DE1621783A1 - Method for replicating, in particular a deformation image - Google Patents

Description

;. 16 a 1783

Patent attorneys Dipl.-Ing, R "Weickmann, Dr. Ing. Ä.V] eickmann

Dipl. -Ing. H. We ι g km αν ν, Dipl.-Ph ys. Dr. K. Fincke Dipl.-Ing. K A. Weigkmann »Dipl.-Chem. B, Huber

SBPO '; ■ "■ - .." ;. ': ■,;

XEROX CORPORATION,. s Munich 27, 7.

Rochester, W * Y. 14 603 / TTSA möhlstrasse 22 »phone number 483921/22

Procedures for specialist training in particular of a deformation pattern a

The invention relates to a
in particular to a method for the formation of a deformation image. ...; ■ - ^; -. "

Thermoplastic for the production of image patterns on the surface "throw ormbar he Staff £ Two methods are generally known. The first be generated using the 'Matttierurigsbildei · ^1', is in the TJS Patents 3,196,008, 3,196,001 and 3,258,336 The second, with which "relief images" are created, is described in WS patents 3,055,006, 3,063,87.2 and 3,113,179 * In each of these processes, the surface of a softened thermoplastic material reacts to electrostatic forces Deformation. The fundamental difference between ^^ "matting" and "relief" is that the matting on evenly charged surface areas is considered to be uniform

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Distribution of surface wrinkles or wrinkles occurs, while the relief formation is only caused by electrostatic gradients and a single deformation line occurs along the line formed by a charge gradient. Rice formation does not occur if the charge is distributed evenly. This is a. There is an important difference, which is important not only for the purpose of the application, but also for the different mechanisms of the two processes. In the usual generation of matting images, a latent electrostatic image or charge pattern is created on a non-conductive film, which can be softened, for example, by the action of heat or solvent vapor. The film is then softened until the electrostatic forces of the charge pattern outweigh the surface tension forces of the film. If this threshold value is reached, very small ocher surface folds spontaneously appear on the surface of the film. or -runzelni formed, the depth of which in a respective part of the surface generally depends on the strength of the charge present in each case and the thickness of the film. This gives the picture a matte appearance. In another embodiment, the film can be softened before the charge pattern is applied if, in the softened state, it has a sufficiently poor conductivity to store the charge desired the frozen image

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by softening the thermoplastic film again delete and a sufficiently low "viscosity for certain Maintain time to through the surface tension one To achieve smoothing of the film surface.

More recently it has been found that imaging by Obuerflachendeformatipm especially suitable for holography is. "As by Dennis Gabor in the essay" A New Microscopic Principle "in Nature 161, pages 777 to 778, (1940), the holographic method consists of two Steps, the defraction image being one with more coherent Radiation, e.g. laser light, of the illuminated object onto a radiation-sensitive layer is recorded. These Recording, known as a hologram, becomes then for the reconstruction of an image generating wave front by illumination with coherent electromagnetic Radiation -used. This process has been further developed an off-optical axis reference beam formed from coherent light is used and is incident at an angle to the coherent light beam used to illuminate the hologram, whereby an interference pattern on the photosensitive recording disk arises. After the development, this plate or the hologram is again provided with coherent radiation illuminated, and the image is reconstructed off the optical axis at an angle equal to the angle of incidence is proportional to the original reference ray. This method

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Although research is mostly done with amplitude holograms has been worked, it is also possible to produce phase holograms * where the imaging is stored in a phase modulated pattern rather than an amplitude modulated pattern becomes, for example, in an article by G- * ii. Rogers in Proceedings of the Royal Society, Edinberg *

Describes 193, 1953, and in a .Aufsatz -vonW-T.Cathey ir. In 'Journal of the Optical Society of America, 55 _r 457 (1965). Such phase holograms have been used so far. made of conventional silver holographic films by bleaching the silver and using a phase difference caused by changes in the G-el swelling and / or the refractive index. Although there are certain advantages over amplitude holograms, the manufacture of phase holograms is extremely difficult and complicated.

Be used k.önnai _t holograms excellent quality - It was recently discovered that the Deformationsabbildungs- ^ understanding described learn for the production phase-won?. This process is described in patent application R 45 090 IXa / 42h. Here, phase holograms are produced on a thermoplastic layer that can be molded, which is located as a coating on a thermoconductive layer. The deformable layer is evenly charged electrostatically and exposed to the object as well as to reference rays of coherent radiation to which the photoconductor is sensitive dei the Brweichungstemperaifcur * · "heated werformbaren layer. at this temperature, spontaneous surface deformation occurs entspreohtnd the pattern. the layer is then cooled drawing for fixing. holographic. on. If erwünsoht _s may He did" overheating währeiid held exposure "as that this

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struierte.Image can be observed simultaneously with the generation of the hologram., This method enables the? simple generation of phase holograms * of excellent quality and resolution. Lead viewing with normal light _{appears. |?;} appears the Image area, however, as · an arbitrary.distributed.es: Mustsr very: reluctant to have fine, almost invisible elevations and depressions. Since the mean depth of these deformations is often less than 1 micron, they cannot be recognized with the naked eye.,

Despite the excellent quality, these phase holograms also have certain specialist parts. The slightly TFerformbaren substances often melt at low temperatures, have a sticky surface and are soft, are easily affected by falsifying handling, "accidental exposure to dust or excessively high temperatures M5xmen. While a desirable property is' that the deformable plates for Reuse can be erased by softening the layer again and smoothing the surface by viscosity forces% this temperature sensitivity is undesirable for permanent recording · It is difficult »from. The casting of a holographic original with a Sohi iron is difficult, since the heating of the original causes a destruction of the holographic pattern

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This dious task is solved by a procedure for, in particular, a deferral bill, which consists of the following issues

a) BLlddng a first, negative mother plate by on the deformation image at a temperature below 95 ° C a layer of a hardenable substance that is neutral to the surface of the picture is deformed and

- is deducted from this as a negative replica,

b) Formation of a second, positive mother plate by adding a liquefied, film-forming substance the. first mother board is poured and removed as a positive replica from it

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A: exemplary embodiment of the method according to the invention is described below with reference to the figure in which the Sequence of a Nachbildungsverjverfahren is shown.

As can be seen from Mgur liörviirgjsht, the deformationBMid to be reproduced is first generated using a conventional method. Preferably, the surface of this original image to be treated for curing or solidification, as will be described below W iiti *

Then we d ^; a first replica generated by a substance is poured onto the öriginalbild ^, _t of this did not affect

• Then, τοη the first shedding: a second shedding is poured. .--. '■. ■. -; -. -; ■. .'- / ■■ ". ■■

The second replica thus generated is then transferred to an image carrier transferred, so that there is a final positive Hacking the original image results, and the first Uachbil4iang is used again as a mother plate or it is put on a thin sheet of silver

electrically formed »

A third Iiaohbilduag is made with silver and niofcel so this came either as a press die for short operation ■ uses weEuchten> or it becomes a firmer Uickel with it

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plate, cut after passiming? !! as? P * eima1 * »iz @ used for extended periods of time

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YiTie noqli eyläute ^ i; will, feonnen hurried dea? veis n ^ nnrfcen TerfaJjrensschrilite Mnaiphtliph. the gung, fabrics? gewiinscktien j ^ zsiil van Kppieniiisw » will. IIIeaes procedure enables the creation of lae formations an original that is very sensitive to pressure, Solvent or heat is - "'fflat exceptionally good

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The deformatipnSMld to be reproduced can be produced according to a suitable process, the process according to the invention is especially suitable for the formation of the phase holograms of the patent application R 45 090 IXa / 42h. It is also suitable for the reproduction of materialized images of the type described in UB patent specification 5 "-XS & 001 and of relief images of the type described in US patent specification 5,005,006. The deformation images generated by this method are generally broken ? eehliehimii sensitive to heat or friction

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-diei (ilya0i? pl-s xmä l? mta, ßi * ythjel-bol.eateT ' wop. partially / Κρίρρίιρηΐιρι, Polya.lphacnietJb.ylstyrPl, Terpolymers Styrpl, Inden wad Isoprene? Piccolyte SOO (S-70 and S ^ l -

vpm Bet ^ pinene, gets lent iron Pennsylvania Industrial Chemical Company naoh ring and Eugelanalyse determined Schmelzpunktenvy; om 7O ⁰ C and 10O ⁰ C) ~ <* Piccopale 70 SF and Picöopale 85 (unresponsive Olefindienharze the Pennsylvania Industrial Chemical Company Schmelzpunfcten of 70 ⁰ C and 85> ° C and molecular weights of 800 and 100O) J ^Piecolastic. "Α x 75" D IOQ and E 'IOO (polystyrene resins with melting points of 75 ⁰ G, 100 ⁰ C and 100 ° C from Pennsylvania Industrial Chemical Company)! Amberol ST-137 X (a. Non-reactive, unmodified phenol-formaldehyde resin from Eöhm & Haas)? Neolyn 23 (© in. U.kydharz from Hercules Chemical Company); polycarbonates, polyolulfones _f polyvinyl chloride, blends of Silicone and styrene adhesives with a low molecular weight as well as mixtures of these substances should be used in thermoplastic materials as little barfeial as possible, and at room temperature

1621703

weichungstemp be ^ temperature non-conductive, so that its surface in J. properly pending from the OlaerflächeBi- ■■■ "■" ■■ --'- '' ■ '■■' ■ -i - '"-'--""^;: . ^{: <} "" ■■ - ■■ ".. - ^; '■ "■"' - -.:. ■ - -: charge pattern foxed. In general, these preferred fabrics are somewhat soft and clumpy at room temperature, and the surface defoimation properties deteriorate with slight heating or contact with most organic solvents. Therefore, the sheets with a 'picture * must be treated carefully »

Palis desired j can be the thermoplastic insulating material layer be provided on a photoconductive Ispliers t off layer or by storing suitable conductive materials or. through & S ensiti vation of the resin to form a foot oil capable Charge-transferring compound photoconductive · Irish® as a coating to be applied photoconductive SchichteEL consist of amorphous selenium »from pigment material and bath products with photoconductive pigments, Cadmium sulphide> cadmium silk, zinc sulphide, zinc selenide,

, Lead iodide, lead selenide, dispersed in a non-transparent film-forming binder, such as a silicone resin ^^^ eIn. Styrene-butadiene resin or the like, suitable organic Ifffeöleiters can also be designed as cover layers - the heat-deformable layer is mixed in if you want these IOtoconductors to be sensitized, where small proportions of sarbene or Iiewissäuren are imxwe ^ jä ^ i » : 1i70r4θ ^ - »V ..! Ξj0iβ-ehe. organic iOtoconductors are l _f 4 ^ icyanHa & £ iii $ ^ in ^^

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oxidiazole * N-vinylcarbazoleJ phthalocyanines, quinacridones and their mixtures. The deformable layer consists of a suitable aromatic polymer, it can itself made photoconductive by composition with a suitable Lewis acid. Typical Lewis acids are 2,4,7-trinitro-g-flu.orenone, 4-, 4 * -bis- (dimethyl-amino) benzophenone, tetra-chlorophthalic anhydride, ghloranil, picric acid, t 1,3 * 5-Iranitrο-benzene and their mixtures.

The surface deformation image can be deformed on the heated Layer can be formed by any suitable method. Generally speaking, there are the imaging steps from a uniform electrostatic charge the surface of the layer, exposure of the surface with a light pattern to be reproduced and softening of the layer for spontaneous formation of the surface deformation image. Are the deformable layer and / or the photoconductive Layer on a conductive surface, such as a Metal foil or a polymeric PiIm with a transparent conductive coating, so can be the uniform electrostatic Charging, for example, by corona discharge, like them in U.S. Patent 2,588,699. Of course However, other methods can also be used through this charge be realized, for example by triboelectric Charging as described in U.S. Patent 2,297,691 beiL is. Are the heat-deformable layer and / or the photographic

, 1 0 98 U / 17 3-5

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If the conductive layer is self-supporting or if it is on a non-conductive base, the uniform charging can be carried out, for example, with the double coronary process, as described in US Pat. No. 2,885,556 If the moldable layer is inherently photoconductive, the development can follow the exposure step immediately it generally advantageous "to charge the surface of verfombareii layer, for example by 'corona charging again to a material suitable for the development Oberflächenladüngsmuster to erzeugen.- If a phase hologram are made _r so, the exposure made by the process described in the aforementioned patent application . The development can be carried out in any suitable manner, the surface of the deformable layer being reached for the formation of the deformation image. In general, the plate is preferably heated to the softening temperature of the deformable layer, the deformation image is generated and then the plate is cooled below the softening temperature to fix the image .

With this procedure, original files result in high ■

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solution on fabrics, which by. Heat, solvents, or abrasion can be affected. The deformation pictures. Will iff general erased when the surface of the deformation layer after being softened by heat or solvent the image-wise distributed charge pattern was derived.

As a. first step in creating replicas. a deformation of the image to the OriginaTbild preferably such treated contact ,, that a "surface skin" having a thickness greater than about -0 _r 3 microns is formed. The fixing of the surface deformation through the formation of such surface skins is described in more detail in patent application R 41 261 IXa / 57e. This surface skin is harder and less soluble and thus gives the original image a higher resistance to abrasion, less heating or contact with small amounts of solvent vapor. Any suitable method can be used to form the surface skin. It can be created in place or by applying one substance to another. Typical processes for skin formation are exposure to activating light, X-rays, beta rays, gamma rays, electron bombardment, corona discharge, high voltage discharge _t exposure to visible light, exposure to air, exposure to chemical substances such as oxidizing agents and / or agents for the formation of cross connections, Addition of sensitizers to increase the sensitivity of the heat-deformable layer to the treatment for skin formation, spraying, dew coating, as well

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any suitable combination of the methods * Depending on the composition of the deformable layer, the degree and duration of exposure to the various radiation sources can be changed to form a suitable surface skin. For the deformable substances that are preferably to be used, it has been found that a sufficiently long exposure to ultraviolet radiation results in a surface skin which exhibits excellent fixation properties. Therefore, the XJltraviolettbelichtung is preferably applicable method for forming the surface skin ^1.

The second step in the replication method according to the invention is the production of a negative replica by casting the original deformation image.

Any suitable curable material can be used to produce the negative replica can be used. It is important, that the fabric is generating a replica with high Resolution enables. Furthermore, the shrinkage on solidification is allowed of the substance may only be slight. In addition, a Heating above 93 ° C for solidification is not necessary and no heat is generated during curing. There. the most of the substances in the deformation patterns are susceptible to damage by most organic solvents the substance to be infused should not contain any proportions of this Lq-

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solvent. contain * Typical hardened substances such as metal alloys: with a low melting point, such as Cerralow 117 ,. a bismuth alloy from Cerro Corporation , waxes such as Epolene-12. _; a low molecular weight polyethylene wax available from Eastman Chemical Co, J Gelatin * such as food productive polyvinyl alcohols such as Elvanol 71-30 and Elvanol 72-60; available from duPont ElectrochemicalJ silicone rubber * - safety cards with one or more components, such as RTV-Il, RTV-20, RTV-60, RTV-112, RTV-116 and RTV-118, available from General Electric, Silastic RTV-501, Silastic RTV S-5137A, Silastic RTV S-5138A, Silastic RTV S-5302, and Silastic RTV S-5303; available toil Dow Corning, as well as mixtures of these substances. This first negative replica is preferably made with a curable substance. Silicon rubber compounds which cure at temperatures below approx. 93 ° C enable optimum results. Silicon rubber resulted in the replica with the highest resolution among all curable substances tested. Silicon rubbers are made from silicone rubber .. you can dimethyl siloxane kopplymerisiert with lesser amounts of other divalent silicon contained. For example, may be copolymerized PoIydimethylsiloxane with about 5 to about 15 $ Diphenylsilikon, DiäthylsilikorL or Methylphenylsililmrai. The silicone rubber may also active groups such as _SiH? SiOH or SiOC ₂ ^, included, and vinyl, fluorocarbon or

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Nitrile groups can enter the silicone molecule. be inserted. ! If desired, can, finely divided '^ i'ülliaittel, "like Silica gel, ■ potassium carbonate, titanium dioxide, iron oxide odeir their mixtures with the silicone rubber be g-smisoht. to the dielectric strength of the final silicone rubber: - replica to "" increase. In general, sick increases the image resolution The decreasing mean diameter of the MODL. substance particles. Typical fillers have a particle diameter from about 10 millimicrons "to about 1 micron * Any suitable catalyst, such as metallic soaps, peroxides, and others Substances that generate free radicals can cause hardening the siliconeunmii bonds that need a catalyst, be used. ! Typical catalysts are benzoyl peroxide, Oichlorbenzoyl peroxide, di-tert-butyl peroxide ,,. t-batyl peroxide and their mixes. The speed of curing depends τοπ on the relative amount of the catalyst used away. Satisfactory curing speeds achieved one at up to 5 wt .- ^ catalyst, based on the weight of the silicone rubber, it is believed that the Hardening through the formation of transverse siloxane structures between the polymer chains occurs «the curable Substance is used to remove trapped air "VTakuum entered and then in the melt with deia ^ to be reproduced Deformation image brought into contact " he hardened and peeled off from the original image "

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The next step of the invention _: Nachb: p / dungsver- _:. driving consists of making a second, positive replica, which is cast from the first, negative replica. Any suitable film-forming material that can be liquefied and does not adhere to the first replica can be used for this purpose. It is dissolved in a solvent. The relative amount of solution used is not critical, most important is the final formation of a continuous film. Typical film-forming substances are solutions of polystyrene in toluene, polymethyl methacrylate in methyl ethyl ketone, polyethylene methacrylate in ethylene dichloride, cellulose acetate butyrate in ethyl acetate, curable epoxy resins, curable polyester resins, curable polyester resins, methyl ester, methyl ester, methyl ester, methylphenyl and methyl ester, such as methylphenyl and methyl ester, such as methylphenyl, molten polyvinyl ester, and molten polyvinyl ester, such as methylphenyl and molten polyvinyl chloride Acrylic resins, in particular polyisobutyl methacrylate, are preferably used because they cure uniformly without the formation of bubbles and are compatible with the generally used base, which often consists of acrylic materials. Therefore, these substances are preferably used for the production of the second “positive replica”. To form a flat, second replica: the material is applied as a dümjieg flüpsige layer on a base and / or on the first replica · During, before or after the solidification of the liquid layer or layers, the base is easier on the first replica Pressure on

# «If the solidification doesn’t occur before laying on * then the liquid surface or layers are allowed to harden long enough or troctaeu * i) as (Mproduct is a strong fläölie second (positive) li ^^ ibildsiög of the original parts * is allowed ? a liquid Schioiit of the sweetener on de £ dea first Jaehbildung look lierfestigeii, Htävör the atxfgelegt wia d _r so is the transfer of / v ^ erfestigten BehiQht on iiie IDhterlötge occasionally Einwirkutög dureli iron heat the tJhterläge gate atif barren during tfbertragung? - The solidified layer is particularly noticeable volatile solvents are dissolved Poured Sehichii on the Iffiiterlag from # so a softening of the layer and / or the Mterlag # can be carried out with a solvent * or a suitable adhesive applied to the bonding of the layer aii: the base itoterlage may be of any suitable thicknessV rigid or 1 £ ieMbe ^ _f ^

be durchsiehtig and kantt as BandV sheet »plate ο · ä, off '. ■ gjefSi & 3? t be * BLe tteterlage should However, at least have a smooth \ surface that carries the second ifeöhbildung without destroying the image · üie first liaehbildung scarcely as Middle plate

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to generate a multitude of final second :? » Hac ^ toiXdtWD ^ eii ^ ea ^ be turned. The process of producing the second cooling preferably consists of the steps of preparing the hardenable sweetener in a sticky state and transferring the solidified substance to the surface of a base by drying it. The pressure used is not critical, but it should be sufficient "to ensure good contact between the casting material and the surface, the base. Excellent replicas are obtained" if the material is so sticky "that it takes 5 seconds to get under light pressure, ie thumb press., on one. Sheet of clear cellulose acetate adheres and remains after! DrenMing the first faehbildung. Although melted or hardenable cast materials are to be used,! Βοή also gets optimal results with solutions of film-forming! Polymers iii non-solvents. Solutions YQXi. Film-forming polishes reach the tacky state more quickly than other hardenable substances with less energy expenditure and produce images with a higher resolution. The amount of Gußlösting; sqII are sufficient to form a dry layer with a smooth ^^ deformation-free outer surface,

If an otter plate made of metal is desired, a KaOhbilditing ^ iBit metal surface is produced. Argh chemical Reiniguiag and Sensiti-orientation of the second pberflache After ** · forming a metal such as silver *, ßhemisch reduced and 89afgesprüht to the second Kachbildung up to a thickness _t

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which ensures the absence of pores and withstands the subsequent electrical electroplating current. This thickness is preferably approx. 7.5 or 10 × 10 "~ cm for this purpose. This coating creates the very conductive surface required for the galvanic production of a good metal mother plate. A suitable process for sensitization and silver plating is described by AM Max in" Application of Electroforming to the Manufacturing of Disk Records "in ASM Special Technical Publication Fr, 318. (1962). The second replica is then placed in a" G-aXvanisierungsbad made of UickeXsuXfamat, and nickel is galvanically applied to the conductive surface The bath is kept at a temperature of about 54 ° 0, while the current for a 30 cm plate is about 50 A. Electroplating is continued until the layer is sufficiently thick to support itself Security against image destruction results with a thickness of the UTi disgusting layer between approx * O ₉ I? "And Ö _r 3 nmu Danm the metal layer is from the Plastic underlay is lifted, whereby it separates slightly from this »and thus results in a third, silver-plated lietäll mother plate with a negative image *. This © metal nut plate can now for pressing iron -iiaohbilaiingesi the original deformation image ^ iisrondet -We & lfiatj Wosu dl ^{©; s.} 3aaehst © lxend described Preßvarfahren serve "Is may -Jedoch / if erv ^ ünschtp auQh eiaa- ümsrhat tape flat © hmgeätsXXt wa3 <? ä @ yes <. ^ orsugswelse you will

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Mder -used, because with these a fast and even Deposit results. .- · / ■. "

To form a more permanent metal replica, the Surface of the third, negative replica with a Potassium dichromate solution treats the surface chemically to passivate. This treatment allows electroplating a replica made entirely of nickel on the silvered! surface, but prevents a bond between the two Metals together. The result is a permanent, fourth nickel replica with a positive image. If desired, can, also a fifth nickel replica with a negative image can be obtained from the "wied replica. Also, if Desires. the surface can be chrome-plated to extend the life of the press plate *.

Independently are b.eaen with the understanding described for the preparation · lierfahrert eimei * Yielzahl final isweiter Uächbildungen or prepared by pressing the final Kachbildungen the original Defonaationsbildes of the Yerfahren for the preparation of the final Y Metallpreßplatte "The baschriebene in the following procedure after the ErfiMung is ei "L Keißpreß -"? EIel dütoter, dry eggs thermoplastic; · (Cellulose acetate, with- oiiösr £ $ taa? L £ ö -won. Oa ^: 0.08 to approx.

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tive press plates have kianit, 3Jer Ifoermoplas tables previously heated to a temperature 80 that none Impacts occur if he is against them Press plate throws pressed * Since the depth of the Cflaerflachende ^

especially in the course of a hplograpMseiien Qris nitr very small iai; (on the order of 0.5 microns) triti; little or no. The dissolving of the slight yerlageruriig _{on r} heahsiiens, At the end of the geit the pressed thenaoplastic film is loosened, surprisingly; is; borrowed this without a previous one. You get a hot-pressed technical picture of the original deformatiQbisMldes with good quality. For this experience, any suitable thermoplastic substance can be used, O) ypishe such substances are leetate, such as cellular acetate _?

such as polyvinyl chloride, 'Sol.jm &i' onharze and liisehungen these substances, Satisfactory lilder sipii ergjehen with soei ^ most tested theamoplasti ^ chen substances "bfii eiiiem pressing pressure between approximately? 27 IMCL 4018 atutf when a Vorerwäriaung of thermopläStiSQhen lilms ^ is üngeföhr mx The temperature of the softening agent is made "a pressure plate temperature of cat 49 ^Q 0 feis ca" 204 ^ G for a pure pessibility of less than about 30 seconds if used. In general, higher jerks are used örf-orderlichji if lower press plate temperatures

will. It turned out that the last replica on ^ elliil <? seäe: etat arise whoin a pressure of approx *

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27 "to -408- a tu, a Yor heating temperature Ms of approx. 93 ⁰ O, a press plate temperature of approx. 49 ⁰ G Ms approx. 149 ⁰ C and a pressing time of approx. 1 Ms 10 seconds can be used. therefore used for hot-pressing the most precise replicas on cellulose acetate. However, any other suitable material can also be used for this purpose. Cold-pressing can also be used. However, hot pressing is preferably used since a lower pressure from τ is sufficient and the destruction of the image area is substantially reduced. For the production of holographic reflection images. Metal-drawn plastic films can be used. A transparent plastic post-molding can also be metallized after the image has been produced. Both sides of the plastic film can be pressed simultaneously or in succession with the same or different holograms. Of course, the press nut plate can either be flat or pulled onto a cylinder, with which it is rolled over the thermoplastic film.

It should be noted that with the above-described hot. pressing process the thermoplastic film is under pressure for a comparatively short time and is then removed hot _r so that the softened plastic does not remain in the mold during cooling. Surprisingly, when looking directly at the picture, there is no change in shape despite: the fact that the material was not cooled down before it was removed from the mold.

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Reduction of the press form after, the production of each replica superfluous and allows extremely fast production of a number of very good replicas with one single mother board. In contrast to softening with solvents, this hot pressing process has the advantage that it works completely dry and a refresher or subsequent delivery of the solvent is not required »-

The following examples are provided for further explanation of the method according to the invention for simulating a Deformation image * All parts "refer to the Weight, unless otherwise stated. The examples preferably represent embodiments of the method according to the invention.

EXAMPLE · I

First, an original holographic image is produced. A coating solution is formed which contains approx. 20 parts of polyvinyl carbazole, approx. 0 * 1 part of Brilliant ö-reen Special (a triphenylmethane dye from Allied Chemical Company), approx. 100 parts of dioxane and approx. contains ·. This solution "is applied to the conductive surface of an HBSA-G glass plate (oil base, coated with an extremely thin, transparent layer of zinc oxide, manufactured by the Pitt ©" bu3? G Plate Glass Company). dry strength of esa, '7 microa applied. *; Aixf \ ~ άί ea © fotoleitfäMg © Sohisfet

BAD OBSG'NAL

Apply a layer of Staybjelite Ester 10 (a (glycerol ester of 60% hydrogenated rosin available from Hercules Chemical Company) "to a dry thickness of about 1 micron. This layer is applied by moving your backing at a rate 12 _and 5 cm per minute from a 20 foigen solution of the resin, generally a kerosene solvent. After drying, the complete image plate consists of a conductive base, a photoconductive layer and a deformable thermoplastic layer. This plate is exposed to corona discharge in the dark The plate is then exposed in an arrangement as shown in FIG. 1 of patent application R 45 090 IXa / 42k '. using a helium-neon continuous wave Iiasers operating in Tem-00 mode at 6328 Angstroms (Model 5200 from Perkin Elmer Com pany) The. Reference beam is incident at an angle of approx. 30 ° «

If you charge again, the plate will then slowly rise their expansion temperature is heated. The reconstructed image can be observed simultaneously with the formation of the hologram, lfaoh good development of the deformations. the plate becomes Pixiermig & © s picture cooled down. There is a holo-on E @ ielmi2ög of the highest quality with a bucket

- ■ 27

Resolution τοή approx. 800 lines per mm.

The hologram becomes the ultraviolet for about 6 hours light from a quartz silver arc lamp from General Electric. 100 watts exposed at a distance of approx. 15 cm. As above described, the surface is made resistant, ■ "■" ■ "." ■■ "..." "- ■" - '-

Ga, 100 parts RTV-II (a vulcanizing at room temperature Silicone rubber verbizidurig from General Electric Company) mixed with approx. 0.3 parts of an associated catalyst « This mixture is in a vacuum dryer at one pressure held by less than 0.17 atii about trapped air bubbles to remove · On the surface of the mixture this gets a foam Mlduiig caused. After about 5 minutes it will the pressure was slowly brought to atmospheric pressure. The original hologram will be. then, face up, "into the ground a rectangular shape of. 12 * 7 mm laid, paint tray the surface of the evacuated silicone rubber Mix this carefully in the mold up to a height from approx. 9> 5 mm poured in, so that> all contours are completely filled. The resin is then at room temperature for 48 hours cooled down for a long time. With larger amounts of the catalyst can the curing line; be shortened significantly. The out-v hardened rubber is then peeled off, the original. It results in a flexible, permanent, first, negative mother-

10981 4/1 731 bath

replica made of rubber. The original hologram is through does not damage this cast.

~ 1B ± ne casting solution is then prepared * by dissolving approx. 17 parts of powdered Elvaeite No. 2045 (a polyisobutyl methacrylate resin, available from EI duPont de Nemours & Go.) And approx. 28 parts of purified ethylene dichloride. The solution is left to stand for a few hours in order to allow air bubbles to escape from the stirred liquid. * A piece of clear Plexiglas (polymethyl methacrylate, available from Rohm & Haas) with a thickness of approx. DLp35 ram becomes slightly larger than the rubber sheet tailored. A. thick casting of the replica solution is poured onto one edge of the Plexiglas window and onto one edge of the rubber mold. Then the solution is rolled out into a thin layer on both surfaces with glass tafers. The coated plastic underlay is immediately placed on the coated rubber surface in such a way that the two surfaces merge from one side to the other, like when a door is closed. Weight, which creates a pressure of approx. 0.01 at, creates the layer of solution, placed on the plastic plate, and the arrangement is dried for approx. 3 hours at room temperature. The result is a rigid, transparent, second, positive plastic replica of good quality. The first mother plate made of silicone rubber remains

109814/17 3 5

1821733

undamaged.

Then a hologram in the form of a metal replica is produced.After chemical cleaning and sensitization of the surface of the second replica with a tin oxychloride solution, silver is chemically reduced from an ammonia-containing silver nitrate solution while it is sprayed onto the plastic sewing. The silver layer obtained has a thickness of approx. 7 10 ° "cm. The training course forms the very conductive surface required for the production of a good galvanic metal sheet formation. The nickel layer with a thickness of approx . 3 mm is then electroplated the silver surface in a Hickelsulfamatbadl at a temperature of about 54 ⁰ C and a G-esamtstrom applied for a 30 cm ·· plate of 50 amperes. After the G-al ^ wanialerung is nickel is "silver easily removed from the plastic mold and it results in a third negative metal mother plate with a silver furnace surface · This replica is suitable as a press plate for short operation;

Using this plate, several NaohbiX-applications of the master hologram are then produced · Bin trooksner cellulose acetate film with a thickness of about 0.18 mm is heated to about 88 ⁰ C. The metal mother plate is heated to approx. 138 ° C and pressed under a pressure of approx. 54 ° on the cellulose acetate film against a flat cushion * pressure

109814 / T 7 3 6

BATH ORIGINAL

and temperature are maintained for about 5 seconds. At the At the end of the pressing time, the plastic film is loosened without prior cooling. An excellent replica results of the original hologram. over 100 other replicas are hot-pressed in a similar manner before a noticeable decrease in quality is observed.

EXAMPLE II

As in Example I, there are an original hologram, a catalytically formed first and a cast second mother plate manufactured. In this case, a more permanent motherboard should be hot-pressed so that a larger number can be made from replicas. After coating the plastic replica with silver and a 0.3 mm strong, galvanically formed nickel layer becomes the silver surface treated with a potassium dichromate solution for passivation ». This enables the galvanic / anA sizing of a further one Nickel layer on the silver surface without a silver-nickel bond to create. After a 0.25 mm thick nickel layer has been formed in this way, it is separated from the silver-nickel mother plate Nickel b-existing, positive fourth replica. This can in a hot press process as described in Example I. is »for the production of pressed negative plastic replicas be used. For many holographic uses the negative replica is suitable. Palis desired, can.

1098U / 1735

this metal mother plate is provided with a chrome coating that extends their lifespan, why a Current of approx. 575 amps with a 55 cm plate is used.

BEISEEEI ₁ III ;

The (positive) fourth replica from Example II, formed entirely from nickel, is coated with a solution of approx. 16 g of polyisobutyl methacrylate dissolved in approx. 200 ml of methyl ethyl ketone by brushing on. The liquid film formed. is air-dried at room temperature for about 20 seconds; until it becomes sticky. A thin cellulose acetate film with Eiber thickness of about 0.15 mm is uniformly pressed by a rubber roller on the sticky layer The cellulose acetate is then subtracted from the fourth mother plate _o The transferred film shows good Bafiung on the cellulose acetate film. Over 100 more top-up fertilizers are applied in a similar manner to the fourth sewing; produced with no noticeable drop in quality.

EXAMPLE XT . '-'-.- .. -

An original hologram and a catalytically cast first Mother patties are made as in Example I- * In this one ! • All should be a second replica faster than in the example I am educated The first motherboard is in a Bath of. approx. 2 g polymethyl methacrylate, yellow in 200 ml

10 9 B14 / 17 3 p

/. ._ ■■■ -

■■■■■ - 32 -. . ;

Methyl ethyl ketone, immersed "and. Slowly within 3 seconds pulled out. The liquid film formed is stored at room temperature for approx. Dried for 30 seconds until it becomes sticky. The sticky one Film is then attached to a thin cellulose acetate butyrate sheet pressed with a thickness of approx. 0.25 mm. The first motherboard is removed immediately after the application of pressure. The transferred film shows surprisingly strong adhesion the slide * The total to form the second replica time required is almost 360 times faster than that for the second butter plate manufacturing steps described in Example I. The first mother board is again in the ■ prominent toe very! Even way of making more than 100 good second replicas used without noticeable deterioration in qualityβ One of the second generated in this way Replicas will then be used to manufacture a third motherboard as used in Example I.

'EXAMPLE · Y.: "' ..

The procedure of Example IV is repeated except that a polyethylene terephthalate film sheet is used cellulose acetate butyrate having a thickness of ₉ Q 3 at the place of. The quality of the second replicas produced correspond to those from Example IV ₉ λ

SAO

10 98 U / 1735

■ ■ ''. . ■ :; - 33 - ■; ■ '■; ,; ■ ";. V

EXAMPLE · ■ l / I - '".

The animal driving described in Example 17 is repeated with the difference that ^J is the I ^ ssigkeitsfilm rolled onto the surface of the first mother board, to a niohtklebrigen state after which it is dried for about 1 minute and then about 4 seconds / long for a cellulose acetate . Butyrate film is pressed, which is on a hot plate with a temperature of about IDQ ⁰ G. The first mother plate is then separated from the transferred ^ iIm g, * It is used in the manner described above for the production of more than 100 second replicas of good quality. One of the second roof formations is then used to make a third otter plate as in Example I. - - ■■ - ■:

Although special components and amounts of substance in the above description of preferred embodiments of the invention Procedure were specified »can also ^ other substances and conditions? as listed above can be used with similar results. Additionally can add other substances to the various educational substances can be added in order to have an aynergetic, TE-improving or otherwise changing effect on their properties achieve. For example, temperature changes or Release agents can be used if desired *

109014/173 5 -V 8AD OBIG ^ AU

- 34 Further embodiments and changes to the present one

Invention are those skilled in the art to the knowledge of the above Description possible. These are all taken care of by the The basic idea of the invention includes »·

1Q98U / T13S

Claims (18)

- 55 - · Godfather η t a η s ρ r ü c h e s 1". Yerfahren for the replication, in particular of a face image, characterized by the following step a) forming a first negative mother plate by at a temperature below 93 ° C a layer of a curable, deformed from the BiIdoberflache neutral substance and i as a negative ÜTachbildung of. this is withdrawn to the image deformation ", b) Formation of a second, positive mother plate by a liquefied, film-forming substance poured onto the first motherboard and used as a positive shed from this, is deducted ». 2. ¥ learn after. _G Jbaspruch 1, characterized in that the fumbildende material is liquefied by dissolution in a solvent. . " 3 »A method according to claim 2, characterized in ₉ characterized in that the solution of the film-forming substance on the first negative .Mufterplatte is deposited ia an amount sufficient the outer surface deformatiönsfreien to form a thin, dry layer having a smooth *, and that the smooth surface A pad is pressed against the smooth, deformation-free outer surface before the mother plate is separated and the shed is pressed. 1098 14/1735 BAD . - 36- ■ 4 * Method according to claim 3, characterized in that the Solution of the film-forming substance is dried to a tacky state before coming to the smooth surface of the Funds will be brought together. 5 * method: according to claim 3 »characterized in that the smooth surface of the pad before putting it together with the thin, dried layer is heated, 6. The method according to claim i, characterized in that the film-forming substance is a synthetic resin 7. VerfaJirennabh claim 6, characterized in that according to the separation of the motherboard and the replica a third, negative replica by the deposition of a thin layer of silver on the surface of the second, positive replica, electroplating a nickel layer on the silver layer and Separation of the silver layer from the second, positive replica is made. 8. 'The method according to Altspruch 7, characterized in that the , Silver layer up to a thickness of 7.6 χ 10 ~ "cm to 10 χ 10 om is applied \. 9. The method according to claim 7 »characterized in that the Nickel layer up to a thickness of 0.13 mm to 0.3 mm is applied. V 1098 U / 1735 ■: 783 10.! / "Experienced according to one of the. Claims 7 Ms 9» characterized in that that of the image of deformation there is a fourth, positive one Metal reproduction through passivation of the silver surface the third, negative replica, galvanized one Niekelschioht on the silver surface and separation of the Silver surface is made from the fourth, positive replica. ■■■■■■■. ■ ■: '■■: ■.' ■■■■■. ^: ■ \ 11. The method according to any one of claims 7 to 9 »characterized in that that a fourth, positive replica by pressing the third replica is made against the surface of a deformable thermoplastic film, the · Pressure to deform the surface of the thermOplastic Film is sufficient in image-wise distribution 12. The method according to claim 11, characterized in that the fourth OÖsitive replica duroli application of the thermoplastic vision Film on a base, preheating the thermoplastic * Standing film, preheating of the third replica, pressing the third replica against the; thermoplastic film for a time of less than 30 seconds and abaiah «of the so educated fourth, positive N & öhbildung from the third replica is produced, the third replica being the Maintains pressing temperature, 13 · Method according to claim 11 or 12> thereby, geksniizeiohnetf 109814/1735 1021783 that the thermoplastic! film, made of cellulose acetate with a Thickness of 0.08 mm to 0.25 mm. " 14, method according to claim 11, characterized in that the ■ fourth, positive replica by placing the thermoplastic film on a base, heating the thermoplastic film to a pre-temperature in the softening at calibration, heating the third replica to a pre-temperature between 49 ⁰ G and 204 ⁰ G, pressing the third replica against the thermoplastic film for a time of less than 30 seconds and peeling the fourth replica thus formed from the third replica is produced, the third replica remaining at the pressing temperature. 15. Verfahrea according to one of the AEßsprüche β to 14, characterized in that that a thin layer of the liquefied synthetic resin is applied to the first replica, and that the free surface of the thin layer before peeling off the second, positive replica thus formed from the first replica is brought into contact with a base. ■; 16. » Method according to claim 15, characterized in that the thin layer of the liquefied resin is hardened to a sticky state before the free surface comes into contact with the substrate * 1098HZ ₁₇₃₅ ■ \; - 39 - '■' ■ '■; ■ .- * .. '■ 17. Verfahrennach claim 15 ₁ characterized gekennzeiohnet that the thin layer of the liquefied resin is cured after contacting the free surface with the "pad. 18. The method according to claim 15 * characterized in that the thin layer of the liquefied resin is cured before the contact of the free surface with the substrate and that at least the base simultaneously with the transfer of the thin layer of the cured resin to the base Heat energy is supplied. 19 * Method according to one of claims 6 to 14, characterized in that the second, positive simulation by Deposition of a thin layer of the liquefied resin on the surface of a support and casting of the thin Layer the liquefied resin against the first, negative Replica is made. 20 ». Method according to one of the claims 6 to 19 »characterized in that that the second, positive! specialist training a solution of an acrylic resin in an organic solvent is formed * 23U method according to one of claims 6 to 19, characterized in that that the second, positive replica is formed from a molten thermoplastic resin. 9 8 14/1 7 3 5 ^{BAD 0RiG1NAL} Process according to one of Claims 1 to .21, characterized in that that the curable substance is a silicone rubber. : 23 · Method according to one of the preceding claims, characterized in characterized in that before the production of the first, negative replica, the deformation image to be replicated for Generation of a surface skin is treated, which consists of a harder substance with a higher viscosity at softening temperature the original image area exists as that of the original deformation image 24 · The method according to claim 23, characterized in that the Surface skin is at least 0.3 microns thick. 25ο Process for the production of a large number of practically identical holographic images, characterized by the following steps: a) Generation of an electrostatic charge image on a deformable thermoplastic material, which is a corresponds to holographic interference pattern, b) heating the deformable thermoplastic material until it is deformed into a pattern of elevations and depressions according to the charge pattern, c) Exposure of the holographic original produced in this way with activating radiation for one to form one Surface skin made from a substance with a higher viscosity 10 98 14/1735 ■ ν \ '; . ■ '■ ".-. ■' BAD than the thermoplastic. Substance at softening temperature sufficient time such that the surface skin has a Thickness of at least 0.3 microns; d) Generation of a first, negative! shed formation; of the holographic image through; ; .1.) Deformation of a layer from a mixture of a curable silicone rubber on the picture, 2.) curing of the rubber, and 3.) Peel off the negative! Shedding formed in this way, ' e) Generation of a second, positive replica by: 1.) Hardening of a thin layer of a liquefied, curable resin on the first, negative replica, -and : -. 2.) Removal of the second, positive shedding formed in this way from the first shedding,. f) Creation of a third, negative metal mother plate through 1.) Formation of a silver layer with a thickness of ' 7.6 to 10 χ 10 ". Cm on the surface of the .second, positive replica ,,
2.) G-galvanization of a nickel layer up to one Thickness from 0.13 to 0.3 mn. on the Silbersohieh'-ft, - and 3.) Separation of the silver layer from the second, positive shedding, creating a third shedding in the pona of a metal mother plate,. g) Creation of a fourth, positive subject formation through BATH . Ί 0 9- «7 4/1735 ■ - 42 - 1 ») Application of a film of thermoplastic material with a thickness of 0.08 to 0.25 mm and a softening temperature of 49 ⁰ C to 204 ⁰ C on a base, 0 2 ..) heating of the themoplas tical film to a Yort temperature up to 93 ° E, 3 ..) j heating of the metal mother plate to a temperature of 49 ⁰ C to 204 ⁰ C ,, ' 4 «.) Pressing the metal mother plate against the thermoplastic Fabric for less than 50 seconds at a pressure of 27 to 408 atmospheres, and 5.) Removal of the fourth positive produced in this way Machformation of the metal mother plate while this maintains its pressing temperature, and h) repetition of step g,) at least once with a new one thermoplastic material: · ■ 1098 14/1735