CA2077536A1 - Electrolessly deposited metal holograms - Google Patents
Electrolessly deposited metal hologramsInfo
- Publication number
- CA2077536A1 CA2077536A1 CA002077536A CA2077536A CA2077536A1 CA 2077536 A1 CA2077536 A1 CA 2077536A1 CA 002077536 A CA002077536 A CA 002077536A CA 2077536 A CA2077536 A CA 2077536A CA 2077536 A1 CA2077536 A1 CA 2077536A1
- Authority
- CA
- Canada
- Prior art keywords
- relief
- metal
- holographic
- patterned
- polymeric substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 64
- 239000002184 metal Substances 0.000 title claims abstract description 64
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 238000000151 deposition Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229920006037 cross link polymer Polymers 0.000 claims 2
- 239000000463 material Substances 0.000 description 6
- 238000001465 metallisation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000012704 polymeric precursor Substances 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H1/0252—Laminate comprising a hologram layer
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H1/024—Hologram nature or properties
- G03H1/0244—Surface relief holograms
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2250/00—Laminate comprising a hologram layer
- G03H2250/36—Conform enhancement layer
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2250/00—Laminate comprising a hologram layer
- G03H2250/39—Protective layer
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Holo Graphy (AREA)
Abstract
Electrolessly deposited metal holograms comprising a polymeric substrate (1) having a holographic relief-patterned surface and a metal reflective layer (2) electrolessly deposited to conform to and reproduce the holographic relief pattern. Light incident to the metal surface is reflected to provide a holographic reproduction of a holographic image inherent in said relief-patterned polymeric substrate.
Description
2077~36 O91t1497~ PCT/US91/01262 ELECTROLESSLY DEPOSITED METAL HOLOGRAMS
Disclosed herein are holograms comprising a relief-patterned metal surface electrolessly deposited to conform to a relief-patterned polymeric substrate.
Also disclosed are methods for producing electrolessly deposited metal holograms.
BACKGROUND OF THE INVENTION
Holograms and other types of diffraction gratings comprising reflective metal surface on a relief-patterned substrate are commonly used for decorative packaging, artistic images and security devices, e.g. on credit cards, currency and other official documentsu Such holograms can be prepared by a variety of methods such as embossing deformable metal foil laminates with a holographic image stamp.
Due to the resilience of laminate components, such embossed holograms tend to be of poor quality especially when subjected to elevated temperatures.
An alternative method is disclosed by D'Amato et al. in European Patent Publication 0 338 378 where a holographic polymeric substrate is formed by casting and curing a polymer precursor in contact with a holographic relief-patterned mold to form a polymeric substrate with a holographic relief-patterned surface; a metal reflective surface is then deposited on the relief-patterned surface, e.g. by vapor deposition techniques. The resulting relief-patterned metal surface serves to reflect incidentlight into a reconstructed image of the hologram. A
disadvantage of such metal deposition is the requirement to conduct such metal deposition in a vacuum environment and to mask areas where metal deposition is not desired especially if the hologram is mounted on a document.
~.
W091/1497~ 2 0 7 7 ~ 3 ~ PCT/US91/01262 ~
An object of this invention is to provide such reflective metal holograms which can be prepared by metal deposition techniques that do not require vacuum environments or masking. One method for depositing metal onto polymeric substrates is electroless deposition. However, electroless deposition of metal has some disadvantages which do not commend it to such hologram preparation. For instance, many techniques for electroless deposition of metal onto plastics require etching to achieve a effective level of adhesion; such etching, e.g. with strong acids or solvents, can destroy the holographic relief pattern of the polymeric substrate surface.
Moreover, electroless deposition techniques often utilize catalytic materials of a size on the order of magnitude of the holographic relief pattern;
deposition of dispersed particulate catalytic materials can distort the reproduction of the holographic relief pattern in the metal coating.
Disclosed herein are holograms comprising a relief-patterned metal surface electrolessly deposited to conform to a relief-patterned polymeric substrate.
Also disclosed are methods for producing electrolessly deposited metal holograms.
BACKGROUND OF THE INVENTION
Holograms and other types of diffraction gratings comprising reflective metal surface on a relief-patterned substrate are commonly used for decorative packaging, artistic images and security devices, e.g. on credit cards, currency and other official documentsu Such holograms can be prepared by a variety of methods such as embossing deformable metal foil laminates with a holographic image stamp.
Due to the resilience of laminate components, such embossed holograms tend to be of poor quality especially when subjected to elevated temperatures.
An alternative method is disclosed by D'Amato et al. in European Patent Publication 0 338 378 where a holographic polymeric substrate is formed by casting and curing a polymer precursor in contact with a holographic relief-patterned mold to form a polymeric substrate with a holographic relief-patterned surface; a metal reflective surface is then deposited on the relief-patterned surface, e.g. by vapor deposition techniques. The resulting relief-patterned metal surface serves to reflect incidentlight into a reconstructed image of the hologram. A
disadvantage of such metal deposition is the requirement to conduct such metal deposition in a vacuum environment and to mask areas where metal deposition is not desired especially if the hologram is mounted on a document.
~.
W091/1497~ 2 0 7 7 ~ 3 ~ PCT/US91/01262 ~
An object of this invention is to provide such reflective metal holograms which can be prepared by metal deposition techniques that do not require vacuum environments or masking. One method for depositing metal onto polymeric substrates is electroless deposition. However, electroless deposition of metal has some disadvantages which do not commend it to such hologram preparation. For instance, many techniques for electroless deposition of metal onto plastics require etching to achieve a effective level of adhesion; such etching, e.g. with strong acids or solvents, can destroy the holographic relief pattern of the polymeric substrate surface.
Moreover, electroless deposition techniques often utilize catalytic materials of a size on the order of magnitude of the holographic relief pattern;
deposition of dispersed particulate catalytic materials can distort the reproduction of the holographic relief pattern in the metal coating.
Despite the disadvantages inherent in many electroless deposition techniques, this invention provides a hologram comprising a relief-patterned metal surface electrolessly-deposited to conform to a relief-patterned polymeric substrate, whereby light incident to the surface of said metal opposite to said polymeric substrate is reflected to provide a holographic reproduction of a holographic image inherent in said relief-patterned polymeric substrateO
Such metal surface is provided in a thin, conforming layer that reproduces the holographic relief-patterned surface of the polymeric substrate by electroless deposition techniques.
This invention also provides methods of preparing electrolessly deposited metal holograms, e.g. preparing a polymeric substrate having a holographic relief-patterned surface and electrolessly :: , ~ WO91/1497~ 20~7~ PCT/US9l/olt62 depositing a conforming holographic metal reflective layer on said relief-patterned surface. In a preferred embodiment a polymeric substrate having a holographic relief-patterned surface is prepared by casting and curing polymeric precursor in a holographic relief-patterned mold. The conforming holographic metal reflective surface is prepared by electrolessly depositing metal onto the holographic relief-patterned surface in a method comprising:
(a) coating a holographic relief-patterned polymeric substrate surface with a film-forming solution of a polymer and a Group 8 metal;
(b) drying said film-forming solution to form a polymeric film essentially conforming to and reproducing said holographic relief pattern;
(c) heating said polymeric film to provide a catalytic surface thereon;
(d) applying to said catalytic surface an electroless depositing metal solution for sufficient time to electrolessly deposit thereon a metal surface which essentially conforms to and reproduces said holographic relief pattern. The electrolessly deposited metal layer allows light incident to the holographic reproduced metal surface, which is opposite to the holographic relief-patterned polymeric substrate, to be reflected to provide a holographic reproduction of an holographic image inherent in said relief patterned polymeric substrate.
BRIEF_DESCRIPTION OF T~E DRAWING
Figure l is a schematic representation of an electrolessly deposited metal hologram according to this invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to Figure l there is illustrated a polymeric substrate l which can be prepared by molding a molten thermoplastic, e.g. a high glass temperature thermoplastic such as a polyimide or polyetherketone, - : . - : - ~ . - .
Wo91/14979 2 0 7 7 ~ ~ ~ PCT/US91/01~62 ~
in a mold having a holographic relief pattern on its surface. Preferably, such polymeric substrate can be prepared by casting and curing thermoset polymer precursor, e.g. crosslinkable material such as an acrylate, urethane or epoxy polymer precursor, in a mold having a holographic relief pattern. Methods for preparing such substrates are known in the art and are disclosed by D'Amato et al. in European Patent Publication 0 338 378, the specification of which is incorporated herein by reference.
Conforming to the holographic relief pattern of the polymeric substrate is an electrolessly deposited metal layer 2 which provides reflective surfaces from which incident light can be reflected into a reconstructed image of the hologram inherent in the holographic relief pattern. As indicated above many electroless deposition techniques are inherently incompatible for use in preparing holographic metal surfaces. It has been discovered that electroless deposition techniques such as those disclosed by Norgan et al. in U.S. Patent 4,9lO,072 and by Vaughn -in U.S. Application Serial No. 07/454,565, the specifications of both of which are incorporated herein by reference, are surprisingly advantageous and efficacious in the preparation of holographic metal surfaces. The improved electroless deposition methods of this invention comprise: (a) coating a holographic relief-patterned polymeric substrate l with a film-forming solution, preferably substantially aqueous, comprising a polymer, e.g. polyvinyl alcohol, and a Group 8 metal, e.g. a palladium salt; (b) drying said film-forming solution to form a polymeric film essentially conforming to and reproducing said holographic relief pattern; (c) heating said polymeric film by exposure to a temperature of at least about 200 C to provide a catalytic surface thereon; (d) applying to said catalytic surface an electroless .
:, .
2 0 7 7 ~ 3 o 09~/1497~ PCT/US91/01262 depositing metal solution for a contact time of less than 20 seconds to electrolessly deposit thereon a metal surface 2 which essentially conforms to and reproduces said holographic relief pattern. The drying and heating can be simultaneously effected.
The contact time for applying said electroless deposition solution should be sufficient to electrolessly deposit a metal layer 2 in sufficient thickness, e.g. at least about 5 nanometers thick, to provide a mirror like surface and sufficiently thin, e.g. not more than about 300 nanometers thick so as to not obscure the underlying holographic image. A
balance of good reproduction of the holographic image and durability of a mirror like finish is achieved when the metal layer is between about 10 and 100 nanometers thick. Most preferred metal layers are about 20 to 60 nanometers thick. Preferred contacts times are less than 10 seconds, more preferably less than 5 seconds. The contact time can be effectively reduced by adjusting the electroless deposition environment, e.g. by elevating temperatures of the substrate and the electroless deposition solution for instance up to about 80 - 90 C.
Useful metals for the electrolessly deposited layer include nickel, cobalt, copper, palladium, silver, platinum and gold which can be applied as a single metal layer or a laminate of metal layers. The metal layer can be optionally overcoated with a protective wear layer, e.g of a clear acrylate -or urethane topcoat which does not interfere with the transmission of light to and from the metal layer. -An advantage of the electrolessly deposited holograms of this invention is the application of methods of preparation thereof to continuous processing of web material containing such holograms including web material comprising holograms of extended length as on artistic or decorative sheets -W09l~l4975 2 0 7 7 ~ 3 ~ PCT/US91/01262 ~
and web material comprising holograms on selected areas of the web as on security documents. Such continuous processes are disclosed in European Patent Publication 0 338 378 referred to hereinabove. The electroless deposition methods can be effected by applying the film forming solution and electrolessly depositing metal solutions from solution saturated surfaces in register with a moving web so as to contact the holographic relief surface of the polymeric substrate and catalyzed relief surface, respectively.
The following examples serve to illustrate certain embodiments and aspects of this invention but are not intended to imply any limitation of the scope of the invention.
EXAMPLE
This example illustrates the electroless deposition of a nickel onto a relief-patterned polymeric substrate.
A catalytic metal solution was prepared from 0.1 g palladium (II) acetate, 2.0 ml water and 10 ml acetone. A water soluble polymer solution was prepared from 0.12 g polyvinylalcohol (12S,000 M.W., 88 mole % hydrolyzed) and 0.013 g Triton X-100 polyoxyethylene surfactant (Rohm & Haas) and about 6 ml water. The catalytic metal solution, followed by 50 ml of rinse water and 0.25 ml triethylamine, was mixed with the water soluble polymer solution to provide a substantially aqueous film forming solution.
A polymeric substrate having a hologram generating relief-patterned surface was coated by wiping the surface with a sponge saturated with the film forming solution. The film forming solution was dried by holding the dry side of the polymeric substrate in a 220- C air stream for about 10 seconds to provide a catalytic surface on the hologram generating relief-patterned surface. The polymeric substrate was placed .
: . . ~; -, .
~ ~91/1497~ 2 o 7 ~ i PCT/US91/0l262 on a 95- C surface while the catalytic surface was covered for about 5 seconds with a solution of electroless depositing nickel solution (obtained from MacDermid, Inc. identified as XD7054EN) comprising 6 g/l nickel and 30 g/l sodium hypophosphite monohydrate -adjusted to pH 5.5 with ammonium hydroxide solution and maintained at about 80- C. After the 5 second exposure, the nickel solution was rinsed off with water providing a reflective holographic nickel surface.
While specific embodiments have been described herein, it should be apparent to those skilled in the art that various modifications thereof can be made without departing from the true spirit and scope of the invention. Accordingly, it is intended that the following claims cover all such modifications within the full inventive concept.
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. , . - . . . . -. .: . . : . : . .
- . , ~ ' '' ' ,
Such metal surface is provided in a thin, conforming layer that reproduces the holographic relief-patterned surface of the polymeric substrate by electroless deposition techniques.
This invention also provides methods of preparing electrolessly deposited metal holograms, e.g. preparing a polymeric substrate having a holographic relief-patterned surface and electrolessly :: , ~ WO91/1497~ 20~7~ PCT/US9l/olt62 depositing a conforming holographic metal reflective layer on said relief-patterned surface. In a preferred embodiment a polymeric substrate having a holographic relief-patterned surface is prepared by casting and curing polymeric precursor in a holographic relief-patterned mold. The conforming holographic metal reflective surface is prepared by electrolessly depositing metal onto the holographic relief-patterned surface in a method comprising:
(a) coating a holographic relief-patterned polymeric substrate surface with a film-forming solution of a polymer and a Group 8 metal;
(b) drying said film-forming solution to form a polymeric film essentially conforming to and reproducing said holographic relief pattern;
(c) heating said polymeric film to provide a catalytic surface thereon;
(d) applying to said catalytic surface an electroless depositing metal solution for sufficient time to electrolessly deposit thereon a metal surface which essentially conforms to and reproduces said holographic relief pattern. The electrolessly deposited metal layer allows light incident to the holographic reproduced metal surface, which is opposite to the holographic relief-patterned polymeric substrate, to be reflected to provide a holographic reproduction of an holographic image inherent in said relief patterned polymeric substrate.
BRIEF_DESCRIPTION OF T~E DRAWING
Figure l is a schematic representation of an electrolessly deposited metal hologram according to this invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to Figure l there is illustrated a polymeric substrate l which can be prepared by molding a molten thermoplastic, e.g. a high glass temperature thermoplastic such as a polyimide or polyetherketone, - : . - : - ~ . - .
Wo91/14979 2 0 7 7 ~ ~ ~ PCT/US91/01~62 ~
in a mold having a holographic relief pattern on its surface. Preferably, such polymeric substrate can be prepared by casting and curing thermoset polymer precursor, e.g. crosslinkable material such as an acrylate, urethane or epoxy polymer precursor, in a mold having a holographic relief pattern. Methods for preparing such substrates are known in the art and are disclosed by D'Amato et al. in European Patent Publication 0 338 378, the specification of which is incorporated herein by reference.
Conforming to the holographic relief pattern of the polymeric substrate is an electrolessly deposited metal layer 2 which provides reflective surfaces from which incident light can be reflected into a reconstructed image of the hologram inherent in the holographic relief pattern. As indicated above many electroless deposition techniques are inherently incompatible for use in preparing holographic metal surfaces. It has been discovered that electroless deposition techniques such as those disclosed by Norgan et al. in U.S. Patent 4,9lO,072 and by Vaughn -in U.S. Application Serial No. 07/454,565, the specifications of both of which are incorporated herein by reference, are surprisingly advantageous and efficacious in the preparation of holographic metal surfaces. The improved electroless deposition methods of this invention comprise: (a) coating a holographic relief-patterned polymeric substrate l with a film-forming solution, preferably substantially aqueous, comprising a polymer, e.g. polyvinyl alcohol, and a Group 8 metal, e.g. a palladium salt; (b) drying said film-forming solution to form a polymeric film essentially conforming to and reproducing said holographic relief pattern; (c) heating said polymeric film by exposure to a temperature of at least about 200 C to provide a catalytic surface thereon; (d) applying to said catalytic surface an electroless .
:, .
2 0 7 7 ~ 3 o 09~/1497~ PCT/US91/01262 depositing metal solution for a contact time of less than 20 seconds to electrolessly deposit thereon a metal surface 2 which essentially conforms to and reproduces said holographic relief pattern. The drying and heating can be simultaneously effected.
The contact time for applying said electroless deposition solution should be sufficient to electrolessly deposit a metal layer 2 in sufficient thickness, e.g. at least about 5 nanometers thick, to provide a mirror like surface and sufficiently thin, e.g. not more than about 300 nanometers thick so as to not obscure the underlying holographic image. A
balance of good reproduction of the holographic image and durability of a mirror like finish is achieved when the metal layer is between about 10 and 100 nanometers thick. Most preferred metal layers are about 20 to 60 nanometers thick. Preferred contacts times are less than 10 seconds, more preferably less than 5 seconds. The contact time can be effectively reduced by adjusting the electroless deposition environment, e.g. by elevating temperatures of the substrate and the electroless deposition solution for instance up to about 80 - 90 C.
Useful metals for the electrolessly deposited layer include nickel, cobalt, copper, palladium, silver, platinum and gold which can be applied as a single metal layer or a laminate of metal layers. The metal layer can be optionally overcoated with a protective wear layer, e.g of a clear acrylate -or urethane topcoat which does not interfere with the transmission of light to and from the metal layer. -An advantage of the electrolessly deposited holograms of this invention is the application of methods of preparation thereof to continuous processing of web material containing such holograms including web material comprising holograms of extended length as on artistic or decorative sheets -W09l~l4975 2 0 7 7 ~ 3 ~ PCT/US91/01262 ~
and web material comprising holograms on selected areas of the web as on security documents. Such continuous processes are disclosed in European Patent Publication 0 338 378 referred to hereinabove. The electroless deposition methods can be effected by applying the film forming solution and electrolessly depositing metal solutions from solution saturated surfaces in register with a moving web so as to contact the holographic relief surface of the polymeric substrate and catalyzed relief surface, respectively.
The following examples serve to illustrate certain embodiments and aspects of this invention but are not intended to imply any limitation of the scope of the invention.
EXAMPLE
This example illustrates the electroless deposition of a nickel onto a relief-patterned polymeric substrate.
A catalytic metal solution was prepared from 0.1 g palladium (II) acetate, 2.0 ml water and 10 ml acetone. A water soluble polymer solution was prepared from 0.12 g polyvinylalcohol (12S,000 M.W., 88 mole % hydrolyzed) and 0.013 g Triton X-100 polyoxyethylene surfactant (Rohm & Haas) and about 6 ml water. The catalytic metal solution, followed by 50 ml of rinse water and 0.25 ml triethylamine, was mixed with the water soluble polymer solution to provide a substantially aqueous film forming solution.
A polymeric substrate having a hologram generating relief-patterned surface was coated by wiping the surface with a sponge saturated with the film forming solution. The film forming solution was dried by holding the dry side of the polymeric substrate in a 220- C air stream for about 10 seconds to provide a catalytic surface on the hologram generating relief-patterned surface. The polymeric substrate was placed .
: . . ~; -, .
~ ~91/1497~ 2 o 7 ~ i PCT/US91/0l262 on a 95- C surface while the catalytic surface was covered for about 5 seconds with a solution of electroless depositing nickel solution (obtained from MacDermid, Inc. identified as XD7054EN) comprising 6 g/l nickel and 30 g/l sodium hypophosphite monohydrate -adjusted to pH 5.5 with ammonium hydroxide solution and maintained at about 80- C. After the 5 second exposure, the nickel solution was rinsed off with water providing a reflective holographic nickel surface.
While specific embodiments have been described herein, it should be apparent to those skilled in the art that various modifications thereof can be made without departing from the true spirit and scope of the invention. Accordingly, it is intended that the following claims cover all such modifications within the full inventive concept.
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Claims (16)
1. A hologram comprising a relief-patterned metal surface electrolessly-deposited to conform to a relief-patterned polymeric substrate, whereby light incident to the surface of said metal opposite to said polymeric substrate is reflected to provide a holographic reproduction of a holographic image inherent in said relief patterned polymeric substrate.
2. A hologram according to claim 1 wherein said relief-patterned polymeric substrate comprises a crosslinked polymer.
3. A hologram according to claim 2 wherein said electrolessly deposited metal comprises nickel, cobalt, copper, palladium, silver, platinum or gold.
4. A hologram according to claim 1 wherein said electrolessly deposited metal layer is 5 to 300 nanometers thick.
5. In a hologram comprising a reflective metal surface in contact with a relief-patterned polymeric substrate, the improvement wherein said reflective metal surface is electrolessly deposited onto said relief-patterned polymeric substrate to provide holographic image producing surfaces on both the relief-patterned polymeric substrate side and opposite side of said metal surface, wherein light incident to both of said metal surfaces is reflected to provide a holographic reproduction of a holographic image inherent in said relief patterned polymeric substrate.
6. A method of preparing electrolessly deposited metal holograms comprising:
(a) forming a polymeric substrate having a holographic relief-patterned surface;
(b) electrolessly depositing thereon a metal layer conforming to and reproducing said holographic relief pattern.
(a) forming a polymeric substrate having a holographic relief-patterned surface;
(b) electrolessly depositing thereon a metal layer conforming to and reproducing said holographic relief pattern.
7. A method according to claim 6 wherein said substrate is formed by casting and curing crosslinkable polymer precursor against a holographic relief-patterned mold.
8. A method according to claim 7 wherein said electrolessly depositing comprises (a) coating said holographic relief-patterned surface with a film-forming solution of a polymer and a Group 8 metal; (b) drying said film-forming solution to form a polymeric film essentially conforming to and reproducing said holographic relief pattern; (c) heating said polymeric film to provide a catalytic surface thereon; (d) applying to said catalytic surface an electrolessly depositing metal solution to electrolessly deposit thereon a metal which essentially conforms to and reproduces said holographic relief pattern;
wherein light incident to the surface of said metal, which is opposite to the holographic relief-patterned polymeric substrate, is reflected to provide a holographic reproduction of a holographic image inherent in said relief patterned polymeric substrate.
wherein light incident to the surface of said metal, which is opposite to the holographic relief-patterned polymeric substrate, is reflected to provide a holographic reproduction of a holographic image inherent in said relief patterned polymeric substrate.
9. A method according to claim 8 wherein said heating is effected by exposure of said polymeric film to a temperature of at least about 200° C to provide a catalytic surface thereon.
10. A method according to claim 8 wherein said electrolessly depositing metal solution is applied to said catalytic surface for a contact time of less than 20 seconds to electrolessly deposit thereon a metal which essentially conforms to and reproduces said holographic relief pattern.
11. A method according to claim 9 wherein said drying and heating are simultaneously effected by exposure to a temperature of at least about 200° C.
12. A method according to claim 8 wherein said relief-patterned polymeric substrate comprises a crosslinked polymer.
13. A method according to claim 8 wherein said electrolessly deposited metal comprises nickel, cobalt, copper, palladium, silver, platinum or gold.
14. A method according to claim 8 wherein said applying of an electroless deposition solution is effected for sufficient time to provide an electrolessly deposited metal layer of 5 to 300 nanometers thick.
15. A method according to claim 8 wherein said film forming solution is substantially aqueous.
16. A method according to claim 8 wherein a plurality of said holograms is prepared on a moving web.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US49816390A | 1990-03-22 | 1990-03-22 | |
| US497,960 | 1990-03-22 | ||
| US07/497,960 US5087510A (en) | 1990-03-22 | 1990-03-22 | Electrolessly deposited metal holograms |
| US498,163 | 1990-03-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2077536A1 true CA2077536A1 (en) | 1991-09-23 |
Family
ID=27052660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002077536A Abandoned CA2077536A1 (en) | 1990-03-22 | 1991-02-26 | Electrolessly deposited metal holograms |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0521042A1 (en) |
| JP (1) | JPH05505887A (en) |
| CN (1) | CN1055247A (en) |
| AU (1) | AU641231B2 (en) |
| CA (1) | CA2077536A1 (en) |
| IL (1) | IL97630A0 (en) |
| WO (1) | WO1991014975A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6867983B2 (en) | 2002-08-07 | 2005-03-15 | Avery Dennison Corporation | Radio frequency identification device and method |
| GB0902398D0 (en) | 2009-02-13 | 2009-04-01 | Conductive Inkjet Tech Ltd | Diffractive optical elements |
| CN108463519B (en) * | 2015-09-24 | 2020-12-25 | 杨军 | Thin film coating composition and coating method |
| KR102696144B1 (en) * | 2021-08-10 | 2024-08-20 | (주) 제이피이 | Color Changeable Interior film and method of manufacturing the same using nano pattern |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3585113A (en) * | 1965-12-23 | 1971-06-15 | Rca Corp | Process for fabricating replicating masters |
| NL8304084A (en) * | 1983-11-29 | 1985-06-17 | Philips Nv | METHOD FOR APPLYING A METAL MIRROR. |
| KR860009325A (en) * | 1985-05-07 | 1986-12-22 | 기다지마 요시도시 | Transparent Hologram |
| US4900618A (en) * | 1986-11-07 | 1990-02-13 | Monsanto Company | Oxidation-resistant metal coatings |
| GB8803252D0 (en) * | 1988-02-12 | 1988-03-09 | Markem Syst Ltd | Method of manufacturing relief holograms |
-
1991
- 1991-02-26 JP JP91506040A patent/JPH05505887A/en active Pending
- 1991-02-26 EP EP19910906231 patent/EP0521042A1/en not_active Withdrawn
- 1991-02-26 CA CA002077536A patent/CA2077536A1/en not_active Abandoned
- 1991-02-26 AU AU74780/91A patent/AU641231B2/en not_active Withdrawn - After Issue
- 1991-02-26 WO PCT/US1991/001262 patent/WO1991014975A1/en not_active Application Discontinuation
- 1991-03-21 CN CN91101847A patent/CN1055247A/en active Pending
- 1991-03-21 IL IL97630A patent/IL97630A0/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| IL97630A0 (en) | 1992-06-21 |
| AU7478091A (en) | 1991-10-21 |
| AU641231B2 (en) | 1993-09-16 |
| EP0521042A1 (en) | 1993-01-07 |
| CN1055247A (en) | 1991-10-09 |
| WO1991014975A1 (en) | 1991-10-03 |
| JPH05505887A (en) | 1993-08-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 19940827 |