KR20040068564A - Process for making angstrom scale and high aspect functional platelets - Google Patents

Abstract

The process for producing functional or decorative flakes or microplates comprises the steps of alternately applying a multilayer sandwich of deposited metal and release coat to a rotating cooling drum or a suitable carrier medium in a deposition chamber. The alternating metallization layers are applied by vapor deposition, and the intervening release layer is preferably a solvent soluble thermoplastic polymer material or a weakly crosslinked polymer material applied by the deposition source contained in the deposition chamber. The multilayer sandwich laminated in the vacuum chamber is removed from the drum or carrier and treated with a suitable organic solvent to dissolve the release coating from the metal in a stripping process that essentially leaves the metal flakes free of the release coat. The solvent and dissolved release material are removed by centrifugation to form a cake of concentrated flakes that can be air milled and released in the desired medium, and further sized and homogenized for end use in ink, paint or coating. . In one embodiment the final treated flake comprises a single layer thin film metal or metal alloy flake or flake of an inorganic material, and in another embodiment the flake is double-sided with a protective polymer coating applied from an appropriate vacuum deposition source, etc. in the deposition chamber. This is covered. The release coat material may be a radiation curable, low density crosslinkable deposited polymer material. By exposure to a high energy radiation source, the release material is essentially viscous and crosslinked with sufficient release material to produce a solvent soluble release coat layer. In one embodiment, the multilayer deposit passes from the deposition chamber through a vacuum lock, into a separate stripping chamber adjacent to the deposition chamber and is deposited on a seamless belt. The two chambers are maintained at a vacuum pressure below atmospheric pressure while depositing the flake material onto the seamless belt. The deposit reduces the speed of the belt and revolves the vacuum deposition source in the deposition chamber, thereby periodically sealing the deposit trapping device through the vacuum lock under the seamless belt in the stripping chamber to seal the stripping chamber. Removed. The vacuum lock is maintained at sub-atmospheric vacuum pressure in the stripping chamber during the performance of the process of removing the multi-layer deposited material from the seamless belt.

Description

Process for producing functional microplate with high aspect ratio of angstrom size {PROCESS FOR MAKING ANGSTROM SCALE AND HIGH ASPECT FUNCTIONAL PLATELETS}

Conventional aluminum flakes are produced in ball mills containing steel balls, aluminum metal, mineral alcohols, and usually stearic or oleic acid fatty acids. The steel balls are made flat of aluminum and crushed into flakes. When milling by the ball mill is complete, the slurry is passed through a mesh screen for particle sizing. At this time, flakes of size that cannot pass through the screen are returned to the ball mill for further processing. Appropriately sized flakes are passed through the screen into the filter press where excess solvent is separated from the flakes. The filter cake is then loosened with the added solvent. Such conventional aluminum flakes generally have a particle size of about 2 to about 200 μm and a particle thickness of about 0.1 to about 2.0 μm. These flakes are characterized by high diffuse reflectance, low specular reflectance, rough irregular flake microsurfaces and relatively low aspect ratios.

Another method of making metal flakes is Avery Dennison Corporation's method for making flakes sold under the trade name Metalure. In this method, both sides of the polyester carrier are gravure coated with a solvent-based resin solution. The coated dry web is then transferred to a metallizing facility where both sides of the coated sheet are metallized with the deposited aluminum thin film. The sheet with the metal thin film is then conveyed to a coating facility, where both sides of aluminum are coated with a secondary film of a solvent-based resin solution. The dried product of the coated metal sheet is transferred back to the metallization plant to cover the secondary film of aluminum deposited on both sides thereof. The multilayer sheet thus obtained is then transferred to a facility for further processing, in which the coating is stripped from the carrier in a solvent such as acetone. At this time, in the stripping process, the continuous layer is pulverized into particles contained in the slurry. The solvent elutes the polymer between the metal layers in the slurry. The slurry is then sonicated and centrifuged to remove the solvent and dissolved coating to yield a cake of concentrated aluminum flakes having a solid content of about 65%. The cake thus obtained is then released in a suitable vehicle and further sized to a flake of controlled size for use in inks, paints and coatings by homogenizing. The metal flakes prepared by this method for use in printable applications such as inks are characterized by having a particle size of about 4 to 12 μm and a thickness of about 150 to about 250 mm 3. Coatings made from these flakes have high positive reflectance and low diffuse reflectance. The flakes have a flat mirrored surface and a high aspect ratio. The coating also has a high level of application area per pound of flakes used, as compared to the case of metal flakes produced by other methods.

The flakes are also manufactured in a polymer / metal vacuum deposition process, which according to the process comprises an intervening layer of cross-linked polymer between the deposited aluminum layers, A thin layer of deposited aluminum is formed on a thin plastic carrier such as polyester or polypropylene. Typically, the crosslinked polymer layer is a polymeric acrylate deposited in the form of a vaporized acrylate monomer. The multilayer sheet material is crushed into multilayer flakes useful for optical properties. Coatings made from such multilayer flakes tend to have high diffuse reflectance and low forward reflectance. The flakes have a low aspect ratio and undesirable low opacity when made into ink.

The present invention is directed to a method of making angstrom sized flakes or microplates that can be used for both functional and decorative applications. Some of the flakes prepared according to the method of the present invention reach the nanoscale range. The flakes may be metal, metallic compounds, nonmetals or transparent flakes. Functional applications of the flakes include light of a particular wavelength to protect the pigment coating on which the flake layer is based, or a protective coating that can be added with some level of stiffness to form the desired specific properties for the finish coating by the flakes. Uses in protective coatings that can be used to block are included. Reflective metal flakes are useful for a variety of optical or decorative applications, including inks, paints or coatings. Other uses of flakes include microwave and electrostatic applications, along with chemical and biological applications.

1 is a schematic functional block diagram illustrating a prior art process for producing metal flakes.

2 is a schematic front view of a vacuum deposition chamber for applying a multilayer coating in a first embodiment of a process according to the present invention.

3 is a schematic cross-sectional view showing a series of layers in one embodiment of a multilayer sheet material according to the present invention.

4 is a schematic cross-sectional view illustrating a multilayer sheet material according to another embodiment of the present invention.

5 is a functional block diagram schematically showing the processing steps in the first embodiment of the present invention.

6 is a schematic cross-sectional view illustrating a single layer flake made by the process of the present invention.

7 is a schematic cross-sectional view of a multilayer flake made by the process of the present invention.

8 is a front view of a schematic showing a second embodiment for producing a metal flake of the present invention.

9 is a functional block diagram schematically illustrating a processing step for producing flakes from a multilayer material produced according to a second embodiment of the present invention.

FIG. 10 is a half schematic front view of a bell jar vacuum chamber. FIG.

11 is a half schematic side view of a vacuum chamber containing a rotating drum and heater block assembly.

FIG. 12 is a side view of the rotary drum and heated polymer vapor chamber shown in FIG. 11.

FIG. 13 is a half schematic side view illustrating a vacuum chamber and heater block assembly similar to FIGS. 11 and 12 in combination with a wire feed device for delivering polymer release coating material to a rotating drum surface in a vacuum chamber.

FIG. 14 is a side view of the rotary drum and heater block assembly shown in FIG. 13.

FIG. 15 shows one embodiment of a combination of wire feed mechanism and steam line for delivering a polymer release coating material to a vacuum chamber.

FIG. 16 is a side view of the heated polymer steam tube and rotating drum shown in FIG. 15.

15A and 16A illustrate alternative embodiments of the wire feed mechanism shown in FIGS. 15 and 16.

FIG. 17 is a half schematic side view illustrating a heated melt tube device for delivering a polymer based coating material to a vacuum chamber. FIG.

FIG. 18 is a side view of the heated polymer steam tube and rotating drum shown in FIG. 17.

FIG. 19 is a half schematic side view illustrating a process for making a carrier sheet material with a polymer release coating in accordance with the principles of the present invention.

20 is a half schematic front view illustrating a melt pump process for delivering a polymer release material to a vacuum chamber.

FIG. 21 is a semi- schematic side view illustrating a process for depositing a multilayer deposit and removing the multilayer deposit from a seamless belt in each vacuum chamber maintained at a vacuum pressure below atmospheric pressure.

FIG. 22 is a half schematic side view similar to FIG. 21 showing a deposit trapping device sealed with a stripping chamber.

FIG. 23 is a semi-schematic side view similar to FIGS. 21 and 22 but showing a series of additional steps of stripping the multilayer deposit from a seamless belt and collecting it in a closed collection device.

One of the objects of the present invention is that while the process of the present invention also reduces the manufacturing cost of other flake material, which will be described below, it reduces the manufacturing steps of high reflective metal flakes and consequently reduces the manufacturing cost.

In addition to metal flakes, glass (SiO ₂ ) flakes are applied for many industrial applications. Conventional glass flakes generally have a thickness of about 1 to 6 μm and a diameter of about 30 to about 100 μm. These glass flakes can be used for addition to polymers and coatings to enhance various functional properties. Examples include the addition of glass flakes as additives for making thinner and flatter coatings. Another object of the present invention is to produce very thin, flat and flat flakes, such as metal or glass flakes, for example to take advantage of the various functional properties of flakes in polymers, coatings and films.

Weinert, U. S. Patent No. 6,270, 840, describes a method of making metal flakes for the purpose of improving the method of removing vacuum deposited flake material from the deposition surface. The patent describes a method of applying flake material to an endless belt that passes through a deposition chamber and through a separate stripping chamber adjacent to the deposition chamber. In this method, the vacuum pressure in the deposition chamber is maintained at a level higher than the vacuum pressure in the adjacent stripping chamber, while the pressure in both chambers is kept below atmospheric pressure while using the flake material. The object of the method according to the invention is to reduce the energy costs associated with disrupting the process in any chamber, where the process of destroying the vacuum pressure and then pumping the chamber down to an effective vacuum pressure level may be required. . The deposition chamber is periodically opened to the atmosphere to remove the deposited material, for example to further process such as removing the material from the deposition surface to convert the material to flakes. The aforementioned Weinert process is a continuous process, which includes depositing a layer of flake material onto the seamless belt and then removing the belt from a stripping chamber in each passage of the belt through a deposition apparatus. In order to maintain this process in a continuous process, the stripping chamber is immersed in the solvent and dissolves the release material, the high pressure flake removal technique, the chamber for cleaning and collecting the flake material. A stripping station housed therein.

The present invention provides a semi-continuous process that allows a plurality of layers of flake material to be installed in a deposition chamber, and then periodically removes all at once by passing each of the multilayer deposits to the deposition chamber. It is an improvement of the Weinert process in adjacent individual vacuum stripping chambers. According to the present invention, before the plurality of flake material layers are removed from the adjacent chamber, the material layers can be deposited at high speed, and because the deposition process is continuously operated at a pressure below atmospheric pressure, energy costs and manufacturing time are reduced. Can be saved.

The invention includes a flake forming process that applies a multilayer film to a polymer carrier sheet, such as a thin, flexible polyester, or to a polished metal casting surface, such as a rotating metal drum. In either case, the process is carried out in a vacuum deposition chamber. In one embodiment, the multilayer film is applied to a polyester (PET) carrier sheet. The vacuum chamber is equipped with multiple deposition sources. The deposition source may be vaporization at high temperatures caused by resistance or heating by EB. Air is evacuated from the chamber and the wound PET film is released through the coating and deposition source while maintaining contact with the cooling drum. Alternating layers of material may be coated on the moving PET web. As an example, an organic solvent soluble deposited thermoplastic polymer release material (deposit thickness of about 100 to about 400 microns), followed by a metal layer such as aluminum (deposit thickness of about 5 to about 500 microns), followed by another layer of solvent soluble release material This formed thing is mentioned. Also, for example, inorganic compounds for the production of other metals, alloys or glass flakes may be used in place of aluminum. By reversing the web path, deactivating the secondary coating source and then repeating the first step, a plurality of layers can be coated on the PET without breaking the vacuum, thereby increasing productivity. By adding two deposition sources between the coating source and the metal deposition source, an additional protective layer can be coated on each side of the metal layers. To remove the sandwich from the PET, multilayer coated PET is introduced into an organic solvent stripping process. The polymer release coating material is dissolved by the organic solvent, leaving the deposited flake material essentially free of the release material. The solvent is then centrifuged to give a cake of concentrated flakes.

In another embodiment, the same coating and deposition technique as above is used to directly coat an alternating layer on a release coated cooling drum contained within a vacuum deposition chamber. The drum is rotated through a coating and deposition source to build up a multilayer sandwich of deposited thermoplastic release material and flake material in alternating layer form. The coarse may then be air-milled to produce flakes, with the introduction of a multilayer sheet into an organic solvent with or without proper agitation, or by grinding the multilayer sheet to further reduce particle size. It is made into rough flakes and then introduced into the solvent slurry so that the remaining layers can be separated. By removing the solvent by centrifugation, a cake of concentrated metal flakes can be prepared which essentially contains no release material. The cake of concentrated flakes or solvent and slurry of flakes can then be further sized and homogenized to suit the end use in ink, paint, plastic or coating by releasing the slurry in the desired medium.

Another embodiment of the invention includes a process for making a release coated heat resistant polymer carrier sheet in a vacuum deposition chamber. The carrier sheet may comprise a web of polyester (PET) as described above. The release coating comprises an organic solvent soluble thermoplastic polymer material deposited on a polyester carrier. The release coated carrier provides a flexible carrier having a flat surface upon which the flake material, such as metal or glass, is deposited to provide an effective release surface for producing angstrom sized flakes. The flakes become extremely thin and flat when released from the thermoplastic release coating through a suitable organic solvent.

Another embodiment of the present invention includes techniques for controlling the delivery of the deposited thermoplastic polymer release coating material to a vacuum chamber. These techniques include rotating drums, heater blocks and E-beam embodiments; Some embodiments include a wire feeding mechanism that is used to coat the polymer onto wires that feed into the vacuum chamber and heat to evaporate the polymer to deposit the polymer on a rotating drum or other carrier surface.

Another embodiment is the use of angstrom sized particles produced by the present invention, wherein the application of angstrom sized particles and the application of angstrom sized particles comprising flakes used to control the rate of water vapor delivery in the barrier material. Electrical applications include flakes that can be used to fabricate structures with extremely high capacitance.

According to another embodiment of the present invention, an apparatus and method for depositing multilayer flake material to remove the material from the deposition surface comprises a deposition chamber adjacent to the stripping chamber. The two chambers are separated by a vacuum lock so that a vacuum pressure that can be independently controlled in each chamber is maintained. The deposition surface, preferably in the form of a seamless belt, passes through the vacuum deposition chamber and passes through the vacuum lock into the stripping chamber. In another embodiment, the vacuum deposition chamber and the stripping chamber are both maintained at vacuum pressure below atmospheric pressure. The vacuum deposition chamber includes a multilayer deposition of the flake material layer and multiple deposition sources for covering the release coating layer deposited on the belt as the seamless belt passes through the deposition chamber. The belt must pass through the stripping chamber if the deposit is not removed from the belt upon stacking the multilayer deposition of the flake material and the release coating layer on the seamless belt.

The multilayer deposit is then periodically stripped from the belt in the stripping chamber using a flake layer stripping device, a device that strips the deposit and collects it for further processing into flakes. In one embodiment, the vacuum pressure in the stripping chamber is maintained at a vacuum pressure higher than the vacuum pressure in the deposition chamber but below atmospheric pressure.

In one embodiment of the present invention, the belt is run at high speed upon deposition of a flake and release coating layer on the seamless belt. In addition, when periodically stripping the multilayer deposits from the seamless belt, the speed of the belts is reduced when removing the deposits from the belts in the stripping chamber.

As such, although some techniques may be used to strip the multilayer deposit from the belt, in one embodiment the movable cradle is maintained in a vacuum housing at a vacuum pressure essentially the same as the vacuum pressure in the stripping chamber. . These cradles are sealed in a stripping chamber and remove the deposit from the belt through the stripping mechanism described above and collect it in the cradle. The cradle is then removed from the stripping chamber and the stripping chamber is sealed from outside using a vacuum lock so that the internal pressure remains below atmospheric pressure.

These and other aspects of the invention will be more fully understood by reference to the following detailed description and the accompanying drawings.

A better understanding of a particular aspect of the present invention is described with reference to FIG. 1, which is a prior art for the manufacture of metal flakes according to a process currently utilized by Avery Dennison Corporation to manufacture flakes sold under the trade name Metalure. The process of technology is shown. According to this prior art process, in step 12, both sides of the polyester carrier sheet 10 are gravure coated with the solvent-based resin solution 14. The coated web dry matter is then transferred to a metallization installation 16 where both sides of the coated and dried carrier sheet are metallized with a thin film of deposited aluminum. The multilayer sheet thus obtained is then transferred to a facility for further processing in step 18, where the coating is stripped from the carrier in a solvent such as acetone to form a solvent-based slurry 20 that dissolves the coating from the flakes. Next, the slurry is sonicated and centrifuged to remove cake 22 of concentrated aluminum flakes by removing acetone and dissolved coating. The flakes are then released in a solvent and the particle size is controlled by homogenization treatment or the like in step 24.

This process has proved very successful in producing extremely thin metal flakes with high aspect ratios and high specular reflectances (the aspect ratio is the ratio of average particle size divided by average particle thickness). Although this metalure process is successful, a reduction in manufacturing costs is desired because the manufacturing costs are increased in order to repeatedly transport the coated web between the gravure coating and the metallization plant. There is also a manufacturing cost problem associated with the inability to reuse the PET carrier after stripping.

2-5 show one embodiment of a process for producing the metal flakes shown in FIGS. 6 and 7. This process can also be used for the production of glass flakes described below, and can also be used for the production of nanospheres as described below. FIG. 2 shows a vacuum deposition chamber 30 containing a suitable coating and metallization device for manufacturing the multilayer coating flake 32 of FIG. 7. Alternatively, the specific coating apparatus in the vacuum chamber of FIG. 2 may not be operated to produce the single layer flake 34 of FIG. 6, as will be apparent from the description below.

Referring to FIG. 2, vacuum deposition chamber 30 includes a vacuum source (not shown) used in a conventional manner for evacuation of such deposition chambers. The vacuum chamber also preferably includes an auxiliary turbopump (not shown) for maintaining the vacuum at the required level in the chamber without breaking the vacuum. The chamber also includes a polished cooled metal drum 36 in which a multilayer sandwich 38 is fabricated on the surface. First, an embodiment of the present invention is described with respect to the manufacture of the flakes 32 shown in FIG. 7, which in one embodiment is a protective coating bonded to both the inner metallized film layer 40 and the metal film both sides. An outer layer 42. The protective coating may comprise an inorganic material or a polymer material, both of which are deposited under vacuum.

The vacuum deposition chamber is circumferentially spaced around the drum to apply the solvent soluble or soluble release coating, the protective outer coating, the metal layer, the additional protective outer coating on the metal layer and the additional release layer in this order to the drum. Suitable coating and deposition sources apart. More specifically, the sources of these coating and deposition apparatus housed within the vacuum deposition chamber are (see FIG. 2) a release system source 44, a first protective coating source 46, a metallization source 48 and a second protective Coating source 50. These coatings and / or deposition sources may be laminated with thin layers as the drum rotates, for example sequentially: multi-layer coating sandwich 36 such as release-coating-metal-coating-release-coating-metal-coating-release and the like. Spaced in the circumferential direction around the rotating drum to form a. This sequential layer stacked in the multilayer sandwich 38 is schematically shown in FIG. 4, and also the drum 36 as the carrier in that case.

In one embodiment, the release coating can be formed as a flat, uniform barrier layer that is solvent soluble or soluble, separating the metal or glass flake layers from each other, and depositing an intervening metal or glass flake layer. To provide a flat surface, which may later be separated by dissolution or the like when the metal or glass flake layers are separated from each other. The release coating is a dissolvable thermoplastic polymer material having a glass transition temperature (Tg) high enough to prevent the previously deposited release layer from melting due to the heat of condensation of the deposited metal layer (or other flake layer). The release coating must be able to withstand the heat of condensation of the vaporized metal or glass flake layer as well as the ambient heat in the vacuum chamber. The release coating is applied in layers to insert various materials and stacks of materials so that they can later be separated by solubilizing the release layer. The release layer is preferably as thin as possible because the thin layer is relatively soluble and leaves less residue in the final product. In addition, compatibility with various printing and paint systems is desired. The release coating is solvent soluble, soluble in organic solvents, preferably thermoplastic polymers. In a preferred embodiment, the release coating source 44 may comprise a suitable coating apparatus for applying the polymer material as a hot melt layer or for extruding the release coat polymer directly into the drum, although the release coating apparatus may comprise a suitable monomer. Or a deposition source for vaporizing the polymer to deposit on the drum or sandwich layer surface. Various examples of deposition apparatus for applying the polymer release coat to the deposition surface are described below. The release material condenses and solidifies upon contact with the cooled drum or upon contacting the multilayer sandwich previously stacked on the cooled drum. The multilayer film laminated on the drum has a sufficient thickness so that the drum cooled through the film can take off sufficient heat to effectively solidify the release coat deposited on the outer surface of the metal or glass flake layer. Another polymer release coating material may be a weakly crosslinked polymer coating that is not soluble but swells in a suitable solvent to separate from the metal or glass flake material. In addition, the soluble release material may comprise a polymer material polymerized by chain extension rather than crosslinking.

Preferred polymer release coatings in the present invention are styrene polymers, acrylic resins or blends thereof. If the cellulosic material can be coated or evaporated without adversely affecting the release properties, it may be a suitable release material.

Preferred organic solvents in the present invention for dissolving the polymer release layer include acetone, ethyl acetate and toluene.

Following the application of the release coating with reference again to the flake manufacturing process illustrated in FIG. 2, the drum passes through a first protective coating source 46 to apply a protective layer to the release coat. This protective layer may be a deposited functional monomer, such as an acrylate or methacrylate material, which is then cured by EB radiation or the like for crosslinking or polymerization of the coating material; Alternatively, the protective material may be a thin layer of radiation cured polymer that can later be disassembled and flaked. Alternatively, the protective layer can be a deposited inert material, insoluble inorganic material or glass flake material forming a rigid transparent coat that bonds to both sides of the metal layer. Preferred protective coatings are rigid, impermeable materials that can be deposited in alternating layers of metal, such as aluminum, to provide some level of wear resistance, weathering protection, and resistance to water and acids. Examples of such protective materials are described below.

The rotating drum then transfers the coating through metallization source 48 to deposit a layer of metal, such as aluminum, on the coating layer. A number of metal or inorganic compounds may be deposited as thin films so that other materials and release layers can be inserted and later separated within the thin metal flakes. In addition to aluminum, such materials include copper, silver, chromium, nichrome, tin, zinc, indium, zinc sulfide, and the like. The metal coating can also include an optical filter made by the deposition of a multi-directional reflection enhancing stack (layer of highly reflective material) or a suitable layer with controlled thickness and refractive index.

The rotating drum then transfers the stack through the second coating source 50 to reapply a similar protective coating layer to the metallized film, such as by deposition and curing of a hard protective polymer material or deposition of an inorganic material.

The rotation of the drum then transfers the sandwich material through a release coat source, etc., in sequence, again in a complete circle, to deposit the coated metal layer.

Inorganic materials such as oxides and fluorides may also be deposited by the deposition source 48 to produce a thin layer that can separate to form flakes. Such coatings include magnesium fluoride, silicon monoxide, silicon dioxide, aluminum oxide, aluminum fluoride, indium tin oxide and titanium dioxide.

Suitable deposition sources include EB, resistive, sputtering and plasma deposition techniques for depositing thin coatings of metals, inorganic compounds, glass flake materials and polymers.

When a multilayer sandwich is produced in the vacuum chamber, the multilayer sandwich is removed from the drum and in a state in which further processing illustrated in FIG. 5 can be performed.

A continuous process of laminating the multilayer sandwich is shown in step 52 of FIG. The multilayer sandwich is then stripped from the drum in step 54 by a process in which the layers separated by the release material are broken down into individual layers. The sandwich layer can be introduced directly into the organic solvent or stripped by compression and grinding or scraping. In the illustrated embodiment, the multilayer sandwich is milled in step 56 to produce coarse flakes 58. The coarse flakes are then mixed with a suitable solvent in slurry 60 to dissolve the release coat material from the surface of the multilayer flakes 32. Alternatively, the multilayer sandwich is separated into individual layers by step 63 of introducing the material stripped from the drum to form a layer directly into the solvent in step 60. The release coat material applied in the vacuum deposition chamber is selected so that it can be dissolved from the flakes by the solvent in the slurry process. In one embodiment, the slurry is subjected to centrifugation step 61 to remove solvent or water to form a cake of concentrated flakes. The cake of concentrated flakes can then be released in the desired medium in the particle size control step 62 to be further sized and homogenized for end use such as for example ink, paint or coating. Alternatively, the flakes are released in the solvent (without centrifugation) and the particle size is controlled in step 62.

As another processing technique, the multilayer sandwich can be removed from the drum and " air " milled (must use an inert gas to prevent ignition or explosion), or it can be reduced to small particle size and then processed in a two stage solvent process. have. The first step begins with a swelling process in which a small amount of solvent is used to dissolve the release coat layer. A second, different solvent is then added as a finishing solvent to complete the release coat dissolution process and increase compatibility with the final ink or coating. This process avoids subsequent centrifugation and homogenization steps.

In an alternative embodiment utilizing the vacuum chamber 30 of FIG. 2, the protective coating sources 46, 50 can be omitted and the process of manufacturing the single layer flake 34 illustrated in FIG. 6 can be used. have. In this case forming several layers on the surface of the drum 36 for forming the multilayer sandwich 38 is a continuous layer such as release-metal-release-metal-release as illustrated in step 64 of FIG. It includes. Alternatively the single layer flake may comprise a layer of inorganic or glass flake material, as described above.

It is possible to build a number of different materials and stacks of materials that are sandwiched by the soluble release layer so that they can be separated from each other by dissolution of the release material. Examples of such structures are; (1) release / metal / release; (2) release / protective layer / metal / protective layer / release; (3) release / nonmetallic layer / release; And (4) release / multi-directional reflection enhanced stacks / releases and the like.

8 and 9 show another process for producing the flakes illustrated in FIG. 6 or 7. In the embodiment illustrated in FIG. 8, the process apparatus extends from the first reversible winding station 72 to the second reversible winding station 73 around a predetermined length of the cooled rotating drum 68 and drum surface. And a deposition chamber 66 containing an elongate insoluble polyester carrier film 70. The length surrounding the drum surface is controlled by two idle rollers 74. The vacuum chamber also includes a standard vacuum pump and an auxiliary turbopump to maintain the degree of vacuum during the coating. The rotation of the drum causes the polyester film to form a first release coat source 76, a first protective coating source 78, a metallization source 80, a second protective coating source 82 and a second release coat source 84. Proceeds in the order of). Thus, as the drum rotates counterclockwise with respect to FIG. 8, the total length of the polyester carrier is released from the station 72 and subsequently passed through the coating process from the sources 76, 78, 80, 82, 84 and then the station. Coiled at (73). The polyester carrier then reverses the web path and deactivates the second release coating source 84 and then repeats the first step, this time in reverse order such that the coating is applied sequentially from the sources 82, 80, 78, 76. Winding again). Next, the entire PET coated film is wound on a station 72 and then in the same order as used for the manufacture of the multilayer sandwich 38 of FIG. 4 (and the resulting coated metal flakes 32 of FIG. 7). The sequence of steps is repeated to laminate the layers.

As an alternative, if it is necessary to produce a single layer metal or glass flake as shown in Fig. 6, the protective coating sources 78 and 82 are deactivated, thereby making the multilayer sandwich 64 shown in Fig. 70).

9 shows the treatment of a multilayer coated sandwich 86 deposited on a polyester film that is removed from the vacuum chamber 66 and introduced into the organic solvent stripping process of step 88 to remove the sandwich material from the PET. The solvent is then centrifuged to form a cake of concentrated flakes 90 which is subsequently subjected to particle size control (homogenization) in step 92.

Suitable carriers on which the multilayer sandwich material can be deposited must ensure the deposition of a flat, flat thin layer. With metal drums, belts or plates, which may be stainless steel or chrome plated, polyester films or other polymer films with high tensile strength and durability against high temperatures can be used.

In one embodiment of the invention, a polymer release coat is applied for the purpose of facilitating later separation of the flake layer laminated to the multilayer sandwich material. The use of a crosslinked polymer layer bonded between deposited metal layers in a polymer / metal deposition process in the prior art inhibits the later metalization layer from separating into flakes. Polymerization of the polymer layer by EB hardening or the like prevents subsequent redissolution of the polymer layer, so that the aluminum flake layer is not easily separated. In the process of the invention, intervening polymer layers are vaporized and deposited while the vacuum deposition chamber is in a vacuum. The polymer release material is preferably a flowable low viscosity, relatively low molecular weight, very clarified thermoplastic polymer or monomer that is essentially free of volatiles that can occur during the coating process. Such materials are preferably not blends of different polymer materials, including additives, solvents, and the like. When the polymer material is heated to its melting temperature, coating temperature or deposition temperature, continuous operation of the vacuum pump in the vacuum chamber is not adversely affected by volatile materials. Preferred release coat materials promote intercoat separation between alternately formed vacuum deposited metal layers or glass flake layers or multilayer flake layers. The release layer achieves this object by the property of being soluble in a suitable organic solvent. The release material is also capable of EB vaporization as well as metallization and requires sufficient adhesion to allow stack stacking on the rotating drum. Preferred release coat materials should have a molecular weight or high enough resistance to melting to withstand heat buildup without becoming flowable on drums or other carriers. The heat accumulation not only originates in the metal deposited on the release layer but also in the implementation of the deposition source inside the chamber. The ability of the release coat to withstand flowability can ensure that high brightness flakes can be made because the release coat surface on which the metal is deposited remains flat. The release material must also be one capable of withstanding the heat of the EB deposition process. It should also not be a material that adversely affects the vacuum pressure maintained in the chamber, such as certain materials of low molecular weight, i. In order to maintain the production rate without breaking the vacuum it is necessary to maintain a minimum working vacuum in the chamber. Essentially all release coat material must be removed from the flakes during the subsequent stripping and processing with organic solvents. However, if some small amount of release coat material remains on the flakes even after the flake layer has loosened into particles, the system will withstand some residues from the release coat, especially if the flakes are subsequently used in a compatible acrylic ink or coating system. Can be.

Referring to the embodiment of FIG. 2, a multilayer sandwich is produced by applying the coating directly to a rotating drum, which is a preferred process since it costs less to manufacture than coating a PET carrier. Each such cycle includes breaking the vacuum, taking the sandwich out for further processing outside the vacuum chamber, and then redrawing the vacuum. The speed at which the process can run in stacking layers can vary from about 500 to 2,000 feet per minute. Only metallization in vacuum can be operated at high speed.

In embodiments where monolayer flakes are made, the flakes may have a high aspect ratio. This is due in part to the ability to cleanly remove the intervening release coat layer from the metalized flakes. In thermosetting or crosslinked polymer layers bonded between metal layers, the layers cannot be easily separated and the flakes obtained have a low aspect ratio. In one embodiment, the process of the present invention produces single layer reflective aluminum flakes having a thickness of about 5 to 500 microns and a particle size of about 4 to 12 microns.

The release coat material is applied in extremely thin layers, from about 0.1 to about 0.2 μm for the coated layer and from about 100 to 400 microns for the EB deposited layer.

In an embodiment in which the metal flake is coated on the opposite side of the protective polymer film layer, the protective coating layer is applied to a thickness of about 150 GPa or less. Preferred protective coating materials are silicon dioxide or silicon monoxide and may be aluminum oxide. Other protective coatings may include aluminum fluoride, magnesium fluoride, indium tin oxide, indium oxide, calcium fluoride, titanium dioxide, and sodium aluminum fluoride. Preferred protective coatings are those in which the flakes are compatible with the ink or coating system ultimately used. When the protective coating is used on metal flakes, the aspect ratio of this multilayer flake is still higher than the aspect ratio for conventional flakes, but will reduce the aspect ratio of the final flake product. However, the flakes are more rigid than single layer flakes, and this stiffness provided by clean glassy coated metal flakes is in some cases fluidized bed chemicals that directly apply a particular optical or functional coating to the flakes. The coated flakes are useful for deposition (CVD) processes. OVD coating is one example. CVD coatings can be added to the flakes to prevent the flakes from being attacked by other compounds or water. Colored flakes, such as flakes coated with gold or iron oxide, can also be prepared. Other uses of coated flakes include waterproof flakes in which metal flakes are encapsulated in an outer protective coat, and microwave active applications in which encapsulation of the outer coat inhibits arcing from metal flakes. Flakes can also be used in electrostatic coatings.

In yet another embodiment, it may be the case that the release coat layer comprises certain crosslinked resin-based materials, such as acrylic monomers crosslinked to solids by UV or EB curing. In this case, the multilayer sandwich is treated with a specific material that is removed from the drum or de-polymerizes the release coat layer by cutting off the chemical bonds formed from the crosslinking material while on the carrier. This process can use conventional devices utilizing deposition and EB-enabled curing or plasma techniques.

The process of the present invention enables the production of reflective flakes at high production speeds and low cost. Uncoated flakes prepared by the present invention may have a high aspect ratio. If the aspect ratio is defined as the ratio of particle size to thickness, and the average flake size is about 6 μm × 200 mm 3 (1 μm = 10,000 mm 3), the aspect ratio 60,000 / 200 is about 300: 1. This high aspect ratio is comparable to the aforementioned Metalure flakes. For embodiments where the flakes are coated on both sides with a protective layer, the aspect ratio of these flakes is about 60,000 / 600 or about 100: 1.

Embossed flakes can also be produced by the process of the invention. In this case, the carrier or deposition surface (drum or polyester carrier) may be embossed in a holographic or diffraction grating pattern or the like. The first release layer copies the pattern and the subsequent metal or other layer and the intervening release layer will duplicate the same pattern. The stack can be stripped and broken down into embossed flakes.

One process for accelerating the production of flake products made by the present invention utilizes three side by side vacuum chambers separated by air locks. The central chamber houses the drum and the deposition apparatus required to apply a layer of flake material and release coat to the drum. Once the deposition cycle is complete, the drum and coating are transferred from the deposition chamber to the vacuum chamber downstream via the airlock to maintain the vacuum in both chambers. The central chamber is then sealed. The drum housed in the upstream chamber is then moved to the central chamber for further deposition. This drum is moved through the airlock to maintain vacuum in both chambers. Next, the central chamber is sealed. The coated drum in the downstream chamber is removed, and the deposition layer is stripped and cleaned and replaced in the upstream chamber. This process allows for continuous coating in the central vacuum chamber without breaking the vacuum.

Example 1

The following multilayer structure was made: release layer / metal layer / release layer. The release layer was a Dow 685D extrusion grade styrene resin and the metal layer was aluminum, 90101E-AL000-3002 manufactured by Materials Research Corp.

The configuration was repeated 50 times. That is, alternating layers of aluminum and styrene release coat were formed.

The styrene pellets used in the release layer were adjusted as follows:

The styrene pellets were melted and heated in a vacuum oven at 210 ° C. for 16 hours and then transferred to a desiccator for cooling.

This material was contained using a graphite crucible coated with aluminum foil.

This graphite crucible was placed in a copper clad Arco Temiscal single pocket electron beam gun hearth.

Aluminum pellets were melted into a copper coated Arco Temiscal 4 pocket electron beam gun hearth.

The electron beam gun was part of a 15 KV Arco Temiscal 3200 load-lock system. A 2 mil PET film from SKC was cut into three circles 17 inches in diameter and attached to a 17 inches diameter stainless steel satellite disk located in a vacuum chamber. The chamber was closed, roughened to 10 μm and cryopumped to a vacuum of 5 × 10 −7 Torr.

The release material and the metal material were deposited alternately. The release layer was first deposited at 200 Hz as measured by the Inficon IC / 5 deposition controller. Similarly, a metal layer deposited at 160 Hz, as measured by the IC / 5 controller, was formed following the release layer. The controller for the aluminum layer was calibrated with a MacBeth TR927 transmission densitometer with green filter. As described above, this configuration was repeated 50 times. The deposited aluminum layer had a good thickness of 1.8 to 2.8 optical density as measured by MacBeth densitometer. This value represents the metal film opacity through the light transmission reading.

When the deposition was complete, nitrogen was used to evacuate the chamber to ambient pressure and to remove the PET disk. The disc was washed with ethyl acetate and then used with an IKA Ultra Turrax T45, measured on an Image-pro plus image analyzer using a 20X objective lens and averaged from a set of 400 particles to reach a particle size of 3 × 2 μm. Homogenization.

Next, ink was made from the dispersion and applied onto Lenetta cards for ACS spectrophotometer testing. This test measures flake brightness. ACS values above about 68 are considered desirable for this particular product. ACS readings were 69.98 for the Metalure control and 70.56 for the batch. The ink was applied to a clean polyester surface and the density read as a result of 0.94 for the batch and 0.65 for the Metalure control. Readings were made on a MacBeth densitometer using a green filter.

Example 2

The following multilayer structures were made: release layer / protective coat / metal layer / protective coat / release layer.

Three separate structures were created as follows:

Structure 1

Release Layer Dow 685D

Protective Coat Cerac Silicon Oxide S-1065

Metal Layer Materials Research Corp. 90101E-AL000-3002

Protective Coat Cerac Silicon Oxide S-1065

Release Layer Dow 685D

Structure 2

Release Layer Dow 685D

Protective Coat Cerac Aluminum Oxide A-1230

Metal Layer Materials Research Corp. 90101E-AL000-3002

Protective Coat Cerac Aluminum Oxide A-1230

Release Layer Dow 685D

Structure 3

Release Layer Dow 685D

Protective Coat Cerac Magnesium Fluoride M-2010

Metal Layer Materials Research Corp. 90101E-AL000-3002

Protective Coat Cerac Magnesium Fluoride M-2010

Release Layer Dow 685D

The configuration was repeated 10 times in the same process as described in Example 1 and evaluated as a protective coating flake. That is, as a result of this test, a layer of flake material on a carrier is laminated under vacuum between intervening layers of soluble release material, while the flake layer is continuously deposited while depositing the release layer and the flake layer from a deposition source operated in a vacuum chamber. It has been shown that multilayer flakes having optical utility can be prepared by laminating (without breaking vacuum) and then by stripping and controlling particle size.

Example 3

The following multilayer structure was created:

Structure 1

Release Layer Dow 685D

Nonmetallic Silicon Oxide S-1065

Release Layer Dow 685D

Structure 2

Release Layer Dow 685D

Stacked Titanium Dioxide Cerac T-2051

Stacked Silicon Dioxide Cerac S-1065 + Oxygen

Metal Layer Materials Research Corp. 90101E-AL000-3002

Stacked Silicon Dioxide Cerac S-1065 + Oxygen

Stacked Titanium Dioxide Cerac T-2051

Release Layer Dow 685D

The above configuration was repeated 10 times in the same process as described in Example 1. As a result of this test, the deposition process can form a stacked layer of an optical stack between release coat layers interposed in a vacuum chamber, which is then useful for applications such as inks and coatings by controlling stripping and particle size. It was shown that the flakes having have been obtained.

Example 4

The following structures may be possible structures for decorative flakes:

Structure 1

Release Layer Dow 685D

Stacked Iron Oxide Cerac I-1074

Stacked Silicon Dioxide Cerac S-1065 + Oxygen

Stacked Iron Oxide Cerac I-1074

Release Layer Dow 685D

Structure 2

Release Layer Dow 685D

Stacked Iron Oxide Cerac I-1074

Stacked Silicon Dioxide Cerac S-1065 + Oxygen

Metal Layer Materials Research Corp. 90101E-AL000-3002

Stacked Silicon Dioxide Cerac S-1065 + Oxygen

Stacked Iron Oxide Cerac I-1074

Release Layer Dow 685D

The structure may also be used for gonio chromatic shift.

Example 5

The polymer release coat layer was deposited in a vacuum chamber using an EB source and coated with the deposited aluminum layer.

I created the following structure:

Structure 1

Dow 685D styrene resin was heated in an oven at 210 ° C. for 16 hours. The material is EB deposited on the polyester at a thickness of 200-400 mm 3, metalized with one layer of aluminum with a density of 2.1-2.8.

Structure 2

Piolite AC styrene / acrylate from Goodyear was heated at 190 ° C. for 16 hours. The material is EB deposited on the polyester to a thickness of 305 mm 3, metalized with one layer of aluminum at a density of 2.6.

Structure 3

BR-80 acrylic copolymer manufactured by Dianol America was heated at 130 ° C. for 16 hours. The material is EB deposited on the polyester to a thickness of 305 mm 3, metalized with one layer of aluminum at a density of 2.6.

Structure 4

Dow 685D styrene resin was heated at 210 ° C. for 16 hours. The material is EB deposited on the polyester to a thickness of 200 mm 3, metalized with one layer of aluminum at a density of 2.3. This process was repeated to form a separate 10 layer aluminum stack by interposing a release coat layer.

The materials forming these layers were stripped from the PET carrier using ethyl acetate solvent and scaled down to controlled particle size in a T8 laboratory homogenizer. The obtained flakes were similar in optical properties to metal flakes in terms of similar brightness, particle size, opacity and aspect ratio.

In a further test using a structure similar to structure 1, aluminum metallized to optical density 2.3 was stripped from the PET carrier in acetone and crushed into flakes. In this test, the effect of varying the release coat thickness was observed. The test results showed the best release properties in the EP deposited release coats ranging from about 200 to about 400 mm 3.

Example 6

Several tests were conducted to determine various polymer release coat materials that may be useful in the present invention. Laboratory Bell Jar tests were conducted to determine polymers that could be EB deposited. Good results were obtained using methyl methacrylate (Elvacite 2010 manufactured by ICI) and UV cured monomer (39053-23-4 manufactured by Allied Signal). Poor results were observed using butyl methacrylate (Elvacite 2044) (vacuum lost at EB), cellulose (turned black at 230 ° F.) and polystyrene rubber (carbonized).

Example 7

The test described in Example 1 showed that a release coat made of Dow 685D styrene polymer could form usable flake products. Several different tests were conducted using the Dow 685D styrene resin release coat as follows:

(1) The conditions were adjusted to 190 DEG C and coated with 1,000 Pa and metallized with aluminum. The resin film was laminated too high to form an opaque metallization layer.

(2) the conditions were not met in the oven; The E-beams moved the beads in the crucible when attempting to EB melt the styrene beads.

(3) The mixture was coated with 75 to 150 kPa under conditions of 210 ° C. and then metallized. The stripping of aluminum was poor or not stripping at all.

(4) The coating was carried out at 210 DEG C at 600 DEG C and the aluminum monolayer was metallized to a density of 1.9. The aluminum was slowly stripped to obtain flakes with curls.

According to the present invention, a thin decorative and functional microplate made of a single layer or a multilayer material having a single layer having an average outer dimension of about 0.01 to 150 µm and having a thickness of about 5 to 500 mm 3 and a multilayer of about 10 to 2000 mm 3 is provided. It can manufacture. The flakes or particles produced by the process of the present invention are called angstrom scale particles because they are useful flake materials that can be made with the aforementioned low angstrom range thickness. Some particles produced by the present invention can be regarded as nanoscale particles. As is well known, 10 Hz is 1 nm and the nanoscale range is generally 1 to 100 nm. Thus, some of the angstrom scale particles (thickness and / or particle size) according to the invention fall within the nanoscale range.

These particles may themselves be used as functional platforms or may be coated with other active materials. These particles may be mixed in other materials or coated on other material surfaces. As mentioned above, these particles are prepared by depositing a material or layer of material such that a polymer release layer is inserted into a single layer or multilayer microplate. The support system for this layer sandwich can be a plate, film, belt or drum. The functional material can be applied by a PVD (Physical Deposition) process, and the release layer can also be applied by PVD.

Once the sandwich layer with the release layer is inserted, the material can be removed from the support system and the functional layers can be separated from the release layer. This can be done cryogenically using a suitable solvent or supercritical fluid. The resulting material is turned into a microplate and can be sized by grinding, homogenization, sonication or high pressure impact.

By centrifugation or filtration, a cake, slurry or dry material is obtained. Other active materials may be added to the particles via CVD, or other active materials may be reacted with materials such as silanes to promote adhesion. The material may then be mixed or coated onto the surface of such material, for example, for paint, coating, ink, polymer, solids, solutions, films, fibers, or gels for functional use.

Various angstrom scale flake structures according to the present invention include: (1) aluminum, alloy and other metal (described below) single layer flakes; (2) monolayer dielectrics, inorganic flakes or crosslinked polymer flakes; (3) multilayer inorganic compounds; (4) optical stacks; (5) inorganic flakes or organic / metal / inorganic flakes or organic multilayer flakes; (6) metal / inorganic / metal flakes; And (7) CVD or chemically reacted surface coating flakes.

The use of these nanoscale particles and particles having a high aspect ratio is as follows.

Optical aesthetic

Materials having a high aspect ratio can provide a metallic effect with high brightness as well as a coloring effect. The manufacture of these materials includes metals such as aluminum, silver, gold, indium, copper, chromium or alloys and aluminum-copper, copper-zinc-silver, chromium-nickel-silver, titanium nitride, titanium zirconium nitride and zirconium nitride. Metal combinations may be used. Sandwiches of metal and dielectric materials can produce a variety of colors and effects. Inert materials can be used as the outer layer to protect the inner layer from oxidation and corrosion. Some examples of sandwiches are SiO / Al / SiO, MgF / Al / MgF, Al / SiO / Al, Al / MgF / Al, and the like, but various other combinations are possible. Flakes of metal or metal oxides can be used as a base to attach both organic and inorganic materials that provide a pigmented color.

Optical function

Particles with a high aspect ratio of nanoscale may have many applications that utilize optical properties. Particles such as aluminum oxide, titanium dioxide, zinc oxide, indium tin oxide, indium oxide and the like may be bonded to the coating and polymer to reflect, scatter or absorb UV and IR light. In addition, phosphorescent and fluorescent materials can be used to produce other important effects.

Mechanical properties

To enhance the properties of these particles, these particles can be combined or applied to surfaces in the material. Particles of silicon monoxide, aluminum dioxide, titanium dioxide, and other dielectrics can be incorporated into the material to improve properties such as flame retardancy, dimensional stability, abrasion and abrasion resistance, water vapor permeability, chemical resistance, and stiffness.

chemistry

Active materials can be applied to the surface of these particles to provide a slightly higher surface area that can be incorporated into chemical treatment. These particles with high surface areas are ideal for catalysts. It may be a flake made to support the microplate or the active coating of the active material. Examples of active materials are platinum, palladium, zinc oxide, titanium dioxide, silicon monoxide and the like. Flakes made of a metal (lithium) doped material can be used in the battery.

Electrical properties

Electrical properties can be imparted to various materials by combining particles of various materials as single and multiple layers to achieve conductivity, capacitance, EMI and RFI. Absorption, transmission and reflection of microwave and radar energy can be controlled by coating or mixing metal particles or metal dielectric sandwiches. Superconducting materials, such as magnesium boride, can also be made of angstrom scale particles.

Biological properties

The active material can be effectively delivered to the surface by forming an antifungal or antibacterial coating on these thin microplates and then binding to the ink and coating.

Nanoparticles

Nanoparticles can be produced by depositing flake material as discrete particles. In the industry, it is well known that nucleation and film growth play an important role in the formation of high quality PVD coatings. During the initial deposition, as the deposition continues, nuclei grow in size and number. As the process continues, these islands begin to combine with each other in the channel which will later be filled to form the final continuous film. To make nanoparticles, the coating process only reaches the island stage before the next layer of release material is applied. This allows small particles to be trapped between the release layers in the multilayer structure described below. The particles can later be released by dissolving the release material using a suitable solvent.

Another process for making nanoscale particles is to produce flake materials up to 50 mm 3 and then reduce the particle diameter in a second operation.

Use of Flake Materials in Coatings

Flakes material for use in this application were introduced into the coating according to the following procedure:

The various material compositions of the material were converted to flake form. The converted flakes were then bound in the media on a surface area basis.

Medium composition:

Toluene 28 pts

Isopropanol 28 pts

Methyl ethyl ketone 28 pts

Elvacite 2042 16 pts

The net weight of the flakes used in this example was determined by deriving from the thickness and density of the compounds. This induction was used to study the effects of the compounds. The flakes were applied in slurry form in acetone. The first step in the process was to determine the weight percentage of solids. After finding the solids, the amount of slurry material to be used can be determined by the table below.

material density Flake thickness Dry flakes per 100 g of media solution Percent solids in slurry Weight to be used per 100 g of media solution Titanium dioxide 4.26 200Å 0.09 g Titanium monoxide 4.93 200Å 0.08 g Silicon dioxide 2.2 200Å 0.20 g Silicon monoxide 2.13 200Å 0.20 g Aluminum oxide 3.97 200Å 0.10 g Indium oxide 7.13 200Å 0.06 g Indium tin oxide 4.48 200Å 0.09 g Zinc oxide 5.6 75Å 0.03 g indium 7.3 200Å 0.06 g Magnesium fluoride 3.18 200Å 0.13 g silicon 2.33 200Å 0.16 g

The flakes were mixed into the medium at the appropriate weight. The slurry was then coated onto a 0.002 inch thick gloss polyester film with a final coating thickness of 2.6-3.0 g / m 2. The coating was left to dry and tested in the following two ways.

Thermal reflectivity evaluation method:

The prepared coating was transferred to the surface of a rigid polyvinylchlorolide (PVD) sheet decorated with EF18936L using heat and pressure. After transfer, the polyester film was removed. Panels of 3 inch size were prepared using blanks (media without flakes) and test flakes. These panels were then evaluated using the ASTM D4809-89 method to predict heat accumulation in the PVC laminate product. Results were reported for both blank and test flake panels.

UV protection rating method:

A film comprising the following materials was coated on a rigid PVC sheet to make a basic test sheet:

Color coat I80126 medium 59.5 pts

I80161 white dispersion 27.0 pts

I8980 Isoindolinone Yellow Dispersion 5.4 pts

MEK methyl ethyl ketone 8.1 pts

Application to 0.002mil glossy polyester using two 137HK printing plates

Size L56537

Application after color coat using one 137HK printing plate

Blanks and slurries are prepared on polyester as in the previous method and transferred to the panels described above. Both blank and test plate panels are placed in a Sunshine Carbon Arc (Atlas) weatherometer installed on the Dew Cycle protocol. Initial gloss and color are read and recorded every 500 hours of operation.

The multilayer particle release layer can be prepared from conventional organic solvent based polymers deposited by PVD processes. Various different materials can be used, such as polymers, oligomers, monomers, and the like. These materials can be evaporated by electron beam, sputtering, induction and resistance heating.

One of the difficulties with using bulk polymers in this process is the problem of effectively supplying polymers without prolonged exposure to high temperatures, which can be adversely affected. Another difficulty is to evaporate the polymer and direct its vapor to the support system without contaminating or degrading the vacuum system.

Several approaches can overcome these problems with polymer delivery. One approach is to coat the polymer on a carrier material such as a wire or ribbon made of metal or material capable of withstanding vaporization temperatures. The coated material at this time is then supplied to a polymer vapor die, where the material is heated to vaporize the polymer and the vapor is directed to the support system. Another approach is to melt the polymer to lower its viscosity and then extrude or pump into the polymer vapor die. Capillary extrusion systems (capillary viscometers) such as gear pumps, extruders or polymer vapor dies can provide a vaporization surface that is heated to an appropriate temperature. The die then directs steam to the support system. It is necessary to provide a cooling surface in order to condense all the sprayed polymer vapors leaving the polymer die support system area and to pump this area differentially.

Bell Jar Process

Referring to FIG. 10, the bell jar 100 capable of vacuuming is deformed by providing a heater block 102 provided on the bottom of the bell jar. The block includes a heated polymer vapor chamber 104 having a cavity 106 cut out to hold a desired sample. A crucible 108 made of aluminum foil is mounted to the block and about 0.3 g of the desired material is placed in the crucible. The crucible is then placed in a heater block.

A deposition gauge 109 is placed on top of the heater block one inch from the top of the block. As the block heats up, the gauge measures the amount of material evaporated in angstroms per second.

The polyester sheet 110 is clamped between two posts (not shown) on top of the deposition gauge. The material evaporated from the block is deposited on this film. In another step, the film is metalized.

Once the sample, deposition gauge and polyester film are in place, close the bell jar and start the vacuum cycle. The system is evacuated to a pressure of 2 × 10 ⁻⁵ torr to 6 × 10 ⁻⁵ torr and ready for the experiment to begin.

The heater block starts near room temperature. When the desired vacuum is reached, power on the block. The block is set to heat to 650 ° C. within a 20 minute interval. Every minute measurement is performed. The time, current block temperature (° C.), deposition gauge scale (눈금 / sec) and current vacuum pressure (torr) are recorded every minute. The experiment ends when the deposition gauge crystal is broken or all of the material has evaporated and the deposition gauge scale has dropped to zero.

At the end of the experiment, open the bell jar in the atmosphere. Take out the polyester, remove it for metallization and discard the used crucible. The data is then plotted for comparison with all other material experiments.

Belza polymer experiment

Several experiments with different polymers were conducted in a bell jar metallization device. For all these experiments the procedure described in "Bell Jar Procedure" was followed. For each experiment, the experiment time, temperature, deposition gauge scale, and vacuum pressure were recorded. From these data it is possible to determine what greatly affects the vacuum and which material provides the highest deposition rate. Higher deposition rates mean that devices with the ultimate fabrication size can be run at higher speeds. However, materials that have a relatively large effect on vacuum pressure can cause cleaning problems and possible pump down problems after extended operating periods.

Experiment 1, experiment 2, experiment 6, and experiment 7 were carried out using Dow 685D polystyrene. The reported molecular weight of this polymer is about 300,000. All four experiments showed similar results. The deposition rate was maintained at about 10 kW / sec until the temperature reached about 550 ° C. There was little effect on vacuum until it rose to this temperature. The pressure was raised to less than approximately 2 × 10 ⁻⁵ torr. At temperatures above 550 ° C. the speed rose rapidly and the pressure rose within the range of 1.2 × 10 ⁻⁴ to 1.8 × 10 ⁻⁴ torr. This is still a minimal impact on vacuum pressure.

Experiment 3 was carried out using Elvacite 2045, an isobutyl methacrylate having a molecular weight of 193,000. The deposition rose to 26.5 kV / sec at a temperature of 500 ° C. At this temperature, the vacuum pressure rose from the starting pressure of 5.2x10 ^-5 torr to 3.6x10 ^-4 torr.

The fourth experiment used Elvacite 2044, n-butyl methacrylate with a molecular weight of 142,000. The deposition for 2044 reached a peak value of 30 μs / sec at 500 ° C. At this temperature, the vapor pressure reached 2.0 x 10 ^-4 torr.

Experiment 5 and Experiment 19 were carried out using copolymer Endex 160. Endex 160 reached maximum deposition at 413 ° C. at a rate of 11 μs / sec. The deposition gave little impact on the vacuum while the vacuum was finally raised by only 1.0 × 10 ⁻⁶ torr to a final scale of 4.4 × 10 ⁻⁵ torr.

The eighth experiment was carried out using Elvacite 2008, a methyl methacrylate having a molecular weight of 37,000. The highest deposition rate was obtained at 630 ° C. at a rate of 67 kV / sec. The final vacuum pressure rose to 1.0 × 10 ⁻⁴ torr.

Experiment 9 and Experiment 10 were carried out using Piccolastic D125. This material is a styrene polymer with a low molecular weight of 50,400. The deposition rate was reached at 108 ° C./sec at 500 ° C. and there was minimal impact on the vacuum during the experiment.

Experiment 11 and experiment 12 were carried out using Piccolastic A75. This is another styrene monomer but has a low molecular weight of 1,350. The deposition rate started very early and rose up to 760 kW / sec when the temperature reached 420 ° C. In both experiments there was also a minimal impact on the vacuum pressure.

Experiment 13 and experiment 14 were carried out using standard polystyrene having a molecular weight of 50,000 manufactured by Polyscience. These samples have a very dense molecular weight distribution. In the case of these experiments, a deposition rate of 205 Pa / sec was obtained at a temperature of 560 ° C. At such deposition, the vacuum pressure rose to 6.2 × 10 ⁻⁵ torr, which was 1.4 × 10 ⁻⁵ torr higher than the starting pressure.

Experiments 15 and 16 were carried out using another standard polystyrene manufactured by Polyscience, but it had a molecular weight of 75,000. The deposition rate reached about 30 kW / sec at a temperature of 590 ° C. At this temperature, the vacuum pressure rose to 3.0 × 10 ^-4 torr, which was a marked rise.

Example 17 was carried out using Endex 155, a copolymer of aromatic monomers having a molecular weight of 8,600. The maximum deposition reached 78 kV / sec at 530 ° C. At the end of the experiment, the vacuum pressure rose to 1.0 x 10 ^-4 torr.

Experiment 18 was carried out using another standard polystyrene manufactured by Polyscience. This sample had a molecular weight ranging from 800 to 5,000. The deposition was as high as 480 kW / sec at a temperature of 490 ° C. There was little or no impact on vacuum throughout the experiment.

Experiment 20 was performed using standard polymethyl methacrylate manufactured by Polyscience. This sample had a molecular weight of 25,000. The final deposition rate was obtained at 645 ° C. at 50 μs / sec. Under this condition, the vacuum pressure rose to 1.0 × 10 ^-4 torr.

Experiment 21 was carried out using Elvacite 2009, a methyl methacrylate polymer treated to contain no sulfur. The molecular weight of this material was 83,000. The final deposition rate of 26 kV / sec was reached at 580 ° C. The vacuum pressure rose from the initial scale of 4.2x10 ^-5 torr to 1.8x10 ^-4 torr.

Experiment 22 and Experiment 26 were carried out using Elvacite 2697, a treated product of methyl / n-butyl methacrylate copolymer. The molecular weight of this material was 60,000. Elvacite 2697 had a final deposition rate of 20 kW / sec at a temperature of 580 ° C. Vacuum pressure rose to 1.0 x 10 ^-4 torr at the end of the experiment.

Experiment 23 was carried out using Elvacite 2021C, treated methyl methacrylate. This material had a molecular weight of 119,000. The final deposition rate of 30 kV / sec was reached at 590 ° C. This experiment had a significant impact on the vacuum because it was 4.4 × 10 ⁻⁴ torr, one digit higher than the initial vacuum pressure.

Experiment 24 was carried out using polyketoneyl Lawter K1717. The maximum deposition rate of 300 ms / sec was reached at 300 ° C. At this temperature, the vacuum pressure rose to 7.0 x 10 ^-5 torr. At the end of the experiment, a large amount of soot remained in the crucible. This indicates that some of the material did not simply evaporate but actually burned.

Experiment 25 was performed using Solsperse 24000, a dispersant. This sample also burned during the experiment by leaving soot residue in the crucible. However, there was a record of deposition rate at 360 ° C. up to 100 μs / sec. Vacuum pressure rose 1.0 × 10 ⁻⁵ torr over the course of the experiment.

Experiment 27 was carried out using Elvacite 2016, an untreated methyl / n-butyl methacrylate copolymer. It has a molecular weight of 61,000. At 630 ° C., the deposition rate reached 135 kV / sec. Under this condition, the vacuum pressure rose significantly to 3.0 × 10 ^-4 torr.

Experiment 28 was carried out using Elvacite 2043, an ethyl methyl acrylate polymer having a molecular weight of 50,000. The deposition rate at 600 ° C. was 98 kV / sec. Under this condition, the vacuum pressure was 1.0 × 10 ^-4 torr.

Experiment 29 was conducted using Kraton G1780. This material is a multiarm copolymer of 7% styrene and ethylene / propylene. The deposition rate reached up to 70 kW / sec at a temperature of 600 ° C. The final vacuum pressure rose to 8.2 × 10 ⁻⁵ torr. During the experiment the deposition rate remained very constant, especially at high temperatures, showing no drastic fluctuations common to all other experiments.

Experiment 30 was conducted using Kraton G1701. This material is a linear diblock polymer of 37% styrene and ethylene / propylene. The highest deposition rate of 102 kV / sec was reached at a temperature of 595 ° C. The vacuum pressure at the final conditions was 8.6 × 10 ⁻⁵ torr.

Experiment 31 was conducted using Kraton G1702. This is a linear diblock polymer of 28% styrene and ethylene / propylene. The final deposition rate of 91 kPa / sec was reached at a temperature of 580 ° C. The vacuum pressure rose to 8.0x10 <^-5> torr under this condition.

Experiment 32 was conducted using Kraton G1730M. This is a linear diblock polymer of 22% styrene and ethylene / propylene. The maximum deposition rate of 80 kV / sec was reached at a temperature of 613 ° C. The vacuum pressure at this temperature was 8.0 × 10 ^-5 torr.

Experiment 33 was performed using 1201 Creanova which is a synthetic resin based on urethane-modified ketone aldehyde. This material achieved a deposition rate of 382 kV / sec at a temperature of 535 ° C. The impact on vacuum at this temperature was minimal.

Experiment 34 was conducted using Kraton G1750M. It is a multiarm copolymer of 8% styrene and ethylene / propylene. The deposition rate 170 kPa / sec was reached at a temperature of 625 占 폚. Under this condition, the vacuum pressure rose to 9 × 10 ^-5 torr.

From these experiments we came to the following conclusions. The greatest value of these experiments lies in quantifying the effect of various resins on vacuum pressure. From the above experiments, it was found that there is a correlation of molecular weight against vacuum impact. The lower the molecular weight of the material, the less impact the evaporated material will have on the vacuum pressure of the system. There does not appear to be a correlation between temperature and deposition.

Procedure of block equipped drum

Referring to FIGS. 11 and 12, the evacuable chamber 112 houses a rotating drum 114, a deposition gauge 116, and a heater block 118. The heater block includes a heated polymer vapor chamber 120 mounted with a crucible 122 having a polymer source 124. The diameter of the drum 114 is about 1 foot and the width on the surface is 6 inches. The drum can rotate at a maximum speed of 2 rpm. The heater block has a cylindrical shape with a slot 126 cut into an area. The slot is open into the cavity 128 penetrating the center of the block. The block has three independent heaters that can be used to control the temperature of the block. The deposition gauge 116 may be disposed about one inch in front of the slot to measure the amount of material passing through the slot in Angstroms per second (μs / sec). This embodiment shows an electron beam gun 130 in a vacuum chamber, but no EB gun is used in this procedure. This procedure can be used to screen polymers to determine their ability to be deposited, and thus can be used as a polymer release coat.

The heater block can be opened to prepare a sample and the material is loaded into the cavity. When this is done, the chamber closes and the vacuum cycle begins. The chamber is evacuated until the pressure reaches at least 6 x 10 ^-5 torr.

The block starts near room temperature. Once the desired vacuum is reached, the power to the three heaters is turned on. The heater is set to heat to the desired temperature within 20 minute intervals. Measurements are sent to computer files approximately every six seconds. The time, the block temperature in three zones (° C.), the deposition gauge scale (sec / sec) and the current vacuum pressure (torr) are recorded. The experiment ends when the deposition gauge crystal is broken or all of the material has evaporated and the deposition gauge scale has dropped to zero.

At the end of the experiment, the chamber is opened to the atmosphere. Replace the deposition crystals and load new material into the block for the next experiment.

Polystyrene Experiments on Polymer Blocks

Dow 685D polystyrene was used in each experiment and six separate experiments were performed. It is reported that the molecular weight of this polystyrene is about 300,000. In the experiment, the highest block temperature varied with the rise time to reach the final temperature.

In Experiment 1, the blocks were programmed to reach 300 ° C. within 10 minutes of rise time. As the experiment progressed, the polymer deposition rate was very low, below 5 dB / sec. This rate was maintained throughout the experimental period.

In the second experiment the block was programmed to reach a final temperature of 325 ° C. without setting the rise time. The controller was allowed to raise the temperature at the rate of rotation possible. When the temperature was reached, the deposition rate remained at about 30 kPa / sec. There was some variation, but this rate remained constant until 15 minutes after the start of the experiment, and then began to drop noticeably. At the end of the experiment, which lasted 20 minutes, the deposition rate dropped to 15 kW / sec. This slowdown is thought to be due to the depletion of the polymer supply.

In a third experiment, the block was programmed to reach a maximum temperature of 350 ° C. within 10 minutes of rise time. The deposition rate was about 6 kV / sec when the temperature was reached. As the experiment progressed, the rate finally reached a peak of 14 dB / sec about 13 minutes after the experiment. At the end of the experiment, which elapsed 20 minutes, the deposition rate dropped back to about 6 kW / sec. Polystyrene is supposed to start depolymerization at theoretically about 350 ° C. The deposition rate in the experiments may have been lower because the temperature is causing not only this depolymerization but also the evaporation detected by the deposition gauge.

Experiment 4 was set to 375 ° C. without rise time for temperature. The deposition rate rose to 30 to 35 kW / sec in about 10 minutes, but this rate was not maintained. As the temperature exceeded 350 ° C., the deposition rate increased significantly and became irregular. The deposition rate varied from 40 to 120 kW / sec without a regular pattern. After 15 minutes of experiment time, the deposition gauge crystals were broken and the experiment was stopped. Above 350 ° C., the polymer absorbed enough energy to depolymerize, and since that time, very low molecular weight materials occurred at high rates. This material includes monomers and dimers of the original polystyrene. This lower end material is not useful for the formation of the poly film.

The final temperature in the fifth experiment was 375 ° C., but in this case the rise time was 10 minutes. Deposition was initially very constant, but deposition was irregular above die 350 ° C. The deposition was stable at a rate of about 20 kW / sec until reaching 350 ° C. However, as the temperature exceeded 350 ° C., the deposition rate became irregular again. The deposition rate varied from 30 kPa / sec to 140 kPa / sec, this time ending the experiment again at 18 minutes due to crystal fracture.

The final temperature in the final experiment was 375 ° C., but in this case the rise time was 20 minutes. The same was done with the two experiments described above. The deposition was stable at a rate of about 20 kW / sec until reaching 350 ° C. However, as the temperature exceeded 350 ° C., the deposition rate became irregular again. The deposition rate varied from 30 kPa / sec to 140 kPa / sec, and this time the experiment was over again at 23 minutes due to crystal fracture.

From these experiments we came to the following conclusions. It appears that in these experiments polystyrene exhibits depolymerization or other physical degradation at temperatures of about 350 ° C. In experiments above this temperature, irregularities appeared at approximately the same temperature in all three cases. At 350 ° C. in the experiment, the deposition rate indicated that another process occurred because a higher rate appeared at the lower 325 ° C. setpoint. Unless depolymerization or other processes took place, the deposition rate at 350 ° C. would have been higher than the rate at 325 ° C. In addition, in the experiment at 375 degreeC, the oil-type film was observed at the end of an experiment. This material was found to be polystyrene by FTIR analysis, and the oily properties indicate that it is probably a low molecular weight material of polystyrene. This is another proof that the original polymer (molecular weight 300,000) was depolymerized. The experiment at 350 ° C. left a slightly sticky residue but it was not the same oil type as the residue from the 375 ° C. experiment. Experiments run at 300 ° C. and 325 ° C. left a solid film that was not tacky or oily. From this series of experiments it appears that the range of about 300 ° C. to less than about 350 ° C., more preferably 325 ° C., is the temperature at which the polymer deposition is to be performed. Preferred temperatures are sufficiently low that polymer degradation does not increase. Such temperatures also provide high deposition rates that remain stable throughout the process.

Block-equipped drums and E-beams (in block crucibles)

In this embodiment, the vacuum chamber 112, the heater block 118, and the rotating drum 114 illustrated in FIGS. 11 and 12 are used together with the electron beam gun 130.

The heater block can be opened to add material and the material is loaded into the cavity 128. The drum is covered with PET film. E-beam guns are a common one used industrially. It has four copper hearths on a rotating plate. One hearth is placed in line with the E-beam gun at a time. The material to be evaporated is placed directly in the hearth or in a suitable crucible placed in the appropriate turret position. A second deposition gauge (not shown) is located near the crucible upper drum surface. The deposition gauge can measure the amount of material evaporated from the crucible in angstroms per second (Å / sec). When this is done, the chamber closes and the vacuum cycle begins. The chamber is evacuated until the pressure reaches at least 6 x 10 ^-5 torr.

Once the desired vacuum is obtained, the power to be supplied to the three heaters is turned on. The heater is set to rise to the desired temperature within 20 minute intervals. Measurements are sent to a computer file approximately every six seconds. The time, the block temperature in three zones (° C.), the deposition gauge scale (sec / sec) and the current vacuum pressure (torr) are recorded. Power is supplied to the E-beam apparatus. The power supplied to the electron gun can be increased in 0.1% increments. Power is increased to the point just before evaporation and soak or condition is allowed. After immersion, the power is increased until the desired deposition rate is obtained and then the shutter is opened when deposition of the polymer begins. The drum starts to rotate. The experiment ends when the deposition gauge crystal is broken, or all material is evaporated and the deposition gauge scale drops to zero. At the end of the experiment the E-beam shutter closes and drum rotation stops, the connection of power is released from the E-beam and the block heater is turned off. After the cooling period has elapsed the chamber is opened to the atmosphere. The coated material is removed.

Flake Material Operation in E-Beams

The following materials were deposited in an E-beam metallization apparatus to make flake material. The materials were micrographed as follows and the photograph is shown in the appendix.

metal Deposition Rate (Å / sec) Power Target thickness Opinion Indium metal 80 10.6% 475 Silvery appearance Magnesium fluoride 80 7.9% 475 Ultra clear film Silicon monoxide 80 8.6% 475 Brown, transparent film Titanium dioxide 25 10.4% -400 Clarity and iridescent film Zinc oxide 30 10.9% ~ 200 Black residue scattered Aluminum oxide 60 10.8% 350 Clarified and slightly iridescent Indium oxide 60 10.1% 350 Silver-like film Indium tin oxide 60 10.3% 350 Silver-like film Chrome metal 60 14.0% 350 Chrome coloring SiO / Al / SiO Sandwich Silicon metal 60 12.2% 350 Silver-like film Phelly material copper metal 60 9.8% 350 Copper coloring film Copper (Only enough to get a bottle of flake) Copper tinted flakes

Examples from the table above:

Additional Example 1

The following structural agents were prepared: One roll of 48 gauge polyester printed with a thermoplastic release coat was metalized with indium in a Temiscal electron beam metallization apparatus. The roll was removed from the metallization apparatus and passed through a laboratory stripper using acetone to separate indium from the polyester. The indium and acetone solutions were then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using the Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes. The particle sizes reported below are in accordance with the following rules: D10: 10% of the measured particles are below the reported diameter; D50: 50% of the measured particles are below the reported diameter; D90: 90% of the measured particles are below the reported diameter. The finish particle size of the flakes was D10 = 3.3, D50 = 13.2, D90 = 31.2.

Photo exemplified in p1 of the appendix:

30 "homogenized indium

30 "homogenized particle size (unit μm): D10 = 8.21, D50 = 26.68, D90 = 65.18.

6 minutes 30 seconds homogenized

Finish Particle Size (μm): D10 = 3.33, D50 = 13.21, D90 = 31.32.

Additional Example 2

The following structural agents were prepared: One roll of 48 gauge polyester printed with a thermoplastic release coat was metallized with TiO ₂ in a Temiscal electron beam metallization apparatus. The roll was removed from the metallization apparatus and passed through a laboratory stripper using acetone to separate TiO ₂ from polyester, followed by pouring out TiO ₂ and acetone solution and centrifuging to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using a Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes before and after homogenization.

Photo exemplified in p2 of the appendix:

266 TiO _{2 in} "current state" prior to particle sizing

Particle Size (Unit μm): D10 = 16.20, D50 = 44.17, D90 = 104.64

15 minutes homogenized

Finish particle size (unit μm): D10 = 7.83, D50 = 16.37, D90 = 28.41.

Additional Examples 3 and 4

The following structural agents were prepared: One roll of 48 gauge polyester printed with a thermoplastic release coat was metallized with MgF ₂ in a Temiscal electron beam metallization apparatus. The roll was removed from the metallization apparatus and passed through a laboratory stripper using acetone to separate MgF ₂ from polyester. The MgF ₂ and acetone solution was then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using a Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes before and after homogenization.

Photos exemplified in p3 and p4 of the appendix:

MgF ₂ taken “as is” before particle sizing

Grain Size (Unit μm): D10 = 16.58, D50 = 150.34, D90 = 398.17

11 minutes homogenized.

Finish grain size (unit μm): D10 = 0.43, D50 = 16.95, D90 = 45.92.

Additional Examples 5 and 6

The following structural agents were prepared: One roll of 48 gauge polyester printed with a thermoplastic release coat was metallized with SiO in a Temiscal electron beam metallization apparatus. The roll was removed from the metallization apparatus and passed through a laboratory stripper using acetone to separate SiO from the polyester. The SiO and acetone solutions were then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using a Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes before and after homogenization.

Photos exemplified in p5 and p6 of the appendix:

SiO filmed "as is" before particle sizing

Grain Size (Unit μm): D10 = 17.081, D50 = 67.80, D90 = 188.31

17 minutes homogenized.

Finish grain size (unit μm): D10 = 5.75, D50 = 20.36, D90 = 55.82.

Additional Examples 7, 8 and 9

The following structural agents were prepared: One roll of 48 gauge polyester printed with a thermoplastic release coat was metalized with ZnO in a Temiscal electron beam metallization apparatus. The roll was removed from the metallization apparatus and passed through a laboratory stripper using acetone to separate ZnO from the polyester. The ZnO and acetone solutions were then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using a Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes before and after homogenization.

Photos exemplified in p7, p8 and p9 of the appendix:

ZnO taken “as is” before particle sizing

Particle size (unit μm): D10 = 23.58, D50 = 63.32, D90 = 141.59

Finish particle size (unit μm): D10 = 7.69, D50 = 18.96, D90 = 38.97.

Additional Examples 10, 11, and 12

The following structural agents were prepared: One roll of 48 gauge polyester printed with a thermoplastic release coat was metallized with Al ₂ O ₃ in a Temiscal electron beam metallization apparatus. The roll was removed from the metallization apparatus and passed through a laboratory stripper using acetone to separate Al ₂ O ₃ from polyester. The Al ₂ O ₃ and acetone solution was then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using a Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes before and after homogenization.

Photos exemplified in p13 and p14 of the appendix:

Al ₂ O ₃ taken “as is” before particle sizing.

Particle size (unit μm): D10 = 6.37, D50 = 38.75, D90 = 99.94

Homogenized for 9 minutes.

Finish particle size (unit μm): D10 = 1.98, D50 = 16.31, D90 = 39.77.

Additional Examples 13 and 14

The following structural agents were prepared: One roll of 48 gauge polyester printed with a thermoplastic release coat was metallized with In ₂ O ₃ in a Temiscal electron beam metallization apparatus. The roll was removed from the metallization apparatus and passed through a laboratory stripper using acetone to separate In ₂ O ₃ from polyester. The In ₂ O ₃ and acetone solution was then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using a Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes before and after homogenization.

Photos exemplified in p13 and p14 of the appendix:

In ₂ O ₃ taken “as is” before particle sizing.

Particle Size (μm): D10 = 18.88, D50 = 50.00, D90 = 98.39

Homogenized for 3 minutes.

Finish grain size (unit μm): D10 = 8.89, D50 = 20.22, D90 = 38.92

Relative Refractive Index Used: 2.64-2.88

Additional Examples 15, 16, and 17

The following structural agents were prepared: One roll of 48 gauge polyester printed with a thermoplastic release coat was metalized with indium tin oxide (ITO) in a Temiscal electron beam metallization apparatus. The roll was removed from the metallization apparatus and passed through a laboratory stripper using acetone to separate ITO from polyester. The ITO and acetone solutions were then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using a Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes before and after homogenization.

Photos exemplified in p15, p16 and p17 of the appendix:

ITO taken “as is” before particle sizing.

Particle Size (μm): D10 = 21.70, D50 = 57.00, D90 = 106.20

Homogenized for 6 minutes.

Finish Particle Size (μm): D10 = 10.40, D50 = 20.69, D90 = 36.32.

Additional Examples 18, 19, 20, and 21

The following structural agents were prepared: One roll of 48 gauge polyester printed with a thermoplastic release coat was metallized with Si in a Temiscal electron beam metallization apparatus. The roll was removed from the metallization apparatus and passed through a laboratory stripper using acetone to separate Si from the polyester. The Si and acetone solutions were then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using a Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes before and after homogenization.

Photos illustrated at p18, p19, p20 and p21 in the appendix:

Si taken in "At Current State" before particle sizing.

Grain Size (Unit μm): D10 = 20.20, D50 = 57.37, D90 = 140.61

Homogenized for 20 minutes.

Finish grain size (unit μm): D10 = 11.9, D50 = 27.0, D90 = 55.5.

The following structural agents were prepared: One roll of 48 gauge polyester printed with a thermoplastic release coat was metallized with a sandwich of SiO, Al, SiO in a Temiscal electron beam metallization apparatus. The roll was removed from the metallization apparatus and passed through a laboratory stripper using acetone to separate the sandwich from the polyester. The SiO, Al, SiO and acetone solutions were then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied onto slides and micrographed on an Image Pro Plus image analyzer from Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using a Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes before and after homogenization.

Photos exemplified in p22 and p23 of the appendix:

SiO Al SiO Sandwich taken “as is” before particle sizing

Particle Size (μm): D10 = 29.7, D50 = 77.6, D90 = 270.2

Additional Examples 24 and 25

The following structural agents were prepared: One roll of 48 gauge polyester printed with a thermoplastic release coat was metalized with chromium in a Temiscal electron beam metallization apparatus. The roll was removed from the metallization apparatus and passed through a laboratory stripper using acetone to separate chromium from polyester. The chromium and acetone solution was then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using a Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes before and after homogenization.

Photos exemplified in p24 and p25 of the appendix:

Chrome taken "as is" before particle sizing

Particle size (unit μm): D10 = 13.1, D50 = 8.9, D90 = 59.8

Homogenized for 3 minutes.

Finish grain size (unit μm): D10 = 9.82, D50 = 19.81, D90 = 37.55

Additional Example 26

The following structural agents were prepared: One roll of 48 gauge polyester printed with a thermoplastic release coat was metalized with a M-401 copper, zinc and silver alloy from Phelly Materials, Emerson, NJ, in a Temiscal electron beam metallization apparatus. The roll was removed from the metallization apparatus and passed through a laboratory stripper using acetone to separate the alloy from polyester. The alloy and acetone solution was then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using a Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes before and after homogenization.

Photo exemplified in p26 of the appendix:

Alloy taken "as is" before particle sizing

Particle Size (μm): D10 = 69.6, D50 = 161.2, D90 = 313.4

Homogenized for 20 minutes.

Finish grain size (unit μm): D10 = 13.32, D50 = 27.77, D90 = 51.28

13 and 14 show a vacuum chamber, a rotating drum, and a polymer vapor chamber similar to those of FIGS. 11 and 12 except that the polymer is transferred to the chamber by a wire feeding mechanism 136, which will be described in more detail below. In this embodiment, the heater block has small holes at both ends that allow passage of the coated wire 143 into the heated slot area. The coated wire is released from the spool 164 and proceeds through the block at a predetermined rate, where the polymer is evaporated into the slot area and the used wire is rewound to the second spool 166. The slot is open into the cavity through the center of the block. In this embodiment, the area around the heater block and drum is pumped to selectively cool the area where the polymer coated on the wire condenses. This prevents vapor from leaking in the direction of the E-beam region of the chamber.

Additional Example 27

Example: Drum with polymer block and E-beam (wire feed):

Release Material Styron Support Material Aluminum Source Dow Source Mat.Research Corp.No. 685D No. 90101E-AL000-30002PVD Condition: E-beam release support Drum revolutions Wire coat Wirepower Thickness Thickness Speed Size Weight Speed 15% 200Å 150Å 1 RPM 100 0.005 0.0005 6in./diameter g / in.

Under the conditions set forth above, the following structural agents were prepared: 48 gauge polyester wound on drums for easy removal, polymer release coated with styrene and metalized with aluminum in a Temiscal electron beam metallization apparatus. The polyester film was removed from the metallization device and passed through a laboratory release device using acetone to separate aluminum from the release layer and the polyester film. The aluminum and acetone solution was then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using the Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes.

Photo exemplified in p27 of the appendix:

Particle Size at Startup

D10 = 13.86, D50 = 34.65, D90 = 75.45

Homogenized.

Finish Particle Size (μm): D10 = 5.10, D50 = 13.19, D90 = 25.80

Additional Example 28

Example: Drum with polymer block and E-beam (wire feed):

Release Material Styron Support Material Silicon Dioxide Source Dow Source CeracNo. 685D No. S-1060PVD Condition: E-beam release support Drum Rotation Wire Coat Wire Power Thickness Thickness Speed Size Weight Speed 8% 200Å 200Å 1 RPM 100 0.005 0.0005 6in./diameter g / in.

Under the conditions set forth above, the following structural agents were prepared: 48 gauge polyester wound on drums for easy removal, polymer release coated with styrene and metallized with silicon monoxide in a Temiscal electron beam metallization apparatus. The polyester film was removed from the metallization apparatus and passed through a laboratory release apparatus using acetone to separate silicon monoxide from the release layer and the polyester film. The silicon monoxide and acetone solution was then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics.

The flakes are shown in the photograph in Appendix p28.

Additional Example 29

Example: Drum with polymer block and E-beam (wire feed):

Release Material Styron Support Material Magnesium Fluoride From Dow From CeracNo. 685D No. M-2010PVD Condition: E-Beam Release Support Drum Speed Wire Coat Wire Power Thickness Thickness Speed Size Weight Speed 7.5% 200Å 200Å 1 RPM 100 0.005 0.0005 6in./diameter g / in.

Under the conditions set forth above, the following structural agents were prepared: 48 gauge polyester wound on drums for easy removal, polymer release coated with styrene and metallized with magnesium fluoride in a Temiscal electron beam metallization apparatus. The polyester film was removed from the metallization apparatus and passed through a laboratory release apparatus using acetone to separate the magnesium fluoride from the release layer and the polyester film.

The silicon monoxide and acetone solution was then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics.

The flakes are shown in the photograph in Appendix p29.

Drum with steam line and E-beam

(Wire supply)

Figures 15, 16, 15A and 16A illustrate the delivery of a coated polymer to a vacuum chamber comprising a rotating drum, a deposition gauge, a polymer vapor tube with a polymer coated wire supply system and an electron beam (E-beam) gun. Two separate embodiments of the wire feed mechanism are shown. The drum is as described above. The steam tube has a path of heated polymer vapor surrounded by a water cooled tube separated by a vacuum gap. Slots in the tube allow the evaporated polymer to pass through and reach the drum surface. The steam tube creates a differential pressure region adjacent the heater block to prevent steam from leaking into the E-beam region of the chamber. In the embodiment shown in FIGS. 15A and 16A, the wire feed housing houses the wire feed spool and take-up spool. The wire is unwound and coated with polymer and passed around the heater block. The polymer is evaporated from the coated wire and transferred to the drum surface. 16A shows the outer tube with the slot facing the drum. The outer tube is cooled and the inner steam tube is heated. This figure also shows a heater block with a wire wrap. The wire enters the steam tube and turns the heated tube back into the winding spool.

The vacuum chamber 132 and heater block 134 shown in the embodiments of FIGS. 15 and 16 are similar to those described above except that the polymer for the release layer is fed into the vacuum chamber via a wire supply device 136 coated. . The vacuum chamber includes a rotating drum 128, a deposition gauge 140, and an electron beam (E-beam) gun 142. As mentioned earlier, the drum has a diameter of about 1 foot and a width on the surface of 6 inches. The drum can rotate at a maximum speed of 2 rpm. The heater block 134 includes a heated polymer vapor chamber 144 that is cylindrical in shape with a slot 145 recessed in one region. The heated inner tube is shown at 146. The wire supply device 136 includes an elongated housing 147 for receiving a wire 148 coated with a polymer and then supplied into the heater block. The wire is wound around a heated shoe 149. The wire feeder also includes a turbo pump 150, an ion gauge and a thermocouple gauge 154. The coated wire is released from the spool 156 and passes through the heater block at a predetermined speed, in which the polymer evaporates and enters the slot area 158 where the used wire is then used as the second spool 160. Rewind to The slot is open into the cavity through the center of the heater block. The pump assists in delivering the vaporized polymer to the drum surface. The heater block has three independent heaters that can be used to control the temperature of the block. The deposition gauge 140 is disposed about 1 inch in front of the slot. The deposition gauge can measure the amount of material passing through the slot in Angstroms per second (cc / sec).

In use, the drum is covered with PET film. Wire supply mechanisms and heater blocks are used for coating a layer of polymeric release material on a carrier, and then operating an E-beam gun to coat a layer of metal or other material on the release coat, and the like. E-beam gun 142 is a common one used industrially. It has four copper hearths on a rotating plate. One hearth is placed in line with the E-beam gun at a time. The material to be evaporated is placed directly in the hearth or in a suitable crucible liner placed in the appropriate turret position. A second deposition gauge (not shown) is located near the crucible upper drum surface. The deposition gauge can measure the amount of material evaporated from the crucible in angstroms per second (Å / sec). When this is done, the chamber closes and the vacuum cycle begins. The chamber is evacuated until the pressure reaches at least 6 x 10 ^-5 torr.

Once the desired vacuum is obtained, the power to be supplied to the three heaters is turned on. The heater is set to rise to the desired temperature within 20 minute intervals. Measurements are sent to a computer file approximately every six seconds. The time, the block temperature in three zones (° C.), the deposition gauge scale (sec / sec) and the current vacuum pressure (torr) are recorded. Power is supplied to the E-beam apparatus. The power supplied to the gun can be increased in 0.1% increments. Power is increased to the point just before evaporation and immersion or adjustment is allowed. After immersion, the power is increased until the desired deposition rate is obtained, then the shutter is opened, the polymer coated wire mechanism is set at the desired rate and deposition of the polymer begins. The drum starts to rotate. At the end of the experiment, the E-beam shutter closes and drum rotation is stopped, the connection of power is terminated from the E-beam and the block heater and wire supply are turned off. After the cooling period has elapsed the chamber is opened to the atmosphere. The coated material is removed.

In the embodiment shown in FIGS. 15A and 16A, the steam tube has small holes at both ends that allow the coated wire 162 to enter the heated block in the steam tube. The coated wire is released from the first spool 164 and proceeds through the tube at a predetermined rate, where the polymer evaporates and enters the slot region 158, whereupon the used wire is second spool 166. Rewind to The steam pipe wall is heated by a strip heater and the block has one independent heater that can be used to control the temperature of the system. Deposition gauge 168 is disposed about 1 inch in front of the slot. The deposition gauge can measure the amount of material passing through the slot in Angstroms per second (cc / sec).

The drum is covered with PET film. The E-beam gun has four copper hearths on the rotating plate. One hearth is placed in line with the E-beam gun at a time. The material to be evaporated is placed directly in the hearth or in a suitable crucible liner placed in the appropriate turret position. A second deposition gauge (not shown) is located near the crucible upper drum surface. The deposition gauge can measure the amount of material evaporated from the crucible in angstroms per second (Å / sec). When this is done, the chamber closes and the vacuum cycle begins. The chamber is evacuated until the pressure reaches at least 6 x 10 ^-5 torr. Once the desired vacuum is obtained, the power to be supplied to the tube and the block heater is turned on. The heater is set to rise to the desired temperature within 20 minute intervals. Measurements are sent to a computer file approximately every six seconds. The time, the block temperature in three zones (° C.), the deposition gauge scale (sec / sec) and the current vacuum pressure (torr) are recorded. Power is supplied to the E-beam apparatus. The power supplied to the gun can be increased in 0.1% increments. Power is increased to the point just before evaporation and immersion or adjustment is allowed. After immersion, the power is increased until the desired deposition rate is obtained, then the shutter is opened, the polymer coated wire mechanism is set at the desired rate and deposition of the polymer begins. The drum starts to rotate. At the end of the experiment, the E-beam shutter is closed and drum rotation is stopped, the connection of power is terminated from the E-beam and the block heater and wire supply are turned off. After the cooling period has elapsed the chamber is opened to the atmosphere. The coated material is removed.

Additional Example 30

Example: Drum with steam line and E-beam (wire feed):

Release Material Styron Support Material Aluminum Source Dow Source Mat.ResearchNo. 685D No. 90101E-AL000-30002PVD Condition: E-beam release support Drum revolutions Wire coat Wirepower Thickness Thickness Speed Size Weight Speed 20% 200Å 150Å 1 RPM 100 0.005 0.0005 6in./diameter g / in.

Under the conditions set forth above, the following structural agents were prepared: 48 gauge polyester wound on drums for easy removal, polymer release coated with styrene and metalized with aluminum in a Semiscal electron beam metallization apparatus. The polyester film was removed from the metallization device and passed through a laboratory release device using acetone to separate aluminum from the release layer and the polyester film. The aluminum and acetone solution was then decanted and centrifuged to concentrate the flakes. The obtained flakes were applied on slides and micrographed on an Image Pro Plus image analyzer manufactured by Media Cybernetics. The particle size was then reduced using an IKA Ultra Turex T50 homogenizer for flakes in solution. The particle size distribution was measured using the Horiba LA 910 laser scattering particle size distribution analyzer for the obtained flakes. The finish particle size of the flakes is D10 = 3.3, D50 = 13.2, D90 = 31.2

Pictured in Appendix p30:

30 "homogenized aluminum film

30 "homogenized particle size in μm: D10 = 8.21, D50 = 26.68, D90 = 65.18

Homogenized for 6 minutes 30 seconds.

Finish grain size (unit μm): D10 = 3.33, D50 = 13.21, D90 = 31.32

Examples: Drum and E-beam (wire feed) nanoparticles with steam pipes:

Release Material Styron Support Material Aluminum Source Dow Source Mat.ResearchNo. 685D No. 90101E-AL000-30002PVD Condition: E-beam release support Drum revolutions Wire coat Wirepower Thickness Thickness Speed Size Weight Speed 17% 200Å 3Å 2.2 RPM 100 0.005 0.0005 6in./diameter g / in.

Under the conditions set forth above, the following structural agents were prepared: 48 gauge polyester wound on drums for easy removal, polymer release coated with styrene and metalized with aluminum in a Temiscal electron beam metallization apparatus. The polyester film was removed from the metallization device and passed through a laboratory release device using acetone to separate aluminum from the release layer and the polyester film. The resulting aluminum particle slurry was stored in a bottle for further study.

The purpose of the experiment was to obtain nanoparticles of aluminum obtained by managing the deposition process such that aluminum remains in an island growth state as it deposits on the release layer. The islands of uncoalesced aluminum are then coated with a release material and then recoated with the islands of aluminum. This process is repeated until 100 multilayer sandwiches of release / aluminum islands / releases are formed.

Drum with polymer block and E-beam (melt pump extruder)

Referring to Figures 17 and 18, the vacuum chamber and heater blocks similar to those described above are modified to deliver molten polymer (the thermoplastic polymer used as the release coat material) to the vacuum chamber. The vacuum chamber includes a rotating drum 168, a deposition gauge, a stainless steel heater block 170, and an electron beam (E-beam) gun 172. The diameter of the drum is about 1 foot and the width on the surface is 6 inches. The drum can rotate and the rotation speed and rotation speed are monitored. The slot of the heater block is open into the cavity passing through the center of the block. The block has three independent heaters that can be used to control its temperature. Molten polymer is supplied to the block by two heated capillaries 174 connected to a polymer crucible located at both ends of the block. These capillaries are connected to a melt pump located outside the chamber. It is supplied by the melter 175 and the extruder 176 which receive the conditioned polymer and are blanketed with nitrogen. A deposition gauge placed about 1 inch in front of the slot measures the amount of material passing through the slot in angstroms per second (cc / sec).

The polymer is pumped to the cavities at both ends of the heater block to add material. The drum is covered with PET film. The E-beam gun has four copper hearths on the rotating plate. One hearth is placed in line with the E-beam gun at a time. The material to be evaporated is placed directly in the hearth or in a suitable crucible liner placed in the appropriate turret position. A second deposition gauge is located near the drum surface above the crucible. The deposition gauge measures the amount of material evaporated from the crucible in angstroms per second (Å / sec). When this is done, the chamber closes and the vacuum cycle begins. The chamber is evacuated until the pressure reaches at least 6 x 10 ^-5 torr. Once the desired vacuum is obtained, the power to be supplied to the tube and the block heater is turned on. The heater is set to rise to the desired temperature within 20 minute intervals. Measurements are sent to a computer file approximately every six seconds. The time, the block temperature in three zones (° C.), the deposition gauge scale (sec / sec) and the current vacuum pressure (torr) are recorded. Power is supplied to the E-beam apparatus. The power supplied to the gun can be increased in 0.1% increments. Power is increased to the point just before evaporation and immersion or adjustment is allowed. After immersion, the power is increased until the desired deposition rate is obtained and then the shutter is opened when the polymer begins to deposit. The rotation of the drum begins and the melt pump is set to the desired speed. The experiment ends when the deposition gauge crystal is broken or all material is evaporated and the deposition gauge scale drops to zero. At the end of the experiment, the E-beam shutter is closed, drum rotation is stopped, the melt pump is stopped, the connection of power is disconnected from the E-beam, and the block heater is turned off. After the cooling period has elapsed the chamber is opened to the atmosphere. The coated material is removed.

Release Coated Carrier Film Process

In one embodiment the invention can be used to make release coated polymer carrier films such as release coated polyester (PET). Referring to FIG. 19, a polyester carrier film 180 is wound around a rotary cooling drum 182 housed in a vacuum chamber 184. The film passes about a rotational cooling drum surface area of about 300 ° or more from a film unwind station 186, and the coated film is then wound in a film rewind station 188. A polymer delivery source 190 guides the polymer material towards the carrier film, and an E-beam gun 192 vaporizes the polymer to coat the carrier polymer on the film surface. The polymer coating is cured and then wound up in the rewind station. The process provides a thermoplastic polymer release coated heat resistant polymer carrier film, wherein the film provides good release properties for the flake material applied to the film by deposition techniques in a vacuum chamber. The film provides an effective release for forming thin, flat angstrom flakes.

Polystyrene experiment

Experiments in the electron beam metallization apparatus have shown that the heater block temperature has a great influence on the state of the polystyrene after the polystyrene has been evaporated and deposited. In all experiments, Dow 685D polystyrene was used as the deposition material. This material has a molecular weight (MW) of about 300,000.

The experiment was performed in 25 degreeC increments in the temperature of a heater block in the range of 300 degreeC-375 degreeC. The rate at which the blocks heat up varied but did not appear to have as severe an effect as the final temperature. All experiments were performed according to the Drum with Block Procedure described above.

In the first experiment, ten pellets of Dow 685D polystyrene were loaded into the block. The temperature for the heater was set to 300 ° C. Deposition at this temperature is minimal. The gauge scale ranged from 5 to 10 ms / sec. At the end of the experiment there were few visible residues.

In the next experiment, the temperature of the block was set to reach 325 ° C. Deposition increased within the range of 20-30 dl / sec. At the end of the experiment, there was visible film deposition. The film was clarified in color and was a tacky solid.

Next, the temperature of the block was programmed to reach 350 ° C. The deposition rate was similar to the experiment set at 325 ° C. At the end of the experiment, the film was different from the film formed in the previous experiment. The film in this experiment was felt to be more tacky and showed some discoloration.

Finally, the block was set to rise in temperature to 375 ° C. The deposition rate increased to almost 40 kW / sec. At the end of the experiment, yellow oil remained on the film surface. The oil was easily wiped off, but there were no traces of polystyrene film clarified underneath.

From these experiments it was concluded that polystyrene begins to degrade at temperatures above 350 ° C. This confirms the values given in the literature. At temperatures above 350 ° C. the polystyrene evaporates and then depolymerizes and appears to leave a residue of nearly pure styrene monomer. This was confirmed by FTIR analysis of the residue.

In further studies, samples of Dow polystyrene were sent to an external laboratory for analysis. A method was devised to determine what evaporated from the polymer when raised to the desired operating temperature. The temperature was set to rise to 325 ° C. at a rate of 30 ° C./min using the “Direct Insertion Probe” method in conjunction with GC-MS analysis. When the maximum temperature was reached, the state was maintained for 10 minutes.

An ion counter in the apparatus indicated when the material was evaporating from the solid pellet. Two peaks appeared during the experiment, one at about 260 ° C. and one at 325 ° C. These two peaks were subjected to GC-MS analysis. The first peak showed a large concentration of low molecular weight material including but not limited to monomers and dimers of polystyrene. The second peak does not represent as many volatiles in the GC-MS analysis. The analysis concluded that primary heating releases large quantities of unpolymerized material and many other low molecular weight volatiles from bulk polystyrene. After prolonged heating, the desired polymer is evaporated and deposited on the desired surface. It was concluded that optimal performance would require preheating the bulk polymer or otherwise adjusting to remove as much of the "low end" material as possible.

In another experiment, we used the same direct insertion probe method to gain a deeper insight into what happens at the first peak shown in the first experiment. In this experiment, the heat applied was raised to 260 ° C. and maintained at that temperature. This is the temperature at which the peak appeared in the first experiment. The purpose was to specify by GC-MS what was evaporating at this temperature and to see if the material could be removed from the bulk material by a preheating step.

The peak appeared at the same near position and a large amount of low molecular weight material was revealed by GC-MS. It contained a small amount of styrene monomer, but there were many other organic fragments. After about 10-12 minutes, the peak disappeared. This indicated that the volatiles were removed from the bulk material and the preheating method was effective to form a clean polymer film.

From this series of tests, a new method was developed to increase the efficiency of depositing polystyrene films with Dow 685D polymer. First, the bulk material is heated to a temperature of 260-300 ° C. During this preheating process, the film must be recovered to prevent the lower product from reaching the web. This step can also be done outside the vacuum or at least outside the deposition chamber so that contamination can be minimized. After sufficient time has elapsed, the temperature should be raised to 325 ° C. This temperature provides the highest deposition rate without causing degradation of the polystyrene.

Similar experiments with other polystyrene samples were conducted to elicit further consideration. In this case we used 4,000 MW and 290,000 MW polystyrene supplied from Pressure Chemical. These samples have very narrow molecular weight distributions as polystyrene standards. These samples are also free of almost all contaminants found in most commercial polymers. From these experiments, the inventors concluded the following. The use of 4,000 MW material has less impact on vacuum pressure than 290,000 MW material. The higher the molecular weight, the higher the pressure. We have confirmed this by running TGAs on both materials. It was found by TGAs that the 4,000 MW material actually exhibited the onset of weight loss at temperatures higher than that observed for the 290,000 MW polymer.

Polymer conditioning

Before the polymer can be used in the deposition process, the polymer must be adjusted to remove moisture and low molecular weight material from the bulk polymer. Using Dow 685D polystyrene, we achieved this in a two step control process. In a first step, an amount of polystyrene was placed in a vacuum oven and held at 225 ° C. for 16 hours. This temperature is high enough to drain almost all of the moisture in the polymer. This temperature is also chosen because it is lower than the temperature at which the degradation of the polymer appears. In experiments conducted at 275 ° C., the polystyrene sample showed marked degradation after 16 hours of conditioning. After the adjustment period has elapsed, the polymer is taken out and placed in a desiccator to not absorb moisture during cooling.

The second step of polymer control is performed when the polymer is in a state that can be used in the metallization device. The polymer was removed from the desiccator and immediately placed in the metallization device to minimize moisture increase. Before the deposition began, the polymer block containing the first stage controlled polymer was heated to 275 ° C. and held at that temperature for 20 minutes. All moisture remaining at this temperature is released and low molecular weight substances in the polymer are removed. Low molecular weight materials include many of the other impurities found in unreacted monomers and bulk polystyrene. After holding at 275 ° C. for the required conditioning time, the polymer is ready for deposition.

By utilizing the two step control process, the final film has a consistent molecular weight and is free of almost all low molecular weight impurities. This provides a much more consistent and reliable film.

Reuse of Solvents and Polymers

When the current release coat is stripped and the flakes collected, the solvent used is subjected to a distillation process for solvent regeneration with the dissolved release coat. Once the solvent is regenerated, the distillation column bottoms product is disposed of as hazardous waste. In this experiment we attempted to reuse the bottom product as a release coat. The collected bottom bottom product was 24% NVM. Using 3 parts of IPAC and 1 part of NPAC, the material was reduced to 8.3% NVM. This lacquer was applied on 2 mil polyester using a # 2 Meyer rod. The resulting coating had a coat weight of 0.3 g / m 2 and was clarified. The coating was then metallized with aluminum in a bell jar metallization apparatus. The obtained aluminum layer had an optical density of 2 to 2.5 as measured by Macbeth densitometer.

Next, the structure obtained for release from polyester was dissolved in acetone over 30 seconds. The flakes were then applied onto the slides and analyzed. The flakes produced in this way ranged from 400 to 600 μm with flat surfaces and were difficult to distinguish from current products.

Wire coating

20 illustrates a wire coating apparatus for coating a polymer on a wire surface used in the wire feeding implementation described above.

material:

Mixture of Dow 685 Polystyrene Polymer Completely Dissolved in Xylene

Dow 685 45 pts by wt.

Xylene 55 pts by wt.

0.005 inch gauge nickel / chrome helix from Consolidated Electronic Wire and Cable

Description of the device:

Referring to FIG. 20, the coating apparatus consists of four parts: the unwinder 200, the coating body 202, the drying tube 204 and the winder 206. The spool of wire is limited to movement between the two sides while allowing the wire to be released with minimal resistance. The coating body includes a Becton Dickson 5 'disposable syringe that is syringe body 208 and a Becton Dickson 20GI Precision Glide needle that is syringe needle 210. Disposable syringes are filled with a coating mixture and the needle metered into the wire surface an amount of material. The drying tube is made of copper plumbing tubing. Top to bottom tubes are ½ inch tubes 212, 6 inches long, reducer 214 from ½ inches to ¾ inches, ¾ inch tubes 216, 2 inches long, ¾ inch tubes 220 4) is made of a ¾ inch T-shaped tube 218 extending in the vertical direction. An exhaust fan 222 is attached to this pipe that introduces air from the device. The straight portion of the T-tube is attached with a 5 ft long ¾ inch copper tube 224. This part is the dry part of the device. Another ¾ inch T-shaped tube 226 is attached to the 5 foot portion. A vertical T-tube is attached to a 3 inch long ¾ inch tube 228 connected to an upwardly angled 90 degree elbow 230. This elbow is attached with a 1½ tube 232 and a ¾ inch threaded connector 234. The connector attaches to a 2 inch long ¾ inch black tube reducer. A 5-inch long 2-inch pipe 236 is screwed into this reducer. The two inch pipe supports a barrel of hot air gun. The vertical portion of the T tube is attached to a 2 inch long ¾ inch tube 238, which again scales down from 240 to ½ inch. Finally, a six inch portion of ½ inch tube 242 is attached.

Description of coating application:

The coating is applied to the wire using the device presented above. The wire is unwound from the spool and fed through a syringe body containing a mixture of polystyrene polymer and solvent. As the wire exits the syringe body through the syringe needle, the wire is covered with the mixture. The coated wire is fed through a copper tube through which heated air passes. Air is drawn in from the outlet port at the top of the tube at a higher rate than heating air supplied from the port at the bottom of the tube. Additional air required at the exhaust port is supplied at both ends of the tube through which the wire enters and exits. The amount of heated air supplied to the tube was controlled using rheostat. 85% of the total output was found to be the desired temperature. Higher temperatures create bubbles in the coating and lower temperatures make drying poor. The wire passed through a drying tube and wound on a spool. The desired feed rate of wire was 22 inches per minute through the drying tube. The speed of the winding spool was manually controlled using another resistor. As the wire is wound more and more on the spool, the resistance setting is lowered to counteract the faster tension while the wire is wound. The final coating of the wire surface ranged from 0.4 to 0.5 mg / inch.

DOW STYRON 685D

Sample Preparation and Analysis:

About 75 mg of polystyrene resin was separately dissolved in 10 ml of tetrahydrofuran (THF) from each plastic container and spun for about 3 hours. Each THF solution was filtered through a 0.45 μm PTFE filter and placed in an autosampler bottle.

The GPC instrument was a Waters 2690 pumping system with a Waters 410 refractive index detector. The columns were three Plgel Mixed-C 300 mm × 7.5 manufactured by Polymer Labs. The mobile phase was THF under the condition of 1.0 ml / min. Injection size was 50 μl. The calibration was performed on 12 sets of polystyrene standards obtained from Polymer Labs, which ranged from 580 to 1,290,000 Da. Waters' Millennium version 3.2 software was used with the GPC option. Calibration was performed daily and a check sample of SRM 706 polystyrene obtained from the National Institute of Standards and Technology was analyzed daily with each batch of samples.

result:

The calculated value for the quasi-quantity distribution of the soluble polymer portion of the sample is shown in the following table. Values for the peak molecular weight (Mp), number average molecular weight (Mn) and weight average molecular weight (Mw) are expressed in units of 1000 to provide accurate numbers of significant figures. As the quality control data indicates, the relative deviation of 10% for Mn and 5% for Mw is not significant.

Sample Mp Mn Mw Dispersion STYRON 685D 266k 107k 313k 2.94 STYRON 685D Duplicate 272k 138k 320k 2.32 STYRON 685D Average 269k 123k 317k 2.63

Pressure Chemical Co. Provided Polystyrene Polymer Characterization Data

Nominal 290,000 MW Styrene By Lalls: M _w = 287,000 By exclusion chromatography by size: M _w = 288,800 1 × 60 cm Plgel 5 Micron Mixed Gel M _n = 274,600 THF @ 1 ml / min, 20 ml @ 0.02% M _p = 293,000 By intrinsic viscosity: M _v = 288,800 Toluene @ 30 ℃ (v) Mv calculated from 12 × 10 ⁻⁵ M ⁰ .71 (h) = 0.904 Nominal 4,000 MW Styrene By vapor osmometer: M _n = 3,957 THF, 38C, 4 concentration 08 membrane By exclusion chromatography by size: M _w = 4,136 M _n = 3,967 M _p = 4,000 By intrinsic viscosity: M _v = 4,075 THF @ 30 ℃ Mv calculated from (h) = 1.71 × 10 ⁻³ M _v .712 (h) = 0.06

Preparation of Dried Nanoscale and Angstrom Scale Particles:

The method of washing the residual release coating from the flakes after the flakes have been removed from the drum or carrier is as follows. All use filters such as the Buchner funnel and Whatman microfiber filter, each with a 4,000 ml capacity from Fisher Scientific and having a side outlet for vacuum filtration. First, put the flakes in a funnel equipped with a filter and vacuum. Wash the flakes by rinsing in an appropriate volume. The solvent used may be acetone, ethyl acetate or alcohol depending on the solubility of the release coat. The flakes should be washed to the desired level until the residual release coat is removed or reduced. The filtered material may then be heat treated to remove volatiles. It can also be annealed by heating the filter cake to a higher temperature. The solvent used may be distilled for regeneration and reuse. The still product bottoms can be recycled and reused in the release coating as mentioned above. In manufacture, a larger vacuum filtration apparatus can be used.

Barrier material

Experiments were conducted to determine the effect of flake size, pigment-to-binder ratio and coat weight on moisture vapor transmission rate (MVTR) and oxygen permeability of the flake containing film. The flake size was 20 μm in large and 12 μm in small.

MVTR test data was as follows:

Flake size P: B Coat weight (g / ㎡) MVTR (g / ㎡-day) versus 3: 1 3.14 4.86 versus 1: 1 3.62 5.85 small 3: 1 3.18 1.82 small 3: 1 0.8 8.86 versus 3: 1 0.74 15.0 versus 3: 1 3.14 4.86 versus 3: 1 3.14 4.86 small 3: 1 3.18 1.82 versus 1: 1 3.62 5.85 versus 1; 1 1.38 11.90 Clarified medium 1.08 74.4 Dart is SF-502 nylon film 58.3

Pigment: Aluminum Flake

Binder: Cellulose Ink Medium

Further test data showed a MVTR of 1.2, a pigment to binder ratio of 5: 1 and a coat weight of 5 g / m 2 for small particles.

The data indicate that suitably selected flakes can have surprising effects on MVTR. For example, the table shows that the MVTR of a nylon film is reduced from 75 g / m 2 -day to 1.8 g / m 2 -day, with the best conditions being high P: B, small particle size (eg Angstrom scale flakes of the invention). ) And high coat weight. Further test data shows much better results.

Based on these data, for example, application to angstrom scale particles (those having a thickness of less than about 100 microns and a particle size of less than about 20 microns) can include a moisture permeation barrier material. In use, the flakes essentially line up parallel to the common plane and form a barrier to water molecules passing through the flake containing film. For example, flakes such as glass flakes can be used in polymer films such as PVC to inhibit plasticizer migration.

Electrical applications

By moving the release coated carrier at high speed, the deposited metal, such as aluminum, will create discrete islands (the nano-particles described above). These particles (when removed from the release layer) can be blended in the flake containing film or used as such in the polymer film. Nano-particle containing films can increase electrical capacity. Capacitance is proportional to the dielectric constant and area, and inversely proportional to the separation distance between the capacitor plates. Nano-particles dispersed between relatively large particle size flakes increase the dielectric constant, thus increasing the capacitance.

Other uses for nanoparticles are described in Handbook of Deposition Technologies for Films and Coatings, "Nucleation, Film Growth, and Microstructural Evolution," Joseph Green, Noyes Publication (1994).

Multilayer stripping process

Referring to FIG. 21, the multilayer deposition apparatus 250 includes a vacuum chamber 252, each separated into adjacent vacuum portions, including a deposition chamber 254 and a stripping chamber 256. These two chambers are divided by one or more dynamic locks 258 so that the vacuum pressure present in one chamber is at a level independent of, or maintained at, the vacuum pressure present in the adjacent chamber. Can be. The deposition surface or substrate, which is in the form of a deposition surface or substrate, preferably seamless belt 260, passes through the dynamic lock past the deposition chamber and then is introduced into a stripping chamber. This seamless belt can be made of a suitable material such as stainless steel or high temperature polymer. One end of the seamless belt is wound around an upstream guide roll 262 in a deposition chamber, and the other end of the belt is wound around a downstream guide roll 264 in a stripping chamber.

The deposition chamber comprises a series of axially spaced vacuum deposition sources, such as individual distillers, wherein the deposition source is a bottom run of the belt in the direction that the seamless belt passes through the deposition chamber. Arranged along 266. The deposition source can be any release coat material or flake material deposition source as described above. For example, in the embodiment of FIG. 21, the deposition source deposition source 268 and the metal may be applied to the deposition source in order to apply a multilayer stack of alternating deposition metal layers coated on the thermoplastic soluble release coat layer, as described above. Deposition sources 270 may be alternately included. Further, in order to apply a multilayer flake material coating between adjacent release coat layers, the deposition source may alternately include one release coat source and a plurality of flake material sources disposed spaced adjacent to the source. . In addition, other embodiments may be used to coat the release coat / flake layer material in the deposition chamber as described above.

The deposition chamber is pumped down to form a vacuum level in the deposition chamber required to effectively coat the deposition layers of the release and flake materials as described above. The vacuum pressure state in the deposition chamber is independent of the vacuum pressure state operated in the stripping chamber adjacent thereto.

Within the stripping chamber, the multilayer deposits of the flake material and the intervening release coat layer are periodically removed from the seamless belt. In the illustrated embodiment, a vacuum lock 272 in the form of a sliding door is sealed to an opening 274 facing down, installed at the bottom of the stripping chamber. An outer vacuum housing 276 installed under the stripping chamber surrounds the opening of the vacuum lock and the bottom of the stripping chamber. The outer vacuum housing includes a bottom facing bottom opening 278 spaced below the bottom movable surface 280 of the seamless belt, wherein the multilayer deposit of material on the seamless belt is a bottom portion. Stripped from the opening.

A rolling cart 282 independently movable with respect to the vacuum deposition apparatus is used to capture the flake / release coat material stripped from the seamless belt. The rolling cart includes an upwardly facing cradle 284 supported on a platform 286 that is movable in the vertical direction by the reciprocating motion or other lift mechanism of the hydraulic piston arm 288. The cradle is supported on the platform by a hydraulic piston arm 289 which reciprocates in the vertical direction. In the illustrated embodiment, the cradle flakes a liquid solvent, such as an organic solvent, under pressure to physically remove the multilayer deposit from the seamless belt, ie, mechanical means for dry stripping, or to remove the multilayer deposit from the belt. It includes a stripping mechanism 290 that can receive a power spray device that blows up.

In conventional operation of the vacuum deposition apparatus, both the deposition chamber and the stripping chamber are pumped to a vacuum pressure below atmospheric pressure. The vacuum pressure in the stripping chamber may be at a level higher than the vacuum pressure in the deposition chamber, preferably as below mentioned below atmospheric pressure. In one embodiment of the invention, the vacuum pressure in the deposition chamber is carried out with a vacuum of less than about 10 ⁻³ mbar. The vacuum pressure state in the stripping chamber is preferably carried out with a vacuum degree in the range of about 0.5 mbar to 200 mbar. This pressure state depends on the vapor pressure of the solvent used in the stripping process and can be adjusted to a vacuum pressure state known in the art.

22 and 23 illustrate the stripping process. According to the process of the present invention, it is possible to deposit a plurality of layers of deposition material on the seamless belt by a deposition process performed in the deposition chamber. As multilayer deposits are deposited on the seamless belt, the belt continues to pass through the stripping chamber. The speed of the seamless belt is operated at a relatively high speed during the deposition operation, and then the speed of the belt is significantly lowered when the multilayer deposit is stripped from the belt in the stripping chamber. At the same time, the deposition source in the deposition chamber revolves at low speed while the vacuum pressure is maintained in the stripping chamber to remove the deposit.

Figure 22 illustrates the initial stage of the stripping process. The rolling cart 282 is installed below the bottom opening 278 of the outer vacuum housing 276 and the hydraulic piston 288 is outside of the cart, which holds the platform at a level below the pressure for the bottom opening. It is activated to lift to the side. The bottom opening seals the cradle portion of the cart inside the housing. The vacuum lock 272 is sealed in the opening of the stripping chamber to isolate the pressure in the stripping chamber from inside the sealed housing present around the cradle. With the cart installed in place, the vacuum is evacuated to a level balanced with the vacuum pressure level maintained in the stripping chamber from within the housing. With the pressure balance, the vacuum lock 272 is opened. As shown in Fig. 23, this vacuum lock is released from the sealed position and slides into the housing, thereby opening the opening 274 between the stripping chamber and the cradle portion of the cart. The hydraulic piston arm 288 is then activated to lift the cradle to a position just below the bottom movable surface 280 of the belt adjacent to the multilayer deposit to be stripped. In this position, the stripping mechanism 290 is activated to remove the multilayer deposit from the bottom of the seamless belt. As noted above, the multilayer deposit is removed by a stripping mechanism 290 housed in a cart, where the stripping mechanism is a mechanical means for physically removing the deposit, or a power spray using an appropriate liquid, such as an organic solvent. power spray). In the present invention, it is preferred to dry strip the deposit from the medium. Material removed from the belt falls into the cradle in the direction of gravity. Removal of the deposition material occurs when the interiors of the stripping chamber 256 and the lower housing 276 are under vacuum pressure below atmospheric pressure.

After removing the deposition material, the vacuum lock 272 is closed to seal the vacuum, after which the cart is rolled outward from the position shown in FIG. At this time, the vacuum housing is sealed and the cradle is lowered to a lower position. The vacuum lock 272 is then closed to seal the stripping chamber while maintaining the pressure of the stripping chamber at a pressure below atmospheric pressure. The platform portion of the cart is then lowered away from the bottom opening 278 of the housing 276. The lower position of the cart opens the lower housing and provides atmospheric pressure to the lower housing. The cart is then removed for further processing of the removed flake material. The removed material is processed at atmospheric pressure to complete removal of the flake material from the dissolved release coat material and further processing to produce a flake material of the desired particle size as described above.

Deposition sources 268 and 170 are then activated in the deposition chamber and the seamless belt can be run again at a production rate for further deposition of the multilayer deposition material.

The present invention provides a semi-continuous process for fabricating and stripping multilayer flake materials, wherein the speed of the deposition surface, such as a seamless belt, can be manipulated at high speeds during the deposition process and at reduced speeds in the stripping state. Since the vacuum pressure in the deposition chamber and the stripping chamber is maintained at a level below atmospheric pressure, it is possible to reduce the energy required to evacuate many chambers.

Claims (53)

A method for producing a multilayer deposited flake material, (a) providing a vacuum deposition apparatus having a vacuum deposition chamber and a stripping chamber adjacent the chamber, wherein the vacuum pressure in each chamber is individually controlled; (b) passing a deposition surface in the form of a seamless belt through the deposition chamber and the stripping chamber; (c) in the deposition chamber, a multi-layer deposit in which the deposited layer of vaporized polymer release coat material and flake material is separated by an intervening release coat layer and deposited on the surface of the release coat layer. Alternately depositing on the deposition surface under vacuum so as to be sequentially deposited on the substrate, while the multilayer deposits on the deposition surface pass through the stripping chamber while successive layers of the deposit are deposited on the deposition surface; And (d) while deposition of the flake material and release coat material in the deposition chamber is stopped, removing the multilayer deposit in the stripping chamber while removing the pressure of the stripping chamber while maintaining the vacuum pressure below atmospheric pressure. Steps to How to include. The method of claim 1, The deposition surface is operated at a relatively high speed when the deposition layer is stacked in the deposition chamber, and the deposition surface is slowly operated at a relatively low speed when the deposition layer is removed from the deposition surface in the stripping chamber. Characterized in that the method. The method of claim 2, The deposition layer is deposited at a vacuum pressure lower than the vacuum pressure maintained in the stripping chamber. Characterized in that the method. The method of claim 1, Separating the vacuum pressure in the vacuum deposition chamber and the vacuum pressure in the stripping chamber, The multilayer deposit, Install a flake collection device in a vacuum housing adjacent the stripping chamber and in communication with each other; Sealing the flake collecting device in the vacuum housing to maintain the collecting device in a vacuum pressure environment similar to the vacuum pressure in the stripping chamber; Using the capture device sealed in the vacuum housing, the flake capture device is removed from the deposition surface by collecting the deposition material removed from the deposition surface. Characterized in that the method. The method of claim 4, wherein The flake collecting device is movable outside of the deposition apparatus sealed and opened in the vacuum housing. Characterized in that the method. The method of claim 4, wherein The flake capture device comprises a flake removal device that is used to physically remove the multilayer deposit from the deposition surface in the stripping device. Characterized in that the method. A method of making a multilayer deposit of flake material, (a) passing a deposition surface through a deposition chamber and a stripping chamber adjacent the deposition chamber; (b) depositing alternate deposition layers of release coat and flake material layers on said deposition surface at sub-atmospheric pressure in a deposition chamber; (c) reducing the deposition rate, then depositing the multilayer deposit on the deposition surface and removing the multilayer deposit from the deposition surface while maintaining the pressure of the stripping chamber below atmospheric pressure in the stripping chamber. How to include. The method of claim 7, wherein Deposition of the flake layer and release layer material is manipulated while slowly moving the deposition surface and removing deposits from the deposition surface. Characterized in that the method. The method of claim 7, wherein The deposition surface is operated at a relatively high speed when the deposition layer is stacked in the deposition chamber, and when the deposition layer is removed from the deposition surface in the stripping chamber, the deposition surface is slowly operated at a relatively low speed. Characterized in that the method. The method of claim 7, wherein The deposition layer is deposited at a vacuum pressure lower than the vacuum pressure maintained in the stripping chamber. Characterized in that the method. The method of claim 7, wherein Separating the vacuum pressure in the vacuum deposition chamber and the vacuum pressure in the stripping chamber, The multilayer deposit, Install a flake collection device in a vacuum housing adjacent the stripping chamber and in communication with each other; Sealing the flake collecting device in the vacuum housing to maintain the collecting device in a vacuum pressure environment similar to the vacuum pressure in the stripping chamber; Using the capture device sealed in the vacuum housing, the flake capture device is removed from the deposition surface by collecting the deposition material removed from the deposition surface. Characterized in that the method. The method of claim 11, The flake collecting device is movable outside of the deposition apparatus sealed and opened in the vacuum housing. Characterized in that the method. The method of claim 11, The flake capture device comprises a flake removal device that is used to physically remove the multilayer deposit from the deposition surface in the stripping device. Characterized in that the method. The method of claim 7, wherein Providing a release coat source and a metal deposition source toward the deposition surface, respectively, in the vacuum deposition chamber; And The polymer release coat layer vaporized from the release coat source and the flake material layer deposited from the flake deposition source are sequentially stacked so that a multilayer deposition separated by an intervening release coat layer and deposited on the surface of the release coat layer is deposited. Alternately depositing on the deposition surface under vacuum; The release coat layer comprises a thermoplastic polymer material vaporized under vacuum such that a flat, continuous solvent soluble and soluble barrier layer and a support surface, each having a flake material layer formed thereon, are formed. Characterized in that the method. The method of claim 14, Removing the multilayer deposit in the stripping chamber and then treating the release coat layer with a solvent that dissolves and separates the flakes to produce a flake having a flat, flat surface that is essentially free of release coat material. To do How to feature. The method of claim 14, The flake layer comprises a deposition material selected from the group consisting of metals, inorganic materials and nonmetals in elemental form. Characterized in that the method. The method of claim 16, The base metal comprises silicon monoxide, silicon dioxide or a polymer material, and the inorganic material is selected from the group consisting of magnesium fluoride, silicon monoxide, silicon dioxide, aluminum oxide, aluminum fluoride, indium tin oxide, titanium dioxide and zinc sulfide felled Characterized in that the method. The method of claim 16, Wherein said release coat material is selected from styrene or acrylic polymers, or blends thereof. The method of claim 14, And wherein said flake layer is deposited to a film thickness of less than about 400 microseconds. As a method for producing a metal flake, Providing a vacuum deposition chamber containing a deposition surface; Providing a release coat source, a metal deposition source, and a high energy radiation source in the vacuum deposition chamber to face the deposition surface, respectively; The polymer release coat layer vaporized from the release coat source and the deposited metal layer from the metal deposition source are sequentially deposited under vacuum such that a multilayer deposit separated by an intervening release coat layer and deposited onto the surface of the release coat layer is sequentially deposited. Alternately depositing onto the deposition surface; And By removing the multilayer deposit from the vacuum chamber and treating with an organic solvent that dissolves the release coat layer to produce a single layer metal flake having a highly reflective mirrored surface essentially free of the release coat material. Separating into metal flakes, The release coat layer is vaporized under vacuum and deposited on the deposition surface to expose a radiation source for curing and crosslinking the release coat material such that each metal layer is formed with a flat continuous barrier layer and a support surface. Contains a low density polymer material, The deposited polymer release coat layer is soluble in an organic solvent, The metal layer comprises an elemental metal deposited with a film thickness of less than about 400 microns. Characterized in that the method. The method of claim 20, The release layer and the metal layer are in thermal contact with the cooled rotating drum. The method of claim 20, Having a glass transition temperature of the release coat material associated with the thermal conductivity of the release coat such that the heat of condensation of the deposited metal layer does not melt the previously deposited release layer. Characterized in that the method. The method of claim 20, Wherein said release coat material is selected from styrene or acrylic polymers, or blends thereof Characterized in that the method. The method of claim 20, The metal layer is selected from the group consisting of aluminum, copper, silver, chromium, tin, zinc, indium and nichrome. The method of claim 20, And wherein the optical density of the deposited metal layer is less than about 2.8 (MacBeth densitometer). The method of claim 20, And wherein said release coat layer has a thickness in the range of about 200 to about 400 mm 3. The method of claim 20, And said metal flakes have an aspect ratio of at least 300. The method of claim 20, In order to deposit the deposit, the combination of the release coat / metal layer was repeatedly laminated at least 10 times. Characterized in that the method. Providing a vacuum deposition chamber containing a deposition surface; Providing a release coat source, a metal deposition source, and a high energy radiation source in the vacuum deposition chamber to face the deposition surface, respectively; Vacuum depositing the polymer release coat layer vaporized from the release coat source and the reflective metal layer deposited from the metal deposition source to sequentially deposit the multilayer deposits separated by an intervening release coat layer and deposited on the surface of the release coat layer. Alternately depositing on the deposition surface under the; And By removing the multilayer deposit from the vacuum chamber and treating with an organic solvent that dissolves the release coat layer to produce a single layer aluminum flake having a highly reflective mirrored surface essentially free of the release coat material. Separating into metal flakes, The release coat layer comprises a polymeric material vaporized under vacuum comprising polystyrene or acrylic resin or blends thereof, and is deposited on the deposition surface such that a flat, continuous barrier layer and support surface on which each metal layer is formed are formed. Exposed to a radiation source for curing and crosslinking the release coat material, The reflective metal layer comprises deposited aluminum in elemental form, applied to a film thickness of less than about 400 microns. Reflective metal flakes are the manufacturing method. The method of claim 29, Wherein the release coat / metal layer combination has been repeatedly stacked at least 10 times to deposit the deposit. Providing a vacuum deposition chamber containing a deposition surface; Depositing a release coat source, an inorganic flake material deposition source and a high energy radiation source in the vacuum deposition chamber, respectively, facing the deposition surface direction; The polymer release coat layer vaporized from the release coat source and the inorganic material deposited from the flake material deposition source are sequentially stacked so that a multilayer deposition separated by an intervening release coat layer and deposited on the surface of the release coat layer is deposited. Alternately depositing on the deposition surface under vacuum; And The multilayer deposit is removed from the vacuum chamber and treated with an organic solvent that dissolves the release coat layer to produce a monolayer flake of inorganic material essentially free of the release coat material, thereby separating it into inorganic material flakes. Including the steps of: The release coat layer comprises a low crosslink density polymer material vaporized under vacuum and is deposited on the deposition surface such that a flat, continuous barrier layer and a support surface on which each inorganic flake material layer is formed, form the release surface, the release Exposed to a radiation source for curing and crosslinking the coat material, The inorganic flake material layer comprises a deposited inorganic material selected from the group consisting of magnesium fluoride, silicon monoxide, silicon dioxide, aluminum oxide, aluminum fluoride, indium tin oxide, titanium dioxide and zinc sulfide. Method for producing reflective metal flakes. Providing a vacuum deposition chamber containing a deposition surface; Depositing a release coat source, a non-metal deposition source and a high energy radiation source in the vacuum deposition chamber, respectively, facing the deposition surface direction; Removing the multilayer deposit from the vacuum chamber and treating it with an organic solvent that dissolves the release coat layer to produce a single layer of nonmetallic flakes essentially free of the release coat material, thereby separating it into nonmetallic flakes. Including, The release coat layer comprises a low crosslink density polymer material vaporized under vacuum and is deposited on the deposition surface such that a flat, continuous barrier layer and support surface on which each nonmetal layer is formed is formed, thereby providing the release coat material. Exposed to a radiation source for curing and crosslinking, the deposited release coat layer is soluble in an organic solvent, The nonmetallic layer is deposited to a film thickness of less than about 400 microns. Method for producing nonmetal flakes. 33. The method of claim 32, Wherein said non-metallic material comprises silicon monoxide, silicon dioxide or a polymeric material. Providing a vacuum deposition chamber containing a deposition surface; Depositing a release coat source, a flake deposition source and a high energy radiation source in the vacuum deposition chamber, respectively, facing the deposition surface direction; Vacuum depositing the polymer release coat layer vaporized from the release coat source and the deposition flake material layer from the flake deposition source to sequentially deposit the multilayer deposits separated by an intervening release coat layer and deposited on the surface of the release coat layer. Alternately depositing on the deposition surface under the; And Removing the multilayer deposit from the vacuum chamber and dissolving the release coat layer to treat it with an organic solvent that produces a flake having a flat and flat surface essentially free of the release coat material, thereby separating it into flakes. Including, The release coat layer comprises a low crosslink density polymer material vaporized under vacuum and is deposited on the deposition surface such that a flat, continuous solvent soluble and dissolvable barrier layer and support surface are formed on which each flake material layer is formed. Exposed to a radiation source for curing and crosslinking the release coat material. Method of making flakes. The method of claim 34, wherein Wherein the combination of release coat / flake layer has been repeatedly stacked at least 10 times to deposit the deposit. The method of claim 34, wherein And wherein said flake layer comprises a deposited material selected from the group consisting of metals, inorganic materials and nonmetals in elemental form. The method of claim 36, The nonmetal comprises silicon monoxide, silicon dioxide or a polymer material, the inorganic material selected from the group consisting of magnesium fluoride, silicon monoxide, silicon dioxide, aluminum oxide, aluminum fluoride, indium tin oxide, titanium dioxide and zinc sulfide Characterized in that the method. The method of claim 37, Wherein said release coat material is selected from styrene or acrylic polymers, or blends thereof. The method of claim 38, And wherein said flake layer is deposited to a film thickness of less than about 400 microseconds. Providing a vacuum deposition chamber containing a deposition surface; Depositing a release coat source, a flake material deposition source, and a high energy radiation source in the vacuum deposition chamber to face the deposition surface direction, respectively; A multilayer stack of flake material layers vaporized from the release coat source and deposited flake layers from the flake material deposition source separated by an intervening release coat layer and deposited on the surface of the release coat layer. Alternately depositing on the deposition surface under vacuum such that they are stacked sequentially; And Removing the multilayer stack from the vacuum chamber and treating with an organic solvent that dissolves the release coat layer to produce a monolayer of flakes essentially free of the release coat material, thereby separating it into flakes. and, The release coat layer comprises a low crosslinking density polymer material deposited on a deposition surface that has been cured and crosslinked under vacuum by exposure to the radiation source to form a flat continuous barrier layer and a support surface, each having a layer of flake material formed thereon. and, The flake material layer comprises a deposition material applied at a film thickness of about 5 to about 500 microns Method for preparing angstrom sized flakes. The method of claim 40, Wherein said release coat material comprises a weakly crosslinked polymer material having a weak bond strength or a polymer material polymerized by chain extension. The method of claim 40, And the release coat material has a glass transition temperature to prevent the heat of condensation of the deposited metal layer from melting the previously deposited release layer. The method of claim 40, Wherein said release coat material is selected from styrene or acrylic polymers, or blends thereof Characterized in that the method. The method of claim 40, The metal layer is selected from the group consisting of aluminum, copper, silver, chromium, tin, zinc, indium and nichrome. The method of claim 40, The vacuum chamber comprises an inorganic flake material deposition source such that a deposited inorganic flake layer is formed, The inorganic flake layer comprises a deposited inorganic material selected from the group consisting of magnesium fluoride, silicon monoxide, silicon dioxide, aluminum oxide, aluminum fluoride, indium tin oxide, titanium dioxide and zinc sulfide. Characterized in that the method. An apparatus for producing nanoscale flakes, A vacuum deposition chamber containing a deposition surface; A release coat source and a flake deposition source adapted to face the deposition surface direction in the vacuum deposition chamber, respectively, The release coat source and the flake deposition source are separated by an intervening release coat layer to sequentially deposit a multilayer deposit of flake material comprising discrete islands of flake material deposited on the surface of the release coat layer. A polymer release coat layer vaporized from the source and a deposited discrete island of flake material from the flake deposition source are controlled to alternately deposit on the deposition surface under vacuum; The release coat layer comprises a polymeric material vaporized under vacuum such that a flat, continuous solvent soluble and soluble barrier layer and support surface on which each flake material is formed is formed, The multilayer deposit is separated into nanoscale flake particles by treating with an organic solvent that dissolves the release coat layer and produces a flake having a flat and flat plane that is essentially free of the release coat material. Removable from vacuum deposition chamber Device. 47. The method of claim 46 wherein And wherein said flake layer comprises a deposited material selected from the group consisting of metals, inorganic materials and nonmetals in elemental form. The method of claim 47, The nonmetal comprises silicon monoxide, silicon dioxide or a polymer material, the inorganic material selected from the group consisting of magnesium fluoride, silicon monoxide, silicon dioxide, aluminum oxide, aluminum fluoride, indium tin oxide, titanium dioxide and zinc sulfide Wherein the metal is selected from the group consisting of aluminum, copper, silver, chromium, indium, nichrome, tin and zinc Device characterized in that. 47. The method of claim 46 wherein And said release coat material is selected from styrene or acrylic polymers, or blends thereof. 47. The method of claim 46 wherein And wherein said flake layer is deposited to a flake thickness (discontinuous island) of less than about 100 nm. 47. The method of claim 46 wherein And wherein said release coat layer comprises a thermoplastic polymer material. 47. The method of claim 46 wherein The release coat layer comprises a weakly crosslinked resin material that is soluble in an organic solvent such that flakes that are essentially free of the release material are produced. Device characterized in that. 47. The method of claim 46 wherein And said release coat layer is soluble in an organic solvent.