Multi-layer coating process involving use of aqueous basecoat composition containing crosslinked polymer microparticles and having a pseudoplastic or thixotropic character.

INVENTION This invention relates to the application of protective and decorative coatings to surfaces and in particular to car body surfaces.

Prior to use and especially in the automotive industry, coating compositions containing metallic adhesives are so-called metallic finishes which, for example, have a different effect. To maximize this effect tones

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-2 preparation of this coating composition for resin film formations and also liquid medium »It is possible c

to combine difficulty in the preparation of a simple composition or to cover this objective purpose and at the same time to achieve a high degree of luster (polishing) in the final filtration of the industry as desired. For this reason, one of the methods proposed for the production of metal fluorescents is a two-layer method, in which it is first applied by spraying, on the surface of the substrate, containing a substrate, or It is customary to give an excellent result of metallic emphasis and then to apply it on the base coat and again by spraying, a non-pigmented surface coating, which gives the desired degree of gloss without altering in any way the characteristics of the base coat.

For a successful dual-impregnation metal filing system of this type the basic impregnation / clear impregnation is a basic criterion that the base impregnation membrane must be capable of withstanding solvent resistance. The assembly of the clarity of the incidence was or the last brunt of the trim to avoid disorder of the metal piMemon and therefore the proceedings of the reinforcement of metallic emphasis is now very well -groomed.

One of the known base coatings / coatings systems in which the base coatings and clear coatings are prepared with an organic solvent, this description is in most cases satisfactory.^Λ-δΐά -&gt; / of w

Using an additive capable of imparting a gel-like character to the newly formed base coat or additive or which has been used primarily is the acidic butyl cellulose. The transition between relative low Viscosities, which requires a basic acceleration composition for the launcher and the joy of this simulated gel, which is assisted by by evaporation during the passage from the ejection device to the substrate.

In order to avoid air pollution, it has developed significantly in recent years to formulate compositions which use water as an ear diluent from organic solvents. * A number of such compositions have been proposed for use in the automotive industry. * However, to date it has not been possible to use water-based formulations.^{, Ζ}The factor which contributes to the impediment to the successful achievement of such an objective is the greatest difficulty in securing the controllable selective loss of solvent by mixing a costly regulation of ambient humidity in the spray area. * However, we have now found that a basic aqueous coating is satisfactory and can be based on an aqueous dispersion of a crosslinked polymer microcloth.

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Accordingly, according to the present invention there is provided a method for producing a protective and / or decorative multi-layer coating on the surface of a substrate which comprises the steps of: (I) application in (a) a film-forming material; (b) a volatile liquid medium for said material; and (C) pigment particles; dispersed in the aforementioned liquid medium * (2) forming a polymeric film, on the surface of the composition or applied in step (I) * (3) applied to the base coat film or thus obtained of a transparent outer coating composition and which comprises (which) forms (which) comprises a volatile liquid carrier for said polymer; and (4) forming a second polymer film on the base coat from the composition or applied to step (3), characterized by Components (a) and (b) of the base coat composition are provided by a dispersion in an aqueous medium of crosslinked polymeric microparticles having a diameter in the range of up to 10 microns being insoluble in water. , medium and is stable against coarse thrombosis, where or dispersion has a pseudoplastic or thixotropic character.

Crosslinked polymer microparticles can consist of various types of polymers. Of particular interest for this purpose are acrylate additive polymers which are derived from one or more alkyl acrylic acid or methacrylic acid, possibly together with other ethylene unsaturated monomers. Suitable acrylics or

-5-Methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate and acrylic 2-acrylate. Other suitable, copolymerizable monomers include vinyl dioxide, vinyl propionate, acryluitrile, styrene and vinyltoluene. Because there is a requirement that the polymer be crosslinked, it may be included in polymers in which the polymer has a small monomer ratio or is multifunctional for the polymerization reaction, e.g. Dimetharyllide, athleteer, metharylline, or two -sided* Alternatively are possible, polymerization, such as epoxy and carboxylenes (e.g., glycidyl methacrylate and methacrylic acid), anhydride and hydroxylenosis or isocyanate and hydroxylenosis.

The chemical composition and degree of crosslinking of the polymer apd microparticles may be such that they have a TG (glass transition temperature, rubber) lower than room temperature, whereas the microparticles have a rubber nature. Alternatively, it may be such that TI^vvS is greater than room temperature, ie the particles are hard and glassy.

As already mentioned, polymeric microparticles need to be dispersed in the composition of the base coating in a state or which is stable against gross thrombosis, i.e. a state in which, even with low

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Solid content, or dispersion of solids or no aggregates at all * thus does not rule out the possibility of a small degree of particle clotting, especially at higher solids content. * This situation can be achieved, e.g. by deprivation stabilization, i.e. by forming a fragment of a chain of various polymers around the fragment, which are crosslinked by aqueous means of the composition and therefore exist in an extensional chain configuration. In this text, the diluted substance indicates that the subject matter is polymer chains, if they are independent molecules, they are in fact soluble in the unrefined aqueous medium; more points' g along these, this deprivation barrier is permanently connected to the microparticles. The polymeric microparticles which are thus immobilized in such a way can be conveniently produced by a polymerization method of dispersing the appropriate monomers within the aqueous medium in the presence of a solid deprivation. * 0 stabilizer is amphipathic in nature. i.e. contains some two basic polymeric components of different characteristics: one component is a polymeric chain which is soluble in the aqueous medium and the other component is a polymeric chain which is not soluble in the same medium or which is soluble in the same medium. on the small particles of the polymer which by definition are soluble in the aqueous medium. Suitable dispersion polymerization methods are described in the current patent application No. 7940088, published as application no. 2039497 A). The aqueous medium in which it is carried out

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polymerization is made up of water that does not mix with me. ενννν ευαυ /

volatile co-solvent organism, while the mixture as a whole is

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Soluble dissolution of the monomers, either closed or in total, would be substantially possible if they were insoluble in water alone.

These methods further comprise the need for the polymerization to be carried out at a temperature which is at least 100 ° C higher than the glass transition temperature of the polymer to be formed and thus to exist in such a way that it never exists. The amphipathic deprivative stabilizer may be added to the polymerization mixture as one of the foregoing, or may be formed in situ during the polymerization by a polymer which is strongly by hydrogen removal to inoculate a portion of the polymerizable monomer. Deprived stabilized microparticle dispersions obtained by this method are very suitable for the formulation of base coat compositions which will be used in accordance with the present invention without the ability to do so. Deteriorating the stability of the dispersed phase gives a product in which any continuous phase consists only of water.

Alternatively, the dispersion of the polymeric microparticles can be obtained by polymerizing an aqueous emulsion of the appropriate monomers, wherein the thrombus stabilizer is obtained by the presence of particles in the form of particles, or electrodes water-soluble, polymerization starting catalyst. These polymerization methods are described in detail in the literature. _ \ ·

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Polymeric microparticles can also be prepared by a method of non-aqueous polymer dispersion of monomers, followed by transfer of the resulting polymer to the aqueous medium. Such a method is described in the later British patent application n. No. 42457/77 (now published as non-compliant no. 2006229 A). It comprises in the first step the formation of a deprive stabilized dispersion in a non-aqueous liquid polymer which is insoluble in aqueous liquids and the like water, for use by any of those known in the art. preparation of such dispersions. then to a secondary polymerization step in the dispersion or thus obtained in the presence of a deprivative stabilizer, one or more of the monomers thereof can form a second polymer which is initially soluble in the solvent. and finally transfer of the resulting composite polymer microparticles from the non-aqueous medium to the aqueous medium.

The foregoing discussion arises in the case where cross-linked polymer particles consist of an additive polymer, which is a more common type of polymer for the purposes of the present.

It is possible, however, for the microparticles to Alternatively consist of a condensing polymer, e.g. a polyester which is prepared from a polyhedral alcohol and polycarboxylic acid. Κατάλληλοι πολυϋδρικαί άλκοδλαι περιλαμβάνουν τάς αίθυλενογλυκδλη, προπυλευογλυκδλη, βουτυλευογλυκδλη, Ι:6-εξυλευογλυκδλη, νεοπεντυλογλυκδλη, διαιθυλενογλυκδλη, τρ ιαιθυλενογλυκδλη, τετραθυλευογλυκδλη, γλυκερίνη, τρ ιμεθυλοπροπάυ ιου, τρίμεθυλολοαιθάν ιον, πευτοερυθριτδλη, δ ιπενταερυθρ ιτδλη, τρ ιπενταερυθριτδλη, έξαυίτριδλη, λ

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Styrofoam and allyl alcohol alcohols (e.g., sold under the MONSANTO CHEHIOAE COMPANY classification as RJ 100); : NIAX is a registered trademark). Suitable polycarboxylic acids include the electrode (or its anhydride), adipic acid, azelaic acid, sebastic acid (or its anhydride), fumaric acid, or acetic acid, ), isophthalic acid, terephthalic acid, trimellitic acid (or its anhydride) and pyromellitic acid (or its anhydride). Such polymers are forced to form crosslinks by the addition of materials with greater functionality than the two (basics) in the starting synthesis, although in this case, due to the formation of the characteristic thereby adding polymerization, it can be difficult or assuring that all of these species will in fact be cross-linked.

It should be borne in mind that the methods mentioned above have been mentioned above for the preparation of polymer microparticles themselves by polymerization of monomers of the type added in an aqueous medium, which are generally not of any kind due to the type of application. condensation reaction. The condensation polymer particles, however, can be readily prepared by dispersing polymerization in non-aqueous media according to the methods described in the British patent specification. I37353I * I »4O3» 794 and I 419 199 and the methods of obtaining microparticles with cross-links are included in these descriptions. Such microparticles can therefore be submitted in a non-dispersible dispersing medium.

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-10 middle, in the second step of the polymerization method of the British Patent Application method. 42457/77 (published or notification no. 2006229 A) or which is mentioned above, followed by their transfer to the selected water medium.

By aqueous means meant herein is either water only or water mixed with a water-miscible organic liquid such as methanol; the aqueous medium may also contain water-soluble substances which are detail below.

Pigment particles which have already been defined and which are dispersed in the aqueous medium of the base coat composition may have a size ranging from 1 to 5 microns and may consist of any of the following: including inorganic pigments such as titanium dioxide, iron oxide, chromium oxide, chromic lead and soot and organic pigments such as phthalocyanine and phthalocyanine green. For the purposes of the present, the coagulant means is also meant to include the usual filler minerals and diluents, such as talc or kaolin.

The method of the invention is of particular interest in the case of base coat compositions which contain metal foil pigments which are intended for the production of metallic gloss finishes, mainly on the surface of suitable surfaces.

-IIthe aluminum foils and the copper blade blades. In this regard, the invention also offers advantages in producing solid paint finishes, as discussed below. In general, pigments of all kinds can be incorporated into the base coat compositions in an amount of 2 ° / to 100 ° / on the total weight of the composition. Where metal pigments are used, they are preferably used in an amount of 5 ° / ° to 30 ° / by weight over the aforementioned total weight.

These pigments, whether metallic or otherwise, can be incorporated into the base coat compositions with the aid of known pigment dispersion victims suitable for use in aqueous systems.

The presence of the crosslinked polymeric particles in the base coat composition imparts to the membrane or structure therefrom the desired ability to break down it also contains the substance, therefore, It would not be possible to achieve a successful core investment / diversion investment system.

In addition to this basic feature, it is also required, as mentioned above, that the dispersion of insoluble microparticles be pseudoplastic or thixotropic in nature. From this serum it is understood that the apparent viscosity of the dispersion differs imperceptibly from the degree of shear in the dispenser or dispersion and more specifically that the apparent viscosity of the small shear is greater than that of the large. The change of Viscosity

-12 as a consequence of the change of the applied shear may be instantaneous or it may be necessary for a certain period of time for which it is within the time scale of the measurement of Viscosity. The reason for this Characterization in the dispersion on which the base coat composition is based is very obvious in the case in which the composition contains a well-coated metal foil. It is then desirable that the total concentration of non-volatile solids present be relatively small in order to achieve a substantial shrinkage of the base coat film after application to the substrate leaflet and therefore excellent result of metallic emphasis. However, where this basic coating composition is to be applied to a spray-based substrate, the composition should be sufficiently low in viscosity to effectively ignite the spray gun when is large enough to prevent the formation of wrinkles or drops on the membrane, or the formation of anomalies (uneven distribution and orientation) of the metal plate, even if the Loss of Water and other solvents by evaporation between the spray gun and the substrate is small alone (due to the high humidity of the perimeter).

The existence of such pseudoplastics * '\ ·. ~ Properties are often expressed by the quotient value; c ^_a (viscosity effect in POISE) at select values ​​of D (shear rate in seconds "^Ι). In the case of base coat compositions with metal nozzles used in accordance with the invention, the value is V! , with content (X

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-15 microns 50 ° / by weight of non-volatiles, should preferably be less than 0.5 POISE with shear rate D — T

10000 δευτ και. greater than 20 POISE with speed D 1.0 sec^- · By greater extreme preference or base investment composition should have a value \ ^_a less than 0.25 POISE at a value of D 10000 sec and greater than 40 POISE at a value of D

1.0 δευτ * · £. In the case of a solid base coat composition containing pigmented non-metallic sheets it is preferable to V |_a and again with a roof content of less than 50 ° / but less than I POISE in D ^ IOOOO sec ”^ and greater than 5 POISE in D = I sec” ^ * by greater extreme preference, it is less than 0.7 POISE 13 = 10,000 sec^-} 'and larger of 10 POISE in 13 = 1.0 sec^-^. * However, due to the nature of the pseudoplastic or thixotropic behavior, it can be operated completely and accurately with a few selected viscosity / shear data; much depends on the method used Therefore, if the above quotation marks are to be regarded as incomprehensible, we must be obsessed with achieving the benefits of the invention; these are, easy to determine, by means of a practical test, by a single dispersion, or by a base coat composition or which is derived therefrom, has the necessary degree of pseudoplasticity or dichotomy.

There are many ways in which it is possible to impart a pseudo-plastic or $ 1xdrop character to the dispersion of a physical investment. Visualized cases₎ it is not specifically required

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-14 meters before this. It is possible, e.g. wherein microparticles have been prepared by the above discolored method or which is described in British Patent Application no. 42457/77 (published in application no. 2006229 A).

This method primarily involves the production of suitable polymeric microparticles by a method of polymerizing the dispersion of the appropriate monomers followed by polymerization of other monomers to produce a^ΓThe second polymer is essentially non-crosslinked and has a hydrophilic character so that it is initially soluble in the aqueous medium within which it is to be formed. or final dispersions at a suitable pH. * However, in reality, not all of this second polymer dissolves in the aqueous medium during the transfer of the product of these two non-aqueous polymerization steps. A substantial portion of the second polymer remains attached to the polymer microparticles and the microparticles are thus stabilized in a dispersion within the aqueous medium. say Properties. Further monomers which are suitable for use in the second stage of polymerization are e.g. ύδροξυαλκυλεστέρες τοΰ άκρυλίκοΰ δξέος, ή τοΰ μεθακρυλικού δξέος, μονοακρυλικοί ή μονομεθακρυλικοί έστέρες πολυγλυκολών όπως πολυα ιθυλενογλυκόλης, μονοβίνυλαιθέρες όπως πολυγλυκδλη, ή βίνυλοπυρρολιδδνη, ένδεχομένως έν μίγματι μέ μικρότερες άναλογίες μή-ύδροφίλων μονομερών δπως δ μεθακρυλικός μεθυλεστήρ, δ άκρυλικός βουτυλεστήρ, δ δξ ικδς βινυλεστήρ ή τά στυρένιον.

-15 * Alternatively, or in addition it is possible to achieve the required solubility in the aqueous medium by using as the main component monomer an acrylic ester containing basic groups, e.g. Dimethylaminoethyl methacrylate or diethylamino methacrylate, while these groups can then be converted to salt groups by reaction with a suitable acid, e.g. lactic acid, soluble in aqueous medium. Again, a second polymer may be derived from comonomers which contain a significant proportion of a polymeric carboxylic acid, such as acrylic acid, or methacrylic acid, and then may be dissolved in a solution containing water. ΐυοα ιθαυόλην. In general, therefore, the second polymer may be non-ionic anionic or cationic in nature.

Where the polymer microparticles have been prepared by an aqueous emulsion polymerization process as is known in the art, it is possible to produce a second, initially water-soluble polymer by further polymerizing, in the presence of the same aqueous medium, in the presence of the same aqueous medium. which contains acidic groups which form salts which may give water solutes. Suitable monomers are thus polymerizable carboxylic acids such as acrylic acid or methacrylic acid, if desired in combination with minor proportions of non-hydrophilic monomers such as methyl methacrylate and also hydrophilic monohydrates. hydroxyethyl methacrylate and hydroxypropyl methacrylate.

Where polymeric microparticles have been prepared by a polymerization dispersion method in the aqueous medium as described in the above correlation, prior to the subsequent application of a patent for broth. 794-0088 (or published application no. 20594-97 A), II, a water-soluble polymer may be readily produced by further polymerization within the same medium of suitable monomers, such as those referred to in the preceding paragraph, also water-soluble salt derivatives are created,

Not all water-soluble polymers which are present in the presence of the microparticles in any of the methods described above are capable of imparting the desired pseudoplastic properties by means of a formulation which which includes e.g. Viscosity measurements at different shear rates selected as described above, or by actual application of the compositions to a substrate.

In order to produce a suitable water-soluble polymer on the surface, or in addition thereto, it is possible to add such a polymer, as a Pre-formed component, to the aqueous dispersion of the micro. Suitable polymers are those which, when dissolved in the aqueous medium even at low concentrations, cause a substantial assistance (increase in output) of the composition. For example, it is possible to add one or more viscosity boosting materials.

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-Based on polymer emulsions. * However, not all such Viscosity augmentation materials are suitable for the purpose of the present as some Viscosity augmentation materials are not capable of imparting the necessary pseudoplastic Properties to the synthesis. On the other hand, certain Viscosity-increasing materials which, when dissolved only in the aqueous medium, do not exhibit such Properties, may impart these Properties after the dispersion of the microparticles by micro-interaction, e.g. or by the interaction of polar groups). One of the most suitable Viscosity boosters available is ACRYSOL ASEGO, which is manufactured by ROHM 8s HAAS (ACRYSOL).

It follows that any water-soluble polymer originally combined with the polymer microparticles or added to the dispersion of the microparticles, for the purpose of imparting pseudoplasticity or inert properties to the dispersant , or may, if desired, be of the type which may obtain cross-links. This means that chemically capable groups can be reacted with which the crosslinking agent may be compelled, with the aid of an added crosslinking agent, to obtain a crosslinking bond after the crosslinking. Accordingly, the polymer may contain, as already mentioned, hydroxyl or carboxylic groups derived from monomers bearing these groups and may subsequently be crosslinked with the aid of an immortal, e.g. in a methylated form of melamine formaldehyde concentrate which is soluble in aqueous water;

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-18 In the previous description it appears that the synthesis of basic festivities can be exclusively multicolored, multicolor, pm &amp; chidia, the waterproofing of the water. in it. However, it is also preferable to add to the composition also a large portion of which forms a film which is soluble in the aqueous medium, in order to ensure a continuous application of the , There will be a material which may be agglomerated so as to fill the gaps between the microparticles and thus create a cohesively suitable film (membrane) in step (2). This mission may indeed be accomplished by a portion of an originally water-soluble polymer contained in the composition, as described above for the purpose of imparting a pseudoplastic or viscous formulation. a polymer which is required for that purpose, It may be desirable to supplement it with one or more other water-soluble materials which form membranes and which are added to the composition, which may possibly already contain active ingredients. Accordingly, the composition may contain contents and oligomers of a substance which may be converted into large products after application of the composition, but which alone do not contribute significantly to the viscosity of the viscosity.

From this point of view we can amplify the very small volatile compounds such as 2-ethyl-1, 3-hexaudyl, low molecular weight propylene glycol, low molecular weight, triplex compounds or ethyl cyclosing compounds. glycerol and trimethylT-propane, β-hydroxy-alkylamide N, N, N, N -tetra ^ - (β-hydroxyethyl)

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-19adipamide and cyclic amide and ester, such as e-caprolactam and e-caprolactin. Where these materials are not substantially soluble in pure water, they may be soluble in an aqueous medium which consists of water together with an organic liquid immiscible with water as previously described. Any of these oligomeric substances may be converted to a high molecular weight polymer, after application of the base coating composition to the substrate, for also within the composition. Particularly useful for this purpose are those which are soluble, which are soluble in the aqueous medium of the composition, in particular large-formaldehyde concentrates such as hexa (alkoxymethyl) alkalis and melamine melamine.

Alternative components which contain and subsequently produce a film-forming polymer, or a base coating composition, or containing a preformed polymer, in the application of the substrate. which does not confer pseudoplastic properties thereof or may contain dispersed particles in a polymer which does not form cross-links and which is stabilized in a similar manner to any existing particles in any of the small particles. Ingredients, if desired, may contain functional group (active) moieties such as hydroxyl groups; for which crosslinking may be obtained after application of the composition on the substrate, by means of any crosslinking agent e.g. by an aminoretin.

The relative proportions of the various components of the basic curing composition can vary in large degrees and the proportions in each individual system are often better determined by experiments, but with reference to some specific factors. In particular, if the ratio of the polymer microparticles is too large in relation to each other, there is a film-forming material in the composition, as described above, the latter material will not be sufficient to fill the gaps between the microparticles; following the application of the clear impregnation composition there will be a submerged stress or this composition within the basic impregnation film, with consequent loss of rigidity * * On the other hand, the proportion of microparticles is too small, this may not give the desired acceleration of the composition the desired degree of protection against the onset of aggression or a smaller particle content may be balanced by this reflection by leaving the base film to evaporate or dry for a longer period of time before applying the clear liquid. Generally, a Satisfactory percentage of microparticles is in the range of 5-80^The/ i on the weight of the total volatile content of the base coating composition. The percentage depends, therefore, to some extent on the nature of the solid content in the basic coating composition, whether metallic or non-metallic. For metal compositions, the preferred microparticle content range is 40-75 ° /_Qby weight on the previous basis. For solid color formulations ", due to the general larger size required

In order to achieve suitable opacity, a very small membrane thickness, or a preferred microparticle content area is rather smaller, i.e. 10-50 ° / by weight on the same base as before. * The reduced microparticle ratio prevents an excessively large total volume of dispersed, dispersed material that could occur in a porous film of the base liner and subsequent filtration through it and beyond.

And in general it is possible to state that, by analogy, it is used in the synthesis of a viscosity-enhancing substance or a second polymer which, by virtue of which it gives a pseudoplastic property, together aircraft or existing container, Another film-forming material may be in the range of 0-30 ° / by weight and where there is a crosslinking agent such as an amino acid, which may also amount to 30 ° / by weight of the total content of the underlying investment composition. * The base coat composition may not, however, be further contained in a catalyst for any crosslinking reaction, or which may take place after application of the composition to the substrate. This may be a water-soluble acidic compound, such as p-toluenesulphonic acid, orthophosphoric acid, malic acid or other potent carboxylic acid, such as a tetrachlorophthalic acid, a non-ferrous acid.

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The nature of the polymeric component which forms a film in the coating composition used in step (5) of the process of the invention is by no means crucial. It can generally be used

<img file="GR74115B_D0012.tif" />

plastic type. A suitable class of polymers is those which are derived from one or more ethylated unmodified monomers. Particularly useful members of this category are Acrylic Addition Polymers which are standard for the manufacture of Investments in the automotive industry, i.e. polymers or copolymers with one or more

Alkyl esters of the acrylic acid or the methacrylate acid, optionally together with other ethylene unsaturated monomers. Suitable Acrylic Esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate and 2-acrylic acrylic. Suitably other copolymer copolymerizable monomers include vinyl dioxide, butyl propionate, acryluitrile, styrene and vinyltoluene. Where required The acrylic polymer is of the thermosetting type with crosslinked, suitable functional monomers used.

2-Hydroxypropyl ester, 2-hydroxypropyl methacrylate, N- &lt;chloroxymethyl) ac (Vylamide and N- (alkoxymethyl) methacrylamide, wherein the alkoxy groups are possible, e.g.

* The formulation of External Investment is possible in such a case: it also contains a means of creating cross-sections

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A nitrogenous resin, i.e., a formaldehyde condensate with a nitrogenous compound, such as urea, thiourea, melamine, or benzoguanamine, or a lower alkyl ether of such concentrate containing up to 4 concentrates. Particularly suitable crosslinking agents are mylamine-formaldehyde condensation products in which a significant proportion of the methyl groups have been etherified by reaction with butanes.

The exterior coating composition may include a suitable catalyst for the crosslinking reaction between the acrylic polymer and the crosslinking agent, e.g. of a compound with a reactive reaction such as butyl maleate, sulfuric acid butyl phosphate and p-toluenesulfonate. Alternatively the catalytic activity may result from the incorporation of free radical groups into the acrylic polymer e.g. by using acrylic acid or methacrylic acid as a comonomer in the preparation of the polymer.

The outer liner polymer may be present either in solution or in a stable dispersion within the volatile liquid carrier of the outer liner composition, in other words, the solid carrier may or may not be highly soluble. exterior lining. Where the liquid is a solvent, it may be any organic liquid or mixture of liquid liquids, which are suitably used as soluble polymers in the coating compositions, e.g. and oil fractions of different regions boiling points which are mainly state but also have a significant aromatic percentage, esters such as butyl acid, ethylene glycolate and 2-ethoxyethyl acetate,

-24— ketides such as acetone and methyl isobutyl ketones and alcohols but butyl alcohol. The liquid or mixtures of liquid which is ultimately selected as a liquid bearing depends on the nature of the polymer exterior coating, regardless of the principle by which it is applied in a variety of technologies.

Where the liquid carrier is a working non-solvent it tends to have a rather lower polarity than that previously mentioned and may be composed of one or more alkaline hydrocarbons with a small, or slightly brittle, hydrocarbon content. Highly polarized liquids such as those already mentioned so as to give the total mixture is not a solvent for the outer coating polymer. In such a case, the exterior coating composition is a non-aqueous polymer dispersion and the flavor is a deprive stabilized dispersion in which the polymer particles are a non-aqueous polymer which is stabilized by a polymer compound. This is combined with a dispersed polymer. Known principles according to which such dispersions can be prepared have extensively described in the patent literature and other literature, e.g. in the British patent descriptions no. 941,305 * 1,052,241 * 1,122,597 * and 1,231,614 and in td

DISPERSION POLYMERIZATION IN ORGANIC MEDIA Published by KEJ BARRETT (JOHN WILEY AND SONS, 1975).

<img file="GR74115B_D0014.tif" />

Alternatively, the exterior cladding composition may be based on water and in this case the exterior cladding polymer may also be in a stable or dispersible state. In the case of a dispersion, it may be statically stabilized, e.g. when prepared by a method of polymerizing aqueous dispersion method therein of patent application No. 7940088 (published application no.

2039497A) or which has already been mentioned, or which has been stabilized by a load, e.g. when prepared by known aqueous emulsion polymerization methods.

* Suitable for the polymer microparticles of the base coat composition, the outer liner polymer is always of the thermosetting type and is therefore capable of obtaining cross-links after application to the substrate with the aid of the substrate.

Usually the composition of the exterior cladding is substantially useless so that the effect of adding the coagulant due to the base coat is not significantly altered, but may be desired in some cases. in the composition of external investment.

In the first step of the process of the invention, the base coat composition is applied to the surface of the substrate, or which may have previously been subjected to a pre-treatment or otherwise treated by other process. Substrates which are of major interest in X4

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-26 of the invention are metals such as steel or aluminum, which are commonly used in the manufacture of car bodies and other materials such as glass, ceramics, wood or acrylic and plastics can be used in the presence of high temperature which achieves the final hardening of the multi-layer coating. After applying the base coat composition, a polymer film is formed therefrom on the surface of the substrate.^ΧIt is desired that this can be achieved by subjecting the substrate and applied to the west in heat to evaporate the water and to remove any liquid solvent in the heat by creating a temperature in which it can be used. base coating film in cases where the composition comprises a thermosetting film forming material type. However, a particular advantage of the present invention is that it is sufficient to allow only a short drying time to ensure that the exterior coating composition can be applied to the first layer without a base coat. of the latter in any way that could e.g. to prevent the right orientation of the metal source, in order to achieve the best result of metallic appearance. Suitable drying conditions in each individual case depend, inter alia, on ambient humidity but generally a drying time of 1 to 5 minutes at temperatures from 15 ° to 80 ° C is suitable to ensure the supply. Α,.

of the two infusions. At the same time or base coat film-

<img file="GR74115B_D0016.tif" />

It is suitably eroded by the exterior cladding composition so as to achieve Satisfactory adhesion of the layers between them.

After application of the exterior coating composition to the base coat film, the coated substrate may be subjected to a heat treatment or curing process in which the volatile liquid coating is formed. / or where the underlying investment is, creates cross-links with the help of cross-links in one or more of the contents. * This heating or hardening process is usually carried out at a temperature within the range of I00-I40 ° C, but if desired, a lower temperature may be used if the binding is sufficient to activate the mechanism.

In carrying out the process of the invention, the base coatings and exterior coatings may be applied to the substrate by any conventional method, whether by brushing, spraying, dipping or flowing, preferably by flow. are achieved in this way with regard to the control of the pigment and in particular the orientation of the metallic pigment and the gloss. Any of the spray methods can be known as compressed air spraying, electrostatic spraying, hot spray and airless spraying and is suitable for either method.

<img file="GR74115B_D0017.tif" />

The viscosity of the applied base film is preferably ranging from 0.5 to 1.5 mm of the liner and of the outer coating up to 3 mm of the liner (thickness in each case.

As is apparent from the foregoing description, the advantage of the invention as regards the bursts of metallic smoothness Water, not to mention the control of the orientation of the metal pigments. Where we deal with other color whistles, the control orientations of the pigment are of course no longer an important factor, but there is an advantage that the base coat film is not disturbed by the subsequent application of the effluent composition and it has also been found that the base coat film is present to a much lesser degree does not contain polymer microparticles.

The invention is described but is not limited to the following examples, in which the parts and percentages are given by weight._The In these examples, the apparent values ​​of quotient viscosity of the base coat compositions are determined using two different instruments. Values ​​V (at 10,000 s) The shear velocity is measured using the cone viscometer and ICI plate in the modification or which is designed to cover it.

<img file="GR74115B_D0018.tif" />

-29 section. This instrument is described in JOURNAL THE S.Lj OIL AND COLOR CHEMISTS ”ASSOCIATION, July 1966, in CH MONK Article and manufactured by RESEARCH EQUIPMENT (LONDON) LIMITEB.

The values ​​of I. The second shear velocity are measured using a RHEOMAT 30 viscometer with a cylinder with a cover A and counterweight (Counterweight) * each sample is subjected to an applied shear velocity of 660 sec.^-^ until a shear stress reading is obtained steadily after which the shear speed changes immediately to 1.0 s, “; ή and the shear stress is measured and the viscosity of the data is calculated. RHE0MAT 30 manufactured by Zurich CONTRAVES AG RHE0MAT is a registered trademark.

___ EXAMPLE ___ I__

A, Preparation of dispersion of microparticles of aliphatic hydrocarbon polymers,

To a Reactor Equipped with a Stirrer, Thermometer, Rectifier, and Provision for Unilateral Addition to the Returning Extract, 35,429 parts of hepta are added. The latter is boiled at reflux temperature (95-96 ° C) and then the following components are added which have previously been mixed:

Methyl methacrylate 5.425

Azodisobutyruutrile 0.420 vaccine copolymer stabilizer (33 ° /_The solution as described below) 1.964 parts parts parts' &lt;

<img file="GR74115B_D0019.tif" />

-30Τά περιεχόμενα τοϋ άυτιδραστήρος διτηροϋντα® είς θερμοκρασίαν ζέσεως ύπδ ήυορθωμέυου ψυκτήρα έπί 3θ λεπτά ούτως δστε υά σχηματίζουν μίαν διασποράν έμβολιασμοϋ τοϋ πολυμερούς καί έν συνεχεία τροφοδοτούνται τά άκδλουθα προηγουμένως άναμιχθέυτα συστατικά είς τδ έπαυερχδμενου άπδσταγμα μέ σταθερά ταχύτητα έπί διάστημα 3 ώρωυιμεθακρυλικδς μεθυλεστήρ μεθακρυλικδς άλλυλεστήρ άζοδιϊσοβουτυρονιτρίλιου σταθεροποιητής vaccine copolymer (33 ° / g solution as described below)

25,000 parts

0.775 parts 0.338 parts

5.5 * 6 parts

After completing the feed the contents of the reactor are kept at boiling temperature under a reflux condenser for one hour and then 12,874 parts of heptane are added continuously with boiling. speed per hour:

<td>methacrylic methyl ester</td><td> 3.883</td><td>parts</td>

<td>acrylic butyl</td><td>3.ΟΘ6</td><td>parts</td>

<td>Hydroethyl acrylate</td><td> 2.044</td><td>parts</td>

<td>acrylic dxy</td><td> 1.226</td><td>parts</td>

<td>azodiisobutyronitrile</td><td> 0.071</td><td>parts</td>

Vaccine copolymer stabilizer (33 ° / g solution as described below) 2.149 parts

<img file="GR74115B_D0020.tif" />

V

After completing this feed, the reaction mixture is heated to reflux on a well. A steady dispersion of crosslinked polymer microparticles having a total non-volatile solids content of 43.5-44.5 ° Z is obtained₀ and volatile solids content which is Insoluble in any polar solvent (i.e. gel content) 34.5-35 ° / θ.

The vaccine copolymer stabilizer used in the above method was obtained as follows. 12-Hydroxystearate is concentrated to an acid value of approximately 31-34 mg KOH / g (Corresponding to molecular weight 1650-800) and then Reacted with an Equivalent amount of 1 with a mixture of methyl methacrylate and acrylic acid in a ratio of 95 ^ 5. The copolymer virus is used as a 35 ° solution /₀ in a mixture of ethyl ester 11.60⁰/, toluene 14.44 ° /, Aliphatic hydrocarbon mp 98-I22 ° C 61.29 ° / and Aliphatic hydrocarbon m.p. I38-I65 ° C /_Q

Β, Μεταφορά των πολυμρρών_μικροτ§μαχ], δίων έν_ singingπορα_έντ0ς_ ύδοστικοΟ__ϋόσου_

A reactor equipped with a stirrer, thermometer and volatile solvent removal device by distillation is added / -

<td>raised water</td><td> 72.308</td><td>parts</td>

<td>butoxyethanol</td><td> 10.332</td><td>parts</td>

<td>dimethylamioethanol</td><td> 0.529</td><td>parts</td>

<img file="GR74115B_D0021.tif" />

-32 The contents of the Reactor are heated to 100 ° C and then 46.4-97 parts of the dispersion of microparticles are added. the contents of the Reactor. * The amount required to make this is about 2 hours and the extract is mainly consisting of seven with a little water, It rises to 29-3th parts.

The product is a stable aqueous dispersion of polymeric microparticles having a non-volatile solids content of 20-22^θ/₀ at PH 7.2-7.5.

G. 52222 ^ 225__22252 ^ 2 ^ 22122..51112 ^ 2222- ^ 0 ^ ιυ ίου_

Add a self-priming mixing tank

Yolton Aluminum metal content, 65 ° /) 5.8 parts butozyethanand 2.9 parts

These ingredients are stirred together for 15 minutes and then an additional 2.9 parts of butoxyetahydl is added at a constant rate within 3 minutes and then the mixture is stirred for 1 hour. Then add 4.84 parts of hexamethoxymethylmelamine and continue Stirring for 1 hour. Finally, add 1.93 parts of hexamethoxymethylmelamine and 0.97 parts of butoxyethydride and stir for 1 hour.

<img file="GR74115B_D0022.tif" />

<td colspan="3">The following ingredients:</td>

<td>Aluminum concentrate from step G</td><td> 19.34</td><td>parts</td>

<td>dispersion of microparticles from grade B</td><td> 79.61</td><td>parts</td>

<td>hexamethoxymethylmelamine</td><td> 0.46</td><td>parts</td>

<td>dimethylamioethole salt of p-toluenesulphate δξέος, 10 ° / solution in desalinated water</td><td> 3.57</td><td>parts</td>

Stir together for 1 hour. The base coat composition thus obtained has the following characteristics Solid content: 27.2 ° /

Apparent Viscosity 35 POISE with shear rate B-I sec 0.06 POISE at shear rate approximately

D-I0,000 sec !.

E. Preparation of acrylic polymer for clear synthesis _ΐ5 £ § ίί2ίΐίί? £ _

To two reactors fitted with an evaporator, a thermometer and a rectifier are added: wood 22,260 parts of aromatic hydrocarbon

σ.ζ. 190-210 ° C 10,000 parts

The mixture is refluxed (I42-I46 ° C) and the following previously unmixed ingredients are added at a constant rate of 3 hours:

-1*-

<td>στυρέυιου</td><td> 21.49</td><td>parts</td>

<td>acrylic ethyl ester</td><td> 4.51</td><td>parts</td>

<td>2-ethyl acetate acrylate</td><td> 12.75</td><td>parts</td>

<td>acrylic hydroxyethyl ester</td><td> 10.05</td><td>parts</td>

<td>acrylic acid</td><td> 0.49</td><td>parts</td>

<td>buckwheat hydroperoxide.</td><td>I.4I</td><td>parts</td>

έ &lt;| ί

Self-cooling bodies are refluxed λας 2 hours and then added: isobutyl alcohol 12.72 parts wood 3.22 parts

A clear polymer solution with a solids content of 50 ° / th is thus obtained.

F. Preparation of clear composition __ ^ Z! 2ϋ§ ^ 2222_§31ϋ222ϊ222 ^ ΣΏ2_ * Mix the following components: Polymer solution of grade E 55; 2 parts butylized resin

Flow-assisted polymer, 10 ° / well solution

<td>ζυλολίου</td><td> 0.1</td><td>parts</td>

<td>Equivalent to butyl alcohol</td><td> 2.0</td><td>parts</td>

<td>ξυλδλιου</td><td> 15.1</td><td>parts</td>

<img file="GR74115B_D0023.tif" />

-35 Obtain a clear solution with 44.4 ° /_Q solids. This has a Viscosity of 40 seconds (BS B4 cover at 25 ° C).

C γή Applying a basic investment to a solid investment in a

A metal frame is prepared with a first formulation and a surface formulation. An evaporation period of two minutes is allowed between the coatings * or the paint flow rate in the spray gun was 400 mm / min.

After the application of the second step of basic acceleration, the frame is blown with Air at 25 ° C and two layers of clear coating composition are applied as described in step F, where the clear coating composition is B3 with a thin layer before it. at 25 ° C). The two layers are applied dry on dry with an evaporation period of 2 minutes between the two coatings. After a final three-minute evaporation, the frame is placed in an oven at I25-I3 ° C for 3 minutes.

The resulting Silver metal cladding has an excellent metallic finish and no Absence of shear and was Equivalent in appearance to the finest metallic finish finishes obtained by a complete coating system. * The gloss and adhesion between the layers was good and there were penetrations of the clear lining as well as the base lining.

<img file="GR74115B_D0024.tif" />

-56 ___ TRADITION_2 ____

Prepare a metal frame with primary composition and surface composition and then spray two coats of the basic metal casting composition described in step D of Example I, without further dilution at 25 ° C and temperature.₀ Leave a two-minute evaporation period between the two coats * or a color flow rate of 4-00 mm / min in the spray gun.

After applying the second basic dressing the frame is dried at 55-42 ° C for 10 minutes and then two coats of the clear dressing composition described in step 4 are applied; F of Example I, while the clear coating has been previously diluted with xylene to a viscosity of 45 seconds (BS B5 cover at 25 ° C). The two layers are applied dry-on-dry with a period between two two-minute evaporation layers. After a final three-minute evaporation the frame is introduced into an oven at I25 ° -50 ° C for 5P minutes.

* The investment thus obtained had the same exceptional characteristics as the one described in Example I.

___ TRADITION_5 ____

A. Preparation of aqueous dispersion polymers

The following premixes are prepared: (I) Monomeric premix

<td>methacrylics</td><td>methyl ester</td><td> 18.550</td><td>parts</td>

<td>methacrylate</td><td>άλλυλεστήρ</td><td> 1.540</td><td>parts</td>

<td>στυρέυιου</td><td></td><td> 4-. 700</td><td>parts</td>

Ακρυλικός βουτυλεστήρ μεθακρυλικδν όξύ πρωτεύουσα δκτυλομερκαπτάυη αλας άμμωνίου θειϊκής έυώσεως (έυυεϋλοφαινδλη ♦ 5 ΡΡΎΡ αίθυλευοξειδίου) (II) Διάλυμα καταλύτου έυάρξεως ύπερθειϊκδν άμμώνιον άπιουίσθέυ ύδωρ (III) _Διάλυμα^&amp;πι$ανειακώς...ένεργού ούσίας μεθακρυλικδς μεθυλεστήρ άλας άμμωνίου θειϊκές έυώσεως (έυυεύλοφαινδλη ♦ 5 EPYL ethyl oxide)

18,800 parts I.4.0 parts 0.159 parts

0.185 parts

0.130 parts 4.010 parts

20,000 parts

20,000 parts

To the reactor, equipped with a stirrer, thermometer, rectifier and controlled intake device of two separate liquid supplies, we add:

turbid water A 47,641 parts surfactant solution (LK) 0.100 parts

The contents are heated to 80-85 ° C, then 2,000 parts of the monomeric premix (i) are added and the mixture is maintained at 80-85 ° C for 15 minutes. Then 1,068 parts of the starting catalyst solution (ii) are added and the mixture is kept at the same temperature for 20 minutes.

* The following premix ingredients are then fed at a constant rate within 5 hours: -3842.944 parts monomeric premix (I) hydroxyisopropyl methacrylate ¢ .350 parts

During the same 5-hour period, 3,672 portions of the starting catalyst solution (tt) are fed. Specifically and at a constant rate, the reaction mixture is then maintained at 80-85 ° C for 1 hour and then cooled to a constant room temperature. dispersion of crosslinked polymer microparticles. The dispersion had a total solids content of 46.6 ° / and a non-volatile solids content insoluble in any working solvent 44.5 ° /.

Π2 £ 222ί225_222θ ^ 22ϊ2_β22ά2ί5 £ _ ^ Ξ £ ϊ2 ^ 22ί!? 2_

2,563 parts of the Commercial Viscosity Substance known as ACRYSOL ASE 60 ("ACRYSOL is a registered trademark of ROHM Q HAAS COMPANY") are stirred with a sufficient solution of 25 ° C to dimethylamide. Additional deionized water is then added to a total of 23,956 parts. Πρδμιγμ.α (V) _

A mixture of 29,299 parts dispersion of microparticles of grade A above and 18,614 parts of non-dispersible water is brought to pH 7.65 &amp; L &amp;. Add sufficient solution of 25 ° / dimethylamium ethanol in undiluted water. The 23,956 parts of premix (IV) of which was obtained as described above were then miscible.

To a non-combustible mixer we add: -

<img file="GR74115B_D0025.tif" />

-39Aluminum bolt (metal jig 65 ° /₀) 5,153 parts

2-butoxyethanl 15,193 parts

Stir the load for 15 minutes and then add the following ingredients: = hexamethoxymethylmelamine 3.6% parts

Polypropylene glycol (part molecular weight 400) 2,464 parts and irradiation is continued for one hour. * Then premix (V) 71,869 parts are added

Repeated water 1,625 parts and stirring is continued for one hour. The base effect composition or which has thus been obtained has the following characteristics: Solid content: 20. $ ° / apparent values ​​^_a 34.6 POISE with shear rate

- I δευτ^-^

0.42 POISE with D-I0,000 sec^-1

Preparation of Acrylic polymer for composition of a transparent coating x

42.20 parts of equal propane are added to a reactor equipped with a Stirrer, thermometer and Rectifier. Heat to boiling temperature at reflux (84 ° C) and then add the following premix ingredients at constant speed for 3 hours: -40-

<td>methacrylic methyl ester</td><td> 19.85</td><td>parts</td>

<td>Butyl acrylic</td><td> 24.80</td><td>parts</td>

<td>methacrylic hydroxyethyl ester</td><td> 2.48</td><td>parts</td>

<td>Acrylic dxy</td><td> 2.48</td><td>parts</td>

<td>equal</td><td> 7.4-5</td><td>parts</td>

benzoyl peroxide (60 ° / slurry Inside dimethyl phthalate) 0.74 parts

Automatic bodies are kept at room temperature under reflux for an additional 2 hours. A polymer solution with a content of 50 ° / solids is obtained. Remove this solution by direct distillation,

28.87 parts isopropanol and to the solution is added water, 1.86 parts dimethylaminoethanes followed by 80.35 parts desalinated water.

* The Dilution of Azeotropo Equivalent to Water and Water is then continued until a temperature of 96-98 ° C and additionally Desalinated Water to Replace the Distillate. The total volume of Removable Distillate was 118.83 parts and the total volume of Extra Desalinated Water was 114.65 parts. An aqueous solution of Acrylic polymer having a solids content of 33.5 ° / was thus obtained.₀»

D. Preparation of composition &amp; ^ 2ΐυγοϋς_Επενδύσεω2_ ^_:έ_§Ασιυ_τδ_-ΰδω £.

<td>Mix the following ingredients polymer solution Apd step C Above hexamethoxymethylmelamine βουτοξυαιθαυδλη Desalinated Water dimethylammioethole salt of</td><td colspan="2">between: - 75.16 parts 6.29 parts 12.26 parts 5.50 parts</td>

<td></td><td></td><td></td>

-41n-toluenesulphuric acid (PH 7.6) 0.79 parts

The clear coating composition thus obtained had a solids content of 31.5 ° / and a viscosity of 0.5 POISE.

Ε, Εφαρμογή ιας ιας_ βασικής έπεν &amp; ύσεωςκαί μ. Ιας_δ ι&gt; αυχοϋς_έπε v &amp; ^ _ ύσεως__εΙς_ευα_υπόστ £ ωμα_ ^ ροεττοιμάζεται μία μεταλλικόν πλαίσιου με πρωτεύουσα σύνθεσιν και σύνθεσιν έπιφανέις έφαιν further dilution, at a temperature of 25 ° C and a relative humidity of 51 ° /_The · Leave between the layers a minute period of evaporation or flow rate of the paint in the spray gun was 400 mm / min.

After applying the third base coat, the frame is dried at 35-42 ° C for 10 minutes and then three coats of the clear coating composition described in step D above are applied. The three layers are applied dry-on-surface with an evaporation period of two minutes between layers and a final evaporation period of 5 minutes. The panel is then preheated to 70 ° C and subsequently introduced into an oven at 10 ° C for 3 minutes.

The coating thus obtained had an excellent metallic appearance * and was Shear Free and Equivalent to the appearance of the best metallic color system externally created by anyone. The stylbdtis and or prdsfysis between them. layers were good and there was no sinking of the clear coating-of the basic coating ^

<img file="GR74115B_D0026.tif" />

-42—

EXAMPLE 4

A. Preparation of aqueous dispersion of polymer microspheres

In a Reactor equipped with a Thermometer Stirrer. Corrected condenser and control device for intake of two separate liquid supplies, add: -

<td>άφαλατωθέν ΰδωρ</td><td> 29.030</td><td>parts</td>

<td>and This is followed by a mixture of premix</td><td></td><td></td>

<td>methyl methacrylate</td><td> 0.029</td><td>parts</td>

<td>ammonium sulphate (volatile</td><td></td><td></td>

<td>phenyl ♦ 5 μg ethyl oxide)</td><td> 0.029</td><td>parts</td>

The reactor contents are heated to 80-85 for 15 minutes and the following premix ingredients are added:

Methyl acrylate methyl acrylic methyl ester

0.069 parts 0.069 parts of the reaction mixture is maintained at 80-85 ° C and then a mixture is added:

for 15 minutes desalinated water over ammonium

0.67 parts 0.021 parts

After reactor contents are maintained at 80-85 ° C for an additional 20 minutes, feed the following ingredients

<td>premix efts of the reactor with</td><td>steadily</td><td>speed seven</td>

<td>3 hours apart: -</td><td></td><td></td>

<td>* Acrylic butyl</td><td> 10.758</td><td>parts</td>

<td>methacrylic methyl ester</td><td> 10.189</td><td>parts</td>

<td>methacrylic allyl ester</td><td> 0.686</td><td>parts</td>

<td>ammonium sulfate salt</td><td></td><td></td>

<td>(Evil υ 5 μg of ethyl-</td><td></td><td>i</td>

<td>oxide)</td><td> 0.081</td><td>* 'Λ parts</td>

<img file="GR74115B_D0027.tif" />

-45 and simultaneously fed into the reactor at a constant speed and over a period of 3 hours a solution of 0.037 parts of ammonium persulfate in 4,985 parts of desalinated water:

After replenishment of the upper feedings, the contents of the reactor are maintained at 80-85 ° C for 1 hour. 34,716 parts of desalinated water are then added and the temperature is adjusted to 80-85 ° C. then add the raw premix ingredients at constant speed and within 1 hour: -

<td>Methacrylic acid</td><td> 0.950</td><td>parts</td>

<td>acrylic butyl</td><td> 2.035</td><td>parts</td>

<td>hydroxyethyl acrylate</td><td> 1.357</td><td>parts</td>

<td>methacrylic methyl ester</td><td> 0.950</td><td>parts</td>

<td>ammonium sulfate salt</td><td></td><td></td>

<td>(anneilofeys ^ n ♦ 5 mg ethyl-</td><td></td><td></td>

<td>ξείδιον)</td><td> 0.028</td><td>parts</td>

and at the same time at constant speed and within the same period of 1 hour, feed in the reactor a solution of 0.019 parts of ammonium persulfate and 0.016 parts of sodium borate in 0.596 parts of desalinated water.

After the two additions are complete, the temperature of the reaction mixture is maintained at 80-85 ° C for 1 hour and then cooled rapidly to obtain a stable aqueous dispersion of polymer microparticles. The dispersions had a total solids content of 30 ° / and a volatile solids content insoluble in organic solvents 27 ° /,

B. Western blotting composition The dispersion obtained in step A is brought to pH 8.0 by the addition of dimethylaminoethanol and 54.15 parts of it are added to a mixer. Then we add

-44in unprofitable order, the following ingredients;

* Desalinated Sodium 18.91 parts Butoxyethydride 8.12 parts Aluminum color concentrate (as described in Example 1 (C)) 18.02 parts

The mixture is stirred for 1 hour to give a basic curing composition or having the following characteristics: solid content: 25.8 ° / apparent viscosity N: PO: 20 POISE with shear rate D-PO per cent 0.000 D^-1 _ £ 5 £ ϊδύσεω £ _

In a frame metal prepared with a capital composition and a surface composition, spray-free and without further dilution two coats of a basic basic acceleration composition described above at a temperature of 22 ° C; The clear acceleration formulation is then applied and was or which is described in step P of Example I and the method for applying both formulations and of basic acceleration and clear acceleration was otherwise the same as described in step G of Example I.

<img file="GR74115B_D0028.tif" />

-45The results obtained were similar to those described in step G of example I.

Comparative Example A.

A. Manufacture of silver-plated metallic basic casting &amp; new

To a stirring mixer add: Aluminum pulp (metal container, 65 ° /₀ ) 6.0 parts

2-butoxyethaudyl 18.7 parts

The contents are stirred for 30 minutes, then the following are added: hexamethoxymethylmalamine 4.3 parts propylene glycol (average molecular weight 400) 2.9 parts and stirring is continued for a further hour. * Then add under stirring and within 3 minutes

51.2 parts of an aqueous solution of acrylic polymer with 33.5 ° / sterva prepared as described in Example 5 (C) below, followed by the addition of 16.9 parts of desalinated water.

A basic coating composition is thus obtained which has the same pigment-binder ratio, the same hexamethoxymethylmelamine ratio as total non-volatile materials and a very similar value (0.3 PO3) of viscous effect. as shown in Example I for a basic coating composition according to the invention. Td apparent viscosity at high speed

<img file="GR74115B_D0029.tif" />

A cross-section of the composition or which does not contain polymeric microparticles has been shown to be suitable for application by spraying on a substrate but having an apparent viscosity thereof at a low shear rate, i.e., which is approximately 1.0 °. indicates that the composition has diseases of pseudoplastic or thixotropic properties; The base coat composition is applied in a wide frame and is coated with an acrylic clear coating composition in the same manner as described in Example 1 (G) while the applied clear coating composition or example (1) was ( F). 'The silver metal cladding or thus obtained had a very "metallic emphasis" on the forehead and showed a shear area, also showing blisters during the kiln work.

Examples 1-4 illustrate the invention as applied to the production of a "metallic luminosity".

EXAMPLE b - - _

Grind the crude ingredients between the millstones with a ball for 16 hours.

<td>Titanium dioxide</td><td> 31.5</td><td>parts</td>

<td>2-butoxyethanol</td><td> 18.9</td><td>parts</td>

<td>desalinated water</td><td> 18.9</td><td>parts</td>

<td>dimethylaminoethaudyl</td><td> 0.2</td><td>μ ύρη</td>

<td>hexamethoxymethylmelamine</td><td colspan="2">7.7 / IW, · * / ν '&lt;</td>

<img file="GR74115B_D0030.tif" />

/' &gt;

ί 'ί Oik

The resulting grinding base, or which has a particle size of less than 0.5 microns, is then diluted with II.6 parts of 2-butoxy ethanol and II.6 parts of desalinated water, in part _

The following ingredients are ground together in a ball mill for 16 hours:

<td>Pigeon blue phthalocyte</td><td> 12.9</td><td>parts</td>

<td>2-butoxyethenyl</td><td> 23.8</td><td>parts</td>

<td>Αφαλατωθέυ ΰδωρ</td><td> 23.8</td><td>parts</td>

<td>διμ ε θυλαμιυοαιθανδλη</td><td> 0.2</td><td>parts</td>

<td>hexamethoxymethylmelamine</td><td> 9.7</td><td>parts</td>

The resulting Grinding base or having a particle size of less than 0.5 microns, is then diluted with

14.8 parts of 2-butoxyethenyl and 14.8 parts of desalinated water. C, Preparation of aqueous-solution ^ -Ac ^ material ^ ^ o ^ etho ^ 'Mix the following ingredients:

<td>methacrylic methyl ester</td><td> 19.9</td><td>parts</td>

<td>Butyl acrylic</td><td> 24.8</td><td>parts</td>

<td>hydroxyethyl methacrylic</td><td> 2.5</td><td>parts</td>

<td>Acrylic dxy</td><td> 2.5</td><td>parts</td>

<td>Ίσοπροπαυδλη</td><td> 7.4</td><td>parts</td>

<td>βevzooylperoxide</td><td> 0.7</td><td>parts</td>

A mixture of 15.0 μl of the above mixture and 42.2 μl of isopropavid is filled into a flask equipped with a stirrer and arranged to add liquid feed at a controlled rate. Boil the contents of the flask at reflux (84 ° C) and add the remainder of the above mixture (42.8 parts) to them at constant

-48speed speed 3 hours. The Reaction mixture was refluxed for 2 hours to give a polymer solution with a roof content of 51.0 ° /. To this solution is then added 1.8 parts of dimethylammioethidate, the mixture is reheated to a reflux temperature of 10 ° C. The resulting aqueous acrylic polymer solution had a content of 33.5 ° /_The

D, _Πα £ ασκευή__συνθύσεως_ £ πλέ_βασικής ^ 5 £ ϊύύσεω £ _

Mix the following ingredients in the order in which they are referred to:

Grinding as described

<td>τδ (Α), above Blue grind as described</td><td> 52.25</td><td>parts</td>

<td>Td (B), above Dispersion of microparticles</td><td> 8.39</td><td>parts</td>

<td>described in Example 1 (B) ' Acrylic polymer solution</td><td> 14.62</td><td>parts</td>

<td>as described (O) Above 10 ° / aqueous solution π-toluenesulfonic acid which has a pH adjustment of 7.6</td><td> 24.33</td><td>parts</td>

<td>by the addition of dimethylamyethoethyl</td><td> 0.41</td><td>parts</td>

The resulting base coat composition has a Viscosity of 16.0 POISE with a shear rate of Id^-^ and 0.53 ^ 0132 with a shear rate of 10,000 sec^-^.

-49Ε * 2φαρ ^ ογή_ε ί £ _ενα_ύπδστ £ ω) ΐα_§ασικής_έπευδύσεως_καί_διαυγούς_ ** **** · *, ί ”^ έπενδύσεως ^

Prepare a metal frame with a primary formulation and a surface formulation and then apply two coats of the blue basic blown composition described in (D) above by spraying, without further dilution and humidity 22 ° C. Leave between the two layers for an evaporation period of two minutes. After applying the second base coat, the frame is blown with air at 25 ° C and two coats of liner composition are applied as described in Example 1 (F), while the clear liner composition has previously diluted to 4 degrees prior to dilution. measured at BS B3 cover at 25 ° C. The two external impressions are applied dry-on with a two-minute evaporation period between layers. After a final evaporation of three minutes, the frame was scaled to I25- * 30 ° C for 3 °.

„_5ϋΙ^Kbased^Kέν_πα £ اد_ιγ ^ α_Β__

Α. Πα £ 22^K£ 25_222θέσεως_ ^ πλέ_§αοΛΧ22_έπενδύσεως_αυευ_πολυ ^ ε £ ώυ „^ ά^K£ οτε ^ αχιδίωυ_ * We mix the raw ingredients in the unfavorable order: -

<img file="GR74115B_D0031.tif" />

' 4?

<td colspan="3">White base mill</td>

<td>described in Example 5 (A)</td><td> 54.8</td><td>parts</td>

<td>Blue base mill as described</td><td></td><td></td>

<td>in example 5 (E)</td><td> 8.8</td><td>parts</td>

<td>Hexamethoxymethylmelamine</td><td> 0.3</td><td>parts</td>

Acrylic polymer solution as described in Example 5 (C) 55.7 parts ° / aqueous solution of p-toluenesulphonic acid, which was adjusted to pH 7.6 by the addition of dimethylamioethyl ether 0.4 parts with the resulting PO compound present δευτ * '¹and 0.83 POISE with a shear rate of 10000 sec.

J

B. Application to Plywood Lining Coating The method of Example 5 (E) is repeated but by substituting the base coat composition or which is described in Example 5 (D) by the base layer A) above. In this case, significant bubbles were observed ”in the basic case, ie. The air that is trapped in the basal layer is separated as bubbles, which distort the surface of the membrane and damage its smooth appearance. Furthermore, it is possible to leave a deeper gap of three minutes between the application of the second base coat and that of the first clear

-51investment, because Otherwise the basic investment is destroyed

From the clear :? Investment with a detrimental effect on the final appearance of the frame.

CLAIMS_

A method for the production of protective media and / or