GB1604525A - Imaging system and products useful therein - Google Patents

Description

(54) NOVEL IMAGING SYSTEM AND PRODUCTS USEFUL THEREIN (71) We, POLYCHROME CORPORATION, a corporation organised and existing under the laws of the State of New York, United States of America, of 137 Alexander Street, Yonkers, State of New York, 10702, United States of America. (Assignees of KEN-ICHI SHIMAZU and TAKAO NAKAYAMA), do hereby declare the invention, for which we ray 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 energy sensitized sheet constructions which, upon exposure to a suitable energy source through a screened image can accurately and simultaneously reproduce said image in both its negative and positive forms. More particularly, this invention relates to novel, energy sensitive sheet constructions which, when exposed to a suitable light or thermal energy source through a screened image, will yield simultaneously both a negative and positive reproduction of said screened image.

The novel energy sensitive sheet construction of this invention are particularly useful in the graphic arts field. For example, in the lithographic printing arts, it is frequency necessary or desirable to convert a negative film image to a positive one for further use in the preparation of lithographic printing plates. Heretofore, this conversion from negative to positive image, and vice versa, has been time consuming, expensive and inefficient. We have now discovered a novel imaging system which can directly, efficiently and inexpensively be employed to produce both positive and negative image reproductions simultaneously.

The present invention provides a multilayered sheet construction capable by delamination after imagewise exposure to an energy source of simultaneously reproducing both positive and negative forms of a photographic mask which comprises in order of Juxtaposition 1. a substantially gas impermeable first substrate, ii. an energy sensitive composition layer adjacent to the undersurface of said first substrate, said energy sensitive composition layer being capable of decomposing with concurrent generation of gas upon exposure to an energy source to which it is sensitive whereby a bubble of gas is formed which imparts to the construction an immediately visible image and exerts pressure upon the adjacent layers to facilitate their separation upon being delaminated, iii. an imaging layer, iv. an adhesive composition layer and v. a second substrate supporting said adhesive layer in which the bond strengths between the layers is such that the weakest bond is either (a) that between the adhesive composition layer and the second substrate layer so that upon delamination the positive form of the photographic mask comprising the imaging and adhesive layers will adhere to the second substrate, while the negative form comprising the energy sensitive composition, the imaging layer and the adhesive layer will adhere to the first substrate, or (b) is that between the adhesive composition layer and the imaging layer so that upon delamination the positive form of the photographic mask comprising the imaging and adhesive layers will adhere to the second substrate, while the negative form comprising the imaging and photosensitive layers will adhere to the first substrate, and in which the transparency of the layers other than the energy sensitive composition layer is such that the energy sensitive composition layer can be exposed to said energy source through the first or second substrate or both.

The invention also includes a modification of the above defined multilayer construction in which the imaging and adhesive composition layers are combined to form a single layer and in which the weakest bond is that between the second substrate layer and the combined imaging and adhesive composition layer.

To date, it has been a problem in the art to provide an imaging system which would allow the quick, easy and dependable availability of an image reproduction, in both its positive and negative forms, having a quality suitable for use in the graphic arts and other image reproducing applications. As part of the present invention it has been found that by forming a specific layered construction and exposing it through a photographic image to an energy source, the layers may be immediately separated whereby a positive reproduction of the mask image is apparent on one leaf of the separated construction and a negative of said image appears on the other leaf. Furthermore, these images are visible immediately upon exposure and are available after separation for a series of other uses without any further developing treatment. This is an important point since other prior art systems require some post treatment, such as image curing or development, before a useful product can be attained. One such prior art method requires development by heat treatment, another requires solvent development. Importantly, the present disclosure requires no chemical or other processing subsequent to exposure as is required by such other prior art methods.

Applications for which this dry transfer system is useful include, direct transferability of the image to other surfaces, manufacture of color proofing guides, art composition, engineering drawings, letter and figure transfers, photo-composition, photoresists, nameplates, presensitized printing plates, and bimetaprinting plates.

Advantages over the prior art include, the elimination of chemical processing or other treatment to attain the image after exposing; availability of a colored image without subsequent treatments; finer image resolution and a higher degree of energy response sincethe imaging layer which may be colored is not blended with the energy sensitive layer whereby the functions interfere with one another; no fixing is required; the image is instantly visible upon exposure and may be evaluated for quality without further processing, allowing a continued or multiple exposure if necessary or desirable. Other advantages include safe room light handling; no pollution or exposure of workers to caustic chemicals; and transferable images in both the positive and negative forms. Importantly, there need not be any alteration of exposures when different colored constructions are selected since the image layer has no effect on the sensitivity of the energy sensitive agent.

In systems where both the energy sensitive agent and the imaging agent are blended into one layer the imaging layer absorbs a quantity of the supplied exposure energy and, depending on the amount absorbed by different colorants, the exposure must be adjusted by some factor when changing from one color to another. This adjustment is not required with the instant system.

It is known in the prior art that photosensitive diazo compounds liberate nitrogen gas upon photodecomposition. Specifically, British patent 712,966 describes one method of prepanng a print material whereby a diazo and resin composition is coated on a base, however this disclosure requires development by subjecting an image to elevated temperatures after exposure to actinic light through a mask.

Japanese patent S38-9663 demonstrates one type of peel apart system whereby a photosensitive composition is situated between a base and a film sheet whereby the photosensitive composition has a stronger bonding force exerted on the film than on the base before exposure and a stronger bonding force on the base then on the film after imagewise exposure. This system has proved to be substantially unworkable since such subtle reversals in adhesive properties are difficult to achieve with consistent results. Still another method, as developed by the Fuji (Registered Trade Mark) Photo Film Company employs two light sensitive layers containing photopolymers which have different adhesive attractions for a base and a covering film sheet.

U.S. Patents 3,060,024 and 3,060,025 show another system whereby high polymers are imagewise formed. Upon exposure certain areas are rendered tacky, particles are dusted on to tacky areas, a transfer sheet is applied to the substrate and heated and the films then separated. It must be noted that no visible image exists immediately prior to article dusting.

In the instant invention there is no required application of dusted particles subsequent to exposure and no surface heating thereafter.

U.S. Patent 2,760,863 describes another system whereby insoluble high polymers are formed by photopolymerization and non-image areas are removed by washing with a solvent after exposure.

U.S. Patent 3,136,637 provides still another imaging system, which also requires solvent development.

The instant invention is distinctly different from each cited reference. The present invention discloses an article with separate photosensitive and image forming layers. After exposure by well known methods, a visible image is instantly apparent. No further processing or development by heat or ultraviolet treatment or solvents is required. Also, there is no reversal of adhesive attraction by the photosensitive layer either from the top cover to the base sheet ot vice versa when viewed both before and after imagewise exposure. The differential mechanism which is the main feature is a delamination of the layers after exposure. That is, the energy sensitive layer, which before exposure adhered to its adjacent layers has now decomposed at the exposed areas with a concurrent emission of gas which exerts an outward pressure and separation from its corresponding adjacent layers at these exposed areas. No element of the prior art demonstrates this phenomenon.

The present invention provides a multi-layered energy sensitive image forming construction which is capable, upon imagewise exposure, of providing both positive and negative reproductions of an image by means of a delamination process.

Importantly, either the first substrate layer or the second substrate layer or both must be substantially transparent in order to permit radiant energy, preferably in the form of light or heat, to penetrate therethrough and reach the energy sensitive layer beneath it. The first substrate layer must also be substantially gas impermeable. The energy sensitive layer must be capable of decomposing with the concurrent generation of a gas, such as nitrogen. The imaging layer typically comprises a resinous material which may have additives such as colorants or adhesives blended with it. The adhesive composition layer is employed to aid in the separation of the positive and negative images. The second substrate layer provides a foundation for the system of layers. This second substrate layer may be a specialized or proprietary base material to which, prior to irradiation, is applied a multilayer construction formed by use of only the other layers.

Upon imagewise exposure of the construction through a photographic image or mask, the radiant energy is selectively transmitted through one of the transparent substrate layers and causes activation of the energy sensitive layer whereby gas is released as a result of the decomposition of the energy sensitive material. A gas bubble is then formed between the first subtrate layer and the imaging layer where the energy sensitive layer was exposed. This breaks any adhesive bonds which may have existed between the energy sensitive layer and the first substrate layer or the imaging layer. Not only is there no adhesion between these layers but the gas pressure from the bubble acts to press these layers apart forcefully. Upon viewing the construction through the first substrate layer, the image imparted to it is clearly visible by means of these bubble gas pockets. By separating both the first and second substrate layers, the adhesive forces exerted between the layers are such that the imaging layer is selectively adherent to both the first and second substrate layers such that a positive reproduction of the original image is apparent upon the first substrate layer and a negative reproduction of the image is apparent upon the second substrate layer. Importantly, the binding force between the layers to be separated must be the weakest bond of any other interface of the construction. Both positive and negative images are now available for use in any of a variety of ways as hereinbefore discussed.

The present invention seeks to provide a multilayered image forming construction which is capable of providing image reproduction in both its positive and negaive form, which does not require additional treatment or development after exposure, which has an image forming layer substantially free of mixture with the energy sensitive material and an enery sensitive layer substantially free of image forming material, and which manifests a visible image immediately after exposure to an energy source by means of a delamination process as a result of gas emission from decomposition of an energy sensitive material.

The present invention will now be described with reference to the accompanying drawings in which: Figure I is a cross section of a five layered construction being imagewise exposed to an energy source through a photographic image or mask; Figure 2 is a cross section of a five layered construction after peel apart wherein the adhesive composition layer employed has a greater bonding strength to the second substrate layer than to the imaging layer; Figure 3 is a cross section of a five layered construction after peel apart wherein the adhesive composition layer employed has a greater bonding strength to the imaging layer than to a second substrate layer; Figure 4 is a cross section of a four layered construction being exposed imagewise to an energy source through a photographic image or mask wherein the imaging and adhesive composition layers are combined in one and the same layer. Note that this image-adhesive composition must always have a greater bonding strength to the energy sensitive layer than to the second substrate layer for operation; Figure 5 is a cross section of a four layered construction of figure 4 after peel apart; Figure 6 is a cross section of a four layer construction which when applied to a suitable substrate will produce the embodiment of Figure 1; Figure 7 is a cross section of a three layered construction which when applied to a suitable substrate will produce the embodiment of Figure 4; Figure 8 is a cross section of a five layered construction similar to figure 1, after imagewise exposure but before peel apart, showing the bubble formation where the energy sensitive material was exposed with the concomitant discharge of gas.

Referring now to the drawings, figure 1 shows a five layered construction produced according to the method of the present invention. It is shown to comprise a base support 10, an adhesive layer 12 in intimate contact with said base support, an image forming layer 14 in contact with said adhesive layer and an energy sensitive layer 16 which is capped with a top layer 18. When the construction is exPosed to radiant energy 20 through a mask 22, said radiant energy 22 passes through said top layer which is transparent and reacts with the energy sensitive layer at section 24.

Figure 8 is demonstrative of the operative mechanism of the invention. The construction is shown to form a gas bubble at 24 where the energy sensitive composition has been exposed but none where it has not been exposed. This gas is released as the product of the decomposition of said energy sensitive material at the exposed portion 24. This bubble exerts an outward pressure upon the top surface layer 18 which appears as a visible image.

Figures 2 and 3 demonstrate the end product after the top and bottom layers have been peeled apart. The difference noted demonstrates alternate results which depends upon the binding characteristics of the adhesive layer. If the adhesive clings more forcefully to the base than to the imaging layer, then the configuration of figure 2 is attained. If however, the adhesive binds more forcefully to the imaging layer than the base, then the product of figure 3 is attained. Note that in either case a positive image is reproduced on the top leaf and a negative image is reproduced on the bottom leaf.

Figure 4 shows a multilayered aggregation whereby both the imaging and adhesive functions are combined within a single, integrated layer 26. The exposure mechanism is exactly the same as demonstrated in figure 6, however, upon being peeled apart, the embodiment of figure 5 is attained. In short, element 26 is a blend of elements 12 and 14 into a single stratum.

Figures 6 ad 7 illustrate four and three layer constructions which are applied to a suitable second substrate layer to form the constructions of Figures 1 and 4 respectively they are used to form the multilayered construction of the present invention when a specialized or proprietary base is required as the second substrate.

In accordance with the present invention it has been found that the second substrate layer, may be comprised of any solid sheet material having a substantially regulator surface.

These include, but are not limited to the following compositions and combinations thereof: glass, metals, for example, aluminum sheets, paper, silicon, and films or sheets comprised of: Acrylonitrile-butadiene-styrene terpolymers (ABS) Cellulose Acetate Cellulose triacetate Cellulose acetate butyrate Cellulose propionate Polybutylene Polybutadiene Polycarbonate Polyester Polyethersulfone Polyethylene (Low, medium and high density) Ethylene-propylene copolymers Ethylene vinyl acetate copolymers Nylons (polyamides) Acrylonitrile copolymers Ionomers Polyimides Polymethylmethacrylates Polychlorotrifluoroethylenes Fluoronated ethylene propylene copolymers Perfluoroalkoxy resins Ethylene-chlorotrifluoroethylene copolymers Ethylene-tetrafluoroethylene copolymers Polyvinyl fluoride resins Polyvinylidene fluoride resins Polypropylenes Polystyrene (and oriented polystyrene) Polyurethane elastomers Polyvinyl chloride - plasticized Polyvinyl chloride - unplasticized Polyvinyl chloride copolymer resins Polyvinylidene chloride and its copolymers Polyvinyl acetate Polyvinyl alcohol.

Adhesives which may be employed in the formation of the adhesive layer of the present invention include those which may be activated by pressure, heat or ultraviolet radiation or combinations thereof. These may include one or more of the following compositions: a) polymers, copolymers, terpolymers, etc., graft copolymers, block copolymers, etc., prepared from one of more of the following monomers: Ethylene, Propylene, 1-Butene, Isobutylene, 1-Pentene, 1-Hexene, 1-Heptene, 1-Octene, 1-Decene, 1-Dodecene, a Olefins (Cll-C18), Butadiene, Isoprene, 1,3-pentadiene, Chloroprene, 2,3 Dichloro-1,3 butadiene, Dipentene, Styrene, a Methyl styrene, t-Butyl styrene, 4 Methyl pentyl styrene, Divinyl benzene, Cyclopentene, Cyclohexene, Cycloheptene, Cyclooctene, Cyclononene, 4-Methyl cyclopentene, 4-Ethyl cyclopentene, 4-Pentyl cyclopentene, 4-Hexyl cyclodecene, Cyclopentadiene, 1,3 Cyclohexadiene, 1,3,5, Cyclooctatriene, 1,3,5 Cyclododecatriene, 3-allyl indene, B-piene, A -Carene, Methyl acrylate, Ethyl acrylate, n-Butyl acrylate, Isobutyl acrylate, 5-Butyl acrylate, 2-Methyl butyl acrylate, Methyl pentyl acrylate, Methyl pentyl acrylate, n-Hexyl acrylate, n-Heptyl acrylate, 2-Ethylhexyl acrylate, n-Octyl acrylate, n-Nonyl acrylate, n-Decyl acrylate, n-Undecyl acrylate, Lauryl acrylate, 6-Methoxy acrylate, Hydroxyethyl acrylate, Hydroxypropyl acrylate, Methoxy butyl acrylate, Butanediol monoacrylate, Etylene glycol monoacrylate, Diethylene glycol triacrylate, Trimethylolpropane triacrylate, Tetraethylene glycol diacrylate, Tetraethylene glycol di(chloroacrylate), 3-Chloro-2-hydroxypropyl acrylate, 2-Cyanoethyl acrylate, Glycidyl acrylate, Methyl methacrylate, n-Butyl methacrylate, t-Butyl methacrylate, n-Hexyl methacrylate, 2-Ethylhexyl methacrylate, n-Nonyl methacrylate, n-Decyl methacrylate, n-Dodecyl methacrylate, 1-Chlorodecyl methacrylate, Hydroxypropyl methacrylate, Diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, Tetraethylene glycol dimethacrylate, Trimethylol propane trimethacrylate, Dipropylene glycol dimethacrylate, Di(pentamethylene glycol) dimethacrylate, Ethylene glycol dimethylmethacrylate, 2-Cyanoethyl methacrylate, Dimethylamino ethyl methacrylate, Glycidyl methacrylate, Tnmethoxysilylpropyl methacrylate, Acrylic acid, Methacrylic acid, Crotonic acid, Fumaric acid, Succinic anhydride, Itaconic acid, Maleic anhydride, Methylene glutaric acid, n-t-Cl2 Maleamic acid, Vinyl acetate, Vinyl chloride, Vinylidene chloride, Vinyl benzyl alcohol, Sodium vinyl sulfonate, Methyl vinyl ether, Ethyl vinyl ether, Isobutyl vinyl ether, Acrylonitrile, Methacrylonitrile, Methylene glutaro nitrile, (3-Propiolactone, N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl imidazole, Acrylamide, Methacrylamide, N-t-Butyl acrylamide, N-Octyl acrylamide, Diacetone acrylamide, N-Methylol acrylamide N-n-Butoxymethyl methacrylamide, N-Methylol methacrylamide, Trimethylamine methacrylamide, Triethylamine methacrylamide, Tributvlamine methacrylamide, 3-(2-acryloxyethyl dimethylammonium) propionate betaine, 3-(2-Methacryloxyethyl dimethylammonium) propionate betaine, 3-(2-Acryloxyethyl dimethylammonium) sulfonate betaine, 1,1-Dimethyl-1(2-dryroxypropylamine)4-isopropenyl benzamide, Trimethylamine 4-isopropenyl benzimide, Trimethylamine 4-isopropenyl benzimide, Trimethyl amine 4-vinyl benzimide, N-('-Aminoethyl) aziridine, N-(2-Cyanoethyl) aziridine, N-(2-Hydroxyethyl aziridine, Acrolein, Diketene, Dibutyl fumarate, Ethyl acid maleate, Dioctyl maleate, Methyl hydrogen fumarate, Acrylic acid 2-isocyanate ester, Acrylol malonic acid diethyl ester, Phenyl allyl alcohol a-Propane sulfone Allyl glycidyl ether, and 3-Methacryloxypropyl tromethoxysilane.

b) Natural and synthetic polymers and elastomers such as: Natural rubber, Gelatin, Cellulose acetate butyrate, Polyamides, Polyterpene resins, Extract acid polyepoxide resins, Silicone resins, Chlorinated rubber, Ethyl cellulose, Polyvinyl alcohol, Phenol-formaldehyde resins, Polyurethane resins, Isocyanate cross linked polyester resins, and Hydroxy terminated polysiloxanes.

c) Polymers and elastomers listed above which have been subjected to various chemical modifications such as hydroxylation, carboxylation, thiolation, sulfonation and the like.

Optionally, these adhesives may be blended with a variety of additives to alter the physical properties of the composition. Examples of such additives include fillers such as fine silica and calcium carbonate to control tackiness, and plasticizers, such as dioctyl phthalate and castor oil, to lower melting points.

The adhesive compositions may be applied to its base support by any convenient method known in the art, such as, spraying, brushing, rolling or meniscus coating the adhesive ether in its existing state, by means of an appropriate solvent system or by heat melting into the molten state. Such solvent systems which may be employed herein, may include any organic solvent in an amount up to about 98% of the total application constituents. The balance of the solution may comprise from about 20% to about 100% by weight of a polymeric composition as hereinbefore mentioned, from about 0% to about 70% by weight of a plasticizer. Adhesion properties may be controlled by the selection of ingredients and the particular method of application selected.

The image forming layer may comprise a binding resin which includes thermoplastic and photopolymerizable resms. These may be composed of any of these polymers previously listed as available to form the adhesive layer, also these photopolymers enumerated in U.S.

Patents No's. 2,760,863; 3,060,024, and 3,060,025 and in the publication, Light Sensitive Systems by Jaromir Kosar, John Wiley and Sons, New York, 1965. Optionally this imaging layer may contain any coloring agent which includes all those listed in the Color Index or metallic particles such as, iron oxide, aluminum powder of bronze powder which may be vapor or vacuum deposited, to also provide magnetic or conductive properties to the layer.

The image layer may also optionally contain other additives such as a dispersant, for example, cobalt naphthenate or iron naphthenate. These ingredients may optionally be mixed in a solvent system wherein the solvent constituents comprise up to 98% of the total composition. The non solvent constituents ma be present in the following percentages by weight: binding resin from about 0% to 100 o, colorant or metallic particles from 0% to about 90% and dispersant from 0% to about 20%.

When the imaging and adhesive functions are incorporated into a single layer, the stratum consists of a selection of the imaging ingredients which also demonstrate the requisite adhesive properties.

The energy sensitive layer may include any composition which is capable of generating a gas upon exposure to its activation energy source. These include heat sensitive materials such as, benzoyl peroxide and azo bisisobutyronitrile and such photo-sensitive compositions as the diazo and azide substances which may include the reaction product of paradiazo diphenyl amine-para-formaldehyde condensate and 2-hydroxy-4-methoxy benxophenone sulfonic acid; P-N,N-dimethylaminobenzenediazonium zinc chloride P-N,N-diethylaminobenzenediazonium zinc chloride 4- p-tolyl-mercapto)2,5-dimethoxybenzene diazonium zinc chloride 4-p-tolyl-mercapto )-2,5-diethoxybenzene diazonium zinc chloride 4-morpholino-2,5-dibutoxybenzenediazoniu zinc chloride 4-morpholino-2,5-dibotoxybenzenediazonium fluoborate P-N-ethyl-N-benzylaminobenzene diazonium zinc chloride 4-diazo-diphenylamine sulfate 1-diazo-4-N ,N-dimethylamino-benzene zinc chloride 1-diazo-4-N,N-diethylamino-benzene zinc chloride 1-diazo-4-N-ethyl-N-hydroxyethylamino-benzene 1/2 zinc chloride 1-diazo-4-N-methyl-N-hydroxyethylamino-benzene 1/2 zinc chloride 1-diazo-2,5-diethoxy-4-benzoylammo-benzene, 1/2 zinc chloride 1-diazo-4-N-benzylamino-benzene, 1/2 zinc chloride 1-diazo-4N,N-dimethylamino-benzene borofluoride 1-diazo-4-morpholino:benzene, 1/2 zinc chloride 1-diazo-4-morpholino-benzene-borofluoride 1-diazo-2,5-dimethoxy-4-p-tolylmercaptobenzene, 1/2 zinc chloride 1-diazo-2-ethoxy-4-N ,N-dimethylaminobenzene, 1/2 zinc chloride p-diazo-dimethyl aniline, 1/2 zinc chloride 1-diazo-4-N,N-diethylamino-benzene, 1/2 zinc chloride 1-diazo-2,5-dibutoxy-4-morpholino-benzene sulfate 1-diazo-2 ,5-diethoxy-4-morpholino-benzene, 1/2 zinc chloride 1-diazo-2 ,5-dimethoxy-4-morpholino benzene, zinc chloride 1-diazo-2,5-diethoxy-4-morpholino-benzene, 1/2 zinc chloride 1-diazo-2,5-diethoxy-4-morpholino-benzene-borofluoride 2-diazo-1-naphthol-5-sulfonic acid, sodium salt 1-diazo-4-N,N-diethylamino-benzene, borofluoride 1-diazo-2,5-diethoxy-4-p-tolylmercapto-benzene, 1/2 zinc chloride 1-diazo-3-ethoxy-4-N-methyl-N-benzylamino-benzene, 1/2 zinc chloride, 1-diazo-3-chloro-4-N ,N-diethylamino-benzene, 1/2 zinc chloride 1-diazo-3-methyl-4-pyrrolidino-benzene chloride, zinc chloride 1-diazo-3-methyl-4-pyrrolidino-benzene-borofluoride 1-diazo-2-chloro-4-N ,N-dimethylamino-5-methoxy-benzene, borofluoride 1-diazo-3-methoxy-4-pyrrolidino benzene, zinc chloride condensation product of 4-diazo diphenylamine sulfate and formaldehyde zinc chloride p-azide cinnamic acid 2, 6-di(4'-azidebenzal)-4methylcyclohexanone 3-azide phthalic anhydride 4,4'-diazide-3,3'-dimethyl-biphenyl 4,4'-diazide-3 ,3 '-dichloro-biphenyl 4,4'-diazidebenzol acetylacetone 4,4'-diazide-3 ,3 -dimethoxy-biphenyl 4,4'-diazide diphenylmethane 4,4'-diazide diphenyl sulfone 2,6-di-(4'-azidebenzal)-cyclohexanone 4,4'-diazidebenzalacetone-2,2'-disulfic acid sodium salt 4,4' -diazide stilbene-2,2'-disulfic acid sodium salt azidopyrenes, such as, 1-azido-pyrene, 6-nitro-1-azidopyrene, 1,6diazidopyrene, 1,8diazido-pyrene, 1-propionyl-6-azidopyrene, 1-acetyl-6-azidopyrene, 1-n-butyryl-6azidopyrene, 1-n-propionyl-8-bromo-6-azidopyrene; and 8-n-propionyl-1 ,Odiazidop me; and the aromatic diazo-oxide compounds, for example, beuzoquinone diazides, naphthoquinone diazides. Also included are those gas generating photosensitive compositions listed in Light Sensitive Systems, ibid.

These energy sensitive substances may be combined with a binder resin such as those listed as appropriate for use in conjunction with the adhesive layer. Optionally, additiv Industries) and .5 g of water.

These two coated films were then laminated together forming an image layer-adhesive layer interface to form the basic construction of figure 1.

The construction was exposed to actinic light from a carbon arc source through an original transparency for 30 seconds from the side of the 3 mil polyester film. When this laminated sheet was delaminated after light exposure, a negative image was obtained on the 1/2 mil polyester film and a positive image was obtained on the sheet of 3 mil polyester film.

The positive image was projected onto a screen by using an overhead projector, clean images were viewed on the screen.

Example 2 A construction was produced according to Example 1 except the imaging layer comprised: Versamide 754 (available from General Mills) 45 g Toluene 135 ml Isopropyl alcohol 81 ml Cyclohexanol 30 ml Rhodamine B-MS40 1.5 g where MS40 is ultraviolet absorber available from G.A.F. Corporation.

Vivid red images were obtained by laminating the adhesive layer described in example 1, exposing and peeling. This image was useful for overhead projection and for an overlay color proof by overlapping on the other color images.

Example 3 Example 2 was repeated with water soluble methylene blue dye in place of solvent soluble Rhodamine B-MS40 dye.

Vivid blue images were obtained by exposure and peeling.

Example 4 The formulations below were coated successively on a 1 ml polyester sheet: a) A photosensitive layer comprising a combination of: Epon Resin (Shell Chemical) 5 g p-diazo-dimethylaniline 1/2 ZnCl2 15 g Ethylene dichloride 80 ml Methanol 25 ml Methyl Cellosolve (Reg. Trade Mark) 25 ml Dimethyl formamide 25 ml b) An image layer comprising a combination of: Versamide 754 20 g Toluene 135 ml Isopropyl alcohol 81 ml Cyclohexanol 30 ml At the same time 10 g of silicone adhesive (General Electric: Siligrip SR-573) diluted with 5 g of toluene was coated on a 3 ml polyester film support sheet. This coated support sheet was laminated with the cover sheet to form the basic construction of figure 1. Actinic light from a carbon arc was imagewisely exposed through a photograhic mask for 30 seconds from the cover sheet side. After peeling, the support sheet was dusted with carbon black; a strong light-fast positive black image was obtained.

Example 5 The following energy sensitive composition was coated onto a 3 mil polyester film: Epon Resin 1031 (commercially available from Shell Chemical Co.) 5 g Z,6-di(4'-azide benzol)-4-methyl cyclo hexanone 5 g Ethylene dichloride 80 ml Methanol 10 ml Methyl Cellosolve (Reg. Trade Mark) 10 ml Dimethyl formamide 20 ml This was overcoated with the imaging layer composition of example 2. Tucktape #21 (available from the Technical Tape Corporation) was then laminated on the above sheet.

Negative and positive images were obtained by peeling apart the tape and the film after a 60 second exposure to a carbon arc lamp.

Example 6 The energy sensitive layer formulation of Example 5 was coated on a 3 mil Mylar (Reg.

Trade Mark film and then the following image layer composition was overcoated thereon: Pliolite S-SE (Goodyear Chemical) 17.6 g Titanium Dioxide 95 g Zinc oxide 10.6 g Lead Naphthanate 3.3 g Toluene 400 ml Isopropyl alcohol 20 ml Tuck tape #21 was then laminated on the above sheet. A positive opaque white image was obtained on the tuck tape and a negative image was obtained on the 3 mil Mylar, after a 45 second ultraviolet radiation exposure when exposed through positive transparency.

Example 7 The following photosensitive layer composition was coated onto a 3 mil polyester film and overcoated with the image layer of Example 2: Epon Resin 1031 (commercially available from Shell Chemical Co.) 5 g 2,6-di(4'-azide benzol)-4-methyl cyclohexanone 5 g N-hydrothioacridone 0.2g Ethylene dichloride 80 ml Methanol 10 ml Methyl Cellosolve (Reg. Trade Mark) 10 ml Dimethyl formamide 20 ml A strip of tuck tape #21 was then laminated on the above layer. Negative and positive images were obtained by peeling apart the film and the tape after a 20 second exposure from a carbon arc lamp.

Example 8 The photosensitive layer of Example 1 was coated on a 3 mil polyester film. An aluminum layer was then formed on this coated sheet by a standard vacuum evaporation method. A strip of tuck tape No. 21 was then laminated to this construction. The construction was then imagewise exposed to U.V. light from the side of the 3 mil polyester through a negative original. These films were then delaminated after an exposure of 30 seconds, whereby a positive metal image was obtained on the 3 mil film base. Similar results were obtained when a thin layer of resin was coated on the polyester prior to aluminum deposition. lhe resin formulation comprised: Versamide 754 20 g Toluene 135 ml Isopropyl alcohol 81 ml Cyclohexanol 30 ml When this metal image was mounted for slide projection, a clear image was recognized on the screen.

Example 9 A thermosensitive composition of the following formulation was coated on a 5 mil mylar film: Epon Resin 1031 (Shell Chemical Co.) 5 g Azobisisobutyronitril 10 g Ethylene dichloride 80 ml Toluene 30 ml Dimethyl formamide 30 ml An image layer of the following formulation was then applied to the coated Mylar: (Reg.

Trade Mark) Pliolite S-SE 10 g Toluene 150 ml Isopropyl alcohol 150 ml Brill Basic Blue pure 0.5 g A strip of tuck tape #21 was then laminated on the above construction. The composite film was then passed through a 3M thermofax machine together with a typewritten letter.

After peeling, a copy of the letter was clearly visible on the film. Heated areas adhered to the tuck tape and unheated areas remained on the mylar substrate after peeling off this sheet.

Example 10 The energy sensitive layer and image layer of Example 1 were coated on a 3 mil polyester film and further overcoated with an adhesive layer composition consisting of 5 g of acrylic adhesive (Franklyn Chem., Covinax 117), dissolved in 0.5g of surfactant (Mona, "Cyna" 50% in water). A 0.5 mil polyester film was then laminated as cover sheet. Actinic light was imagewisely exposed for 30 seconds through the 3 mil Mylar (Reg. Trade Mark). When the laminated sheets were peeled apart, a positive image was obtained on the cover sheet and negative image was obtained on the 3 mil mylar.

Example 11 Example 10 was repeated using bond paper in place of the 0.5 mil polyester. By delamination after a 30 second exposure to actinic light through the 3 mii polyester, a positive image was obtained on the paper and a negative imagewise was obtained on the 3 mil mylar. A glue was coated on the backside of paper with the image to be used as paper label.

Example 12 The energy sensitive layer in Example 1 was coated on a degreased smooth aluminum sheet and was overcoated with the imaging layer formulation in Example 2. A cover sheet was prepared by coating a 1 mil polyester film with 10 g of Siliconic adhesive resin (General Electric's Siligrip SR-573) diluted with 5 g of toluene. The cover sheet was then laminated on the aluminum base. U.V. light was imagewise exposed for 30 seconds from the side of the 1 mil polyester film through a positive transparency. When this laminated sheet was peeled, a positive image was obtained on the aluminum base and a negative image was obtained on the 1 mil polyester film. A glue was coated on the backside of the aluminum plate with the red image so as to be useful as a name plate.

Example 13 The following formulations were successively coated on a 3 mil polyester film: Firstly a sensitizer layer comprising a combination of: Epon 1031 (Shell Chemical Co.) 5 g p-diazo dimethylaniline 1/2 ZnCl2 15 g Ethylene dichloride 80 ml Methanol 25 ml Methyl Cellosolve (Reg. Trade Mark) 25 ml Dimethyl formamide 25 ml Secondly an imaging layer comprising a combination of: Versamide 754 (General Mills) 20 g Carbon black 5 g Toluene 40 ml Isopropyl alcohol 40 ml Iron naphthanate 5 g Lastly an adhesive layer comprising a combination of: Acrylic adhesive Covinax 113 5 g 50% of surfactant (CyNa) in water 0.5 g Water 0.5 g A 2 mil polyester film was laminated on the above sheet as in the figure 1 basic construction. This was exposed to actinic light from a carbon arc lamp through a transparent original for 30 seconds from the side of the 3 mil polyester film. When this sheet was laminated after light exposure, a negative image was obtained on the 2 mil polyester film and positive image was obtained on the base sheet of 3 mil polyester film. As these images were projected onto a screen by using an overheated projector, clean images were obtained on the screen.

Example 14 The procedure of Example 13 was followed except the imaging layer comprised: Versamide 754 (General Mills) 45 g Toluene 135 ml Isopropyl alcohol 81 ml Rhodamine B-MS 40 1.5 g and a copper circuit board was laminated to the adhesive layer replacing the 2 mil polyester dilm.

Actinic light was exposed for 45 seconds through a transparent negative original from the side of 3 mil polyester When the 3 mil polyester film was delaminated after light exposure, vivid red positive images were obtained on the circuit board. Copper on the unimaged area was etched by immersing the plate in a copper etching solution. After copper etching, a positive print circuit was obtained by taking off the red image with a mixture of methanol and ethylene dichloride.

Example 15 A light sensitive composition comprising: Epon 1031 (Shell Chemical Co.). 5 g 2,6-di(4'-diazide benzol)-4-methyl cyclohexanone 5 g N-hydrothioacridone 0.2 g Ethylene dichloride 80 ml Methanol 10 ml Methyl Cellosolve (Reg. Trade Mark) 10 ml Dimethyl formamide 20 ml was coated on a 2 mil polyester film and overcoated first with the image layer of Example 14 and an adhesive layer comprising: Silicone adhesive Siligrip SR-529 20 ml Toluene 80 ml A silk screen was then laminated on the glue surface of above sheet. Actinic light was exposed for 35 seconds through the positive transparent original from the side of the 3 mil polyester film. When the 3 mil polyester film was peeled apart after exposure, vivid red negative images were obtained on the silk screen. Sirk screen printing was demonstrated by using this screen. A clear positive ink image was obtained on paper by going through the inked non-image area.

Example 16 Four sheets of 2 mil polyester were coated with the sensitizer layer of Example 13. Each sheet was then respectively coated with an imaging laycr having a different color. These formulations were: For red image composition: Versamide 754 (General Mills) 45 g Toluene 135 g Isopropyl alcohol 81 ml Cyclohexanol 30 ml Rhodamine B-MS40 1.0 g For yellow: 1.0 g of Astragon Yellow-MS40 instead of Rhodamine B-MS40 was added into above formulation.

For blue: 1.0 g of Brill Brilliant Blue instead of Rhodamine B-MS40 was substituted in above formulation.

For black: The composition for the imaging layer in Example 13 was used.

The adhesive composition of Example 15 was then applied to each of the four colored constructions. A sheet of plain white paper was then laminated on the glued surface of the yellow image construction, exposed to actinic light through a color separated transparency and delaminated to show a yellow image on the white sheet. The same sheet was then successively laminated to each of the other colored constructions, exposed through respective color separated transparencies in correct registration, and delaminated. By this process a one sheet color proof of the original image was obtained.

Example 17 The sensitizer formulation of Example 13 was coated on a 2 mil polyester film and then coated with the following image layer: Versamide 940 (General Mills) 20 g Toluene 40 ml Isopropyl alcohol 40 ml This was then coated with the adhesive formulation of Example 13 and a 3 mil polyester film was then laminated to this construction. Actinic light was then imagewisely exposed through a transparent original from the side of the 3 mil polyester film. After delamination carbon black was dusted on the surface of the 3 mil mylar and a positive powder image was obtained. As this image was projected by overhead projector, a clean image was obtained on the screen.

Example 18 The sensitizer of Example 13, the image layer of Example 14 and the adhesive of Example 15 were successively coated on a 2 mil polyester film. 3 mil polyester film was then laminated on the above sheet. After imagewise exposure and delamination, each sheet was respectively again laminated on a silk screen. Then each silk screen was exposed by U.V.

light from the side of polyester film. As the polyester films were delaminated, both negative and positive silk screen printing masters were obtained. Silk screen printings were demonstrated by use of these screens, producing clean positive and negative ink images on paper.

AT WE CLAIM IS: 1. A multilayered sheet construction capable by delamination after imagewise exposure to an energy source of simultaneously reproducing both positive and negative forms of a photographic mask which comprises in order of juxtaposition i. a substantially gas impermeable first substrate, ii. an energy sensitive composition layer adjacent to the undersurface of said first

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

Claims (22)

**WARNING** start of CLMS field may overlap end of DESC **. Example 16 Four sheets of 2 mil polyester were coated with the sensitizer layer of Example 13. Each sheet was then respectively coated with an imaging laycr having a different color. These formulations were: For red image composition: Versamide 754 (General Mills) 45 g Toluene 135 g Isopropyl alcohol 81 ml Cyclohexanol 30 ml Rhodamine B-MS40 1.0 g For yellow: 1.0 g of Astragon Yellow-MS40 instead of Rhodamine B-MS40 was added into above formulation. For blue: 1.0 g of Brill Brilliant Blue instead of Rhodamine B-MS40 was substituted in above formulation. For black: The composition for the imaging layer in Example 13 was used. The adhesive composition of Example 15 was then applied to each of the four colored constructions. A sheet of plain white paper was then laminated on the glued surface of the yellow image construction, exposed to actinic light through a color separated transparency and delaminated to show a yellow image on the white sheet. The same sheet was then successively laminated to each of the other colored constructions, exposed through respective color separated transparencies in correct registration, and delaminated. By this process a one sheet color proof of the original image was obtained. Example 17 The sensitizer formulation of Example 13 was coated on a 2 mil polyester film and then coated with the following image layer: Versamide 940 (General Mills) 20 g Toluene 40 ml Isopropyl alcohol 40 ml This was then coated with the adhesive formulation of Example 13 and a 3 mil polyester film was then laminated to this construction. Actinic light was then imagewisely exposed through a transparent original from the side of the 3 mil polyester film. After delamination carbon black was dusted on the surface of the 3 mil mylar and a positive powder image was obtained. As this image was projected by overhead projector, a clean image was obtained on the screen. Example 18 The sensitizer of Example 13, the image layer of Example 14 and the adhesive of Example 15 were successively coated on a 2 mil polyester film. 3 mil polyester film was then laminated on the above sheet. After imagewise exposure and delamination, each sheet was respectively again laminated on a silk screen. Then each silk screen was exposed by U.V. light from the side of polyester film. As the polyester films were delaminated, both negative and positive silk screen printing masters were obtained. Silk screen printings were demonstrated by use of these screens, producing clean positive and negative ink images on paper. AT WE CLAIM IS:

1. A multilayered sheet construction capable by delamination after imagewise exposure to an energy source of simultaneously reproducing both positive and negative forms of a photographic mask which comprises in order of juxtaposition i. a substantially gas impermeable first substrate, ii. an energy sensitive composition layer adjacent to the undersurface of said first

substrate, said energy sensitive composition layer being capable of decomposing with concurrent generation of gas upon exposure to an energy source to which it is sensitive whereby a bubble of gas is formed which imparts to the construction an immediately visible image and exerts pressure upon the adjacent layers to facilitate their separation upon being delaminated, m. an imaging layer, iv. an adhesive composition layer and v. a second substrate supporting said adhesive layer in which the bond strengths between the layers is such that the weakest bond is either (a) that between the adhesive composition layer and the second substrate layer so that upon delamination the positive form of the photographic mask comprising the imaging and adhesive layers will adhere to the second substrate, while the negative form comprising the energy sensitive composition, the imaging layer and the adhesive layer will adhere to the first substrate, or (b) is that between the adhesive composition layer and the imaging layer so that upon delamination the positive form of the photographic mask comprising the imaging and adhesive layers will adhere to the second substrate, while the negative form comprising the imaging and photosensitive layers will adhere to the first substrate, and in which the transparency of the layers other than the energy sensitive composition layer is such that the energy'sensitive composition layer can be exposed to said energy source through the first or second substrate or both.

2. A modification of the multilayered sheet construction claimed in claim 1, in which the imaging and the adhesive composition layers are combined to form a single layer and in which the weakest bond is that between the second substrate layer and the combined imaging and adhesive composition layer.

3. A multilayered sheet construction as claimed in claim 1 or 2 in which the energy sensitive composition layer is sensitive to thermal or light energy.

4. A multilayered sheet construction as claimed in any of claims 1 to 3 in which the first substrate layer is flexible and transparent.

5. A method of fabricating the multilayered sheet construction claimed in claimed, which comprises forming a plurality of layers, each layer other than the first to be formed being applied to or formed on the surface of an adjacent layer whereby to form a multilayered sheet construction having the layers defined in claim 1 in the juxtapositions defined in claim 1, the bond strengths between adjacent layers being so determined that the weakest bond is either that between the adhesive composition layer and the second substrate layer or is that between the adhesive composition layer and the imaging layer.

6. A modification of the method claimed in claim 5, in which the multilayered sheet construction has the layers defined in claim 2 in the juxtaposition defined in claim 2 and in which the bond strengths of adjacent layers are so determined that the weakest bond strength is that between the combined imaging and adhesive compositions layer and the second substrate layer and whereby there is fabricated a multilayered sheet construction as claimed in claim

7. A method as claimed in claim 5 or 6 in which the energy sensitive composition layer is sensitive to thermal or light energy.

8. A multilayered sheet construction whenever produced by the method of claim 5, 6 or 7.

9. A method of fabricating the multilayered sheet construction claimed in claim 1, which comprises applying to or forming on a preformed multilayered sheet construction, a second substrate layer, said preformed construction in order of juxtaposition i. a substantially gas impermeable first substrate, ii. an energy sensitive composition layer adjacent the undersurface of said first substrate, said energy sensitive composition layer being capable of decomposing with concurrent generation of gas upon exposure to an energy source to which it is sensitive and, lii. an imaging layer in w which the application of the second substrate layer is achieved by interposing an adhesive composition layer between said second substrate layer and the imaging layer of the preformed construction, the bond strengths between adjacent layers of the final construction being such that the weakest bond is either that between the adhesive composition layer and the second substrate layer or is that between the adhesive composition layer and the imaging layer.

10. A method as claimed in claim 9 in which the adhesive composition layer forms part of the preformed multilayered sheet construction.

11. A method as claimed in claim 9 in which the adhesive composition layer is first applied to the second substrate layer, which is being applied to or formed on the imaging layer.

12. A modification of the method claimed in claim 9 in which the preformed multilayered sheet construction defined therein, the imaging layer and the adhesive composition layer are combined into a single imaging and adhesive composition layer, the second substrate layer is applied to or formed on the combined imaging and adhesive composition layer and the bond strengths between the adjacent layers of the preformed multilayered construction and the bond strength between the second substrate layer and the combined imaging layer and adhesive composition layer are such that the weakest bond is that between the second substrate layer and the combined imaging and adhesive composition layer, whereby to form a multilayered sheet construction as claimed in claim 2.

13. A method as claimed in any of claims 9 to 12 in which the energy sensitive composition layer is sensitive to thermal or light energy

14. A method of reproducing both positive and negative forms of a photographic mask which comprises exposing a multilayered sheet construction as defined in claim 1 or 2 through a photographic mask to an energy source to which the energy sensitive composition layer is sensitive whereby to decompose said energy sensitive composition layer at the portions thereof exposed to the energy source and subsequently delaminating the exposed multilayered sheet construction at the interface having the weakest bond strength whereby to simultaneously form both a positive and negative form of the photographic mask.

15. A method as claimed in claim 14 in which a single sheet is successively utilized to form the second substrate layer of a plurality of multilayered sheet constructions which are successively exposed and subsequently delaminated whereby to produce a second substrate layer having a plurality of superimposed negative images thereon.

16. A method as claimed in claim 15 in which the imaging layers of the successive multilayered sheet constructions have different colours whereby to produce a final multicoloured negative image.

17. A method as claimed in claim 14 in which the second substrate layer is a silk screen.

18. A multilayered sheet construction whenever produced by the method of any of claims 9 to 13.

19. A multilayered sheet construction as claimed in claim 1 or 2 substantially as hereinbefore described with reference to and as illustrated in Figures 1 and 4 of the accompanying drawings and in any one of the Examples

20. A multilayered sheet construction as claimed in claim 8, substantially as hereinbefore described with reference to and as illustrated in Figures 1 and 4 of the accompanying drawings and in any one of Examples 1 to 9 and 12 to 18.

21. A multilayered sheet construction as claimed in claim 18 substantially as hereinbefore described with reference to and as illustrated in Figures 6 and 7 of the accompanying drawings and in Examples 10 and 11.

22. A method as claimed in claim 14 substantially as hereinbefore described with reference to and as illustrated in Figures 1 to 8 of the accompanying drawings and in any one of the Examples.