GB1563010A

GB1563010A - System image producing element

Info

Publication number: GB1563010A
Application number: GB46816/76A
Authority: GB
Original assignee: Kimoto Co Ltd
Current assignee: Kimoto Co Ltd
Priority date: 1976-04-14
Filing date: 1976-11-10
Publication date: 1980-03-19
Also published as: SU948301A3; FR2371706A1; NL185425B; JPS52126220A; CH628160A5; JPS5613305B2; FR2371706B1; AU1946676A; DD130507A5; DE2716422A1; SE435214B; CA1094377A; NL7704083A; DE2716422C2; NL185425C; BE853618A; IT1094789B

Abstract

The element consists of a base, a thin layer of metal or a metal compound, and a photosensitive layer. The latter contains a polymeric binder and a photosensitising material, selected from benzophenone, a quinone, diazonium or amido compound. Said layer also has the property of reducing the interface adhesion between the metal layer and the photosensitive layer after exposure. By means of this element it is possible, by exposing and peeling off the photosensitive layer, to produce an image pattern made of metal or a metal compound.

Description

(54) DRY SYSTEM IMAGE PRODUCING ELEMENT (71) We, KIMOTO & CO., LTD., a Japanese body corporate of 7-1, Shinjuku 2-chome, Shinjuku-ku, Tokyo, Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to a dry system image producing element capable of producing images by development using a dry process, and to a process for producing an image made from a thin metal or metal compound layer, said layer having been deposited on a substrate.

Various processes have already been proposed for producing an image on a substrate, for example, (1) by exposing to light and element comprising a substrate and a photosensitive coating containing a photosensitizer such as a silver halide, a photosensitive polymer or a photopolymerisable monomer, or (2) by exposing to light an element comprising a photoconductive layer and effecting toner development. However, such prior art involves mherent disadvantages: For example, where a silver halide is used, development, fixing, washing with water and drying are required; where a photosensitive polymer, or a photopolymerisable monomer is used, development, etching and drying are required; and where a photoconductive material is used, activation, use of toner and fixing by heat are required. Thus, with the prior art it is necessary to use special chemical treatment and/or apparatus with resulting high cost and environmental pollution caused by chemicals.

The present invention provides a dry system image producing element which is capable of producing images by development using a dry process and which avoids the abovementioned defects. the image producing element of this invention possesses a high y-value, high contrast and good resolving power and can produce an image having improved opacity. The image producing element of this invention can also provide an electroconductive pattern on a substrate.

According to the present invention there is provided a dry system image producing element capable of producing images by development using a dry process, said element comprising, in order, a substrate, a thin intermediate layer of a metal or a metal compound, and a top photosensitive layer containing a polymeric film-forming binding material and a photosensitizer selected from benzophenone. a quinone compound. a diazonium compound and an azido compound. and in which the interfacial adhesion between the intermediate layer and the substrate is less than that between the top layer and the intermediate layer but on exposure of the top layer to light the latter adhesion is capable of being decreased to a level such that it is less than the interfacial adhesion between the intermediate layer and the substrate.

When the element according to this invention is exposed to light through a mask having a desired pattern, the interfacial adhesion between the intermediate layer and the exposed portion of the top layer can be reduced to a level below that of the interfacial adhesion between the intermediate layer and the substrate whereas the level of adhesion of the non-exposed portion does not change. Thus. when the top layer is peeled off. the non-exposed portion of the layer of metal or metal compound is removed with the top layer and a pattern in the metal or metal compound and corresponding to the exposed portion of the element is left on the substrate.

It will be understood that as used herein the term "thin" in connection with the intermediate layer means that the layer must be sufficiently thin that it will part at the boundaries between exposed and unexposed portions of the element when the top layer is peeled off.

The substrate which may be employed according to this invention may be any of a variety of materials capable of accepting a thin metal layer thereon, such as a film forming thermoplastic polymeric material, glass or metal. Examples of suitable thermoplastic materials are various synthetic resins, for example, a polyester such as polyethylene terephthalate, a polycarbonate, a polyolefin such as polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate and a copolymer thereof and cellulose derivatives, for example, diacetylcellulose, triacetylcellulose, propylcellulose and a mixed cellulose ester. Other sheet-like materials such as paper, woven fabric and non-woven fabric which have been coated with the above-mentioned film forming material may also be used.

The substrate material may be incorporated with various additives, such as pigment, dyestuff and filler to give a writing or printing ink accepting property, opacity and coloration.

The metal layer on the surface of the substrate may be produced by, for example, vacuum plating such as vacuum evaporation and cathodic sputtering, electroless plating or by a combination of electrolytic plating with vacuum plating or electroless plating. The thickness of the metal layer is preferably more than 10 mp. A thinner layer generally is not sufficiently opaque to light, so the image produced on the substrate is hardly visible.

Although the upper limit of the thickness is not critical, in general, a thickness of up to 1000 mll preferably from 20 to 500 mu is used. For special usage as a printed circuit, a metal layer of more than 1000 mu in thickness may be successfully used.

Among various metals suitable for evaporation plating, aluminium and zinc are most preferred; but next preferred metals are silver, gold and nickel. Other metals, such as chromium, cobalt, iron, germanium, magnesium, manganese, platinum and tin may also be used. Cadmium sulfide, magnesium fluoride and titanium dioxide are examples of metal compounds suitable for vacuum plating.

Electroless plating may be carried out in a conventional way by subjecting the substrate to sensitizing and activation treatments, followed by immersion in an aqueous solution containing a metal salt and a reducing agent to deposit a metal layer on the substrate. For this purpose, copper, nickel, cobalt, gold. palladium, silver and nickel-cobalt and nickel-phosphorus alloys are suitable.

In general, the vacuum evaporation process is preferable 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 top layer comprises a polymeric binding material and a photosensitizer. Since the layer is peeled off from the substrate after printing exposure treatment, it is important that the binding material possesses a good film forming property and has high film strength; further, the material is preferably non-blocking in order that a stack of elements do not stack together 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 copolymer. vinyl chloride/vinyl acetate/ maleic anhydride, acrylonitrile or vinyl alcohol terpolymer, vinyl chloride/vinylidene chloride/acrylonitrile, vinyl acetate or methyl methacrylate terpolymer. an acrylic ester/ methyl methacrylate or styrene copolymer, a thermoplastic polyester or copolyester such as polyethylene terephthalate and ethylene terephthalate/isophthalate copolymer, an alcohol soluble polyamide, a polyurethane. polybutyral and polyvinyl alcohol: cellulose derivatives such as acetylcellulose, acetyl-butylcellulose. nitrocellulose and ethylcellulose; and rubber derivatives such as cyclized rubber and rubber chloride. These polymeric materials may be used alone or in any combination.

In general, the binding material is used in the form of a solution in an appropriate organic solvent, examples of which include methyl ethyl ketone, toluene, cyclohexanol, methanol, ethanol. i-propanol, methyl cellosolve. ethyl cellosolve and cellosolve acetate.

In selecting the solvent. caution should be taken to insure that the solvent is capable of dissolving the photosensitizer employed but does not dissolve or swell the substrate material.

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 of an emulsion or a dispersion.

The photosensitizers which may be used according to this invention are classified and exemplified as follows: a) Benzophenone b) Quinone compounds of which examples are: 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 compounds of which examples are: 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-diethoxybenzene diazonium zinc chloride, 4-(p-methoxybenzoylamino)-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 aminobenzene diazonium zinc chloride, 1,2-diazonapthol-5 sulfonic acid sodium salt, and zinc chloride salt of a condensate of 4-diazo-diphenylamine sulfuric acid and formaldehyde.

d) Azido compounds of which an example is: 2,6-Di(4'-azido benzal)cyclohexanone.

According to this invention, it is important to select an appropriate combination of the photosensitizer and the binding material, in order to sufficiently decrease the interfacial adhesion between the metal layer and the exposed portion of the photosensitive layer, upon exposing the element to light.

For the benzophenone and the quinone compounds, preferred binding materials are 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 and nitrocellulose, since these materials can produce a high quality image. A cellulose derivative and a rubber derivative may also be used, for example. acetylcellulose, acetylbutylcellulose, 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 linear polyester and copolyester, an alcohol soluble polyamide, polyvinyl alcohol, acrylic ester/methyl methacrylate or styrene copolymer, polyurethane emulsion and polyvinyl chloride emulsion may also be used.

The amount of photosensitizer to be used on the basis of the binding material may be from 1 to 20% and preferably 5 to 10% by weight of the benzophenone or the quinone compound, and from 0.1 to 10% preferably 1 to 6% by weight of the diazonium or azido compound. A large amount of the photosensitizer causes coloration of the photosensitive layer which decreases the photosensitivity.

A solvent solution, an aqueous solution or an emulsion containing the photosensitiser 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 of such coating material may vary depending upon the coating process employed and the amount to be applied and is in general from 5 to 30neo by weight.

The coating material preferably is applied in such an amount that the dried photosensitive layer is from 0.5 to 100 R and more preferably 2 to 20 in thickness.

Any dyestuff and pigment may be incorporated in the coating material so far as they do not adversely affect the transparency and the photosensitizing mechanism of the resulting photosensitive layer. In particular. a body pigment may conveniently be added thereby producing a matte layer which gives a drawing ink and printing ink acceptable surface. The final product may then be readily written on by hand or by a typewriter to give a desired pattern which is reproduced as a metal image on the substrate upon exposure of the element to light. If desired, the element according to this invention may be provided with a supporting layer on the photosensitive layer in order to improve the mechanical strength of the layer to be peeled off. For this purpose, 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 ester, transparent paper or synthetic resin saturated paper.

When the image producing element according to the invention is exposed to light through a desired pattern and the photosensitive layer is peeled off an image made of the metal or metal compound and corresponding to the portion of the element which has been exposed to light is produced on the substrate. As the light source. one emitting ultraviolet to visible light of short wave length may be employed; for example, a carbon arc lamp, a high pressure mercury arc lamp or a fluorescent argon lamp is preferred. but a tungsten lamp, 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 sunlight. The period for which the image producing element requires to be 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 satisfactory exposure time for a 3.0 KW carbon arc lamp at a distance of 80 cm.

The invention is now described in greater detail with the aid of the accompanying drawings, in which Figure 1 illustrates a cross-sectional view of the image producing element according to this invention and Figure 2 illustrates the state of the photosensitive layer being peeled off after exposure to the light to obtain an image or a pattern 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 exposed portion of the photosensitive layer and the metal layer is decreased to below that between the metal layer and the substrate.

Thus, upon peeling off the photosensitive layer, there is produced a metal pattern 18 on the substrate corresponding to the exposed portion and a metal pattern 20 on the photosensitive layer corresponding to the unexposed portion; in other words a positive pattern is produced on the substrate and a negative pattern on the photosensitive layer.

The metal pattern on the substrate thus produced has 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 projection, an electrode for electroluminescence and a label.

It has also been found that the loss in the interfacial adhesion between the exposed portion of the photosensitive layer and the metal layer may be recovered if the element is subsequently subjected to a heat treatment. Therefore, it is possible, after heating an image producing element which has been exposed to light in a desired pattern, to expose the entire photosensitive layer to light again whereby to reduce the interfacial adhesion between the metal layer and that portion of the photosensitive layer that was not exposed to light during the first exposure, and then by peeling off the photosensitive layer to produce a reverse pattern made from the metal layer on the substrate corresponding to the initially non-exposed portion.

Caution should be taken that the heating temperature and the heating time are not such as to decompose the unexposed photosensitizer 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 described with specific reference to a sheet-like element; however, it should be understood that a dry system image producing element in accordance with the invention can also be fabricated in three dimensional form 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 photosensitive layer, and (c) writing a desired light shielding pattern, for example, in black ink, on the photosensitive layer.

When the element thus obtained is exposed to light, followed by peeling off the photosensitive layer: there is obtained an opaque metal pattern on the three dimensional body. The product is especially suitable for display and electroluminescence purposes.

The following Examples illustrate the invention. However, it should be understood that this invention is in no way limited to these Examples. In the Examples, percentage is given by weight.

Example 1 Twenty grams of a copolymer of 86% of vinyl chloride, 13% of vinyl acetate and 1% of maleic anhydride available from Union Carbide Corporation, New York, N.Y., U.S.A.

under the name of 'Vinylite VMCH" ( Vinylite'' is a Registered Trade Mark) and 0.8 g of 4-(p-tolyl mercapto)-2.5-diethoxy benzene diazonium zinc chloride available from Kabushiki Kaisha Daito Kogyosho, Tokyo, Japan under the name of "WH-1500" were dissolved in 80 g of methyl ethyl ketone to obtain a photosensitive composition containing 20.63% of solid material.

qn the surface of a 100u thick polyethylene terepthalate film was deposited by vacuum evaporation a 100 mtt thick aluminum layer, on which the photosensitive composition was coated by a wire bar and dried at 90"C to give a 5 u thick photosensitive layer to obtain an image producing element.

A negative original was positioned on the photosensitive layer and the assembly was exposed to light from a carbon arc lamp at a distance of 80 cm for 30 seconds. Upon immediately peeling off the photosensitive layer, there were obtained a sharp negative aluminum pattern on the polyester film and a positive pattern on the photosensitive layer.

The negative pattern had a resolving power of 72/mm, a transmission density of 3.5, high contrast of y value being 20 and good dot reproducibility. The product was suitable for use as a process film.

Example 2 A photosensitive composition was prepared following the procedure of Example 1, excepting that 0.8 g of 4-(p-methoxy benzoylamino)-2,5-diethoxybenzene diazonium zinc chloride was used as the photosensitizer.

On the surface of a 12 u thick polyethylene terephthalate film was deposited by vacuum evaporation a 80 mu thick zinc layer, on which the photosensitive composition was coated by a wire bar and dried at 90"C for one minute to give a 9 u thick layer.

The element thus produced was exposed to light as in Example 1 to obtain a sharp negative zinc pattern on the substrate and a positive pattern on the photosensitive layer.

Example 3 Twenty grams of a copolymer used in Example 1 and 2.0 g of 1,4-napthoquinone were dissolved in a mixture of 40.0 g of methyl ethyl ketone, 35 g of toluene and 5 g of cyclohexanone to prepare a 21.57% weight solution of the photosensitive composition in the solvent mixture.

On the surface of a 75u thick diacetylcellulose film was deposited by vacuum evaporation a 50 mu thick aluminum layer on which the photosensitive composition was coated by a wire bar and dried at 900C for 2 minutes to obtain a 10 > thick layer.

A positive original was positioned on the photosensitive layer and the assembly was exposed to light using an electrographic machine of Ricopy SM 1500 (available from Ricoh Co., Ltd., Tokyo, Japan) provided with a 1500 W mercury arc lamp at printing exposure of a dial figure of 10. After the photosensitive layer was peeled off, a sharp negative aluminum pattern was obtained on the substrate.

Example 4 Twenty grams of a copolymer of 87% vinyl chloride and 13% vinyl acetate available from Union Carbide Corporation under the name of "Vinylite VYHH" and 0.8 g of 4-(p-tolyl mercapto)-2,5-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% weight soltuion of the photosensitive composition in the solvent mixture.

The photosensitive composition was coated by a wire bar on a 50 mu thick silver layer deposited on a glass plate and dried by hot air at 90"C for 2 minutes to obtain a 9 u thick photosensitive layer.

According to procedures similar to those of Example 1, the element thus obtained was exposed to light through a positive original, then a negative silver pattern was obtained on the glass plate after peeling off the photosensitive layer.

Example 5 A polyethylene terephthalate film having a thickness of 100 u was immersed in the following sensitizing bath 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 50 mu thick nickel-phosphorus alloy layer: Sensitizing bath Sic12 10 g HC1 40 ml H2O 1000 ml Temperature 25"C Activating bath PdC13 0.5 g HC1 5 ml H2O 1000 ml Temperature 23"C Plating bath NiSO4 40 g Sodium citrate 24 g Sodium hypophosphite 20 g Sodium acetate 14 g Ammonium chloride 5 g H2O to make 100 ml The photosensitive composition prepared in Example 2 was coated onto the alloy layer.

The element thus 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 was obtained on the polyester film upon peeling off the photosensitive layer.

Example 6 Twenty grams of a copolymer as in Example 1 and 2 g of benzophenone were dissolved in 80 g of methyl ethyl ketone to prepare a photosensitive composition.

On one side of a 100 mu thick polyethylene terephthalate film was deposited a 100 mu thick aluminum layer by vacuum evaporation. Another side was coated with a mixture of 10 g of yellow fluorescent pigment, 5 g of a linear polyester resin, 38 ml of methyl ethyl ketone and 15 ml of cyclohexanone and dried to obtain a 10 u thick yellow coating.

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 the material 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 obtained on a film which emitted a yellow fluorescence. Thus, the product was suitable for advertisement.

Example 7 A 400 mu thick aluminum layer was deposited by vacuum evaporation on one side of a 188 u thick 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 of 80 cm for 30 seconds. Then, 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.

Example 8 A 20.75% weight solution of a photosensitive composition was prepared by mixing 20 g of a copolymer as used in Example 1, 1 g of 2,6-di(4'-azidobenzal) cyclohexanone, 40 g of methyl ethyl ketone and 40 g of toluene. On one side of a 100 u thick polyethylene terephthalate film was deposited by vacuum evaporation a 100 mu thick aluminum layer, on to which the photosensitive composition was coated and dried at 900C for one minute to obtain a 4 u thick coating.

A solution of 15 g of acetyl-butylcellulose in 60 g of toluene and 25 g of methanol was overcoated and dried at 90"C for two minutes to give a 15 u thick reinforcement layer.

The product was exposed to light together with a positive original using the machine employed in Example 3 at a dial figure of 1.5. After peeling off the coated layers, a negative aluminum pattern was obtained on the polyester film and a positive pattern on the photosensitive layer.

Example 9 Japanese tissue paper (available from Mitsubishi Paper Mills, Ltd., Tokyo, Japan under the name of "Kyokuryu") was adhered onto the photosensitive layer of the element employed in Example 1 with an acrylic ester emulsion (available from Chuo Rika Kogyo Kabushiki Kaisha, Tokyo, Japan under the name of "B52H") in an amount of 30 g/m2 and dried at 600C for 3 minutes.

Letters were written by a typewriter on the Japanese tissue paper side and the product exposed to light with the machine employed in Example 1 for 30 seconds. Upon peeling off the photosensitive layer, a negative aluminum pattern of the typewritten letters was obtained on the polyester film..

Example 10 A photosensitive composition was prepared by dissolving 20 g of polyvinyl alcohol (available from Toa Gosei Chemical Industry Co., Ltd., Tokyo, Japan under the name of "NH-20") and 0.8 g of 4-(p-tolyl mercapto)-2,5-diethoxybenzene diazonium tetrafluoroborate in 180 g of water, the solid content being 10.36%.

Aluminum was deposited by vacuum evaporation in a thickness of 100 mu on a biaxially oriented polypropylene film having a thickness of 75 . The photosensitive composition was coated onto the aluminium layer and dried by hot air at 100"C for one minute into a photosensitive layer having a thickness of 3 EL.

A positive original was overlaid onto the photosensitive layer and the assembly was exposed to light from a 2 KW xenon arc lamp at a distance of 100 cm for 3 minutes. The photosensitive layer was peeled off to obtain a negative aluminum pattern on the film and a positive pattern on the photosensitive layer.

Example 11 On one side of a 50 u thick polyethylene terephthalate film pigmented with carbon black was deposited a 70 mu thick aluminum layer by vacuum evaporation, and the other side was coated with an acrylic pressure-sensitive adhesive available from Nippon Carbide Industries Co., Ltd., Tokyo, Japan under the name of "Nissetsu PEllSA" in a thickness of 30 u 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 90"C for one minute to obtain a 5 u thick photosensitive layer.

A negative original was overlaid on the element thus produced and the assembly was subjected to an exposure treatment according to the procedures in Example 1. After peeling off the photosensitive layer, a positive pattern in silver tint and comprised of aluminum was obtained on the black film. The product could be attached to a desired place as a label after removing the release sheet.

Example 12 A photosensitive composition containing 10.18% of solids was prepared by dissolving 10 g of partially hydrolysed polyvinyl butyral containin 3% of acetyl group, 65+ 3% of butyral group and 35 1 5% of hydroxy group and 0.2 g of 4-(p-tolyl mercapto)-2,5diethoxybenzene diazonium zinc chloride in a mixture of 45 g of methyl ethyl ketone, 27 g of toluene and 18 g of cyclohexanone.

On a 100 y thick polyethylene terephthalate film was deposited by vacuum evaporation a 100 mu thick aluminum layer on to which the photosensitive composition was coated by a A 100cm thick polyethylene terephthalate film was deposited with aluminum in a thickness of 100 mu by vacuum evaporation, followed by coating with the photosensitive composition and drying at 1000C for 30 seconds to produce a photosensitive layer 3 u thick.

A 12 u thick polyethylene terephthalate film was laminated on the photosensitive layer by means of a 30 11 thick acrylic adhesive layer (available from Nippon Carbide Industries Co., Ltd. under the name of "Nissetsu PE11SA") to obtain an image producing element.

According to the procedures in Example 1, 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 reinforced by the laminated film and hence had improved mechanical strength, the peeling off operation was readily effected, the resulting element was suitable for use in a large size, and the positive pattern produced on the photosensitive layer was used for various purposes.

Example 14 An image producing element produced by 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 10.

The exposed element was heated at 90"C for 30 seconds and then the overall photosensitive surface was exposed to light again with the machine at a printing exposure of the dial figure being 10.

20 minutes after the second exposure, the photosensitive layer was peeled off to obtain a positive aluminum pattern on the substrate film and a negative pattern on the photosensitive layer.

WHAT WE CLAIM IS: 1. A dry system image producing element capable of producing images by developement using a dry process, said element comprising, in order, a substrate, a thin intermediate layer of a metal or a metal compound, and a top photosensitive layer containing a polymeric film-forming binding material and a photosensitiszer selected from benzophenone, a quinone compound, a diazonium compound and an azido compound, and in which the interfacial adhesion between the intermediate layer and the substrate is less than that between the top layer and the intermediate layer but on exposure of the top layer to light the latter adhesion is capable of being decreased to a level such that it is less than the interfacial adhesion between the intermediate layer and the substrate.

2. A dry system image producing element according to Claim 1, wherein said layer of a metal or a metal compound has been formed by vacuum evaporation or electroless plating or a combination of electrolytic plating with vacuum evaporation or electroless plating.

3. A dry system image producing element according to Claim 1 or Claim 2, wherein said binding material is a film forming, water or organic solvent soluble synthetic resin, a cellulose derivative or a rubber derivative.

4. A dry system image producing element according to any one of Claims 1 to 3, wherein said quinone compound is 1 4-naphthoquinone, 2-methyl-i ,4-naphthoquinone, antraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroantraquinone or p-toluquinone.

5. A dry system image producing element according to any one of Claims 1 to 3, wherein said diazonium compound is 4-(p-tolyl mercapto)-2,5-diethoxybenzene diazonium zinc chloride, sodium sulfate or tetrafluoroborate, 4-(p-tolyl mercapto)-2,5dimethoxybenzene diazonium zinc chloride, 4-(p-methyl benzoylamino)-2,5-diethoxy- benzene diazonium zinc chloride, 4-(p-methoxybenzoylamino)-2,5-diethoxybenzene diazonium zinc chloride, 4-morpholino-2,5-butoxybenzene diazonium zinc chloride or tetrafluoroborate, 4-morpholinobenzene diazonium tetrafluoroborate, 4-pyrrolidino-3methylbenzene 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 aminobenzene diazonium zinc chloride, 1,2-diazonaphthol-5-sulfonic acid sodium salt, or a zinc chloride salt of a condensate of 4-diazodiphenylamine sulfuric acid and formaldehyde.

6. A dry system image producing element according to any one of Claims 1 to 3, wherein said azido compound is 2,6-di(4'-azidobenzal) cyclohexanone.

7. A dry system image producing element according to Claim 1, Claim 2 Claim 3 or Claim 4 wherein said photosensitive top layer contains a benzophenone or quinone compound as photosensitizer and 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, nitrocellulose, acetylcellulose acetyl-butylcellulose, ethylcellulose, cyclized rubber or rubber chloride as polymeric binding material.

8. A dry system image producing element according to Claim 1, Claim 2, Claim 3,

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

A 100cm thick polyethylene terephthalate film was deposited with aluminum in a thickness of 100 mu by vacuum evaporation, followed by coating with the photosensitive composition and drying at 1000C for 30 seconds to produce a photosensitive layer 3 u thick.

A 12 u thick polyethylene terephthalate film was laminated on the photosensitive layer by means of a 30 11 thick acrylic adhesive layer (available from Nippon Carbide Industries Co., Ltd. under the name of "Nissetsu PE11SA") to obtain an image producing element.

According to the procedures in Example 1, 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 reinforced by the laminated film and hence had improved mechanical strength, the peeling off operation was readily effected, the resulting element was suitable for use in a large size, and the positive pattern produced on the photosensitive layer was used for various purposes.

Example 14 An image producing element produced by 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 10.

The exposed element was heated at 90"C for 30 seconds and then the overall photosensitive surface was exposed to light again with the machine at a printing exposure of the dial figure being 10.

20 minutes after the second exposure, the photosensitive layer was peeled off to obtain a positive aluminum pattern on the substrate film and a negative pattern on the photosensitive layer.

WHAT WE CLAIM IS: 1. A dry system image producing element capable of producing images by developement using a dry process, said element comprising, in order, a substrate, a thin intermediate layer of a metal or a metal compound, and a top photosensitive layer containing a polymeric film-forming binding material and a photosensitiszer selected from benzophenone, a quinone compound, a diazonium compound and an azido compound, and in which the interfacial adhesion between the intermediate layer and the substrate is less than that between the top layer and the intermediate layer but on exposure of the top layer to light the latter adhesion is capable of being decreased to a level such that it is less than the interfacial adhesion between the intermediate layer and the substrate.
2. A dry system image producing element according to Claim 1, wherein said layer of a metal or a metal compound has been formed by vacuum evaporation or electroless plating or a combination of electrolytic plating with vacuum evaporation or electroless plating.
3. A dry system image producing element according to Claim 1 or Claim 2, wherein said binding material is a film forming, water or organic solvent soluble synthetic resin, a cellulose derivative or a rubber derivative.
4. A dry system image producing element according to any one of Claims 1 to 3, wherein said quinone compound is 1 4-naphthoquinone, 2-methyl-i ,4-naphthoquinone, antraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-chloroantraquinone or p-toluquinone.
5. A dry system image producing element according to any one of Claims 1 to 3, wherein said diazonium compound is 4-(p-tolyl mercapto)-2,5-diethoxybenzene diazonium zinc chloride, sodium sulfate or tetrafluoroborate, 4-(p-tolyl mercapto)-2,5dimethoxybenzene diazonium zinc chloride, 4-(p-methyl benzoylamino)-2,5-diethoxy- benzene diazonium zinc chloride, 4-(p-methoxybenzoylamino)-2,5-diethoxybenzene diazonium zinc chloride, 4-morpholino-2,5-butoxybenzene diazonium zinc chloride or tetrafluoroborate, 4-morpholinobenzene diazonium tetrafluoroborate, 4-pyrrolidino-3methylbenzene 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 aminobenzene diazonium zinc chloride, 1,2-diazonaphthol-5-sulfonic acid sodium salt, or a zinc chloride salt of a condensate of 4-diazodiphenylamine sulfuric acid and formaldehyde.
6. A dry system image producing element according to any one of Claims 1 to 3, wherein said azido compound is 2,6-di(4'-azidobenzal) cyclohexanone.
7. A dry system image producing element according to Claim 1, Claim 2 Claim 3 or Claim 4 wherein said photosensitive top layer contains a benzophenone or quinone compound as photosensitizer and 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, nitrocellulose, acetylcellulose acetyl-butylcellulose, ethylcellulose, cyclized rubber or rubber chloride as polymeric binding material.
8. A dry system image producing element according to Claim 1, Claim 2, Claim 3,

Claim 5 or Claim 6 wherein said photosensitive top layer contains a diazonium compound or azido compound as photosensitizer and 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, nitrocellulose, acetylcellulose, acetyl-butylcellulose, ethylcellulose, cyclized rubber, rubber chloride, polyvinyl butyral, a thermoplastic linear polyester or copolyester, an alcohol soluble polyamide, polyvinyl alcohol, acrylic ester/methyl methacrylate or styrene copolymer or polyurethane as polymeric binding material.
9. A dry system image producing element according to Claim 1, substantially as hereinbefore described and as illustrated in any one of the Examples.
10. A process for producing an image which comprises exposing to light through a pattern a dry system image producing element as claimed in any one of Claims 1 to 9 whereby to reduce the level of interfacial adhesion between the exposed portion of the top layer and the intermediate layer to below that between the intermediate layer and the substrate and thereafter peeling off the top layer to leave on the substrate an image pattern made of the metal or metal compound and corresponding to the exposed portion.
11. A process for producing an image which comprises: exposing to light through a pattern a dry system image producing element as claimed in any one of Claims 1 to 9 whereby to reduce the level of interfacial adhesion between the exposed portion of the top layer and the intermediate layer to below that between the intermediate layer and the substrate subjecting the thus exposed element to a heat treatment whereby to restore the interfacial adhesion between the exposed portion of the top layer and the intermediate layer to a level higher than that between the intermediate layer and the substrate, exposing the overall surface of the top layer to light whereby to reduce the level of interfacial adhesion between the intermediate layer and the portion of the top layer not unexposed to light in the first exposure to below that between the intermediate layer and the substrate, and peeling off the top layer to produce on the substrate an image pattern made of the metal or metal compound corresponding to the initially unexposed portion.
12. An image obtained by the method claimed in Claim 10 or Claim 11.