DE2446250A1 - PROCESS FOR THE PRODUCTION OF A FASTENING ORGANIC COATING ON A METALLIC SUBSTRATE - Google Patents

Description

DipHng. IblfMenges

8011 Pöring / Munich Commerzbank Munich

Hubertusstrasse 20 '4406120

Telephone (08106) 21 76

Telegrams postal check Munich

PATENT QUANTITY Zomeding 307487-803

26 Sep 1974

Lawyer file I 108

Jones & Laughlin Steel Corporation, Pittsburgh, Pa. 15230, V.St.A.

Process for producing a firmly adhering organic coating on a metallic one Substrate

: ■ £ invention relates generally to a method for producing adherent organic coatings on a métallisé - ^"ri substrate under vacuum and the product of this traversing ·· 's The method includes applying at least ^zwe!." Z.viicrenüberzügen on a metallic substrate before roughening an organic layer. This approach leads to a · * "" ^{w, r} t = CRGA ends "- · '.-''; ■ coating and coated to an improvement in Korrciioiooeständigkei * α- · substrate.. All coatings are, i- "j .iusna, .. re of an organic top coat, applied under pressures: ie below atmospheric pressure

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BATH ORIGINAL

Process, a wire-brushed substrate is first coated with a layer of vapor-deposited zinc in vacuo and then _s .misch Ge-coated with at least one layer of vapor-deposited in vacuum metal, alloy of inorganic material or one of them. Finally, a slightly volatile, polymerizable organic primer coating is applied to the coated substrate while it is still under the influence of the reduced vacuum pressure. The organic coating is polymerized by irradiation while it is still under the influence of vacuum.

To increase corrosion resistance for outdoor applications, steel strip is usually coated with an organic compound such as paint, Plastic or lacquer, coated. Organic coatings usually contain a primer and a top coat. A The main part of such strip steel products consists of fire-resistant zinccem material. It has been shown that hot-dip galvanized strip material very difficult in coil coating plants because of the poor macro and micro uniformity of its galvanized surface is to be processed. Such surface irregularities often prevent the required from being carried out satisfactorily Cleaning and inorganic pretreatment steps before paint application. In addition, even if galvanized strip material processed satisfactorily on a coil coating machine has been, the corrosion resistance of the coated product is often due to the changing conditions of the hot-dip galvanized Unsatisfactory surface. In any case, the product is of the method according to the invention, in comparison, with the hot-dip galvanized Products, by a higher adhesive strength of the organic material and in general by a better or at least same corrosion resistance in the primer and top coat condition marked.

The basis for the above determination of corrosion resistance properties to be compared form the results of salt spray tests. The tests were carried out on steel substrates coated with zinc layers, a barrier layer, a primer and a thermosetting top coat. Top coat formulations

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were generally made from a thermosetting acrylic. These samples were compared with hot-dip galvanized samples that in conventional Pretreated with a thermosetting epoxy primer primed and topped with the same thermosetting acrylic ■ were coated with resin.

The coated panels were noted for corrosion, blistering in connection with corrosion and loss of adhesion to torn markings due to undercutting in one corrosive environment evaluated. Before testing, two intersecting cracks were formed on part of the surface of each sample carved into the metal substrate with a hard metal tool. A Salt spray test (ASTM designation B 117-64) is an accelerated one Corrosion test method. Inspections were performed after 250, 500 and 1000 hours, unless previously failed occurred.

The invention is fully under vacuum in a continuous manner up to and alternatively up to and including the topcoat executed. This process sequence is advantageous because two separate work processes in the existing technology, i.e. hot-dip galvanizing and coil coating, combined with each other are. In addition, much greater control can be exercised over the process so that the product is uniform better properties can be produced. The better properties are a result of the fact that an organic Pretreatment is achieved by simply evaporating a thin barrier layer in a controlled manner with no difficulty adheres to the previously applied zinc coating. It can thus be seen that cleaning and complicated surface reactions with a water-based solution are not required, as is the case with conventional processing of coated strip material from Case is. The application and subsequent adherence of the organic Overlay on the separating layer is achieved with minimal difficulty, because the surface composition and topography by the steps of vapor deposition of zinc and the barrier material in the Vacuum checked.

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Recently, in US Pat. No. 3,674,445, it has been described that metallic Substrates coated with zinc vapor deposited in a vacuum can be coated with an adherent organic coating. However, such a product does not contain a layer of a metal, an alloy or an inorganic which is vapor-deposited in a vacuum Earth between the zinc and the organic layers. This additional layer provides a barrier or chemical Effect and leads to improved corrosion resistance and equivalent organic adhesive force values compared to the product according to U.S. Patent 3,674,445.

As can be seen from the above description of the prior art, is the product of the invention from the point of view of the adhesive strength of the organic material to the hot-dip galvanized material and superior to vacuum vapor deposition coated material from the viewpoint of corrosion resistance. The product of the invention thus has a combination of the most desirable features of the known products.

The invention creates a method by means of which firmly adhering organic coatings can be applied to metallic substrates.

The invention also provides a completely under the influence of vacuum Process to be carried out, which firmly adhering organic coatings on metallic substrates.

The invention also provides firmly adhering organic coatings a metallic substrate which has been coated in succession with vacuum-deposited zinc and a barrier material.

Finally, the invention provides a very corrosion-resistant / organic-coated product which is superior to that is that by conventional hot-dip galvanizing and coil plating is produced, as well as is superior to that by the direct application of an organic coating on a in a vacuum

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hot-dip galvanized metallic substrate has been produced. These and further features and advantages of the invention will emerge from the following description of preferred exemplary embodiments of the invention with reference to the drawings. In the drawings show:

Fig. 1 is a diagram of an embodiment of an apparatus used to manufacture a product can, which has an organic primer coating; as the figure shows, a metal coil, for example a steel coil, placed in an evacuated chamber, wire-brushed, with two layers of vacuum evaporation provided, roller-cooled, provided with an organic primer layer, polymerized by irradiation and led out of the evacuated chamber again,

Figure 2 is a schematic of one embodiment of an apparatus that can be used to make an article having organic primer and organic topcoat layers; as the figure shows, we- ¹ while a metallic coil using a device processed, which resembles in Fig. 1 except the coated with the cured primer substrate is further coated with an organic top coat layer and cured by radiation before it from is directed back out of the chamber,

3 shows a diagram of a further embodiment of a device, which can be used to manufacture a product that uses organic · primer and organic Has topcoat layers; As this figure shows, a metal coil is made using an apparatus processed which is essentially similar to that shown in Fig. 2, the difference being that the Topcoat layer is applied under atmospheric pressure and cured after the substrate is evacuated Left chamber

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4 shows a metallic substrate, for example steel, on which four layers have been applied, the first two layers being zinc or a barrier material vapor-deposited in a vacuum, while the last two layers are an organic primer or an organic top coat, _s and

5 'shows a metallic substrate, for example steel, to which five layers have been applied, with the first layer of vacuum deposited zinc and the second and third layers of vacuum deposited Barrier material, while the last two layers are an organic primer and an organic Top coat are.

The method according to the invention comprises the following steps: placing a metallic substrate in an evacuated chamber, wire brushing the substrate, vapor deposition of a zinc layer in a vacuum on the brushed substrate surface, vapor deposition of at least one barrier material layer in a vacuum on the previously applied zinc layer, application of a weakly volatile one , polymerizable organic primer coating on the barrier layer and dispensing the coated substrate from the evacuated chamber. The organic coating is polymerized by radiation before it leaves the chamber. An organic topcoat layer can then be applied to the primer layer. The top coat can be applied and polymerized in the evacuated chamber or then under atmospheric pressure.

The product produced by the above method comprises a metallic one Substrate, which in the vacuum deposited intermediate layers of zinc and at least one barrier material as well as a layer ■ or contains layers of organic matter. The barrier material can be either a metal, an alloy, an inorganic mass or a mixture of these »

A suitable device for applying an organic primer layer is shown schematically in FIG. A metal band

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is fed from a supply reel 4 through an evacuated chamber 2 passed through and wound onto a take-up reel 5. the Tape entry contains sealing rollers 6 and 7 through which the Tape is passed through. The spool 5 is driven so that the tape 1 moves at a desired feed speed continuously moved. The chamber 2 is via an outlet 3 evacuated with the aid of suitable vacuum pumps (not shown). A suitable chamber vacuum value is in a range in On the order of about 5 x 10 - to about 5 χ 10 mm Hg Entering the chamber 2, the belt 1 is mechanically rubbed off by a rotating wire brush 10 so that the belt is cleaned by grinding and in the right condition for subsequent vapor deposition is brought by zinc in a vacuum. A molten zinc bath, which is contained in a crucible 11, is provided by suitable devices, which can be an electron beam gun or a resistance heater, heated to evaporation. A bath of molten barrier material is contained in a crucible 12 and is used for vacuum deposition on the previously applied zinc layer. Inorganic materials such as oxides can be pre-sintered by electron beam bombardment Oxide disks can be conveniently evaporated. The crucible 12 can also be made by electron beam bombardment or by a resistance heating device be heated. A roller 13 is arranged so that by contact with the roller surface a suitable roller cooling of the coated strip 1 can be carried out. Although only one roller 13 is shown, it understands however, that one or more roller surfaces can be used! The roller cooling is used to adjust the Belt temperature to a value that is compatible with the application of an organic coating. An applicator roller 14 is used to apply a layer of an organic mass to the barrier layer by rolling - a roller 15 changes the direction of the feed path, and finally the organic material coated tape is exposed to radiation from an electron gun 16 is sent out, cured before it leaves the chamber 2 by sealing rollers 8 and 9. It can be seen that an or both sides of the tape can be coated by other arrangements or by additions to the above device.

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The arrangement shown in Fig. 2 shows an expedient device for applying and polymerizing organic primer and topcoat layers within the evacuated chamber 2. The primer is applied in the same manner as in FIG upset. The organic top coat is applied by a counter-rotating applicator roller arrangement 17, and the direction of movement the tape 1 is deflected by a roller 18 so that it is via an electron beam cannon 19 to cure the top coat goes away. The cannon 19 is typically low Voltages (<150 kV) operated. After curing or polymerizing of the top coat, the coated tape is passed out of the chamber 2 through the sealing rollers 8 and 9.

Fig. 3 shows an expedient device for applying and polymerizing organic primer and topcoat layers which constitute an alternative to the device of FIG. the The primer layer is applied and polymerized in the same way, but the topcoat layer is replaced by a counter-rotating applicator roller arrangement 20 at a point outside the evacuated chamber 2 applied. After the belt movement

direction has been changed by a roller 21, an electron beam is used cannon 22 for polymerizing the top coat under atmospheric pressure. The cannon is typically used with high voltages (> 250 kV) operated.

After entering the evacuated chamber, the metallic substrate 1 is mechanically rubbed off so strongly that an activated one Surface condition is achieved. Such a surface condition leads to the creation of a zinc layer with a higher adhesive force, which is vapor-deposited in a vacuum. A suitable method for Activation of the surface of metallic substrates is described in GB-PS 1,222,198.

Following the surface preparation of the substrate, a Zinc layer evaporated on the substrate surface in a vacuum. This Step can be carried out by heating a source containing liquid zinc in vacuo and generating the generated by the source

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Zinc vapors are condensed on the moving substrate. These steps, i.e. surface preparation and application of Zinc lead to a zinc surface morphology that is generally smooth, clean and free of secondary phases that negate the adhesive force is. The zinc surface has a platelet structure, which is due to the creation of numerous breakpoints on a microscale is very favorable for the subsequent adherence of organic material.

Zinc layers with a thickness of more than about 2.5 μm, which are deposited in a vacuum, form a topographical structure of platelets, which promote the subsequent excellent adhesion of organic matter. In this respect, it has been also found that strip temperatures of more than 120 ⁰ C at the end of vapor deposition of zinc in vacuo also favor the formation of a platelet structure which is sufficiently rough to promote the adhesion.

It has been found that the beneficial effect of zinc surface morphology can be retained if an intermediate layer of a barrier material between the zinc layer and the organic layer is arranged. The barrier layer should have a thickness which is controlled so that it is at least used to cover it the zinc layer is sufficient that it does not, however, have a thickness which corresponds to the favorable zinc surface morphology obtained by vapor deposition in a vacuum changed significantly. As will be apparent to those skilled in the art, the upper thickness range is thus a function of the particular one Zinc structure, and thus it can be expected to vary according to the zinc application practice used in a particular case will change something. The carrier layer does not reduce the beneficial effect on the subsequent adherence of the organic Mass and causes a noticeable improvement in the corrosion resistance of the final product.

The barrier material can be made of metal, alloy, inorganic mass or a combination thereof. Examples of such materials include tin, aluminum, alloys

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24A6250

aluminum-based aluminum-tin alloys., silicon oxides and like oxides. Silica coatings well meet the requirements when used as a single coating or as a second coating in conjunction with a first aluminum coating be applied.

Silicon oxide coatings are applied by evaporating SiOp. The SiOg vapor becomes somewhat oxygen-deficient as it travels from the source to the substrate under the reduced pressures in the chamber. The applied silicon oxide layer thus contains a little less than the stoichiometric amount of oxygen. Silicon oxide coatings considerably greater than 0.635 µm thick are undesirable. This has its basis in a substantial reduction of the adhesive force of the organic mass, which results because of the brittleness, which is in silicon oxide layers having a thickness of more than 0 _s 635 order is formed.

After the barrier layer has been applied, the strip temperature can be adjusted by means of roller cooling. The purpose of this step is to adjust the belt temperature to a range compatible with the application of a particular organic formulation. It can be seen that in some cases a temperature adjustment may not be necessary because the strip itself reaches an appropriate temperature without the need for roller cooling. This step is therefore to be regarded as an optional step in the above-mentioned sense. The roller cooling can also be used advantageously to reduce the time or the advancing space which is required for the strip to cool to the desired coating temperature. In general, however, ribbon processing in vacuum equipment is often limited because of the difficulty in removing heat from the ribbon in lower temperature ranges in which radiant cooling is not effective. Cooling by dissipating heat from the belt to a heat sink such as a roller is often a required measure.

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In the context of the invention, a metal strip which has been coated with zinc and a thin barrier layer can pass through Roller cooling can be rapidly cooled in a manner that does not significantly affect the surface morphology of the coated substrate interferes with and consequently does not hinder the basic process described here and the results.

Roll cooling of the intermediate coated tape can be carried out effectively. For example, led a water-cooled rotating roller (wrapping around 180 °) having a diameter of 68.5 cm in a reduction of the strip temperature of about 230 C to about 65 ⁰ C in less than two seconds. If uninterrupted roller contact is not established due to poor belt shape and low belt tension, the main part of the cooling takes place through radiation, which is ineffective in this temperature range. In such cases it becomes necessary to use high tape tension to ensure that a poorly shaped tape is drawn just over the chill roll and that good roll contact is made across the width of the tape. It is also preferred that the chill roll have a diameter as large as practical and that the wrap angle be as large as possible. Both of the above features maximize cooling due to increased contact times. The chill roll should have been given a smooth finish so that there is maximum contact with the cover protrusions, and it should also have sufficient water cooling from the inside of the roll to dissipate the heat transferred from the belt to the roll body. In addition, the roller should be arranged to make initial contact with the freshly coated surface so that coating protrusions can be deformed to make good contact with the smooth roller surface.

The entire heat dissipation through the roller cooling can be measured by measuring of water flow and inlet and outlet water temperatures be monitored. If the belt speed, belt thickness, belt width and starting belt temperature are known, the belt temperature can be adjusted according to the Roller cooling can be calculated. Such a calculation enables thus that a control of the end belt temperature through the use

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from the chill roll interior with controlled inlet temperature supplied water is achieved.

Following the roller cooling or the application of the barrier layer in a vacuum, depending on the case, the substrate is coated with a slightly volatile organic material while it is still under the influence of vacuum. The application of the coating under the influence of vacuum offers the advantage that apart from possible gas absorption, no contamination of the belt is possible. On the other hand, by applying organic Materials in environments outside the vacuum chamber appear to increase the risk of detrimental contamination be evoked.

At this stage of the process is the preparation of the intermediate has been carefully controlled so that a product with higher organic coating adhesion and with better Corrosion resistance properties can be achieved. Preparing the coated substrate for applying the organic Material has been checked from two points of view. First of all, the morphology of the coating surface has the desired one Platelet topography. Second, the temperature of the ribbon is controlled to allow for flow and leveling on a macro scale of the organic material over the vaporized surface is possible, while the vacuum environment allows unhindered flow between the platelet structure enables on a microscale. This group of conditions ensures a higher adhesive force of the organic material and a higher corrosion resistance when the Coating layer is then polymerized.

A preferred range of thicknesses for the organic primer assumes about 4.5 µm to 7.5 µm and thicknesses in a range of about 3.8 µm up to 10.1 μm are useful overall. Because the one with barrier material ■ coated zinc flake tips generally have a height in the On the order of 3.8 µm, this value is the thickness of the organic Material usually required to match the porosity of the coated substrate and around the surface up to

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to cover the tips. Therefore, the minimum thickness should be approximated 4.5 µm to ensure that the substrate is sufficiently coated with the organic material that the achievement is achieved of better corrosion resistance properties is ensured. On the other hand, the corrosion resistance is at Primer thicknesses of over 7.5, so as not to be significantly improved, and it results from the manufacture of primer coats above this, thickness value, there is hardly any advantage. Primer coats are generally applied to a thickness of about 6.35 µm.

Roller coating is a convenient method of applying the organic coating. This general type of coating technique is commonly used to cover moving parts Substrates used and need not be further described. Other processes such as extrusion coating, curtain or Powder coating can also be used in the invention will.

After application, the organic layer is polymerized in place by exposure to radiation, for example an electron beam or an ultraviolet radiation. The polymerization occurs while the coated Tape is still inside the evacuated chamber, since low beam voltages can advantageously be used. The curing or polymerizing of organic coating materials by means of radiation is known. These methods are described, for example, in U.S. Patent 3,547,683 and British Patent Nos. 801,479 and 949,192 described. Since radiation polymerization is a conventional technique, no further explanation is needed this step may be required.

In order for a coil-coated product to be of maximum use, it should have both organic primer and organic Have topcoat layers. Primer coats usually contain an anti-corrosive pigment which suppresses chemically supported by under-film corrosion and formulated in this way can ensure that the bond strength to the substrate is maximized. As

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As mentioned above, primers are generally applied to a thickness of the order of 6.35 µm. With this thickness value and in view of the relatively low pigment content used in foundations, the Primers generally have poor hiding power and poor resistance to the degradation effects of sunlight. Thus, in order to achieve reproducible color coatings that do not depend on the substrate and the coloring of the primer a top coat is required. Top coat thicknesses are generally greater than 17.78 µm and are preferably on the order of 25.4 µm to achieve complete obscuration of the substrate color. Top coats have im generally higher pigment contents than primers and are consequently in terms of opacity and resistance to The degradation effects of sunlight and moisture are better. Top coats should also be malleable and have good adhesion to the primer coat. To achieve good Molding properties, the majority of coil coating topcoats have thicknesses of no more than about 25.4 µm.

A fairly wide range of topcoat formulations are suitable for the implementation of the invention. Such formulations contain both conventional and thermosetting topcoats such as acrylic resins, siliconized acrylic resins, fluorocarbons and electron beam curable acrylic resins. At this point it should be mentioned that the application of the top coat layer The primer can be done in three ways. These are:

I) vacuum application and curing, Z) in-line application after the tape exits the vacuum chamber and electron beam curing in the atmosphere, and 3) application and curing by conventional means in a separate device.

During the application and curing of top coats in a vacuum, roughly as shown in Fig. 2, the previously applied primer coat becomes a very much prior to the application of the top coat exposed to weak electron radiation. This process continues

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set so that the topcoat can be applied to a primer which has cured to such an extent that there is no mixing of one organic layer with the other organic layer. A weakly hardened primer however, it ensures good adhesion between the coatings. Since the top coat is applied with thicknesses, the greater are than the thickness of the primer, and with an evenly smooth surface, the topcoating is provided by means of opposite directions Rolling is a preferred application technique. Other methods, such as curtain or extrusion coating, can can also be used, but they can only be carried out under vacuum with relatively greater difficulty. That Curing of the top coat can be carried out by a low voltage electron beam (<150 kV). At this In the first stage of the process, the primer and top coat are fully cured at the same time.

In contrast to applying the top coat and curing under vacuum, the primer coat should be cured to a greater extent if in-line application of the top coat is applied after the exit from the evacuated chamber, namely because the Giundierüng a considerably larger Requires a degree of curing so that it can be moved through the sealing rollers 8.9. If that's with primer coated material emerges from the evacuated chamber 2, the top coat layer is applied by counter-roller coating and curing takes place by means of an electron beam high voltages (> 250 kV). Such application and curing processes are common. As in the case of the procedural example, in which the application of the top coat and the curing were carried out under vacuum, the curing of the primer takes place and the top coat at the same time. One could consider the possibility of being in series with the vacuum system a conventional apparatus for thermosetting the topcoat to order to produce a fully coated product, however, process control would become quite difficult because of it

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required, the lower operating speed of the topcoat curing line to be compared with the higher working speed of the vacuum system. This factor is in use a topcoat curing system with an electron beam is not important.

In the case in which the application and curing of the top coat do not take place in a row, the vacuum primer coated substrate is made in commonly available devices introduced, which is solvent-based, by heat contain curable topcoat material. Cleaning or phosphating facilities are not required.

A suitable primer material used in the invention should be slightly volatile so that it can be applied under vacuum, and it should also be irradiated, be polymerizable for example by electron beams or ultraviolet radiation. Such organic materials include Acrylic, epoxy, and siliconized versions of these formulations. An acrylic ester is a preferred formulation.

As the above explanation of the method shows, there is a wide range of variables with regard to the invention. the The following specific conditions have been found to achieve a very adherent and corrosion-resistant primer coating from an acrylic ester found suitable.

After surface activation by wire brushes, the zinc layer deposited in vacuo should have a thickness of more than about 2.54 μm, so that a surface morphology of platelets results which is favorable for the adhesion of organic material. In relation to this requirement also strip temperatures the formation of a platelet structure which is sufficiently rough to promote the adhesion Favoring about 120 ⁰ C at the completion of vapor deposition of zinc.

The quality of the top coat is achieved by vapor deposition of a thin aluminum

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layer improved in a vacuum directly on the previously applied zinc layer. The aluminum layer .should have a thickness of the order of magnitude from 0.25 µm to 0.50 µm. A layer of silicon oxide with a thickness of 0.38 µm to 0.63 µm, consisting of a S ^ source has been applied is with a view to promoting While not as effective in adhesion as the aluminum layer, it is satisfactory either as a substitute layer can be used for the aluminum layer or as an additional layer that is vapor-deposited onto the aluminum layer.

A strip temperature range of about 65 ⁰ C to about 120 ⁰ C is preferred for the roll coating of Akrylestern. This temperature range ensures that the application and leveling or leveling of organic material takes place properly before curing. Roll cooling of the strip is necessary in order to achieve the correct strip temperature in this case. For the application of Akrylesterüberzügen in the thickness range of 3.8 to to 10.1 um, it is expedient, the organic formulation, approximately 77 ⁰ C to heat, in order to achieve the desired viscosity to flow out and equalizing.

A specific example of the procedure when applied to a 30 cm wide strip of low carbon steel is described below. The 0.045 cm thick tape was passed through an evacuated chamber at a speed of 30 m / min.

A dry, cleaned tape with a temperature of 55 ^° C. was introduced into an evacuated chamber. The strip inlet temperature resulted from the heat absorbed from the cleaning bath.

The tape was then brushed with a brush driven at 7 A, 440 V by a three-phase motor with an idle speed of 500 rpm. The brush rotated in the opposite direction to the direction of belt movement. Due to the brush friction the strip temperature rose from 55 ⁰ C to 105 ⁰ C.

A zinc layer with a thickness of .15.2 µm was brushed on top of the

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Tape evaporated in a vacuum. A graphite resistance heater source was used. This process led to a strip temperature increase to 220 ⁰ C.

An aluminum layer 0.5 µm thick was vacuum deposited on the zinc layer. An electron beam heated source was used. This process led to a temperature increase to 230 ^° C.

The coated tape was then wrapped around a water-cooled roller with a diameter of 68 cm with a wrap angle of 180. The contact time was 2 s This led to a reduction of the strip temperature of 230 ° to 65 ⁰ C..

A Akrylesterüberzug having a thickness of 6.3 m was applied by direct drawing by means of upper rollers at about 65 ⁰ C to the coated strip.

Finally, the coated tape was emitted using an electron gun (150 kV, IO mA) Radiation that scanned, cured, or polymerized the tape at 100 cycles / s.

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Claims (35)

Sponsorship claims: 1. Process for producing a firmly adhering organic coating on a metallic substrate under vacuum, characterized by the following steps: a) introducing the metallic substrate into an evacuated chamber, b) wire brushing at least one surface of the metallic Substrate, c) Vapor deposition of a zinc layer on the brushed surface in a vacuum of the metallic substrate, d) Evaporation of a thin barrier layer from a material in a vacuum which is selected from the group consisting of a metal, an alloy, an inorganic mass and mixtures the same consists, directly on the surface of the zinc layer, e) Application of a slightly volatile, polymerizable organic Primer coating on the surface of the coated metallic substrate, f) at least partial polymerisation of the organic coating, in which it is exposed to radiation, and g) Application of the substrate coated with organic material from the evacuated chamber. 2. The method according to claim 1, characterized in that the zinc layer in a vacuum
is vaporized. layer in vacuum to a thickness of at least about 2.5 µm 3. The method according to claim 1 or 2, characterized in that the metallic substrate upon completion of the vapor deposition of zinc has a temperature of at least about 120 C. 4. The method according to any one of claims 1 to 3, characterized by next step: Checking the thickness of the barrier layer within a thickness range sufficient to cover the zinc layer so that the zinc layer surface morphology does not is changed significantly. 5098U / 1217 5. The method according to claim 4, characterized in that the barrier layer comprises aluminum. 6. The method according to claim 4, characterized in that the barrier layer comprises silicon oxide. 7. The method according to claim 5, characterized by the following further Step: Vapor deposition of a second barrier layer made of silicon oxide directly onto the aluminum barrier layer in a vacuum. 8. The method according to claim 5, characterized in that the aluminum barrier layer a thickness of about 0.25 µm to 0.50 µm is given. 9. The method according to claim 6, characterized in that the silicon oxide barrier layer a thickness of about 0.38 µm to 0.63 µm is given. 10. The method according to claim 7, characterized in that the aluminum barrier layer has a thickness of about 0.25 µm to 0.50 µm and the silicon oxide layer has a thickness of about 0.38 µm to 0.63 µm is given. 11. The method according to any one of claims 1 to 10, characterized in, that the material for the organic coating is selected from a group consisting of acrylic resins, epoxy resins, siliconized Versions of acrylic resins and epoxy resins and mixtures thereof. 12. The method according to claim 11, characterized in that the acrylic resin is an acrylic ester. 13. The method according to any one of claims 1 to 12, characterized by the following further step: lowering the temperature of the coated metallic substrate before applying the organic coating. 14. The method according to claim 13 _S, characterized in that the 5098U / 1 21 7 Temperature adjustment by cooling the coated metallic Substrate is made by contact with a surface of a roller. 15. The method according to any one of claims 1 to 14, characterized in that that the organic coating is applied by roller application will. 16. The method according to any one of claims 1 to 15, characterized by the following further step: applying a polymerizable organic top coat on the at least partially polymerized organic primer coating and polymerizing the organic topcoat and sealing off any remaining Polymerization of the organic primer coating. 17. The method according to any one of claims 1 to 16, characterized in that that the organic coating by the application of electron beams is polymerized. 18. The method according to any one of claims 1 to 16, characterized in, that the organic coating is polymerized by the application of ultraviolet radiation. 19. The method according to any one of claims 1 to 18, characterized in, that steel is used for the metallic substrate. 20. The composite article produced by the method according to any one of claims 1 to 19, characterized by a metallic one Substrate, through a zinc layer vapor-deposited onto the substrate in a vacuum, through a zinc layer vapor-deposited onto the zinc layer in a vacuum thin barrier layer made of a material which is selected from the group consisting of a metal, an alloy, an inorganic Contains mass and mixtures thereof, and by a firmly adhering layer of a weakly volatile organic mass, which at least is partially polymerized. S098U / 1217 21. The article according to claim 20, characterized in that the zinc layer has a platelet structure and a thickness of at least about 2.5 µm. 22. Object according to claim 20 or 21, characterized in that that the barrier layer ranges from a thickness sufficient to cover the zinc layer to a thickness in which the Zinc layer surface morphology is not significantly changed. 23. The object of claim 22, characterized. That the Barrier layer comprises aluminum. 24. The object of claim 22, characterized in that the barrier layer comprises silicon oxide. 25. The object of claim 23, characterized in that the aluminum barrier layer has a thickness of about 0.25 µm to 0.50 µm. 26. The article of claim 24 _S characterized in that the silicon oxide barrier layer has a thickness of about 0.38. to about 0.63 µm. 27. The article according to claim 23, characterized by a further barrier layer vapor-deposited onto the aluminum barrier layer in a vacuum made of silicon oxide. 28. The article of claim 27, characterized in that the aluminum barrier layer has a thickness of about 0.25 µm to about 0.50 µm and that the silica barrier layer has a thickness of from about 0.38 µm to about 0.63 µm. • 29. Object according to one of claims 20 to 28, characterized in that that a further organic layer is superimposed on the organic layer and that both organic layers polymerize are. 30. Object according to one of claims 20 to 29, characterized 5098U / 1217 indicates that the at least partially polymerized organic mass comprises a material which is selected from the group, those made from acrylic resins, epoxy resins, siliconized versions of acrylic resins and epoxy resins and mixtures thereof. 31. The object of claim 30, characterized in that the at least partially polymerized organic composition is an acrylic ester is. 32. The article of claim 20, characterized in that the metallic Substrate includes steel. 33. Article according to claim 20, characterized in that the at least partially polymerized organic layer has a thickness from about 3.8 µm to about 10.2 µm. 34. Object according to one of claims 20 to 33, characterized in that that the substrate is made of steel, that the zinc layer deposited in vacuo has a thickness of at least about 2.5 µm has that a vacuum deposited aluminum layer has a thickness of about 0.25 to 0.50 .um and that an at least partially polymerized acrylic ester coating a thickness of about 5.0 µm to has about 7.6 um. 35. Article according to claim 34, characterized by a polymerized A layer of an organic composition having a thickness of at least about 17.8 µm selected from the group consisting of consists of acrylic resins, polyester, siliconized versions of acrylic resins, and polyester, and mixtures thereof. 5098U / 1217 JW Blank page