CA1094377A - Dry system image producing element having a photosensitive layer on a metal layer - Google Patents
Dry system image producing element having a photosensitive layer on a metal layerInfo
- Publication number
- CA1094377A CA1094377A CA266,883A CA266883A CA1094377A CA 1094377 A CA1094377 A CA 1094377A CA 266883 A CA266883 A CA 266883A CA 1094377 A CA1094377 A CA 1094377A
- Authority
- CA
- Canada
- Prior art keywords
- layer
- photosensitive layer
- substrate
- chloride
- intermediate layer
- 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.)
- Expired
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/50—Mask blanks not covered by G03F1/20 - G03F1/34; Preparation thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/54—Absorbers, e.g. of opaque materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
- G03F7/346—Imagewise removal by selective transfer, e.g. peeling away using photosensitive materials other than non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/04—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching
- H05K3/046—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed mechanically, e.g. by punching by selective transfer or selective detachment of a conductive layer
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Materials For Photolithography (AREA)
Abstract
DRY SYSTEM IMAGE PRODUCING ELEMENT
Abstract of the Disclosure:
There is disclosed a dry system image producing element comprising a substrates a thin metal layer and a photosensitive layer. After exposing the element to light through a desired pattern, the photosensitive layer is peeled off to obtain a light barrier pattern made from the metal on the substrate corresponding to -the photo-sensitized portion.
Abstract of the Disclosure:
There is disclosed a dry system image producing element comprising a substrates a thin metal layer and a photosensitive layer. After exposing the element to light through a desired pattern, the photosensitive layer is peeled off to obtain a light barrier pattern made from the metal on the substrate corresponding to -the photo-sensitized portion.
Description
~ 3~oJ
This invention relates to a dry sys-tem image pro-ducing element and a process ~or producing an image made :~rom a thin metal or metal compound layer, said layer having been deposited on a substrate. In more par~icular, this invention rela-tes to such element comprising a sub-strate, a thin layer of a metal or a metal compound and a pho-tosensitive layer containing a pho-tosensitizer and a polymeric binding material 9 said photosensitive layer being capable of decreasing the inter~acial adhesion between said metal or metal compound layer and said photo-sensitive layer upon exposure to light, and to a process for producing an image made from a metal or metal compound layer wherein such image producing elemen-t is exposed to light through a pattern and the photosensitive layer is peeled off to obtain an image or pattern made ~rom the metal or metal compound layer on the subs-trate correspond-ing to the photosensitized portion.
Various processes have already been proposed for producing an image on a substrate, for example, (l) by exposing to light an element comprising a substrate and a photosensitive coating containing a photosensitizer such as a silver halide, a pho-tosensitive polymer or a photopoly~erisable monomer, or (2) by exposing to light an element comprising a photoconductive layer and e~ect-ing toner development. Ho~ever, such prior art i~volvesinherent disadvantages~ For example, where a silver halide is used, development, fixing, washing with water and drying are required; where a photosensitive polymer or a photo-polymerisable monomer is used, developmen-t, etching and dr~ing are required; and where a photoconductive material _ ~ _ is used, activationJ use of toner and fixing hy hea-t are re~uired. Thus, with the prior art it is necessary to use special chemical trea-tment and/or apparatus with resulting high cost and environmental pollution caused by chemicals.
Accordingly, an object of this inven-tion is to provide a dry system image producing element which avoids the abovementioned defects.
Another object is to provide an image producing element which possesses a high Y-value, high contrast and good resolving power and which can produce an image having improved light barrier effect.
Still another object is to provide an image produc-ing element which can provide an electroconductive pattern on a substrate.
The dry system image producing element according to this invention comprises a tough substrate having a smooth surface, a thin layer of a metal or a metal com-pound (hereinafter referred to as the "metal layeri') and a photosensitive layer containing a polymeric binding material which is a film forming material and a benzophenone9 quinone compound, diazonium compound or azido compound photosensitizer, said photosensitive layer being capable of decreasing the interfacial adhesion between -the metal layer and the photosensitive layer upon exposure to light.
Thus, when the element according to this inven-tion is exposed to light through a mask having a desired pattern, the interfacial adhesion between the metal layer and the photosensitized portion of the pho-tosensitive layer decreasesg but such adhesion in respect o~ the non~photosensi-tized ~ 7'~
portion does not change. Then, when the photosensitive layer is peeled off, a metal pattern corresponding to the photosensitized portion remains on the substrate but the non-pho-tosensitized portion of the metal layer is removed In this connection, it is essential that the ~`
adhesion of the binding material to the metal layer be higher than that of ~he metal layer -to the substrate.
The substrate which may be employed according to this invention includes a variety o~ materials capable of accepting a thin metal layer thereon~ such as a film forming thermoplastic polymeric material, glass or metal.
Examples of the thermoplas-tic material are various synthetic resins, for example, a polyester such as polyethylene terephthalate, a polycarbonate, a polyolefin such as polypropylene, polyvinyl chloride, polystyrene9 polymethyl methacrylate and a copolymer thereo.~ and cellulose deriva-tives, for example, diacetylcellulose, triacetylcellulose, propylcellulose and a mixed cellulose ester. Other sheet-like materials such as paper, woven ~abric and non woven fabric which have been coated with the above-mentioned ~ilm forming material may also be used~
The substrate material may be incorporated with various additives, such as pigment~ dyestuf~ and filler to give a writing OI` printing ink accepting property, opacity and coloration~ -The thin metal layer on the surface of the substrate may be produced by, ~or exampleg vacuum plating such as vacuum evaporation and cathodic spattering, electroless plating or a combination of electrolytic plating therewith~
The thickness of the metal layer is preferably more than 3~`~'7 10 m~. A thinner layer does no-t effectively have su~ficient light barrier effect, so the image produced on the substrate is hardly visible. Although the upper limit of the thick-ness is not critical~ in general, a thickness of up to 1000 m~ preferably from 20 to 500 m~ is used. For special usage as a printed circuit, a metal layer of more than 1000 m~ in -thickness may be successfully used.
Among various metals suitable for evaporation plat-ing, aluminum and zinc are most preferred9 but next prefer-red metals are silver9 gold and nickel, but other metals, such as chromium, cobalt, iron, germaniu~m, magnesium, ;
manganese, platinum and tin may also be exemplified.
Cadmium sulfide, magnesium ~luoride and titanium dioxide are metal compounds suitable for vacu~ plating~
Electroless plating may be carried out in a con~en-tional way by subjecting the substrate to sensi-ti~ing and activation treatments, followed by immersing it in an aqueous solutlon containing metal salt and a reducing agent to deposit a metal layer on the substrate~ For this purpose9 copper, nickel, cobalt, gold, palladium, silver and nickel-cobalt and nickel-phosphorus alloys are suitable.
In general, the vacuum evaporation process is prefer-able to electrolytic or electroless plating because with it a wide range of metals can be used,-the operation is conducted in a simple way at high speed and little or no waste material is produced.
The photosensitive layer comprises a polymeric bind-ing material and a photosensitizer. Since the layer is peeled off from the substrate after printing exposure trea-tment, it is important that the binding material :~0~43~'7 possesses a goocl film forming property and has high fiIm s-trength~ further, the ma-terial is preferably non-blocking in order -that a stack of elements does not cause blockin~
wi-th each other during handling and storage~
Examples of the binding material which may be used according to this invention include various synthetic resins, for example, polyvinyl chloride, vinyl chloride/
vinyl acetate copolymer/ vinyl chloride/vinylidene chloride copol~mer, vinyl chloride/vinyl acetate/maleic anhydride, acrylonitrile or vinyl alcohol terpolymer, vinyl chloride/
vinylidene chloride/acrylonitrile, vinyl acetate or methyl methacrylate terpolymer, an acrylic es-ter/methyl methacrylate or styrene copolymer, a thermoplastic polyester or copoly-ester such as polye-thylene terephthala-te and ethylene terephthalate/isophthalate copolymer, an alcohol soluble polyamide, a polyurethane, polybutyral and polyvinyl alcohol; cellulose derlvatives such as acetylcellulose, acetyl-butylcellulose, nitrocellulose and ethylcellulose 9 : and rubber derivatives such as cyclized rubber and rubber chlorideO These polymeric materials may be used alone or in any combination.
In general, the binding material is used in the form of a solu-tion in an appropriate organic solvent, examples o~ which are,~or example, methyl ethyl ketone, toluene, cyclohexanol, methanolg ethanol, i-propanol9 * * *
me-thyl Cellosolve, e-thyl Cellosolve and Cellosolve acetateO
In selecting the solvent, caution should be taken to insure that the solvent is capable o~ dissolving the photosensitizer employed but does not dissolve or swell the substrate material.
* Trade Mark -- 6 ~
3~t7 When the binding material is polyvinyl alcohol, an aqueous solution thereof is also adequate. Polyvinyl : chloride and polyurethane may also be used in the form o~ an emulsion or a dispersion.
The photosensitizers which may be used according to this invention are classified and exemplified as ~ollowso a~ Benzophenone b) Quinone compoundso 1,4-Naphthoquinone~ 2-methyl-1,4-naphthoquinone, anthraquinone, 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-chloroanthraquinone and p-toluquinone, especially the former two being preferred.
c) Diazonium compoundso 4 (p-Tolyl mercapto)--2~5-diethoxybenzene diazonium zinc chloride, sodium sulfa-te or tetra~luoroborate, 4-(p-tolyl mercapto)~2,5-dimethoxybenzene diazonium zinc chloride, 4-(p-methyl benzoylamino)-?,5-diethoxybenzene diazoni~ zinc chloride, 4-~p-methoxybenzoylamino) 2,5-diethoxybenzene diazonium zinc chloride, ~;
4-morpholino-2,5-butoxybenzene diazoni~ zinc chloride or tetrafluoroborate, 4-morpholinobenzene diazonium tetrafluorokorate, 4-pyrrolidino-3-methylbenzene diazonium tetra~
fluoroborate, p-N,N-dimethyl aminobenzene diazonium zinc chloride9 p-N,N-diethyl aminobenzene diazonium zinc chloride or tetrafluoroborate, 3~
p-N-ethyl-N-hydroxy aminobenzene diazonium zinc chloride, 1,2-diazonaphthol-5-sul~onic acid sodium salt, and zinc chloride salt of a condensate of 4-diazo-diphenylamine sul~uric acid and formaldehyde.
d) Azido compoundo
This invention relates to a dry sys-tem image pro-ducing element and a process ~or producing an image made :~rom a thin metal or metal compound layer, said layer having been deposited on a substrate. In more par~icular, this invention rela-tes to such element comprising a sub-strate, a thin layer of a metal or a metal compound and a pho-tosensitive layer containing a pho-tosensitizer and a polymeric binding material 9 said photosensitive layer being capable of decreasing the inter~acial adhesion between said metal or metal compound layer and said photo-sensitive layer upon exposure to light, and to a process for producing an image made from a metal or metal compound layer wherein such image producing elemen-t is exposed to light through a pattern and the photosensitive layer is peeled off to obtain an image or pattern made ~rom the metal or metal compound layer on the subs-trate correspond-ing to the photosensitized portion.
Various processes have already been proposed for producing an image on a substrate, for example, (l) by exposing to light an element comprising a substrate and a photosensitive coating containing a photosensitizer such as a silver halide, a pho-tosensitive polymer or a photopoly~erisable monomer, or (2) by exposing to light an element comprising a photoconductive layer and e~ect-ing toner development. Ho~ever, such prior art i~volvesinherent disadvantages~ For example, where a silver halide is used, development, fixing, washing with water and drying are required; where a photosensitive polymer or a photo-polymerisable monomer is used, developmen-t, etching and dr~ing are required; and where a photoconductive material _ ~ _ is used, activationJ use of toner and fixing hy hea-t are re~uired. Thus, with the prior art it is necessary to use special chemical trea-tment and/or apparatus with resulting high cost and environmental pollution caused by chemicals.
Accordingly, an object of this inven-tion is to provide a dry system image producing element which avoids the abovementioned defects.
Another object is to provide an image producing element which possesses a high Y-value, high contrast and good resolving power and which can produce an image having improved light barrier effect.
Still another object is to provide an image produc-ing element which can provide an electroconductive pattern on a substrate.
The dry system image producing element according to this invention comprises a tough substrate having a smooth surface, a thin layer of a metal or a metal com-pound (hereinafter referred to as the "metal layeri') and a photosensitive layer containing a polymeric binding material which is a film forming material and a benzophenone9 quinone compound, diazonium compound or azido compound photosensitizer, said photosensitive layer being capable of decreasing the interfacial adhesion between -the metal layer and the photosensitive layer upon exposure to light.
Thus, when the element according to this inven-tion is exposed to light through a mask having a desired pattern, the interfacial adhesion between the metal layer and the photosensitized portion of the pho-tosensitive layer decreasesg but such adhesion in respect o~ the non~photosensi-tized ~ 7'~
portion does not change. Then, when the photosensitive layer is peeled off, a metal pattern corresponding to the photosensitized portion remains on the substrate but the non-pho-tosensitized portion of the metal layer is removed In this connection, it is essential that the ~`
adhesion of the binding material to the metal layer be higher than that of ~he metal layer -to the substrate.
The substrate which may be employed according to this invention includes a variety o~ materials capable of accepting a thin metal layer thereon~ such as a film forming thermoplastic polymeric material, glass or metal.
Examples of the thermoplas-tic material are various synthetic resins, for example, a polyester such as polyethylene terephthalate, a polycarbonate, a polyolefin such as polypropylene, polyvinyl chloride, polystyrene9 polymethyl methacrylate and a copolymer thereo.~ and cellulose deriva-tives, for example, diacetylcellulose, triacetylcellulose, propylcellulose and a mixed cellulose ester. Other sheet-like materials such as paper, woven ~abric and non woven fabric which have been coated with the above-mentioned ~ilm forming material may also be used~
The substrate material may be incorporated with various additives, such as pigment~ dyestuf~ and filler to give a writing OI` printing ink accepting property, opacity and coloration~ -The thin metal layer on the surface of the substrate may be produced by, ~or exampleg vacuum plating such as vacuum evaporation and cathodic spattering, electroless plating or a combination of electrolytic plating therewith~
The thickness of the metal layer is preferably more than 3~`~'7 10 m~. A thinner layer does no-t effectively have su~ficient light barrier effect, so the image produced on the substrate is hardly visible. Although the upper limit of the thick-ness is not critical~ in general, a thickness of up to 1000 m~ preferably from 20 to 500 m~ is used. For special usage as a printed circuit, a metal layer of more than 1000 m~ in -thickness may be successfully used.
Among various metals suitable for evaporation plat-ing, aluminum and zinc are most preferred9 but next prefer-red metals are silver9 gold and nickel, but other metals, such as chromium, cobalt, iron, germaniu~m, magnesium, ;
manganese, platinum and tin may also be exemplified.
Cadmium sulfide, magnesium ~luoride and titanium dioxide are metal compounds suitable for vacu~ plating~
Electroless plating may be carried out in a con~en-tional way by subjecting the substrate to sensi-ti~ing and activation treatments, followed by immersing it in an aqueous solutlon containing metal salt and a reducing agent to deposit a metal layer on the substrate~ For this purpose9 copper, nickel, cobalt, gold, palladium, silver and nickel-cobalt and nickel-phosphorus alloys are suitable.
In general, the vacuum evaporation process is prefer-able to electrolytic or electroless plating because with it a wide range of metals can be used,-the operation is conducted in a simple way at high speed and little or no waste material is produced.
The photosensitive layer comprises a polymeric bind-ing material and a photosensitizer. Since the layer is peeled off from the substrate after printing exposure trea-tment, it is important that the binding material :~0~43~'7 possesses a goocl film forming property and has high fiIm s-trength~ further, the ma-terial is preferably non-blocking in order -that a stack of elements does not cause blockin~
wi-th each other during handling and storage~
Examples of the binding material which may be used according to this invention include various synthetic resins, for example, polyvinyl chloride, vinyl chloride/
vinyl acetate copolymer/ vinyl chloride/vinylidene chloride copol~mer, vinyl chloride/vinyl acetate/maleic anhydride, acrylonitrile or vinyl alcohol terpolymer, vinyl chloride/
vinylidene chloride/acrylonitrile, vinyl acetate or methyl methacrylate terpolymer, an acrylic es-ter/methyl methacrylate or styrene copolymer, a thermoplastic polyester or copoly-ester such as polye-thylene terephthala-te and ethylene terephthalate/isophthalate copolymer, an alcohol soluble polyamide, a polyurethane, polybutyral and polyvinyl alcohol; cellulose derlvatives such as acetylcellulose, acetyl-butylcellulose, nitrocellulose and ethylcellulose 9 : and rubber derivatives such as cyclized rubber and rubber chlorideO These polymeric materials may be used alone or in any combination.
In general, the binding material is used in the form of a solu-tion in an appropriate organic solvent, examples o~ which are,~or example, methyl ethyl ketone, toluene, cyclohexanol, methanolg ethanol, i-propanol9 * * *
me-thyl Cellosolve, e-thyl Cellosolve and Cellosolve acetateO
In selecting the solvent, caution should be taken to insure that the solvent is capable o~ dissolving the photosensitizer employed but does not dissolve or swell the substrate material.
* Trade Mark -- 6 ~
3~t7 When the binding material is polyvinyl alcohol, an aqueous solution thereof is also adequate. Polyvinyl : chloride and polyurethane may also be used in the form o~ an emulsion or a dispersion.
The photosensitizers which may be used according to this invention are classified and exemplified as ~ollowso a~ Benzophenone b) Quinone compoundso 1,4-Naphthoquinone~ 2-methyl-1,4-naphthoquinone, anthraquinone, 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-chloroanthraquinone and p-toluquinone, especially the former two being preferred.
c) Diazonium compoundso 4 (p-Tolyl mercapto)--2~5-diethoxybenzene diazonium zinc chloride, sodium sulfa-te or tetra~luoroborate, 4-(p-tolyl mercapto)~2,5-dimethoxybenzene diazonium zinc chloride, 4-(p-methyl benzoylamino)-?,5-diethoxybenzene diazoni~ zinc chloride, 4-~p-methoxybenzoylamino) 2,5-diethoxybenzene diazonium zinc chloride, ~;
4-morpholino-2,5-butoxybenzene diazoni~ zinc chloride or tetrafluoroborate, 4-morpholinobenzene diazonium tetrafluorokorate, 4-pyrrolidino-3-methylbenzene diazonium tetra~
fluoroborate, p-N,N-dimethyl aminobenzene diazonium zinc chloride9 p-N,N-diethyl aminobenzene diazonium zinc chloride or tetrafluoroborate, 3~
p-N-ethyl-N-hydroxy aminobenzene diazonium zinc chloride, 1,2-diazonaphthol-5-sul~onic acid sodium salt, and zinc chloride salt of a condensate of 4-diazo-diphenylamine sul~uric acid and formaldehyde.
d) Azido compoundo
2,6-Di(4' azido benzal)cyclohexanoneO
According to this invention, it is important to select an appropriate combination of the pho-tosensitizer and the binding material, in order to sufficiently decrease the interfacial adhesion o~ the metal layer and photosensi-tized portion o~ photosensitive layer, upon exposure the element to light.
For the benzophenone and the quinone compounds, preferred binding materials are po;Lyvinyl chloride, vinyl chloride/vinyl acetate copolymer, vinyl chloride/vinyl acetate/maleic anhydride, acrylonitrile or vin~l alcohol terpolymer, vinyl chloride/vinylidene chloride copolymer, vinyl chloride/~inylidene chloride/acrylonltrile terpolymer and nitrocellulose, since these materials can produce a high quality image. A cellulose derivative and a rubber derivative may also be used, for example9 acetylcellulose9 acetyl-butylcellulose, ethylcellulose, cyclized rubber and rubber chloride.
For the diazonium and azido compounds, polyvinyl butyral is suitable in addition to the polymeric materials mentioned in connection with the benzophenone and the quinone compounds. Further, a thermoplastic polyester and copolyester~ an alcohol soluble polyamide7 polyvinyl alcohol~ acrylic ester/methyl methacrylate or styrene
According to this invention, it is important to select an appropriate combination of the pho-tosensitizer and the binding material, in order to sufficiently decrease the interfacial adhesion o~ the metal layer and photosensi-tized portion o~ photosensitive layer, upon exposure the element to light.
For the benzophenone and the quinone compounds, preferred binding materials are po;Lyvinyl chloride, vinyl chloride/vinyl acetate copolymer, vinyl chloride/vinyl acetate/maleic anhydride, acrylonitrile or vin~l alcohol terpolymer, vinyl chloride/vinylidene chloride copolymer, vinyl chloride/~inylidene chloride/acrylonltrile terpolymer and nitrocellulose, since these materials can produce a high quality image. A cellulose derivative and a rubber derivative may also be used, for example9 acetylcellulose9 acetyl-butylcellulose, ethylcellulose, cyclized rubber and rubber chloride.
For the diazonium and azido compounds, polyvinyl butyral is suitable in addition to the polymeric materials mentioned in connection with the benzophenone and the quinone compounds. Further, a thermoplastic polyester and copolyester~ an alcohol soluble polyamide7 polyvinyl alcohol~ acrylic ester/methyl methacrylate or styrene
3~7 copolymer, polyurethane emulsion and polyvinyl chloride emulsion may also be used.
; The amount of photosensitizer to be used on the basis o~ the binding material is from 1 -to 20%9 preferably 5 to 10% by weight in case of the ben~ophenone or the quinone compound, and from 0~1 to 10% pre~erably 1 to 6%
by weight in case of the diazonium or azido compoundt A large amount of the photosensltizer causes coloration of the photosensitive layer which decreases the photo~
sensiti~ity.
A solvent solution9 an aqueous solu-tion or an emulsion con-taining the photosensitizer and the binding material may be applied to the metal layer on the substrate by any conventional coating technique including conveniently reverse, gravier and kiss roll coating. The solid content o~ such coating material may vary depending upon coating process employed and the amount to be applied ancl is in general from 5 to 30% by weight. The coating material is applied in such an amount ~hat the dried photosensitive layer is from 0.5 to 100~ and preferably 2 to 20~ in thickness.
Any dyestu~f and pigment may be incorporated in the coating material so far as they do not adversely af~ect the transparency and the photosensitizing mechanism o~ the resulting photosensitive layer. In particular, a body pigment may conveniently be added thereby producing a mat layer which gives a drawing ink and printing ink acceptable surface. Thus, the ~inal product is readily written by hand or typewriter to give a desired pattern which is reproduced as a metal image on the substrate upon 3 7~7 exposure of the element to light. If desired, the element according to this invention may be provided with a support-ing layer on the photosensitive layer in order to improve the mechanical strength of the layer to be peeled off.
Thus, it is preferred to use a transparent material such as a film made of a thermoplastic polyester, polypropylene, a polyamide, polyvinyl chloride or a cellulose es-ter, transparent paper or s~nthetic resin satura-ted paper.
The image producing element according to the invention is exposed to light through a desired pattern and the photosensitive layer is peeled off, then an image made of the metal corresponding to the photosensitized portion is produced on the substrate. ~s the light source, one emit~
ting ultraviolet to visible light of short wave length is employed; for example, a carbon arc l~mpJ a high pres-sure mercury arc lamp or a fluorescent argon lamp is preferred, but a tungsten lampJ a xenon arc lamp, a mercury arc lamp or a metal halide arc lamp may also be used. The cheapest light source is of course the sunlight.
The period for which -the image producing element is exposed to light varies depending upon the type of photosensitive layer, the wave length emitted from -the light source and the distance from the light source. It has been found that, for example, 30 seconds is a sa-tisfactory exposure time for a 3.0 ~IJ carbon arc lamp at a distance of 80 cm.
This invention will be explained referring to the accompanying drawings, in which Figure 1 illustrates a cross-sectional view of the image producing element accord-ing to this invention and Figure 2 illus-trates the state ~0 of the photosensitive layer being peeled off after exposure ~'3~37~
to the light to obtain an image or a pat-tern of the metal on the substrate.
In Figure 1, the image producing element 10 comprises a substrate 12, a metal layer 14 and a photosensitive layer 16 containing a photosensitizer and a polymeric binding material. The element is exposed to the light L through a mask M having a desired negative pattern whereby the interfacial adhesion between the photosensitized portion and the metal layer is decreased. Thus~ upon peeling off the layer, there are produced a metal pattern 18 on the substrate corresponding to the photosensitized portion and a metal pattern 20 on the photosensitive layer cor-responding to the non-photosensitized portiony in other words a positive pattern is on the substrate and a negative pattern on the photosensitive layer.
The metal pattern on the substra-te -thus produced is used :~or a wide variety of usages such as an intermediate or secondary original, a lithographic plate, a process film, a printed circuit, an original copy for display and projec-tion, an electrode ~or electroluminescence and a label.
It ha~ also been ~o~md that the loss in the inter-facial adhesion between the photosensitized portion and the metal layer is recovered~ when the photosensitized element is subjected to a heat treatment9 Therefore, it is possibleg after heating an image producing element which has been exposed to light in a desired pattern, to expose the overall photosensitive la~er to light again, ~ollowed by peeling off the photosensitive layer to pro-duce a reverse pattern made from the metal layer on the substrate corresponding to the initially non~
L~1 3 7~
photosensitized portion.
Caution should be taken that the heating tempera-ture and the heating time are not such as to decompose the unexposed photosensitiæer too much.
According to this invention, therefore, it is possible to select either a negative-positive process or a positive-positive process to produce a desired metal pattern on the substrate.
This invention has been explained speci~ically 10 referring to a sheet-like element, however, it should be understood that a dry system image producing element is also ~abricated in any of complicated three dimensional shape by, for example, the following steps-(a) depositing a thin metal layer on a three dimensional body, (b) coating a photosensitive composition on the metal layer and drying it -to obtain a photo-sensitive layer, and (c) writing a desired light shielding patte~n, for example, in black ink, on the photosensitive - layer.
The element thus obtained is exposed to light, ~ollowed by peeling off the photosensitive layer9 there is obtained a light barrier metal pattern on the three dimensional body. The product is especially suitable for display and electroluminescence purposes~
~his invention will be explained in detail by means o~ Examples. However, it should be understood that this invention is in no way limited to these Examples. In the Examples, percentage is given by weight.
3~3'~'7 ExamE~e 1 ~. .
Twenty ~rams o~ a copolymer o~ 86% of vinyl chloride~
13~ of vinyl ace-tate and 1% of maleic anhydride available -~rom Union Carbide Corporation, New York, N.Y,, U~S~A~ under the name of "Vinylite*VMCH" and 0.8 g of 4-(p tolyl mercapto)-29 5-diethoxy benzene dia7onium zinc chloride available from Kabushiki Kaisha Daito Kogyosho, Tokyo~ Japan under the name of "~ 1500*;'were dissolv2d in 80 g of meth~l ethyl ketone to obtain a pho-tosensitive composltion containing 20.63~ of solid material.
On the surface of a lOO~ polyethylene -teraph-thalate film was deposited by vacuum evaporation a lOO m~ aluminum layer7 -to which the photosensi-tive composition was coated by a wire bar and dried at 90C into 5~ photosensi-ti~e layer to ob-tain an image producing element.
A negative original was positioned on the pho-to-sensitive layer and the assembly was exposed to light from a carbon arc lamp at a distance o~ 80 cm for 30 seconds.
Upon peeling of~ i~mediate7y the photosensiti~e layer, there were obtained a sharp negative aluminum pattern on the polyester ~ilm and a positive pattern on the pho-to-sensitive layer.
The negative pattern had a resolving power of 7~/mm, a transmission densi-ty of 3.5, high contrast of ~ value belng 20 and good dot reproducibility. The product was suitable for use as a process ~ilm.
Example 2 A photosensitive composition was prepared ~ollowing to the procedures of Example lg excepting that 008 g o~
~0 4-(p~methoxy benzoylamino)-2,5-diethoxybenzene diazonium * Trade Marks ~ 3'~
zi.nc chloride was used.
Qn the surface of a 12~ polyethylene terephthalate film was deposi-ted by vacuum evaporation a 80 m~ zinc layer, on which the photosensitive composition was coated by a wire bar and dried at 90C for one minute in-to a 9 layer.
The element thus produced was exposed to ligh-t as in Example 1 to ohtain a sharp negative zinc pattern on tha substrate and a positive patte.rn on the photosensitive layer. - . .
E~ample 3 Twenty grams of a copolymer as used in Example 1 and 2~0 g of 1,4-naphthoquinone were dissolved in a mixture of 40.0 g o~ methyl ethyl ketone, 35 g of toluene and 5 g o~ cyclohexanone to prepare a 21.57% pho-tosensi-tive composition.
On the surface of a 75~ diacetylcellulose film was deposited by vacuum evaporation a 50 m~ aluminum layer on ~hich the photosensitive composi~ion was coated by a wire bar and dried at 90C for 2 minutes to obtain a 10 layer~
A positive original was posi-tioned on the photo-sensitive layer and the assembl~ was exposed to light using an elec-trographic machine of Ricopy*SM 1500 (available from Ricoh Co.~ Ltd., Tokyo, Japan) provided with a 1500W
~e~cury arc lamp at printing exposure of a dial ~igure of 10. After the photosensitive layer was peeled off, a sharp negative aluminum pattern was obtained on the substrate.
* Trade Mark 9~3~'7 Twenty grams of a copolymer of 87% vinyl chloride and 1~% vinyl acetate available from Union Carbide Corpora-tion under the name of l'Vinylite VYHH" and 0.8 g of 4-(p-tolyl mercapto)-295-diethoxybenzene diazonium zinc chloride were dissolved in a mixture of 40 g of methyl ethyl ketone and 40 g of toluene to prepare a 20.63%
photosensitive composition.
The photosensitive composition was coated by a wire bar on a 50 m~ silver layer deposited on a glass plate and dried by hot air at 90C for 2 minutes to obtain a photosensitive layer.
According to procedures similar to those o~ Example 1, the element thus ob-tained was exposed to light through a positive original, then a negative silver pattern was obtained on the glass plate after peeling off the photo-sensitive layer.
Example 5 A polyethylene terephthalate ~ilm having a thick-ness of 100 ~ was immersed in the following sensitizingbath for 3 minutes and thoroughly washed with water, then immersed in the following activating bath for 3 minutes and washed with running water thoroughly~ and immersed in ; the following plating bath for 2 minutes to obtain a 25 nickel-phosph~rus allo~y layer of 50 m~ thick~
Sensitizing bath SnC12 10 g HCl 40 ml H20 1000 ml Temperature 25C
~o~377 Activating bath PdC13 -5 g HCl 5 ml H20 1000 ml Temperature 23C
Plating bath NiS04 40 g Sodium citrate 24 g Sodium hypophosphi~e 20 g Sodium acetate 14 g Ammonium chloride 5 g H20 to make 100 ml The photosensitive composition prepared in Example 2 was coated onto the alloy layer~ The element thu~
produced was exposed to light using a positive original with the machine of Example 3 at a dial figure of 5~
A sharp negative alloy pattern wa~ obtained on the poly-ester film upon peeling off the photosensitive layer.
Twenty grams of a copolymer as in Example 1 and 2 g o~ benzophenone was dissolved in 80 g of methyl ethyl ketone to prepare a photosensitive composition, On one side of a 100 m~ polyethylene terephthalate film was deposited a 100 m~ aluminum layer by vacuum evaporation. Another side was coated with a mixture of 10 g of yellow fluorescent pigment9 5 g of a linear poly-ester resin, 38 ml of methyl e-thyl ketone and 15 ml of cyclohexanone and dried -to obtain a 10 ~ yellow coating.
~ 3'7~
The photosensitive composition was coated by a wire bar onto the aluminum layer and dried as in Example 2.
A positive original was disposed on the coating and exposed to light with the machine used in Example 3 at a dial figure of 2.
After peeling off the coating, a negative aluminum pattern in silver was ob-tained on a film which emitted a yellow fluorescence. Thus, the product was suitable for advertisement.
~z A 400 m~ aluminum layer was deposited by vacuum evaporation on one side of a 188 ~ polyethylene terephthalate film, and then coated with a photosensitive composition prepared as in Example 1.
A negative white screen having a screen ruling of 300 per inch was overlaid on the photosensitive layer and the assembly was exposed to light with a pneumatic printer provided with a 3 KW carbon arc lamp at a distance o~ 80 cm for 30 seconds. Then9 the photosensitive layer was peeled off to obtain a positive aluminum screen deposited on the film.
The product was suitable for use as a transparent electrode of a flexible electro luminescence sheet.
A 20.75% photosensitive composition was prepared by mixing 20 g of a copolymer as u~ed in Example 1, 1 g of 2,6-di(4'-azido~enzal) cyclohexanone, 40 g of methyl ethyl ketone and 40 g of toluene, On one side of a 100 polyethylene terephthalate film was deposited by vacuum e~aporation a 100 m~ aluminum layer, to which the 3'~3`~'~
photosensltive composition was coated and dried a-t 90~C
for one minute -to obtain a 4 ~ coa~ing.
A solution of 15 g o~ acetyl-butylcellulose in 60 g o:f -toluene and 25 g of methanol was overcoated and dried at 90C for two minutes to give a 15 ~ reinforcement.
The product was exposed to light together l`~ith a positive original using the machine employed in ~xample a-t a dial figure o~ 1.5. After peeling o~f the coated layers~ a negative aluminum pattern was obtained on the polyes~er film and a positive pattern on the photosensi-tive layer.
, amp~Q g Japanese -tissue paper (available :Erom Mitsubish-Paper Mills, Ltd. 9 Tokyo, Japan under the name of "Kyokuryu*"~
was adhered onto the photosensitive layer with an acrylic ester emulsion (available ~rom Chuo Rika Kogyo Kabushiki ~aisha, Tokyo, Japan under thQ name of "B52H") in an amount of 30 g/~2 and dried at 60~C for 3 minutes, Letters were wri~ten by a ~ypewriter on the Japanese tissue paper side and exposed to light with the machine employed in Example 1 for ~0 seconds. Upon peeling o~
the photosensitive layer, a negative aluminum pattern of -tha typewritten letters was obtained on the polyester ~ilm, Example 10 A photosensitive composition was prepared by dis~
solving 20 g of polyvinyl alcohol (available ~rom Toa Go~ei Chemical Industry Co.~ Ltd., Tokyo, Japan under the name o~ "NH-20*,")and 0.8 g o~ (p-tolyl mercapto)-2,5-diethoxybenzene diazonium tetra~luoroborate in 180 g of l~ater, the solid content being 10~36%.
* Trade Marks 3~
Al~inum was deposi-ted by vacuum evaporation in a thickness o~ 100 m,u on a biaxially orlented polypropylene film having a thickness of 75 ~. The photosensitive composition was coated onto the aluminum layer and dried by ho-t air at 100C for one minute into a photosensitive layer having a -thickness of 3 ,u.
A positive original was overlapped on the photo-sensi~tive la~er and -the assembly was exposed to light from a 2 h~ xenon arc lamp at a distance of 100 cm ~or 3 minutes. The photosensitive layer was peeled of~ to obtain a negative aluminum pa-ttern on the film and a positive pattern on -the photosensitive layer.
Exam~le_ll On one side of a 50 ~ polyethylene terephthalate film pigmented with carbon black was deposited a 70 m~
aluminum layer by vacuum evaporation, and another side was coated with an acrylic pressure sensitive adhesive available ~rom Nippon Carbide Industries Co., Ltd,, Tokyo, Japan under the na~.~ of l'Nissetsu*PE115A'I in a thickness of 30 ~ and a release paper sheet was placed thereon.
A photosensitive composition prepared as in Example 1 was coated onto the aluminum layer by a wire bar and ~:
dried by hot air at 90C for one minute to obtai~ a 5 photosensitive layer.
A negative original was overlapped on the element thus produced and the assembl~ was subjected -to an exposure treatment according to the procedures in Example 1, After peeling of.~ the pho-tosensitive layer, a positive pattern in silver tin-t was obtained on the black film. The product could be attached to a desired place as a label * Trade Mark 3~7~7 a~ter removing the release sheet~
Ex~
.
A photosensitive composition containing 10~18% of solid was prepared by dissolvin~ 10 g of polyvinyl butylel con~aining 3% of acetyl group, 65 -~ 3,' o~ butyral group and 35 ~ 5% of hydroxy group and 0.2 g of 4-(p-tolyl mercapto)-2~5-diethoxybenzene dia~onium zinc chloride in a mixture of 45 g o:E methyl ethyl ketone, 27 g o~ toluene ancl 1~ g of cyclohexanone.
On a 100 ~ polyethylene terephthalate ~ilm was deposited by vacuum evaporation a 100 m~ aluminum layer to which the photosensitive composition was coated by a wire bar and dried at goc for one minute to obtain a 5 photosensitive layer.
With the machine used in Example 3 a-t a printing figure of 5, the element was exposed -to light together with a positive original, .~ollowed by peeling of:~ the photosensi-tive layer to obtain a nega-tive all~minum pattern on the ~ilm. The produc^t was suitable ~or use as a lithographic pla-te.
~xampl~ 13 A photosensitive composition was prepared by dis-solving 0.4 g of 1,~-diazonaphthol-5-sulfonic acid sodium salt in 50 g of polyvinyl chloride emulsion available ~rom Nisshin Chemic~l Industries Co., Ltd., Tok~o~ Japan under the name o~ "Vinyblane* 320~"
A 100 ~ polyethylene terephthalate ~ilm was deposited with aluminum in a thickness of 100 m~ by vacuum evapora-tion~ ~ollowed by coa-ting wi-th the pho-tosensitive composi-tion and drying at 100 C ~or 30 seconds to produce a * Trade Mark -- 20 --. .
~ 3 ~7 photosensitive layer o~ 3 ~ thick.
A 12 ~ polyethylene terephthalate film was laminated on the photosensitive layer by means of a 30 ~ acrylic adhesive layer (available from Nippon Carbide Industries Co., Ltd. under -the name of "Nissetsu PEl15Ai') to obtain an image producing element.
According to the procedures in Example l, the element was exposed to light, followed by peeling off -the photosensitive layer to obtain a negative pattern on the film.
Since the photosensitive layer was reinf'orced by the laminated film and hence had improved mechanical strength, the peeling off operation was readily ef~ected, the resul-ting element was suitable for use in a large size, and the positive pattern procluced on the photosensi-tive layer was used for various purposes.
An image producing element produced ~y procedures similar to those of Example 6 was exposed to light using a positive original with the machine employed in Example 3 at a printing exposure of lO.
The exposed element was heated at 90C for 3Q
seconds and then the overall photosensitive surfaoe was exposed to light again with the machine at a printing exposure of the dial figure being lO. ~ ~?
After 20 minutes from the second exposure7 the photosensitive layer was peeled of~ to obtain a positive aluminum pattern on the substra-te film and a negative pattern on the photosensitive layer~
; The amount of photosensitizer to be used on the basis o~ the binding material is from 1 -to 20%9 preferably 5 to 10% by weight in case of the ben~ophenone or the quinone compound, and from 0~1 to 10% pre~erably 1 to 6%
by weight in case of the diazonium or azido compoundt A large amount of the photosensltizer causes coloration of the photosensitive layer which decreases the photo~
sensiti~ity.
A solvent solution9 an aqueous solu-tion or an emulsion con-taining the photosensitizer and the binding material may be applied to the metal layer on the substrate by any conventional coating technique including conveniently reverse, gravier and kiss roll coating. The solid content o~ such coating material may vary depending upon coating process employed and the amount to be applied ancl is in general from 5 to 30% by weight. The coating material is applied in such an amount ~hat the dried photosensitive layer is from 0.5 to 100~ and preferably 2 to 20~ in thickness.
Any dyestu~f and pigment may be incorporated in the coating material so far as they do not adversely af~ect the transparency and the photosensitizing mechanism o~ the resulting photosensitive layer. In particular, a body pigment may conveniently be added thereby producing a mat layer which gives a drawing ink and printing ink acceptable surface. Thus, the ~inal product is readily written by hand or typewriter to give a desired pattern which is reproduced as a metal image on the substrate upon 3 7~7 exposure of the element to light. If desired, the element according to this invention may be provided with a support-ing layer on the photosensitive layer in order to improve the mechanical strength of the layer to be peeled off.
Thus, it is preferred to use a transparent material such as a film made of a thermoplastic polyester, polypropylene, a polyamide, polyvinyl chloride or a cellulose es-ter, transparent paper or s~nthetic resin satura-ted paper.
The image producing element according to the invention is exposed to light through a desired pattern and the photosensitive layer is peeled off, then an image made of the metal corresponding to the photosensitized portion is produced on the substrate. ~s the light source, one emit~
ting ultraviolet to visible light of short wave length is employed; for example, a carbon arc l~mpJ a high pres-sure mercury arc lamp or a fluorescent argon lamp is preferred, but a tungsten lampJ a xenon arc lamp, a mercury arc lamp or a metal halide arc lamp may also be used. The cheapest light source is of course the sunlight.
The period for which -the image producing element is exposed to light varies depending upon the type of photosensitive layer, the wave length emitted from -the light source and the distance from the light source. It has been found that, for example, 30 seconds is a sa-tisfactory exposure time for a 3.0 ~IJ carbon arc lamp at a distance of 80 cm.
This invention will be explained referring to the accompanying drawings, in which Figure 1 illustrates a cross-sectional view of the image producing element accord-ing to this invention and Figure 2 illus-trates the state ~0 of the photosensitive layer being peeled off after exposure ~'3~37~
to the light to obtain an image or a pat-tern of the metal on the substrate.
In Figure 1, the image producing element 10 comprises a substrate 12, a metal layer 14 and a photosensitive layer 16 containing a photosensitizer and a polymeric binding material. The element is exposed to the light L through a mask M having a desired negative pattern whereby the interfacial adhesion between the photosensitized portion and the metal layer is decreased. Thus~ upon peeling off the layer, there are produced a metal pattern 18 on the substrate corresponding to the photosensitized portion and a metal pattern 20 on the photosensitive layer cor-responding to the non-photosensitized portiony in other words a positive pattern is on the substrate and a negative pattern on the photosensitive layer.
The metal pattern on the substra-te -thus produced is used :~or a wide variety of usages such as an intermediate or secondary original, a lithographic plate, a process film, a printed circuit, an original copy for display and projec-tion, an electrode ~or electroluminescence and a label.
It ha~ also been ~o~md that the loss in the inter-facial adhesion between the photosensitized portion and the metal layer is recovered~ when the photosensitized element is subjected to a heat treatment9 Therefore, it is possibleg after heating an image producing element which has been exposed to light in a desired pattern, to expose the overall photosensitive la~er to light again, ~ollowed by peeling off the photosensitive layer to pro-duce a reverse pattern made from the metal layer on the substrate corresponding to the initially non~
L~1 3 7~
photosensitized portion.
Caution should be taken that the heating tempera-ture and the heating time are not such as to decompose the unexposed photosensitiæer too much.
According to this invention, therefore, it is possible to select either a negative-positive process or a positive-positive process to produce a desired metal pattern on the substrate.
This invention has been explained speci~ically 10 referring to a sheet-like element, however, it should be understood that a dry system image producing element is also ~abricated in any of complicated three dimensional shape by, for example, the following steps-(a) depositing a thin metal layer on a three dimensional body, (b) coating a photosensitive composition on the metal layer and drying it -to obtain a photo-sensitive layer, and (c) writing a desired light shielding patte~n, for example, in black ink, on the photosensitive - layer.
The element thus obtained is exposed to light, ~ollowed by peeling off the photosensitive layer9 there is obtained a light barrier metal pattern on the three dimensional body. The product is especially suitable for display and electroluminescence purposes~
~his invention will be explained in detail by means o~ Examples. However, it should be understood that this invention is in no way limited to these Examples. In the Examples, percentage is given by weight.
3~3'~'7 ExamE~e 1 ~. .
Twenty ~rams o~ a copolymer o~ 86% of vinyl chloride~
13~ of vinyl ace-tate and 1% of maleic anhydride available -~rom Union Carbide Corporation, New York, N.Y,, U~S~A~ under the name of "Vinylite*VMCH" and 0.8 g of 4-(p tolyl mercapto)-29 5-diethoxy benzene dia7onium zinc chloride available from Kabushiki Kaisha Daito Kogyosho, Tokyo~ Japan under the name of "~ 1500*;'were dissolv2d in 80 g of meth~l ethyl ketone to obtain a pho-tosensitive composltion containing 20.63~ of solid material.
On the surface of a lOO~ polyethylene -teraph-thalate film was deposited by vacuum evaporation a lOO m~ aluminum layer7 -to which the photosensi-tive composition was coated by a wire bar and dried at 90C into 5~ photosensi-ti~e layer to ob-tain an image producing element.
A negative original was positioned on the pho-to-sensitive layer and the assembly was exposed to light from a carbon arc lamp at a distance o~ 80 cm for 30 seconds.
Upon peeling of~ i~mediate7y the photosensiti~e layer, there were obtained a sharp negative aluminum pattern on the polyester ~ilm and a positive pattern on the pho-to-sensitive layer.
The negative pattern had a resolving power of 7~/mm, a transmission densi-ty of 3.5, high contrast of ~ value belng 20 and good dot reproducibility. The product was suitable for use as a process ~ilm.
Example 2 A photosensitive composition was prepared ~ollowing to the procedures of Example lg excepting that 008 g o~
~0 4-(p~methoxy benzoylamino)-2,5-diethoxybenzene diazonium * Trade Marks ~ 3'~
zi.nc chloride was used.
Qn the surface of a 12~ polyethylene terephthalate film was deposi-ted by vacuum evaporation a 80 m~ zinc layer, on which the photosensitive composition was coated by a wire bar and dried at 90C for one minute in-to a 9 layer.
The element thus produced was exposed to ligh-t as in Example 1 to ohtain a sharp negative zinc pattern on tha substrate and a positive patte.rn on the photosensitive layer. - . .
E~ample 3 Twenty grams of a copolymer as used in Example 1 and 2~0 g of 1,4-naphthoquinone were dissolved in a mixture of 40.0 g o~ methyl ethyl ketone, 35 g of toluene and 5 g o~ cyclohexanone to prepare a 21.57% pho-tosensi-tive composition.
On the surface of a 75~ diacetylcellulose film was deposited by vacuum evaporation a 50 m~ aluminum layer on ~hich the photosensitive composi~ion was coated by a wire bar and dried at 90C for 2 minutes to obtain a 10 layer~
A positive original was posi-tioned on the photo-sensitive layer and the assembl~ was exposed to light using an elec-trographic machine of Ricopy*SM 1500 (available from Ricoh Co.~ Ltd., Tokyo, Japan) provided with a 1500W
~e~cury arc lamp at printing exposure of a dial ~igure of 10. After the photosensitive layer was peeled off, a sharp negative aluminum pattern was obtained on the substrate.
* Trade Mark 9~3~'7 Twenty grams of a copolymer of 87% vinyl chloride and 1~% vinyl acetate available from Union Carbide Corpora-tion under the name of l'Vinylite VYHH" and 0.8 g of 4-(p-tolyl mercapto)-295-diethoxybenzene diazonium zinc chloride were dissolved in a mixture of 40 g of methyl ethyl ketone and 40 g of toluene to prepare a 20.63%
photosensitive composition.
The photosensitive composition was coated by a wire bar on a 50 m~ silver layer deposited on a glass plate and dried by hot air at 90C for 2 minutes to obtain a photosensitive layer.
According to procedures similar to those o~ Example 1, the element thus ob-tained was exposed to light through a positive original, then a negative silver pattern was obtained on the glass plate after peeling off the photo-sensitive layer.
Example 5 A polyethylene terephthalate ~ilm having a thick-ness of 100 ~ was immersed in the following sensitizingbath for 3 minutes and thoroughly washed with water, then immersed in the following activating bath for 3 minutes and washed with running water thoroughly~ and immersed in ; the following plating bath for 2 minutes to obtain a 25 nickel-phosph~rus allo~y layer of 50 m~ thick~
Sensitizing bath SnC12 10 g HCl 40 ml H20 1000 ml Temperature 25C
~o~377 Activating bath PdC13 -5 g HCl 5 ml H20 1000 ml Temperature 23C
Plating bath NiS04 40 g Sodium citrate 24 g Sodium hypophosphi~e 20 g Sodium acetate 14 g Ammonium chloride 5 g H20 to make 100 ml The photosensitive composition prepared in Example 2 was coated onto the alloy layer~ The element thu~
produced was exposed to light using a positive original with the machine of Example 3 at a dial figure of 5~
A sharp negative alloy pattern wa~ obtained on the poly-ester film upon peeling off the photosensitive layer.
Twenty grams of a copolymer as in Example 1 and 2 g o~ benzophenone was dissolved in 80 g of methyl ethyl ketone to prepare a photosensitive composition, On one side of a 100 m~ polyethylene terephthalate film was deposited a 100 m~ aluminum layer by vacuum evaporation. Another side was coated with a mixture of 10 g of yellow fluorescent pigment9 5 g of a linear poly-ester resin, 38 ml of methyl e-thyl ketone and 15 ml of cyclohexanone and dried -to obtain a 10 ~ yellow coating.
~ 3'7~
The photosensitive composition was coated by a wire bar onto the aluminum layer and dried as in Example 2.
A positive original was disposed on the coating and exposed to light with the machine used in Example 3 at a dial figure of 2.
After peeling off the coating, a negative aluminum pattern in silver was ob-tained on a film which emitted a yellow fluorescence. Thus, the product was suitable for advertisement.
~z A 400 m~ aluminum layer was deposited by vacuum evaporation on one side of a 188 ~ polyethylene terephthalate film, and then coated with a photosensitive composition prepared as in Example 1.
A negative white screen having a screen ruling of 300 per inch was overlaid on the photosensitive layer and the assembly was exposed to light with a pneumatic printer provided with a 3 KW carbon arc lamp at a distance o~ 80 cm for 30 seconds. Then9 the photosensitive layer was peeled off to obtain a positive aluminum screen deposited on the film.
The product was suitable for use as a transparent electrode of a flexible electro luminescence sheet.
A 20.75% photosensitive composition was prepared by mixing 20 g of a copolymer as u~ed in Example 1, 1 g of 2,6-di(4'-azido~enzal) cyclohexanone, 40 g of methyl ethyl ketone and 40 g of toluene, On one side of a 100 polyethylene terephthalate film was deposited by vacuum e~aporation a 100 m~ aluminum layer, to which the 3'~3`~'~
photosensltive composition was coated and dried a-t 90~C
for one minute -to obtain a 4 ~ coa~ing.
A solution of 15 g o~ acetyl-butylcellulose in 60 g o:f -toluene and 25 g of methanol was overcoated and dried at 90C for two minutes to give a 15 ~ reinforcement.
The product was exposed to light together l`~ith a positive original using the machine employed in ~xample a-t a dial figure o~ 1.5. After peeling o~f the coated layers~ a negative aluminum pattern was obtained on the polyes~er film and a positive pattern on the photosensi-tive layer.
, amp~Q g Japanese -tissue paper (available :Erom Mitsubish-Paper Mills, Ltd. 9 Tokyo, Japan under the name of "Kyokuryu*"~
was adhered onto the photosensitive layer with an acrylic ester emulsion (available ~rom Chuo Rika Kogyo Kabushiki ~aisha, Tokyo, Japan under thQ name of "B52H") in an amount of 30 g/~2 and dried at 60~C for 3 minutes, Letters were wri~ten by a ~ypewriter on the Japanese tissue paper side and exposed to light with the machine employed in Example 1 for ~0 seconds. Upon peeling o~
the photosensitive layer, a negative aluminum pattern of -tha typewritten letters was obtained on the polyester ~ilm, Example 10 A photosensitive composition was prepared by dis~
solving 20 g of polyvinyl alcohol (available ~rom Toa Go~ei Chemical Industry Co.~ Ltd., Tokyo, Japan under the name o~ "NH-20*,")and 0.8 g o~ (p-tolyl mercapto)-2,5-diethoxybenzene diazonium tetra~luoroborate in 180 g of l~ater, the solid content being 10~36%.
* Trade Marks 3~
Al~inum was deposi-ted by vacuum evaporation in a thickness o~ 100 m,u on a biaxially orlented polypropylene film having a thickness of 75 ~. The photosensitive composition was coated onto the aluminum layer and dried by ho-t air at 100C for one minute into a photosensitive layer having a -thickness of 3 ,u.
A positive original was overlapped on the photo-sensi~tive la~er and -the assembly was exposed to light from a 2 h~ xenon arc lamp at a distance of 100 cm ~or 3 minutes. The photosensitive layer was peeled of~ to obtain a negative aluminum pa-ttern on the film and a positive pattern on -the photosensitive layer.
Exam~le_ll On one side of a 50 ~ polyethylene terephthalate film pigmented with carbon black was deposited a 70 m~
aluminum layer by vacuum evaporation, and another side was coated with an acrylic pressure sensitive adhesive available ~rom Nippon Carbide Industries Co., Ltd,, Tokyo, Japan under the na~.~ of l'Nissetsu*PE115A'I in a thickness of 30 ~ and a release paper sheet was placed thereon.
A photosensitive composition prepared as in Example 1 was coated onto the aluminum layer by a wire bar and ~:
dried by hot air at 90C for one minute to obtai~ a 5 photosensitive layer.
A negative original was overlapped on the element thus produced and the assembl~ was subjected -to an exposure treatment according to the procedures in Example 1, After peeling of.~ the pho-tosensitive layer, a positive pattern in silver tin-t was obtained on the black film. The product could be attached to a desired place as a label * Trade Mark 3~7~7 a~ter removing the release sheet~
Ex~
.
A photosensitive composition containing 10~18% of solid was prepared by dissolvin~ 10 g of polyvinyl butylel con~aining 3% of acetyl group, 65 -~ 3,' o~ butyral group and 35 ~ 5% of hydroxy group and 0.2 g of 4-(p-tolyl mercapto)-2~5-diethoxybenzene dia~onium zinc chloride in a mixture of 45 g o:E methyl ethyl ketone, 27 g o~ toluene ancl 1~ g of cyclohexanone.
On a 100 ~ polyethylene terephthalate ~ilm was deposited by vacuum evaporation a 100 m~ aluminum layer to which the photosensitive composition was coated by a wire bar and dried at goc for one minute to obtain a 5 photosensitive layer.
With the machine used in Example 3 a-t a printing figure of 5, the element was exposed -to light together with a positive original, .~ollowed by peeling of:~ the photosensi-tive layer to obtain a nega-tive all~minum pattern on the ~ilm. The produc^t was suitable ~or use as a lithographic pla-te.
~xampl~ 13 A photosensitive composition was prepared by dis-solving 0.4 g of 1,~-diazonaphthol-5-sulfonic acid sodium salt in 50 g of polyvinyl chloride emulsion available ~rom Nisshin Chemic~l Industries Co., Ltd., Tok~o~ Japan under the name o~ "Vinyblane* 320~"
A 100 ~ polyethylene terephthalate ~ilm was deposited with aluminum in a thickness of 100 m~ by vacuum evapora-tion~ ~ollowed by coa-ting wi-th the pho-tosensitive composi-tion and drying at 100 C ~or 30 seconds to produce a * Trade Mark -- 20 --. .
~ 3 ~7 photosensitive layer o~ 3 ~ thick.
A 12 ~ polyethylene terephthalate film was laminated on the photosensitive layer by means of a 30 ~ acrylic adhesive layer (available from Nippon Carbide Industries Co., Ltd. under -the name of "Nissetsu PEl15Ai') to obtain an image producing element.
According to the procedures in Example l, the element was exposed to light, followed by peeling off -the photosensitive layer to obtain a negative pattern on the film.
Since the photosensitive layer was reinf'orced by the laminated film and hence had improved mechanical strength, the peeling off operation was readily ef~ected, the resul-ting element was suitable for use in a large size, and the positive pattern procluced on the photosensi-tive layer was used for various purposes.
An image producing element produced ~y procedures similar to those of Example 6 was exposed to light using a positive original with the machine employed in Example 3 at a printing exposure of lO.
The exposed element was heated at 90C for 3Q
seconds and then the overall photosensitive surfaoe was exposed to light again with the machine at a printing exposure of the dial figure being lO. ~ ~?
After 20 minutes from the second exposure7 the photosensitive layer was peeled of~ to obtain a positive aluminum pattern on the substra-te film and a negative pattern on the photosensitive layer~
Claims (10)
1. A dry system image producing element capable of pro-ducing images when developed using a dry process which consists essentially of a substrate having a surface, a thin intermediate layer of a metal or metal compound covering said substrate surface and adherent thereto, and a photosensitive layer on top of said intermediate layer and adherent thereto, said photo-sensitive layer consisting essentially of a polymeric binding material, and a photosensitizer selected from the group consist-ing of benzophenone, quinone compounds, diazonium compounds and azido compounds, said intermediate layer having greater adhesion to the unexposed photosensitive layer than to said substrate, said intermediate layer having decreased adhesion to said photosensi-tive layer after said element has been exposed to light through a pattern, in those portions of the element receiving light through said pattern so that the adhesion between said inter-mediate layer and the exposed portions of the photosensitive layer becomes less than the adhesion between said intermediate layer and said substrate,whereby after exposure, when said photosensitive layer and said substrate are peeled apart, the portions of said intermediate layer under the unexposed portions of said photosensitive layer are removed with said photosensitive layer, and the portions of said intermediate layer under the exposed portions of said photosensitive layer remain adherent on the substrate, forming an image of said pattern.
2. A dry system image producing element as claimed in Claim 1, wherein said thin layer of a metal or a metal compound is a vacuum evaporated layer or an electroless plated layer or a combination of an electrolytic plated layer therewith.
3. A dry system image producing element as claimed in Claim 1, wherein said binding material is selected from the group consisting of a film forming, water or organic solvent soluble synthetic resin, a cellulose derivative and a rubber derivative.
4. A dry system image producing element as claimed in Claim 1, wherein said quinone compound photosensitizer is select-ed from the group consisting of lr4-naphthoquinone,2-methyl-1, 4-naphthoquinone, anthraquinone, 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-chloroanthraquinone and p-toluquinone.
5. A dry system image producing element as claimed in claim 1, wherein said diazonium compound photosensitizer is selected from the group consisting of:
4-(p-tolyl mercapto)-2,5-diethoxybenzene diazonium zinc chloride, sodium sulfate or tetrafluoroborate, 4-(p-tolyl mercapto)-2,5-dimethoxybenzene diazonium zinc chloride, 4-(p-methyl benzoylamino)-2,5-dietoxy-benzene diazonium zinc chloride, 4-(p-methoxybenzoyl-amino)-2,5-diethoxybenzene diazonium zinc chloride, 4-morpholino-2,5-butoxybenzene diazonium zinc chloride or tetrafluoroborate, 4-morpholinobenzene diazonium tetrafluoroborate, 4-pyrrolidino-3-methylbenzene diazonium tetrafluoroborate, p-N,N-dimethyl aminobenzene diazonium zinc chloride,p-N, N-diethyl aminobenzene diazonium zinc chloride or tetrafluoroborate, p-N-ethyl-N-hydroxy amino benzene diazonium zinc chloride, 1, 2-diazonaphthol-5-sulfonic acid sodium salt, and zinc chloride salt of a condensate of 4-diazodiphenylamine sulfuric acid and formaldehyde.
4-(p-tolyl mercapto)-2,5-diethoxybenzene diazonium zinc chloride, sodium sulfate or tetrafluoroborate, 4-(p-tolyl mercapto)-2,5-dimethoxybenzene diazonium zinc chloride, 4-(p-methyl benzoylamino)-2,5-dietoxy-benzene diazonium zinc chloride, 4-(p-methoxybenzoyl-amino)-2,5-diethoxybenzene diazonium zinc chloride, 4-morpholino-2,5-butoxybenzene diazonium zinc chloride or tetrafluoroborate, 4-morpholinobenzene diazonium tetrafluoroborate, 4-pyrrolidino-3-methylbenzene diazonium tetrafluoroborate, p-N,N-dimethyl aminobenzene diazonium zinc chloride,p-N, N-diethyl aminobenzene diazonium zinc chloride or tetrafluoroborate, p-N-ethyl-N-hydroxy amino benzene diazonium zinc chloride, 1, 2-diazonaphthol-5-sulfonic acid sodium salt, and zinc chloride salt of a condensate of 4-diazodiphenylamine sulfuric acid and formaldehyde.
6. A dry system image producing element as claimed in Claim 1, wherein said azido compound photosensitizer is 2,6-di (4'-azidobenzal)cyclohexanone.
7. A dry system image producing element as claimed in Claim 1, wherein said photosensitive layer contains a benzophe-none or quinone compound photosensitizer and at least one compound selected from the group consisting of polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, vinyl chloride/vinyl acetate/maleic anhydride, acrylonitrile or vinyl alcohol terpoly-mer, vinyl chloride/vinylidene chloride copolymer, vinyl chloride/vinylidene chloride/acrylonitrile terpolymer, nitro-cellulose, acetylcellulose, acetyl-butylcellulose, ethylcellulose, cyclized rubber and rubber chloride.
8. A dry system image producing element according to Claim 1, wherein said photosensitive layer contains a diazonium compound or azido compound photosensitizer and at least one compound selected from the group consisting of polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, vinyl chloride/
vinyl acetate/maleic anhydride, acrylonitrile or vinyl alcohol terpolymer, vinyl chloride/vinylidene chloride copolymer, vinyl chloride/vinylidene chloride/acrylonitrile terpolymer, nitro-cellulose, acetylcellulose, acetyl-butylcellulose, ethyl-cellulose, cyclized rubber, rubber chloride, polyvinyl butyral, a thermoplastic linear polyester or copolyester, an alcohol soluble polyamide, polyvinyl alcohol, acrylic ester/methyl methacrylate and styrene copolymer or polyurethane.
9. A process for producing an image which comprises exposing to light through a pattern, an element which consists essentially of a substrate having a surface, a thin intermediate layer of a metal or metal compound covering said substrate surface and adherent thereto, and a photosensitive layer on top
vinyl acetate/maleic anhydride, acrylonitrile or vinyl alcohol terpolymer, vinyl chloride/vinylidene chloride copolymer, vinyl chloride/vinylidene chloride/acrylonitrile terpolymer, nitro-cellulose, acetylcellulose, acetyl-butylcellulose, ethyl-cellulose, cyclized rubber, rubber chloride, polyvinyl butyral, a thermoplastic linear polyester or copolyester, an alcohol soluble polyamide, polyvinyl alcohol, acrylic ester/methyl methacrylate and styrene copolymer or polyurethane.
9. A process for producing an image which comprises exposing to light through a pattern, an element which consists essentially of a substrate having a surface, a thin intermediate layer of a metal or metal compound covering said substrate surface and adherent thereto, and a photosensitive layer on top
Claim 9 continued of said intermediate layer and adherent thereto, said photo-sensitive layer consisting essentially of a polymeric binding material, and a photosensitizer selected from the group con-sisting of benzophenone, quinone compounds, diazonium compounds and azido compounds, said intermediate layer having greater adhesion to the unexposed photosensitive layer than to said substrate, said intermediate layer having decreased adhesion to said photosensitive layer after said element has been exposed to light through said pattern, in those portions of the element receiving light through said pattern so that the adhesion between said intermediate layer and the exposed portions of the photo-sensitive layer becomes less than the adhesion between said intermediate layer and said substrate, and peeling off the photosensitive layer to produce on the substrate, an image pattern made from the metal or metal compound corresponding to the photosensitized portion.
10. A process for producing an image which comprises exposing light through a pattern, an element which consists essentially of a substrate having a surface, a thin intermediate layer of a metal or metal compound covering said substrate surface and adherent thereto, and a photosensitive layer on top of said intermediate layer and adherent thereto, said photo-sensitlve layer consisting essentially of a polymeric binding material, and a photosensitizer selected from the group con-sisting of benzophenone, quinone compounds, diazonium compounds and azido compounds, said intermediate layer having greater adhesion to the unexposed photosensitive layer than to said substrate, said intermediate layer having decreased adhesion to said photosensitive layer after said element has been exposed to light through said pattern, in those portions of the element
10. A process for producing an image which comprises exposing light through a pattern, an element which consists essentially of a substrate having a surface, a thin intermediate layer of a metal or metal compound covering said substrate surface and adherent thereto, and a photosensitive layer on top of said intermediate layer and adherent thereto, said photo-sensitlve layer consisting essentially of a polymeric binding material, and a photosensitizer selected from the group con-sisting of benzophenone, quinone compounds, diazonium compounds and azido compounds, said intermediate layer having greater adhesion to the unexposed photosensitive layer than to said substrate, said intermediate layer having decreased adhesion to said photosensitive layer after said element has been exposed to light through said pattern, in those portions of the element
Claim 10 continued receiving light through said pattern so that the adhesion between said intermediate layer and the exposed portions of the photosensitive layer becomes less than the adhesion between said intermediate layer and said substrate, subjecting the element to a heat treatment, exposing the overall surface of the photosensitive layer to light and peeling off the photosensitive layer to produce on the substrate an image pattern made of the metal or metal compound corresponding to the initially non-photosensitized portion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4208376A JPS52126220A (en) | 1976-04-14 | 1976-04-14 | Dry image forming material and method of forming image |
| JP42083/1976 | 1976-04-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1094377A true CA1094377A (en) | 1981-01-27 |
Family
ID=12626139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA266,883A Expired CA1094377A (en) | 1976-04-14 | 1976-11-30 | Dry system image producing element having a photosensitive layer on a metal layer |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS52126220A (en) |
| BE (1) | BE853618A (en) |
| CA (1) | CA1094377A (en) |
| CH (1) | CH628160A5 (en) |
| DD (1) | DD130507A5 (en) |
| DE (1) | DE2716422C2 (en) |
| FR (1) | FR2371706A1 (en) |
| GB (1) | GB1563010A (en) |
| IT (1) | IT1094789B (en) |
| NL (1) | NL185425C (en) |
| SE (1) | SE435214B (en) |
| SU (1) | SU948301A3 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5479027A (en) * | 1977-12-05 | 1979-06-23 | Kimoto Kk | Dry picture forming material |
| JPS54179986U (en) * | 1978-06-07 | 1979-12-19 | ||
| EP0042632A1 (en) * | 1980-06-20 | 1981-12-30 | Agfa-Gevaert N.V. | Recording material and method for the production of metal images |
| JPS5858546A (en) * | 1981-10-02 | 1983-04-07 | Kimoto & Co Ltd | Photosensitive mask material for photoengraving |
| JPS59198445A (en) * | 1983-04-27 | 1984-11-10 | Kimoto & Co Ltd | Image forming material by stripping |
| JPS60238826A (en) * | 1984-05-14 | 1985-11-27 | Kimoto & Co Ltd | Image forming material |
| JPS61243603A (en) * | 1985-04-19 | 1986-10-29 | 岡村 一 | Candle stand |
| DE69524589D1 (en) * | 1995-08-08 | 2002-01-24 | Agfa Gevaert Nv | Process for forming metallic images |
| EP0762214A1 (en) * | 1995-09-05 | 1997-03-12 | Agfa-Gevaert N.V. | Photosensitive element comprising an image forming layer and a photopolymerisable layer |
| JP2001284350A (en) * | 2000-03-31 | 2001-10-12 | Nitto Denko Corp | Pattern-forming method and adhesive sheet for peeling off thin film |
| JP2009032912A (en) * | 2007-07-27 | 2009-02-12 | Sony Corp | Method of manufacturing semiconductor device, and method of manufacturing organic light-emitting device |
| JP6744213B2 (en) * | 2013-10-30 | 2020-08-19 | ネーデルランドセ・オルガニサティ・フォール・トゥーヘパスト−ナトゥールウェテンスハッペライク・オンデルズーク・テーエヌオー | Substrate with electrical circuit pattern, method and system for providing same |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2999016A (en) * | 1955-03-24 | 1961-09-05 | Keuffel & Esser Co | Drawing material |
| DE1252060B (en) * | 1961-10-23 | |||
| DE1447012B2 (en) * | 1963-07-20 | 1972-12-21 | Kalle Ag, 6202 Wiesbaden-Biebrich | NEGATIVE WORKING, SENSITIZED COPPER-ALUMINUM BIMETAL PLATE |
| DE1572153B2 (en) * | 1966-06-27 | 1971-07-22 | E I Du Pont de Nemours and Co , Wilmington, Del (V St A ) | PHOTOPOLYMERIZABLE RECORDING MATERIAL |
| DE1597644C3 (en) * | 1966-11-03 | 1973-09-20 | Teeg Research Inc., Detroit, Mich. (V.St.A.) | Process for the production of deer images |
| DE1671625A1 (en) * | 1967-01-24 | 1971-09-16 | Kalle Ag | Composite material for the production of multi-metal printing forms |
| ZA711869B (en) * | 1970-05-27 | 1971-12-29 | Gen Electric | Aqueous electrocoating solutions and method of making and using same |
| JPS4837643A (en) * | 1971-09-15 | 1973-06-02 | ||
| JPS5821257B2 (en) * | 1974-04-25 | 1983-04-28 | 富士写真フイルム株式会社 | Red-spotted moth |
| JPS516530A (en) * | 1974-07-04 | 1976-01-20 | Toray Industries | GAZOKEISEIZ AIRYO |
-
1976
- 1976-04-14 JP JP4208376A patent/JPS52126220A/en active Granted
- 1976-11-10 GB GB46816/76A patent/GB1563010A/en not_active Expired
- 1976-11-30 CA CA266,883A patent/CA1094377A/en not_active Expired
-
1977
- 1977-04-14 SU SU772470055A patent/SU948301A3/en active
- 1977-04-14 NL NLAANVRAGE7704083,A patent/NL185425C/en not_active IP Right Cessation
- 1977-04-14 FR FR7711275A patent/FR2371706A1/en active Granted
- 1977-04-14 DE DE2716422A patent/DE2716422C2/en not_active Expired
- 1977-04-14 CH CH463577A patent/CH628160A5/en not_active IP Right Cessation
- 1977-04-14 DD DD7700198405A patent/DD130507A5/en unknown
- 1977-04-14 SE SE7704316A patent/SE435214B/en not_active IP Right Cessation
- 1977-04-14 IT IT23664/78A patent/IT1094789B/en active
- 1977-04-14 BE BE176737A patent/BE853618A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| SU948301A3 (en) | 1982-07-30 |
| FR2371706A1 (en) | 1978-06-16 |
| AU1946676A (en) | 1978-06-29 |
| SE435214B (en) | 1984-09-10 |
| FR2371706B1 (en) | 1980-04-25 |
| DE2716422C2 (en) | 1987-10-01 |
| JPS5613305B2 (en) | 1981-03-27 |
| CH628160A5 (en) | 1982-02-15 |
| NL185425C (en) | 1990-04-02 |
| JPS52126220A (en) | 1977-10-22 |
| IT1094789B (en) | 1985-08-02 |
| DD130507A5 (en) | 1978-04-05 |
| GB1563010A (en) | 1980-03-19 |
| NL185425B (en) | 1989-11-01 |
| NL7704083A (en) | 1977-10-18 |
| BE853618A (en) | 1977-08-01 |
| DE2716422A1 (en) | 1977-11-03 |
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