high voltage to the coating material composition for application (direct charging). Alternatively, instead of rotational atomizers, pneumatic atomizers can be used, which atomize the coating material composition employed in the form of drops, directly, without the formation of filaments beforehand. Following application of the respective coating material composition to the substrate, the resultant film—where appropriate following additional application of other coating material compositions over it, in the form of further films—is cured or baked to give the resultant desired coating.
Optimization of coatings, especially coatings obtained in this way, with regard to particular desired properties of the coating, such as prevention or at least reduction in the tendency for development, or the incidence of optical defects and/or surface defects such as, for example, pinholes, clouding, and/or in the leveling properties, is comparatively complicated and is typically only possible by empirical means. This means that such coating material compositions or, typically, entire test series thereof, within which different parameters have been varied, must first be produced and then, as described in the preceding paragraph, must be applied to a substrate and cured or baked. After that, the series of coatings then obtained must be investigated with regard to the desired properties, in order to allow any possible improvement in the properties investigated to be assessed. Typically, this procedure has to be multiply repeated with further variation of parameters, until the desired improvement in the property or properties of the coating investigated, after curing and/or baking, has been achieved.
It is known practice in the prior art to investigate and to characterize the coating material compositions used for producing such coatings on the basis of their shear viscosity behavior (shear rheology) to provide a better understanding of their particular application characteristics. Here it is possible to make use, for example, of capillary rheometers. A disadvantage of this procedure, focused on investigation of the shear rheology, however, is that it fails to take account, or to take adequate account, of the quite significant influence of the extensional viscosity that occurs in the course of the atomization (extensional rheology). The extensional viscosity is a measure of the flow resistance of a material in an extensional flow. Such extensional flows occur typically, in addition to the shear flows, in all technical processes that are relevant in this regard, as in the case, for example, of capillary inlet and capillary outlet flows. In the case of a Newtonian flow behavior, the extensional viscosity can be calculated from its constant ratio to the conventionally determined shear viscosity (Trouton ratio). In the case of a nonnewtonian flow behavior, which in practice, across a swathe of applications, occurs with far greater frequency, on the other hand, it is typically necessary for the extensional viscosity, as a parameter independent of the shear viscosity, to be determined experimentally with the aid of an extensional rheometer, for adequate consideration of the extensional rheology in the aforesaid description and characterization. Particularly when the aforesaid atomization methods are being carried out, the extensional viscosity may have a quite significant influence on the atomization process and on the breakdown into drops which then form the spray mist. Techniques for determining the extensional viscosity are known in the prior art. It is typical here to determine the extensional viscosity by means of Capillary Breakup Extensional Rheometers (CaBERs). To date, however, there has been no available technique for giving adequate consideration equally to both extensional forces and shearing forces, without actually atomizing the material under investigation.
There is therefore a need for a method which makes it possible, by investigating the atomization behavior of coating material compositions, to achieve an improvement in certain desired properties of the coatings to be produced by means of this atomization, such as the prevention or at least reduction of the tendency for formation or the incidence of optical defects and/or surface defects, without having to go through the commonly required complete operation of coating and baking for producing such coatings. Equally, however, such a method should take account not only, adequately, of the shear rheology it entails, but also the extensional rheology.
A problem addressed with the present invention, therefore, is that of providing a method which makes it possible to analyze and more particularly to improve certain desired properties of coatings to be produced by atomization, such as the prevention or at least reduction in the tendency for formation and/or the incidence of optical defects and/or surface defects, without having to apply the respective coating material composition for use to a substrate by means of a conventional coating process and in particular without having to cure and/or bake the resulting film in order to produce the coating, since to do so is comparatively costly and inconvenient and is disadvantageous at least on economic grounds. Such a method ought equally to take adequate account of the extensional behavior that occurs in the course of the atomization. A particular problem addressed with the present invention is that of providing such a method for aqueous basecoat materials as coating material compositions.
This problem is solved by the subject matter claimed in the claims and also by the preferred embodiments of that subject matter that are described in the description hereinafter.
A first subject matter of the present invention is a method for determining the drop size distribution within a spray and/or the homogeneity of said spray, the spray being formed on atomization of a coating material composition, comprising at least the steps (1) to (3), specifically
The determination, in accordance with the invention, of the size distribution of the drops formed by the atomization as per step (1) entails the determination of at least one characteristic variable known to the skilled person, such as suitable average diameters of the drops, such as, in particular, the D10 (arithmetic diameter; “1,0” moment), D30 (volume-equivalent average diameter; “3,0” moment), D32 (Sauter diameter (SMD); “3,2” moment), dN,50% (number-based median) and/or dV,50% (volume-based median). The determination of the drop size distribution here encompasses the determination of at least one such characteristic variable, more particularly a determination of the D10 of the drops. The aforesaid characteristic variables are in each case the corresponding numerical mean of the drop size distribution. The moments of the distributions are labeled here using the upper-case letter “D”; the index specifies the corresponding moment. The characteristic variables labeled with the lower-case letter “d” here are the percentiles (10%, 50%, 90%) of the corresponding cumulative distribution curve, with the 50% percentile corresponding to the median. The index “N” pertains to the number-based distribution, the index “V” to the volume-based distribution.
It has surprisingly been found that the method of the invention allows the atomization behavior of a wide variety of different coating material compositions, and especially of aqueous basecoat materials, to be investigated and characterized. This is accomplished, surprisingly, on the basis of the drop size distribution within a spray and/or on the basis of the homogeneity of said spray, the spray being formed on atomization of a coating material composition, in particular by virtue of the traversing optical measurement through the entire spray during the implementation of step (2). This traversing optical measurement opens up the possibility in particular of a (free) choice of the traversing axis and/or of a (free) choice of the traversing velocity when implementing step (2) of the method of the invention, and, relative to conventional raster-resolved point measurements, has the advantage that not only is it possible for drop size distribution and/or homogeneity to be captured holistically, but that the measurement, moreover, can be performed within a substantially shorter time (a factor of 5 to 25 relative to conventional raster-resolved point measurements). Moreover, the consumption of material is significantly lower, and the method overall is therefore more economical, since it is no longer necessary to conduct a multiplicity of individual measurements (the finer the raster, the greater the number of point measurements required in the case of raster-resolved point measurements).
The at least one characteristic variable of the drop size distribution within the spray, and/or the homogeneity of the spray, that are determined by means of the method of the invention can be incorporated into an electronic database, or such a database can be compiled and/or updated. A second subject of the present invention is therefore a method for compiling and/or updating an electronic database containing at least one characteristic variable of the drop size distribution within the spray and/or of the homogeneity of the spray of atomized coating material compositions which differ from one another, the method comprising at least steps (1) to (3), (4A) and (5A), specifically
steps (1), (2), and (3) as per the method of the invention for determining at least one characteristic variable of the drop size distribution within a spray and/or of the homogeneity of said spray for a first coating material composition (i),
(4A) incorporation of the at least one characteristic variable of the drop size distribution within the spray and/or of the ascertained homogeneity of the spray, ascertained as per step (3) for the first coating material composition (i), into an electronic database, and
(5A) repetition at least once of the steps (1) to (3) and (4A) for at least one further coating material composition, different from the first coating material composition (i).
The incorporation of the characteristic variable of the drop size distribution within the spray and/or of the homogeneity into the database as per step (4A) preferably further includes the incorporation into the database of the respective standard deviations of these characteristic values determined.
When the methods of the invention are implemented, the influence of the extensional viscosity that occurs on atomization of coating material compositions which can be employed for producing coatings is adequately considered. This is so in particular because, when the methods of the invention are implemented, comparatively high extension rates are considered, namely extension rates of up to 100 000 s−1, and hence extension rates higher than those in the case of conventional CaBER measurements for determining the extensional viscosity, for which, especially in the case of basecoat materials, only extension rates of up to 1000 s−1 are achieved, and the determination of at least one characteristic variable of the drop size distribution and/or of the homogeneity therefore takes place at aforesaid comparatively high extension rates. By means of the methods of the invention, therefore, in contrast to conventional CaBER methods, the extensional viscosity and the extension rates that occur are adequately considered. As a result of the fact that the methods of the invention, with step (1), themselves include the implementation of atomization, it is possible to give consideration both to shear rheology and to extensional rheology within a single method, sufficiently, and not using techniques which are able to capture only individual elements (shear rheology or extensional rheology).
It has in particular been surprisingly found that by means of the method of the invention, particularly in the case of aqueous basecoat materials which are used as coating material compositions in the atomization, conclusions can be drawn about the particle size distributions determined for the drops, i.e., the drop size distribution ascertained, particularly on the basis of determinations of the D10 values as a characteristic variable of the drops, and/or of the homogeneity of the spray on the appearance of the coating to be produced. Smaller drop sizes denote a “finer” atomization of the coating material composition used. Maximally fine atomization is desirable since it entails a lower wetness, in other words a less wet appearance to the film formed after application of the coating material composition used. The skilled person is aware that too great a wetness can lead to unwanted incidence of pops and/or pinholes, to a poorer shade and/or flop, and/or to the occurrence of clouding. Equally, corresponding conclusions can be drawn on the basis of the ratio of quotient TT1/TTotal1 to the quotient TT2/TTotal2, as a measure of the local distribution of transparent and nontransparent drops and hence as a measure of the homogeneity of the spray mist formed in the atomization. In a spray mist formed in an atomization such as a rotational atomization, the fraction of nontransparent drops, in other words, for example, the fraction of drops containing (effect) pigment, increases from inside to outside because of the centrifugal force. If there is a comparatively sharp change in the ratio of the quotient TT1/TTotal1 to the quotient TT2/TTotal2 within the spray mist, with increasing distance from the edge of the bell (if a rotary atomizer is used in step (1)), this means that there is a significant change in the composition of the spray mist from inside to outside. Via the determination of the ratio of the quotient TT1/TTotal1 to the quotient TT2/TTotal2, or on the basis of the determination as to how sharply this ratio changes from inside to outside, it is therefore possible to state whether a material used is more strongly separated, on application, into regions with different concentrations of (effect) pigments, with increasing values of the aforesaid ratio, and is therefore less homogeneous or more susceptible to the formation of surface defects such as streaks, than another material.
Surprisingly, by implementing the method of the invention on the basis of at least one characteristic variable of the defined drop size distribution and/or of the homogeneity, it is possible to achieve an investigation of and in particular an improvement in certain desired properties of coatings to be produced by means of the atomization, particularly with regard to preventing or at least reducing the tendency to formation and/or the incidence of optical defects and/or surface defects, without in this case having to apply the particular coating material composition to a substrate by means of a conventional painting procedure and to carry out curing and/or baking of the resulting film in order to produce the coating.
A further subject of the present invention is therefore a method for screening coating material compositions in the development of paint formulations, which comprises at least steps (1) to (3), (4B), (5B), and (6B), and also optionally (7B), where within the steps (1) to (3) first of all at least one characteristic variable is determined of the drop size distribution within the spray and/or the homogeneity of said spray, in accordance with the method of the invention described above for determining the drop size distribution within a spray and/or the homogeneity of said spray. These steps (1) to (3) therefore correspond to steps (1) to (3) of the first subject of the present invention.
The method for screening coating material compositions in the development of paint formulations comprises at least the steps (1) to (3), (4B), (5B), and (6B), and also optionally (7B), namely
It has surprisingly been found that the method of the invention for screening coating material compositions in development of paint formulations is less costly and inconvenient than typical methods and therefore has (time-)economic and financial advantages over corresponding conventional methods. By means of the method of the invention it is possible surprisingly, on the basis of the ascertained drop size distribution and/or the homogeneity, to estimate, with a sufficiently high probability, whether certain optical defects and/or surface defects can be expected in the coating to be produced, without producing the coating at all, especially in the case of aqueous basecoat materials. This is accomplished, surprisingly, by determination of the drop size distribution and/or of the homogeneity of the drops which occur on atomization, forming the spray mist, and by a correlation of these ascertained characteristic variables with the incidence of the aforesaid optical defects and/or surface defects, or their prevention/reduction. Depending on these particle size distributions occurring during atomization, and/or on the homogeneity of the drops, it is possible accordingly to be able to monitor the resulting properties such as optical properties and/or surface properties of the coating to be produced and in particular to prevent or at least reduce the incidence of optical defects and/or surface defects. In other words, by means of the method of the invention, because of the investigation of the atomization behavior of a coating material composition, it is possible to make predictions regarding qualitative properties of the eventual coating (such as the incidence of pinholes, clouding, streaking, leveling, or appearance). In particular it has surprisingly been found that they correlate with these properties better than other techniques known from the prior art. The method of the invention therefore permits a simple and efficient technique for quality assurance and enables purposeful development of coating material compositions without the need for recourse to comparatively costly and inconvenient coating procedures on (model) substrates. In particular it is possible here to omit the step of curing and/or baking.
Method of the Invention for Determining the Drop Size Distribution and/or the Homogeneity
A first subject of the present invention is a method for determining the drop size distribution within a spray and/or the homogeneity of said spray, the spray being formed on atomization of a coating material composition, which comprises at least steps (1) to (3).
The atomization is carried out preferably by means of a rotary atomizer or a pneumatic atomizer.
The concept of “rotary atomizing” or of “high-speed rotary atomizing” is one which is known to the skilled person. Such rotary atomizers feature a rotating application element that atomizes the coating material composition to be applied into a spray mist in the form of drops, owing to the acting centrifugal force. The application element in this case is a preferably metallic bell cup.
In the course of rotary atomization by means of atomizers, so-called filaments develop first, at the edge of the bell cup, and then go on, in the further course of the atomization process, to break down further into aforesaid drops, which then form a spray mist. The filaments therefore constitute a precursor of these drops. The filaments may be described and characterized by their filament length (also referred to as “thread length”) and their diameter (also referred to as “thread diameter”).
The concept of “pneumatic atomization” and pneumatic atomizers used for this purpose are likewise known to the skilled person.
When the method of the invention is carried out, sufficient consideration is given to the extensional viscosity which occurs during the atomization. The skilled person is aware of the concept of extensional viscosity, with the unit Pascal-seconds (Pa·s), as a measure of the flow resistance of a material in an extensional flow. Techniques for determining the extensional viscosity are likewise known to the skilled person. The extensional viscosity is typically determined using what are called Capillary Breakup Extensional Rheometers (CaBERs), which are sold by Thermo Scientific, for example.
Step (1) of the method of the invention relates to the atomization of the coating material composition by means of an atomizer, with the atomization producing a spray. The atomizer is preferably, as mentioned above, a rotary atomizer or a pneumatic atomizer. Where a rotary atomizer is used, it preferably has as its application element a bell cup which is capable of rotation. Here, optionally, the atomized coating material composition may undergo electrostatic charging at the edge of the bell cup by the application of a voltage. This is not necessary, however, for the implementation of the method of the invention, particularly for the implementation of step (1) of the method of the invention.
Where a rotary atomizer is used in step (1), the speed of rotation (rotational velocity) of the bell cup is adjustable. In the present case the rotation speed is preferably at least 10 000 revolutions/min (rpm) and at most 70 000 revolutions/min. The rotational velocity is preferably in a range from 15 000 to 70 000 rpm, more preferably in a range from 17 000 to 70 000 rpm, more particularly from 18 000 to 65 000 rpm or from 18 000 to 60 000 rpm. At a rotation speed of 15 000 revolutions per minute or above, a rotary atomizer of this kind, in the sense of this invention, is referred to preferably as a high-speed rotary atomizer. Rotational atomization in general and high-speed rotational atomization in particular are widespread within the automobile industry. The (high-speed) rotary atomizers used for these processes are available commercially; examples include products of the Ecobell® series from the company Dürr. Such atomizers are suitable preferably for electrostatic application of a multiplicity of different coating material compositions, such as paints, that are used in the automobile industry. Particularly preferred for use as coating material compositions within the method of the invention are basecoat materials, more particularly aqueous basecoat materials. The coating material composition may be applied electrostatically, but need not be. In the case of electrostatic application, there is electrostatic charging of the coating material composition, atomized by centrifugal forces, at the bell cup edge, by preferably direct application of a voltage such as a high voltage to the coating material composition that is to be applied (direct charging).
The discharge rate of the coating material composition to be atomized, during the implementation of step (1), is adjustable. The discharge rate of the coating material composition for atomization, during the implementation of step (1), is preferably in a range from 50 to 1000 mL/min, more preferably in a range from 100 to 800 mL/min, very preferably in a range from 150 to 600 mL/min, more particularly in a range from 200 to 550 mL/min.
The discharge rate of the coating material composition for atomization, during the implementation of step (1), is preferably in a range from 100 to 1000 mL/min or from 200 to 550 mL/min, and the rotary speed of the bell cup in the case of rotational atomization is preferably in a range from 15 000 to 70 000 revolutions/min or from 15 000 to 60 000 rpm.
The coating material composition used in step (1) of the method of the invention is preferably a basecoat material, more preferably an aqueous basecoat material, more particularly an aqueous basecoat material which comprises at least one effect pigment.
Step (2) of the method of the invention sees the drops of the spray formed by atomization as per step (1) being captured optically by a traversing optical measurement through the entire spray.
The implementation of this traversing measurement allows the entire spray, and hence the entire drop spectrum forming the spray, to be captured in its entirety. As a result, the capture of all of the drop sizes forming the spray is made possible. The entire spray can be measured in its entirety (and not just individual regions of the spray). The traversing measurement allows locationally resolved—i.e., point-specific—optical measurement of the drops at numerous locations in the atomization spray, and so determination in the subsequent step (3) is made more precise than if the measurement did not take place traversingly. The implementation of the traversing measurement takes place preferably by moving the atomizing head of the atomizer used during the implementation of step (2). Alternatively, however, a relative movement of the measuring system is likewise possible.
The traversing optical measurement as per step (2) may be carried out at different traversing speeds. This speed may be linear or nonlinear. Through the choice of the traversing speed it is possible to simplify the area weighting: for instance, an increase in the traversing speed with increase of the area segments fulfills this purpose, and so the product of area and residence time is constant. The traversing speed is preferably selected such as to obtain at least 10 000 counts per area segment of the spray. The term “counts” in this context refers to the number of drops detected in the measurement within the spray or within different area segments of the spray. The area segments represent positions within the spray.
The optical capture as per step (2) of the method of the invention is accomplished preferably by means of an optical measurement which is based on scattered light investigations on the drops contained within the spray, and is carried out on these drops. This measurement is preferably accomplished using at least one laser.
The optical capture as per step (2) of the method of the invention takes place preferably by means of phase Doppler anemometry (PDA) and/or by means of the time-shift technique (TS). From the optical data obtained when carrying out step (2) by means of PDA, it is possible in step (3) to determine at least one characteristic variable of the drop size distribution. From the optical data obtained when carrying out step (2) by means of TS, it is possible in step (3) to determine both at least one characteristic variable of the drop size distribution and the homogeneity of the spray.
The optical measurement takes place preferably on a measurement axis which is traversed repeatedly, as depicted in
Step (2) may be carried out at different tilt angles of the atomizer relative to the measuring facility carrying out the measurement as per step (2). Accordingly it is possible to vary the tilt angle from 0 to 90°. In
The optical capture as per step (2) takes place preferably with a detector.
The procedure for determining the drop size distribution may take place by means of phase Doppler Anemometry (PDA). This technique is known fundamentally to the skilled person, from, for example, F. Onofri et al., Part. Part. Sys. Charact. 1996, 13, pages 112-124 and A. Tratnig et al., J. Food. Engin. 2009, 95, pages 126-134. The PDA technique is a measurement method based on the formation of an interference plane pattern in the intersection volume of two coherent laser beams. The particles moving in a flow, such as, for example, the drops of the atomization spray mist, i.e., spray, that are investigated in accordance with the present invention, scatter light, when passing through the intersection volume of the laser beams, with a frequency referred to as the Doppler frequency, which is directly proportional to the viscosity at the location of the measurement. From the difference in phase position of the scattered light signal at preferably at least two detectors used, these detectors being sited at different locations in the space, it is possible to determine the radius of curvature of the particle surface. In the case of spherical particles, this leads to the particle diameter; in the case of drops, therefore, it leads to the respective drop diameter. For high measurement accuracy it is advantageous to design the measuring system, particularly in relation to the scattering angle, in such a way that a single scattering mechanism (reflection or first-order refraction) is dominant. The scattered light signal is typically converted by photomultipliers into electronic signals, which are evaluated, using covariance processors or by means of an FFT analysis (Fast Fourier Transformation analysis), for the Doppler frequency and the difference in the phase positions. The use of a Bragg cell here makes it possible, preferably, to carry out controlled manipulation of the wavelength of one of the two laser beams, and so to generate an ongoing interference plane pattern.
PDA systems measure the phase shifts (that is, the difference in the phase positions) customary in received light signals by using different receiving apertures (masks).
Within step (2) of the method of the invention, in the case of implementation by means of PDA, a mask is preferably employed that can be used to detect drops having a maximum possible drop diameter of 518.8 μm.
Corresponding instruments suitable for implementing the PDA method are available commercially, an example being the Single-PDA from DantecDynamics (P60, Lexel argon laser, FibreFlow).
During implementation of step (2), the PDA is operated preferably in forward scattering at an angle of 60-70° with a wavelength of 514.5 nm (polarized orthogonally) in reflection. The receiving optics in this case preferably have a focal length of 500 mm; the transmitting optics preferably having a focal length of 400 mm.
The optical measurement according to step (2) by means of PDA takes place traversingly in a radial-axial direction in relation to the tilted atomizer used, preferably at a 45° tilt angle. In principle, however, as mentioned above, tilt angles in a range from 0 to 90°, preferably >0 to <90°, such as from 10 to 80°, are possible. The optical measurement takes place preferably 25 mm vertically below the flank of the atomizer that is inclined to the traversing axis. Measurements have shown the process of drop formation to be concluded at this position. One such setup is shown, by way of example, in
Alternatively or additionally to the PDA technology, the drop size distribution may be determined using the time-shift technique. The time-shift technique (TS) is likewise fundamentally known to the skilled person, from, for example, an article by W. Schafer et al., ICLASS 2015, 13th Triennial International Conference on Liquid Atomization and Spray Systems, Tainan, Taiwan, pages 1 to 7, and an article by M. Kuhnhenn et al., ILASS Europe 2016, 27th Annual Conference on Liquid Atomization and Spray Systems, Sep. 4-7, 2016, Brighton UK, pages 1 to 8, and also from W. Schafer et al., Particuology 2016, 29, pages 80-85.
The time-shift technique (TS) is a measurement method which is based on the backscattering of light (e.g., laser light) by particles such as, in the case of the present invention, by the drops of the spray mist (spray) resulting from the atomization. The TS technique is based on the light scattering of an individual particle from a shaped light beam such as a laser beam. The scattered light of the individual particle is interpreted as the sum total of all orders of scattering present at the location of the detector used. In approximation to the geometric optics, this corresponds to the analysis of the propagation of individual light beams through the particle, with a varying number of internal reflections. The laser beam used for implementing the time-shift technique is typically focused by lenses. The light which has been scattered by the particles is divided into perpendicularly polarized and parallel-polarized light, and is captured separately by preferably at least two photodetectors. The signal coming from the detectors in turn supplies the necessary information for ascertaining a determination of the drop size distribution and/or homogeneity. The wavelength of the light of the illuminating beam used is in the same order of magnitude as or smaller than that of the particles to be measured. The laser beam ought therefore to be selected so that it does not exceed the size of the drops, in order to give the time-shift signal. If this value is exceeded, the signal is no longer a suitable basis for the determination of the size referred to above. Otherwise the problem arises that the signal components of the different scatterings overlap and can therefore not be captured and distinguished individually. The time-shift technique can be used for determining characteristic properties of the particles, such as for determining the drop size distribution. Moreover, the time-shift technique (TS) allows differentiation between bubbles, i.e., transparent drops (T), and solids-containing particles, i.e., nontransparent drops (NT). Corresponding instruments suitable for these purposes are available commercially, examples being instruments from the SpraySpy® series from AOM Systems. The implementation of traversing measurements by means of instruments from the SpraySpy® series, while being fundamentally known, is nevertheless only utilized in the prior art in order to determine the width of the spray jet, but not in order to determine the homogeneity of the spray and/or characteristic variables of the drop size distribution.
The optical measurement according to step (2) by means of TS takes place traversingly in a radial-axial direction in relation to the tilted atomizer used, preferably at a 45° tilt angle. In principle, however, as mentioned above, tilt angles in a range from 0 to 90°, preferably >0 to <90°, such as from 10 to 80°, are possible. The optical measurement takes place preferably 25 mm vertically below the flank of the atomizer that is inclined to the traversing axis. Measurements have shown the process of drop formation to be concluded at this position. One such setup is shown, by way of example, in
Step (3) of the method of the invention envisions the determination of at least one characteristic variable of the drop size distribution within the spray and/or the homogeneity of the spray on the basis of optical data obtained by virtue of the optical capture as per step (2).
As already mentioned above, the determination of the drop size distribution of the drops formed by the atomization as per step (1), in accordance with the invention, preferably entails the determination of corresponding characteristic variables known to the skilled person, such as the D10 (arithmetic diameter; “1,0” moment), D30 (volume-equivalent average diameter “3,0” moment), D32 (Sauter diameter (SMD); “3,2” moment), dN,50% (number-based median) and/or dV,50% (volume-based median), with at least one of these characteristic variables of the drop size distribution being determined within step (3). In particular, the determination of the drop size distribution encompasses a determination of the D10 of the drops. This is done in particular if step (2) is carried out by means of PDA and/or TS.
If step (2) is carried out by means of PDA, the optical data obtained after implementation of step (2) are preferably evaluated via an algorithm for any desired tolerances within step (3). A tolerance of around 10% for the PDA system used limits the validation to spherical drops; an increase also brings slightly deformed drops into the assessment. As a result, it becomes possible to assess the sphericity of the measured drops along the measurement axis.
If step (2) is carried out by means of TS, the optical data obtained after implementation of step (2) are preferably likewise evaluated via an algorithm for any desired tolerances.
The homogeneity of the spray refers to the ratio of the two quotients TT1/TTotal1 and TT2/TTotal2 to one another, as a measure of the local distribution of transparent and nontransparent drops at two different positions within the spray, with TT1 corresponding to the number of transparent drops at the first position 1, TT2 to the number of transparent drops at the second position 2, TTotal1 to the number of all the drops in the spray, and hence to the sum total of transparent drops and nontransparent drops, at position 1, and TTotal2 to the number of all the drops in the spray, and hence to the sum total of transparent drops and nontransparent drops, at position 2, with position 1 being nearer to the center of the spray than position 2. The homogeneity may be determined in particular if TS is used when carrying out step (2).
Position 1, which is closer to the center of the spray than position 2, preferably represents an area segment within the spray that is different from position 2. Position 1—being located closer to the center of the spray than position 2—is located further in the interior of the spray than position 2, which, correspondingly, is located further outward in the spray, and at any rate further outward than position 1. If the spray is imagined in the form of a cone, position 1 is located further in the cone interior than position 2. Both positions, 1 and 2, preferably lie on a measurement axis which leads through the entire spray. This is depicted by way of example in
The data thus obtained by means of TS as per implementation of step (2) can therefore be evaluated for the transparent spectrum (T) and for the nontransparent spectrum (NT) of the drops. The ratio of the number of measured drops in both spectra serves as a measure of the local distribution of transparent and nontransparent drops. An integral assessment along the measurement axis is possible. Specifically, the ratio of the transparent drops (T) to the total number of drops (Total) is determined preferably at a position of x=5 mm or x=25 mm along the measurement axis. These positions then correspond to the aforesaid positions 1 (x=5 mm) and 2 (x=25 mm). A ratio is formed in turn from the corresponding values, in order to describe the spray jet homogeneity, which changes from the inside outward.
Method of the Invention for Compiling and/or Updating an Electronic Database
A further subject of the present invention is a method for compiling and/or updating an electronic database containing at least one characteristic variable of the drop size distribution within the spray and/or of the homogeneity of the spray of atomized coating material compositions which differ from one another, the method comprising at least the steps (1) to (3), (4A) and (5A), specifically
steps (1), (2), and (3) as per the method of the invention for determining the drop size distribution within a spray and/or the homogeneity of said spray for a first coating material composition (i), i.e.,
All preferred embodiments described hereinabove in connection with the method of the invention for determining the drop size distribution within a spray and/or the homogeneity of that spray are also preferred embodiments in relation to the method for compiling and/or updating an electronic database.
The incorporation of the at least one characteristic variable of the drop size distribution within the spray and/or of the homogeneity of the spray, as determined, into the database, as per step (4A), preferably also entails, as already observed above, the incorporation of the respective standard deviations into the database. The standard deviation may take adequate account of any inhomogeneity and/or incompatibility occurring in the particular coating material composition used, during the atomization.
Step (5A) envisions repetition at least once of steps (1) to (3) and (4A) for at least one further coating material composition, different from the first coating material composition (i), such as for at least one second coating material composition (ii).
The repetition as per step (5A) is carried out preferably for a multiplicity of corresponding coating material compositions which are different in each case. The repetition therefore takes place at least once to x times, where x is a positive integer ≥2. Since the method of the invention is a method for compiling and/or for updating an electronic database, there is no upper limit here on the number of coating material compositions to be used: the higher the number of repetition steps (5A) and/or the higher the number of coating material compositions used within the repetition step (5A), the greater the quantity of information that is incorporated into the database about the characteristic variables of the drop size distribution within the spray, and/or the homogeneity of the spray of these compositions, during the atomization, and this of course is advantageous. For example, the parameter x may be in the range from 2 to 1 000 000 or from 5 or 10 or 50 or 100 to 1 000 000.
By means of the method of the invention for compiling and/or updating an electronic database, an electronic database of this kind is preferably expanded and updated continuously. This database is then able to furnish information about characteristic variables of the drop size distribution within the spray and/or the homogeneity of the spray of a multiplicity of different atomized coating material compositions. The electronic database is preferably an online database. Step (4A) is preferably carried out by means of software support.
Incorporated into the database when implementing the method of the invention for compiling and/or updating an electronic database, within step (4A), are preferably not only the ascertained characteristic variables of the drop size distribution within the spray and/or the homogeneity of the spray, but also, instead, all method parameters selected and/or mandated for the implementation of steps (1) to (3). In addition to these method parameters or alternatively to them, all product parameters relating to the coating material compositions used in the method of the invention are preferably likewise incorporated into the database, and especially the particular formulas for their preparation and/or the components used for their preparation, and their corresponding amounts.
The at least one further coating material composition used in step (5A), such as at least one coating material composition (ii), is different from the first coating material composition (i). Similarly, all further coating material compositions used in a repetition of step (5A) are different not only from each of the coating material compositions (i) and (ii) but also from one another.
The at least one further coating material composition used in step (5A), such as at least one second coating material composition (ii), preferably has a pigment content identical to that of the first coating material composition (i) or a pigment content which deviates by at most ±10% by weight, more preferably by at most ±5% by weight, from the pigment content of the coating material composition (i), based on the amount of pigment present in the coating material composition (i), and which, moreover, comprises the identical pigment or pigments or the substantially identical pigment or pigments to the coating material composition (i). The same applies, preferably, to each further coating material composition of those used when repeating step (5A): preferably each of these further coating material compositions has a pigment content identical to that of the first coating material composition (i) or a pigment content which deviates by at most ±10% by weight, more preferably by at most ±5% by weight, from the pigment content of the coating material composition (i), based on the amount of pigment present in the coating material composition (i), and which, moreover, comprises the identical pigment or pigments or the substantially identical pigment or pigments to the coating material composition (i). If a defined effect pigment is used in the first coating material composition (i), for example, the identical effect pigment, in the case of identical pigments, is also present as effect pigment in each further one of the coating material compositions used when repeating step (5A).
The method of the invention for compiling an electronic database, besides steps (1) to (3), (4A), and (5A), preferably further comprises at least the further steps (3A), (3B), and (3C), specifically
(3A) application of the first coating material composition (i) atomized in step (1) to a substrate, to form a film located on the substrate, and baking of this film to form a coating located on the substrate,
(3B) analysis and assessment of the coating obtained after step (3A) for the incidence or nonincidence of surface defects and/or optical defects, and
(3C) incorporation of the results obtained after implementation of step (3B) into the electronic database,
where step (5A) of the method of the invention in this case comprises the repetition of these steps (3A), (3B), and (3C) for at least one further coating material composition, different from the first coating material composition (i), such as at least one second coating material composition (ii).
In this way, the database compiled by means of the method of the invention preferably includes not only the characteristic variables of the drop size distribution within the spray and/or the homogeneity of the spray determined for the coating material compositions used, such as those of the coating material compositions (i), (ii), and each further coating material composition used, but also, moreover, includes data concerning the assessment of the coatings obtainable from each of these compositions, with regard to the possible incidence of surface defects and/or optical defects. This enables a direct correlation of the characteristic variables of the drop size distribution within the spray and/or the homogeneity of the spray, occurring and determined for the atomization of the compositions, with the incidence or nonincidence of surface defects and/or optical defects in and/or on the coating, within the database. These data can then be called up from the database.
Step (3A) uses preferably metallic substrates. Also possible in principle, however, are nonmetallic substrates, especially plastics substrates. The substrates that are used may have been coated. If a metal substrate is to be coated, then, before the surfacer or primer-surfacer or the basecoat is applied, the metal substrate is additionally coated, preferably, with an electrocoat. If a plastics substrate is being coated, then preferably, before the surfacer or primer-surfacer or the basecoat is applied, the plastics substrate is preferably pretreated. The techniques most commonly employed for such pretreatment are flaming, plasma treatment, and corona discharge. Flaming is employed with preference. The coating material compositions used, such as the coating material compositions (i), (ii), and each further coating material composition used, are preferably basecoat materials, more particularly waterborne basecoat materials. Correspondingly, the coating obtained after step (3A) is preferably a basecoat. Application of the basecoat material or materials to a metal substrate in step (3A) may take place at the film thicknesses customary in the context of the automobile industry, in the range from, for example, 5 to 100 micrometers, preferably 5 to 60 micrometers, especially preferably 5 to 30 micrometers. The substrate used preferably has an electrocoat (EC), more preferably an electrocoat applied by cathodic deposition of an electrocoat material. Baking is preferably preceded by drying in accordance with known techniques. For example, (1-component) basecoat materials, which are preferred, can be flashed off at room temperature (23° C.) for 1 to 60 minutes and subsequently dried preferably at possibly slightly elevated temperatures of 30 to 90° C. Flashing off and drying in the context of the present invention refer to the evaporation of organic solvents and/or water, making the paint drier but not yet curing it, or not yet forming a fully crosslinked coating film. Curing, in other words baking, is accomplished preferably thermally at temperatures from 60 to 200° C. The coating of plastics substrates is basically similar to that of metal substrates. Here, however, curing generally takes place at much lower temperatures, of 30 to 90° C. Step (3A), after application of the first coating material composition (i), atomized in step (1), to a substrate, may optionally include the application of a further coating material composition and curing thereof. Especially if the first coating material composition (i) atomized in step (1) is a preferably aqueous basecoat material, it is possible for a commercial clearcoat material to be applied over it by commonplace techniques, in which case the film thicknesses are again within the commonplace ranges, such as 5 to 100 micrometers, for example. After the clearcoat has been applied, it may be flashed off at room temperature (23° C.) for 1 to 60 minutes, for example, and optionally dried. The clearcoat is then preferably cured, i.e., baked, together with the applied, atomized first coating material composition (i). Baking is accompanied by crosslinking reactions, for example, to produce a multicoat effect finish, and/or color and effect finish, on a substrate.
In step (3B), preferably, the incidence or nonincidence of surface defects and/or optical defects selected from the group of pinholes, runs, pops, streakiness and/or cloudiness is investigated and assessed, and/or the appearance (visual aspect) of the coating is investigated and assessed. The coating is preferably a basecoat such as a waterborne basecoat. Incidence of pinholes is investigated and assessed in accordance with the method of determination described hereinafter, by counting of the pinholes on wedge application of the coating to a substrate as per step (3A) in a film thickness range from 0 to 40 μm (dry film thickness), with the ranges from 0 to 20 μm and from >20 to 40 μm being counted separately, standardization of the results to an area of 200 cm2, and summation to give a total number. Preferably just a single pinhole is a defect. The incidence of pops is investigated and assessed in accordance with the method of determination described hereinafter, by determination of the popping limit, i.e., the film thickness of a coating, such as a basecoat, from which pops occur, in accordance with DIN EN ISO 28199-3, section 5 (date: January 2010). With preference just a single pop is a defect. Incidence of cloudiness is investigated and assessed in accordance with the method of determination described hereinafter using the cloud-runner instrument from BYK-Gardner GmbH, with determination of the three characteristic variables of “mottling15”, “mottling45”, and “mottling60” as measures of the cloudiness, measured at the angles of 15°, 45°, and 60° relative to the angle of reflection of the measurement light source used; the higher the value or values of the corresponding characteristic variable or variables, the more pronounced the cloudiness. Appearance is investigated and assessed in accordance with the method of determination described hereinafter, by assessing the leveling on wedge application of the coating to a substrate as per step (3A) in a film thickness range from 0 to 40 μm (dry film thickness), with different regions, such as 10-15 μm, 15-20 μm, and 20-25 μm, for example, being marked, and with the investigation and assessment being performed within these film thickness regions using the Wave scan instrument from Byk-Gardner GmbH. In that case a laser beam is directed at an angle of 60° onto the surface to be investigated, and over a measuring distance of 10 cm the fluctuations of the reflected light in the short wave region (0.3 to 1.2 mm) and in the long wave region (1.2 to 12 mm) are recorded by means of the instrument (long wave=LW; short wave=SW; the lower the figures, the better the leveling). Incidence of runs is investigated and assessed in accordance with the method of determination described hereinafter, by determination of the running tendency in accordance with DIN EN ISO 28199-3, section 4 (date: January 2010). A defect occurs, preferably, when runs occur starting from a film thickness which is below a film thickness amounting to 125% of the target film thickness. For example, if the target film thickness is 12 μm, a defect occurs if there are runs at a film thickness of 12 μm+25%, in other words at 16 μm. Film thicknesses here are determined in each case in accordance with DIN EN ISO 2808 (date: May 2007), method 12A, preferably using the MiniTest® 3100-4100 instrument from ElektroPhysik. In all cases the thickness in question is the dry film thickness in each case.
The skilled person knows the terms “pinholes”, “pops”, “runs”, and “leveling”, from Rompp Chemie Lexikon, Lacke and Druckfarben, 1998, 10th edition, for example. The concept of cloudiness is likewise one known to the skilled person. The cloudiness of a paint finish is understood according to DIN EN ISO 4618 (date: January 2015) to refer to the disparate appearance of a finish due to irregular regions, distributed randomly over the surface, that differ in their color and/or gloss. A dappled inhomogeneity of this kind is disruptive to the uniform overall impression conveyed by the finish, and is generally undesirable. A method for determining the cloudiness is specified hereinafter. While the cloudiness is distinguished by aforesaid regions in the form of dapples, the concept of “streakiness”, in contrast, is understood as a phenomenon caused by poor overlap of spray jets, giving rise in turn to the regular streak-like light and dark regions. A method for determining the streakiness is specified hereinafter.
Method of the Invention for Screening Coating Material Compositions when Developing Paint Formulations
A further subject of the present invention is a method for screening coating material compositions when developing paint formulations.
Steps (1) to (3) of the method for screening coating material compositions when developing paint formulations are identical to steps (1) to (3) of the method for determining the drop size distribution within a spray and/or the homogeneity of said spray. With regard to these steps, therefore, reference is made to the observations above.
The method of the invention for screening coating material compositions in the development of paint formulations comprises at least the steps (1) to (3), (4B), (5B), and (6B), and also optionally (7B), namely
steps (1), (2), and (3) as defined within the method of the invention for determining the drop size distribution within a spray and/or the homogeneity of said spray are, for a coating material composition (X1), therefore
The method of the invention for screening coating material compositions when developing paint formulations therefore allows an adaptation in the sense of a reduction of characteristic variables, arising during the atomization, of the drop size distribution within the spray and/or of the homogeneity of the spray of coating material compositions such as the coating material composition (X1), on the basis of and/or in comparison to known corresponding characteristic variables or homogeneities of comparative coating material compositions such as the coating material composition (X2).
The term “substantially identical pigment” is understood in the sense of the present invention in connection with effect pigments to mean that the effect pigment or pigments present in the coating material composition (X1) and that or those present in the coating material composition (X2), as a first condition (i), have an identical chemical composition to an extent of at least 80% by weight, preferably at least 85% by weight, more preferably at least 90% by weight, very preferably at least 95% by weight, more particularly at least 97.5% by weight, based in each case on their total weight, but preferably in each case to an extent of less than 100% by weight. Effect pigments present in (X1) and (X2) are substantially identical, for example, if they are in both cases aluminum effect pigments but have a different coating—for example, in one case a chromation and in the other case a silicate coat, or in one case being coated and in the other case not. A further, additional condition (ii) for “substantially identical pigments” in the sense of the present invention in connection with effect pigments is that the effect pigments differ from one another in their average particle size by at most ±20%, preferably at most ±15%, more preferably at most ±10%. The average particle size is the arithmetic numerical mean of the measured average particle diameter (dN,50%) as determined by laser diffraction in accordance with ISO 13320 (date: 2009). The concept of the effect pigment per se is elucidated further and in more detail hereinafter.
The term “substantially identical pigment” in the sense of the present invention in connection with color pigments is understood to mean that the color pigment or pigments present in the coating material composition (X1) and that or those present in the coating material composition (X2), as a first condition (i), differ from one another in their chromaticity by at most ±20%, preferably at most ±15%, more preferably at most ±10%, more particularly at most ±5%. The chromaticity here denotes the
C
ab*=[(a*)2+(b*)2]1/2 a,b-chromaticity CIE 1976 (CIELAB chromaticity):
and is determined according to DIN EN ISO 11664-4 (date: June 2012). A further, additional condition (ii) for “substantially identical pigments” in the sense of the present invention in connection with color pigments is that the color pigments differ from one another in their average particle size by at most ±20%, preferably at most ±15%, more preferably at most ±10%. The average particle size is the arithmetic numerical mean of the measured average particle diameter (dN,50%) as determined by laser diffraction in accordance with ISO 13320 (date: 2009). The concept of the color pigment per se is elucidated further and in more detail hereinafter.
The method of the invention, in the event that according to step (6B) a selection is made of the coating material composition (X1) for application to a substrate, preferably includes at least the additional steps (6C), (6D), and (6E), namely
If the verification on the basis of the comparison as per step (4B) in step (5B) reveals that there are no recorded data in the database concerning a coating material composition (X2) having a pigment content identical to or differing by not more than ±10% by weight from that of the coating material composition (X1), based on the amount of pigment present in the coating material composition (X1), and which does not contain the identical pigment or pigments or the substantially identical pigment or pigments to the coating material composition (X1), then preferably step (6B) is implemented nonetheless. On further implementation of aforesaid steps (6C), (6D), and (6E), it is advantageously possible in this way for the database obtainable by means of the method of the invention for compiling and/or updating an electronic database to be further updated.
The method of the invention for screening coating material compositions when developing paint formulations, within step (4B) and/or (5B), preferably accesses a database compiled and/or updated by means of the aforesaid method of the invention for compiling and/or updating an electronic database, that has been compiled and/or updated by implementation not only of steps (1) to (3), (4A), and (5A) but also at least the further steps (3A), (3B), and (3C), with step (5A) having included the repetition of these steps (3A), (3B), and (3C). In other words, the comparison as per step (4B) and/or the verification as per step (5B) is carried out preferably on the basis of an electronic database containing not only the ascertained characteristic variable of the drop size distribution within the spray and/or the homogeneity determined for the spray of the coating material compositions used in the method of the invention for compiling and/or updating the database, but also, moreover, the results of the investigations and assessments relating to the incidence or nonincidence of surface defects and/or optical defects of coatings produced from these coating material compositions in accordance with step (3A).
If the verification in step (5B) based on the comparison as per step (4B), based on such a database preferably compiled and/or updated, reveals that the database includes stored data relating to a coating material composition (X2) having a pigment content identical with that of the coating material composition (X1) or differing by not more than ±10% by weight from that of the coating material composition (X1), based on the amount of pigment present in the coating material composition (X1), and which contains the identical pigment or pigments or the substantially identical pigment or pigments to the coating material composition (X1), and whose atomization has led to an ascertained characteristic variable of the drop size distribution within the spray and/or defined homogeneity of the spray that is already lower than the ascertained characteristic variable of the drop size distribution within the spray and/or the determined homogeneity of the spray of the coating material composition (X1), then in accordance with step (6B), as implemented above, there is an adaptation of at least one parameter.
The adaptation of at least one parameter within the formula of the coating material composition (X1) as per step (6B) preferably comprises at least one adaptation selected from the group of adaptations of the following parameters:
By means of parameter (v) it is possible in particular to raise or lower the spray viscosity of the coating material composition (X1). Parameters (vii) and/or (viii) comprise in particular the replacement and/or the addition of thickeners as additives, and, respectively, the changing of their amount in (X1). Such thickeners are described in more detail below in the context of component (d). Parameters (i) and/or (ii) comprise in particular the replacement and/or the addition of binders, or the changing of their amount in (X1). The concept of the binder is elucidated in more detail hereinafter. It also embraces crosslinkers (crosslinking agents). Accordingly, the parameters (i) and/or (ii) also comprise a change in the relative weight ratio of crosslinker and of that binder constituent which enters into a crosslinking reaction with the crosslinker. Parameters (i) to (iv) comprise in particular the replacement and/or the addition of binders and/or pigments, or the changing of their amount in (X1). Accordingly, these parameters (i) to (iv) implicitly also embrace a change in the pigment/binder ratio within (X1).
All preferred embodiments described hereinabove in connection with the method of the invention for determining the drop size distribution within a spray and/or the homogeneity of said spray and the method of the invention for compiling and/or updating an electronic database are also preferred embodiments in relation to the method for screening coating material compositions when developing paint formulations.
Employed preferably in step (1) of the method of the invention is a basecoat material, more preferably an aqueous basecoat material, as coating material composition, more particularly an aqueous basecoat material which comprises at least one pigment such as an effect pigment. The method of the invention for screening coating material compositions when developing paint formulations accordingly relates in particular to the screening of aqueous basecoat materials which comprise at least one pigment such as an effect pigment, and is therefore carried out with consideration of the influence of the type of the at least one pigment contained therein, such as an effect pigment, the amount thereof, based on the total weight of the basecoat material, and/or the pigment/binder ratio in the basecoat material.
By means of the method of the invention it is possible in particular, on the basis of the ascertained determination of at least one characteristic variable of the drop size distribution within the spray such as the D10 and/or of the homogeneity of said spray, to achieve an investigation of and more particularly an improvement in certain desired properties of coatings to be produced by means of the atomization, particularly with regard to the prevention or at least a reduction in the tendency for formation and/or incidence of optical defects and/or surface defects. This includes in particular a reduction in pinholes or an increase in pinhole robustness, an improvement in leveling, and reduction/prevention of cloudiness and of streakiness.
The method of the invention comprises at least the steps (1) to (3), (4B), (5B), and (6B), and also optionally (7B), but may optionally include further steps as well. Steps (1) to (3), (4B), (5B), and (6B) are preferably carried out in numerical order. Preferably, however, the method contains no step which envisions curing and/or baking of the coating material composition (X1) employed.
The embodiments below pertain not only to the method of the invention for determining the drop size distribution and/or homogeneity of the spray but also to the method of the invention for compiling an electronic database and to the method of the invention for screening coating material compositions when developing paint formulations. The embodiments that are described below pertain in particular to the aforesaid coating material compositions (X1), (X2), (i), and (ii) that are used.
The coating material composition used in accordance with the invention preferably comprises
The term “comprising” or “embracing” in the sense of the present invention, especially in connection with the coating material composition used in accordance with the invention, preferably has the meaning of “consisting of”. With regard to the coating material composition used in accordance with the invention, for example, it may comprise not only components (a), (b), and (c) but also one or more of the other, optional components identified hereinafter. All these components may each be present in their preferred embodiments as stated below.
The coating material composition used in accordance with the invention is preferably a coating material composition which is employable in the automobile industry. Here it is possible to use coating material compositions which can be employed as part of an OEM paint system, and those which can be employed as part of a refinish system. Examples of coating material compositions employable in the automobile industry are electrocoat materials, primers, surfacers, basecoat materials, especially waterborne basecoat materials (aqueous basecoat materials), topcoat materials, including clearcoat materials, especially solventborne clearcoat materials. The use of waterborne basecoat materials is particularly preferred.
The concept of the basecoat material is known to the skilled person and defined for example in Römpp Lexikon, Lacke and Druckfarben, Georg Thieme Verlag, 1998, 10th edition, page 57. A basecoat material, accordingly, is more particularly an interim coating material which imparts color and/or imparts color and an optical effect, used in automotive finishing and general industry coating. It is applied in general to a surfacer- or primer-pretreated metal or plastics substrate, or occasionally directly to the plastics substrate. Other possible substrates include existing finishes, possibly further requiring pretreatment (by sanding, for example). It is now entirely customary for more than one basecoat to be applied. In such a case, accordingly, a first basecoat represents the substrate for a second basecoat. To protect a basecoat, particularly from environmental effects, at least one additional clearcoat is applied over it. A waterborne basecoat material is an aqueous basecoat material in which the fraction of water is >the fraction of organic solvents, based on the total weight of water and organic solvents in % by weight within the waterborne basecoat material.
The fractions in % by weight of all components present in the coating material composition used in accordance with the invention, such as components (a), (b), and (c), and optionally one or more of the further, optional components identified hereinafter, add up to 100% by weight, based on the total weight of the coating material composition.
The solids content of the coating material composition used in accordance with the invention is preferably in a range from 10 to 45% by weight, more preferably from 11 to 42.5% by weight, very preferably from 12 to 40% by weight, more particularly from 13 to 37.5% by weight, based in each case on the total weight of the coating material composition. The solids content, i.e., the nonvolatile fraction, is determined as per the method described hereinafter.
The term “binder” refers in the sense of the present invention and in agreement with DIN EN ISO 4618 (German version, date: March 2007) preferably to the nonvolatile fractions—those responsible for forming the film—of a composition such as the coating material composition employed in accordance with the invention, with the exception of the pigments and/or fillers it contains. The nonvolatile fraction may be determined according to the method described hereinafter. A binder constituent, accordingly, is any component which contributes to the binder content of a composition such as the coating material composition used in accordance with the invention. An example would be a basecoat material, such as an aqueous basecoat material, which comprises at least one polymer employable as binder as component (a), such as, for example, a below-described SCS polymer; a crosslinking agent such as a melamine resin; and/or a polymeric additive.
Particularly preferred for the use as component (a) is what is called a seed-core-shell polymer (SCS polymer). Such polymers, and aqueous dispersions comprising such polymers, are known from WO 2016/116299 A1, for example. The polymer is preferably a (meth)acrylic copolymer. The polymer is used preferably in the form of an aqueous dispersion. Especially preferred for use as component (a) is a polymer having an average particle size in the range from 100 to 500 nm, preparable by successive radial emulsion polymerization of three monomer mixtures (A), (B), and (C), preferably different from one another, of olefinically unsaturated monomers in water, where
the mixture (A) comprises at least 50% by weight of monomers having a solubility in water of less than 0.5 g/l at 25° C., and a polymer prepared from the mixture (A) possesses a glass transition temperature of 10 to 65° C.,
the mixture (B) comprises at least one polyunsaturated monomer, and a polymer prepared from the mixture (B) possesses a glass transition temperature of −35 to 15° C., and
a polymer prepared from the mixture (C) possesses a glass transition temperature of −50 to 15° C.,
and wherein
i. first the mixture (A) is polymerized,
ii. then the mixture (B) is polymerized in the presence of the polymer prepared under i., and
iii. thereafter the mixture (C) is polymerized in the presence of the polymer prepared under ii.
The preparation of the polymer comprises the successive radial emulsion polymerization of three mixtures (A), (B), and (C) of olefinically unsaturated monomers in each case in water. It is therefore a multistage radical emulsion polymerization where i. first the mixture (A) is polymerized, then ii. the mixture (B) is polymerized in the presence of the polymer prepared under i. and, furthermore, iii. the mixture (C) is polymerized in the presence of the polymer prepared under ii. All three monomer mixtures are therefore polymerized by a radical emulsion polymerization (i.e. stage or else polymerization stage), carried out separately in each case, with these stages taking place successively. In terms of time, the stages may take place immediately after one another. It is equally possible, after the end of one stage, for the reaction solution in question to be stored for a certain period and/or transferred to a different reaction vessel, and only then for the next stage to be carried out. The preparation of the polymer preferably comprises no polymerization steps other than the polymerization of the monomer mixtures (A), (B), and (C).
The mixtures (A), (B), and (C) are mixtures of olefinically unsaturated monomers. Suitable olefinically unsaturated monomers may be mono- or polyolefinically unsaturated. Examples of suitable monoolefinically unsaturated monomers include, in particular, (meth)acrylate-based monoolefinically unsaturated monomers, monoolefinically unsaturated monomers containing allyl groups, and other monoolefinically unsaturated monomers containing vinyl groups, such as vinylaromatic monomers, for example. The term (meth)acrylic or (meth)acrylate for the purposes of the present invention encompasses both methacrylates and acrylates. Preferred for use at any rate, though not necessarily exclusively, are (meth)acrylate-based monoolefinically unsaturated monomers.
The mixture (A) comprises at least 50% by weight, and preferably at least 55% by weight, of olefinically unsaturated monomers having a water solubility of less than 0.5 g/l at 25° C. One such preferred monomer is styrene. The solubility of the monomers in water is determined by means of the method described hereinafter. The monomer mixture (A) preferably contains no hydroxy-functional monomers. Likewise preferably, the monomer mixture (A) contains no acid-functional monomers. Very preferably the monomer mixture (A) contains no monomers at all that have functional groups containing heteroatoms. This means that heteroatoms, if present, are present only in the form of bridging groups. This is the case, for example, in the (meth)acrylate-based monoolefinically unsaturated monomers described above that possess an alkyl radical as radical R. The monomer mixture (A) preferably comprises exclusively monoolefinically unsaturated monomers. The monomer mixture (A) preferably comprises at least one monounsaturated ester of (meth)acrylic acid with an alkyl radical, and at least one monoolefinically unsaturated monomer containing vinyl groups and having, disposed on the vinyl group, a radical which is aromatic or that is mixed saturated aliphatic-aromatic, in which case the aliphatic fractions of the radical are alkyl groups. The monomers present in the mixture (A) are selected such that a polymer prepared from them possesses a glass transition temperature of 10 to 65° C., preferably of 30 to 50° C. The glass transition temperature here can be determined by means of the method described hereinafter. The polymer prepared in stage i. by the emulsion polymerization of the monomer mixture (A) is also called seed. The seed possesses preferably an average particle size of 20 to 125 nm (measured by dynamic light scattering as described hereinafter; cf. determination methods).
The mixture (B) comprises at least one polyolefinically unsaturated monomer, preferably at least one diolefinically unsaturated monomer. A corresponding preferred monomer is hexanediol diacrylate. The monomer mixture (B) preferably contains no hydroxy-functional monomers. Likewise preferably, the monomer mixture (B) contains no acid-functional monomers. Very preferably, the monomer mixture (B) contains no monomers at all that have functional groups containing heteroatoms. This means that heteroatoms, if present, are present only in the form of bridging groups. This is the case, for example, in the above-described (meth)acrylate-based, monoolefinically unsaturated monomers possessing an alkyl radical as radical R. Besides the at least one polyolefinically unsaturated monomer, the monomer mixture (B) preferably at any rate includes the following monomers: firstly, at least one monounsaturated ester of (meth)acrylic acid with an alkyl radical, and secondly at least one monoolefinically unsaturated monomer containing vinyl groups and having, arranged on the vinyl group, a radical which is aromatic or which is mixed saturated aliphatic-aromatic, in which case the aliphatic fractions 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 in the monomer mixture (B). The monomers present in the mixture (B) are selected such that a polymer prepared therefrom possesses a glass transition temperature of −35 to 15° C., preferably from −25 to +7° C. The glass transition temperature here may be determined by the method described hereinafter. The polymer prepared in the presence of the seed in stage ii. by the emulsion polymerization of the monomer mixture (B) is also referred to as the core. After stage ii., therefore, the resultant polymer comprises seed and core. The polymer which is obtained after stage ii. preferably possesses an average particle size of 80 to 280 nm, preferably 120 to 250 nm (measured by dynamic light scattering as described hereinafter; cf. determination methods).
The monomers present in the mixture (C) are selected such that a polymer prepared therefrom possesses a glass transition temperature of −50 to 15° C., preferably of −20 to +12° C. This glass transition temperature may be determined by the method described hereinafter. The olefinically unsaturated monomers of the mixture (C) are preferably selected such that the resultant polymer, comprising seed, core, and shell, has an acid number of 10 to 25. Accordingly, the mixture (C) preferably comprises at least one alpha-beta unsaturated carboxylic acid, especially preferably (meth)acrylic acid. The olefinically unsaturated monomers in the mixture (C) are preferably selected, additionally or alternatively, in such a way that the resulting polymer, comprising seed, core, and shell, has an OH number of 0 to 30, preferably 10 to 25. All of the aforementioned acid numbers and OH numbers are values calculated on the basis of the entirety of monomer mixtures employed. The monomer mixture (C) preferably comprises 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. With particular preference the monomer mixture (C) comprises at least one alpha-beta unsaturated carboxylic acid, at least one monounsaturated ester of (meth)acrylic acid having an alkyl radical substituted by a hydroxyl group, and at least one monounsaturated ester of (meth)acrylic acid with an alkyl radical. Where the present invention refers to an alkyl radical without further particularization, the reference is always to a pure alkyl radical without functional groups and heteroatoms. The polymer prepared in stage iii. by the emulsion polymerization of the monomer mixture (C) in the presence of seed and core is also referred to as the shell. The result after stage iii., therefore, is a polymer which comprises seed, core, and shell, in other words polymer (b). After its preparation, the polymer (b) possesses an average particle size of 100 to 500 nm, preferably 125 to 400 nm, very preferably of 130 to 300 nm (measured by dynamic light scattering as described hereinafter; cf. determination methods).
The coating composition used in accordance with the invention preferably comprises a fraction of component (a) such as at least one SCS polymer in a range from 1.0 to 20% by weight, more preferably from 1.5 to 19% by weight, very preferably from 2.0 to 18.0% by weight, more particularly from 2.5 to 17.5% by weight, most preferably from 3.0 to 15.0% by weight, based in each case on the total weight of the coating material composition. The determination and specification of the fraction of component (a) within the coating material composition may be made via the determination of the solids content (also called nonvolatile fraction, solids, or solids fraction) of an aqueous dispersion comprising component (a).
Additionally or alternatively, preferably additionally, to the at least one above-described SCS polymer as component (a), the coating material composition used in accordance with the invention may comprise at least one polymer different from the SCS polymer, as binder of component (a), more particularly at least one polymer selected from the group consisting of polyurethanes, polyureas, polyesters, poly(meth)acrylates and/or copolymers of the stated polymers, more particularly polyurethane-poly(meth)acrylates and/or polyurethane-polyureas.
Preferred polyurethanes are described for example in German patent application DE 199 48 004 A1, page 4, line 19 to page 11, line 29 (polyurethane prepolymer B1), in European patent application EP 0 228 003 A1, page 3, line 24 to page 5, line 40, in European patent application EP 0 634 431 A1, page 3, line 38 to page 8, line 9, and in international patent application WO 92/15405, page 2, line 35 to page 10, line 32.
Preferred polyesters are described 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 also page 28, line 13 to page 29, line 13.
Preferred polyurethane-poly(meth)acrylate copolymers ((meth)acrylated polyurethanes) and their preparation are described for example in WO 91/15528 A1, page 3, line 21 to page 20, line 33 and also in DE 4437535 A1, page 2, line 27 to page 6, line 22.
Preferred polyurethane-polyurea copolymers are polyurethane-polyurea particles, preferably those having an average particle size of 40 to 2000 nm, where the polyurethane-polyurea particles, in each case in reacted form, comprise at least one polyurethane prepolymer containing isocyanate groups and comprising anionic groups and/or groups which can be converted into anionic groups, and also at least one polyamine containing two primary amino groups and one or two secondary amino groups. Such copolymers are used preferably in the form of an aqueous dispersion. Polymers of these kinds are preparable in principle by conventional polyaddition of, for example, polyisocyanates with polyols and also polyamines. The average particle size of such polyurethane-polyurea particles is determined as described below (measured by means of dynamic light scattering as described hereinafter; cf. determination methods).
The fraction in the coating material composition of such polymers different from the SCS polymer is preferably smaller than the fraction of the SCS polymer. The polymers described are preferably hydroxy-functional and especially preferably possess an OH number in the range from 15 to 200 mg KOH/g, more preferably of 20 to 150 mg KOH/g.
With particular preference the coating material compositions used in accordance with the invention comprise at least one hydroxy-functional polyurethane-poly(meth)acrylate copolymer; with further preference they comprise at least one hydroxy-functional polyurethane poly(meth)acrylate copolymer and also at least one hydroxy-functional polyester and also, optionally, a preferably hydroxy-functional polyurethane-polyurea copolymer.
The fraction of the further polymers as binders of component (a)—additionally to an SCS polymer—may vary widely and is preferably in the range from 1.0 to 25.0% by weight, more preferably 3.0 to 20.0% by weight, very preferably 5.0 to 15.0% by weight, based in each case on the total weight of the coating material composition.
The coating material composition may further comprise at least one conventional, typical crosslinking agent. If it comprises a crosslinking agent, the species in question is preferably at least one amino resin and/or at least one blocked or free polyisocyanate, preferably an amino resin. Among the amino resins, melamine resins in particular are preferred. Where the coating material composition includes crosslinking agents, the fraction of these crosslinking agents, more particularly amino resins and/or blocked or free polyisocyanates, more preferably amino resins, in turn preferably melamine resins, is preferably in the range from 0.5 to 20.0% by weight, more preferably 1.0 to 15.0% by weight, very preferably 1.5 to 10.0% by weight, based in each case on the total weight of the coating material composition. The fraction of crosslinking agent is preferably smaller than the fraction of the SCS polymer in the coating material composition.
The skilled person is familiar with the terms “pigments” and “fillers”.
The term “filler” is known to the skilled person from DIN 55943 (date: October 2001), for example. A “filler” in the sense of the present invention is preferably a component which is substantially, preferably completely, insoluble in the coating material composition used in accordance with the invention, such as a waterborne basecoat material, for example, and which is used in particular for the purpose of increasing the volume. “Fillers” in the sense of the present invention are preferably different from “pigments” in their refractive index, which for fillers is <1.7. Any customary filler known to the skilled person may be used as component (b). Examples of suitable fillers are kaolin, dolomite, calcite, chalk, calcium sulfate, barium sulfate, graphite, silicates such as magnesium silicates, especially corresponding phyllosilicates such as hectorite, bentonite, montmorillonite, talc and/or mica, silicas, especially fumed silicas, hydroxides such as aluminum hydroxide or magnesium hydroxide, or organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or polymer powders.
The term “pigment” is likewise known to the skilled person, from DIN 55943 (date: October 2001), for example. A “pigment” in the sense of the present invention refers preferably to components in powder or platelet form which are substantially, preferably entirely, insoluble in the coating material composition used in accordance with the invention, such as a waterborne basecoat material, for example. These “pigments” are preferably colorants and/or substances which are used as pigment by virtue of their magnetic, electrical and/or electromagnetic properties. Pigments differ from “fillers” preferably in their refractive index, which for pigments is 1.7.
The term “pigments” preferably subsumes color pigments and effect pigments.
A skilled person is familiar with the concept of color pigments. For the purposes of the present invention, the terms “color-imparting pigment” and “color pigment” are interchangeable. A corresponding definition of the pigments and further specifications thereof are dealt with in DIN 55943 (date: October 2001). Color pigment used may comprise organic and/or inorganic pigments. Particularly preferred color pigments used are white pigments, chromatic pigments and/or black pigments. Examples of white pigments are titanium dioxide, zinc white, zinc sulfide, and lithopones. Examples of black pigments are carbon black, iron manganese black, and spinel black. Examples of chromatic pigments are chromium oxide, chromium oxide hydrate green, cobalt green, ultramarine green, cobalt blue, ultramarine blue, manganese blue, ultramarine violet, cobalt and manganese violet, red iron oxide, cadmium sulfoselenide, molybdate red and ultramarine red, brown iron oxide, mixed brown, spinel phases and corundum phases, and chromium orange, yellow iron oxide, nickel titanium yellow, chromium titanium yellow, cadmium sulfide, cadmium zinc sulfide, chromium yellow, and bismuth vanadate.
A skilled person is familiar with the concept of effect pigments. A corresponding definition is found for example in Römpp Lexikon, Lacke and Druckfarben, Georg Thieme Verlag, 1998, 10th edition, pages 176 and 471. A definition of pigments in general and further particularizations thereof are dealt with in DIN 55943 (date: October 2001). Effect pigments are preferably pigments which impart optical effect or color and optical effect, especially optical effect. The terms “optical effect-imparting and color-imparting pigment”, “optical effect pigment” and “effect pigment” are therefore preferably interchangeable. Preferred effect pigments are, for example, platelet-shaped metallic effect pigments such as leaflet-like aluminum pigments, gold bronzes, oxidized bronzes and/or iron oxide-aluminum pigments, pearlescent pigments such as pearl essence, basic lead carbonate, bismuth oxychloride and/or metal oxide-mica pigments and/or other effect pigments such as leaflet-like graphite, leaflet-like iron oxide, multilayer effect pigments from PVD films and/or liquid crystal polymer pigments. Particularly preferred are effect pigments in leaflet form, especially leaflet-like aluminum pigments and metal oxide-mica pigments.
The coating material composition used in accordance with the invention, such as a waterborne basecoat material, for example, with particular preference includes at least one effect pigment as component (b).
The coating material composition used in accordance with the invention preferably comprises a fraction of effect pigment as component (b) in a range from 1 to 20% by weight, more preferably 1.5 to 18% by weight, very preferably from 2 to 16% by weight, more particularly from 2.5 to 15% by weight, most preferably from 3 to 12% by weight or from 3 to 10% by weight, based in each case on the total weight of the coating material composition. The total fraction of all pigments and/or fillers in the coating material composition is preferably in the range from 0.5 to 40.0% by weight, more preferably from 2.0 to 20.0% by weight, very preferably from 3.0 to 15.0% by weight, based in each case on the total weight of the coating material composition.
The relative weight ratio of component (b) such as at least one effect pigment to component (a) such as at least one SCS polymer in the coating material composition is preferably within a range from 4:1 to 1:4, more preferably in a range from 2:1 to 1:4, very preferably in a range from 2:1 to 1:3, more particularly in a range from 1:1 to 1:3 or from 1:1 to 1:2.5.
The coating material composition used in accordance with the invention is preferably aqueous. It is preferably a system comprising as its solvent (i.e., as component (c)) primarily water, preferably in an amount of at least 20% by weight, and organic solvents in smaller fractions, preferably in an amount of <20% by weight, based in each case on the total weight of the coating material composition.
The coating material composition used in accordance with the invention preferably comprises a fraction of water of at least 20% by weight, more preferably of at least 25% by weight, very preferably of at least 30% by weight, more particularly of at least 35% by weight, based in each case on the total weight of the coating material composition.
The coating material composition used in accordance with the invention preferably comprises a fraction of water that is within a range from 20 to 65% by weight, more preferably in a range from 25 to 60% by weight, very preferably in a range from 30 to 55% by weight, based in each case on the total weight of the coating material composition.
The coating material composition used in accordance with the invention preferably comprises a fraction of organic solvents that is within a range of <20% by weight, more preferably in a range from 0 to <20% by weight, very preferably in a range from 0.5 to <20% by weight or to 15% by weight, based in each case on the total weight of the coating material composition.
Examples of such organic solvents include heterocyclic, aliphatic or aromatic hydrocarbons, mono- or polyhydric alcohols, especially methanol and/or ethanol, ethers, esters, ketones, and amides, such as N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, toluene, xylene, butanol, ethyl glycol and butyl glycol and also their acetates, butyl diglycol, diethylene glycol dimethyl ether, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, acetone, isophorone, or mixtures thereof.
The coating material composition used in accordance with the invention may optionally further comprise at least one thickener (also referred to as thickening agent) as component (d). Examples of such thickeners are inorganic thickeners, as for example metal silicates such as phyllosilicates, and organic thickeners, as for example poly(meth)acrylic acid thickeners and/or (meth)acrylic acid-(meth)acrylate copolymer thickeners, polyurethane thickeners, and also polymeric waxes. The metal silicate is selected preferably from the group of the smectites. The smectites are selected with particular preference from the group of the montmorillonites and hectorites. The montmorillonites and hectorites are selected more particularly from the group consisting of aluminum magnesium silicates and also sodium magnesium phyllosilicates and sodium magnesium fluorine lithium phyllosilicates. These inorganic phyllosilicates are sold under the brand name Laponite®, for example. Thickeners based on poly(meth)acrylic acid and (meth)acrylic acid-(meth)acrylate copolymer thickeners are optionally crosslinked and/or neutralized with a suitable base. Examples of such thickening agents are “alkali swellable emulsions” (ASEs) and hydrophobically modified variants of them, the “hydrophobically modified alkali swellable emulsions” (HASE). These thickeners are preferably anionic. Corresponding products such as Rheovis® AS 1130 are available commercially. Thickeners based on polyurethanes (e.g., polyurethane associative thickeners) are optionally crosslinked and/or neutralized with a suitable base. Corresponding products such as Rheovis® PU1250 are available commercially. Examples of suitable polymeric wax include optionally modified polymeric waxes based on ethylene-vinyl acetate copolymers. A corresponding product is available commercially under the designation Aquatix® 8421, for example.
Depending on desired application, the coating material composition used in accordance with the invention may comprise one or more commonly employed additives as further component or components (d). By way of example, the coating material composition may comprise at least one additive selected from the group consisting of reactive diluents, light stabilizers, antioxidants, deaerating agents, emulsifiers, slip additives, polymerization inhibitors, initiators for radical polymerizations, adhesion promoters, flow control agents, film-forming assistants, sag control agents (SCAs), flame retardants, corrosion inhibitors, siccatives, biocides, and flatting agents. They may be used in the known and customary proportions.
The coating material composition used in accordance with the invention may be produced using the customary and known mixing methods and mixing units.
The nonvolatile fraction (the solids content) is determined according to DIN EN ISO 3251 (date: June 2008). 1 g of sample is weighed out into an aluminum dish which has been dried beforehand and the dish with sample is dried in a drying cabinet at 125° C. for 60 minutes, cooled in a desiccator, and then reweighed. The residue relative to the total amount of sample used corresponds to the nonvolatile fraction. The volume of the nonvolatile fraction may be determined if necessary, in accordance with DIN 53219 (date: August 2009) optionally.
The number-average molecular weight (Mn) is determined, unless otherwise specified, using a model 10.00 vapor pressure osmometer (from Knauer) on concentration series in toluene at 50° C. with benzophenone as a calibration substance for determining the experimental calibration constant of the instrument used, in accordance with E. Schröder, G. Müller, K.-F. Arndt, “Leitfaden der Polymercharakterisierung” [Principles of polymer characterization], Akademie-Verlag, Berlin, pp. 47-54, 1982.
The OH number and the acid number are each determined by calculation.
The average particle size is determined by dynamic light scattering (photon correlation spectroscopy) (PCS) in a method based on DIN ISO 13321 (date: October 2004). Measurement takes place using a Malvern Nano S90 (from Malvern Instruments) at 25±1° C. The instrument covers a size range from 3 to 3000 nm and is equipped with a 4 mW He—Ne laser at 633 nm. The respective samples are diluted with particle-free deionized water as dispersing medium and then measured in a 1 ml polystyrene cuvette at suitable scattering intensity. Evaluation took place using a digital correlator with assistance from the Zetasizer software 7.11 (from Malvern Instruments). Measurement is carried out five times and the measurements are repeated on a second, freshly prepared sample. For the SCS polymer, the average particle size refers to the arithmetic numerical mean of the measured average particle diameter (Z-average mean; numerical average; dN,50%). The standard deviation of a 5-fold determination in this case is 4%. For the polyurethane-polyurea particles that can be employed, the average particle size refers to the arithmetic volume mean of the average particle size of the individual preparations (V-average mean; volume average; dV,50%). The maximum deviation of the volume average from five individual measurements is ±15%. Verification takes place with polystyrene standards each having certified particle sizes between 50 to 3000 nm.
The film thicknesses are determined in accordance with DIN EN ISO 2808 (date: May 2007), method 12A, using the MiniTest® 3100-4100 instrument from ElektroPhysik.
To assess the incidence of pinholes and the film thickness-dependent leveling, wedge-format multicoat paint systems are produced in accordance with the following general protocol:
a steel panel with dimensions of 30×50 cm, coated with a standard electrocoat (CathoGuard® 800 from BASF Coatings GmbH), is provided at one longitudinal edge with an adhesive strip (Tesaband, 19 mm) to allow determination of film thickness differences after coating. A waterborne basecoat material is applied electrostatically as a wedge with a target film thickness (film thickness of the dried material) of 0-40 μm. The discharge rate here is between 300 and 400 ml/min; the rotary speed of the ESTA bell is varied between 23 000 and 43 000 rpm; the exact figures for each of the application parameters specifically selected are stated below within the experimental section. After a flash-off time of 4-5 minutes at room temperature (18 to 23° C.), the system is dried in a forced air oven at 60° C. for 10 minutes. Following removal of the adhesive strip, a commercial two-component clearcoat material (ProGloss® from BASF Coatings GmbH) is applied by gravity-fed spray gun, manually, to the dried waterborne basecoat film, with a target film thickness (film thickness of the dried material) of 40-45 μm. The resulting clearcoat film is flashed off at room temperature (18 to 23° C.) for 10 minutes; this is followed by curing in a forced air oven at 140° C. fora further 20 minutes.
Incidence of pinholes is assessed visually according to the following general protocol: the dry film thickness of the waterborne basecoat is checked, and for the basecoat film thickness wedge, the ranges of 0-20 μm and also of 20 μm to the end of the wedge are marked on the steel panel. The pinholes are evaluated visually in the two separate regions of the waterborne basecoat wedge. The number of pinholes per region is counted. All results are standardized to an area of 200 cm2 and then summed to give a total number. Additionally, where appropriate, a record is made of the dry film thickness of the waterborne basecoat wedge from which pinholes no longer occur.
The film thickness-dependent leveling is assessed according to the following general protocol: the dry film thickness of the waterborne basecoat is checked, and for the basecoat film thickness wedge, different regions, for example 10-15 μm, 15-20 μm, and 20-25 μm, are marked on the steel panel. The film thickness-dependent leveling is determined and assessed using the wave scan instrument from Byk-Gardner GmbH, within the basecoat film thickness regions ascertained beforehand. For this purpose, a laser beam is directed at an angle of 60° onto the surface under investigation, and fluctuations in the reflected light in the short wave range (0.3 to 1.2 mm) and in the long wave range (1.2 to 12 mm) are recorded by the instrument over a distance of 10 cm (long wave=LW; short wave=SW; the lower the figures, the better the appearance). Furthermore, as a measure of the sharpness of an image reflected in the surface of the multicoat system, the characteristic parameter of “distinctness of image” (DOI) is determined with the aid of the instrument (the higher the value, the better the appearance).
For determining the cloudiness, multicoat paint systems are produced according to the following general protocol:
A steel panel with dimensions 32×60 cm, coated with a conventional surfacer system, is further coated with a waterborne basecoat material by means of dual application: application in the first step is made electrostatically with a target film thickness of 8-9 μm, and in the second step, after a 2-minute flash-off time at room temperature, it is made likewise electrostatically with a target film thickness of 4-5 μm. After a further flash-off time at room temperature (18 to 23° C.) of 5 minutes, the resulting waterborne basecoat film is dried in a forced air oven at 80° C. for 5 minutes. Both basecoat applications are made with a rotary speed of 43 000 rpm and a discharge rate of 300 ml/min. Applied atop the dried waterborne basecoat film is a commercial two-component clearcoat material (ProGloss from BASF Coatings GmbH), with a target film thickness of 40-45 μm. The resulting clearcoat film is flashed off at room temperature (18 to 23° C.) for 10 minutes; this is followed by curing in a forced air oven at 140° C. for a further 20 minutes.
The cloudiness is then assessed using the cloud-runner instrument from BYK-Gardner GmbH in accordance with alternative b). The instrument outputs parameters including the three characteristic parameters of “mottling15”, “mottling45”, and “mottling60”, which can be seen as a measure of the cloudiness measured at angles of 15°, 45°, and 60° relative to the reflection angle of the measurement light source used. The higher the value, the more pronounced the cloudiness.
The streakiness is assessed by means of the method described in patent specification DE 10 2009 050 075 B4. The homogeneity indices stated and defined therein, or the averaged homogeneity index, are equally able to capture the incidence of streaks in the application, despite those indices having been used in the stated patent specification for the purpose of assessing cloudiness. The higher the corresponding values, the more pronounced the streaks visible on the substrate.
9. Determining the Particle Size Distribution Including the D10 and Also the Ratio of the Characteristic Variables TT1/TTotal1 and TT2/TTotal2 as a Measurement of the Homogeneity of the Spray Arising from Atomization, by Means of the Method of the Invention
The parent particle size distributions are determined using a commercial single PDA from DantecDynamics (P60, Lexel argon laser, FibreFlow) and also a commercial time-shift instrument from AOM Systems (SpraySpy®). Both instruments are constructed and aligned in accordance with the manufacturer information. The settings for the time-shift instrument SpraySpy® are adapted by the manufacturer for the range of materials to be used. The PDA is operated in forward scattering at an angle of 60-70° with a wavelength of 514.5 nm (orthogonally polarized) in reflection. The receiving optics here have a focal length 500 mm, the transmitting optics a focal length of 400 mm. For both systems, the construction is aligned relative to the atomizer. The general construction is evident from
10. Determining the Solubility of the Monomers of the Mixture (A) in Water that can be Used for Preparing SCS Polymers
The solubility of the monomers in water is determined via establishment of equilibrium with the gas space above the aqueous phase (in analogy to the reference X.-S. Chai, Q. X. Hou, F. J. Schork, Journal of Applied Polymer Science vol. 99, 1296-1301 (2006)). For this purpose, in a 20 ml gas space sample tube, a defined volume of water, such as 2 ml, is admixed with the respective monomer in a mass so great that it is unable to dissolve, or at any rate to dissolve completely, in the volume of water selected. Additionally an emulsifier (10 ppm, based on total mass of the sample mixture) is added. To obtain the equilibrium concentration, the mixture is shaken continually. The supernatant gas phase is replaced by inert gas, thus re-establishing an equilibrium. In the gas phase removed, the fraction of the substance to be detected is measured (by means of gas chromatography, for example). The equilibrium concentration in water can be determined by plotting the fraction of the monomer in the gas phase as a graph. The slope of the curve changes from a virtually constant value (S1) to a significantly negative slope (S2) as soon as the excess monomer fraction has been removed from the mixture. The equilibrium concentration here is reached at the point of intersection of the straight line with the slope (S1) and of the straight line with the slope (S2). The determination described is carried out at 25° C.
11. Determination of Glass Transition Temperatures of Polymers Obtainable from Monomers of Mixtures (A), (B), and (C), Respectively
The glass transition temperature Tg is determined experimentally in a method based on DIN 51005 (date: August 2005) “Thermal Analysis (TA)—terms” and DIN 53765 “Thermal Analysis—Dynamic Scanning calorimetry (DSC)” (date: March 1994). This involves weighing out a 15 mg sample into a sample boat and introducing the boat into a DSC instrument. Cooling takes place to the starting temperature, after which 1st and 2nd measurement runs are carried out under inert gas purging (N2) of 50 ml/min at a heating rate of 10 K/min, with cooling backto the starting temperature between the measurement runs. Measurement takes place in the temperature range from approximately 50° C. lower than the expected glass transition temperature to approximately 50° C. higher than the expected glass transition temperature. The glass transition temperature recorded, in accordance with DIN 53765, section 8.1, is the temperature in the 2nd measurement run at which half of the change in specific heat capacity (0.5 delta cp) has been reached. It is determined from the DSC diagram (plot of heat flow against temperature). It is the temperature corresponding to the point of intersection of the midline between the extrapolated baselines before and after the glass transition with the measurement plot. For a useful estimation of the glass transition temperature to be expected in the measurement, the known Fox equation can be employed. Since the Fox equation represents a good approximation, based on the glass transition temperatures of the homopolymers and their parts by weight without including the molecular weight, it may be used as a useful tool for the skilled person at the synthesis stage, allowing a desired glass transition temperature to be set via a few goal-directed trials.
An assessment is made of the wetness of a film formed after application to a substrate of a coating material composition such as a waterborne basecoat material. The coating material composition in this case is applied electrostatically by means of rotary atomizing as a constant layer in the desired target film thickness (film thickness of the dried material) such as a target film thickness within a range from 15 μm to 40 μm. The discharge rate is between 300 and 400 ml/min and the rotary speed of the ESTA bell of the rotary atomizer is in a range from 23 000 to 63 000 rpm (the precise details of the application parameters specifically selected in each case are stated at the relevant points hereinafter within the experimental section). A visual assessment of the wetness of the film formed on the substrate is made one minute after the end of application. The wetness is recorded on a scale from 1 to 5 (1=very dry to 5=very wet).
To determine the propensity toward popping, a multicoat paint system is produced in a method based on DIN EN ISO 28199-1 (date: January 2010) and DIN EN ISO 28199-3 (date: January 2010) in accordance with the following general protocol: a perforated steel plate with dimensions of 57 cm×20 cm (according to DIN EN ISO 28199-1, section 8.1, version A), coated with a cured cathodic electrocoat (EC) (CathoGuard® 800 from BASF Coatings GmbH), is prepared in analogy to DIN EN ISO 28199-1, section 8.2 (version A). This is followed, in a method based on DIN EN ISO 28199-1, section 8.3, by electrostatic application of an aqueous basecoat material in a single application in the form of a wedge with a target film thickness (film thickness of the dried material; dry film thickness) in the range from 0 μm to 30 μm. The resulting basecoat film, without a flash-off time beforehand, is subjected to interim drying in a forced air oven at 80° C. for 5 minutes. The determination of the popping limit, i.e., of the basecoat film thickness from which pops occur, is made according to DIN EN ISO 28199-3, section 5.
To determine the propensity toward running, multicoat paint systems are produced in a method based on DIN EN ISO 28199-1 (date: January 2010) and DIN EN ISO 28199-3 (date: January 2010) in accordance with the following general protocol:
A perforated steel plate with dimensions of 57 cm×20 cm (according to DIN EN ISO 28199-1, section 8.1, version A), coated with a cured cathodic electrocoat (EC) (CathoGuard® 800 from BASF Coatings GmbH), is prepared in analogy to DIN EN ISO 28199-1, section 8.2 (version A). This is followed, in a method based on DIN EN ISO 28199-1, section 8.3, by electrostatic application of an aqueous basecoat material in a single application in the form of a wedge with a target film thickness (film thickness of the dried material) in the range from 0 μm to 40 μm. The resulting basecoat film, after a flash-off time at 18-23° C. of 10 minutes, is subjected to interim drying in a forced air oven at 80° C. for 5 minutes. The plates here are flashed off and subjected to interim drying while standing vertically.
A perforated steel plate with dimensions of 57 cm×20 cm (according to DIN EN ISO 28199-1, section 8.1, version A), coated with a cured cathodic electrocoat (EC) (CathoGuard® 800 from BASF Coatings GmbH) and also with a commercial aqueous basecoat material (ColorBrite from BASF Coatings GmbH), is prepared in analogy to DIN EN ISO 28199-1, section 8.2 (version A). This is followed, in a method based on DIN EN ISO 28199-1, section 8.3, by electrostatic application of a clearcoat material in a single application in the form of a wedge with a target film thickness (film thickness of the dried material) in the range from 0 μm to 60 μm. The resulting clearcoat film, after a flash-off time at 18-23° C. of 10 minutes, is subjected to curing in a forced air oven at 140° C. for 20 minutes. The plates here are flashed off and subjected to curing while standing vertically.
The propensity toward running is determined in each case in accordance with DIN EN ISO 28199-3, section 4. In addition to the film thickness at which a run exceeds the length of 10 mm from the bottom edge of the perforation, a determination is made of the film thickness from which a first propensity to run at a perforation can be observed visually.
The hiding power is determined in accordance with DIN EN ISO 28199-3 (January 2010; section 7).
The inventive and comparative examples below serve to illustrate the invention, but should not be interpreted as limiting.
Unless otherwise stated, the figures in parts are parts by weight, and figures in percent are percentages by weight in each case.
1.1 The meanings of the components identified below and used in preparing the aqueous dispersion AD1 are as follows:
DMEA dimethylethanolamine
DI water deionized water
EF 800 Aerosol EF-800, commercially available emulsifier from Cytec
APS ammonium peroxodisulfate
1,6-HDDA 1,6-hexanediol diacrylate
2-HEA 2-hydroxyethyl acrylate
MMA methyl methacrylate
1.2 Preparation of the aqueous dispersion AD1 comprising a multistage SCS polyacrylate
80 wt % of items 1 and 2 as per table 1.1 below are placed in a steel reactor (5 L volume) with reflux condenser and are heated to 80° C. The remaining fractions of the components listed under “Initial charge” in table 1.1 are premixed in a separate vessel. This mixture and, separately therefrom, the “Initiator solution” (table 1.1, items 5 and 6), are added dropwise to the reactor simultaneously over the course of 20 minutes, a fraction of the monomers in the reaction solution, based on the total amount of monomers used in stage i., not exceeding 6.0 wt % throughout the reaction time. 30 minutes of stirring follow.
The components indicated under “Mono 1” in table 1.1 are premixed in a separate vessel. This mixture is added dropwise to the reactor over the course of 2 hours, a fraction of the monomers in the reaction solution, based on the total amount of monomers used in stage ii., not exceeding 6.0 wt % throughout the reaction time. 1 hour of stirring follows.
The components indicated under “Mono 2” in table 1.1 are premixed in a separate vessel. This mixture is added dropwise to the reactor over the course of 1 hour, a fraction of the monomers in the reaction solution, based on the total amount of monomers used in stage iii., not exceeding 6.0 wt % throughout the reaction time. 2 hours of stirring follows.
Thereafter the reaction mixture is cooled to 60° C. and the neutralizing mixture (table 1.1, items 20, 21, and 22) is premixed in a separate vessel. The neutralizing mixture is added dropwise to the reactor over the course of 40 minutes, the pH of the reaction solution being adjusted to a pH of 7.5 to 8.5. The reaction product is subsequently stirred for 30 minutes more, cooled to 25° C., and filtered.
The solids content of the resulting aqueous dispersion AD1 was determined for reaction monitoring. The result, together with the pH and the particle size determined, is reported in table 1.2.
In a reaction vessel equipped with stirrer, internal thermometer, reflux condenser and electrical heating, 559.7 parts by weight of a linear polyester polyol and 27.2 parts by weight of dimethylol propionic acid (from GEO Speciality Chemicals) were dissolved under nitrogen in 344.5 parts by weight of methyl ethyl ketone. The linear polyester diol was prepared beforehand from dimerized fatty acid (Pripol 1012, Croda), isophthalic acid (from BP Chemicals) and hexane-1,6-diol (from BASF SE) (weight ratio of the starting materials: dimeric fatty acid to isophthalic acid to hexane-1,6-diol=54.00:30.02:15.98) and had a hydroxyl number of 73 mg KOH/g solids fraction, an acid number of 3.5 mg KOH/g solids fraction, a calculated number-average molecular weight of 1379 g/mol, and a number-average molecular weight as determined by vapor pressure osmometry of 1350 g/mol. Added to the resulting solution at 30° C. in succession were 213.2 parts by weight of dicyclohexylmethane 4,4′-diisocyanate (Desmodur W, Covestro AG), with an isocyanate content of 32.0 wt %, and 3.8 parts by weight of dibutyltin dilaurate (from Merck). This was followed by heating to 80° C. with stirring. Stirring continued at this temperature until the isocyanate content of the solution was constant at 1.49 wt %. Thereafter 626.2 parts by weight of methyl ethyl ketone were added to the prepolymer and the reaction mixture was cooled to 40° C. When 40° C. was reached, 11.8 parts by weight of triethylamine (from BASF SE) were added dropwise over the course of two minutes, and the batch was stirred for a further five minutes.
Reaction of the Prepolymer with Diethylenetriamine Diketimine
30.2 parts by weight of a 71.9 wt % dilution of diethylenetriamine diketimine in methyl isobutyl ketone (ratio of prepolymer isocyanate groups to diethylenetriamine diketimine (having one secondary amino group): 5:1 mol/mol, corresponding to two NCO groups per blocked primary amino group) were subsequently admixed over the course of a minute, with the reaction temperature rising briefly by 1° C. following addition to the prepolymer solution. The diluted preparation of diethylenetriamine diketimine in methyl isobutyl ketone was prepared beforehand by azeotropic removal of water of reaction during the reaction of diethylenetriamine (from BASF SE) with methyl isobutyl ketone in methyl isobutyl ketone at 110-140° C. Dilution with methyl isobutyl ketone was used to set an amine equivalent mass (solution) of 124.0 g/eq. IR spectroscopy, on the basis of the residual absorption at 3310 cm−1, found 98.5% blocking of the primary amino groups. The solids content of the polymer solution containing isocyanate groups was found to be 45.3%.
After 30 minutes of stirring at 40° C., the contents of the reactor were dispersed over 7 minutes into 1206 parts by weight of deionized water (23° C.). Methyl ethyl ketone was distilled off under reduced pressure from the resulting dispersion at 45° C., and any losses of solvent and of water were made up with deionized water, to give a solids content of 40 wt %. The resulting dispersion was white, stable, high in solids content and low in viscosity, contained crosslinked particles, and showed no sedimentation at all even after three months.
The characteristics of the resulting microgel dispersion (PD1) were as follows:
Solids content (130° C., 60 min, 1 g): 40.2 wt %
Methyl ethyl ketone content (GC): 0.2 wt %
Methyl isobutyl ketone content (GC): 0.1 wt %
Viscosity (23° C., rotational viscometer, shear rate=1000/s): 15 mPa·s
Acid number: 17.1 mg KOH/g solids content
Degree of neutralization (calculated): 49%
Particle size (photon correlation spectroscopy, volume average): 167 nm
Gel fraction (freeze-dried): 85.1 wt %
Gel fraction (130° C.): 87.3 wt %
The yellow paste P1 is produced from 17.3 parts by weight of Sicotrans yellow L 1916, available from BASF SE, 18.3 parts by weight of a polyester prepared as per example D, column 16, lines 37-59 of DE 40 09 858 A1, 43.6 parts by weight of a binder dispersion prepared as per 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 produced from 50 parts by weight of Titanium Rutile 2310, 6 parts by weight of a polyester prepared as per example D, column 16, lines 37-59 of DE 40 09 858 A1, 24.7 parts by weight of a binder dispersion prepared as per patent application EP 022 8003 B2, page 8, lines 6 to 18, 10.5 parts by weight of deionized water, 4 parts by weight of 2,4,7,9-tetramethyl-5-decynediol, 52% in BG (available from BASF SE), 4.1 parts 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 produced from 57 parts by weight of a polyurethane dispersion prepared as per WO 92/15405, page 13, line 13 to page 15, line 13, 10 parts by weight of carbon black (Monarch® 1400 carbon black from Cabot Corporation), 5 parts by weight of a polyester prepared as per example D, column 16, lines 37-59 of DE 40 09 858 A1, 6.5 parts by weight of a 10% strength aqueous dimethylethanolamine solution, 2.5 parts by weight of a commercial polyether (Pluriol® P900, available from BASF SE), 7 parts by weight of butyl diglycol, and 12 parts by weight of deionized water.
The barium sulfate paste P4 is produced from 39 parts by weight of a polyurethane dispersion prepared as per EP 0228003 B2, page 8, lines 6 to 18, 54 parts by weight of barium sulfate (Blanc fixe micro from Sachtleben Chemie GmbH), 3.7 parts by weight of butyl glycol, and 0.3 part by weight of Agitan 282 (available from Münzing Chemie GmbH) and 3 parts by weight of deionized water.
The steatite paste P5 is produced from 49.7 parts by weight of an aqueous binder dispersion prepared as per WO 91/15528, page 23, line 26 to page 24, line 24, 28.9 parts by weight of steatite (Microtalc IT extra from Mondo Minerals B.V.), 0.4 part by weight of Agitan 282 (available from Münzing Chemie GmbH), 1.45 parts by weight of Disperbyk®-184 (available from BYK-Chemie GmbH), 3.1 parts by weight of a commercial polyether (Pluriol® P900, available from BASF SE), and 16.45 parts by weight of deionized water.
In accordance with patent specification EP 1534792 B1, column 11, lines 1-13, 81.9 parts by weight of deionized water, 2.7 parts by weight of Rheovis AS 1130 (available from BASF SE), 8.9 parts by weight of 2,4,7,9-tetramethyl-5-decynediol, 52% in butyl glycol (available from BASF SE), 3.2 parts by weight of Dispex Ultra FA 4437 (available from BASF SE), and 3.3 parts by weight of 10% dimethylethanolamine in water are mixed with one another; the resulting mixture is subsequently homogenized.
47.38 parts by weight of the aqueous dispersion AD1, 42.29 parts by weight of deionized water, 6.05 parts by weight of 2,4,7,9-tetramethyl-5-decynediol, 52% in butyl glycol (available from BASF SE), 2.52 parts by weight of Dispex Ultra FA 4437 (available from BASF SE), 0.76 part by weight of Rheovis AS 1130 (available from BASF SE) and 1.0 part by weight of 10% dimethylethanolamine in water are mixed with one another and the resulting mixture is subsequently homogenized.
ML1 and ML2 are used for producing effect pigment pastes.
The components listed under “Aqueous phase” in table 5.1 are stirred together in the order stated to form an aqueous mixture. In the next step, a premix is produced in each case from the components listed under “aluminum pigment premix” and “Mica premix”. These premixes are added separately to the aqueous mixture. Stirring takes place for 10 minutes after addition of each premix. Then deionized water and dimethylethanolamine are used to set a pH of 8 and a spray viscosity of 95±10 mPa·s under a shearing load of 1000 s−1, measured using a rotational viscometer (Rheolab QC with C-LTD80/QC heating system from Anton Paar) at 23° C.
The components listed under “Aqueous phase” in table 5.2 are stirred together in the order stated to form an aqueous mixture. In the next step, a premix is produced from the components listed under “aluminum pigment premix”. This premix is added to the aqueous mixture. Stirring takes place for 10 minutes after the addition. Then deionized water and dimethylethanolamine are used to set a pH of 8 and a spray viscosity of 85±5 mPa·s under a shearing load of 1000 s−1, measured using a rotational viscometer (Rheolab QC with C-LTD80/QC heating system from Anton Paar) at 23° C.
Within the series WBL3 to WBL4, the fraction of aluminum pigment and hence the pigment/binder ratio was lowered in each case. The same is true of the series WBL5 to WBL6.
The components listed under “Aqueous phase” in table 5.3 are stirred together in the order stated to form an aqueous mixture. In the next step, a premix is produced from the components listed under “aluminum pigment premix”. This premix is added to the aqueous mixture. Stirring takes place for 10 minutes after the addition. Then deionized water and dimethylethanolamine are used to set a pH of 8 and a spray viscosity of 85±5 mPa·s under a shearing load of 1000 s−1, measured using a rotational viscometer (Rheolab QC with C-LTD80/QC heating system from Anton Paar) at 23° C.
Within the series WBL7 to WBL8, the fraction of aluminum pigment and hence the pigment/binder ratio was lowered in each case. The same is true of the series WBL9 to WBL10.
The components listed under “Aqueous phase” in table 5.4 are stirred together in the order stated to form an aqueous mixture. In the next step, a premix is produced from the components listed under “Aluminum pigment premix”. This premix is added to the aqueous mixture. Stirring takes place for 10 minutes after the addition. Then deionized water and dimethylethanolamine are used to set a pH of 8 and a spray viscosity of 85±5 mPa·s under a shearing load of 1000 s−1, measured using a rotational viscometer (Rheolab QC with C-LTD80/QC heating system from Anton Paar) at 23° C.
Additionally, the samples WBL17 and WBL21 were adjusted to a spray viscosity of 120±5 mPa·s under a shearing load of 1000 s−1, measured using a rotational viscometer (Rheolab QC with C-LTD80/QC heating system from Anton Paar) at 23° C. (resulting in WBL17a and WBL21a).
The components listed under “Aqueous phase” in table 5.5 are stirred together in the order stated to form an aqueous mixture. In the next step, a premix is produced from each of the components listed under “Aluminum pigment premix”. These premixes are added separately to the aqueous mixture. Stirring takes place for 10 minutes in each case after the addition of a premix. Then deionized water and dimethylethanolamine are used to set a pH of 8 and a spray viscosity of 85±10 mPa·s under a shearing load of 1000 s−1, measured using a rotational viscometer (Rheolab QC with C-LTD80/QC heating system from Anton Paar) at 23° C.
The components listed under “Aqueous phase” in table 5.6 are stirred together in the order stated to form an aqueous mixture. In the next step, a premix is produced from the components listed under “Aluminum pigment premix”. This premix is added to the aqueous mixture. Stirring takes place for 10 minutes after the addition. Then deionized water and dimethylethanolamine are used to set a pH of 8 and a spray viscosity of 130±5 mPa·s (WBL31) or 80±5 mPa·s (WBL31a) under a shearing load of 1000 s−1, measured using a rotational viscometer (Rheolab QC with C-LTD80/QC heating system from Anton Paar) at 23° C. In the case of WBL31a, a larger amount of deionized water is used for this purpose.
The components listed under “Aqueous phase” in table 5.7 are stirred together in the order stated to form an aqueous mixture. In the next step, a premix is produced from the components listed under “Butyl glycol/polyester mixture (3:1)”. This premix is added to the aqueous mixture. Stirring takes place for 10 minutes after the addition. Then deionized water and dimethylethanolamine are used to set a pH of 8 and a spray viscosity of 135±5 mPa·s under a shearing load of 1000 s−1, measured using a rotational viscometer (Rheolab QC with C-LTD80/QC heating system from Anton Paar) at 23° C.
The components listed under “Aqueous phase” in table 5.8 are stirred together in the order stated to form an aqueous mixture. After stirring for 10 minutes, deionized water and dimethylethanolamine are used to set a pH of 8 and a spray viscosity of 120±5 mPa·s (WBL34 and WBL35) or 80±5 mPa·s (WBL34a and WBL35a) under a shearing load of 1000 s−1, measured using a rotational viscometer (Rheolab QC with C-LTD80/QC heating system from Anton Paar) at 23° C.
6. Investigations and Comparison of the Properties of the Aqueous Basecoat Materials and of their Resultant Coatings
6.1 Comparison Between Waterborne Basecoat Materials WBL5 and WBL9 in the Incidence of Streakiness and the Homogeneity with the Atomization Spray
The investigations on the waterborne basecoat materials WBL5 and WBL9 (these materials each contain identical amounts of the identical aluminum pigment) with regard to streakiness and spray homogeneity take place as per the methods described above. Table 6.1 summarizes the results.
The numbers 15 to 110 in connection with the homogeneity index HI relate to the respective angles in ° selected when carrying out the measurement, with the respective data to be determined being determined a certain number of ° away from the specular angle. H115, for example, denotes that this homogeneity index pertains to the data captured at a distance of 15° from the specular angle.
WBL5 and WBL9 have identical pigmentation but differ in their basic composition.
The figures in table 6.1 show that the difference in tendency to develop streakiness, which is determined by means of the homogeneity index according to patent DE 10 2009 050 075 B4, correlates with the ratio of TT1/TTotal1 at x=5 mm (inside) and TT2/TTotal2 at x=25 mm (outside):
The greater the value of the ratio formed from TT1/TTotal1 and TT2/TTotal2, the greater the extent to which nontransparent (NT) particles, i.e., particles containing (effect) pigment, increase from inside to outside in an atomization spray. This means that during application, a material is separated more strongly into regions with different concentrations of (effect) pigments, and hence is more inhomogeneous or more susceptible to the development of streaks.
In contrast to prior-art methods such as a time-shift technique, which measures either only transparent or only nontransparent particles, the method of the invention for characterizing the atomization includes a differentiation between transparent and nontransparent particles, and combines the two pieces of information with one another. As shown by the example given above, this differentiation and combination are necessary in order to understand the processes involved in the atomization of pigmented paints.
The investigations on waterborne basecoat materials WBL1 and WBL2 with regard to the incidence of pinholes are made according to the method described above. Table 6.2 summarizes the results.
By comparison with WBL1, WBL2 proved to be much more critical with regard to incidence of pinholes. This behavior correlates with a larger value of D10, obtained experimentally in the case of WBL2 in comparison to WBL1 and being a measure of a coarser atomization and of an increased wetness.
6.3 Comparison Between Waterborne Basecoat Materials WBL3, WBL4, WBL6 to WBL8 and Also WBL10 with Regard to the Assessment of Cloudiness, the Incidence of Pinholes, and the Film Thickness-Dependent Leveling
The investigations on waterborne basecoat materials WBL3, WBL4, WBL6 to WBL8 and also WBL10 with regard to the assessment of cloudiness, of pinholes, and of the film thickness-dependent leveling are made in accordance with the methods described above. Tables 6.3 and 6.4 summarize the results.
In direct comparison of the sample pairings WBL3 and WBL7, WBL4 and WBL8, and WBL6 and WBL10, respectively, each containing the same pigment and also the same amount of pigment, it is found that at a discharge rate of 300 ml/min and a speed of 43 000 rpm, materials WBL7, WBL8, and WBL10 each have a smaller D10 than the corresponding reference sample WBL3, WBL4 and WBL6 and therefore undergo finer atomization. This is reflected in a significantly better pinhole robustness and also in a lower cloudiness.
WBL3 and WBL5 each have a pigment/binder ratio of 0.35, whereas WBL4 and WBL6 each have a pigment/binder ratio of 0.13.
The experimental results show a correlation between the D10 values, and the resultant atomization properties, and the appearance/leveling, here as a function of the film thickness: on comparison with the samples with identical pigment/binder ratio of 0.35 (WBL3 and WBL5) and 0.13 (WBL4 and WBL6) it is found that a larger D10 value, in other words a coarser and hence wetter atomization, leads to poorer leveling, as illustrated by the short wave and DOI figures obtained.
6.4 Comparison Between Waterborne Basecoat Materials WBL3 to WBL10 and WBL17 to WBL20 and Also WBL25 to WBL28 in Relation to Hiding Power, Clouding Propensity, Pinholes and Leveling (Influence of Pigment)
The investigations on the waterborne basecoat materials WBL3 to WBL10, WBL17 to WBL20 and also WBL25 to WBL28 in relation to hiding power, clouding propensity, pinholes and leveling took place in accordance with the methods described above. Illustrated specifically is how the atomization and the resultant coating properties can be influenced by a change in the aluminum pigment used, especially in relation to its particle size. In all of the experiments, the discharge rate was 300 ml/min; the rotational speed of the ESTA bell was 43 000 rpm. Tables 6.5 to 6.9 summarize the results.
1)Characteristic numbers from Eckart technical data sheet
2)p/b = Pigment/binder ratio
1)Characteristic numbers from Eckart technical data sheet
2)p/b = Pigment/binder ratio
1)characteristic numbers from Eckart technical data sheet
2)p/b = Pigment/binder ratio
1)characteristic numbers from Eckart technical data sheet
2)p/b = Pigment/binder ratio
1)characteristic numbers from Eckart technical data sheet
2)p/b = Pigment/binder ratio
In all of the cases investigated (with different pigment contents in each case), a change in the effect pigment used, especially in terms of its lower particle size (based on d50 of the pigment), leads to smaller D10 values. This consequently finer atomatization is beneficial to the hiding power, the clouding propensity, and also pinholes, and to the leveling (SW and DOI).
The investigations on the waterborne basecoat materials WBL17 to WBL24 and also WBL29 and WBL30 in relation to pinholes took place in accordance with the method described above.
Illustrated specifically is how the atomization and the resultant coating properties can be influenced by the amount of the aluminum pigments used. In all of the experiments the discharge rate was 300 ml/min; the rotational speed of the ESTA bell was 43 000 rpm. Table 6.10 summarizes the results.
1)characteristic numbers from Eckart technical data sheet
2)p/b = Pigment/binder ratio
In a comparison of the respective pairs of samples differing only in terms of the pigment/binder ratio, in other words in relation to the amount of pigment, it was found that an increase in the amount of the aluminum pigment used led to better atomization (smaller D10 values) and consequently the pinholes were positively influenced.
6.6 Comparison Between Waterborne Basecoat Materials WBL17 and WBL17a and Also WBL21 and WBL21a in relation to pinholes, degree of wetness, and cloudiness (effect of spray viscosity and amount of water, respectively)
The investigations on the waterborne basecoat materials WBL17 and WBL17a and WBL21 and WBL21a and also WBL31 and WBL31a, respectively, in relation to pinholes, degree of wetness, and cloudiness took place in accordance with the methods described above. Illustrated specifically is how it is possible to influence the atomization and the resultant coating properties on the basis of the spray viscosity established (i.e., on the basis of the amount of water added). In all of the experiments the discharge rate was 300 ml/min; the rotational speed of the ESTA bell was 43 000 rpm. Tables 6.11 and 6.12 summarize the results.
1)set under a shearing load of 1000 s−1
1)set under a shearing load of 1000 s−1
The examples demonstrate that by means of a lower spray viscosity in the atomization of the material, finer droplets (smaller D10 values) are generated, with beneficial consequences for the pinhole sensitivity and also the degree of wetness and the cloudiness of the paint system.
The investigations on the waterborne basecoat materials WBL34 and WBL35 and WBL34a and WBL35a, respectively, in relation to the degree of wetness took place in accordance with the method described above. Illustrated specifically is how it is possible to influence the atomization and the resultant degree of wetness, which is responsible for properties such as cloudiness, pinhole robustness, etc., on the basis of an additional amount of a solvent. The experiments on the samples were carried out at an ESTA bell rotational speed of 43 000 rpm and 63 000 rpm. In all cases the discharge rate was 300 ml/min. Table 6.13 summarizes the results.
For both discharge rates (63 000 rpm and 43 000 rpm) it was shown, for the respective pairs of samples adjusted to the same spray viscosity (120 mPa·s or 80 mPa·s), that by adding butyl glycol there is an influence on the D10 and hence also on the degree of wetness, which is a cause of the sensitivity to clouding or to pinholes, for example; the effect of the solvent is a significant enlargement in the D10 value, as a measure of the particle size during atomization, and hence a significantly wetter deposited film.
6.8 The examples demonstrate that by means of the method of the invention it is possible to make predictions about the atomization of a paint that correlate with qualitative properties of the final coating (number of pinholes, degree of wetness, cloudiness or leveling, and appearance and also hiding power) and in particular correlate better than other methods in the prior art. The method of the invention therefore enables a simple and efficient method for quality assurance. It may help to focus paint developments and in so doing to remove the need at least partly for costly and inconvenient coating operations on model substrates (including baking of the materials).
The investigations on clearcoat materials KL1 and KL1a and also KL1b in relation to their running behavior took place in accordance with the method described above. Illustrated specifically is how it is possible to influence the running behavior on the basis of the spray viscosity, adapted by the addition of a solvent, and also by omitting additives known to the skilled person, such as rheology control agents. The materials under investigation are as follows:
Sample KL1 is a commercial two-component clearcoat material (ProGloss from BASF Coatings GmbH), containing fumed silica as rheological assistant (Aerosil® products from Evonik), with the base varnish having been adjusting using ethyl 3-ethoxypropionate to a viscosity of 100 mPa·s at 1000/s.
Sample KL1a corresponds to KL1, with the difference that the base varnish was adjusted using ethyl 3-ethoxypropionate to a viscosity of 50 mPa·s at 1000/s.
Sample KL1b corresponds to KL1, with the difference that it contains no fumed silica as rheological assistant. The base varnish was likewise adjusted using ethyl 3-ethoxypropionate, as in the case of KL, to a viscosity of 100 mPa·s at 1000/s.
The experiments were carried out on the samples at an ESTA bell rotational speed of 55 000 rpm. The discharge rate was 550 ml/min. Table 7.1 summarizes the results.
The results demonstrate that by means of receptive measures which influence the viscosity behavior, such as reducing the spray viscosity (KL1a) and eliminating the fumed silica-based rheological assistants (KL1b), in comparison to the reference KL1, the atomization is impaired (larger D10 values), resulting in a deterioration in the running stability.
The examples demonstrate that by means of the method of the invention it is possible, for clearcoat materials as well, in particular, to make predictions about the atomization of a paint that correlate with qualitative properties of the final coating (running behavior), and in particular correlate better than other methods in the prior art. The method of the invention therefore enables a simple and efficient method for quality assurance. It may help to focus paint developments and in so doing to remove the need at least partly for costly and inconvenient coating operations of model substrates (including baking of the materials).
| Number | Date | Country | Kind |
|---|---|---|---|
| 18179608.7 | Jun 2018 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2019/066683 | 6/24/2019 | WO | 00 |
